WO2022222707A1 - Advanced treatment and recycling apparatus for ship exhaust desulfurization washing wastewater - Google Patents

Advanced treatment and recycling apparatus for ship exhaust desulfurization washing wastewater Download PDF

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WO2022222707A1
WO2022222707A1 PCT/CN2022/083704 CN2022083704W WO2022222707A1 WO 2022222707 A1 WO2022222707 A1 WO 2022222707A1 CN 2022083704 W CN2022083704 W CN 2022083704W WO 2022222707 A1 WO2022222707 A1 WO 2022222707A1
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washing
wastewater
washing water
advanced treatment
reuse
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PCT/CN2022/083704
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French (fr)
Chinese (zh)
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张丽
杨懿
张文婷
杨佳
李庆华
石佳玉
祁振皓
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上海海事大学
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • 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
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Definitions

  • the invention belongs to the technical field of ship tail gas desulfurization washing wastewater treatment, and particularly relates to a ship tail gas washing wastewater treatment device.
  • the closed-circuit ship exhaust desulfurization and scrubbing method which has become the mainstream development technology at present, has improved the secondary pollution discharge problem of open-circuit and hybrid systems, but there are still key bottlenecks in this method and technology.
  • the physical and chemical properties of the washing water in the washing system are always in the optimal working conditions.
  • the treatment technologies for ship exhaust washing wastewater mainly include: Chinese patents "A new integrated device for ship wastewater treatment (CN201110087069.9)” and “An improved ship water treatment equipment (CN201520809429.5)” ”, the above invention sequentially passes wastewater through multiple chambers or layers, and undergoes treatment processes such as aeration, sedimentation, filtration, biochemistry, and disinfection.
  • the invented equipment has a high degree of integration, the treatment capacity per unit time is small, and it is not It is suitable for the requirement of large circulating water volume of the ship exhaust gas desulfurization washing system; and the invention introduces a microbial decomposition process to remove organic pollutants in the washing wastewater, which is limited by the high acid-base and high organic toxicity generated in the ship exhaust gas washing process. and other harsh water quality, the species and abundance of microorganisms are seriously affected, resulting in poor impact resistance in the microbial degradation process section, and the water quality of the treated washing water fluctuates sharply, failing to meet the reuse or discharge standards, and even affecting the normal process of the waste gas cleaning system. , so the risk is very high.
  • the technology proposed in the Chinese patent “A Device and Method for Desulfurization Wastewater from Ships (CN201310422883.0)” is mainly micro-bubble + chemical flocculation + adsorption. Saturation, low utilization rate of sewage recycling, etc.
  • the wastewater is introduced into the cyclone separation unit to separate out the sludge, and the remaining wastewater enters the electrochemical treatment unit for oxidative degradation, and the wastewater is discharged after treatment.
  • the system saves the dosing device, but the pH value of the wastewater cannot meet the discharge requirements; in addition, the wastewater is directly separated by cyclone without coagulation treatment, which cannot fully separate the suspended solids such as oil pollution; it also uses an electrolysis device, which saves energy higher.
  • the purpose of the present invention is to provide an advanced treatment and reuse device for ship exhaust washing wastewater, so as to solve the problems of incomplete removal of pollutants and low efficiency, large sludge output, high energy consumption and washing water recycling rate existing in the prior art. lower issues.
  • the present invention provides a device for advanced treatment and reuse of ship exhaust gas scrubbing wastewater, which is used to treat and recover the scrubbing wastewater formed after the scrubbing tower processes the exhaust gas, including:
  • the washing water storage tank one side is connected to the water inlet pipeline, and the other side is connected to the washing tower through the conveying pipeline;
  • One end of the washing water circulation pipeline is connected with the outlet at the bottom of the washing tower, and the other end is divided into two parts to form the first circulation pipeline and the second circulation pipeline;
  • Wastewater processors including ultrasonic components and photocatalytic components, are used to degrade and remove pollutants in wastewater;
  • the first circulation pipeline is connected with the washing water storage tank to form a first circulation system;
  • the second circulation pipeline is sequentially connected with the filter, the waste water processor and the washing water storage tank , forming a second circulatory system.
  • the photocatalytic assembly includes an excitation light source and a photocatalyst.
  • the dominant wavelength emitted by the excitation light source is in the range of 185 nm to 420 nm.
  • the photocatalyst is a semiconductor catalyst.
  • the semiconductor catalyst is a supported catalyst.
  • the power used by the ultrasonic component ranges from 20 kHz to 80 kHz.
  • a PAHs concentration detector is provided on the conveying pipeline.
  • the washing water storage tank is provided with a liquid level gauge.
  • the washing water storage tank is provided with a pH meter.
  • the device provided by the present invention has the following advantages:
  • the advanced treatment and reuse device of the ship's tail gas washing wastewater adopts a wastewater processor to treat the washing wastewater.
  • the wastewater processor includes an ultrasonic component, a photocatalytic component and an ultrafiltration component.
  • ultrasonic degradation, photolysis and multiple The three purification effects of phase photocatalytic oxidation are carried out at the same time, and ultrasonic and heterogeneous photocatalysis also have a synergistic effect, which can degrade and remove suspended solids, oil stains, sulfites, polycyclic aromatic hydrocarbons and other pollution in the washing wastewater more efficiently and thoroughly.
  • the wastewater processor does not introduce any chemicals, which greatly reduces the negative impact on the ecological environment during the wastewater treatment process.
  • the advanced treatment and reuse device of the ship's exhaust gas washing wastewater is equipped with a second circulation system, so that the washing water of the closed-circuit ship exhaust gas cleaning system can be completely purified and replenished online in the form of bypass with the ship, which not only improves the closed-circuit ship exhaust gas cleaning system.
  • the service time and recycling rate of the scrubbing water in the exhaust gas cleaning system reduce the demand for supplementary water from sources such as seawater, and also save a lot of supplementary consumption of alkaline scrubbers, thereby reducing the storage of chemicals on board It reduces the hidden danger of ship navigation safety.
  • the advanced treatment and reuse device of the ship's tail gas washing wastewater can detect the concentration of PAHs in the washing wastewater and control the working conditions of the first and second circulation systems, so that the ship's tail gas desulfurization and washing system can efficiently desulfurize and wash the tail gas at the same time. , to treat the PAHs in the washing wastewater to reduce the environmental risk caused by the enrichment of PAHs in the washing wastewater.
  • the device provided by the present invention adopts a supported catalyst.
  • the use of the supported catalyst can reduce the loss of the photocatalyst, simplify the treatment equipment, increase the service life of the equipment, and improve its use. stability in the process.
  • the advanced treatment and reuse device of the ship's tail gas washing wastewater does not need to install an electrolysis device, and the energy consumption is low.
  • the second circulation system of the advanced treatment and reuse device of the ship's tail gas washing wastewater has no direct impact on the structure of the original ship's tail gas desulfurization and washing system, that is, the structure of the first circulation system, and the added treatment equipment hardly increases the overall structure.
  • the complexity of the structure, and the manipulation is simple.
  • the installed processing equipment is small in size, low in energy consumption, high in processing efficiency, and has a wide range of applications.
  • the processing scale can be flexibly adjusted by increasing or decreasing the number of ultrasonic components and photocatalytic components.
  • Fig. 1 is a process flow chart of washing water treatment using the advanced treatment and reuse device of ship exhaust washing wastewater according to the present invention.
  • Washing water storage tank 1 conveying pipeline 2; lift pump 21; washing tower 3; ship engine 4; washing water circulating pipeline 5; first circulating pipeline 51; second circulating pipeline 52; Second return pump 521; filter 522; waste water processor 523; feed pump 6; PAHs concentration detector 7.
  • the present invention provides a device for advanced treatment and reuse of ship exhaust gas scrubbing wastewater, the device is used to treat the scrubbing wastewater formed after the scrubbing tower processes the exhaust gas, and includes:
  • the washing water storage tank 1 one side of the said washing water storage tank 1 is connected with the water inlet pipeline provided with the inlet pump 6, and the other side is connected with the washing tower 3 through the conveying pipeline 2 provided with the lifting pump 21, and the said A PAHs concentration detector 7 is arranged on the conveying pipeline;
  • the washing water circulation pipeline 5 has one end connected to the bottom outlet of the washing tower 3, and the other end is divided into two to form the first circulation pipeline 51 and the second circulation pipeline 52;
  • the filter 522 is used to filter impurities in the waste water
  • Wastewater processor 523 the wastewater processor 523 includes a wastewater processor, including ultrasonic components and photocatalytic components, for degrading and removing pollutants in wastewater;
  • the first circulation line 51 is provided with a first return pump 511, which is connected with the washing water storage tank 1 to form a first circulation system; the second circulation line 52 is provided with a second return pump in sequence.
  • the return pump 521 is connected to the filter 522, the waste water processor 523 and the washing water storage tank 1 in sequence to form a second circulation system, both of which are used for recycling the washing waste water.
  • the photocatalytic assembly includes an excitation light source and a photocatalyst.
  • the main wavelengths emitted by the excitation light source are in the range of 185nm to 420nm, and the optimal light source is a light source with dominant wavelengths of 254nm and 185nm;
  • the photocatalysts are semiconductor photocatalysts such as metal oxides, sulfides, and selenides excited by ultraviolet and visible light.
  • titanium dioxide and modified titanium dioxide treated by nitrogen doping, dye sensitization and other processes containing zinc oxide, nickel oxide, bismuth oxyiodide, bismuth vanadate, bismuth molybdate, graphene-like carbon nitride and other materials
  • titanium dioxide and modified titanium dioxide treated by nitrogen doping, dye sensitization and other processes containing zinc oxide, nickel oxide, bismuth oxyiodide, bismuth vanadate, bismuth molybdate, graphene-like carbon nitride and other materials
  • Various compound semiconductor photocatalysts include: titanium dioxide and modified titanium dioxide treated by nitrogen doping, dye sensitization and other processes, containing zinc oxide, nickel oxide, bismuth oxyiodide, bismuth vanadate, bismuth molybdate, graphene-like carbon nitride and other materials
  • the semiconductor catalyst is a supported catalyst
  • the supporting matrix can be inorganic or organic structural materials such as ceramics, silica gel, resin, graphite, zeolite, stainless steel, nickel and nickel-based alloys, titanium and titanium-based alloys, and the shape of the supporting matrix can be: Spherical, sheet, mesh, fibrous, foam, sponge.
  • the power range of the ultrasonic component is 20kHz to 80kHz, and the optimal power is 20kHz, which can release a large amount of polycyclic aromatic hydrocarbons attached to macroscopic particles or sludge into the water environment, and can also affect the polycyclic aromatic hydrocarbons that participate in the heterogeneous photocatalytic reaction.
  • the outer wall of the excitation light source is continuously cleaned to ensure the penetration ability of its effective light wave, so that the photocatalytic component works reliably and efficiently.
  • the washing water storage tank 1 is provided with a liquid level meter and a pH meter, which are used for real-time monitoring of the pH and water volume of the washing water in the washing water storage tank 1 .
  • a liquid level meter and a pH meter which are used for real-time monitoring of the pH and water volume of the washing water in the washing water storage tank 1 .
  • the process flow of the advanced treatment and reuse device of the ship exhaust desulfurization washing wastewater provided by the present invention is as follows: the ship engine 4 burns sulfur-containing fuel to generate tail gas and enters the washing tower 3, and the washing water storage tank 1 Under the action of the lift pump 21 and the nozzle (not marked in the figure), the washing water of the ship cleans the sulfur-containing tail gas in the form of droplets in the ship tail gas desulfurization washing tower 3, and the alkaline substances such as sodium hydroxide in the washing water can be mixed with the tail gas.
  • the sulfur-containing components in the solution are fully reacted to generate sodium sulfite or further oxidized to generate sodium sulfate, which is dissolved in the washing water and flows out from the bottom outlet of the washing tower 3 into the washing water circulation pipeline 5.
  • the unburned fuel components, black carbon , PAHs, etc. also enter the washing water circulation pipeline 5 with the washing water, and the clean exhaust gas is overflowed and discharged from the upper port of the washing tower 3; the washing water containing various pollutants entering the washing water circulation pipeline 5 can be equipped with a first reflux.
  • the first circulation line 51 of the pump 511 returns to the washing water storage tank 1 to participate in the exhaust gas washing process again.
  • part of the washing water can also be pumped into the second circulation system through the second return pump 521 for waste water treatment: first pass the filter 522 , after coarse filtration, centrifugal separation and other steps to filter or remove carbon black, insoluble crystalline salt, unburned components and other macroscopic (different from micro-nano-scale particles) pollutants, enter the waste water processor 523, in this
  • the organic pollutants such as PAHs in the washing water are completely decomposed or oxidized through the triple purification of ultrasonic waves, multi-phase photocatalysis and photolysis, and small molecules are easily degraded organic acids and further generate CO 2 , water, inorganic salts, etc.
  • the product, a small amount of insoluble inorganic salts generated, etc., are subjected to ultrafiltration treatment and then enter the sludge storage tank, and are to be transferred to the shore for treatment; at the same time, the treated washing water enters the washing water storage tank 1 through the second circulation pipeline 52, and is not connected with the untreated sludge in the tank.
  • the treated washing water enters again from the top of the washing tower under the action of the lift pump 21 to clean the sulfur-containing tail gas produced by the ship's engine. The above process is repeated continuously.
  • the first circulation system and the second circulation system do not necessarily operate at the same time.
  • the present invention measures the PAHs concentration in the washing water in real time by installing a PAHs concentration detector 7, and then adjusts the first circulation system and the second circulation system.
  • the working state of the circulation system when the washing water first starts to work, the content of PAHs and other pollutants and impurities in the washing wastewater is not much, that is, when the concentration of PAHs in the washing wastewater is not more than 50 ⁇ g/L, only the first circulation system needs to be run at this time. ; As the time of washing waste gas treatment increases, the content of PAHs pollutants and impurities in the washing waste water gradually increases.
  • the second circulation system and the first circulation system work simultaneously; when the pollutant concentration exceeds 50 ⁇ g/L If the concentration is too high and it is located outside the exhaust emission control area of the ship, the first circulation system can be stopped, and only the second circulation system can be opened to efficiently treat the pollutants in the washing wastewater.
  • the ship engine 4 of the applicable vessel is a WARTSILA-SULZER RT fiex50 type low-speed diesel engine, the total exhaust volume is 4 ⁇ 10 4 NM 3 /h, the flow rate of the lift pump 21 is 0-80m 3 /h, and the initial temperature of the flue gas is At 300°C, the initial concentration of SO 2 is about 500 mg/Nm 3 .
  • the generated flue gas is desulfurized and washed by the magnesium-based seawater method.
  • the washing water contains 1% concentration of Mg(OH) 2.
  • the closed-circuit ship exhaust desulfurization and washing system is started for 2 hours.
  • the desulfurization washing water is 2.7m 3 in total.
  • the flow rate of the second reflux pump 521 is 7.5L/min
  • the volume of the reaction chamber of the waste water processor 523 is 0.2m 3
  • 50 ultraviolet lamps with a power of 54w and an emission band of 254nm are arranged at equal intervals in the reactor.
  • the heterotitanium dioxide-supported catalyst is evenly arranged in parallel with the ultraviolet lamp, and the processing frequency of the ultrasonic component is 20KHz. It is calculated that a total of 0.9m 3 of washing water is treated by the waste water processor 523 for 0.5h, and the CODCr degradation rate of the outlet effluent reaches 50.1%.
  • the flow rate of the second return pump 521 is adjusted to be 15L/min
  • the waste water processor 523 is adjusted to work at full power load, and the CODCr degradation rate of the outlet water is detected to be 90.6%.
  • the engine of the applicable ship is a MAN 6S35MC low-speed diesel engine.
  • the total smoke emission of the ship's engine 4 is 28,000kg/h, and the fuel used is high-sulfur 3.5% marine fuel oil.
  • 50L of sodium hydroxide solution with a mass fraction of 20% needs to be consumed per hour, that is, 50L of desulfurization tail gas washing water loses the desulfurization effect.
  • the desulfurization tail gas scrubbing water in the initial scrubbing water storage tank 1 is 0.5 m 3 in total.
  • the flow rate of the second reflux pump 521 is 5L/min
  • the volume of the reaction chamber of the waste water processor 523 is 0.5m 3
  • 100 ultraviolet lamps with a power of 38w and an emission wavelength of 254nm and 185nm are arranged at equal intervals in the reactor, and the spongy oxidation
  • the zinc-supported catalyst was evenly arranged in parallel with the UV lamp, and the treatment frequency of the ultrasonic component was 20 kHz. It is calculated that a total of 0.3 m 3 of washing water is treated by the waste water processor 523 for 1 hour, and the CODCr degradation rate of the effluent at the outlet reaches 76.2%.
  • the flow rate of the second return pump 521 is further adjusted to 8L/min, the waste water processor 523 works at full power load, and the CODcr degradation rate of the outlet water is 95.1% after testing.
  • the present invention provides a device for advanced treatment and reuse of ship tail gas washing wastewater.
  • the device does not need to be equipped with an electrolysis device and has low energy consumption; the technology of filtration and ultrasonic coupling multi-phase photocatalytic oxidation reaction is used to treat the washing wastewater, which can not only degrade and remove pollutants in the washing wastewater efficiently and thoroughly, but also greatly reduce the sludge production. And no chemicals are introduced, which greatly reduces the negative impact on the ecological environment in the process of wastewater treatment; in addition, the device improves the service time and recycling rate of the washing water in the closed-circuit ship tail gas desulfurization washing system, reducing its impact.
  • the demand for supplementary water from sources such as seawater also saves a lot of supplementary consumption of alkaline detergents, thereby reducing the storage of chemicals on board and reducing the potential safety hazards of ships.

Abstract

Disclosed in the present invention is an advanced treatment and recycling apparatus for ship exhaust desulfurization washing wastewater. The apparatus comprises: a washing water storage tank, connected to a washing tower; a washing water circulation pipeline, having one end connected to an outlet at the bottom of the washing tower, and having the other end divided into a first circulation pipeline and a second circulation pipeline; a filter; and a wastewater treatment device, comprising an ultrasonic assembly, a photocatalytic assembly, and an ultrafiltration assembly, wherein the first circulation pipeline is connected to the washing water storage tank to form a first circulation system, and the filter, the wastewater treatment device, and the washing water storage tank are sequentially communicated with each other by the second circulation pipeline to form a second circulation system. The apparatus treats washing wastewater by using a filtering and ultrasonic coupled heterogeneous photocatalytic oxidation reaction technology, such that pollutants in the wastewater can be efficiently and thoroughly removed, and the recycling rate of washing water is also improved; moreover, the washing wastewater is treated without introducing any chemical, such that the negative influence on the ecological environment is small.

Description

一种船舶尾气脱硫洗涤废水的深度处理及回用装置A device for advanced treatment and reuse of ship tail gas desulfurization and washing wastewater 技术领域technical field
本发明属于船舶尾气脱硫洗涤废水处理技术领域，特别涉及一种船舶尾气洗涤废水处理装置。The invention belongs to the technical field of ship tail gas desulfurization washing wastewater treatment, and particularly relates to a ship tail gas washing wastewater treatment device.
背景技术Background technique
随着全球经济及航运物流的快速发展，船舶尾气的排放逐渐成为影响全球大气及海洋的主要污染源之一。2010年7月1日，国际海事组织(IMO)通过《国际防止船舶造成污染公约》(又称MARPOL公约)附则VI正式生效，对船舶尾气排放的硫氧化物(SOx)和氮氧化物(NOx)实行了越来越严格的规定。自2012年起，在公海行驶的远洋船舶的SOx排放浓度降低50％是IMO的第一个目标，以后每隔5年减排指标将重新修订并提升一次，2020年该法规进入第三实施阶段，要求全球远洋船舶应用的二氧化硫排放比已有的3.50％m/m的限值降低85％。With the rapid development of the global economy and shipping logistics, the emission of ship exhaust has gradually become one of the main pollution sources affecting the global atmosphere and ocean. On July 1, 2010, the International Maritime Organization (IMO) passed Annex VI of the International Convention for the Prevention of Pollution from Ships (also known as the MARPOL Convention), which came into effect. ) imposed increasingly stringent regulations. Since 2012, reducing the SOx emission concentration of ocean-going ships on the high seas by 50% is the first goal of IMO. After that, the emission reduction target will be revised and upgraded every five years. In 2020, the regulation will enter the third implementation stage , which requires that the sulfur dioxide emissions used by global ocean-going ships be reduced by 85% compared with the existing limit of 3.50% m/m.
为了努力达到《国际防止船舶造成污染公约》(又称MARPOL公约)中的废气减排指标，目前各国正在大力发展船舶尾气排放污染控制技术，其中的一个主要方向为采用湿法处理对船舶废气中的SOx污染物进行脱除。该方法可细分为开路式、混合式以及闭路式循环洗涤这三种方式，其中，开路式及混合式船舶尾气脱硫方式存在共同的弊端是将尾气中排放的大量未完全燃烧的燃料油、挥发性的润滑油等污染物向海水中转移，使得这些污染物中含有的多环芳烃(PAHs)类污染物大量进入海洋中，PAHs属于持久性难降解污染物，具有致癌、致畸、食物链富集传递等高生物毒性，因而船舶尾气洗涤废水的排海污染问题日益凸显。In order to strive to achieve the exhaust gas emission reduction targets in the International Convention for the Prevention of Pollution from Ships (also known as the MARPOL Convention), countries are now vigorously developing ship exhaust emission pollution control technologies. removal of SOx pollutants. The method can be subdivided into three methods: open-circuit, hybrid and closed-circuit washing. Among them, the open-circuit and hybrid ship exhaust desulfurization methods have the common disadvantage of removing a large amount of incompletely burned fuel oil, Volatile lubricants and other pollutants are transferred to seawater, so that the polycyclic aromatic hydrocarbons (PAHs) contained in these pollutants enter the ocean in large quantities. PAHs are persistent and refractory pollutants with carcinogenic, teratogenic, food chain Due to the high biological toxicity such as enrichment and transfer, the pollution problem of ship exhaust washing wastewater discharge into the sea has become increasingly prominent.
当前成为主流发展技术的闭路式船舶尾气脱硫洗涤法改进了开路式及混合式系统的二次污染排放问题，但目前该方法技术仍存在关键瓶颈问题，即该类闭路式船舶尾气脱硫洗涤系统在工作过程中产生的大量脱硫洗涤废水，尤其是浓缩有高盐、高浓度、高色度、高生物毒性的有机污染物洗涤废水的深度处理技术亟待寻求技术突破，以保障在该类闭路式脱硫洗涤系统中的洗 涤水的理化性质始终处于最优的工作条件。The closed-circuit ship exhaust desulfurization and scrubbing method, which has become the mainstream development technology at present, has improved the secondary pollution discharge problem of open-circuit and hybrid systems, but there are still key bottlenecks in this method and technology. A large amount of desulfurization and washing wastewater generated during the working process, especially the advanced treatment technology of washing wastewater with organic pollutants with high salt, high concentration, high chroma and high biological toxicity, needs to seek technological breakthroughs to ensure that such closed-circuit desulfurization The physical and chemical properties of the washing water in the washing system are always in the optimal working conditions.
在现有技术中，关于船舶尾气洗涤废水的处理技术主要有：中国专利“一种新船舶废水处理一体化装置(CN201110087069.9)”和“一种改进的船舶水处理设备(CN201520809429.5)”，以上发明将废水依次通过多个腔室或者层，分别经过曝气、沉淀、过滤、生化、消毒等处理工艺，发明的设备虽然集成度较高，但是单位时间内处理量较小，不适用于船舶尾气脱硫洗涤系统的较大循环水量的要求；且该发明引入了微生物分解工艺来去除洗涤废水中的有机污染物，受限于船舶废气洗涤过程中产生的高酸碱、高有机毒性等苛刻水质，微生物的种类及丰度受到严重影响，导致微生物降解工艺段的抗冲击性能差，处理后的洗涤水水质急剧波动，不能达到回用或排放标准，甚至影响废气清洗系统的正常工艺，因而风险隐患极大。In the prior art, the treatment technologies for ship exhaust washing wastewater mainly include: Chinese patents "A new integrated device for ship wastewater treatment (CN201110087069.9)" and "An improved ship water treatment equipment (CN201520809429.5)" ”, the above invention sequentially passes wastewater through multiple chambers or layers, and undergoes treatment processes such as aeration, sedimentation, filtration, biochemistry, and disinfection. Although the invented equipment has a high degree of integration, the treatment capacity per unit time is small, and it is not It is suitable for the requirement of large circulating water volume of the ship exhaust gas desulfurization washing system; and the invention introduces a microbial decomposition process to remove organic pollutants in the washing wastewater, which is limited by the high acid-base and high organic toxicity generated in the ship exhaust gas washing process. and other harsh water quality, the species and abundance of microorganisms are seriously affected, resulting in poor impact resistance in the microbial degradation process section, and the water quality of the treated washing water fluctuates sharply, failing to meet the reuse or discharge standards, and even affecting the normal process of the waste gas cleaning system. , so the risk is very high.
中国专利“一种船舶脱硫废水处理装置及方法(CN201310422883.0)”中提出的技术主要为微气泡+化学药剂絮凝+吸附，存在处理工艺流程长、设备数量多、污泥产量大、易吸附饱和、污水循环利用率低等问题。中国专利“船舶废气脱硫废水处理装置及方法(CN201510119019.2)”中，将废水引入旋流分离单元，分离出污泥，剩余废水进入电化学处理单元，进行氧化降解，废水处理后排出。该系统节省了加药装置，但废水pH值不能满足排放要求；此外，未进行混凝处理，就直接对废水进行旋流分离，不能充分分离油污等悬浮物；还使用了电解装置，能耗较高。The technology proposed in the Chinese patent "A Device and Method for Desulfurization Wastewater from Ships (CN201310422883.0)" is mainly micro-bubble + chemical flocculation + adsorption. Saturation, low utilization rate of sewage recycling, etc. In the Chinese patent "Ship Waste Gas Desulfurization Wastewater Treatment Device and Method (CN201510119019.2)", the wastewater is introduced into the cyclone separation unit to separate out the sludge, and the remaining wastewater enters the electrochemical treatment unit for oxidative degradation, and the wastewater is discharged after treatment. The system saves the dosing device, but the pH value of the wastewater cannot meet the discharge requirements; in addition, the wastewater is directly separated by cyclone without coagulation treatment, which cannot fully separate the suspended solids such as oil pollution; it also uses an electrolysis device, which saves energy higher.
中国专利“一种船舶废气脱硫系统废水处理装置(CN201810211847.2)”中，采用气浮、化学絮凝、曝气+平板陶瓷膜过滤+活性炭吸附的三步处理方法进行去除亚硫酸盐、油污、悬浮物等杂质，该方法存在活性炭用量大、易吸附饱和、产生二次污染等缺陷。In the Chinese patent "Wastewater Treatment Device for Ship Waste Gas Desulfurization System (CN201810211847.2)", a three-step treatment method of air flotation, chemical flocculation, aeration + flat ceramic membrane filtration + activated carbon adsorption is used to remove sulfite, oil pollution, This method has defects such as large amount of activated carbon, easy adsorption and saturation, and secondary pollution.
综上，在船舶脱硫洗涤废水处理领域仍然主要采用曝气、气浮、絮凝、沉淀、旋分、吸附、生化、膜过滤、电化学等将污染物转移的传统水处理技术，以上技术不能彻底去除脱硫洗涤水中的有机污染物，尤其是那些难降解、持久性污染物，如PAHs，故当前实际出水中PAHs仍不能达到IMO规定的浓度限值要求，而被迫采用海水稀释来帮助履约，这导致向海洋中排放的实际污染物总量并未减少；另外，现有的船舶洗涤废水处理装置还存在能耗高、循环使用的洗涤水的理化性质不稳定等问题。In summary, traditional water treatment technologies such as aeration, air flotation, flocculation, precipitation, spin separation, adsorption, biochemistry, membrane filtration, electrochemistry, etc. to transfer pollutants are still mainly used in the field of ship desulfurization and washing wastewater treatment. To remove organic pollutants in desulfurization washing water, especially those refractory and persistent pollutants, such as PAHs, the current actual effluent PAHs still cannot meet the concentration limit requirements stipulated by IMO, and forced to use seawater dilution to help compliance, As a result, the actual total amount of pollutants discharged into the ocean has not been reduced; in addition, the existing ship washing wastewater treatment devices also have problems such as high energy consumption and unstable physical and chemical properties of the recycled washing water.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种船舶尾气洗涤废水的深度处理及回用装置，以解决现有技术中存在的污染物去除不彻底且效率低、污泥产量大、能耗高以及洗涤水循环利用率低等问题。The purpose of the present invention is to provide an advanced treatment and reuse device for ship exhaust washing wastewater, so as to solve the problems of incomplete removal of pollutants and low efficiency, large sludge output, high energy consumption and washing water recycling rate existing in the prior art. lower issues.
为了达到上述目的，本发明提供了一种船舶尾气洗涤废水的深度处理及回用装置，该装置用于处理并回收洗涤塔处理尾气后形成的洗涤废水，包括：In order to achieve the above purpose, the present invention provides a device for advanced treatment and reuse of ship exhaust gas scrubbing wastewater, which is used to treat and recover the scrubbing wastewater formed after the scrubbing tower processes the exhaust gas, including:
洗涤水储存罐，其一侧连接进水管路，另一侧通过输送管路与洗涤塔相连；The washing water storage tank, one side is connected to the water inlet pipeline, and the other side is connected to the washing tower through the conveying pipeline;
洗涤水循环管路，其一端与洗涤塔底部出口相连，另一端一分为二形成第一循环管路和第二循环管路；One end of the washing water circulation pipeline is connected with the outlet at the bottom of the washing tower, and the other end is divided into two parts to form the first circulation pipeline and the second circulation pipeline;
过滤器，用于过滤废水中的杂质；以及，Filters for filtering impurities from wastewater; and,
废水处理器，包括超声组件、光催化组件，用于降解去除废水中的污染物；Wastewater processors, including ultrasonic components and photocatalytic components, are used to degrade and remove pollutants in wastewater;
其中，所述的第一循环管路与所述的洗涤水储存罐相连，形成第一循环系统；所述的第二循环管路上依次连通所述的过滤器、废水处理器及洗涤水储存罐，形成第二循环系统。Wherein, the first circulation pipeline is connected with the washing water storage tank to form a first circulation system; the second circulation pipeline is sequentially connected with the filter, the waste water processor and the washing water storage tank , forming a second circulatory system.
所述的光催化组件包括激发光源和光催化剂。The photocatalytic assembly includes an excitation light source and a photocatalyst.
优选地，所述的激发光源发射的主波长范围为185nm～420nm。Preferably, the dominant wavelength emitted by the excitation light source is in the range of 185 nm to 420 nm.
优选地，所述的光催化剂为半导体催化剂。Preferably, the photocatalyst is a semiconductor catalyst.
进一步地，所述的半导体催化剂为负载型催化剂。Further, the semiconductor catalyst is a supported catalyst.
优选地，所述的超声组件采用的功率范围为20kHz～80kHz。Preferably, the power used by the ultrasonic component ranges from 20 kHz to 80 kHz.
优选地，所述的输送管路上设有PAHs浓度检测器。Preferably, a PAHs concentration detector is provided on the conveying pipeline.
优选地，所述的洗涤水储存罐设有液位计。Preferably, the washing water storage tank is provided with a liquid level gauge.
优选地，所述的洗涤水储存罐设有pH计。Preferably, the washing water storage tank is provided with a pH meter.
与现有技术相比，本发明所提供的装置具有以下优点：Compared with the prior art, the device provided by the present invention has the following advantages:
1.该船舶尾气洗涤废水的深度处理及回用装置采用废水处理器处理洗涤废水，该废水处理器包括超声组件、光催化组件及超滤组件，一方面，实现了超声波降解、光解及多相光催化氧化三种净化作用同时进行，且超声波与多相光催化还具有协同作用效应，能够更高效、彻底地降解去除洗涤废水 中的悬浮物、油污、亚硫酸盐、多环芳烃等污染物，且大大降低污泥产量；另一方面，该废水处理器不引入任何化学药品，大大减少了废水处理过程中对生态环境造成的负面影响。1. The advanced treatment and reuse device of the ship's tail gas washing wastewater adopts a wastewater processor to treat the washing wastewater. The wastewater processor includes an ultrasonic component, a photocatalytic component and an ultrafiltration component. On the one hand, ultrasonic degradation, photolysis and multiple The three purification effects of phase photocatalytic oxidation are carried out at the same time, and ultrasonic and heterogeneous photocatalysis also have a synergistic effect, which can degrade and remove suspended solids, oil stains, sulfites, polycyclic aromatic hydrocarbons and other pollution in the washing wastewater more efficiently and thoroughly. On the other hand, the wastewater processor does not introduce any chemicals, which greatly reduces the negative impact on the ecological environment during the wastewater treatment process.
2.该船舶尾气洗涤废水的深度处理及回用装置通过设置第二循环系统，使得闭路式船舶尾气清洁系统的洗涤水能够随船在线以旁路形式彻底净化及补给，不仅提高了闭路式船舶尾气清洁系统中洗涤水的服役时间以及循环利用率，减少了其对海水等来源的补水的需求量，同时也节省了大量的碱性洗涤药剂的补加消耗，从而减少了船上化学药剂的储存量，降低了船舶航行安全隐患。2. The advanced treatment and reuse device of the ship's exhaust gas washing wastewater is equipped with a second circulation system, so that the washing water of the closed-circuit ship exhaust gas cleaning system can be completely purified and replenished online in the form of bypass with the ship, which not only improves the closed-circuit ship exhaust gas cleaning system. The service time and recycling rate of the scrubbing water in the exhaust gas cleaning system reduce the demand for supplementary water from sources such as seawater, and also save a lot of supplementary consumption of alkaline scrubbers, thereby reducing the storage of chemicals on board It reduces the hidden danger of ship navigation safety.
3.该船舶尾气洗涤废水的深度处理及回用装置通过检测洗涤废水中PAHs的浓度并控制第一、第二循环系统的工作状况，可以使船舶尾气脱硫洗涤系统对尾气进行高效脱硫洗涤的同时，对洗涤废水中的PAHs进行处理，减少洗涤废水中PAHs富集所造成的环境风险。3. The advanced treatment and reuse device of the ship's tail gas washing wastewater can detect the concentration of PAHs in the washing wastewater and control the working conditions of the first and second circulation systems, so that the ship's tail gas desulfurization and washing system can efficiently desulfurize and wash the tail gas at the same time. , to treat the PAHs in the washing wastewater to reduce the environmental risk caused by the enrichment of PAHs in the washing wastewater.
4.相较传统的光催化组件中使用粉末态催化剂，本发明提供的装置采用负载型催化剂，负载型催化剂的使用能够减少光催化剂的流失，简化处理设备，增加设备的使用寿命，提高其使用过程中的稳定性。4. Compared with the powder catalyst used in the traditional photocatalytic assembly, the device provided by the present invention adopts a supported catalyst. The use of the supported catalyst can reduce the loss of the photocatalyst, simplify the treatment equipment, increase the service life of the equipment, and improve its use. stability in the process.
5该船舶尾气洗涤废水的深度处理及回用装置无需装设电解装置，能耗低。5. The advanced treatment and reuse device of the ship's tail gas washing wastewater does not need to install an electrolysis device, and the energy consumption is low.
6.该船舶尾气洗涤废水的深度处理及回用装置的第二循环系统对原有船舶尾气脱硫洗涤系统的结构，即第一循环系统的结构无直接影响，加装的处理设备几乎不增加整体结构的复杂度，且操控简单。此外，加装的处理设备体积小、能耗低、处理效率高、适用范围广，实际使用时可通过增减超声组件、光催化组件的个数，灵活调整处理规模。6. The second circulation system of the advanced treatment and reuse device of the ship's tail gas washing wastewater has no direct impact on the structure of the original ship's tail gas desulfurization and washing system, that is, the structure of the first circulation system, and the added treatment equipment hardly increases the overall structure. The complexity of the structure, and the manipulation is simple. In addition, the installed processing equipment is small in size, low in energy consumption, high in processing efficiency, and has a wide range of applications. In actual use, the processing scale can be flexibly adjusted by increasing or decreasing the number of ultrasonic components and photocatalytic components.
附图说明Description of drawings
图1是应用本发明船舶尾气洗涤废水的深度处理及回用装置的洗涤水处理工艺流程图。Fig. 1 is a process flow chart of washing water treatment using the advanced treatment and reuse device of ship exhaust washing wastewater according to the present invention.
附图标识：Attached identification:
洗涤水储存罐1；输送管路2；提升泵21；洗涤塔3；船舶引擎4；洗涤水循环管路5；第一循环管路51；第二循环管路52；第一回流泵511；第二 回流泵521；过滤器522；废水处理器523；进水泵6；PAHs浓度检测器7。Washing water storage tank 1; conveying pipeline 2; lift pump 21; washing tower 3; ship engine 4; washing water circulating pipeline 5; first circulating pipeline 51; second circulating pipeline 52; Second return pump 521; filter 522; waste water processor 523; feed pump 6; PAHs concentration detector 7.
具体实施方式Detailed ways
下面结合附图和特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所公开的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。The embodiments of the present invention are described below with reference to the accompanying drawings and specific specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.
请参阅图1。需要说明的是，本实施例中所提供的图示仅以示意方式说明本发明的基本构想，所以附图中仅显示与本发明中有关的组件而非按照实际实施时的组件数目、形状及尺寸绘制，其实际实施时各组件的型态、数量及比例可为一种随意的改变，且其组件布局型态也可能更为复杂。See Figure 1. It should be noted that the diagrams provided in this embodiment are only to illustrate the basic idea of the present invention in a schematic way, so the drawings only show the components related to the present invention rather than the number, shape and number of components in actual implementation. For dimension drawing, the type, quantity and proportion of each component can be changed at will in actual implementation, and the component layout may also be more complicated.
在本发明的描述中，需要说明的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性。In the description of the present invention, it should be noted that the terms "first" and "second" are only used for description purposes, and cannot be understood as indicating or implying relative importance.
如图1所示，本发明提供了一种船舶尾气洗涤废水的深度处理及回用装置，该装置用于处理洗涤塔处理尾气后形成的洗涤废水，其包括：As shown in Figure 1, the present invention provides a device for advanced treatment and reuse of ship exhaust gas scrubbing wastewater, the device is used to treat the scrubbing wastewater formed after the scrubbing tower processes the exhaust gas, and includes:
洗涤水储存罐1，所述的洗涤水储存罐1一侧连接设有进水泵6的进水管路，另一侧通过设有提升泵21的输送管路2与洗涤塔3相连，所述的输送管路上设有PAHs浓度检测器7；The washing water storage tank 1, one side of the said washing water storage tank 1 is connected with the water inlet pipeline provided with the inlet pump 6, and the other side is connected with the washing tower 3 through the conveying pipeline 2 provided with the lifting pump 21, and the said A PAHs concentration detector 7 is arranged on the conveying pipeline;
洗涤水循环管路5，其一端与洗涤塔3底部出口相连，另一端一分为二形成第一循环管路51和第二循环管路52；The washing water circulation pipeline 5 has one end connected to the bottom outlet of the washing tower 3, and the other end is divided into two to form the first circulation pipeline 51 and the second circulation pipeline 52;
过滤器522，用于过滤废水中的杂质；The filter 522 is used to filter impurities in the waste water;
废水处理器523，所述的废水处理器523包括废水处理器，包括超声组件、光催化组件，用于降解去除废水中的污染物； Wastewater processor 523, the wastewater processor 523 includes a wastewater processor, including ultrasonic components and photocatalytic components, for degrading and removing pollutants in wastewater;
所述的第一循环管路51设有第一回流泵511，且与所述的洗涤水储存罐1相连，形成第一循环系统；所述的第二循环管路52上依次设有第二回流泵521，且依次连通所述的过滤器522、废水处理器523及洗涤水储存罐1，形成第二循环系统，两个循环系统均用于洗涤废水的回收利用。The first circulation line 51 is provided with a first return pump 511, which is connected with the washing water storage tank 1 to form a first circulation system; the second circulation line 52 is provided with a second return pump in sequence. The return pump 521 is connected to the filter 522, the waste water processor 523 and the washing water storage tank 1 in sequence to form a second circulation system, both of which are used for recycling the washing waste water.
所述的光催化组件包括激发光源和光催化剂。该激发光源发射的主波长范围为185nm～420nm，最优为发射主波长为254nm、185nm的光源；所述 的光催化剂为紫外线及可见光激发的金属氧化物、硫化物、硒化物等半导体光催化剂，具体包括：二氧化钛及经氮掺杂、染料敏化等工艺处理的改性二氧化钛、含有氧化锌、氧化镍、碘氧化铋、钒酸铋、钼酸铋、类石墨烯氮化碳等材料的各种复合半导体光催化剂。The photocatalytic assembly includes an excitation light source and a photocatalyst. The main wavelengths emitted by the excitation light source are in the range of 185nm to 420nm, and the optimal light source is a light source with dominant wavelengths of 254nm and 185nm; the photocatalysts are semiconductor photocatalysts such as metal oxides, sulfides, and selenides excited by ultraviolet and visible light. , specifically including: titanium dioxide and modified titanium dioxide treated by nitrogen doping, dye sensitization and other processes, containing zinc oxide, nickel oxide, bismuth oxyiodide, bismuth vanadate, bismuth molybdate, graphene-like carbon nitride and other materials Various compound semiconductor photocatalysts.
所述的半导体催化剂为负载型催化剂，负载基体可以为陶瓷、硅胶、树脂、石墨、沸石、不锈钢、镍及镍基合金、钛及钛基合金等无机或有机结构材料，负载基体的形状可以为球状、片状、网状、纤维状、泡沫状、海绵状。The semiconductor catalyst is a supported catalyst, and the supporting matrix can be inorganic or organic structural materials such as ceramics, silica gel, resin, graphite, zeolite, stainless steel, nickel and nickel-based alloys, titanium and titanium-based alloys, and the shape of the supporting matrix can be: Spherical, sheet, mesh, fibrous, foam, sponge.
所述的超声组件采用功率范围为20kHz～80kHz，最优功率为20kHz，可使附着在宏观颗粒物或污泥上的多环芳烃大量释放进入水体环境中，也可对参与多相光催化反应的激发光源的外壁进行持续清洁，保障其有效作用光波的穿透能力，从而使得光催化组件工作可靠、高效。The power range of the ultrasonic component is 20kHz to 80kHz, and the optimal power is 20kHz, which can release a large amount of polycyclic aromatic hydrocarbons attached to macroscopic particles or sludge into the water environment, and can also affect the polycyclic aromatic hydrocarbons that participate in the heterogeneous photocatalytic reaction. The outer wall of the excitation light source is continuously cleaned to ensure the penetration ability of its effective light wave, so that the photocatalytic component works reliably and efficiently.
所述的洗涤水储存罐1设有液位计和pH计，用于实时监控洗涤水储存罐1中洗涤水的酸碱度和水量。当水量过少时，通过进水泵6泵入适量海水并加入洗涤水中所需的碱性物质，保证洗涤水一直能以适当碱度在系统中足量运行，维持其良好的处理效果。The washing water storage tank 1 is provided with a liquid level meter and a pH meter, which are used for real-time monitoring of the pH and water volume of the washing water in the washing water storage tank 1 . When the amount of water is too small, an appropriate amount of seawater is pumped through the inlet pump 6 and the alkaline substances required in the washing water are added to ensure that the washing water can always run in sufficient quantities in the system with appropriate alkalinity and maintain its good treatment effect.
如图1所示，本发明提供的船舶尾气脱硫洗涤废水的深度处理及回用装置在使用时的工艺流程为：船舶引擎4燃烧含硫燃料产生尾气进入洗涤塔3，洗涤水储存罐1中的洗涤水在提升泵21以及喷头(图中未标识)作用下以雾滴状形式在船舶尾气脱硫洗涤塔3中对含硫尾气进行清洗，洗涤水中的氢氧化钠等碱性物质可与尾气中的含硫组分发生充分反应，生成亚硫酸钠或进一步氧化生成硫酸钠，溶解于洗涤水中随其从洗涤塔3底部出口流出进入洗涤水循环管路5，同时未燃烧完全的燃油组分、黑炭、PAHs等同样随洗涤水进入洗涤水循环管路5，清洁的尾气则从洗涤塔3上口溢出排放；进入洗涤水循环管路5的含有多种污染物的洗涤水，可经设有第一回流泵511的第一循环管路51回到洗涤水存储罐1中重新参加尾气洗涤过程，同时也可通过第二回流泵521将部分洗涤水泵入第二循环系统进行废水处理：首先通过过滤器522，经粗过滤、离心分离等步骤过滤或去除掉其中的炭黑，不溶性结晶盐、未燃烧完全的组分等宏观(区别于微纳米级颗粒)污染物后，进入废水处理器523，在该处理器中同时通过超声波、多相光催化以及光解三重净化作用对洗涤水中的PAHs等有机污染物进行彻底分解或氧化，生成小分子易降解 有机酸并进一步生成CO 2、水、无机盐等产物，生成的少量不溶性无机盐等经超滤处理后进入污泥储存罐，待转岸处理；同时处理后的洗涤水通过第二循环管路52进入洗涤水储存罐1，与罐中未经处理的洗涤水共同在提升泵21的作用下再次从洗涤塔上方进入，对船舶引擎产生的含硫尾气进行清洗。以上过程不断循环进行。 As shown in Figure 1, the process flow of the advanced treatment and reuse device of the ship exhaust desulfurization washing wastewater provided by the present invention is as follows: the ship engine 4 burns sulfur-containing fuel to generate tail gas and enters the washing tower 3, and the washing water storage tank 1 Under the action of the lift pump 21 and the nozzle (not marked in the figure), the washing water of the ship cleans the sulfur-containing tail gas in the form of droplets in the ship tail gas desulfurization washing tower 3, and the alkaline substances such as sodium hydroxide in the washing water can be mixed with the tail gas. The sulfur-containing components in the solution are fully reacted to generate sodium sulfite or further oxidized to generate sodium sulfate, which is dissolved in the washing water and flows out from the bottom outlet of the washing tower 3 into the washing water circulation pipeline 5. At the same time, the unburned fuel components, black carbon , PAHs, etc. also enter the washing water circulation pipeline 5 with the washing water, and the clean exhaust gas is overflowed and discharged from the upper port of the washing tower 3; the washing water containing various pollutants entering the washing water circulation pipeline 5 can be equipped with a first reflux. The first circulation line 51 of the pump 511 returns to the washing water storage tank 1 to participate in the exhaust gas washing process again. At the same time, part of the washing water can also be pumped into the second circulation system through the second return pump 521 for waste water treatment: first pass the filter 522 , after coarse filtration, centrifugal separation and other steps to filter or remove carbon black, insoluble crystalline salt, unburned components and other macroscopic (different from micro-nano-scale particles) pollutants, enter the waste water processor 523, in this In the processor, the organic pollutants such as PAHs in the washing water are completely decomposed or oxidized through the triple purification of ultrasonic waves, multi-phase photocatalysis and photolysis, and small molecules are easily degraded organic acids and further generate CO 2 , water, inorganic salts, etc. The product, a small amount of insoluble inorganic salts generated, etc., are subjected to ultrafiltration treatment and then enter the sludge storage tank, and are to be transferred to the shore for treatment; at the same time, the treated washing water enters the washing water storage tank 1 through the second circulation pipeline 52, and is not connected with the untreated sludge in the tank. The treated washing water enters again from the top of the washing tower under the action of the lift pump 21 to clean the sulfur-containing tail gas produced by the ship's engine. The above process is repeated continuously.
需要说明的是，本发明中第一循环系统和第二循环系统并非一定要同时运行，本发明通过装设PAHs浓度检测器7实时测定洗涤水中的PAHs浓度，进而调节第一循环系统和第二循环系统的工作状态：洗涤水刚开始工作时，洗涤废水中的PAHs等污染物和杂质含量不多，即洗涤废水中的PAHs浓度不大于50μg/L时，此时只需运行第一循环系统；随着洗涤水处理废气的时间增长，洗涤废水中PAHs污染物和杂质含量逐渐增多，当污染物浓度超过50μg/L时，此时第二循环系统与第一循环系统同时工作；当污染物浓度过高，位于船舶尾气排放控制区以外时，可将第一循环系统停止，仅开启第二循环系统对洗涤废水中的污染物进行高效处理。It should be noted that, in the present invention, the first circulation system and the second circulation system do not necessarily operate at the same time. The present invention measures the PAHs concentration in the washing water in real time by installing a PAHs concentration detector 7, and then adjusts the first circulation system and the second circulation system. The working state of the circulation system: when the washing water first starts to work, the content of PAHs and other pollutants and impurities in the washing wastewater is not much, that is, when the concentration of PAHs in the washing wastewater is not more than 50μg/L, only the first circulation system needs to be run at this time. ; As the time of washing waste gas treatment increases, the content of PAHs pollutants and impurities in the washing waste water gradually increases. When the pollutant concentration exceeds 50 μg/L, the second circulation system and the first circulation system work simultaneously; when the pollutant concentration exceeds 50 μg/L If the concentration is too high and it is located outside the exhaust emission control area of the ship, the first circulation system can be stopped, and only the second circulation system can be opened to efficiently treat the pollutants in the washing wastewater.
实施例1Example 1
所适用船只的船舶引擎4为WARTSILA-SULZER RT fiex50型低速柴油机，总排烟量为4×10 4NM 3/h，提升泵21的流量为0-80m 3/h，烟气的初始温度为300℃，SO 2的初始浓度约为500mg/Nm 3。使用镁基海水法对所产生的烟气进行脱硫洗涤处理，洗涤水中含有1％浓度的Mg(OH) 2，该闭路式船舶尾气脱硫洗涤系统共开机2h，初始洗涤水储存罐1中的尾气脱硫洗涤水共2.7m 3。第二回流泵521流量为7.5L/min，废水处理器523反应腔体容积为0.2m 3，50支功率为54w、发射波段为254nm的紫外灯在反应器中等间距排布，网状氮掺杂二氧化钛负载型催化剂与紫外灯平行均匀排布，超声组件处理频率为20KHz。经计算共有0.9m 3洗涤水经废水处理器523处理0.5h，其出口出水的CODCr降解率达到50.1％。调节第二回流泵521流量为15L/min时，调整废水处理器523为全功率载荷工作，出口出水经检测其CODCr降解率为90.6％。 The ship engine 4 of the applicable vessel is a WARTSILA-SULZER RT fiex50 type low-speed diesel engine, the total exhaust volume is 4×10 4 NM 3 /h, the flow rate of the lift pump 21 is 0-80m 3 /h, and the initial temperature of the flue gas is At 300°C, the initial concentration of SO 2 is about 500 mg/Nm 3 . The generated flue gas is desulfurized and washed by the magnesium-based seawater method. The washing water contains 1% concentration of Mg(OH) 2. The closed-circuit ship exhaust desulfurization and washing system is started for 2 hours. The tail gas in the initial washing water storage tank 1 The desulfurization washing water is 2.7m 3 in total. The flow rate of the second reflux pump 521 is 7.5L/min, the volume of the reaction chamber of the waste water processor 523 is 0.2m 3 , and 50 ultraviolet lamps with a power of 54w and an emission band of 254nm are arranged at equal intervals in the reactor. The heterotitanium dioxide-supported catalyst is evenly arranged in parallel with the ultraviolet lamp, and the processing frequency of the ultrasonic component is 20KHz. It is calculated that a total of 0.9m 3 of washing water is treated by the waste water processor 523 for 0.5h, and the CODCr degradation rate of the outlet effluent reaches 50.1%. When the flow rate of the second return pump 521 is adjusted to be 15L/min, the waste water processor 523 is adjusted to work at full power load, and the CODCr degradation rate of the outlet water is detected to be 90.6%.
实施例2Example 2
所适用船舶的发动机为MAN 6S35MC型低速柴油机，机负荷在50％时，船舶引擎4总排烟量为28000kg/h，所用燃油为高硫3.5％船用燃油，在保持 船舶尾气脱硫洗涤塔3脱硫效率为99％以上的条件下，每小时需消耗质量分数为20％的氢氧化钠溶液50L，即有50L的脱硫尾气洗涤水失去脱硫的效果，该闭路式船舶尾气脱硫洗涤系统共开机1h，初始洗涤水储存罐1中的脱硫尾气洗涤水共0.5m 3。第二回流泵521流量为5L/min，废水处理器523反应腔体容积为0.5m 3，100支功率为38w、发射波段为254nm与185nm的紫外灯在反应器中等间距排布，海绵状氧化锌负载型催化剂与紫外灯平行均匀排布，超声组件处理频率为20kHz。经计算共有0.3m 3洗涤水经废水处理器523处理1h，其出口处出水的CODCr降解率达到76.2％。进一步调节第二回流泵521流量至8L/min，废水处理器523为全功率载荷工作，出口出水经检测其CODcr降解率为95.1％。 The engine of the applicable ship is a MAN 6S35MC low-speed diesel engine. When the engine load is 50%, the total smoke emission of the ship's engine 4 is 28,000kg/h, and the fuel used is high-sulfur 3.5% marine fuel oil. Under the condition that the efficiency is above 99%, 50L of sodium hydroxide solution with a mass fraction of 20% needs to be consumed per hour, that is, 50L of desulfurization tail gas washing water loses the desulfurization effect. The desulfurization tail gas scrubbing water in the initial scrubbing water storage tank 1 is 0.5 m 3 in total. The flow rate of the second reflux pump 521 is 5L/min, the volume of the reaction chamber of the waste water processor 523 is 0.5m 3 , and 100 ultraviolet lamps with a power of 38w and an emission wavelength of 254nm and 185nm are arranged at equal intervals in the reactor, and the spongy oxidation The zinc-supported catalyst was evenly arranged in parallel with the UV lamp, and the treatment frequency of the ultrasonic component was 20 kHz. It is calculated that a total of 0.3 m 3 of washing water is treated by the waste water processor 523 for 1 hour, and the CODCr degradation rate of the effluent at the outlet reaches 76.2%. The flow rate of the second return pump 521 is further adjusted to 8L/min, the waste water processor 523 works at full power load, and the CODcr degradation rate of the outlet water is 95.1% after testing.
综上所述，本发明提供了一种船舶尾气洗涤废水的深度处理及回用装置。该装置无需装设电解装置，能耗低；采用过滤以及超声波耦合多相光催化氧化反应的技术处理洗涤废水，不仅能够高效、彻底地降解去除洗涤废水中的污染物，大大降低污泥产量，且不引入任何化学药品，大大减少了废水处理过程中对生态环境造成的负面影响；另外，该装置提高了闭路式船舶尾气脱硫洗涤系统中洗涤水的服役时间以及循环利用率，减少了其对海水等来源的补水的需求量，同时也节省了大量的碱性洗涤药剂的补加消耗，从而减少了船上化学药剂的储存量，降低了船舶安全隐患。To sum up, the present invention provides a device for advanced treatment and reuse of ship tail gas washing wastewater. The device does not need to be equipped with an electrolysis device and has low energy consumption; the technology of filtration and ultrasonic coupling multi-phase photocatalytic oxidation reaction is used to treat the washing wastewater, which can not only degrade and remove pollutants in the washing wastewater efficiently and thoroughly, but also greatly reduce the sludge production. And no chemicals are introduced, which greatly reduces the negative impact on the ecological environment in the process of wastewater treatment; in addition, the device improves the service time and recycling rate of the washing water in the closed-circuit ship tail gas desulfurization washing system, reducing its impact. The demand for supplementary water from sources such as seawater also saves a lot of supplementary consumption of alkaline detergents, thereby reducing the storage of chemicals on board and reducing the potential safety hazards of ships.
尽管本发明的内容已经通过上述优选实施例作了详细介绍，但应当认识到上述的描述不应被认为是对本发明的限制。在本领域技术人员阅读了上述内容后，对于本发明的多种修改和替代都将是显而易见的。因此，本发明的保护范围应由所附的权利要求来限定。While the content of the present invention has been described in detail by way of the above preferred embodiments, it should be appreciated that the above description should not be construed as limiting the present invention. Various modifications and alternatives to the present invention will be apparent to those skilled in the art upon reading the foregoing. Accordingly, the scope of protection of the present invention should be defined by the appended claims.

Claims (9)

  1. 一种船舶尾气脱硫洗涤废水的深度处理及回用装置，该装置用于处理并回收洗涤塔处理尾气后形成的洗涤废水，其特征在于，该装置包括：A device for advanced treatment and reuse of ship tail gas desulfurization and washing wastewater, the device is used to treat and recover the washing wastewater formed after the washing tower processes the tail gas, and is characterized in that the device comprises:
    洗涤水储存罐，其一侧连接进水管路，另一侧通过输送管路与洗涤塔相连；The washing water storage tank, one side is connected to the water inlet pipeline, and the other side is connected to the washing tower through the conveying pipeline;
    洗涤水循环管路，其一端与洗涤塔底部出口相连，另一端一分为二形成第一循环管路和第二循环管路；One end of the washing water circulation pipeline is connected with the outlet at the bottom of the washing tower, and the other end is divided into two parts to form the first circulation pipeline and the second circulation pipeline;
    过滤器，用于过滤废水中的杂质；以及，Filters for filtering impurities from wastewater; and,
    废水处理器，包括超声组件、光催化组件，用于降解去除废水中的污染物；Wastewater processors, including ultrasonic components and photocatalytic components, are used to degrade and remove pollutants in wastewater;
    其中，所述的第一循环管路与所述的洗涤水储存罐相连，形成第一循环系统；所述的第二循环管路上依次连通所述的过滤器、废水处理器及洗涤水储存罐，形成第二循环系统。Wherein, the first circulation pipeline is connected with the washing water storage tank to form a first circulation system; the second circulation pipeline is sequentially connected with the filter, the waste water processor and the washing water storage tank , forming a second circulatory system.
  2. 如权利要求1所述的船舶尾气洗涤废水的深度处理及回用装置，其特征在于，所述的光催化组件包括激发光源和光催化剂。The device for advanced treatment and reuse of ship exhaust gas washing wastewater according to claim 1, wherein the photocatalyst component comprises an excitation light source and a photocatalyst.
  3. 如权利要求2所述的船舶尾气洗涤废水的深度处理及回用装置，其特征在于，所述的激发光源发射的主波长范围为185nm～420nm。The device for advanced treatment and reuse of ship exhaust gas washing wastewater according to claim 2, characterized in that the main wavelength range of the excitation light source emitted is 185nm-420nm.
  4. 如权利要求2所述的船舶尾气洗涤废水的深度处理及回用装置，其特征在于，所述的光催化剂为半导体催化剂。The device for advanced treatment and reuse of ship exhaust gas washing wastewater according to claim 2, wherein the photocatalyst is a semiconductor catalyst.
  5. 如权利要求4所述的船舶尾气洗涤废水的深度处理及回用装置，其特征在于，所述的半导体催化剂为负载型催化剂。The device for advanced treatment and reuse of ship exhaust gas washing wastewater according to claim 4, wherein the semiconductor catalyst is a supported catalyst.
  6. 如权利要求1所述的船舶尾气洗涤废水的深度处理及回用装置，其特征在于，所述的超声组件采用的功率范围为20kHz～80kHz。The device for advanced treatment and reuse of ship exhaust gas washing wastewater according to claim 1, characterized in that, the power range used by the ultrasonic component is 20 kHz to 80 kHz.
  7. 如权利要求1所述的船舶尾气洗涤废水的深度处理及回用装置，其特征在于，所述的输送管路上设有PAHs浓度检测器。The device for advanced treatment and reuse of ship exhaust gas washing wastewater according to claim 1, characterized in that a PAHs concentration detector is arranged on the conveying pipeline.
  8. 如权利要求1所述的船舶尾气洗涤废水的深度处理及回用装置，其特征在于，所述的洗涤水储存罐设有液位计。The device for advanced treatment and reuse of ship exhaust gas washing wastewater according to claim 1, wherein the washing water storage tank is provided with a liquid level gauge.
  9. 如权利要求1所述的船舶尾气洗涤废水的深度处理及回用装置，其特征在于，所述的洗涤水储存罐设有pH计。The device for advanced treatment and reuse of ship exhaust gas washing wastewater according to claim 1, wherein the washing water storage tank is provided with a pH meter.
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