CN102933504B - Emissions control system and method - Google Patents

Emissions control system and method Download PDF

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Publication number
CN102933504B
CN102933504B CN201080038925.5A CN201080038925A CN102933504B CN 102933504 B CN102933504 B CN 102933504B CN 201080038925 A CN201080038925 A CN 201080038925A CN 102933504 B CN102933504 B CN 102933504B
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Prior art keywords
water
solution
exhaust emissions
salt solution
electrolyzer
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CN102933504A (en
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陈嘉平保罗
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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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Sustainable Development (AREA)
  • 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 around, 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 object, ship uses " water ballast " at term of voyage.Although exist, (for example use solid-state material, sand and rock) as the possibility of ballasting, but because water is in ballasting with unload convenient aspect ballasting, since 1880, made water (not only comprising seawater but also comprise fresh water) (Carlton, 1985) always.According to estimates, 30 to 12,000,000,000 tons of water ballasts (Luo Si, 2005) are discharged in the whole world every year.
Water ballast in the world many places discharges in a large number.Water ballast has been considered to the threat to coastal environment.By water ballast and littoral deposit, introduce biological invasion, 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 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 being 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 in system, to design snubber facility.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 the example of not wishing to cushion because of economic cause but 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 to irradiate (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 techniques available 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 fresh water habitat.Temperature and salinity are depended in their distribution.In laboratory scale research, it is reported, poisonous Flagellatae can complete deactivation after the duration of contact of 2 hours at 35 ℃.Some researchists attempt with killing compared with short contacting time of the applied at elevated temperature such as 45 ℃ such as several minutes biological to acceptable level.This technology can be used used heat from ship engine for ballast water treatment.Yet, in actual applications, main concern in industry, whether the heat producing is enough for expecting object.Moreover full-scale test shows, hot water may have damage to ballast tank coating, because higher temperature can promote the corrosion to cabinet greatly.
Ultraviolet ray (UV) is irradiated can kill various types of bacteriums.Yet, use separately UV poor effect, because the turbidity of water ballast is conventionally high, and disinfecting time is often long.In addition, UV is installed in existing ballast tank and is conventionally considered to be unfavorable for ship owner, and cost is conventionally high.
The ballast water treatment technology list that table 1 can be used
Treatment technology Time Inactivation efficiency (%)
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 exposure biological group in the active specy of mixed oxidant gas.In laboratory scale research, have been reported title, within the duration of contact of 2 minutes, the bacterium over 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 compared with mcroorganism.Need 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.Due to the practical difficulty of the amount in a large amount of water ballasts such as joining 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 efficiency and the probability that causes corrosion.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 efficiency of anaerobic bacterium.
Prior art above has common shortcoming: lower efficiency, longer retention time, biological higher regeneration probability and the higher cost being sterilized of removing.These technology are often based on test pilot or laboratory scale, thereby flow velocity is under study for action conventionally low.Water ballast has high flow velocity.For example, 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 ship, and this makes these technology not be suitable for industry.All these have limited their large-scale application aspect ballast water treatment.
Unique feasible measure of still implementing on ship is the exchange of marine (mid-ocean) water ballast.Marine, the water ballast on ship uses open seawater to replace by emptying with refilling ballast tank or ejecting (flow-through) dilution by injection.Water ballast after operation will comprise less pollutent, thereby causes less environmental pollution while 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, be bonded at the structure of ballast tank, thereby be difficult to remove.
The waste gas that ship engine is discharged is another environmental problem occurring.As shown in table 2, waste gas is by CO 2, NO x, SO x, CO and particulate matter form.NO xand SO xbe extremely acid, there is 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 in the past carrys out CO 2surging of concentration, Global warming has 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, SOx discharge reduces gradually.The whole world 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 for example, are more strict for sulphur emissions control area (,, U.S. markon welfare sub-).The sulphur largest percentage in these regions will reduce to 1.0% from 1 day July in 2010, and 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) compared with 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, such as making to be adsorbed on by the factor of the regeneration of sorbent material, in maritime affairs industry, there is no magnetism.In absorption, seawater is used for absorbing sour gas by washer.The current many ships by the world of the washer technology of this business use.The pH of seawater is 8 left and right, indicates very weak alkalescence.Thereby, low with efficiency in sour gas.Remove SO 2processing efficiency be no more than according to reports 20%.Thereby the footprint of efficiency and washer (foot-print) does not have magnetism.New technology for gas processing on 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
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 receiving the entrance of salt solution, described electrolyzer is configured to produce in cathode compartment in basic solution Qie anolyte compartment and produces sterilized solution; For the treatment of the caustic rubber unit from being installed on the exhaust emissions (exhaust emissions) of the engine on ship, described caustic rubber unit is for receiving described basic solution and exhaust emissions 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 to it is carried out disinfection before described water is transferred to ballast tank.
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 at anode, produce sterilized solution and produce basic solution at negative electrode; Transmission is installed on exhaust emissions and described basic solution to the first chamber of the engine on ship; By mixing to process described exhaust emissions at described the first indoor and described basic solution; Transmission from the salt solution flowing into and described sterilized solution to disinfection unit, and; By mix to process described salt solution with described sterilized solution in described disinfection unit.
The present invention thereby relate to a kind of electrolyzer, for by introducing salt water generates basic solution, scrubbing exhaust gas is to produce a kind of liquid, described liquid can environmental protection, the chemical of being disposed and produce of safety (comprises sterilized solution, such as chlorine, OCl -, HOCl etc.) and with to entering, leave and/or reside in the water sterilization in 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 killing the microorganism of water ballast and for generation of for removing the waste gas (SO of washer x, NO xand CO 2) basic solution and reductive agent (Cl 2).
When the ship of this system being installed berthing in harbour, described electrolyzer is operated to produce a series of sterilizing agents, and described sterilizing agent be take the microorganism that kills IMO regulation to meet scope as 0.006 to 0.01kwh/m 3the supervision regulation (regulatory specifications) of utmost point lower power intake.
When ship is in marine navigation and/or while berthing at harbour, electrolyzer can be operated to produce the such mode of basic solution, in described basic solution and carry out the gaseous species in the waste gas of burning in comfortable engine.In addition, in electrolyzer, comprise the NO in the stream energy oxidation gaseous effluent of chlorine.Gas remove efficiency much larger than current available technology.
Will understand is that, for the ship in the fresh water such as canal, river and lake, fresh water can be used by salt adding in fresh water, to the inflow of salt solution to electrolyzer is provided.For fresh water application, salt adding is necessary to improve salinity to the level needing in flowing into.For example, in order to make System Operation, may need the salinity of 20PSU.Salt can be added in inflow in mixing zone.In a further embodiment, mixing zone can comprise solution tank, and fresh water flows in described solution tank, and along with salt adding is to solution tank, solution tank provides enough turbulent flow, the residence time or other because of dissolved salt satisfactorily usually.Salinity sensor can be provided in groove or approach outlet to determine the salinity of water.Described salinity sensor can be connected to Controlling System, the salt amount in 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 shipping chemical; 3. efficiently remove two kinds of harm; 4 easy handlings.In treatment system running, owing to there is magnesium and calcium in water, the electrode in electrolyzer can be attached to surperficial incrustation scale.This incrustation scale, by adversely affecting the operation of electrolyzer, lowers 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 be switched and be removed incrustation scale by polarity.In this process, the polarity of electrolysis is changeable, and the electromotive force on groove is put upside down, and make anode become 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.
Accompanying drawing explanation
In conjunction with the accompanying drawing that shows possible configuration of the present invention, further describing 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 according to the schematic diagram of the electrolyzer of one embodiment of the invention;
Fig. 2 is the schematic diagram of scrubber system according to a further embodiment of the invention.
Fig. 3 is the schematic diagram of ballast water treatment system according to a further embodiment of the invention.
Embodiment
Fig. 1 is the schematic diagram of electrolyzer 5, and electrolyzer 5 is used for produce processing the basic solution of exhaust emissions and the sterilized solution for the treatment of 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 the amount hour when waste gas and/or water ballast, single electrolyzer may be just 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 2.Once ought not need to produce Cl 2time, can use MnO 2.This technology can be used for briny environment; Also can be used for the fresh water environment of salt adding in flowing into fresh water.At cathode compartment 15, can use the Ti electrode of Ni coating to promote the generation of basic solution and hydroxide ion.
Electrolyzer 5 is configured to be received salt solution (such as seawater or be added with the fresh water of salt) 30 and discharged by an entrance to have the chlorine of dissolving and/or the salt solution of oxygen (for example, seawater) 40.
Negative electrode 15 receives salt solution 35 and transmits the basic solution 58 with the sodium hydroxide of dissolving and the salt solution of hydrogen.Basic solution 58 removes hydrogen 70 through gas/water separators 60, with the basic solution 56 after guiding separation, through outlet 45, before using, discharges hydrogen in atmosphere in arriving scrubber system (shown in Fig. 2).Will understand is that, any standard gas/water separator that hydrogen can be separated from basic solution will be enough.Hydrogen can collected and for generation of energy, be included in fuel container and burn or use subsequently.
The ability that produces chloride salt solution (for example, seawater) 40 and basic solution 56 from chamber 10,15 is separately to provide by film isolation is carried out in described chamber 10,15.
When carry out waste gas processing time, for 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, there is following oxidizing reaction:
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, there is reaction as follows:
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 anolyte compartment, produce chlorine.
Because reaction formula (2b) consumes hydrogen ion, because the concentration of reaction formula (2a) oxyhydroxide (OH-) will increase.Thereby, at cathode compartment, produced basic solution (being mainly sodium hydroxide).Be to be noted that gas-water separator 60 may be essential for separation 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 in Fig. 1 (comprises Cl 2) can be used for removing the SO in 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, for the sterilized solution by producing with electrolyzer mixes to entering, reside in or leave the ballast disinfect of ballast tank.When the outlet in anolyte compartment 10, valve 50 cuts out and replacing valve 55 while opening, and can produce this kind of sterilized solution.Chloride salt solution 57 from anolyte compartment 10 mixes the water with from cathode compartment 15 56 (high pH), and causing forming sterilizing agent (is mainly 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 harbour, and more specifically, during coming across the inflow and/or outflow of ballast tank.Compare with ship engine operation, ballast water treatment can be the relatively short time.Therefore, the storage requirement of NaOH can be restricted, and at ship at term of voyage between harbour or even when using engine to provide power for shipping in harbour, NaOH is used fast.
Due to other compounds in water, except NaOCl45, 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 Figures 2 and 3, electrolyzer must be adaptable to change operation.
When ship is 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 his-and-hers watches.
As shown in Figure 1, the anolyte compartment in electrolyzer and cathode compartment produce and discharge from exporting 40 and 45 respectively for sterilized solution and NaOH solution.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, and 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 afterwards.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 is discharged 110,120 and 130 in sea 150 after mixing with large water gaging 105.Because discharge water 130 may still have low pH, add acidity that water 105 can be used to dilution discharge thing 130 to promote pH to meeting in the scope of 6-7 of international norm.For this purpose, the water 105 adding can be any source, and its salts contg is unimportant to object.Therefore,, for fresh water application, 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, and chloride washer 80 and water scrubber 90 are optional in the present invention.
In washer, carry out the processing to waste gas, described washer is conventionally aboard ship installed and is used.Chemical reaction is listed in table 3.Use this kind of system, need less and/or less washer to process Exhaust Gas.
Will understand is that, the washer type of using comprises effluent standard thing washer, and also referred to as wet washing device, the present invention is applicable to any this type of suitable washer.
Ballast water treatment 155 be by use filter, electricity sterilization and neutralize residual oxygenant and complete.The schematic diagram of this process 155 shows in Fig. 3.
First module in processing is to filter 165.From during flowing into 160 introducing process, by using filtration that the micro-filter 190 of one or two automatic cleanings carries out in order to guarantee effectively to remove biology and solid, and reducing the throw out forming in Ballast water tank, 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 there is chlorine, described lived solid can cause forming chemical disinfection byproducts (DBP).Use filtering system 190, the amount of needed sterilizing agent also can reduce the concentration of minimizing and DBP.
Sterilizing agent is that the electrolysis by the salt solution in electrolyzer 215 produces.Total residual oxygen agent (TRO) is measured and is controlled at preset value by computer 182 by TRO analyzer 175,230.Can use with one or one or several rectifier 220 of several refrigerating unit 225.By use control computer 182, for measuring TRO analyzer 175,230 and the flow transmitter of total residual oxygen agent (TRO).Because seawater has corrodibility, anticorrosive will be for building 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 neutralization will be no more than 0.1mg/L (as Cl 2) (peak concentration of permission).The dosage of Sulfothiorine is calculated by following formula:
[Na 2s 2o 3] (mg/L)=[total residual oxygen agent (as chlorine)] x factor
The concentration of total residual oxygen agent (mg/L, as chlorine) is definite by TRO analyzer 175, and TRO analyzer 175 provides the real-time measurement of TRO concentration.Described factor is 0.65-0.75.Neutralized system 180 is comprised of chemical storage container, the volume pump and the computer 182 that inject for chemical.
Ballasting process: shut-off valve 183,243,192 and 208.Open valve 169,179 and 212.Water (can be seawater or fresh water, depending on application), 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 if the hydrogen and/or the chlorine that produce in electrolysis also can be removed by rapid moving when the two concentration is extremely low, as discussed in theoretical calculation and test is measured.
Unload ballasting process: shut-off valve 169,179 and 212.Be limited by selected process, open any one and valve 243 that flow out in valve 183 or 192 or 208.Can open valve 192 or 208 make water before unloading ballasting, be filtered again 190 or sterilization 205.
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).Before pump 170, neutralization solution injects 177 to remove total residual oxygen agent (such as chlorine) to 0.1mg/L.In and concentration by above-mentioned equation, determined.When valve 183, open and when valve 192 and 208 is cut out, for example discharge water 185, to water surrounding (, sea, lake, canal etc.) and without filtering and sterilizing.Yet, two kinds of selections are provided.When valve 192 is opened and when valve 183 and 208 is all cut out, water is filtered 190 and discharge 195.When valve 208 is opened and when valve 183 and 192 is all cut out, water is filtered 190, sterilization 205 and discharge 210.
Cl in table 3 off gas treatment 2theoretical Calculation with NaOH consumption
For typical 5000TEU container-ship, engine power is 50,000kW.In table 4, provided CO 2, SO xand NO xamount.
The estimated value of gaseous species in 5000TEU ship waste gas of table 4
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 providing in Fig. 1 produces 2010kg Cl 2can cause ultimate production 3, the NaOH of 522kg, at NaOH and SO 2between reaction after, the amount of NaOH will for 2734.5kg, (3,522-787.5=2734.5kg), it can be used for removing NO 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 to have the low-volatility fuel of lower cost and the size of 2. washers can reduce greatly.
In further embodiment:
1) consumption of electrolyzer comprises: groove is separated into and produces respectively Cl 2with the anolyte compartment of NaOH and the film of cathode compartment.Stream from two districts 10,15 can merge to produce OCl-and HOCl.
2) said system can be used for the situation of fresh water, and in described fresh water situation, salt adding is to the entrance 30 and 35 of Fig. 1.Will understand is that, NaCl is salt conventional in this process, also can use and depend on KCl, CaCl simultaneously 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 completely.PH after this kind of operation does not become and maintains pH7.5 to 8.5.
Electrode (metal of Pt family and their metal oxide, such as the Ti that scribbles Ru and/or Ir oxide compound) is used to effectively produce sterilizing agent and avoid serious etching problem.Their tools have the following advantages: with lower energy expenditure, obtain higher chlorine and the output of free radical, and the higher resistibility to corrosion.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 of concentration is concerned, because it can stand quick decay (approximately 1 day), and the corrosion under this kind of condition is similar to the situation that there is no sterilizing agent, described in there is no 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 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,, due to the existence of chlorine in water and the impact of chlorine, can avoid corrosion and biological corrosion in ballast tank.
Seawater after above-mentioned sterilization is motionless will stay ballast tank in whole route in.When ship arrives next harbour, water ballast will discharge.A series of measurements of sterilizing agent byproduct, model research and eco-toxicity research confirm, and the water ballast of the processing of discharge has insignificant toxicity to the raw environment in sea.This technology can be used safely.

Claims (17)

1. a treatment system, comprising:
The electrolyzer with anolyte compartment and cathode compartment, described electrolyzer has for receiving the entrance of salt solution, and described electrolyzer is configured to produce basic solution in described cathode compartment and produces sterilized solution in described anolyte compartment;
For the treatment of the caustic rubber unit from being installed on the exhaust emissions of the engine on ship, described caustic rubber unit is for described basic solution and described exhaust emissions being received to first indoor to mix 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 to it is carried out disinfection before described water is transferred to described ballast tank.
2. treatment system according to claim 1, wherein, electrolyzer comprises central compartment, described central compartment tunicle separate in case by anode and cathode isolation at described anolyte compartment and cathode compartment.
3. treatment system according to claim 1 and 2, described sterilized solution comprises chloride salt solution, described treatment system further comprises: chloride scrubber unit, for the described chloride salt solution from described anolyte compartment and described exhaust emissions are received to the second Room to mix described exhaust emissions and described chloride salt solution, described chlorination scrubber unit comprises outlet, and described outlet is for transmitting remainder of exhaust gas discharge to the described chamber of described caustic rubber unit.
4. treatment system according to claim 1 and 2, further comprise water scrubber unit, for receiving to the 3rd Room to mix described remainder of exhaust gas discharge and water by water with from the remainder of exhaust gas discharge of described caustic rubber unit, described water scrubber unit comprises outlet, and described outlet is for discharging treated liquid.
5. treatment system according to claim 1 and 2, 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. treatment system according to claim 1 and 2, wherein said sterilized solution is the chloride salt solution from described anolyte compartment.
7. treatment system according to claim 1 and 2, wherein said sterilized solution is clorox salt solution, described clorox salt solution is mixed by the described basic solution that comes from the chloride salt solution of described anolyte compartment and come from described cathode compartment.
8. treatment system according to claim 1 and 2, further comprise neutralized system, described neutralized system comprises for determining from the analyzer of the total residual oxygen agent of the water of described water inflow and for indicating injector neutralization solution to be injected to the Controlling System of described water according to described definite total residual oxygen agent.
9. treatment system according to claim 1 and 2, the processing of wherein said exhaust emissions comprises: dissolve SO x, CO 2and NO xin any one or its combination.
10. treatment system according to claim 1 and 2, further comprises: mixing zone, described mixing zone be configured to receive fresh water and in described fresh water salt adding to the salt solution of predetermined concentration is provided.
11. treatment systems according to claim 1 and 2, wherein said electrolyzer comprises a collection of electrolyzer, this batch of electrolyzer be configured to basic solution that transmission comes from negative electrode separately to described the first Room and transmission come from described in separately the sterilized solution of anode to described disinfection unit.
12. 1 kinds for the treatment of processs, said method comprising the steps of:
Transmission salt solution is to anode and negative electrode;
Salt solution described in electrolysis, thus at described anode, produce sterilized solution and produce basic solution at described negative electrode;
Described in coming from, transmission is installed on exhaust emissions and described basic solution to the first chamber of the engine on ship;
By mixing to process described exhaust emissions at described the first indoor and described basic solution;
Transmission comes from the water of inflow and described sterilized solution to disinfection unit, and;
By mix to process described water with described sterilized solution in described disinfection unit.
13. methods according to claim 12, before transferring to the step of described the first Room, described method is further comprising 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 the method described in claim 12 or 13, and after described the first indoor described treatment step, described method is further comprising 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. according to the method described in claim 12 or 13, further comprises that transmission comes from the described treated water of described disinfection unit to the step of described ballast tank.
16. according to the method described in claim 12 or 13, further comprising the steps:
Before the step of the described exhaust emissions of described processing, analyze described water;
Determine the required amount that reduces the neutralization solution of total residual oxygenant in described water that adds, and;
Inject the required concentration of described neutralization solution to described water.
17. according to the method described in claim 12 or 13, further comprising the steps:
In predetermined period, put upside down the polarity of the electrode in described electrolyzer, to remove the incrustation scale on described electrode.
CN201080038925.5A 2009-08-03 2010-08-03 Emissions control system and method Expired - Fee Related CN102933504B (en)

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