CN102933504A - Emissions control system and method - Google Patents

Emissions control system and method Download PDF

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Publication number
CN102933504A
CN102933504A CN2010800389255A CN201080038925A CN102933504A CN 102933504 A CN102933504 A CN 102933504A CN 2010800389255 A CN2010800389255 A CN 2010800389255A CN 201080038925 A CN201080038925 A CN 201080038925A CN 102933504 A CN102933504 A CN 102933504A
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water
solution
exhaust emissions
treatment system
salt solution
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CN102933504B (en
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建平·保罗·陈
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National University of Singapore
Port of Singapore Authority
CMA CGM Asia Shipping Pte Ltd
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National University of Singapore
Port of Singapore Authority
American President Lines Co Pte Ltd
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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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • 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
    • 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
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B01D53/965—Regeneration, reactivation or recycling of reactants including an electrochemical process step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B13/00—Conduits for emptying or ballasting; Self-bailing equipment; Scuppers
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4566—Gas separation or purification devices adapted for specific applications for use in transportation means
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46119—Cleaning the electrodes
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • C02F2001/46185—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only anodic or acidic water, e.g. for oxidizing or sterilizing
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • C02F2001/4619—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only cathodic or alkaline water, e.g. for reducing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/008—Originating from marine vessels, ships and boats, e.g. bilge water or ballast water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4613—Inversing polarity
    • 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
    • C02F2209/001—Upstream control, i.e. monitoring for predictive control
    • 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
    • C02F2209/005—Processes using a programmable logic controller [PLC]

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Ocean & Marine Engineering (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Treating Waste Gases (AREA)

Abstract

A treatment system comprising an electrolytic cell, having an anode compartment and a cathode compartment, said electrolytic cell having an inlet for receiving salt water, said cell arranged to produce an alkaline solution within the cathode compartment and a disinfecting solution within the anode compartment; an alkaline scrubber unit for the treatment of exhaust emissions from a ship-mounted engine, said alkaline scrubber unit for receiving the alkaline solution and the exhaust emissions into a first chamber for mixing the exhaust emissions and alkaline solution mix, and; a disinfection unit intermediate a water inflow and a ballast tank, said disinfection unit arranged to receive the disinfecting solution and water from the water inflow so as to disinfect said water before delivery to the ballast tank.

Description

Emission control systems and method
Technical field
The present invention relates to sea-freight (shipping) environmental problem on every side, for example, the control of engine emissions and water ballast management.
Background technology
In order to ensure ship and crewman's safety, the stability of ship is necessary.Based on this purpose, ship uses " water ballast " at term of voyage.(for example use solid-state material although exist, sand and rock) as the possibility of ballasting, but because water in ballasting with unload convenient aspect the ballasting, has made water (not only comprising seawater but also comprise fresh water) (Carlton, 1985) always since 1880.According to estimates, the annual discharging in the whole world 30 to 12,000,000,000 tons of water ballasts (Luo Si, 2005).
Water ballast in the world many places discharges in a large number.Water ballast has been considered to the threat to coastal environment.Introduce biological invasion by water ballast and littoral deposit, these biological invasions enter together with seawater is pumped.The row that comprise the marine species that the biology various in style of the larva of bacterium and other microorganisms, ovum, cyst and each species all can carry at water ballast.The new species of establishing may be harmful to (for example, vibrio cholerae) to HUMAN HEALTH, and may become the threat to the ocean environment species diversity, thereby cause environment, economy and healthy impact.
Since the later stage eighties 20th century, the concern of the non-local biology that transmitted by ship water ballast people such as (, 2007) MICHAEL DRAKEs has been increased.The ER for emission rate of water ballast at short notice can be very high.The normally used traditional method of slip-stick artist is design snubber facility in system.Yet this design often causes system dimension significantly to increase, and can not consider may changing of water yield when water is also in snubber.Moreover, have and do not wish to cushion because of economic cause but the example of discharging as early as possible.
Some research institutions and company are just developing ballast water treatment (BWT) technology.Studied such as heating (auspicious lattice ratio wait for people, 1999), be with pretreated UV irradiation (Sutherland, calendar year 2001), membrane filtration, chlorination (people, calendar year 2001 such as to open; The people such as Robson da Silva, 2004), the treatment technology of ionization, electrolysis and ozonize (people such as He Weixi 2006).Table 1 shows some available techniques of ballast water treatment.
Many study group have all proposed heat treatment technics.Poisonous Flagellatae such as planktonic organism, is larger marine organisms, but is typically found at the fresh water habitat.Temperature and salinity are depended in their distribution.In laboratory scale research, it is reported, but poisonous Flagellatae under 35 ℃ through 2 hours duration of contact after complete deactivation.Some researchists attempt with biological to acceptable level such as killing than short contacting time of 45 ℃ applied at elevated temperature such as several minutes.This technology can use the used heat from the ship engine to be used for ballast water treatment.Yet in actual applications, main concern is in the industry, and whether the heat that produces enough is used for the expection purpose.Moreover full-scale test shows that hot water may have damage to the ballast tank coating, because higher temperature can promote the corrosion to cabinet greatly.
Ultraviolet ray (UV) irradiation can be killed various types of bacteriums.Yet, use separately the UV poor effect, because the turbidity of water ballast is usually high, and disinfecting time is often long.In addition, UV is installed in existing ballast tank usually is considered to be unfavorable for the ship owner, and cost is usually high.
The ballast water treatment technology tabulation that table 1 can be used
Treatment technology Time Inactivation efficient (%)
Heating 2-4 hour 90-99
Ozonize 5-10 hour 96-99.9
The UV that band filters 15 minutes 90-99
Ionization relates to the exposure biological group in the active specy of mixed oxidant gas.In laboratory scale research, have been reported title, within 2 minutes duration of contact, the bacterium above 90% is killed.Carried out onboard test, in this technology, the use of several large size producer gas generators is the problems that will solve.
Ozonize has been reported as a kind of settling mode of water ballast problem.The effective killing microorganisms of this technology, but can not effectively eliminate than mcroorganism.Need the large size ozonizer to process a large amount of water ballasts.Ozone and byproduct thereof may be poisonous to human body.Thereby its operation is often dangerous.
Various types of biocides are studied for ballast water treatment.Because such as the practical difficulty of the amount in a large amount of water ballasts that join in a ship, the transportation of biocide and the operation of processing unit are considered to be unfavorable for industry.In addition, extremely normal concern is efficient and the probability that causes corroding.For example, Hussein and co-worker thereof (2006) control bacterial growth with carbonic acid gas.The method is seemingly effective in their laboratory scale research.Forseeable problem may comprise to the corrosion of Ballast water tank and for larger living organism and the lower efficient of anaerobic bacterium.
Above prior art have common shortcoming: higher regeneration probability and the higher cost of the lower biology that removes efficient, long retention time, is sterilized.These technology are often based on test pilot or laboratory scale, thereby flow velocity under study for action is usually low.Water ballast has high flow velocity.For example, the ballasting water pump has up to 600m 3The flow velocity of/hr.Most of current available BWT technology may be inapplicable.In addition, most of Technology Need changes ballast tank and/or other existing utilities in the ship, and this is not so that these technology are suitable for industry.All these have limited their large-scale application aspect ballast water treatment.
Unique feasible measure of still implementing on the ship is the exchange of marine (mid-ocean) water ballast.Marine, the water ballast on the ship uses open seawater to replace by emptying with refilling ballast tank or ejecting (flow-through) dilution by injection.Water ballast after the operation will comprise less pollutent, thereby cause less environmental pollution when discharging at next harbour.Although this technology is very effective, its problem comprises: microorgranic contaminant removes not exclusively and security.For example, some biologies, particularly microorganism are bonded at the structure of ballast tank, thereby are difficult to remove.
The waste gas that the ship engine is discharged is another environmental problem that occurs.As showing in the table 2 that waste gas is by CO 2, NO x, SO x, CO and particulate matter form.NO xAnd SO xBe extremely acid, have larger henry 's law constant and soluble in water.Thereby they form strong acid in the aqueous solution, become the arch-criminal of acid rain.Further, carbonic acid gas is one of most important greenhouse gases.Because 20-30 comes CO in the past 2The surge of concentration, Global warming have become one of the most serious environmental problem that we face.International Maritime Organizaton (IMO) has implemented to stipulate to manage and control some compositions.For example, SO xDischarging reduces gradually.The whole world the sulphur largest percentage from 4.5% (current regulation) be down to from January 1st, 2012 come into effect 3.5%.Further, be down to from the year two thousand twenty January 1 came into effect 0.5%.These per-cents are more strict for sulphur emissions control area (for example, U.S. markon welfare is inferior).These regional sulphur largest percentage will reduce to 1.0% from 1 day July in 2010, and will further reduce to 0.1% from 1 day January in 2015.Current, the low-volatility fuel of higher sulfur content (low cost) uses the fuel (expensive) than low sulfur content to replace, and this is very high for the obvious cost of ship owner.
Adsorption technology and absorption techniques are generally used for the processing of waste gas.In absorption, can use the sorbent material such as gac.Yet, do not have magnetism in the maritime affairs industry such as making to be adsorbed on the factor of the regeneration of sorbent material.In absorption, seawater is used for by the washer absorption of acid gases.The current many ships by in the world of this commercial washer technology use.The pH of seawater is about 8, indicates very weak alkalescence.Thereby, low with efficient in the sour gas.Remove SO 2Processing efficiency be no more than according to reports 20%.Thereby the footprint of efficient and washer (foot-print) does not have magnetism.The new technology that is used for gas processing on the developing vessel will have higher science and commercial value.
The estimation content of the gaseous species of the waste gas that table 2 diesel motor is discharged
Figure BPA00001515765000041
Summary of the invention
In first aspect, the invention provides a kind for the treatment of system, comprise: have the electrolyzer of anolyte compartment and cathode compartment, described electrolyzer has for the entrance that receives salt solution, and described groove is configured to produce basic solution and produce sterilized solution in cathode compartment in the anolyte compartment; For the treatment of the caustic rubber unit from the exhaust emissions that is installed on the engine on the ship (exhaust emissions), described caustic rubber unit is used for described basic solution and exhaust emissions are received to first indoor with mix waste gas discharge and basic solution mixture, and salt solution flow into ballast tank in the middle of disinfection unit, described disinfection unit be configured to receive described sterilized solution and the salt solution that flows into from salt solution in order to before described water is transferred to ballast tank, it is carried out disinfection.
In second aspect, the invention provides a kind for the treatment of process, said method comprising the steps of: transmission salt solution is to anode and negative electrode; Electrolytic brine, thus produce sterilized solution and produce basic solution at negative electrode at anode; Transmission is installed on exhaust emissions and described basic solution to the first chamber of the engine on the ship; By mixing to process described exhaust emissions at the described first indoor and described basic solution; Transmission from the salt solution that flows into and described sterilized solution to disinfection unit, and; By in described disinfection unit, mixing to process described salt solution with described sterilized solution.
The present invention thereby relate to a kind of electrolyzer is used for by introducing salt water generates basic solution scrubbing exhaust gas in order to produce a kind of liquid, but the quilt of described liquid environmental protection, safety is disposed and produced chemical and (comprises sterilized solution, such as chlorine, OCl -, HOCl etc.) and with to entering, leave and/or reside in the water sterilization in the ballast tank, thus to potential environment sensitive position, kill biological group unloading ballasting.
In one embodiment, the invention provides a kind of for the treatment of the two integrated technology of water ballast and waste gas.A series of electrolyzers can provide sterilizing agent, and described sterilizing agent is for the microorganism that kills water ballast and for generation of the waste gas (SO that is used for removing washer x, NO xAnd CO 2) basic solution and reductive agent (Cl 2).
When the ship that this system is installed berthed in the harbour, described electrolyzer was operated to produce a series of sterilizing agents, and the microorganism that described sterilizing agent will kill IMO regulation is to satisfy scope as 0.006 to 0.01kwh/m 3The supervision regulation (regulatory specifications) of utmost point lower power intake.
When ship berthed in marine navigation and/or at the harbour, electrolyzer can be operated to produce the such mode of basic solution, in the described basic solution and come gaseous species in the waste gas of comfortable engine internal combustion.In addition, comprise the stream of the chlorine NO in can oxidation gaseous effluent in the electrolyzer.Gas remove efficient much larger than current available technology.
Will understand is that for such as the ship in the fresh water in canal, river and lake, fresh water can use by salt adding in fresh water, in order to the inflow of salt solution to electrolyzer is provided.Use for fresh water, salt adding is necessary to improve salinity to the level that needs in flow into.For example, in order to make System Operation, may need the salinity of 20PSU.Salt can be added in the inflow in the mixing zone.In a further embodiment, the mixing zone can comprise solution tank, and fresh water flows in the described solution tank, along with salt adding to solution tank, solution tank provides enough turbulent flow, the residence time or other factors to come satisfactorily dissolved salt.The salinity sensor can be provided in the groove or approach outlet in order to determine the salinity of water.Described salinity sensor can be connected to Controlling System, the salt amount in the described Controlling System control flume.
The advantage of described technology comprises: 1. triangular web is processed two kinds of environmental hazards: water ballast and waste gas; 2. do not need the shipping chemical; 3. efficiently remove two kinds of harm; 4 easy handlings.In the treatment system running, owing to have magnesium and calcium in the water, the electrode in the electrolyzer can be attached to the incrustation scale on surface.This incrustation scale will adversely affect the operation of electrolyzer, lower efficiency, and if let alone no matter can hinder operation.For reducing this impact, water can carry out pre-treatment via ion exchange process.
In a further embodiment, electrode can remove incrustation scale by the polarity switching.In this process, the polarity of electrolysis is changeable, and namely the electromotive force on the groove is put upside down, so that anode becomes negative electrode, and negative electrode becomes anode.This switching can periodically occur, for example every 0.5 to 1 hour, and the time of generation restriction, such as 5 to 190 minutes, until electrode is removed incrustation scale or removes substantially incrustation scale.This has following benefit: the cost of having avoided the electrode aftertreatment that removes incrustation scale of pre-treatment cost and physics.
Description of drawings
Further describing the present invention in conjunction with the accompanying drawing that shows possible configuration of the present invention will be easily.Other configurations of the present invention are possible, thereby the singularity of accompanying drawing is not understood to replace the generality of above stated specification of the present invention.
Fig. 1 is the synoptic diagram according to the electrolyzer of one embodiment of the invention;
Fig. 2 is the synoptic diagram of scrubber system according to a further embodiment of the invention.
Fig. 3 is the synoptic diagram of ballast water treatment system according to a further embodiment of the invention.
Embodiment
Fig. 1 is the synoptic diagram of electrolyzer 5, and electrolyzer 5 is used for producing the sterilized solution of the basic solution of processing exhaust emissions and treatment of ballast water (such as chlorine, OCl -, HOCl etc.).Be to be noted that usually, need to use a series of electrolyzers (a plurality of (multiple) groove) to produce enough basic solutions and sterilized solution for waste gas and ballast water treatment.Yet, only having when the amount of waste gas and/or water ballast hour, single electrolyzer just may be enough.
Electrolyzer comprises anode 20 and negative electrode 25, and they are positioned at anolyte compartment 10 and the cathode compartment 15 of electrolyzer 5 separately. Chamber 10,15 tunicles 65 (for example, diaphragm (diaphragm) and ion-exchange membrane) are separated.Electrode can be to contain a small amount of IrO 2The Ti of composition and/or RuO 2In case ought not need to produce Cl 2The time, can use MnO 2This technology can be used for briny environment; Also can be used for the fresh water environment of salt adding in flowing into to fresh water.Can use the Ti electrode of Ni coating to promote the generation of basic solution and hydroxide ion at cathode compartment 15.
Electrolyzer 5 is configured to receive salt solution (such as seawater or be added with the fresh water of salt) 30 and discharge by an entrance to have the chlorine of dissolving and/or the salt solution of oxygen (for example, seawater) 40.
Negative electrode 15 receives the basic solution 58 that salt solution 35 and transmission have the salt solution of the sodium hydroxide of dissolving and hydrogen.Basic solution 58 removes hydrogen 70 through gas/water separators 60, with the basic solution 56 after guiding separates through outlet 45 and before using in the scrubber system (shown in Figure 2), discharge hydrogen is in atmosphere.Will understand is that any standard gas/water separator that hydrogen can be separated will be enough from basic solution.Hydrogen can collected subsequently and for generation of energy, be included in burning or use in the fuel container.
The ability that produces chloride salt solution (for example, seawater) 40 and basic solution 56 from chamber 10,15 separately is to provide by described chamber 10,15 being carried out the film isolation.
When the processing carried out waste gas, for the anolyte compartment, valve 55 cuts out and replacing valve 50 is opened.The committed step that anode and negative electrode occur is as follows.
At anode 10, following oxidizing reaction is arranged:
1/2Cl 2+e -＝Cl - E 0＝1.391v (1a)
1/4O 2+H ++e -＝1/2H 2O，E 0＝1.23v (1b)
At negative electrode 15, following reaction occurs:
H 2O＝2H ++OH -(2a)
2H ++2e -＝H 2(2b)
Owing to there is overvoltage (over-potential), the actual potential of reaction formula (1b) is higher than (1a).Thereby reaction formula (1a) becomes main reaction.In other words, in the anolyte compartment, produce chlorine.
Because reaction formula (2b) consumes hydrogen ion, because the concentration of reaction formula (2a) oxyhydroxide (OH-) will increase.Thereby, produced basic solution (mainly being sodium hydroxide) at cathode compartment.Be to be noted that gas-water separator 60 may be essential for separating from the hydrogen in the water of cathode compartment 15.
Total reaction is as follows:
2Cl -+2H +＝＝Cl 2+H 2(3)
Stream 40 from anolyte compartment 10 among Fig. 1 (comprises Cl 2) can be used for removing the SO in the waste gas 2And NO, because this two kinds of gaseous species and Cl 2Reaction.From cathode compartment, the further neutralizing acid (H of stream 45 with higher pH 2SO 3, H 2SO 4, HNO 2, HNO 3).
Further, the invention provides a kind of system, be used for by mixing with sterilized solution that electrolyzer produces entering, reside in or leave the ballast disinfect of ballast tank.When for the outlet in the anolyte compartment 10, valve 50 cuts out and replacing valve 55 when opening, and can produce this kind sterilized solution.Chloride salt solution 57 from anolyte compartment 10 will mix with the water 56 (high pH) from cathode compartment 15, and causing forming sterilizing agent (mainly is OCl -, HOCl and Cl 2) 45, be used for treatment of ballast water.Optionally, the chloride water that directly comes from anolyte compartment 10 can be used as sterilized solution.In this operating period, the NaOH that negative electrode 15 produces can store for washer and use.Thereby ballast water treatment can betide ship during the harbour, and more specifically, comes across during the inflow and/or outflow of ballast tank.Compare with the ship engine operation, ballast water treatment can be the time of relatively lacking.Therefore, the storage requirement of NaOH can be restricted, and ship term of voyage between the harbour or even when in the harbour, using engine to provide power as shipping, NaOH is used fast.
Because other compounds in the water except NaOCl 45, also can form other compounds, such as, but not limited to, HOCl, Mg (OCl) 2, KOCl, Ca (OCl) 2, O 3And free radical, they all can help ballast water treatment.
In order to operate under two kinds of different systems as shown in Fig. 2 and 3, electrolyzer must be adaptable in order to change operation.
When ship during in marine navigation, generation large quantity of exhaust gas as shown in table 2.Scrubber system is designed to realize the removing of enhancing of the waste gas gaseous species shown in the his-and-hers watches.
As shown in Figure 1, sterilized solution and NaOH solution are produced by the anolyte compartment in the electrolyzer and cathode compartment respectively and discharge from exporting 40 and 45.As shown in Figure 2, waste gas is washed device system 75 and processes, and scrubber system 75 comprises three different washers 80,85,90, and washer 80 uses chloride water 40, and washer 85 uses alkaline water 40 and washer 90 to make water 95.Three washers serve as the progression stage in treating processes, exhaust emissions 100 enters (second) chamber of chloride scrubber unit 80, and remaining exhaust emissions 135 is passed to (first) chamber of caustic rubber unit 85 after reaching.Still remaining exhaust emissions 140 and then (the 3rd) chamber of being passed to water scrubber unit 90 be with the last processing 130 of dissolved preparation, and follow the discharge 145 of any residual gas.Through each stage 80,85, after 90s, the liquid of processing be discharged in 110,120 and 130 to extra large 150 after large water gaging 105 mixes.Because discharge water 130 may still have low pH, add entry 105 and can be used to the acidity of dilution discharge thing 130 to promote pH in the scope of the 6-7 that meets international norm.For this purpose, the water 105 of adding can be any source, and its salts contg is unimportant to purpose.Therefore, use for fresh water, dilution water 105 does not need to add salt.
Will understand is that effectively the principal benefits of emission control is provided by caustic rubber 85, chloride washer 80 and water scrubber 90 are optional in the present invention.
Carry out the processing to waste gas in washer, described washer is usually aboard ship installed and is used.Chemical reaction is listed in table 3.Use this kind system, need less and/or less washer to process Exhaust Gas.
Will understand is that employed washer type comprises effluent standard thing washer, is also referred to as the wet washing device, the present invention is applicable to any this type of suitable washer.
Ballast water treatment 155 is by finishing with filtration, electricity sterilization and the residual oxygenant that neutralizes.The synoptic diagram of this process 155 shows in Fig. 3.
First module in the processing is to filter 165.During flow into 160 introducing process, the filtration of being undertaken by the micro-filter 190 that uses one or two automatic cleanings is in order to guarantee effectively to remove biology and solid, and reducing the throw out that in Ballast water tank, forms, described throw out is the Probability Area of biological and microbial survival and growth.Filter 165 and can effectively remove various lived solids (bio-solids) (colloidalmaterial), when having chlorine, described lived solid can cause forming chemical disinfection byproducts (DBP).Use filtering system 190, the amount of needed sterilizing agent will reduce and the concentration of DBP also can reduce.
Sterilizing agent is to produce by the electrolysis to the salt solution in the electrolyzer 215.Total residual oxygenant (TRO) is measured by TRO analyzer 175,230 and is controlled at preset value by computer 182.Can use with one or one or several rectifier 220 of several refrigerating unit 225.To use control computer 182, be used for measuring the TRO analyzer 175,230 and flow transmitter of total remaining oxygenant (TRO).Because seawater has corrodibility, anticorrosive will be for making up reactor.
Before unloading ballasting 185, neutralization solution (Sulfothiorine, Na 2S 2O 3) inject 177 before ballasting water pump 170 with residual oxidant reaction so that the TRO after the neutralization will be no more than 0.1mg/L (such as Cl 2) (peak concentration of permission).The dosage of Sulfothiorine is calculated by following formula:
[Na 2S 2O 3] (mg/L)=[total residual oxygenant (such as chlorine)] x factor
The concentration (mg/L is such as chlorine) of total residual oxygenant determines that by TRO analyzer 175 TRO analyzer 175 provides the real-time measurement of TRO concentration.Described factor is 0.65-0.75.Neutralized system 180 by the chemical storage container, be used for volume pump and computer 182 that chemical injects and form.
Ballasting process: shut-off valve 183,243,192 and 208.Open valve 169,179 and 212.Water (can be seawater or fresh water, decide on using) through micro-filter 190, electrochemical disinfection unit 205 and the valve 212 of tactic strainer 165, valve 169, ballasting water pump 170, valve 179, automatic cleaning, then injects ballast tank 240.Open ventilation installation 235 (optionally), even so that the hydrogen that produces in the electrolysis and/or chlorine when the two concentration is extremely low, also can be removed by rapid moving, as in theoretical calculation and test measurement, discussing.
Unload the ballasting process: shut-off valve 169,179 and 212.Be limited by selected process, open any one and valve 243 that flow out in the valve 183 or 192 or 208.But open valve 192 or 208 is so that water was filtered again 190 or sterilize 205 before unloading ballasting.
Water is extracted out with pump from ballast tank 240, and through tactic valve 243, pump 170 and valve 183 (or 192 or 208), then discharges 185 (or 195 or 210).Neutralization solution injects 177 to remove total remaining oxygenant (such as chlorine) to 0.1mg/L before pump 170.In and concentration determined by above-mentioned equation.When valve 183 opens and valve 192 and 208 when cutting out, releasing water 185 is to water surrounding (for example, sea, lake, canal etc.) and without filtering and sterilizing.Yet, two kinds of selections are provided.When valve 192 opens and valve 183 and 208 when all cutting out, water is filtered 190 and discharge 195.When valve 208 opens and valve 183 and 192 when all cutting out, water is filtered 190, sterilize 205 and discharge 210.
Cl in table 3 off gas treatment 2Theoretical Calculation with the NaOH consumption
For typical 5000TEU container-ship, engine power is 50,000kW.Provided CO in the table 4 2, SO xAnd NO xAmount.
The estimated value of gaseous species in a 5000TEU ship of table 4 waste gas
Waste gas CO 2 NO X SO 2
Quantity 25,000kg 850kg 630kg
In order to remove 100%SO 2And 100%NO x(supposition NO), according to table 3, theoretic NaOH and Cl 2Consumption is respectively 787.5kg and 2,010kg.Found through experiments, the system that provides among Fig. 1 produces 2010kg Cl 2Can cause ultimate production 3, the NaOH of 522kg is at NaOH and SO 2Between the reaction after, the amount of NaOH will (3,522-787.5=2734.5kg), it can be used for removing NO for 2734.5kg 2And CO 2
SO 2Compare NO xAnd CO 2More soluble in seawater and basic solution.If do not consider to remove NO xAnd CO 2, we only need 787.5kg NaOH, its need the energy of 2700kW or engine power (50,000kW) 5%.Advantage is: 1. still can use low-volatility fuel with lower cost and the size of 2. washers greatly to reduce.
In further embodiment:
1) consumption of electrolyzer comprises: groove is separated into produces respectively Cl 2With the anolyte compartment of NaOH and the film of cathode compartment.Can merge to produce OCl-and HOCl from two districts 10,15 stream.
2) said system can be used for the situation of fresh water, and salt adding is to the entrance 30 and 35 of Fig. 1 in the described fresh water situation.Will understand is that NaCl is salt commonly used in this process, also can use simultaneously and depend on KCl, CaCl 2And MgCl 2Process.
Experimental data
We are 3-12mg/l (Cl to TRO 2) laboratory scale and the research of semi-industrial scale confirm, at about 0.006kwh/m 3Utmost point lower power intake under can kill the microorganism of IMO regulation fully.PH after this kind operation does not become and maintains pH 7.5 to 8.5.
Electrode (metal of Pt family and their metal oxide are such as the Ti that scribbles Ru and/or Ir oxide compound) is used in order to effectively produce sterilizing agent and avoid serious etching problem.They have following advantage: obtain higher chlorine and the output of free radical with lower energy expenditure, and the higher resistibility to corroding.Recommend RuO m, Ti, IrO nAnd Pt.MnO xElectrode will can not produce oxygen, if do not want chlorine, can use MnO x
The not strain of sterilizing agent of this kind concentration is concerned, because it can stand quick decay (about 1 day), and the corrosion under this kind condition is similar to the situation that does not have sterilizing agent, and described do not have the situation of sterilizing agent through experimental verification (table 5).The operating effect of ballast tank corrosion is inessential.
The effect of electricity sterilization is carried out in corrosion in the table 5 pair ballast tank
Type Weight loss (g) Corrosion rate (mm/yr)
Water ballast (0.062 after 4 days) 0.0156
Chloride water ballast (0.065 after 4 days) 0.0157
In addition, owing to the existence of chlorine in the water and the impact of chlorine, can avoid corrosion and biological corrosion in the ballast tank.
In whole route, will stay in the ballast tank motionless through the seawater after the above-mentioned sterilization.When ship arrives next harbour, water ballast will discharge.A series of measurements of sterilizing agent byproduct, model research and eco-toxicity research confirm that the water ballast of the processing of discharging is given birth to environment to the sea and had insignificant toxicity.This technology can be used safely.

Claims (17)

1. treatment system comprises:
Electrolyzer with anolyte compartment and cathode compartment, described electrolyzer have for the entrance that receives salt solution, and described groove is configured to produce basic solution and produce sterilized solution in described cathode compartment in described anolyte compartment;
For the treatment of the caustic rubber unit from the exhaust emissions that is installed on the engine on the ship, described caustic rubber unit is used for described basic solution and described exhaust emissions are received to first indoor mixing described exhaust emissions and basic solution mixture, and;
Water flow into and ballast tank in the middle of disinfection unit, described disinfection unit be configured to receive described sterilized solution and from the water of described water inflow in order to before described water is transferred to described ballast tank, it is carried out disinfection.
2. treatment system according to claim 1, wherein, electrolyzer comprises the central compartment, described central compartment tunicle separate in case with anode and cathode isolation at described anolyte compartment and cathode compartment.
3. treatment system according to claim 1 and 2, further comprise: chloride scrubber unit, be used for and receive to the second Room to mix described exhaust emissions and described chloride salt solution from chloride salt solution and the described exhaust emissions of described anolyte compartment, described chlorination scrubber unit comprises outlet, and described outlet is used for transmission remainder of exhaust gas discharge to the described chamber of described caustic rubber unit.
4. each described treatment system in 3 according to claim 1, further comprise the water scrubber unit, be used for receiving to the 3rd Room to mix described remainder of exhaust gas discharge and water with water with from the remainder of exhaust gas discharge of described caustic rubber unit, described water scrubber unit comprises outlet, and described outlet is used for discharging treated liquid.
5. each described treatment system in 4 according to claim 1, wherein said disinfection unit is configured to receive the discharge water from described ballast tank, it is carried out disinfection before flowing out described discharge water being transferred to ballast tank.
6. each described treatment system in 5 according to claim 1, wherein said sterilized solution is the chloride salt solution from described anolyte compartment.
7. each described treatment system in 5 according to claim 1, wherein said sterilized solution is clorox salt solution, described clorox salt solution is mixed by the chloride salt solution that comes from described anolyte compartment and the described basic solution that comes from described cathode compartment.
8. each described treatment system in 7 according to claim 1, further comprise neutralized system, described neutralized system comprises for the analyzer of the total residual oxygenant of the water of determining to flow into from described water and is used for indicating injector neutralization solution to be injected the Controlling System of described water according to described definite total remaining oxygenant.
9. each described treatment system in 8 according to claim 1, the processing of wherein said exhaust emissions comprises: dissolving SO x, CO 2And NO xIn any one or its combination.
10. according to the described treatment system of each claim of front, further comprise: mixing zone, described mixing zone be configured to receive fresh water and in described fresh water salt adding in order to the salt solution of predetermined concentration is provided.
11. according to the described treatment system of each claim of front, wherein said electrolyzer comprises a collection of electrolyzer, and this batch electrolyzer is configured to transmit basic solution to described the first Room and transmission that comes from negative electrode separately and comes from the sterilized solution of described separately anode to described disinfection unit.
12. a treatment process said method comprising the steps of:
Transmission salt solution is to anode and negative electrode;
The described salt solution of electrolysis, thus produce sterilized solution and produce basic solution at described negative electrode at described anode;
Transmission comes from described exhaust emissions and described basic solution to the first chamber that is installed on the engine on the ship;
By mixing to process described exhaust emissions at the described first indoor and described basic solution;
Transmission comes from the water of inflow and described sterilized solution to disinfection unit, and;
By in described disinfection unit, mixing to process described water with described sterilized solution.
13. method according to claim 12, before the step that transfers to described the first Room, described method further may further comprise the steps:
Transmission comes from the chloride salt solution and described exhaust emissions to the second chamber of described anolyte compartment;
By mixing to process described exhaust emissions with described chloride salt solution;
Transmit remaining exhaust emissions to described the first Room.
14. according to claim 12 or 13 described methods, after the described first indoor described treatment step, described method further may further comprise the steps:
Transmission comes from remainder of exhaust gas discharge to the three Room of described the first Room;
Transmission water is to described the 3rd Room;
By mixing to process described remainder of exhaust gas discharge with described water;
Discharge described treated liquid.
15. each described method in 14 comprises that further transmission comes from the described treated water of described disinfection unit to the step of described ballast tank according to claim 12.
16. each described method in 15 according to claim 12 further may further comprise the steps:
Before described treatment step, analyze described water;
Determine to reduce in the described water of required adding the amount of the neutralization solution of total residual oxygenant, and;
Inject described required concentration to described water.
17. each described method in 16 according to claim 12 further may further comprise the steps:
In predetermined period, put upside down the polarity of the electrode in the described electrolyzer, in order to remove the incrustation scale on the described electrode.
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