WO2012051875A1 - 高含盐量有机废水的超临界水处理系统 - Google Patents

高含盐量有机废水的超临界水处理系统 Download PDF

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Publication number
WO2012051875A1
WO2012051875A1 PCT/CN2011/078036 CN2011078036W WO2012051875A1 WO 2012051875 A1 WO2012051875 A1 WO 2012051875A1 CN 2011078036 W CN2011078036 W CN 2011078036W WO 2012051875 A1 WO2012051875 A1 WO 2012051875A1
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Prior art keywords
outlet
inlet
reactor
supercritical
tank
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PCT/CN2011/078036
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English (en)
French (fr)
Inventor
王树众
公彦猛
徐东海
唐兴颖
马红和
郭洋
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西安交通大学
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Publication of WO2012051875A1 publication Critical patent/WO2012051875A1/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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • 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
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/38—Gas flow rate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/10—Energy recovery
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies

Definitions

  • the invention relates to a system for harmlessly treating biodegradable organic wastewater by using supercritical water as a reaction medium, in particular to a supercritical water treatment system with high salinity (greater than 2%) organic wastewater.
  • the organic matter and oxygen can be miscible with SCW in any proportion, so that the heterogeneous reaction becomes a homogeneous reaction, which greatly reduces the resistance to mass transfer and heat transfer.
  • Inorganic substances, especially salts have a very low solubility in SCW and are easily separated.
  • Supercritical water treatment technology for organic wastewater includes Supercritical Water Oxidation (SCWO), Supercritical Water Gasification (SCWG) and Supercritical Water Partial Oxidation (Supercritical Water Partial Oxidation). Referred to as SCWPO).
  • SCWO Supercritical Water Oxidation
  • SCWG Supercritical Water Gasification
  • SCWPO Supercritical Water Partial Oxidation
  • SCWO utilizes the special properties of water in supercritical conditions to rapidly decompose organic matter and oxidant in supercritical water to completely decompose organic matter and achieve harmless treatment of organic matter.
  • the SCWG utilizes the special properties of water in a supercritical state. Under the condition of no oxidizing agent, the organic substance undergoes hydrolysis, pyrolysis and the like in supercritical water to form a flammable body mainly composed of hydrogen.
  • SCWP0 is a special property of water under supercritical conditions. Under the premise of providing partial oxidant, the organic matter is decomposed to form a flammable gas mainly composed of hydrogen. The addition of the oxidizing agent causes the substance which is difficult to be decomposed in the gasification to be decomposed, thereby increasing the gasification rate, and at the same time, the oxidizing agent can suppress the generation of the tar and reduce the clogging of the reactor.
  • the SCW0 process is an exothermic reaction, and self-heating can be achieved when the mass fraction of organic matter reaches 2%.
  • Due to the energy recovery and optimization of the supercritical water oxidation treatment system there is no problem. Well solved, so the operating cost of the supercritical water treatment process is still high.
  • the reactor currently used in supercritical water treatment is mainly a tubular reactor.
  • the tubular reactor has a relatively simple structure and is widely used, but has the disadvantages of easy salt plugging, uncontrollable reaction exotherm, difficulty in distinguishing pressure effects and temperature effects.
  • the existing evaporative wall reactor can effectively avoid the problems of salt deposition and corrosion, but also has the problem of low energy utilization efficiency.
  • the object of the present invention is to overcome the deficiencies of existing supercritical water treatment plants and to provide a new system for supercritical water treatment of high salinity organic wastewater.
  • a supercritical water treatment system for high salinity organic wastewater characterized in that it comprises an air preheater, an inlet end of the air preheater shell side is connected with high pressure air, and an outlet end of the air preheater shell side is a mixer inlet end is connected, the inlet end of the mixer simultaneously communicates with the outlet of the waste water preheater shell side, and the waste water preheater shell side inlet communicates with the waste water storage device; the mixer outlet and the first tubular reactor The inlets of the first tubular reactor are connected to the inlet of the second tubular reactor through a pre-desalting device, and the outlet of the second tubular reactor is divided into two paths, the inlet of the first tubular reactor and the third tubular reactor.
  • the other end is connected to the inlet end of the tank reactor, and the outlet end of the third tubular reactor is combined with the outlet end of the tank reactor to be connected to the inlet end of the air preheater tube side, and the air is preheated.
  • the outlet on the side of the heat exchanger is respectively connected with the inlet and the outlet of the waste water preheater tube side, and the distribution between the two flow rates is realized by the regulating enthalpy on the pipeline; the outlet of the waste water preheater tube side and the hot water occur
  • the tank reactor is a tank reactor of a baffle structure, and the bottom salt discharge port communicates with the sewage pipeline through a desalting buffer tank.
  • the pre-desalting device includes a pre-desalter having an inlet connected to an outlet of the first tubular reactor; a supercritical fluid outlet at an upper portion of the pre-desalter communicating with an inlet of the second tubular reactor, and a subcritical fluid at a lower portion of the pre-desalter
  • the outlet is connected to the inlet of a brine chiller tube side, and the outlet of the brine chiller tube side is outputted by the second back pressure ;
  • the bottom of the pre-desalter is provided with a cooling coil, the inlet of which is connected to the outlet of the brine chiller shell side; pre-desalting
  • the outlet of the cooling coil at the bottom of the unit is connected to the hot water utilization device.
  • the hot water utilization device comprises a clean water storage tank connected with tap water, the outlet of which is connected with a clean water pump, the outlet of the clean water pump is divided into three paths, one way is connected with the inlet end of the hot water generator shell side, and one way is combined with the desalting buffer tank
  • the bottom outlet end is connected, the other end is connected to the inlet end of the brine chiller shell side, the outlet end of the hot water generator shell side is in communication with the inlet end of a hot water storage tank, and the outlet of the pre-desalter bottom cooling coil is also The inlet end of the hot water storage tank is connected.
  • the waste water storage device comprises a storage tank with an alkali tank, the inlet end of which is connected to the raw material waste water through a door; the outlet end is connected to the inlet end of the waste water preheater shell side through a material pump, and the storage tank is provided There is a blender.
  • a pipeline filter is disposed on the connecting pipe before the first back pressure and the second back pressure.
  • the invention preheats air and waste water through an air preheater, a waste water preheater, generates hot water through a hot water generator, a brine chiller, and fully utilizes heat of the fluid after the reaction.
  • the first and second tubular reactors and the pre-desalter are provided with electric heaters, which can ensure a certain preheating temperature when the materials enter the pre-desalter, so that the fluid in the pre-desalter is supercritical, and The temperature required to produce a supercritical water reaction has been reached upon entering the reactor.
  • the electric heaters of the first and second tubular reactors are only used when the system is started or the reaction cannot be self-heating, supplementing the heat required for the normal operation of the system.
  • the operating cost of the supercritical water treatment system for high-salt organic wastewater is reduced by fully recycling the heat after the reaction and reducing the electrical heating power during normal operation of the system.
  • the tubular reactor and the tank reactor are simultaneously included in the present invention. If the content of ammonia nitrogen and inorganic salts in the organic waste liquid is low, the supercritical fluid selectively enters the third tubular reactor, and the outer wall of the third tubular reactor is insulated to ensure that the supercritical water reaction continues to occur; The liquid has a high content of ammonia nitrogen and inorganic salts, and the supercritical fluid selectively enters the tank reactor.
  • Tank reaction A catalyst box inside the vessel can be used to place a particulate catalyst, reduce the conditions of the supercritical water reaction, and increase the yield or conversion rate of the target.
  • a pre-desalting device is provided between the first tubular reactor and the second tubular reactor as a pre-desalting device prior to entering the reactor.
  • the upper part of the pre-desalter is electrically heated to ensure that the upper fluid is in a supercritical state, and the inorganic salt is precipitated;
  • a cooling coil is arranged at the bottom to ensure that the lower fluid is in a subcritical state, and the inorganic salt is redissolved.
  • Figure 1 is a schematic view showing the structure of the system of the present invention. Among them: 1, high-pressure air compressor, 2, buffer tank, 3, air preheater, 4, add alkali tank, 5, storage tank, 6, material pump, 7, waste water preheater, 8, mixer, 9, first tubular reactor, 10, pre-desalter, 11, second tubular reactor, 12, third tubular reactor, 13, tank reactor, 14, desalting buffer tank, 15, brine Quencher, 16, filter, 17, first back pressure, 18, hot water generator, 19, filter, 20, second back pressure, 21, gas-liquid separator, 22, water storage tank, 23 , clean water pump, 24, hot water storage tank.
  • the equipment connection method in the supercritical water treatment system with high salinity organic wastewater is as follows:
  • the high pressure air compressor 1 is in communication with the inlet end of the buffer tank 2, the outlet end of the buffer tank 2 is in communication with the inlet end of the air preheater casing side, and the outlet end of the air preheater 3 tube side is connected to the inlet end of the mixer 8.
  • the outlet of the alkali tank 4 is connected to the inlet of the storage tank 5, the outlet end of the storage tank 5 is in communication with the inlet end of the material pump 6, and the outlet end of the material pump 6 is connected to the inlet end of the shell side of the waste water preheater 7, The outlet on the shell side of the waste water preheater 7 is in communication with the feed port of the mixer 8.
  • the outlet of the mixer 8 is connected to the inlet of the first tubular reactor 9, and the outlet of the first tubular reactor 9 is connected to the inlet of the pre-desalter 10.
  • the supercritical fluid outlet at the upper portion of the pre-desalter 10 is connected to the inlet of the second tubular reactor 11.
  • a first stage electric heater (ELEC1) is disposed on the first tubular reactor 9, a second stage electric heater (ELEC2) is disposed on the pre-demineralizer 10, and a third stage electric heater is disposed on the second tubular reactor 11. (ELEC3).
  • the outlet of the second tubular reactor 11 is divided into two paths, one connected to the inlet end of the third tubular reactor 12 and the other connected to the inlet end of the tank reactor 13.
  • the outlet end of the third tubular reactor 12 is merged with the outlet end of the tank reactor 13 to communicate with the inlet end of the tube side of the air preheater 3.
  • the pipe side outlet of the air preheater 3 is divided into two paths, one way is connected with the inlet end of the pipe side of the waste water preheater 7, and one way is connected with the outlet end of the pipe side of the waste water preheater 7 through the electric regulation ⁇ V21 on the pipe
  • the flow of hot fluid into the waste water preheater 7 is regulated.
  • the outlet on the tube side of the waste water preheater 7 is in communication with the inlet on the tube side of the hot water generator 18, and the outlet on the tube side of the hot water generator 18 is connected to the inlet of the line filter 19, the outlet of the line filter 19 and the second back pressure
  • the inlet of the crucible 20 is in communication, and the outlet of the second back pressure crucible 20 is in communication with the inlet of the gas-liquid separator 21.
  • the subcritical fluid outlet at the lower portion of the pre-desalter 10 is connected to the inlet of the tube side of the brine chiller 15,
  • the outlet on the tube side of the brine chiller 15 is connected to the inlet of the line filter 16, and the outlet of the line filter 16 is in communication with the inlet of the first back pressure damper 17.
  • the bottom salt discharge port of the tank reactor 13 communicates with the inlet end of the desalting buffer tank 14, and the bottom outlet end of the desalting buffer tank 14 is connected to the sewage pipe.
  • the outlet of the clean water storage tank 22 is in communication with the inlet of the clean water pump 23, and the outlet end of the clean water pump 23 is divided into three paths, one of which communicates with the inlet end of the shell side of the hot water generator 18; one of which communicates with the bottom outlet end of the desalting buffer tank; The other end is in communication with the inlet end of the shell side of the brine chiller 15, and the outlet end of the shell side of the brine chiller 15 is in communication with the inlet of the cooling coil at the bottom of the pre-demineralizer 10; the outlet end of the hot water generator 16 and the hot water reservoir
  • the inlet end of the tank 18 is in communication.
  • the alkali solution is stored in the alkali addition tank 4, the trickle between the outlet of the alkali tank 4 and the inlet of the storage tank 5 is opened, and the agitator set in the storage tank is started to stir and mix the feed and monitor the mixed feed.
  • the pH is then filtered through a pipe filter at the outlet end of the storage tank 5 to filter out large solid particles.
  • the hot fluid which has entered the side of the waste water preheater by the tube side is preheated to below 25 CTC, and then enters the mixer 8.
  • the supercritical fluid selectively enters the third tubular reactor 12 without performing other desalting operations; if the content of ammonia nitrogen and inorganic salts of the organic waste liquid is high ( NH 3 -N > 50 mg / L), supercritical fluid selectively enters the tank reactor 13, wherein the tank reactor 13 has a catalyst tank inside to hold the particulate catalyst.
  • the inorganic salt is gravity settled to the bottom of the reactor, and a large amount of the cleaned reaction fluid flows countercurrently upward through the catalyst bed and then bucks downward from the tank. The outlet end of the lower portion of the reactor 13 flows out.
  • the high-salt subcritical fluid enters the brine chiller 15 through the outlet of the lower portion of the pre-desalter 10. Cool down. The fluid temperature at the outlet of the tube side of the brine chiller is reduced to about 50 °C. The cooled fluid is passed through a line filter 16, and the fluid is then depressurized to atmospheric pressure via a first back pressure ⁇ 17 for brine collection and post treatment.
  • the hot fluid flowing out of the reactor 12 or 13 sequentially enters the air preheater 3, the waste water preheater 7, and the tube side of the hot water generator 18 to preheat the air and the waste water, and obtain hot water.
  • the tube side outlet of the air preheater 3 is divided into two ways, one way is connected with the inlet end of the waste water preheater 7 tube side, and one way is connected with the outlet end of the waste water preheater 7 tube side, and the regulation ⁇ V21 through the pipeline
  • the distribution between the two flows is realized to ensure that the temperature after the preheating of the wastewater is about 200 °C, which is lower than the temperature at which the wastewater undergoes pyrolysis and coking.
  • the temperature of the fluid at the outlet of the 18-side hot water generator is reduced to about 80 ° C.
  • the cooled fluid passes through the pipe filter 19, and the fluid is then depressurized to atmospheric pressure by the second back pressure ⁇ 20, and then enters the gas-liquid separator 21 for gas-liquid separation.
  • the tap water is pre-stored in the clean water storage tank 22, the tap water is pressurized by the clean water pump 23, and is divided into three paths, one way flows into the shell side of the hot water generator 18, and the hot water for living is obtained by heat exchange, and is stored in the hot water.
  • the storage tank 24 all the clean water flows into the salt discharge outlet pipe of the desalting buffer tank for the desalination operation; the other clear water flows into the shell side of the brine chiller 15, and then enters the cooling coil at the bottom of the pre-demineralizer 10, after two After the secondary heat exchange, domestic hot water is obtained and stored in the hot water storage tank 24.
  • the system of the present invention optimizes the energy recovery system and utilizes the heat of the fluid after the reaction.
  • the air preheater 3 and the waste water preheater 7 preheat the air and the waste water to bring the heat back into the system, and the hot water generator 18 and the brine chiller 15 generate domestic hot water to make full use of the heat of the reacted fluid. .
  • the electric heating ELEC1 and ELEC3 are put into use to supplement the heat required for the normal operation of the system.
  • the electric heating ELEC1, ELEC3 is turned off.
  • the pre-desalter 10 provided in the system of the present invention serves as a pre-desalting device before entering the reactor, and the upper portion of the pre-salter 10 is supercritical fluid through the electric heater ELEC2, at which time inorganic salts are precipitated; gravity sedimentation and flocculation The inorganic salt is dropped to the bottom; the desalted supercritical water flows out through the upper outlet of the pre-desalter 10 into the second tubular reactor 11.
  • a cooling coil is arranged at the bottom of the pre-desalter 10, and the lower fluid is subcritical state by cooling, at which time the inorganic salt is redissolved.
  • the pre-desalter has two outlets, upper and bottom, which regulate the opening of the door on the two outlet pipes for flow distribution to ensure continuous demineralization.
  • the reactor 13 in the system of the present invention is a baffled tank reactor utilizing inorganic salts in supercritical water. With very low solubility characteristics, the inorganic salt first precipitates at the bottom of the reactor 13.
  • the clean water pump 22 is turned on, and the tricks V18 and V17 are opened to fill the desalt buffer 14 with tap water at normal temperature and normal pressure.
  • the trick V15 between the tank reactor 13 and the desalting buffer 14 is opened, and the salt at the bottom of the tank reactor 13 enters the desalting buffer tank 14 under the action of the initial pressure difference and gravity. Then, the door V15 of the inlet end of the desalting buffer tank 13 is closed, and the outlet port V16 is opened to discharge the inorganic salt in the tank.
  • the salt discharging process can be carried out intermittently and repeatedly, thereby realizing the system continuous desalination and intermittent salt discharging function, avoiding the blockage problem caused by salt deposition, and ensuring that the treated liquid does not contain salt or contains a very small amount of salt. Meet the processing requirements.
  • the pipe side outlet of the air preheater 3 is divided into two paths, one of which communicates with the inlet end of the pipe side of the waste water preheater 7, and one of which communicates with the outlet end of the pipe side of the waste water preheater.
  • a thermocouple is arranged at the outlet end of the shell side of the waste water preheater 7, and according to the preheating temperature of the waste water, the distribution between the two flow rates is automatically adjusted through the regulating ⁇ V21 on the pipeline to ensure that the temperature after the heat exchange of the waste water is lower than the waste water The temperature at which pyrolysis and coking occur.
  • the air is mixed with the feed in the mixer 8, which increases the flow rate of the feed and simultaneously reacts with the feed to reduce the formation of clogging substances such as tar.
  • the supply of air in the system of the present invention can be adjusted by bypass venting.
  • different supercritical water treatment modes can be flexibly selected by adjusting the amount of air added and electrically starting and stopping ELEC1 and ELEC3.
  • the easy-to-handle organics prefer SCWG, the more difficult to handle organics can choose SCWP0, and the hard-to-handle organics choose SCW0.
  • the system of the invention can ensure the purpose of resource utilization as much as possible under the premise of ensuring harmless treatment of the feed, and has versatility.
  • the system of the invention integrates the pretreatment, mixing, reaction, gas-liquid separation and collection of the feed, and the integrated performance of the system is good.

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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

高含盐量有机废水的超临界水处理系统 技术领域
本发明涉及一种利用超临界水作为反应介质对难生化降解有机废水进行 无害化处理的系统， 特别涉及一种高含盐量 （大于 2%) 有机废水的超临界水 处理系统。 背景技术
超临界水（Supercritical Water, 简称 SCW)是指温度和压力均高于其临 界点 （T=374. 15 °C， P=22. 12MPa) 的特殊状态的水。 该状态下只有少量的氢 键存在， 介电常数近似于有机溶剂， 具有高的扩散系数和低的粘度。 有机物、 氧气能按任意比例与 SCW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。 而无机物特别是盐类在 SCW 中的溶解度极低， 容易将 其分离出来。
有机废水的超临界水处理技术包括超临界水氧化技术（Supercritical Water Oxidation , 简称 SCWO)、 超临界水气化技术（Supercritical Water Gasification , 简称 SCWG)和超临界水部分氧化技术（Supercritical Water Partial Oxidation, 简称 SCWPO)。
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， 实现有机物的无害化处理。
SCWG是利用水在超临界状态下所具有的特殊性质， 在不加氧化剂的条件 下， 有机物在超临界水中发生水解、 热解等反应， 生成以氢气为主的可燃性 体。
SCWP0是利用水在超临界状态下所具有的特殊性质，在提供部分氧化剂的 前提下， 使有机物分解生成以氢气为主的可燃性气体。 氧化剂的加入使得原 来在气化中难以分解的物质可以分解， 提高气化率， 同时， 氧化剂也可以使 焦油的产生得到抑制， 减少反应器的堵塞现象。
虽然超临界水处理技术已经取得了很大进歩， 但是仍有若干需要解决的 问题， 表现在：
1 ) SCW0过程是一个放热反应， 并且当有机物的质量分数达到广 2 %时就 能实现自热。 但是由于超临界水氧化处理系统能量的回收及优化问题并没有 很好解决， 所以超临界水处理过程的运行成本依然较高。
2 ) 在密度较低的超临界水中， 无机盐在水中的溶解度显著降低。 因此物 料及反应过程中生成的盐很容易从超临界水中析出形成盐沉积。 盐沉积会引 起了系统的管路及反应器堵塞， 同时会使换热器等设备的传热恶化， 最终导 致系统无法正常运行。 而现有的除盐设备或系统受操作条件限制， 不适合超 临界状态下、 安全、 方便的除盐。
3 ) 目前用于超临界水处理中的反应器主要是管式反应器。 管式反应器的 结构相对简单、 应用广泛， 但是具有盐沉淀易堵、 无法控制反应放热、 难以 分清压力影响和温度影响等缺点。 而已有的蒸发壁式反应器虽能有效避免盐 沉积、 腐蚀等问题， 却也存在能量利用效率低的问题。
4) 超临界水氧化处理中， 氨氮的氧化较为困难。 有研究表明： 在无催化 剂时， 当温度低于 64CTC时， 氨没有发生任何的降解； 并且当反应条件达到 680°C、 24. 8MPa， 停留时间为 10s时， 只有 10%的氨被氧化。 另有研究表明： 即使用 Mn02/Ce02作为催化剂，当反应条件为 450°C、27. 6MPa，停留时间为 0. 8s 时， 氨的降解率也只有 40%。 发明内容
本发明的目的是克服现存超临界水处理装置存在的不足， 提供一种新的 针对高含盐有机废水的超临界水处理的系统。
为达到以上目的， 本发明是采取如下技术方案予以实现的：
一种高含盐量有机废水的超临界水处理系统， 其特征在于， 包括空气预 热器， 所述空气预热器壳侧的入口端连接高压空气， 空气预热器壳侧的出口 端与一个混合器入口端连通， 该混合器的入口端同时连通废水预热器壳侧的 出口， 废水预热器壳侧入口连通废水储料装置； 所述混合器的出口与第一管 式反应器的入口相连， 第一管式反应器的出口通过一个预脱盐装置与第二管 式反应器的入口相连， 第二管式反应器的出口分成两路， 一路与第三管式反 应器的入口端连通， 另一路与罐式反应器的入口端连通， 第三管式反应器的 出口端与罐式反应器的出水端汇合为一路后与空气预热器管侧的入口端连 通， 空气预热器管侧的出口分别与废水预热器管侧的入口和出口连通， 通过 管道上的调节闽实现两路流量之间的分配； 废水预热器管侧的出口与热水发 生器管侧的入口连通， 热水发生器管侧的出口通过第一背压闽连通一个气液 分离器； 热水发生器的壳侧连通有热水利用装置； 所述第一管式反应器、 第 二管式反应器和预脱盐装置上均设有加热器。
上述方案中， 所述罐式反应器为折流结构的罐式反应器， 其底部排盐口 通过一个除盐缓冲罐连通排污管道。
所述预脱盐装置包括一个预脱盐器， 其入口连通第一管式反应器的出口； 预脱盐器上部的超临界流体出口连通第二管式反应器的入口， 预脱盐器下部 的亚临界流体出口连通一个盐水急冷器管侧的入口， 盐水急冷器管侧的出口 通过第二背压闽输出盐水； 预脱盐器底部设有冷却盘管， 其进口连通盐水急 冷器壳侧的出口； 预脱盐器底部冷却盘管的出口连通热水利用装置。
所述热水利用装置包括连接自来水的清水储罐， 其出口与一个清水泵连 通， 该清水泵的出口分成三路， 一路与热水发生器壳侧的入口端连通， 一路 与除盐缓冲罐的底部出口端连通， 另一路与盐水急冷器壳侧的入口端连通， 热水发生器壳侧的出口端与一个热水储罐的入口端连通， 预脱盐器底部冷却 盘管的出口也与该热水储罐的入口端连通。
所述废水储料装置包括带有加碱罐的储料罐， 其入口端通过闽门连接原 料废水； 出口端通过一个物料泵与废水预热器壳侧的入口端连通， 储料罐中 设有搅拌器。
所述第一背压闽、 第二背压闽之前的连接管道上均设有管道过滤器。 本发明系统的主要优点是：
1、 本发明通过空气预热器、 废水预热器预热空气和废水、 通过热水发生 器、 盐水急冷器产生热水， 充分利用反应后流体的热量。 本发明系统中第一、 第二管式反应器、 预脱盐器设置电加热器， 可保证物料进入预脱盐器时有一 定的预热温度， 使预脱盐器内的流体为超临界状态， 并在进入反应器时已经 达到发生超临界水反应所需的温度。 其中第一、 第二管式反应器的电加热器 仅仅在系统启动或反应不能自热时投入使用， 补充系统正常运行所需热量。 通过对充分回收利用反应后的热量和降低系统正常运行时的电加热功率， 降 低了高含盐有机废水的超临界水处理系统的运行成本。
2、 本发明中同时包含管式反应器和罐式反应器。 如果有机废液的氨氮及 无机盐含量的较低， 超临界流体选择性的进入第三管式反应器， 在第三管式 反应器外壁进行保温处理保证继续发生超临界水反应； 如果有机废液的氨氮 及无机盐的含量较高， 超临界流体选择性的进入罐式反应器。 其中罐式反应 器内部有催化剂箱可以安放颗粒状催化剂， 降低超临界水反应的条件、 提高 目标物的产率或转化率。
3、 本发明系统中， 在第一管式反应器和第二管式反应器之间设置预脱盐 装置， 作为进入反应器前的预脱盐设备。 预脱盐器上部设置电加热保证上部 流体为超临界状态， 无机盐析出； 底部设置冷却盘管， 保证下部流体为亚临 界状态， 无机盐重新溶解。 附图说明
下面结合附图和具体实施方式对本发明做进一歩详细说明。
图 1 是本发明系统的结构示意图。 其中： 1、 高压空气压缩机， 2、 缓冲 罐， 3、 空气预热器， 4、 加碱罐， 5、 储料罐， 6、 物料泵， 7、 废水预热器， 8、 混合器， 9、 第一管式反应器， 10、 预脱盐器， 11、 第二管式反应器， 12、 第三管式反应器， 13、 罐式反应器， 14、 除盐缓冲罐， 15、 盐水急冷器， 16、 过滤器， 17、 第一背压闽， 18、 热水发生器， 19、 过滤器， 20、 第二背压闽， 21、 气液分离器， 22、 清水储罐， 23、 清水泵， 24、 热水储罐。
图 1中的图例含义见表 1
图 1中的仪表代码含义见表 2。 表 1
图例 名称 图例 名称 图例 名称 手动截止阀 电动调节阀 法兰连接
[ <]
球阀 电加热 Ί - Γ 地沟
Figure imgf000006_0001
(ψ 电动截止阀 止回阀 r 、；' 跨管 管道过滤器 放空管 管线交叉
1 ) 表 2
Figure imgf000007_0001
具体实施方式
参照图 1 所示， 高含盐有机废水的超临界水处理系统中设备连接方式如 下：
高压空气压缩机 1与缓冲罐 2的入口端连通， 缓冲罐 2的出口端与空气 预热器壳侧的入口端连通， 空气预热器 3管侧的出口端与混合器 8入口端连 通。
加碱罐 4的出口与储料罐 5的入口相连， 储料罐 5的出口端与物料泵 6 的入口端连通， 物料泵 6的出口端与废水预热器 7壳侧的入口端连通， 废水 预热器 7壳侧的出口与与混合器 8的进料口连通。
混合器 8的出口与第一管式反应器 9的入口相连， 第一管式反应器 9的 出口与预脱盐器 10的入口相连。 预脱盐器 10上部的超临界流体出口与第二 管式反应器 11 的入口相连。 第一管式反应器 9 上布置第一级电加热器 (ELEC1 ) , 预脱盐器 10上设置第二级电加热器（ELEC2 ) , 第二管式反应器 11 上布置第三级电加热器 （ELEC3)。 第二管式反应器 11的出口分成两路， 一路 与第三管式反应器 12的入口端连通， 另一路与罐式反应器 13的入口端相连。 正常运行时， 只有其中一路反应器工作， 另一路不工作。 第三管式反应器 12 的出口端与罐式反应器 13的出水端汇合为一路， 与空气预热器 3管侧的入口 端连通。 空气预热器 3的管侧出口分为两路， 一路与废水预热器 7管侧的入 口端连通， 一路与废水预热器 7 管侧的出口端连通， 通过管道上的电动调节 闽 V21调节进入废水预热器 7中的热流体流量。 废水预热器 7管侧的出口与 热水发生器 18管侧的入口连通， 热水发生器 18管侧的出口与管道过滤器 19 的入口相连， 管道过滤器 19的出口与第二背压闽 20的入口连通， 第二背压 闽 20的出口与气液分离器 21的入口连通。
预脱盐器 10下部的亚临界流体出口与盐水急冷器 15管侧的入口相连， 盐水急冷器 15管侧的出口与管道过滤器 16的入口相连， 管道过滤器 16的出 口与第一背压闽 17的入口连通。
罐式反应器 13的底部排盐口与除盐缓冲罐 14的入口端连通， 除盐缓冲 罐 14的底部出口端连接排污管道。
清水储罐 22的出口与清水泵 23的入口连通， 清水泵 23的出口端分成三 路， 一路与热水发生器 18壳侧的入口端连通； 一路与除盐缓冲罐的底部出口 端连通； 另一路与盐水急冷器 15壳侧的入口端连通， 盐水急冷器 15壳侧的 出口端与预脱盐器 10底部的冷却盘管入口连通； 热水发生器 16壳侧的出口 端与热水储罐 18的入口端连通。
图 1所示高含盐有机废水的超临界水处理系统的工作原理如下：
1 ) 空气经高压空气压缩机 1加压， 通过缓冲罐 2减少流量波动， 及旁路 放空实现空气流量调节。 然后进入空气加热器 3的壳侧， 被反应器 12或 13 的出口流体加热至约 30CTC直接进入混合器 8与进料（高含盐有机废液）进行 混合。
2 ) 根据进料的物理化学性质， 选择合适的碱和加碱量。 把碱溶液储存于 加碱罐 4中， 开启加碱罐 4出口至储料罐 5入口之间的闽门， 启动设置在储 料罐中的搅拌器对进料进行搅拌混合并监测混合进料的 PH， 然后通过储料罐 5出口端的管道过滤器将大的固体颗粒过滤出来。进料经物料泵 6加压和流量 调节后， 进入废水预热器的壳侧被管侧反应后的热流体预热至 25CTC以下， 而 后进入混合器 8。
3 ) 高压空气 （参与反应的主要是氧气）、 进料在混合器 8 中充分混合后 进入第一管式反应器 9， 而后进入预脱盐器 10。 预脱盐后超临界流体经预脱 盐器 10的上部出口进入第二管式反应器 11。通过管外加热将管内流体加热升 温至超临界温度以上。 如果有机废液的氨氮及无机盐含量较低， 超临界流体 选择性的进入第三管式反应器 12， 不进行其他的除盐操作； 如果有机废液的 氨氮及无机盐含量的较高 （NH3-N〉50mg/L)， 超临界流体选择性的进入罐式 反应器 13， 其中罐式反应器 13内部有催化剂箱可以安放颗粒状催化剂。在罐 式反应器 13中， 依靠盐在超临界水中极低溶解度的特性， 无机盐经重力沉降 至反应器底部， 大量清洁的反应流体逆流向上流动经过催化剂床层反应后折 流向下从罐式反应器 13下部的出水端流出。
4) 高含盐量的亚临界流体经预脱盐器 10下部的出口进入盐水急冷器 15 进行冷却。盐水急冷器 15管侧出口处流体温度降低到 50°C左右。冷却后的流 体经管道过滤器 16， 而后流体经第一背压闽 17减压至大气压， 进行盐水收集 和后处理。
5 ) 从反应器 12或 13流出的热流体依次进入空气预热器 3、 废水预热器 7、 热水发生器 18的管侧去预热空气、 废水， 并得到热水。 其中空气预热器 3 的管侧出口分为两路， 一路与废水预热器 7 管侧的入口端连通， 一路与废水 预热器 7管侧的出口端连通， 通过管道上的调节闽 V21实现两路流量之间的 分配， 保证废水预热后的温度约为 200 °C， 低于废水发生热解和结焦的温度。 热水发生器 18管侧出口处流体温度降低到 80° C左右。 冷却后的流体经管道 过滤器 19， 而后流体经第二背压闽 20减压至大气压， 然后进入气液分离器 21进行气液分离。
6 ) 自来水预先储存在清水储罐 22中， 自来水经清水泵 23加压后分为三 路， 一路流入热水发生器 18的壳侧， 经换热得到生活用热水， 并储存于热水 储罐 24中； 一路清水流入除盐缓冲罐的排盐出口管道， 用于除盐操作； 另一 路清水流入盐水急冷器 15的壳侧， 而后进入预脱盐器 10底部的冷却盘管， 经过两次换热后得到生活用热水， 并储存于热水储罐 24中。
本发明系统对能量回收系统进行了优化处理， 利用了反应后流体的热量。 通过空气预热器 3、 废水预热器 7预热空气和废水将热量重新带入到系统中， 通过热水发生器 18、盐水急冷器 15产生生活用热水， 充分利用反应后流体的 热量。 在系统启动或反应不能自热时， 电加热 ELEC1、 ELEC3投入使用， 补充 系统正常运行所需热量。 反应能够自热时， 则关闭电加热 ELEC1、 ELEC3。 通 过对充分回收利用反应后的热量， 降低了高含盐有机废水的超临界水处理系 统的运行成本。
本发明系统中设置的预脱盐器 10， 作为进入反应器前的预脱盐设备， 通 过电加热器 ELEC2使预脱盐器 10内的上部为超临界流体， 此时无机盐析出； 通过重力沉降、 絮凝等作用， 无机盐降落至底部； 脱盐后的超临界水经预脱 盐器 10上部出口流出进入第二管式反应器 11。 预脱盐器 10底部设置冷却盘 管， 通过冷却保证下部流体为亚临界状态， 此时无机盐重新溶解。 预脱盐器 有上部和底部两个出口， 调节两个出口管道上闽门的开度进行流量的分配， 保证连续除盐。
本发明系统中的反应器 13为折流罐式反应器， 利用无机盐在超临界水中 极低的溶解特性， 无机盐首先沉淀在反应器 13的底部。 开启清水泵 22， 开启 闽门 V18、 V17 , 使除盐缓冲器 14中充满常温常压的自来水。 打开罐式反应器 13至除盐缓冲器 14之间的闽门 V15 , 罐式反应器 13底部的盐在初始压差、 重力的作用下， 进入除盐缓冲罐 14。 而后关闭除盐缓冲罐 13 入口端的闽门 V15 , 打开出口端闽门 V16 , 将罐内无机盐排出。 排盐过程可以间歇式、 反复 进行， 从而实现了系统连续脱盐、 间歇式排盐的功能， 避免了盐沉积所引起 的堵塞问题， 保证了处理后的液体不含盐或含有极少量的盐， 满足了处理要 求。
本发明系统中空气预热器 3 的管侧出口分为两路， 一路与废水预热器 7 管侧的入口端连通， 一路与废水预热器 7管侧的出口端连通。在废水预热器 7 壳侧的出口端设置热电偶， 根据废水的预热温度， 自动调节通过管道上的调 节闽 V21 实现两路流量之间的分配， 保证废水换热后的温度低于废水发生热 解和结焦的温度。 空气在混合器 8中与进料发生混合， 可以增加进料的流速， 同时与进料进行初歩反应， 降低焦油等易堵塞物质的生成。 这些措施有效避 免了进料预热到高温过程中容易产生的堵塞问题。
本发明系统中的空气的供应量可以通过旁路放空来调节， 针对不同的进 料， 通过调节空气的加入量以及电加热 ELEC1、 ELEC3的启停， 可以灵活选择 不同的超临界水处理方式， 容易处理的有机物优先选择 SCWG, 较难处理的有 机物可以选择 SCWP0 , 很难处理的有机物选择 SCW0。 本发明系统可以保证进 料无害化处理的前提下尽可能的实现其资源化利用的目的， 具有多功能性。 本发明系统集进料的预处理、 混合、 反应、 气液分离收集于一体， 系统的集 成性能好。

Claims

WO 2012/051875 +Π χ. ι ^ + _L>PCT/CN2011/078036
1、 一种高含盐量有机废水的超临界水处理系统， 其特征在于， 包括空气 预热器， 所述空气预热器壳侧的入口端连接高压空气， 空气预热器壳侧的出 口端与一个混合器入口端连通， 该混合器的另一个入口端连通废水预热器壳 侧的出口， 废水预热器壳侧入口连通废水储料装置； 所述混合器的出口与第 一管式反应器的入口相连， 第一管式反应器的出口通过一个预脱盐装置与第 二管式反应器的入口相连， 第二管式反应器的出口分成两路， 一路与第三管 式反应器的入口端连通， 另一路与罐式反应器的入口端连通， 第三管式反应 器的出口端与罐式反应器的出水端汇合为一路后与空气预热器管侧的入口端 连通， 空气预热器管侧的出口分别与废水预热器管侧的入口和出口连通， 通 过管道上的调节闽实现两路之间的流量分配； 废水预热器管侧的出口与热水 发生器管侧的入口连通， 热水发生器管侧的出口通过第一背压闽连通一个气 液分离器； 热水发生器的壳侧连通有热水利用装置； 所述第一管式反应器、 第二管式反应器和预脱盐装置上均设有加热器。
2、 如权利要求 1所述的高含盐量有机废水的超临界水处理系统， 其特征 在于， 所述罐式反应器为折流罐式反应器， 其底部排盐口通过一个除盐缓冲 罐连通排污管道。
3、 如权利要求 2所述的高含盐量有机废水的超临界水处理系统， 其特征 在于， 所述预脱盐装置包括一个预脱盐器， 其入口连通第一管式反应器的出 口； 预脱盐器上部的超临界流体出口连通第二管式反应器的入口， 预脱盐器 下部的亚临界流体出口连通一个盐水急冷器管侧的入口， 盐水急冷器管侧的 出口通过第二背压闽输出盐水； 预脱盐器底部设有冷却盘管， 其进口连通盐 水急冷器壳侧的出口； 预脱盐器底部冷却盘管出口连通热水利用装置。
4、 如权利要求 3所述的高含盐量有机废水的超临界水处理系统， 其特征 在于， 所述热水利用装置包括连接自来水的清水储罐， 其出口与一个清水泵 连通， 该清水泵的出口分成三路， 一路与热水发生器壳侧的入口端连通， 一 路与除盐缓冲罐的底部出口端连通， 另一路与盐水急冷器壳侧的入口端连通， 热水发生器壳侧的出口端与一个热水储罐的入口端连通， 预脱盐器底部冷却 盘管出口也与该热水储罐的入口端连通。
5、 如权利要求 1所述的高含盐量有机废水的超临界水处理系统， 其特征 在于， 所述废水储料装置包括带有加碱罐的储料罐， 其入口端通过闽门连接 原料废水； 出口端通过一个物料泵与废水预热器壳侧的入口端连通， 储料罐 中设有搅拌器。
6、 如权利要求 1所述的高含盐量有机废水的超临界水处理系统， 其特征 在于， 所述第一背压闽之前的连接管道上设有管道过滤器。
7、 如权利要求 3所述的高含盐量有机废水的超临界水处理系统， 其特征 在于， 所述第二背压闽之前的连接管道上设有管道过滤器。
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