WO2020155692A1 - 一种以导热油为换热介质的污泥超临界水氧化系统及污泥处理方法 - Google Patents

一种以导热油为换热介质的污泥超临界水氧化系统及污泥处理方法 Download PDF

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WO2020155692A1
WO2020155692A1 PCT/CN2019/113365 CN2019113365W WO2020155692A1 WO 2020155692 A1 WO2020155692 A1 WO 2020155692A1 CN 2019113365 W CN2019113365 W CN 2019113365W WO 2020155692 A1 WO2020155692 A1 WO 2020155692A1
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sludge
heat
thermal hydrolysis
heat transfer
heat exchanger
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French (fr)
Inventor
王树众
杨健乔
张熠姝
徐海涛
王栋
张宝权
李艳辉
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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
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/06—Treatment of sludge; Devices therefor 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
    • 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
    • C02F11/18—Treatment of sludge; Devices therefor by thermal conditioning

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  • the invention belongs to the technical field of chemical industry and environmental protection, and specifically relates to a sludge supercritical water oxidation system using heat transfer oil as a heat exchange medium and a sludge treatment method.
  • Supercritical water refers to water in a special state whose temperature and pressure both exceed the critical point of water (374°C, 22.1MPa). As the phase state of water enters the supercritical state, the density and ion product constant of the water are significantly reduced, and the viscosity is greatly reduced. The decline leads to increased liquidity. At the same time, supercritical water tends to be a non-polar fluid, which can almost completely dissolve organic matter and gas.
  • Supercritical water oxidation (supercritical water oxidation) technology takes advantage of the many advantages of supercritical water, and uses supercritical water as a medium for the oxidation reaction of organic matter in high-concentration organic wastewater/sludge with oxygen, and performs rapid, rapid, Efficient removal.
  • supercritical water oxidation technology has been widely used in the fields of military industry, chemical industry, aerospace, ship and environmental protection, and is used to treat high-concentration refractory organic matter such as wastewater and sludge generated in various fields, and convert organic matter into Harmless carbon dioxide, nitrogen, water and other substances.
  • Supercritical water oxidation technology has the following advantages:
  • the reaction speed is extremely fast, and the oxidation reaction can be completed within hundreds of seconds.
  • the reaction efficiency is high. Because of the high temperature and high pressure environment, the COD removal rate of organic matter can generally reach more than 99%.
  • sludge thermal hydrolysis reaction is irreversible. Once the thermal hydrolysis reaction is completed, there is no need to worry about the transportation of sludge in the system. Therefore, the sludge thermal hydrolysis technology is used as a pretreatment method for sludge supercritical water It is very effective on the oxidation device.
  • the supercritical water oxidation reaction is an exothermic reaction.
  • the exothermic heat of the reaction still remains after the cold material is preheated, which can be directly applied to the heat source of the sludge thermal hydrolysis device.
  • some current devices are also designed in this way.
  • the purpose of the present invention is to provide a sludge supercritical water oxidation system and a sludge treatment method using heat transfer oil as the heat exchange medium.
  • the system has a reasonable structure and can solve the problem of internal coil heating.
  • the problem of scaling and coking of the sludge on the surface of the inner coil of the sludge thermal hydrolysis tank improves the stability and reliability of the system.
  • the invention discloses a sludge supercritical water oxidation system using heat transfer oil as a heat exchange medium, which includes a sludge thermal hydrolysis tank, a heat exchanger, a reactor and a heat transfer oil heat exchanger;
  • the sludge thermal hydrolysis tank is connected to the heat exchanger through a material pump, the tube side outlet end of the heat exchanger is connected to the reactor inlet end, and the reactor outlet end is connected to the shell side inlet end of the heat exchanger.
  • the shell-side outlet of the heat exchanger is connected with the inlet end of the heat transfer oil heat exchanger, and the outlet end of the heat transfer oil heat exchanger is connected with the heating coil set on the outer wall of the sludge thermal hydrolysis tank;
  • It also includes a back pressure valve and a three-phase separator that are connected to the pipe side outlet of the heat transfer oil heat exchanger in sequence.
  • the pipe side outlet end of the heat transfer oil heat exchanger is connected to the back pressure valve inlet, and the outlet of the back pressure valve is separated from the three phases.
  • the inlet of the three-phase separator is connected with an exhaust port at the top of the three-phase separator, a slag discharge port at the bottom, and a liquid discharge port on the cylinder wall.
  • the sludge thermal hydrolysis tank includes a first sludge thermal hydrolysis tank and a second sludge thermal hydrolysis tank that are connected, and the material pump is arranged at the connection between the second sludge thermal hydrolysis tank and the heat exchanger. On the pipeline.
  • it also includes an electric heater connected to the shell side outlet of the heat transfer oil heat exchanger, and the outlet of the electric heater is connected to the heating coil inlet on the outer wall of the second sludge thermal hydrolysis tank.
  • the outlet of the heating coil on the outer wall of the hydrolysis tank is connected with the inlet of the heating coil on the outer wall of the first sludge thermal hydrolysis tank, and the outlet of the heating coil on the outer wall of the first sludge thermal hydrolysis tank is connected with an oil-gas separator through a pipeline;
  • the outlet of the oil-air separator is connected with a filter through a pipeline, and the outlet of the filter is connected to the shell side inlet of the heat transfer oil heat exchanger through a pipeline at the outlet end of the circulating pump, the shell side outlet of the heat transfer oil heat exchanger and the electric heater Connected, another pipeline at the outlet end of the circulating pump is connected with an electric heater, and an automatic regulating valve is arranged on the pipeline.
  • It also includes an electric heater connected to the shell-side outlet of the heat transfer oil heat exchanger.
  • the outlet of the electric heater is connected to the heating coil inlet on the outer wall of the second sludge thermal hydrolysis tank.
  • the outlet of the heating coil is connected with the inlet of the heating coil on the outer wall of the first sludge thermal hydrolysis tank, and the outlet of the heating coil on the outer wall of the first sludge thermal hydrolysis tank is connected with an oil-gas separator through a pipeline;
  • step 1) the sludge is first transported into the first sludge thermal hydrolysis tank, after completing a certain degree of thermal hydrolysis, it enters the second sludge thermal hydrolysis tank to complete the complete thermal hydrolysis reaction;
  • step 3 the heat transfer oil is heated by the heat transfer oil heat exchanger and then enters the electric heater for secondary heating. When reaching a predetermined temperature, it enters the heating coil on the outer wall of the second sludge thermal hydrolysis tank, and transfers the heat to the second sewage.
  • the sludge in the sludge thermal hydrolysis tank then continues to flow into the heating coil on the outer wall of the first sludge thermal hydrolysis tank to heat the sludge in the first sludge thermal hydrolysis tank; then, it flows through the first sludge
  • the heat-conducting oil from the mud thermal hydrolysis tank enters the oil-gas separator, then passes through the filter and the circulating pump in turn, then returns to the heat-conducting oil heat exchanger, and continues to be heated, completing a cycle.
  • another pipeline at the outlet end of the circulating pump is connected to the electric heater, and an automatic regulating valve is provided on the pipeline; the opening of the automatic regulating valve is interlocked with the outlet temperature of the heat transfer oil heat exchanger shell, which can be adjusted through the valve The opening degree controls the amount of heat transfer oil flowing through the heat transfer oil heat exchanger, so that the temperature of the shell side fluid outlet of the heat transfer oil heat exchanger is maintained at the set value.
  • the present invention has the following beneficial effects:
  • the sludge supercritical water oxidation system using heat transfer oil as the heat exchange medium disclosed by the present invention uses heat transfer oil with good fluidity and small heat capacity as the heat exchange medium, and the sludge thermal hydrolysis tank in the supercritical water oxidation device
  • the internal heating method is changed to external wall surface heating, which can solve the problem of sludge scaling and coking on the surface of the internal coil heating type sludge thermal hydrolysis tank.
  • the prior art adopts the method of installing a high-pressure coil in the tank. Because the fluid after the supercritical water oxidation reaction generally has a large amount of inorganic salt ions generated by the reaction and oxygen involved in the reaction, it is highly corrosive and It is a high-temperature and high-pressure fluid, and only high-grade metal materials are needed as equipment materials, and a larger wall thickness needs to be selected for pressure and corrosion resistance.
  • the present invention uses relatively low-temperature, non-corrosive, and normal-pressure heat transfer oil as the heat exchange medium, and can use thinner-walled ordinary stainless steel or even carbon steel as equipment materials, which significantly reduces the cost.
  • the prior art adopts a scheme of installing high-pressure heating coils in a sealed sludge thermal hydrolysis tank, and cannot monitor the wall thickness reduction of the internal coils in real time. If there is corrosion perforation, leakage or even stress Corrosion and cracking will cause serious dangerous accidents in the chemical system "high-low series", that is, high-pressure fluid is discharged into a low-pressure confined space, which may cause the explosion of the entire thermal hydrolysis tank, which is extremely dangerous. However, if the heating coil on the outer wall of the sludge thermal hydrolysis tank disclosed in the present invention is used, the above potential safety accidents will not occur.
  • the sludge will coke and scale on the internal coil of the thermal hydrolysis tank, which will seriously affect the heat exchange effect. Since the sludge thermal hydrolysis tank needs to reach a high temperature higher than 100°C, a constant pressure device must be installed in the tank to avoid high temperature vaporization of the sludge, which means that the device is airtight during operation and cannot be simply disassembled. To clean up the dirt on the surface of the pipeline, it can only be forced to shut down for cleaning, which seriously affects the safety and stability of system operation.
  • the heating coil on the outer wall of the sludge thermal hydrolysis tank disclosed in the present invention can effectively avoid the above-mentioned problems and improve the reliability of the system.
  • the sludge thermal hydrolysis tank is equipped with a stirrer, which can drive the sludge in the tank to continuously rotate and stay in a flowing state. On the one hand, it avoids deposition, on the other hand, it increases the heat transfer coefficient and strengthens the heat transfer.
  • the present invention also discloses a method for treating sludge using the above-mentioned system of the present invention.
  • the heat released by the supercritical water oxidation reaction through the heat transfer oil heat exchanger uses the heat transfer oil as the heat exchange medium to convert the heat of the high-pressure, highly corrosive heat source It becomes a normal pressure and non-corrosive heat source, which improves the safety, economy, and reliability of the system; therefore, the heat transfer oil is used as the heat exchange medium to perform sludge thermal hydrolysis and finally complete the supercritical water oxidation reaction ,
  • the method to achieve the emission standards can fully realize the long-term safe and stable operation of the system.
  • Fig. 1 is a schematic structural diagram of the sludge supercritical water oxidation system using heat transfer oil as the heat exchange medium of the present invention.
  • 1 is the first sludge thermal hydrolysis tank
  • 2 is the second sludge thermal hydrolysis tank
  • 3 is the material pump
  • 4 is the heat exchanger
  • 5 is the reactor
  • 6 is the heat transfer oil heat exchanger
  • 7 is the heat exchanger Back pressure valve
  • 8 is a three-phase separator
  • 9 is an expansion tank
  • 10 is an oil and gas separator
  • 11 is a filter
  • 12 is a circulating pump
  • 13 is an electric heater
  • 14 is an automatic regulating valve.
  • FIG. 1 is a sludge supercritical water oxidation system using heat transfer oil as the heat exchange medium of the present invention, which includes a sludge thermal hydrolysis pretreatment unit, a heat transfer oil heat exchange unit and a supercritical water oxidation unit.
  • the sludge thermal hydrolysis unit includes a first sludge thermal hydrolysis tank 1 and a second sludge thermal hydrolysis tank 2.
  • the first sludge thermal hydrolysis tank 1 and the second sludge thermal hydrolysis tank 2 are connected: sludge The raw materials first enter the first sludge thermal hydrolysis tank 1;
  • the supercritical water oxidation reaction unit includes a heat exchanger 4, a reactor 5, a heat transfer oil heat exchanger 6, a back pressure valve 7 and a three-phase separator 8.
  • the pipe connecting the sludge thermal hydrolysis tank 2 and the heat exchanger 4 There is a material pump 3 on the road, the pipe side outlet end of the heat exchanger 4 is connected with the inlet end of the reactor 5, the outlet end of the reactor 5 is connected with the shell side inlet end of the heat exchanger 4, and the shell side of the heat exchanger 4
  • the outlet is connected to the pipe side inlet end of the heat transfer oil heat exchanger 6, the pipe side outlet end of the heat transfer oil heat exchanger 6 is connected to the inlet of the back pressure valve 7, and the outlet of the back pressure valve 7 is connected to the inlet of the three-phase separator 8,
  • the top of the three-phase separator 8 is provided with an exhaust port, the bottom is provided with a slag discharge port, and the cylinder wall is provided with a liquid discharge port. All three phases can achieve standard discharge
  • the heat transfer oil unit includes a heat transfer oil heat exchanger 6, an electric heater 13, a filter 11, a circulating pump 12, an automatic regulating valve 14, an expansion tank 9, and an oil and gas separator 10.
  • the outlet of the oil-air separator 10 is connected with the inlet of the filter 11, the outlet of the filter 11 is connected with the inlet of the circulating pump 12, the outlet of the circulating pump 12 is connected with the shell side inlet of the heat transfer oil heat exchanger 6, and the heat transfer oil heat exchanger
  • the shell-side outlet of 6 is connected to the electric heater 13, and there is a way from the outlet of the circulating pump 12 directly connected to the electric heater 13.
  • the outer wall coil inlet of the sludge thermal hydrolysis tank 2 is connected, and the outer wall coil outlet of the second sludge thermal hydrolysis tank 2 is connected with the outer wall coil inlet of the first sludge thermal hydrolysis tank 1.
  • the outlet of the outer wall coil of the hydrolysis tank 1 is connected with the inlet of the oil-gas separator 10, the top of the oil-gas separator 10 has a gas outlet connected with the expansion tank 9, and the heat transfer oil heat exchanger 6 is between the shell side outlet and the inlet of the electric heater 13 There is also an outlet connected to the expansion tank 9 on the pipeline.
  • the first sludge thermal hydrolysis tank 1 and the second sludge thermal hydrolysis tank 2 are provided with a stirring device inside, and a heating coil is provided on the outer wall surface, and the heat transfer oil flows in the outer heating coil to transfer heat to the tank On the body wall, the sludge in the tank is driven to rotate by the stirring device.
  • the automatic regulating valve 14 is pneumatic or electric.
  • the invention also discloses a method for thermally hydrolyzing sludge based on the above-mentioned system using heat transfer oil as a heat exchange medium, and finally completing the supercritical water oxidation reaction and realizing discharge compliance, which includes the following steps:
  • the sludge raw material is first transported into the first sludge thermal hydrolysis tank 1, after completing a certain degree of thermal hydrolysis, it enters the second sludge thermal hydrolysis tank 2 to complete the complete thermal hydrolysis reaction.
  • the heat of the sludge thermal hydrolysis tank is provided by the high-temperature heat transfer oil flowing in the heating coil arranged outside the tank.
  • the heat-conducting oil flowing through the first thermal hydrolysis tank 1 enters the oil-air separator 10, then passes through the filter 11 and the circulating pump 12 and then returns to the heat-conducting oil heat exchanger 6 to continue to be heated to complete a cycle.

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Abstract

本发明公开了一种以导热油为换热介质的污泥超临界水氧化系统及污泥处理方法，污泥通入污泥热水解罐，然后经物料泵输送至换热器升温并与氧气混合，在反应器中发生超临界水氧化反应，释放大量热量。反应后的高温流体首先经过换热器，然后经过导热油换热器，将热量传递给导热油。导热油进入污泥热水解罐的外壁盘管实现对污泥热水解罐的加热，保障热水解反应的进行。通过导热油换热器将超临界水氧化反应释放的热量以导热油作为换热介质，将高压、强腐蚀性热源的热量转换成了常压、无腐蚀性热源，全面提高了系统安全性、经济性、可靠性，完成超临界水氧化反应、实现达标排放。

Description

一种以导热油为换热介质的污泥超临界水氧化系统及污泥处理方法 技术领域
本发明属于化工及环保技术领域，具体涉及一种以导热油为换热介质的污泥超临界水氧化系统及污泥处理方法。
背景技术
超临界水是指温度和压力均超过水的临界点(374℃、22.1MPa)的特殊状态的水，随着水的相态进入超临界态，水的密度、离子积常数显著降低，粘度大幅下降导致流动性增强。同时，超临界水趋向于非极性流体，对有机物和气体几乎可以实现完全溶解。
超临界水氧化(supercritical water oxidation)技术是利用了超临界水的诸多优势，将超临界水作为高浓度有机废水/污泥中的有机物与氧气发生氧化反应的媒介，进行有机污染物的快速、高效去除。目前，超临界水氧化技术已经在世界范围内广泛应用于军工、化工、航天、舰船及环保等领域，用于处理各领域产生的废水和污泥等高浓度难降解有机物，将有机物转化为无害的二氧化碳、氮气以及水等物质。超临界水氧化技术具有以下几个优势：
1、反应速度极快，可在数百秒内完成氧化反应。
2、反应效率高，由于是高温高压环境，有机物的COD去除率普遍可以达到99％以上。
3、由于氧化反应自身是放热的，系统中有机物浓度较为充足时可以实现自热。
由于超临界水氧化技术的巨大优势，在包括中国在内的全世界范围内，该技术正在迅速推广。我国目前现有的超临界水氧化装置的主要处理对象为市政污泥以及各个化工行业废水处理厂产生的工业污泥。
然而，在污泥超临界水氧化技术推广应用过程中，发现了如下缺陷：
为了使得污泥具有流动性，能在设备管道中流动，在污泥给料进入超临界水氧化系统之前，普遍需要将其进行稀释处理，使其含水率升高从而降低粘度。另一方面，在待处理污泥中加入大量清水，使得待处理的污泥量增加，从而提高了运行成本，这是任何商业化装置都无法接受的。除了加水稀释外，另一个能提高污泥流动性的方法是加热，因为污泥具有粘度随温度的升高而降低的特性，而且污泥在200℃左右发生热水解反应，该反应可以使得污泥中的部分微生物细胞体受热膨胀而破裂，释放出有机物和水分，从而增大污泥的流动性。污泥热水解反应是不可逆的，一旦完成热水解反应，就不用再担心污泥在系统中输送的问题，因此将污泥热水解技术作为一个预处理手段应用于污泥超临界水氧化装置上是十分有效的。
超临界水氧化反应是放热反应，反应放热在将冷物料完成预热之后仍有剩余，可以直接应用于污泥热水解装置的热源。事实上，当前的一些装置也是这样设计的，通过在热水解罐内设置盘管，使得反应后且经过换热器的高温高压热流体进入热水解罐，与罐中的污泥进行换热，将罐中的污泥加热到预设温度，从而实现污泥热水解反应，降低污泥粘度。
然而，在实际运行的过程中出现了一个十分棘手的问题难以解决，即污泥会在热水解罐的内盘管上结焦、结垢，严重影响换热效果。由于污泥热水解罐需要达到高于100℃的高温，罐内需要设置定压装置来避免污泥高温汽化，也就是说该装置在运行过程中是密闭的，无法简单的通过拆开罐体去清理管道表面的泥垢，只能被迫停机清洗，严重影响系统运行的安全稳定性。
发明内容
为了克服上述现有技术的缺点，本发明的目的在于提供一种以导热油为换热介质的污泥超临界水氧化系统及污泥处理方法，该系统结构设置合理，能够解决 内盘管加热式的污泥热水解罐存在的污泥在内盘管表面结垢、结焦的问题，提高系统的稳定性、可靠性。
为了达到上述目的，本发明采用以下技术方案予以实现：
本发明公开了一种以导热油为换热介质的污泥超临界水氧化系统，包括污泥热水解罐、换热器、反应器和导热油换热器；
其中，污泥热水解罐通过物料泵与换热器相连，换热器的管侧出口端与反应器的入口端相连，反应器的出口端与换热器的壳侧入口端相连，换热器的壳侧出口与导热油换热器的入口端相连，导热油换热器的出口端与污泥热水解罐的外壁设置的加热盘管相连；
还包括与导热油换热器的管侧出口依次相连的背压阀和三相分离器，导热油换热器的管侧出口端与背压阀入口连接，背压阀的出口与三相分离器的入口连接，在三相分离器的顶部设有排气口，底部设有排渣口，筒壁上设有排液口。
优选地，所述污泥热水解罐包括相连的第一污泥热水解罐和第二污泥热水解罐，物料泵设置在第二污泥热水解罐与换热器相连的管路上。
更进一步优选地，还包括与导热油换热器的壳侧出口相连的电加热器，电加热器的出口与第二污泥热水解罐外壁的加热盘管入口相连，第二污泥热水解罐外壁的加热盘管出口与第一污泥热水解罐外壁的加热盘管入口相连，第一污泥热水解罐外壁的加热盘管出口通过管路连接有油气分离器；
油气分离器的出口通过管路连接有过滤器，过滤器的出口通过循环泵出口端的一路管路连接至导热油换热器的壳侧入口，导热油换热器的壳侧出口与电加热器相连，循环泵出口端的另一路管路与电加热器相连，在该管路上设有自动调节阀。
更进一步优选地，还包括膨胀槽，油气分离器的顶端的气体出口与膨胀槽相连。
更进一步优选地，导热油换热器壳侧出口与电加热器入口之间的管路上设有一个与膨胀槽相连的支路。
优选地，污泥热水解罐内设有搅拌装置。
本发明还公开了基于上述的以导热油为换热介质的污泥超临界水氧化系统的污泥处理方法，包括以下步骤：
1)将污泥通入污泥热水解罐中进行热水解反应，由污泥热水解罐外壁的加热盘管中流动的高温导热油提供热水解反应所需热量；
2)完成热水解的污泥经物料泵输送至换热器进行预热，然后进入反应器与氧气混合发生超临界水氧化反应，释放大量热量；
3)反应后的高温流体先经过换热器进行第一阶段换热，将热量直接传递给经过热水解的污泥；然后经过导热油换热器，将尚存的热量传递给导热油；导热油进入污泥热水解罐外壁的加热盘管实现对污泥热水解罐的加热，保障热水解反应的进行；
4)彻底完成热量传递的反应后流体接近常温，经过背压阀降压作用回到常压，然后在三相分离器中完成气液固成分分离，分别实现达标排放。
优选地，污泥热水解罐包括相连的第一污泥热水解罐和第二污泥热水解罐；
还包括与导热油换热器的壳侧出口相连的电加热器，电加热器的出口与第二污泥热水解罐外壁的加热盘管入口相连，第二污泥热水解罐外壁的加热盘管出口与第一污泥热水解罐外壁的加热盘管入口相连，第一污泥热水解罐外壁的加热盘管出口通过管路连接有油气分离器；
油气分离器的出口通过管路连接有过滤器，过滤器的出口通过循环泵出口端的一路管路连接至导热油换热器的壳侧入口，导热油换热器的壳侧出口与电加热器相连；
步骤1)中，污泥首先输送进入第一污泥热水解罐，完成一定程度的热水解 后进入第二污泥热水解罐，完成彻底的热水解反应；
步骤3)中，导热油经导热油换热器加热后进入电加热器进行二次加热，达到预定温度进入第二污泥热水解罐外壁的加热盘管中，将热量传递给第二污泥热水解罐中的污泥，然后继续流到第一污泥热水解罐外壁的加热盘管中，加热第一污泥热水解罐中的污泥；随后，流过第一污泥热水解罐的导热油进入油气分离器，然后依次经过过滤器和循环泵后回到导热油换热器中，继续被加热，完成了一个循环。
优选地，循环泵出口端的另一路管路与电加热器相连，在该管路上设有自动调节阀；自动调节阀的开度与导热油换热器壳侧出口温度联锁，能够通过调节阀门开度控制流过导热油换热器的导热油量，使导热油换热器的壳侧流体出口温度保持在设定值。
与现有技术相比，本发明具有以下有益效果：
本发明公开的以导热油为换热介质的污泥超临界水氧化系统，以流动性好、热容量小的导热油作为换热介质，将超临界水氧化装置中的污泥热水解罐的内加热方式改为外部壁面加热，能够解决内盘管加热式的污泥热水解罐存在的污泥在内盘管表面结垢、结焦的问题，从经济性、安全性及可靠性方面对比，得到本发明的系统的显著优势，结果如下：
第一，经济性：现有技术中采用罐内设置高压盘管的方法，由于超临界水氧化反应后的流体普遍具有大量反应生成的无机盐离子及反应参与的氧气，具有强腐蚀性，而且是高温高压流体，需要才要高等金属材料作为设备材料，而且需要选取较大壁厚来承压、耐蚀。而本发明采用温度相对较低、无腐蚀性、常压的导热油作为换热介质，则可以采用较薄壁厚的普通不锈钢甚至碳钢作为设备材料，显著降低成本。
第二，安全性：现有技术采用在密封的污泥热水解罐中设置高压加热盘管的 方案，无法实时监控内部盘管的壁厚减薄情况，如果出现腐蚀穿孔、渗漏甚至应力腐蚀开裂，则会发生化工系统的严重危险事故“高低串”，即高压流体泄放到了低压密闭空间，有可能造成整个热水解罐的爆炸，危险性极高。而采用本发明公开的污泥热水解罐外壁的加热盘管则不会出现上述潜在安全事故。
第三，可靠性：采用内部盘管加热的方式，污泥会在热水解罐的内盘管上结焦、结垢，严重影响换热效果。由于污泥热水解罐需要达到高于100℃的高温，罐内需要设置定压装置来避免污泥高温汽化，也就是说该装置在运行过程中是密闭的，无法简单的通过拆开罐体去清理管道表面的泥垢，只能被迫停机清洗，严重影响系统运行的安全稳定性。而采用本发明所公开的污泥热水解罐外壁的加热盘管则可以有效避免上述问题，提高系统的可靠性。
进一步地，污泥热水解罐中设置有搅拌器，可以带动罐内的污泥持续转动，一直处于流动状态，一方面避免沉积，一方面增大换热系数，强化换热。
本发明还公开了采用本发明的上述系统处理污泥的方法，通过导热油换热器将超临界水氧化反应释放的热量以导热油作为换热介质，将高压、强腐蚀性热源的热量转换成了常压、无腐蚀性热源，提高了系统安全性、经济性、可靠性；因此，应用了本发明的以导热油为换热介质进行污泥热水解并最终完成超临界水氧化反应、实现达标排放的方法，完全可以实现系统的长期安全稳定运行。
附图说明
图1为本发明的以导热油为换热介质的污泥超临界水氧化系统的结构示意图。
其中，1为第一污泥热水解罐，2为第二污泥热水解罐，3为物料泵，4为换热器，5为反应器，6为导热油换热器，7为背压阀，8为三相分离器，9为膨胀槽，10为油气分离器，11为过滤器，12为循环泵，13为电加热器，14为自动调节阀。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
需要说明的是，本发明的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
下面结合附图对本发明做进一步详细描述：
参见图1，为本发明的一种以导热油为换热介质的污泥超临界水氧化系统，包括污泥热水解预处理单元、导热油换热单元和超临界水氧化单元。
污泥热水解单元包括第一污泥热水解罐1和第二污泥热水解罐2，第一污泥热水解罐1与第二污泥热水解罐2相连：污泥原料首先进入第一污泥热水解罐1；
超临界水氧化反应单元包括换热器4、反应器5、导热油换热器6、背压阀7及三相分离器8，在污泥热水解罐2与换热器4相连的管路上设有物料泵3，换热器4的管侧出口端与反应器5的入口端相连，反应器5的出口端与换热器4的壳侧入口端相连，换热器4的壳侧出口与导热油换热器6的管侧入口端相连，导热油换热器6的管侧出口端与背压阀7入口连接，背压阀7的出口与三相分离器8的入口连接，在三相分离器8的顶部设有排气口，底部设有排渣口，筒壁上设 有排液口，三相均可以实现达标排放。
导热油单元包括导热油换热器6、电加热器13、过滤器11、循环泵12、自动调节阀14、膨胀槽9及油气分离器10。油气分离器10的出口与过滤器11的入口连接，过滤器11的出口与循环泵12的入口连接，循环泵12的出口与导热油换热器6的壳侧入口连接，导热油换热器6的壳侧出口与电加热器13相连，同时从循环泵12的出口还有一路直接与电加热器13相连，二者之间设有自动调节阀14，电加热器13的出口与第二污泥热水解罐2的外壁盘管入口相连，第二污泥热水解罐2的外壁盘管出口与第一污泥热水解罐1的外壁盘管入口相连，第一污泥热水解罐1的外壁盘管出口与油气分离器10入口连接，油气分离器10的顶端有一个气体出口与膨胀槽9相连，导热油换热器6壳侧出口与电加热器13入口之间的管路上也设有一个出口与膨胀槽9相连。
所述的第一污泥热水解罐1、第二污泥热水解罐2内部设有搅拌装置，外壁面设有加热盘管，导热油在外加热盘管中流动，将热量传递给罐体壁面，罐体内的污泥被搅拌装置带动而转动。
所述的自动调节阀14采用气动或电动形式。
本发明还公开了一种基于上述系统以导热油为换热介质进行污泥热水解并最终完成超临界水氧化反应、实现达标排放的方法，包括以下步骤：
1)污泥原料首先输送进入第一污泥热水解罐1，完成一定程度的热水解后进入第二污泥热水解罐2，完成彻底的热水解反应。此时污泥热水解罐的热量由布置在罐体外部的加热盘管中流动的高温导热油提供。
2)完成热水解的污泥经过物料泵3输送到换热器4进行预热，然后进入反应器5与氧气混合发生超临界水氧化反应，反应后的高温流体首先经过换热器4进行第一阶段换热，将热量直接传递给经过热水解的污泥。然后，尚存有相当部分热量的反应后流体流过导热油换热器6，将热量传递给导热油。
3)彻底完成热量传递的反应后流体此时已接近常温，经过背压阀7降压作用回到常压，然后在三相分离器8中完成气液固成分分离，分别实现达标排放。
4)此处介绍导热油换热子系统的实现方法：导热油经导热油换热器6加热后进入电加热器13进行二次加热，然后达到预定温度进入第二污泥热水解罐2外壁的盘管，将热量传递给第二污泥热水解罐2中的污泥，然后继续流到第一热水解罐1外壁的盘管，加热第一热水解罐1中的污泥。此时两个污泥热水解罐中的搅拌器均处于开机工作状态。随后，流过第一热水解罐1的导热油进入油气分离器10，然后依次经过过滤器11和循环泵12后回到导热油换热器6中，继续被加热，完成了一个循环。
所述的步骤4)中，导热油在进入导热油换热器6前具有一个由自动调节阀14控制的短路旁路，该自动调节阀14的开度与导热油换热器6壳侧出口温度联锁，能够通过调节阀门开度控制流过导热油换热器的导热油量，从而使导热油换热器6的壳侧流体出口温度保持在设定值。
本领域的技术人员可以理解，上文所描述的实施例都是示例性的，并且本领域的技术人员可以对其进行改进，各种实施例中所描述的结构在不发生结构或者原理方面的冲突的情况下可以进行自由组合，从而在解决本发明的技术问题。
在详细说明本发明的实施例之后，本领域的技术人员可清楚的了解，在不脱离随附权利要求的保护范围与精神下可进行各种变化与改变，且本发明亦不受限于说明书中所举示例性实施例的实施方式。

Claims (9)

  1. 一种以导热油为换热介质的污泥超临界水氧化系统，其特征在于，包括污泥热水解罐、换热器(4)、反应器(5)和导热油换热器(6)；
    其中，污泥热水解罐通过物料泵(3)与换热器(4)相连，换热器(4)的管侧出口端与反应器(5)的入口端相连，反应器(5)的出口端与换热器(4)的壳侧入口端相连，换热器(4)的壳侧出口与导热油换热器(6)的入口端相连，导热油换热器(6)的出口端与污泥热水解罐的外壁设置的加热盘管相连；
    还包括与导热油换热器(6)的管侧出口依次相连的背压阀(7)和三相分离器(8)，导热油换热器(6)的管侧出口端与背压阀(7)入口连接，背压阀(7)的出口与三相分离器(8)的入口连接，在三相分离器(8)的顶部设有排气口，底部设有排渣口，筒壁上设有排液口。
  2. 根据权利要求1所述的以导热油为换热介质的污泥超临界水氧化系统，其特征在于，所述污泥热水解罐包括相连的第一污泥热水解罐(1)和第二污泥热水解罐(2)，物料泵(3)设置在第二污泥热水解罐(2)与换热器(4)相连的管路上。
  3. 根据权利要求2所述的以导热油为换热介质的污泥超临界水氧化系统，其特征在于，还包括与导热油换热器(6)的壳侧出口相连的电加热器(13)，电加热器(13)的出口与第二污泥热水解罐(2)外壁的加热盘管入口相连，第二污泥热水解罐(2)外壁的加热盘管出口与第一污泥热水解罐(1)外壁的加热盘管入口相连，第一污泥热水解罐(1)外壁的加热盘管出口通过管路连接有油气分离器(10)；
    油气分离器(10)的出口通过管路连接有过滤器(11)，过滤器(11)的出口通过循环泵(12)出口端的一路管路连接至导热油换热器(6)的壳侧入口，导热油换热器(6)的壳侧出口与电加热器(13)相连，循环泵(12)出口端的另一路管路与电加热器(13)相连，在该管路上设有自动调节阀(14)。
  4. 根据权利要求3所述的以导热油为换热介质的污泥超临界水氧化系统，其特征在于，还包括膨胀槽(9)，油气分离器(10)的顶端的气体出口与膨胀槽(9)相连。
  5. 根据权利要求4所述的以导热油为换热介质的污泥超临界水氧化系统，其特征在于，导热油换热器(6)壳侧出口与电加热器(13)入口之间的管路上设有一个与膨胀槽(9)相连的支路。
  6. 根据权利要求1～5中任意一项所述的以导热油为换热介质的污泥超临界水氧化系统，其特征在于，污泥热水解罐内设有搅拌装置。
  7. 基于权利要求1所述的以导热油为换热介质的污泥超临界水氧化系统的污泥处理方法，其特征在于，包括以下步骤：
    1)将污泥通入污泥热水解罐中进行热水解反应，由污泥热水解罐外壁的加热盘管中流动的高温导热油提供热水解反应所需热量；
    2)完成热水解的污泥经物料泵输送至换热器(4)进行预热，然后进入反应器(5)与氧气混合发生超临界水氧化反应，释放大量热量；
    3)反应后的高温流体先经过换热器(4)进行第一阶段换热，将热量直接传递给经过热水解的污泥；然后经过导热油换热器(6)，将尚存的热量传递给导热油；导热油进入污泥热水解罐外壁的加热盘管实现对污泥热水解罐的加热，保障热水解反应的进行；
    4)彻底完成热量传递的反应后流体接近常温，经过背压阀(7)降压作用回到常压，然后在三相分离器(8)中完成气液固成分分离，分别实现达标排放。
  8. 根据权利要求7所述的污泥处理方法，其特征在于，污泥热水解罐包括相连的第一污泥热水解罐(1)和第二污泥热水解罐(2)；
    还包括与导热油换热器(6)的壳侧出口相连的电加热器(13)，电加热器(13)的出口与第二污泥热水解罐(2)外壁的加热盘管入口相连，第二污泥热水解罐 (2)外壁的加热盘管出口与第一污泥热水解罐(1)外壁的加热盘管入口相连，第一污泥热水解罐(1)外壁的加热盘管出口通过管路连接有油气分离器(10)；
    油气分离器(10)的出口通过管路连接有过滤器(11)，过滤器(11)的出口通过循环泵(12)出口端的一路管路连接至导热油换热器(6)的壳侧入口，导热油换热器(6)的壳侧出口与电加热器(13)相连；
    步骤1)中，污泥首先输送进入第一污泥热水解罐(1)，完成一定程度的热水解后进入第二污泥热水解罐(2)，完成彻底的热水解反应；
    步骤3)中，导热油经导热油换热器(6)加热后进入电加热器(13)进行二次加热，达到预定温度进入第二污泥热水解罐(2)外壁的加热盘管中，将热量传递给第二污泥热水解罐(2)中的污泥，然后继续流到第一污泥热水解罐(1)外壁的加热盘管中，加热第一污泥热水解罐(1)中的污泥；随后，流过第一污泥热水解罐(1)的导热油进入油气分离器(10)，然后依次经过过滤器(11)和循环泵(12)后回到导热油换热器(6)中，继续被加热，完成一个循环。
  9. 根据权利要求8所述的污泥处理方法，其特征在于，循环泵(12)出口端的另一路管路与电加热器(13)相连，在该管路上设有自动调节阀(14)；
    自动调节阀(14)的开度与导热油换热器(6)壳侧出口温度联锁，能够通过调节阀门开度控制流过导热油换热器(6)的导热油量，使导热油换热器(6)的壳侧流体出口温度保持在设定值。
PCT/CN2019/113365 2019-01-31 2019-10-25 一种以导热油为换热介质的污泥超临界水氧化系统及污泥处理方法 Ceased WO2020155692A1 (zh)

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