CN106422700A - Efficient and multi-stage multi-pollutant cooperative control process system for ship exhaust gas and method - Google Patents

Efficient and multi-stage multi-pollutant cooperative control process system for ship exhaust gas and method Download PDF

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Publication number
CN106422700A
CN106422700A CN201610883842.5A CN201610883842A CN106422700A CN 106422700 A CN106422700 A CN 106422700A CN 201610883842 A CN201610883842 A CN 201610883842A CN 106422700 A CN106422700 A CN 106422700A
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flue gas
storage tank
pump
water
naoh solution
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CN106422700B (en
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方平
岑超平
陈雄波
唐子君
唐志雄
黄建航
曾文豪
钟佩怡
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South China Institute of Environmental Science of Ministry of Ecology and Environment
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South China Institute of Environmental Science of Ministry of Ecology and Environment
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    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • 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
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
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    • 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
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/76—Gas phase processes, e.g. by using aerosols
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/12—Methods and means for introducing reactants
    • B01D2259/122—Gaseous reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2259/124—Liquid reactants
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • 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
    • C02F2103/08—Seawater, e.g. for desalination

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Abstract

The invention discloses an efficient and multi-stage multi-pollutant cooperative control process system for ship exhaust gas. The system comprises a sea water desalination system, an electrolytic bath system, an H2 storage, metering and injection system, a Cl2 storage, metering and injection system, a NaOH solution storage system, an oxidation absorption system, an absorption liquid circulating system and a tail liquid treatment system. According to the process system, concentrated water or sea water produced by the sea water desalination system is taken as a raw material, H2, Cl2 and NaOH are prepared with an electrolysis method, H2 is used for marine boiler flue gas re-combustion denitration, C12 is used as a ship exhaust pollutant oxidizing agent, NaOH is used as a wet flue gas absorbent, and efficient removal and up-to-standard emission of pollutants such as ship exhaust particles, SO2, NOx, CO, HC and the like are realized. The process system has the advantages that the pollutant removal efficiency is high, multi-pollutant cooperative control is realized, the investment is saved, the application range is wide and the like and is very suitable for marine ship exhaust pollution treatment.

Description

A kind of multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system and method
Technical field
The invention belongs to technical field of air pollution control, and in particular to a kind of multi-stage, efficient ship flue gas multiple pollutant association With control process system and method.
Background technology
China is world shipping big country, and port infrastructure and ship total scale all reach world lead level.At present, entirely On state's own water, ships that transport is more than 170,000 (major part belongs to inland navigation craft), and ten Port of the world has seven in China, and In the first two ten Port of the world, China accounts for ten seats.The prosperity and development of international trade and fishery are developed rapidly in promotion China economy Meanwhile, huge challenge is brought to coastal, waterfront areas ambient air quality.The atmosphere pollution of boat diesel engine discharge is mainly wrapped Include particulate matter (PM), SO2, NOx, Hydrocarbon (HC), CO, VOCs etc., its concentration of emission height, it has also become littoral area is especially It is the main source of atmospheric pollution of port city.For the pollution of effective control ship tail gas, the discharge of minimizing ship atmosphere pollution, In recent years in the world and the country all formulates successively, promulgated related ship atmosphere pollution control policy, standard, big to ship Strict limit value is implemented in gas pollutant emission.Therefore carry out international carriage and must carry out ship air contaminant treatment.But for a long time, Domestic pollution for ship tail gas lacks enough attention, and the ship of construction does not generally individually consider treating tail gas problem, accordingly Treating tail gas Facilities Construction place is not reserved.But with the world for the increasingly strict of ship tail gas emission request, in fuel Substitute and cannot promote on a large scale and individually treating tail gas cannot be carried out very in the case of qualified discharge using control technology in machine Necessary.China can be applied for the existing ripe technology of land stationary source smoke gas treatment at present, but the technique groups of above-mentioned technology Become complicated, equipment is many, occupation of land is big, it is difficult to copy on spot ship.Therefore, how in the limited space of ship, multiple cigarettes are realized The removal of gas pollutant is that researcher needs issues that need special attention.
Administer for ship tail gas, pay close attention to PM, SO at present both at home and abroad2, the pollutant such as NOx control, the control of employing Route processed is mainly the Single Pollution thing control combination route of " denitration+dedusting+desulfurization ".Wherein, for SO2Control, exploitation The technology of application mainly includes that fuel oil is replaced and two big class of tail gas desulfurization.But not only high cost replaced by fuel oil, and domestic at present low The supply Shortcomings of sulfur oil, what is more important changes low sulfur oil can cause the component wears such as oil pump, atomizer to increase, to setting Standby, safe etc. have certain impact, and therefore replacement of fuel cannot be promoted on a large scale.Tail gas desulfurization mainly has dry desulfurization and wet type Two class technology are washed, two class technology are to SO2Clearance all can reach more than 90%, therefore can be led to using the ship of high-sulfur fuel oil Cross tail gas desulfurization technology to realize requirement of the relevant laws and regulations to marine fuel oil sulfur content in the world.But there is investment fortune in such technology The shortcomings of row high cost, occupation of land are big, is mainly applied at present on large-scale ocean-going vessel.For the control of NOx, at present in the world The more control technology of research is mainly SCR (SCR) technology, and the NOx clearance of the technology is generally 70%- 90%, it is applied on the developed country such as Germany, Sweden, Finland ship at present.But the technology is present, and floor space is big, throw The problems such as money and operating cost height, catalyst easy in inactivation (during especially with high-sulfur oils), popularization and application at home are restricted.
Therefore, administer for ship tail gas, at present economic, efficient, the feasible Treatment process of domestic shortage.While with state Inside and outside correlation environmental regulation increasingly strict, carry out ship tail gas administer imperative.Therefore, if combine ship existing with Lifestyle device and pollution control technology, by equipment, technology, method integrated innovation, develop a kind of wide suitable, economical high The ship tail gas Treatment process of effect popularization and application, then will be effectively improved China's ship tail gas treatment status, promote ship tail gas Administer the development of industry.
Content of the invention
In order to overcome the shortcoming and defect of prior art, it is an object of the invention to provide a kind of multi-stage, efficient ship flue gas Multi-pollutant Collaborative Control process system.Sea water desalinating unit that the system is generally installed with existing marine ships, marine boiler, Based on wet desulfurization system etc., by seawater electrolysises slot device is introduced, and above-mentioned technical equipment is optimized, combines and collects Become, realize to particulate matter, SO in ship tail gas2, the pollutant such as NOx, CO, HC high-efficient purification, with contaminant removal efficiency The advantages of height, multiple pollutant Collaborative Control, reduced investment, wide accommodation.
The object of the invention is achieved through the following technical solutions：
A kind of multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system, including seawater desalination system, electrolysis bath System, H2Storage metering injection system, Cl2Storage metering injection system, NaOH solution storage system, oxidative absorption system, absorption Fluid circulation and tail washings processing system；The seawater desalination system and electrolyzer system connection, electrolyzer system also with H2 Storage metering injection system, Cl2Storage metering injection system, the connection of NaOH solution storage system；The H2Storage metered injection system System is connected with marine boiler, marine boiler, diesel engine, Cl2Storage metering injection system is all connected with oxidative absorption system；Described Oxidative absorption system is connected with fluid circulation is absorbed, at the NaOH solution storage system, absorption fluid circulation and tail washings Reason system is sequentially connected.Marine boiler, diesel engine are the equipment on ship.
Preferably, the seawater desalination system is by sea water pump, sea water desalinating unit, fresh water pump, fresh water storage tank and concentrated water pump Composition, described electrolyzer system is made up of concentrated water storage tank, brine pump, ion exchange column and electrolysis bath, the H2Storage metering Spraying system is by H2Storage tank and H2Mixing weighing spraying system constitutes, described Cl2Storage metering injection system is by Cl2Storage tank and Cl2Mixing weighing spraying system constitutes, and the NaOH solution storage system is by NaOH solution storage tank, bypass water pump and lye pump Composition, the oxidative absorption system is made up of mixed pipe line, oxidation reactor and absorption tower, and the absorption fluid circulation is by following Ring pond, water circulating pump and dosing pump composition, the tail washings processing system is made up of dredge pump, sedimentation tank and neutralization pond；
The sea water pump, sea water desalinating unit, concentrated water pump, concentrated water storage tank, brine pump, ion exchange column and electrolysis bath are successively Connection；The electrolysis bath also with H2Storage tank, Cl2Storage tank, lye pump connection；The H2Storage tank, H2Mixing weighing spraying system, ship It is sequentially connected with mixed pipe line with boiler, the Cl2Storage tank, Cl2Mixing weighing spraying system is sequentially connected with mixed pipe line, bavin Oil machine is connected with mixed pipe line；The mixed pipe line, oxidation reactor, absorption tower, water circulating pump and circulating water pool are sequentially connected； The lye pump, NaOH solution storage tank, dosing pump, circulating water pool, dredge pump, sedimentation tank and neutralization pond are sequentially connected；Institute State sea water desalinating unit, fresh water pump and fresh water storage tank to be sequentially connected, the concentrated water storage tank, bypass water pump and NaOH solution storage tank It is sequentially connected.
Described concentrated water storage tank, when seawater desalination system maintenance or the concentrated water water yield are passed through sea water when inadequate；Described bypass Water feeding of water pump end is connected with concentrated water storage tank, and water side is connected with NaOH solution storage tank water inlet pipe, when electrolysis bath is overhauled, concentrated water NaOH solution storage tank is directly entered through bypassing water pump.
Cation exchange resin is filled with described ion exchange column, for the cationes such as Ca, Mg are removed, delays electrolysis Groove fouling and scavenging period, it is ensured that stable operation.
Described electrolysis bath is vertical diaphragm electrolysis bath.
Described mixed pipe line caliber is bigger compared with leading portion smoke pipe, it is ensured that gas mixing is uniform；Described oxidation reactor For an eddy flow-spray column, mixed flue gas are 0.1-0.5s by bottom eddy flow entrance reactor, gas residence time；Described Absorption tower is an eddy flow-filler-spray column, is inside filled with the rustless steel Pall ring of 0.5m thickness, and during operation, flue gas is revolved by bottom Stream and on, alkali liquor sprayed by top and under, the reaction of both counter current contacting.
The circulating water pool of described absorption fluid circulation is divided into two lattice, and the absorbing liquid from absorption tower flows into first first Lattice, enter the second lattice through overflow；Saturated absorption liquid is by draining into tail washings processing system outside the first lattice bottom；Alkali liquor and sea water are by second Lattice are added, and mix homogeneously makes absorbing liquid pH value for 8-10, subsequent absorbing liquid tower top spray is evacuated to by water circulating pump and under.
The solid slag that described tail washings processing system is produced pulls in shore after collecting to dispose, and supernatant is neutralized to neutrality by sea water After discharge.
A kind of method using above-mentioned process system multi-stage, efficient Collaborative Control ship flue gas multiple pollutant, including following step Suddenly：
Sea water introduces sea water desalinating unit by sea water pump, obtains fresh water and concentrated water after treatment；Fresh water is imported by fresh water pump Fresh water storage tank is stored, and concentrated water is pumped into concentrated water storage tank through concentrated water；Concentrated water in concentrated water storage tank is pumped into ion exchange column through saline, Water after ion exchange flows into electrolysis bath and carries out electrolytic preparation H2、Cl2, NaOH solution；Obtained H2、Cl2Respectively enter H2Storage Tank and Cl2Storage tank, NaOH solution is pumped into NaOH solution storage tank by alkaline-resisting；
Subsequent H2Enter H2Mixing weighing spraying system is mixed with air, and spraying into marine boiler is used for marine boiler flue gas again Combustion denitration, the position of injection selects in boiler ignition temperature for 800-1200 DEG C of interval, H2Sent out with NO under the high temperature conditions Raw redox reaction, part NO is reduced into N2Remove, after preliminary denitration, flue gas enters mixed pipe line；Flue gas on ship occurs Source is marine boiler and diesel engine, so diesel engine flue gas is also passed into mixed pipe line；
Cl2Enter Cl2After mixing weighing spraying system is mixed with air, mixed pipe line is injected into as ship tail gas dirt Dye thing oxidant；
Flue gas, diesel engine flue gas and Cl after preliminary denitration2Oxidation reactor oxidation reaction is entered after mixed pipe line mixing, Cl wherein2CO, HC etc. are oxidized to CO2、H2O, while by part NO, SO2It is oxidized to NO soluble in water2、SO3；On subsequently State pollutant and absorption tower is entered, the NaOH solution counter current contacting reaction in absorption tower and from NaOH solution storage tank, finally Removed by absorption, purifying smoke qualified discharge after demisting.
The absorbing liquid NaOH solution is recycled by circulating pump, circulating water pool, is introduced through dredge pump after absorbing saturation Sedimentation tank.
The H2After mixing with partial air, according to H2With NOx mol ratio 0.5-1.5：1 ratio is through H2Mixing weighing sprays Penetrate the boiler furnace interval that system sprays into temperature 800-1200 DEG C.
The Cl2After mixing with partial air, according to Cl2With NOx mol ratio 0.5-1.5：1 ratio is through Cl2Mixing weighing Spraying system is added in mixed pipe line.
The ultimate principle of the present invention is：The density wastewater for being produced with the seawater desalination system that marine ships are generally installed or sea Water is raw material, prepares H using electrolysis2、Cl2、NaOH.Wherein H2For the denitration by refueling of ship boiler, remove in boiler smoke Part NOx；Cl2As gaseous oxidant, for CO, HC etc. are oxidized to CO2、H2O, while by part NO, SO2It is oxidized to easily It is dissolved in the NO of water2、SO3；NaOH is used as wet flue gas absorbent.Flue gas on ship is divided into two parts, a part of from boiler, and one Part is from diesel engine.Boiler smoke, diesel engine flue gas and Cl after preliminary denitration2Oxidation reaction is entered after mixed pipe line mixing Device oxidation reaction, subsequent pollutant enter absorption tower, with NaOH solution haptoreaction in the absorption tower, are finally removed by absorption, Purifying smoke qualified discharge after demisting.Additionally, flue gas is after oxidation reactor, big particulate matter partly precipitated is removed, And efficiently removed by approach particulate matters such as physics sedimentation, mechanical retention, solution adhesions further behind absorption tower.This Invention is as follows to the cutting mechanisms of each pollutant：
Electrolysis overall reaction equation：2NaCl+2H2O=Cl2 ↑+H2 ↑+NaOH
Denitration by refueling reaction equation：2H2+ 2NO=2H2O+N2(reaction temperature 800-1200 DEG C)
Oxidation equation formula：Cl2+NO+H2O=NO2+2HCl
Cl2+CO+H2O=CO2+2HCl
(x+4y)Cl2+2HxCy+4yH2O=2yCO2+2(x+4y)HCl
Cl2+SO2+H2O=SO3+2HCl
Absorbing reaction equation：3NO2+ 2NaOH=2NaNO3+NO+H2O
4NO2+O2+ 4NaOH=4NaNO3+2H2O
NO2+ NO+2NaOH=2NaNO2+H2O
SO2+ 2NaOH=Na2SO3+H2O
SO3+ 2NaOH=Na2SO4+H2O
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) density wastewater that the present invention is produced with seawater desalination system is controlled as raw material by the pollution of electrolytic preparation ship tail gas H needed for reason2、Cl2, NaOH, realize comprehensive utilization of waste materials and the treatment of wastes with processes of wastes against one another.
(2) present invention can realize particulate matter, SO2, the pollutant such as NOx, CO, HC while high-efficient purification, using this skill Art can achieve SO2Removal efficiency >=98%, particulate matter, NOx, CO, HC removal efficiency all >=60%, flue gas row up to standard after purification Put.
(3) with investment, operating cost is low, multi-pollutant collaboration compared with Single Pollution thing control combination technology for the present invention The advantages of efficiently removing, is especially suitable for marine ships treating tail gas, is especially suitable for large-scale coastal waters, foreign-going ship.
Description of the drawings
Fig. 1 is a kind of multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system schematic diagram of the present invention.
Fig. 2 is a kind of multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system concrete structure diagram of the present invention.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings, but embodiments of the present invention not limited to this.
A kind of the invention provides multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system, as shown in figure 1, bag Include seawater desalination system, electrolyzer system, H2Storage metering injection system, Cl2Storage metering injection system, NaOH solution storage System, oxidative absorption system, absorption fluid circulation and tail washings processing system；The seawater desalination system and electrolyzer system Connection, electrolyzer system also with H2Storage metering injection system, Cl2Storage metering injection system, NaOH solution storage system are even Connect；The H2Storage metering injection system is connected with marine boiler, and marine boiler and diesel engine are as flue gas occurring source, preliminary de- The flue gas of boiler smoke and diesel engine after nitre is all passed through oxidative absorption system, afterwards and Cl2React, so marine boiler All it is connected with oxidative absorption system with diesel engine, the Cl2Storage metering injection system is connected with oxidative absorption system；The oxygen Change absorption system and be connected with fluid circulation is absorbed, the NaOH solution storage system, absorption fluid circulation and tail washings are processed System is sequentially connected.
Specifically, as shown in Fig. 2 the seawater desalination system is by sea water pump, sea water desalinating unit, fresh water pump, fresh water storage Tank becomes with concentrated water pump group, and described electrolyzer system is made up of concentrated water storage tank, brine pump, ion exchange column and electrolysis bath, described H2Storage metering injection system is by H2Storage tank and mixing weighing spraying system composition, described Cl2Storage metering injection system by Cl2Storage tank and Cl2Mixing weighing spraying system constitutes, and the NaOH solution storage system is by (the i.e. alkali storage of NaOH solution storage tank Tank), bypass water pump and lye pump composition, the oxidative absorption system is made up of mixed pipe line, oxidation reactor and absorption tower, institute State absorption fluid circulation to be made up of absorbing liquid circulating water pool, water circulating pump and dosing pump, the tail washings processing system is by blowdown Pump, sedimentation tank and neutralization pond composition；
The sea water pump, sea water desalinating unit, concentrated water pump, concentrated water storage tank, brine pump, ion exchange column and electrolysis bath are successively Connection；The electrolysis bath also with H2Storage tank, Cl2Storage tank, lye pump connection；The H2Storage tank, H2Mixing weighing spraying system, ship It is sequentially connected with mixed pipe line with boiler, diesel engine is connected with mixed pipe line, the Cl2Storage tank, Cl2Mixing weighing spraying system It is sequentially connected with mixed pipe line；The mixed pipe line, oxidation reactor, absorption tower, water circulating pump and circulating water pool are sequentially connected； The lye pump, NaOH solution storage tank, dosing pump, circulating water pool, dredge pump, sedimentation tank and neutralization pond are sequentially connected；Institute State fresh water pump to be sequentially connected with sea water desalinating unit, fresh water storage tank, the concentrated water storage tank, bypass water pump and NaOH solution storage tank It is sequentially connected；
Cation exchange resin is filled with described ion exchange column, for the cationes such as Ca, Mg are removed, delays electrolysis Groove fouling and scavenging period, it is ensured that stable operation；
The electrolysis bath is vertical diaphragm electrolysis bath；
Described mixed pipe line caliber is bigger compared with leading portion smoke pipe, it is ensured that gas mixing is uniform；Described oxidation reactor For an eddy flow-spray column, mixed flue gas are 0.1-0.5s by bottom eddy flow entrance reactor, gas residence time；Described Absorption tower is an eddy flow-filler-spray column, is inside filled with the rustless steel Pall ring of 0.5m thickness, and during operation, flue gas is revolved by bottom Stream and on, alkali liquor sprayed by top and under, the reaction of both counter current contacting.
The circulating water pool of described absorption fluid circulation is divided into two lattice, and the absorbing liquid from absorption tower flows into first first Lattice, enter the second lattice through overflow；Saturated absorption liquid is by draining into tail washings processing system outside the first lattice bottom；Alkali liquor and sea water are by second Lattice are added, and mix homogeneously makes absorbing liquid pH value for 8-10, subsequent absorbing liquid tower top spray is evacuated to by water circulating pump and under；
The solid slag that described tail washings processing system is produced pulls in shore after collecting to dispose, and supernatant is neutralized to neutrality by sea water After discharge.
Said system is separated the concentrated water for producing and is pumped into concentrated water through concentrated water in actual moving process by seawater desalination system Storage tank is stored, and is subsequently pumped into electrolyzer system by saline.As concentrated water contains Ca, Mg plasma of higher concentration, Yi electricity Extremely upper precipitation, affects electrolysis bath stable operation, and therefore the present invention increases cation exchange resin pre-treating device before electrolysis bath, uses Cation in removal concentrated water.Concentrated water through pre-treatment enters electrolysis bath, produces H in cathode chamber2, NaOH, anode chamber produce Cl2.The H that electrolysis is produced2And Cl2It is respectively fed to H2And Cl2Storage tank, the NaOH solution of generation is pumped into holding vessel by alkaline-resisting.H2With Air mixes in a mixer, sprays into marine boiler by metering injection system, for the denitration by refueling of ship boiler, removes boiler After the NOx of part, oxidation reactor is entered by mixed pipe line in flue gas；The position of injection selects the ignition temperature in the boiler to be 800-1200 DEG C of interval, H2There is redox reaction under the high temperature conditions with NO, part NO is reduced into N2Remove.This work Marine boiler flue gas and diesel engine flue gas are carried out mixed processing by skill, so diesel engine flue gas is also passed into mixed pipe line.Cl2With sky After gas mixing, mixed pipe line is injected into by metering injection system, mixed pipe line caliber is put bigger, it is therefore an objective to make Cl2With first Flue gas, diesel engine flue gas mix homogeneously after step denitration.Mixed flue gas subsequently enter oxidation reactor, wherein Cl2By CO, HC etc. It is oxidized to CO2、H2O, while by part NO, SO2It is oxidized to NO soluble in water2、SO3.Subsequently above-mentioned pollutant enter absorption tower, React with NaOH solution counter current contacting in absorption tower, finally removed by absorption, purifying smoke qualified discharge after demisting.This Outward, mixed flue gas are after oxidation reactor, and as gas flow rate declines, big particulate matter removes part by precipitating, with Efficiently removed by approach such as physics sedimentation, mechanical retention, solution adhesions further through absorption tower particulate matter afterwards.Absorbing liquid NaOH solution is formulated by the concentrated solution from NaOH storage tank and sea water, in the continuous circulation of absorption fluid circulation realization and more New use.The circulatory pool for absorbing fluid circulation is divided into two lattice, and the absorbing liquid from absorption tower flows into the first lattice first, through overflow Enter the second lattice.Saturated absorption tail washings is by draining into tail washings processing system outside the first lattice bottom；Alkali liquor and fresh seawater are by the second lattice Add, after mix homogeneously by water circulating pump be evacuated to tower top spray and under.The absorbing liquid of tail washings processing system is entered, it is heavy to first pass around Form sediment and particulate matter and sediment is removed, storage collected by waste residue, dispose after waiting ship to pull in shore；The waste water of precipitation is then passed through in neutralization pond Neutralized by sea water, pH value is raised to neutral heel row sea.
It is below many using above-mentioned multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system process ship flue gas The specific embodiment of pollutant.
Embodiment 1
The marine boiler discharge flue gas NOx mean concentration of certain marine ships is 1400ppm, marine boiler and marine diesel Mixed flue gas particulate matter, NOx, SO2, CO, HC mean concentration be respectively 800mg/m3、1600ppm、2400ppm、240ppm、 370ppm.The H for being produced by electrolyzer system2After mixing with air, according to H2With NOx mol ratio 1：1 ratio is sprayed through spraying system Enter in the boiler furnace of 1000 DEG C of temperature, after reaction, boiler export flue gas NOx concentration of emission is 920ppm, clearance 34.3%. Boiler smoke is mixed with diesel engine flue gas after preliminary denitration, enters mixing smoke pipe, while the Cl for being produced by electrolyzer system2With After air mixing, according to Cl2With NOx mol ratio 1：1 ratio is sprayed in mixing smoke pipe through spraying system, and mixing smoke pipe caliber is relatively Leading portion amplifies one-level.Cl2Be sufficiently mixed mixing in smoke pipe with flue gas, and with flue gas in NO, SO2, at the beginning of the pollutant such as CO, HC Step reaction, subsequent mixed flue gas enter oxidation reactor, and mixed gas time of staying in oxidation reactor is 0.3s, Cl2With Flue gas pollutant fully reacts, and part CO, HC etc. are oxidized to CO2、H2O, by part NO, SO2It is oxidized to NO soluble in water2、 SO3.Subsequently flue gas enters absorption tower, flue gas and the reaction of absorbing liquid counter current contacting in the absorption tower, absorbing liquid pH value be 9.0, most Whole flue gas pollutant is absorbed removal.Particulate matter, NOx, SO in flue gas after purification2, CO, HC average emission concentration is respectively 180mg/m3, 420ppm, 35ppm, 64ppm, 97ppm, clearance be respectively 77.5%, 73.75%, 98.54%, 73.33%, 73.78%, flue gas qualified discharge.Absorbing liquid enters tail washings processing system after absorbing saturation, first passes around precipitation and removes granule Thing and sediment, storage collected by waste residue, disposes after waiting ship to pull in shore；Waste water through precipitating is neutralized by sea water in neutralization pond, pH Value is raised to neutral heel row sea.
Embodiment 2
The marine boiler discharge flue gas NOx mean concentration of certain marine ships is 1400ppm, marine boiler and marine diesel Mixed flue gas particulate matter, NOx, SO2, CO, HC mean concentration be respectively 800mg/m3、1600ppm、2400ppm、240ppm、 370ppm.The H for being produced by electrolyzer system2After mixing with air, according to H2With NOx mol ratio 1.5：1 ratio is through spraying system Spray in the boiler furnace of 1200 DEG C of temperature, after reaction, boiler export flue gas NOx concentration of emission is 863ppm, clearance 38.36%.Boiler smoke is mixed with diesel engine flue gas after preliminary denitration, enters mixing smoke pipe, while being produced by electrolyzer system Raw Cl2After mixing with air, according to Cl2With NOx mol ratio 1.5：1 ratio is sprayed in mixing smoke pipe through spraying system, mixing Smoke pipe caliber amplifies one-level compared with leading portion.Cl2Be sufficiently mixed mixing in smoke pipe with flue gas, and with flue gas in NO, SO2、CO、HC Deng pollutant initial reaction, subsequent mixed flue gas enter oxidation reactor, and mixed gas time of staying in oxidation reactor is 0.1s, Cl2Fully react with flue gas pollutant, part CO, HC etc. are oxidized to CO2、H2O, by part NO, SO2It is oxidized to readily soluble NO in water2、SO3.Subsequently flue gas enters absorption tower, flue gas and the reaction of absorbing liquid counter current contacting in the absorption tower, absorbing liquid pH value For 8.0, final flue gas pollutant is absorbed removal.Particulate matter, NOx, SO in flue gas after purification2, CO, HC average emission concentration divides Wei not 193mg/m3, 385ppm, 43ppm, 46ppm, 84ppm, clearance be respectively 75.87%, 75.94%, 98.21%, 80.83%th, 77.30%, flue gas qualified discharge.Absorbing liquid enters tail washings processing system after absorbing saturation, first passes around precipitation Particulate matter and sediment is removed, storage collected by waste residue, dispose after waiting ship to pull in shore；Through precipitation waste water by sea water in neutralization pond Neutralization, pH value is raised to neutral heel row sea.
Embodiment 3
The marine boiler discharge flue gas NOx mean concentration of certain marine ships is 1400ppm, marine boiler and marine diesel Mixed flue gas particulate matter, NOx, SO2, CO, HC mean concentration be respectively 800mg/m3、1600ppm、2400ppm、240ppm、 370ppm.The H for being produced by electrolyzer system2After mixing with air, according to H2With NOx mol ratio 0.5：1 ratio is through spraying system Spray in the boiler furnace of 800 DEG C of temperature, after reaction, boiler export flue gas NOx concentration of emission is 1105ppm, clearance 21.07%.Boiler smoke is mixed with diesel engine flue gas after preliminary denitration, enters mixing smoke pipe, while being produced by electrolyzer system Raw Cl2After mixing with air, according to Cl2With NOx mol ratio 0.5：1 ratio is sprayed in mixing smoke pipe through spraying system, mixing Smoke pipe caliber amplifies one-level compared with leading portion.Cl2Be sufficiently mixed mixing in smoke pipe with flue gas, and with flue gas in NO, SO2、CO、HC Deng pollutant initial reaction, subsequent mixed flue gas enter oxidation reactor, and mixed gas time of staying in oxidation reactor is 0.5s, Cl2Fully react with flue gas pollutant, part CO, HC etc. are oxidized to CO2、H2O, by part NO, SO2It is oxidized to readily soluble NO in water2、SO3.Subsequently flue gas enters absorption tower, flue gas and the reaction of absorbing liquid counter current contacting in the absorption tower, absorbing liquid pH value For 10.0, final flue gas pollutant is absorbed removal.Particulate matter, NOx, SO in flue gas after purification2, CO, HC average emission concentration Respectively 165mg/m3, 473ppm, 28ppm, 87ppm, 125ppm, clearance be respectively 79.37%, 70.44%, 98.83%, 63.75%th, 66.22%, flue gas qualified discharge.Absorbing liquid enters tail washings processing system after absorbing saturation, first passes around precipitation Particulate matter and sediment is removed, storage collected by waste residue, dispose after waiting ship to pull in shore；Through precipitation waste water by sea water in neutralization pond Neutralization, pH value is raised to neutral heel row sea.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment Limit, other any spirit without departing from the present invention and the change that is made under principle, modification, replacement, combine, simplify, Equivalent substitute mode is all should be, is included within protection scope of the present invention.

Claims (10)

1. a kind of multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system, it is characterised in that including desalinization system System, electrolyzer system, H2Storage metering injection system, Cl2Storage metering injection system, NaOH solution storage system, oxidative absorption System, absorption fluid circulation and tail washings processing system；The seawater desalination system and electrolyzer system connection, electrolysis bath system System is gone back and H2Storage metering injection system, Cl2Storage metering injection system, the connection of NaOH solution storage system；The H2Storage meter Amount spraying system is connected with marine boiler, marine boiler, diesel engine, Cl2Storage metering injection system all with oxidative absorption system Connection；The oxidative absorption system is connected with fluid circulation is absorbed, the NaOH solution storage system, absorption fluid circulation It is sequentially connected with tail washings processing system.
2. multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system according to claim 1, it is characterised in that The seawater desalination system is become by sea water pump, sea water desalinating unit, fresh water pump, fresh water storage tank and concentrated water pump group, described electrolysis Tank systems are made up of concentrated water storage tank, brine pump, ion exchange column and electrolysis bath, the H2Storage metering injection system is by H2Storage tank And H2Mixing weighing spraying system constitutes, described Cl2Storage metering injection system is by Cl2Storage tank and Cl2Mixing weighing injection system System composition, the NaOH solution storage system is made up of NaOH solution storage tank, bypass water pump and lye pump, the oxidative absorption System is made up of mixed pipe line, oxidation reactor and absorption tower, described absorption fluid circulation by circulating water pool, water circulating pump and Dosing pump constitutes, and the tail washings processing system is made up of dredge pump, sedimentation tank and neutralization pond；
The sea water pump, sea water desalinating unit, concentrated water pump, concentrated water storage tank, brine pump, ion exchange column and electrolysis bath connect successively Connect；The electrolysis bath also with H2Storage tank, Cl2Storage tank, lye pump connection；The H2Storage tank, H2Mixing weighing spraying system, peculiar to vessel Boiler is sequentially connected with mixed pipe line, the Cl2Storage tank, Cl2Mixing weighing spraying system is sequentially connected with mixed pipe line, diesel oil Machine is connected with mixed pipe line；The mixed pipe line, oxidation reactor, absorption tower, water circulating pump and circulating water pool are sequentially connected；Institute State lye pump, NaOH solution storage tank, dosing pump, circulating water pool, dredge pump, sedimentation tank and neutralization pond to be sequentially connected；Described Sea water desalinating unit, fresh water pump and fresh water storage tank are sequentially connected, the concentrated water storage tank, bypass water pump and NaOH solution storage tank according to Secondary connection.
3. multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system according to claim 2, it is characterised in that Cation exchange resin is filled with described ion exchange column.
4. multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system according to claim 2, it is characterised in that Described mixed pipe line caliber is bigger compared with leading portion smoke pipe；Described oxidation reactor is an eddy flow-spray column, mixed flue gas Reactor is entered by bottom eddy flow, gas residence time is 0.1-0.5s；Described absorption tower is an eddy flow-filler-spray Tower, be inside filled with 0.5m thickness rustless steel Pall ring, during operation flue gas by bottom eddy flow on, alkali liquor by top spray and under, Both counter current contacting reactions.
5. multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system according to claim 2, it is characterised in that The circulating water pool of described absorption fluid circulation is divided into two lattice, and the absorbing liquid from absorption tower flows into the first lattice first, through overflowing Stream enters the second lattice；Saturated absorption liquid is by draining into tail washings processing system outside the first lattice bottom；Alkali liquor and sea water are added by the second lattice, Mix homogeneously makes absorbing liquid pH value for 8-10, subsequent absorbing liquid tower top spray is evacuated to by water circulating pump and under.
6. multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system according to claim 2, it is characterised in that The solid slag that described tail washings processing system is produced pulls in shore after collecting to dispose, and supernatant is neutralized to after neutrality by sea water and discharges.
7. a kind of usage right requires that described in 2, multi-stage, efficient ship flue gas multiple pollutant Collaborative Control process system processes ship cigarette The method of gas multi-pollutant, it is characterised in that comprise the following steps that：
Sea water introduces sea water desalinating unit by sea water pump, obtains fresh water and concentrated water after treatment；Fresh water imports fresh water by fresh water pump Storage tank is stored, and concentrated water is pumped into concentrated water storage tank through concentrated water；Concentrated water in concentrated water storage tank is pumped into ion exchange column through saline, through from Water inflow electrolysis bath after son is exchanged carries out electrolytic preparation H2、Cl2, NaOH solution；Obtained H2、Cl2Respectively enter H2Storage tank and Cl2Storage tank, NaOH solution is pumped into NaOH solution storage tank by alkaline-resisting；
Subsequent H2Enter H2Mixing weighing spraying system is mixed with air, sprays into marine boiler de- for marine boiler flue gas reburning Nitre, the position of injection selects in marine boiler ignition temperature for 800-1200 DEG C of interval, and after preliminary denitration, flue gas enters mixed Close pipeline；Diesel engine flue gas is also passed into mixed pipe line；
Cl2Enter Cl2After mixing weighing spraying system is mixed with air, mixed pipe line is injected into as ship tail gas pollutant Oxidant；
Flue gas, diesel engine flue gas and Cl after preliminary denitration2Oxidation reactor oxidation reaction is entered after mixed pipe line mixing, subsequently Absorption tower is entered, the NaOH solution counter current contacting reaction in absorption tower and from NaOH solution storage tank, finally gone by absorption Remove, purifying smoke qualified discharge after demisting.
8. according to claim 7 process ship flue gas multiple pollutant method, it is characterised in that the NaOH solution is followed Ring is used, and introduces sedimentation tank through dredge pump after absorbing saturation.
9. according to claim 7 process ship flue gas multiple pollutant method, it is characterised in that the H2Empty with part After gas mixing, according to H2With NOx mol ratio 0.5-1.5：1 ratio sprays into the boiler furnace interval of temperature 800-1200 DEG C.
10. according to claim 7 process ship flue gas multiple pollutant method, it is characterised in that the Cl2With part After air mixing, according to Cl2With NOx mol ratio 0.5-1.5：1 ratio is added in mixed pipe line.
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CN106865840A (en) * 2017-03-28 2017-06-20 中国科学院城市环境研究所 A kind of ship tail gas and ballast water integrated processing system
CN107013290A (en) * 2017-05-02 2017-08-04 哈尔滨工程大学 One kind is used for marine diesel tail gas comprehensive utilization and treatment system
CN107233798A (en) * 2017-07-07 2017-10-10 环境保护部华南环境科学研究所 Process system and method for industrial furnace flue gas multiple pollutant multi- scenarios method Collaborative Control
CN108514816A (en) * 2018-05-03 2018-09-11 哈尔滨工程大学 One kind being used for boat diesel engine exhaust-gas treatment and waste heat recycling system
CN109592834A (en) * 2019-01-31 2019-04-09 环境保护部华南环境科学研究所 A kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system and method
CN110327776A (en) * 2019-07-16 2019-10-15 威海海洋职业学院 A kind of ship tail gas processing unit and processing method
CN110327776B (en) * 2019-07-16 2023-11-24 威海海洋职业学院 Ship tail gas treatment device and treatment method
CN111603915A (en) * 2020-05-13 2020-09-01 循天能源环境科技有限公司 Flue gas purification process
CN111603915B (en) * 2020-05-13 2022-03-08 循天能源环境科技有限公司 Flue gas purification process
CN114392642A (en) * 2022-01-26 2022-04-26 威海市蓝色经济研究院有限公司 Carbon dioxide capture system in boats and ships are discharged fume

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