WO2012151794A1 - 利用辅助燃料补给热量的超临界水氧化反应器 - Google Patents

利用辅助燃料补给热量的超临界水氧化反应器 Download PDF

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Publication number
WO2012151794A1
WO2012151794A1 PCT/CN2011/078050 CN2011078050W WO2012151794A1 WO 2012151794 A1 WO2012151794 A1 WO 2012151794A1 CN 2011078050 W CN2011078050 W CN 2011078050W WO 2012151794 A1 WO2012151794 A1 WO 2012151794A1
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salt
supercritical water
catalyst tank
zone
end cover
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PCT/CN2011/078050
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English (en)
French (fr)
Inventor
王树众
郭洋
徐东海
公彦猛
唐兴颖
张洁
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Xian Jiaotong University
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/06—Treatment of sludge; Devices therefor by oxidation
    • C02F11/08—Wet air oxidation
    • C02F11/086—Wet air oxidation in the supercritical state

Definitions

  • the invention belongs to the field of environmental protection and chemical industry, and particularly relates to a supercritical water treatment reactor for utilizing supercritical water as a reaction medium for harmless treatment of waste organic liquids such as organic wastewater/waste leachate which are difficult to biodegrade and biodegradable. . Background technique
  • Supercritical water combines the properties of liquid and gaseous water. Its dielectric constant is similar to that of non-polar organic solvents, with high diffusion coefficient and low viscosity. In this state, organic matter and oxygen can be mutually miscible with supercritical water in a maximum ratio, thereby causing the heterogeneous reaction to become a homogeneous reaction, which greatly reduces the resistance of mass transfer and heat transfer. Inorganic salts have extremely low solubility in supercritical water and are easily separated.
  • the continuously variable density, low electrostatic medium constant, and low viscosity of supercritical water make it an ideal reaction medium with high diffusion capacity and high solubility.
  • the temperature and pressure changes can be used to control the reaction environment, coordinate reaction rates and chemical equilibrium, and adjust catalyst selectivity.
  • SCWO Supercritical Water Oxidation
  • SCWO technology for the treatment of difficult to destroy toxic and hazardous substances (such as dye waste, pharmaceutical waste, lubricant waste, insulating oil containing PCBs, radioactive mixed waste, polychlorinated biphenyls, volatile acids, etc.), high concentration is difficult to degrade Organic waste (sludge, paper mill slurry, etc.), military toxic substances (chemical weapons, rocket propellants, explosives, etc.) have unique effects.
  • toxic and hazardous substances such as dye waste, pharmaceutical waste, lubricant waste, insulating oil containing PCBs, radioactive mixed waste, polychlorinated biphenyls, volatile acids, etc.
  • high concentration is difficult to degrade Organic waste (sludge, paper mill slurry, etc.), military toxic substances (chemical weapons, rocket propellants, explosives, etc.) have unique effects.
  • Salt deposition problems Water at normal temperature is an excellent solvent for most salts and has a high solubility. In contrast, most of the salts have very little solubility in low density supercritical water. When the subcritical solution is rapidly heated to the supercritical temperature, since the solubility of the salt is greatly reduced, a large amount of precipitates are precipitated, and the deposited salt may cause blockage of the inlet and outlet of the reactor, which not only affects the normal operation of the reactor, but also Will bring potential equipment hazards.
  • An object of the present invention is to provide a new structure supercritical water oxidation reactor which utilizes an auxiliary fuel as a method of replenishing reaction heat to solve the problem of energy replenishment in a supercritical water oxidation process, thereby improving the economics of the operation process of the apparatus.
  • the reactor is required to be easily disassembled, easy to load and replace the catalyst, easy to access and maintain, safe and reliable, and versatile.
  • a supercritical water oxidation reactor for replenishing heat by using auxiliary fuel comprising a kettle body and a catalyst box therein, wherein an upper end of the kettle body is fixed with an end cover, and a space between the end cover and the top of the catalyst tank top is In the high temperature combustion zone, the bottom of the catalyst tank is a salt separation zone; the bottom of the bottom of the kettle body is provided with a solid salt discharge port, and the solid salt discharge port is a subcritical salt dissolution zone; the bottom of the kettle body is provided with a product outlet and is connected with the subcritical salt dissolution zone.
  • a cooling water outlet and a liquid salt discharge port a cold air inlet and a material inlet are arranged on the end cover, and communicate with the high temperature combustion zone through the axial hole;
  • the fuel core tube is disposed at the center of the end cover and extends axially into the end cover above the high temperature combustion zone There is an annular gap between the outer circumference of the fuel core tube and the end cover, and a hot air inlet is connected to the annular gap through the horizontal hole on the side of the end cover;
  • the fuel core tube extends into the end cover portion and the spiral fin is arranged outside the tube wall;
  • the first temperature measuring sleeve with the armored thermocouple extends axially into the end cap;
  • the catalyst tank is fixed around the vertical section of the central tube, the inclined section of the central tube and the bottom of the kettle body The outlet is connected;
  • a cylindrical porous evaporation wall is arranged near the inner wall of the kettle body, and a second temperature measuring sleeve provided with an e
  • an end cap cooling ring groove is provided under the end cover, including an inner ring for air cooling.
  • the groove and the outer ring groove for material cooling the bottom surface of the inner ring groove has two holes, the inner ring hole is inclined downward toward the fuel core tube, and the outer ring hole is oblique to the porous evaporation wall; the outer ring groove has a ring hole at the bottom The direction is oblique to the fuel core tube.
  • the lower end outlet of the fuel core tube has a blind hole structure, and when the fuel flows out of the blind hole, a jet is formed around the four openings in the obliquely downward direction around the tube wall.
  • the catalyst tank is a cylinder body, and the bottom inlet of the cylinder body and the top outlet of the cylinder body are both porous circular plates, and a spherical box cover which can be easily disassembled is arranged above the top porous circular plate.
  • a third temperature measuring sleeve with a built-in armored thermocouple is arranged near the subcritical salt dissolution zone and the salt separation zone at the bottom of the kettle body.
  • the present invention provides a reactor end cap for a multi-flow conduit for the high temperatures that may be generated after combustion of the fuel. Both the cold oxidant and the material provide a cooling effect on the reactor end cap. Further, a cooling ring groove is provided below the end cap of the reactor to effectively isolate the high temperature combustion zone from the lower surface of the end cap. The diversion holes are arranged under the cooling ring groove in different directions, so that the fuel, the oxidant and the material can achieve sufficient jet collision in the combustion zone from different angles, thereby promoting efficient mixing and combustion of the fuel, which can not only effectively supply the reaction. The heat, and the high temperature emitted during combustion, can effectively decompose refractory substances such as ammonia nitrogen.
  • the peripheral side of the end cap of the present invention has a hot air inlet communicating with the annular gap between the outer side of the fuel core tube and the end cap through the horizontal direction passage as a high temperature oxidant delivery line.
  • the lower part of the core tube is provided with a spiral fin, and the bottom outlet is a blind hole structure, so that the fuel is sprayed obliquely around the lower part, the combustion area is enlarged, and the jet collision with the oxidant fluid is efficiently realized.
  • a catalyst tank and a spherical cover are arranged inside the reactor and fixed on the central pipe by welding, and the inlet and outlet of the catalyst tank are both porous plates.
  • the sealed space formed by the combination of the reactor end cap and the kettle body in which the catalyst tank is disposed forms a multi-folding structure, which can overcome the shortcoming of the tubular reactor, and effectively utilize the volume inside the reactor to increase the reaction time.
  • the supercritical water oxidation reactor for replenishing heat of fuel disclosed by the invention can be widely applied to the harmless treatment and resources of waste organic liquids such as organic wastewater/waste leachate which are highly concentrated and difficult to biodegrade. Utilization process.
  • FIG. 1 is a schematic view showing the structure of a supercritical water treatment reactor for replenishing heat by using auxiliary fuel according to the present invention.
  • a supercritical water oxidation reactor for replenishing heat by means of auxiliary fuel is combined with the end cap 15 and the kettle body 3 by fastening bolts 1 to form a closed reaction space.
  • the space between the end cap 15 and the top of the catalyst box dome is a high temperature combustion zone 16, the lower part of the catalyst tank is a salt separation zone 21, the bottom of the bottom of the kettle body is provided with a solid salt discharge port 6, and the upper region thereof is a subcritical salt dissolution zone. 17.
  • the fuel core tube 12 is axially disposed along the end cap in the center hole of the end cap, and is fixed in the end cap by a screw seal.
  • the fuel core tube is a fuel (methanol) conveying pipe, and the lower end thereof protrudes from the end cap and reaches the upper portion of the high temperature combustion zone 16.
  • the lower end outlet of the fuel core tube is designed as a blind hole structure, and when the fuel flows out of the blind hole, a jet is formed around the four openings in the obliquely downward direction around the pipe wall. To expand the burning area.
  • the end of the end cap is provided with a hot air inlet 11 which communicates with the annular gap between the outer side of the fuel core tube 12 and the end cap through a horizontal direction passage as a high temperature oxidant (hot air or oxygen) delivery line.
  • the fuel core tube is made of corrosion-resistant and high-temperature resistant alloy.
  • the fuel core tube extends into the end cover.
  • the outer side of the tube wall is provided with spiral fins (not shown) to swirl the oxidant (air or oxygen) fluid to promote it. Efficient mixing with fuel and easy installation and positioning of the core tube.
  • the end cover is further provided with a cold air inlet 13 (four distributed around the center hole of the end cover), a material inlet 14 (four uniformly distributed along the outer circumference of the center hole of the end cover), and communicates with the high temperature combustion zone 16 through the axial hole, the low temperature
  • An oxidant (cold air or oxygen) flows into the reactor through the cold air inlet 13.
  • the cold material enters the reactor from the material inlet 14. Both the cold material and the low temperature oxidant can function as end cap cooling.
  • An end cap temperature measuring sleeve 20 with an armored thermocouple is placed axially into the end cap to measure the temperature of the reaction zone.
  • an end cap cooling ring groove 10 is provided below the reactor end cap 15.
  • the ring groove is welded under the end cover, the inner ring groove is an air cooling ring groove (relative to the cold air inlet channel), the bottom of the ring groove has two holes, the inner ring hole is inclined downward toward the fuel core tube, and the outer ring hole is obliquely porous In the direction of the evaporating wall, the former provides secondary air to the fuel to ensure full combustion of the fuel, and the latter provides complete or partial oxidation of the material;
  • the outer ring groove is a material cooling ring groove (relative to the material inlet channel), and the bottom surface has a ring hole downwardly inclined In the direction of the fuel core tube, the low temperature material is effectively wrapped around the flame zone, the effect of the high temperature fluid on the evaporation wall is reduced, and the end cover can be effectively cooled.
  • the reactor end cap is provided with a temperature measuring sleeve 20 and a built-in armored thermocouple for temperature measurement.
  • the structure enables the material, the cold oxidant, the high temperature oxidant and the fuel fluid to collide with jets from different directions, efficiently mixes and forms a high temperature zone, and facilitates the removal of difficult to oxidize substances (such as ammonia nitrogen, etc.).
  • a cylindrical porous evaporation wall 4 is disposed near the inner wall of the kettle body 3.
  • the outer side of the kettle body is provided with an evaporation wall water inlet 9 and a temperature measuring sleeve 19 connected to the annular cavity formed by the porous evaporation wall and the inner wall of the kettle body.
  • the clean water After the clean water is preheated, it enters the evaporation wall ring cavity from the evaporation wall water inlet 9 and passes through the porous evaporation wall to form a uniform water film on the inner side, which can effectively prevent salt deposition and corrosion.
  • the temperature measuring sleeve 19 has a built-in armored thermocouple to measure and monitor the reactor wall temperature, the evaporation wall temperature and the temperature distribution of the reaction fluid inside the reactor to achieve subsequent adjustment of reaction conditions, temperature gradient distribution and safety control. .
  • the catalyst tank 2 is fixed around the vertical section of the central tube 22, and the inclined section of the central tube communicates with the product outlet 7 at the bottom of the kettle body.
  • the catalyst tank 2 is a cylinder, and the bottom inlet and the top outlet are both porous discs.
  • a spherical cover that can be easily disassembled is disposed above the top outlet porous disk, and is fixed to the catalyst tank body by screws.
  • a lifting ring can be arranged above the spherical cover to facilitate mechanical work during catalyst replacement.
  • the lid separates the combustion zone from the catalytic zone, and the heat released by the reaction fluid in the combustion zone can effectively replenish the fluid in the tank cover to meet the process requirements.
  • a cooling water inlet 8 is arranged at the bottom of the kettle body 3, and the amount of cooling water can be adjusted according to the process conditions during the reaction to control the temperature of the molten salt zone.
  • a desalination zone temperature measuring sleeve 18 is arranged near the subcritical salt-dissolving zone 17 and near the salt separation zone 21, and a built-in armored thermocouple penetrates into the desalting zone at the bottom of the catalyst tank, and the temperature of the salt separation zone 21 and the salt storage zone 17 is performed. Detection.
  • the bottom center outlet of the kettle body 3 is a solid salt discharge port 6, and the insoluble salts are intermittently discharged according to actual operation.
  • the dissolved salt is continuously discharged from the reactor through the liquid salt discharge port 5.
  • the specific working process of the present invention is that the fuel and the oxidant are preheated by the high temperature and then enter the inside of the reactor through the fuel core tube 12 and the outer annulus of the core tube, respectively.
  • the fuel and oxidant burn quickly to release a large amount of heat.
  • the low temperature preheated material and a portion of the preheated oxidant enter the reactor end cap cooling ring groove 10 through the material inlet 14 and the cold air inlet 13, respectively.
  • the material, oxidant and fuel are jetted and collided from different directions, and the mixture is efficiently mixed and exothermic in the combustion zone.
  • the reaction fluid flows from the annular gap between the outside of the catalyst tank and the evaporation wall to the lower side of the reactor, and the solid salt is separated from the reaction fluid in the desalting zone 21 by gravity.
  • the fluid flows from the porous disk at the lower end of the catalyst tank into the catalyst tank and then flows to the upper portion of the catalyst bed.
  • the fluid enters the central tube 22 and flows out of the reactor through the product outlet 7 from top to bottom.
  • the separated solid salt enters the molten salt zone 17 and is discharged through the solid salt discharge port 6 at the bottom, and the soluble salt is discharged through the liquid salt discharge port 5 to the reactor.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Description

利用辅助燃料补给热量的超临界水氧化反应器 所属领域
本发明属于环境保护及化工领域， 特别涉及利用超临界水作为反应介质 对高浓度难生化降解的有机废水 /垃圾渗滤液等废有机液体进行无害化处理过 程的一种超临界水处理反应器。 背景技术
超临界水是指温度和压力均高于其临界点 （T=374.2°C， P=22.1MPa) 的 特殊状态的水。 超临界水兼具液态和气态水的性质， 介电常数近似于非极性 有机溶剂， 具有高的扩散系数和低的粘度。 在此状态下， 有机物、 氧气能按 最大比例与超临界水互溶， 从而使非均相反应变为均相反应， 大大减小了传 质、 传热的阻力。 而无机盐类在超临界水中的溶解度极低， 容易将其分离出 来。 因此超临界水这种可连续变化的密度、 低静电介质常数、 低粘滞度的特 性使其成为一种具有高扩散能力、 高溶解性的理想反应介质。 可以利用其温 度与压力的变化来控制反应环境、 协调反应速率与化学平衡、 调节催化剂的 选择性等。
超临界水氧化技术 (Supercritical Water Oxidation,简称 SCWO)是利用水在 超临界状态下所具有的特殊性质， 使有机物和氧化剂在超临界水中迅速发生 氧化反应来彻底分解有机物， 将其完全转化成无害的 C02、 1¾和1¾0等小分 子化合物。 SCWO技术对于处理那些难消毁的有毒有害物质 (如染料废物、 制 药废物、 润滑剂废物、 含 PCBs的绝缘油、 放射性混合废物、 多氯联苯、 易挥 发性酸等)、 高浓度难降解的有机废物（污泥、 造纸厂料浆等）、 军用毒害物质 (化学武器， 火箭推进剂， 炸药等） 具有独特的效果。
虽然超临界水处理技术已经取得了很大进歩， 关于应用超临界水技术的 试验装置和商业装置， 目前国内外已有相关报道， 但是仍有待解决反应器中 盐沉积引起的堵塞问题、 高腐蚀速率问题、 以及运行经济性等问题， 具体表 现在：
1 ) 材料腐蚀问题。 由于超临界水反应装置处于高温、 高压条件下， 尤其 是有机物中含有卤素、 硫或磷等， 在超临界水中分解后会产生酸， 引起设备 的强烈腐蚀； 即使具有较好耐蚀性的镍基材料， 在超临界水中， 特别是在亚 临界水中， 仍容易遭受严重的腐蚀。
2)盐沉积问题。常温下水对大多数盐来说是一种优良溶剂， 溶解度较大。 相反， 大部分盐在低密度的超临界水中溶解度极小。 当亚临界溶液被迅速加 热到超临界温度时， 由于盐的溶解度大幅度降低， 有大量沉淀析出， 沉积的 盐会引起反应器进出口管路堵塞， 这不仅影响了反应器的正常运行， 还会带 来潜在的设备隐患。
3 )经济性问题。虽然 SCWO过程是一个放热反应， 当有机物的质量分数 达到 2~3 %时就能实现自热，但在设备启动过程中依然需要外部热源对其进行 补热。 目前国外的超临界水氧化设备的加热方式绝大部分采用电加热形式， 这不仅造成设备投资费用巨大， 而且对此项技术的大规模工业化应用造成了 巨大障碍。 发明内容
本发明的目的是提供一种利用辅助燃料作为补给反应热量的方法以解决 超临界水氧化过程能量补给的问题的新结构超临界水氧化反应器， 进而提高 装置运行过程的经济性。 除此之外， 要求该反应器方便拆装， 容易装载和更 换催化剂， 易于检修和维护， 能够安全可靠运行， 具有多功能性。
为达到以上目的， 本发明是采取如下技术方案予以实现的：
一种利用辅助燃料补给热量的超临界水氧化反应器， 包括釜体及其中的 催化剂箱， 其特征在于， 釜体上端固联有端盖， 端盖与催化剂箱箱顶上方之 间的空间为高温燃烧区， 催化剂箱下方为盐分离区； 釜体底部中心设有固体 盐排出口， 固体盐排出口上方为亚临界溶盐区； 釜体底部设有产物出口、 与 亚临界溶盐区连通的冷却水出口和液体盐排出口； 端盖上设置冷空气入口和 物料入口， 并通过轴向孔道与高温燃烧区连通； 端盖中心设置燃料芯管轴向 伸进端盖于高温燃烧区上方； 燃料芯管外周与端盖之间有环隙， 端盖侧面开 有热空气入口通过水平孔道与环隙联通； 燃料芯管伸进端盖部分管壁外侧设 有螺旋翅片； 端盖上开有铠装热电偶的第一测温套管轴向伸进端盖内； 催化 剂箱固定在中心管的垂直段周围， 中心管的倾斜段与釜体底部的产物出口连 通； 靠近釜体内壁设置有筒状多孔蒸发壁， 釜体外侧设置有蒸发壁入水口和 铠装热电偶的第二测温套管连通至多孔蒸发壁与釜体内壁所形成的环腔中。
上述方案中， 在端盖下面设置端盖冷却环槽， 包括用于空气冷却的内环 槽和用于物料冷却的外环槽， 内环槽底面有两圈孔， 内圈孔向下斜向燃料芯 管方向， 外圈孔斜向多孔蒸发壁方向； 外环槽底面有一圈孔向下斜向燃料芯 管方向。
所述的燃料芯管下端出口为盲孔结构， 燃料流出盲孔时通过管壁四周斜 下方向的 4个开孔向四周形成射流。
所述催化剂箱为筒体， 该筒体底部入口和筒体顶部出口均为多孔圆板， 其顶部多孔圆板上方设置有可以方便拆卸的球形箱盖。
所述釜体底部亚临界溶盐区与盐分离区附近设有内置铠装热电偶的第三 测温套管。
与现有的超临界水氧化反应器相比， 本发明的优点在于：
1、 本发明针对燃料燃烧后可能产生的高温， 设置多流通管道的反应器端 盖。 冷态氧化剂和物料都能对反应器端盖起到冷却作用。 进一歩的， 在反应 器端盖下方设置冷却环槽， 可将高温燃烧区和端盖下平面有效隔离开。 并在 冷却环槽下面布置有不同方向的导流孔， 使燃料、 氧化剂以及物料从不同角 度在燃烧区实现充分的射流对撞， 促进燃料的高效混合和燃烧， 不仅能有效 的补给反应所需的热量， 而且燃烧时放出的高温能够有效地对氨氮等难降解 物质进行彻底分解。
2、 本发明端盖周侧开有热空气入口通过水平方向孔道与燃料芯管外侧和 端盖之间的环隙连通， 作为高温氧化剂输送管路。 芯管下部设有螺旋翅片， 底部出口为盲孔结构， 使燃料斜向下部四周进行喷射， 扩大燃烧面积， 高效 实现与氧化剂流体的射流对撞。
3、 在反应器底部设置冷却水入口， 通过调节冷却水流量大小， 可精确控 制排盐区温度。 同时当反应器底部脱盐管道发生堵塞， 可以通过调节冷却水 流量以提高底部盐的溶解性； 当发生反应器超温、 超压事故时， 可以通入冷 却水快速降低反应器内部温度和压力， 确保设备的安全运行。
4、 在反应器内部设置催化剂箱及球形箱盖并由焊接的形式固定在中心管 上， 催化剂箱入口和出口均为多孔板。 反应器端盖和内设置催化剂箱的釜体 结合后形成的密封空间， 形成多折流式结构， 能够克服管式反应器尺寸长的 缺点， 有效利用反应釜体内容积， 增加反应时间。
本发明公开的燃料补给热量的超临界水氧化反应器， 可以广泛应用于高 浓度、 难生化降解的有机废水 /垃圾渗滤液等废有机液体的无害化处理和资源 化利用过程。 附图说明
图 1 为本发明利用辅助燃料补给热量的超临界水处理反应器的结构示意 图。 其中 1、 紧固螺栓； 2、 催化剂箱； 3、 釜体； 4、 多孔蒸发壁； 5、 液体盐 排出口； 6、 固体盐排出口； 7、 产物出口； 8、 冷却水入口； 9、 蒸发壁水入 口； 10、 端盖冷却环槽； 11、 热空气入口； 12、 燃料芯管； 13、 冷空气入口； 14、 物料入口； 15、 端盖； 16、 高温燃烧区； 17、 亚临界溶盐区； 18、 脱盐 区测温套管； 19、 蒸发壁环腔测温套管； 20、 反应器端盖测温套管； 21、 盐 分离区； 22、 中心管。 具体实施方式
如图 1所示， 一种利用辅助燃料补给热量的超临界水氧化反应器， 由端 盖 15和釜体 3通过紧固螺栓 1结合形成密闭反应空间。 端盖 15与催化剂箱 圆顶上方之间的空间为高温燃烧区 16， 催化剂箱下方区域为盐分离区 21， 釜 体底部中心设有固体盐排出口 6， 其上方区域为亚临界溶盐区 17。
燃料芯管 12沿端盖轴向布置于端盖中心孔，通过螺纹密封固定于端盖内， 燃料芯管内为燃料 （甲醇） 输送管道， 其下端伸出端盖并达到高温燃烧区 16 上方。 燃料芯管下端出口设计成盲孔结构， 燃料流出盲孔时通过管壁四周斜 下方向的 4个开孔向四周形成射流。 以扩大燃烧面积。 端盖周侧开有热空气 入口 11通过水平方向孔道与燃料芯管 12外侧和端盖之间的环隙连通， 作为 高温氧化剂 （热空气或氧气） 输送管路。
燃料芯管采用耐腐蚀、 耐高温合金材质， 燃料芯管伸进端盖部分管壁外 侧设有螺旋翅片 （图中未画出）， 使氧化剂 （空气或氧气） 流体产生旋流以促 进其与燃料的高效混合， 同时可方便芯管的安装和定位。 端盖上还设置冷空 气入口 13 (沿端盖中心孔四周均布四个）、 物料入口 14 (沿端盖中心孔外周 均布四个）， 通过轴向孔道与高温燃烧区 16连通， 低温氧化剂 （冷空气或氧 气）通过冷空气入口 13流入反应器。 冷态物料由物料入口 14进入反应器内。 冷态物料和低温氧化剂都能起到端盖冷却的作用。 端盖上开有铠装热电偶的 端盖测温套管 20轴向伸进端盖内， 以测量反应区域温度。
为了防止高温燃烧区 16 可能放出过高的热量而造成端盖超温的安全隐 患， 在反应器端盖 15下方设置端盖冷却环槽 10。 环槽焊接在端盖下方， 内环 槽为空气冷却环槽 （相对冷空气入口通道）， 环槽底部有两圈孔道， 内圈孔向 下斜向燃料芯管方向， 外圈孔斜向多孔蒸发壁方向， 前者提供给燃料二次风， 保证燃料充分燃烧， 后者提供给物料进行完全或部分氧化； 外环槽为物料冷 却环槽 （相对物料入口通道）， 底面有一圈孔向下斜向燃料芯管方向， 使低温 物料对火焰区进行有效包裹， 降低高温流体对蒸发壁所造成的影响， 也可对 端盖进行有效冷却。 反应器端盖设置测温套管 20并内置铠装热电偶进行温度 测量。 此结构能够使物料、 冷态氧化剂、 高温氧化剂以及燃料流体从不同方 向形成射流对撞， 进行高效混和并形成高温区， 有利于难氧化物质 （例如氨 氮等） 的去除。
靠近釜体 3内壁设置有筒状多孔蒸发壁 4，釜体外侧设置有蒸发壁入水口 9和测温套管 19连通至多孔蒸发壁与釜体内壁所形成的环腔中。 洁净水预热 后从蒸发壁水入口 9进入蒸发壁环腔后， 穿过多孔蒸发壁并在内侧形成均匀 水膜， 能够有效的防止盐沉积和腐蚀。 测温套管 19内置铠装热电偶来测量和 监测反应器釜体壁温、 蒸发壁壁温以及反应器内部反应流体的温度分布， 以 实现后续反应条件的调节、 温度的梯度分布和安全控制。
催化剂箱 2固定在中心管 22垂直段周围， 中心管的倾斜段与釜体底部的 产物出口 7连通。 催化剂箱 2为筒体， 底部入口和顶部出口均为多孔圆板。 其顶部出口多孔圆板上方设置可以方便拆卸的球形箱盖， 采用螺钉固定于催 化剂箱筒体上。 该球形箱盖上方可设置有吊环， 方便催化剂更换时的机械作 业。 箱盖将燃烧区和催化区隔离开， 而且使反应流体在燃烧区所放出的热量 能够有效地对箱盖内流体进行补热， 以满足流程工艺要求。
釜体 3底部设有冷却水入口 8，可在反应过程中根据工艺条件调节冷却水 量以控制溶盐区温度。 同时还有两个作用： （i)当反应器底部脱盐管道发生堵 塞， 可以通过冷却水的通入提高底部盐的溶解性； （ii) 当发生反应器超温、 超压事故时， 可以通入冷却水快速降低反应器内部温度和压力， 确保设备的 安全运行。 在亚临界溶盐区 17附近和盐分离区 21 附近设置脱盐区测温套管 18并内置铠装热电偶深入到催化剂箱体底部的脱盐区域，对盐分离区 21及储 盐区 17温度进行检测。 釜体 3底部中心出口为固体盐排出口 6， 根据实际操 作情况， 间歇式排出不溶解性盐。 溶解性盐通过液体盐排出口 5连续式排出 反应器。 本发明的具体工作过程是， 燃料和氧化剂通过高温预热后分别通过燃料 芯管 12和芯管外侧环隙进入反应器内部。 当温度达到燃料起燃点时， 燃料和 氧化剂迅速燃烧放出大量热。 经过低温预热的物料和一部分不经过预热的氧 化剂分别通过物料入口 14和冷空气入口 13进入反应器端盖冷却环槽 10中。 物料、 氧化剂与燃料从不同方向进行射流、 对撞， 在燃烧区进行高效混合放 热。 反应流体经过高温燃烧区后， 从催化剂箱外侧和蒸发壁之间的环隙流向 反应器下方， 固体盐在重力作用下与反应流体在脱盐区 21进行分离。 进行重 力除盐过程后， 流体由催化剂箱下端多孔圆板进入催化剂箱后向催化剂床层 上部流动， 经过催化氧化反应过程后， 进入中心管 22， 由上至下通过产物出 口 7流出反应器。 分离后的固体盐进入溶盐区 17， 并通过底部的固体盐排出 口 6排出， 溶解性盐通过液体盐排出口 5排出反应器。

Claims

权 利 要 求 书
1、 一种利用辅助燃料补给热量的超临界水氧化反应器， 包括釜体及其中 的催化剂箱， 其特征在于， 釜体上端固联有端盖， 端盖与催化剂箱箱顶上方 之间的空间为高温燃烧区， 催化剂箱下方为盐分离区； 釜体底部中心设有固 体盐排出口， 固体盐排出口上方为亚临界溶盐区； 釜体底部设有产物出口、 与亚临界溶盐区连通的冷却水入口和液体盐排出口； 端盖上设置冷空气入口 和物料入口通过轴向孔道与高温燃烧区连通； 端盖中心设置燃料芯管轴向伸 进端盖于高温燃烧区上方； 燃料芯管外周与端盖之间有环隙， 端盖侧面开有 热空气入口通过水平孔道与环隙联通； 燃料芯管伸进端盖部分管壁外侧设有 螺旋翅片； 端盖上开有铠装热电偶的第一测温套管轴向伸进端盖内； 催化剂 箱固定在一个中心管的垂直段周围， 中心管的倾斜段与釜体底部的产物出口 连通； 靠近釜体内壁设置有筒状多孔蒸发壁， 釜体外侧设置有蒸发壁入水口 和铠装热电偶的第二测温套管连通至多孔蒸发壁与釜体内壁所形成的环腔 中。
2、 如权利要求 1所述的利用辅助燃料补给热量的超临界水氧化反应器， 其特征在于， 在端盖下面设置端盖冷却环槽， 包括用于空气冷却的内环槽和 用于物料冷却的外环槽， 内环槽底面有两圈孔， 内圈孔向下斜向燃料芯管方 向， 外圈孔向下斜向多孔蒸发壁方向； 外环槽底面有一圈孔向下斜向燃料芯 管方向。
3、 如权利要求 1所述的利用辅助燃料补给热量的超临界水氧化反应器， 其特征在于， 所述的燃料芯管下端出口为盲孔结构， 燃料流出盲孔时通过管 壁四周斜下方向的 4个开孔向四周形成射流。
4、 如权利要求 1所述的利用辅助燃料补给热量的超临界水氧化反应器， 其特征在于， 所述催化剂箱为筒体， 该筒体底部入口和筒体顶部出口均为多 孔圆板， 其顶部多孔圆板上设可拆卸的球形箱盖。
5、 如权利要求 1所述的利用辅助燃料补给热量的超临界水氧化反应器， 其特征在于， 釜体底部亚临界溶盐区与盐分离区附近设有内置铠装热电偶的 第三测温套管。
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CN117046387A (zh) * 2023-08-30 2023-11-14 上海交通大学 内嵌式密封高温高压反应釜装置

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