WO2022143015A1 - 一种微气泡增压循环臭氧催化氧化反应器及处理污水的方法 - Google Patents

一种微气泡增压循环臭氧催化氧化反应器及处理污水的方法 Download PDF

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WO2022143015A1
WO2022143015A1 PCT/CN2021/135580 CN2021135580W WO2022143015A1 WO 2022143015 A1 WO2022143015 A1 WO 2022143015A1 CN 2021135580 W CN2021135580 W CN 2021135580W WO 2022143015 A1 WO2022143015 A1 WO 2022143015A1
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gas
water
tower
reaction
catalytic oxidation
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PCT/CN2021/135580
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English (en)
French (fr)
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李亮
付春明
刘祺
滕厚开
郝亚超
郝润秋
张成凯
李亚宁
肖彩英
周立山
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中海油天津化工研究设计院有限公司
中国海洋石油集团有限公司
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Publication of WO2022143015A1 publication Critical patent/WO2022143015A1/zh

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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
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/78—Details relating to ozone treatment devices
    • C02F2201/784—Diffusers or nozzles for ozonation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/06—Pressure conditions
    • C02F2301/066—Overpressure, high pressure

Definitions

  • the invention relates to the field of sewage treatment, in particular to a microbubble pressurized circulating ozone catalytic oxidation reaction device.
  • Advanced oxidation technology is a common technology for advanced sewage treatment, including ozone oxidation, photocatalysis, wet oxidation, etc.
  • ozone As a strong oxidant, under the action of a catalyst, ozone has the advantages of rapid reaction, complete degradation of organic matter, and no secondary pollution.
  • due to the characteristics of ozone its solubility in water is low and it is easy to decompose, resulting in low ozone utilization efficiency, and most of the ozone escapes or decomposes into oxygen.
  • the ozone reaction device in the form of reaction tower has obvious advantages, the floor space is reduced, and the water depth is increased compared with the reaction tank, which improves the utilization efficiency of ozone and reduces resource consumption while improving the reaction efficiency.
  • the outlet pressure of the ozone generator limits the effective height of the reaction tower to 6 meters, resulting in a limited amount of treated water in the reaction tower.
  • aeration methods are mainly based on aeration discs and aeration heads.
  • the diameter of the bubbles produced is usually millimeters or even centimeters. Large bubble diameters lead to small specific surface area, low mass transfer efficiency, and uneven distribution of bubbles. happening.
  • the purpose of the present invention is to solve the problems of the traditional ozone pool with large footprint, small outlet pressure of the ozone generator, and low ozone utilization rate, and to provide a microbubble pressurized circulating ozone catalytic oxidation reaction device.
  • the present invention provides a microbubble pressurized circulating ozone catalytic oxidation reaction device, which is realized by the following technical solutions:
  • a microbubble pressurized circulating ozone catalytic oxidation reaction device is characterized in that it comprises a reaction tower tower body, a water inlet pipe port is reserved at the bottom of the tower side wall, a water outlet and an exhaust port are arranged at the top of the tower, the water outlet is connected to a reflux tank, and the tower
  • a gas-water mixed liquid distribution device is arranged at the bottom of the tower body, a catalytic bed is fixed in the upper part of the tower body through a grid plate, and a gas-liquid mixing device is arranged outside the bottom of the tower body.
  • An outlet and a water outlet wherein the water inlet is connected with the water inlet pipe, the air inlet is connected with the ozone inlet pipe outside the reaction, the water outlet is connected with the gas-water mixed liquid distribution device through the pipeline, and the middle of the tower body is provided with
  • the supplementary aeration device connected with the ozone inlet pipe; the effective height of the reactor is 10-20m; the water outlet of the reflux tank is respectively connected with the water inlet pipe of the gas-liquid mixing device and the water inlet of the subsequent treatment device through pipes.
  • the outer shape of the reaction tower is cylindrical, the height-diameter ratio is 4:1-8:1, and the material is an oxidation-resistant metal or alloy.
  • the reaction tower body is made of stainless steel 304 and above.
  • the gas-water mixed liquid distribution system is composed of an outer ring coil and a branch pipe, wherein the diameter of the outer ring is larger than that of the branch pipe, and the diameter of the outer ring is larger than that of the branch pipe. connected, and the branch pipe is provided with a circular hole.
  • the catalyst filling height is 1/8 to 1/6 of the height of the reaction tower, and the catalyst is a sphere or a cylinder with a diameter of 3 to 5 mm.
  • the gas-liquid mixing device is a jet device, a gas-liquid mixing pump or a pressurized dissolved gas tank with a circulation ratio of 1 to 9 times.
  • the present invention further provides a method for treating sewage by utilizing the above-mentioned microbubble pressurized and circulating ozone catalytic oxidation reaction device, comprising the following steps: the sewage enters a gas-liquid mixing device for gas-liquid mixing to generate dissolved gas water rich in microbubbles; Dissolved gas water is introduced into the gas-water mixed liquid distribution device installed in the reaction tower through pipelines, and enters the reaction tower evenly through the gas-water mixed liquid distribution device, and is oxidatively decomposed and catalyzed from bottom to top under the action of ozone, ozone and catalyst.
  • reaction product water overflows from the water outlet at the top of the tower to the reflux tank, part of the product water returns to the gas-liquid mixing device and re-enters the reaction tower to continue the reaction, and the other part enters the follow-up treatment device as product water; wherein the reaction tower ozonates the air
  • the volume ratio to sewage treatment is 1:3 to 3:1.
  • the supplementary aeration device is turned on when the volume ratio of the ozonated air in the reaction tower to the sewage treatment volume is less than 1:3.
  • the micro-bubble pressurized circulating ozone catalytic oxidation reaction device of the present invention is more than the traditional ozone tower, which solves the problem that the tower height of the existing ozone generator does not exceed 6 meters due to the limitation of the outlet pressure, and the equipment occupies less space.
  • the land area is greatly reduced.
  • the device of the invention generates dissolved gas water rich in micro-nano bubbles by setting a gas-liquid generating device.
  • the greatly reduced diameter of the bubbles leads to an increase in the specific surface area of the bubbles, and the rising speed, merger and rupture of the bubbles are slowed down, so that the ozone dissolution rate is improved.
  • the liquid mass transfer efficiency is also improved, the amount of catalyst is also reduced, the material cost is reduced, and the ozone utilization rate is greatly improved.
  • the catalyst is not easy to be hardened, and the internal components of the device are not easy to be fouled and blocked, so the backwashing equipment is not installed in the device, which reduces the cleaning cost.
  • Example 1 is a schematic diagram of the structure and work flow of the microbubble pressurized circulating ozone catalytic oxidation reaction device in Example 1.
  • FIG. 2 is a schematic cross-sectional structural diagram of a gas-water mixed liquid distribution device in a microbubble pressurized circulating ozone catalytic oxidation reaction device.
  • the microbubble pressurized circulating ozone catalytic oxidation reaction device in this embodiment has an effective height of 10-20m, including a tower body 1, a gas-water mixed-liquid distribution device 2, a catalytic bed 3, and a gas-liquid mixing device.
  • Device 4 supplemental aeration device 5, exhaust gas destruction unit 6, return tank 7, ozone generator 8.
  • the tower body 1 is cylindrical in shape, with a height-diameter ratio of 4:1 to 8:1.
  • a water inlet port is reserved at the bottom of the side wall, a water outlet and an exhaust port are arranged on the top of the tower, and the water outlet is connected to a return tank 7 .
  • the bottom of the tower is provided with a gas-water mixed liquid distribution device 2, which consists of an outer coil 21 and a branch pipe 22, wherein the diameter of the outer ring is larger than that of the branch pipe, the diameter of the outer ring is connected to the branch pipe, and the branch pipe is provided with a circular hole.
  • a catalyst bed 3 is fixed in the upper part of the tower body through a grid plate, the catalyst filling height is 1/8-1/6 of the height of the reaction tower, and the catalyst is a sphere or a cylinder with a diameter of 3-5mm.
  • a gas-liquid mixing device 4 is provided outside the bottom of the tower body, which is composed of a jet device, a gas-liquid mixing pump or a pressurized dissolved gas tank, and its circulation ratio is 1 to 9 times.
  • the gas-liquid mixing device 4 is provided with a water inlet. , air inlet and water outlet, wherein the water inlet is connected with the water inlet pipe, the air inlet is connected with the ozone inlet pipe outside the reaction, the water outlet is connected with the gas-water mixed liquid distribution device 2 through the pipeline, and the tower body
  • a supplementary aeration device 5 connected to the ozone intake pipe is arranged in the middle, and the supplementary aeration device is turned on when the volume ratio of the ozonated air of the reaction device to the sewage treatment volume is less than 1:3.
  • the water outlet of the return tank is respectively connected with the water inlet pipe of the gas-liquid mixing device 4 and the water inlet of the subsequent processing device through pipes.
  • the working principle is as follows: the ozone gas is produced by the ozone generator 8, and enters the supplementary aeration device 5 all the way, and enters the gas-liquid mixing device 4 all the way. Entering the reaction tower, the ozone microbubbles slowly rise from the bottom of the tower, and the organic matter is decomposed under the action of ozone and catalyst.
  • the upper part of the tower body 1 is provided with a water outlet, and the water outlet is overflow, and enters the reflux tank 7.
  • a wire mesh demister is arranged in the reflux tank 7 to prevent the bubbles from being completely broken. All the way access to the efflux system or the next process equipment.
  • the gas-liquid mixing device 4 can be added or reduced according to the actual sewage situation.
  • the use of the gas-liquid mixing device solves the problem that the effective height of the reaction tower does not exceed 6m due to the limitation of the outlet pressure of the ozone generator. If the ozone dosage is insufficient, the aeration device can be supplemented by valve control to further improve the removal rate of organic matter. Due to the addition of micro-bubbles in the reaction system, the gas-liquid mass transfer effect is greatly enhanced, the amount of catalyst added can be greatly reduced, and the material cost is reduced. Washing system, reducing cleaning costs.
  • a kind of refining sewage which is treated in a 12m reaction unit.
  • a membrane concentrate treated in a 12m reactor.

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

Abstract

一种微气泡增压循环臭氧催化氧化反应器，包括反应塔塔体(1)，塔侧壁底部预留进水管口，塔顶设置出水口和排气口，出水口连接回流罐(7)，塔体(1)底部设置有气水混合液分布装置(2)，塔体(1)中上部通过格栅板固定有催化床(3)，塔体(1)底部外部设置有气液混合装置(4)，气液混合装置(4)上设置有进水口、进气口和出水口，其中进水口与进水管连接，进气口与反应器外部的臭氧进气管连接，出水口经管道与气水混合液分布装置(2)相连，塔体(1)中部设置有与臭氧进气管连接的补充曝气装置(5)；反应器有效高度为10～20m；回流罐(7)的出水口通过管道分别与气液混合装置(4)进水管、后续处理装置进水口连接。还包括一种微气泡增压循环臭氧催化氧化处理污水的方法。

Description

[根据细则37.2由ISA制定的发明名称]　一种微气泡增压循环臭氧催化氧化反应器及处理污水的方法 技术领域
本发明涉及污水处理领域，特别是涉及一种微气泡增压循环臭氧催化氧化反应装置。
背景技术
随着污水排放标准的不断提高，污水处理技术和设备也应不断创新以提高效率、降低成本。高级氧化技术是污水深度处理的常用技术，包括臭氧氧化，光催化，湿式氧化等。臭氧作为一种强氧化剂，在催化剂的作用下，具有反应迅速，降解有机物彻底，无二次污染等优势。然而由于臭氧的特性导致其在水中的溶解度低，易分解，造成臭氧利用效率低，大部分臭氧逸出或分解为氧气。
传统的工业臭氧反应装置多以反应池为主，池底设置曝气装置，这种反应方式不仅受环境影响较大，施工周期长，占地面积大，传质效率差且反应效率低。反应塔形式的臭氧反应装置相较于反应池优势明显，占地面积缩减，且水深较反应池增加，提高了臭氧的利用效率，在提高反应效率的同时减少了资源消耗。但由于目前现有技术的限制，臭氧发生器的出口压力限制了反应塔的有效高度为6米，导致反应塔的处理水量受限。传统的曝气方式多以曝气盘和曝气头为主，产生的气泡直径通常为毫米级甚至厘米级，气泡直径大导致比表面积小、传质效率低，且易出现气泡分布不均匀的情况。
发明内容
本发明的目的是解决传统臭氧池占地面积大，臭氧发生器出口压力小，臭氧利用率低等问题，提供一种微气泡增压循环臭氧催化氧化反应装置。
为实现上述技术问题，本发明提供了一种微气泡增压循环臭氧催化氧化反应装置，通过以下技术方案实现：
一种微气泡增压循环臭氧催化氧化反应装置，其特征在于，包括反应塔塔体，塔侧壁底部预留进水管口，塔顶设置出水口和排气口，出水口连接回流罐，塔体底部设置有气水混合液分布装置，塔体中上部通过格栅板固定有催化床，塔体底 部外部设置有气液混合装置，所述的气液混合装置上设置有进水口、进气口和出水口，其中进水口与进水管连接，进气口与反应外部的臭氧进气管连接，所述的出水口经管道与所述的气水混合液分布装置相连，塔体中部设置有与臭氧进气管连接的补充曝气装置；反应器有效高度为10～20m；回流罐的出水口通过管道分别与所述的气液混合装置进水管、后续处理装置进水口连接。
本发明所述的微气泡增压循环臭氧催化氧化反应装置，优选，所述的反应塔塔体外形为圆柱形，高径比4:1～8:1，材质为耐氧化金属或合金。
本发明所述的微气泡增压循环臭氧催化氧化反应装置，优选，所述的反应塔塔体为不锈钢304及以上。
本发明所述的微气泡增压循环臭氧催化氧化反应装置，优选，所述的气水混合液分布***由外圈盘管和支管组成，其中外圈管径大于支管，外圈管径与支管连通，支管开设圆孔。
本发明所述的微气泡增压循环臭氧催化氧化反应装置，优选，催化剂装填高度为反应塔高度的1/8～1/6，催化剂为球体或圆柱体，直径3～5mm。
本发明所述的微气泡增压循环臭氧催化氧化反应装置，优选，所述的气液混合装置为循环倍率为1～9倍的射流装置、气液混合泵或加压溶气罐。
本发明还进一步提供了一种利用上述微气泡增压循环臭氧催化氧化反应装置处理污水的方法，包括如下步骤，污水进入气液混合装置进行气液混合，产生富含微气泡的溶气水，溶气水通过管路引入设置在反应塔塔内的气水混合液分布装置，通过气水混合液分布装置均匀进入反应塔，自下而上在臭氧、臭氧和催化剂作用下进行氧化分解、催化氧化反应，反应产水从塔顶出水口溢流至回流罐，部分产水回流至气液混合装置重新进反应塔内继续反应，另一部分作为产水进入后续处理装置；其中反应塔臭氧化空气与污水处理体积比为1:3～3:1。
本发明的污水处理方法中，优选当反应塔臭氧化空气与污水处理体积比小于1:3时开启补充曝气装置。
与现有技术相比，本发明微气泡增压循环臭氧催化氧化反应装置较传统的臭氧塔，解决了现有臭氧发生器由于出口压力限制导致塔高不超过6米的问题，使设备的占地面积大大减小。本发明装置通过设置气液发生装置产生富含 微纳米级气泡的溶气水，气泡直径的大大缩小导致气泡比表面积增大，气泡上升的速度、合并、破裂减缓，使臭氧溶解率提高，气液传质效率也随之提高，同时也减少了催化剂的用量，降低材料成本的同时大大提高了臭氧利用率。同时在溶气水的强力冲击下，催化剂不易板结，装置内构件不易结垢堵塞，所以装置内免装反洗设备，降低了清洗成本。
附图说明
图1为实施例1中微气泡增压循环臭氧催化氧化反应装置的结构及工作流程示意图。
图2为微气泡增压循环臭氧催化氧化反应装置中气水混合液分布装置的剖面结构示意图。
图中标记：1-塔体，2-气水混合液分布装置，3-催化床4-气液混合装置，5-补充曝气装置，6-尾气破坏单元，7-回流罐，8-臭氧发生器，21-外圈盘管，22-支管。
具体实施方式
下面通过具体实施例结合说明书附图对本发明的技术方案及技术效果做进一步详细的说明。此处实施例仅用于解释本发明，并不用于限定本发明。
如图1-2所示，本实施例的微气泡增压循环臭氧催化氧化反应装置，有效高度为10～20m，包括塔体1，气水混合液分布装置2，催化床3，气液混合装置4，补充曝气装置5，尾气破坏单元6，回流罐7，臭氧发生器8。塔体1外形为圆柱形，高径比4:1～8:1，侧壁底部预留进水管口，塔顶设置出水口和排气口，出水口连接回流罐7。塔体底部设置有气水混合液分布装置2，由外圈盘管21和支管22组成，其中外圈管径大于支管，外圈管径与支管连通，支管开设圆孔。塔体中上部通过格栅板固定有催化床3，催化剂装填高度为反应塔高度的1/8～1/6，催化剂为球体或圆柱体，直径3～5mm。塔体底部外部设置有气液混合装置4，由射流装置、气液混合泵或加压溶气罐组成，其循环倍率为1～9倍，所述的气液混合装置4上设置有进水口、进气口和出水口，其中进水口与进水管连接，进气口与反应外部的臭氧进气管连接，所述的出水口经管道与所述的气水混合液分布装置 2相连，塔体中部设置有与臭氧进气管连接的补充曝气装置5，反应装置臭氧化空气与污水处理体积比小于1:3时开启补充曝气装置。回流罐的出水口通过管道分别与所述的气液混合装置4进水管、后续处理装置进水口连接。
工作原理如下：臭氧气由臭氧发生器8制得，一路进入补充曝气装置5，一路进入气液混合装置4，气液混合装置4接入处理污水，通过气水混合液分布装置2均匀释放进入反应塔内，臭氧微气泡自塔底缓慢上升，有机物在臭氧和催化剂的作用下被分解。塔体1上部设置出水口，出水方式为溢流，进入回流罐7，回流罐7内设置丝网除沫器，以防气泡不能完全破裂，回流罐出水一路接入气液混合装置进水管，一路接入外排***或下一个工艺设备。气液混合装置4可根据实际污水情况进行增设或缩减，气液混合装置的使用解决了由于臭氧发生器出口压力的限制反应塔有效高度不超过6m的问题。若臭氧投加量不足可通过阀门控制补充曝气装置，进一步提高有机物去除率。由于反应***内微气泡的加入，大大增强了气液传质效果，催化剂的加入量可大幅减少，降低了材料成本，同时在微气泡的强力冲击下，催化剂不易板结，反应装置内免装反洗***，降低了清洗成本。
实施例1
一种炼化污水，在12m的反应装置中处理。原水COD 80mg/L，pH 6.8，水量10m 3/h，臭氧化空气量9m 3/h，停留时间1h，出水COD 36mg/L，COD去除率55％。
实施例2
一种膜浓水，在12m的反应装置中处理。原水COD 240mg/L，水量14m 3/h，臭氧化空气量24m 3/h，停留时间1h，出水COD 106mg/L，COD去除率55.8％。

Claims (8)

  1. 一种微气泡增压循环臭氧催化氧化反应装置，其特征在于，装置有效高度为10～20m；包括反应塔塔体，塔侧壁底部预留进水管口，塔顶设置出水口和排气口，出水口连接回流罐，塔体底部设置有气水混合液分布装置，塔体中上部通过格栅板固定有催化床，塔体底部外部设置有气液混合装置，所述的气液混合装置上设置有进水口、进气口和出水口，其中进水口与进水管连接，进气口与反应外部的臭氧进气管连接，所述的出水口经管道与所述的气水混合液分布装置相连，塔体中部设置有与臭氧进气管连接的补充曝气装置，回流罐的出水口通过管道分别与所述的气液混合装置进水管、后续处理装置进水口连接。
  2. 根据权利要求1所述的微气泡增压循环臭氧催化氧化反应器，其特征在于，所述的反应塔塔体外形为圆柱形，高径比4:1～8:1，材质为耐氧化金属或合金。
  3. 根据权利要求2所述的微气泡增压循环臭氧催化氧化反应器，其特征在于，所述的反应塔塔体为不锈钢304及以上。
  4. 根据权利要求1所述的微气泡增压循环臭氧催化氧化反应器，其特征在于，所述的气水混合液分布装置由外圈盘管和支管组成，其中外圈管径大于支管，外圈管径与支管连通，支管开设圆孔。
  5. 根据权利要求1所述的微气泡增压循环臭氧催化氧化反应器，其特征在于，催化剂装填高度为反应塔高度的1/8～1/6，催化剂为球体或圆柱体，直径3～5mm。
  6. 根据权利要求1所述的微气泡增压循环臭氧催化氧化反应器，其特征在于，所述的气液混合装置为循环倍率为1～9倍的射流装置、气液混合泵或加压溶气罐。
  7. 一种用权利要求1所述的微气泡增压循环臭氧催化氧化反应器处理污水的方法，其特征在于，污水进入气液混合装置进行气液混合，产生富含微气泡的溶气水，溶气水通过管路引入设置在反应塔塔内的气水混合液分布装置，通过气水混合液分布装置均匀进入反应塔，自下而上在臭氧、臭氧和催化剂作用下进行氧化分解、催化氧化反应，反应产水从塔顶出水口溢流至回流罐，部分产水回流至气液混合装置重新进反应塔内继续反应，另一部分作为产水进入后续处理装置；其中反应塔臭氧化空气与污水处理体积比为1:3～3:1。
  8. 根据权利要求7所述的方法，其特征在于，反应塔臭氧化空气与污水处理体积比小于1:3时开启补充曝气装置。
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