CN108187473A - A kind of recycling desulphurization system - Google Patents
A kind of recycling desulphurization system Download PDFInfo
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- CN108187473A CN108187473A CN201810111977.9A CN201810111977A CN108187473A CN 108187473 A CN108187473 A CN 108187473A CN 201810111977 A CN201810111977 A CN 201810111977A CN 108187473 A CN108187473 A CN 108187473A
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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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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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
- B01D53/48—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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
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Abstract
The invention discloses a kind of desulphurization systems with tower external oxidation device, an oxidizing tower is specifically separately provided outside desulfurizing tower so that the vapour-liquid in oxidizing tower contacts to improve oxidation effectiveness solution with ozone after desulfurization, and the treatment process of desulfurization wastewater is optimized, the heavy metal ion in waste water is reduced, and reduces the energy consumption of electric dialyzator.
Description
Technical field
The present invention relates to a kind of desulphurization systems, and in particular to a kind of to carry out desulfurization as raw material using sodium hydroxide and give up to desulfurization
Water carries out the whole system of recycling treatment.
Background technology
China is the country of the energy resource structure based on fire coal, and output of coal is according to No. 1 in the world.Air caused by fire coal
Pollution has dust, SO2, NOX and CO2 etc., and with the continuous growth of consumption of coal, coal fire discharged sulfur dioxide also constantly increases
Add, for years more than 20,000,000 tons, occupied first place in the world, China's acid rain and sulfur dioxide pollution is caused to be on the rise.By dirt
The industrial department of dye divides, and sequence is thermal power plant, chemical plant and smeltery.The discharge capacity of wherein coal-burning power plant's pollutant accounts for entirely
50% or so of portion's industrial discharge total amount.Common fume desulphurization method mainly includes two kinds of dry and wet, with dry desulfurization phase
Than wet desulphurization equipment is small, easy to operate, and desulfuration efficiency is high, and application is relatively broad, such as sodium method, magnesium processes, ammonia process and calcium method
Deng wherein most with sodium method and calcium method.
It is opposite using other desulfurizing agents, sodium hydroxide has absorption efficiency height and absorption rate soon excellent as desulfurizing agent
Gesture, it is more in existing industrially desulfurized middle application, particularly stringenter region is being required environmental protection index.But with hydrogen-oxygen
Change sodium and carry out wet desulphurization generation sodium sulfite for desulfurizing agent, in general, the sodium sulfite in sodium method flue gas desulfurization waste-water is dense
Degree ordinarily is about 10%-20%, even higher, and uses traditional air oxidation, and the oxidation rate of sodium sulfite is slower, therefore
Need higher investment occupation of land and operating cost.Moreover, desulfurization wastewater typically contains a large amount of heavy metal ion, such as Mg2+,
Zn2+, Cu2+, Cr3+, Hg2+, Pb2+ etc., though there is a large amount of solution in the prior art, to above-mentioned heavy metal ion
Processing it is not fully up to expectations, although and traditional bipolar membrane electrodialysis device waste water can be generated bronsted lowry acids and bases bronsted lowry, due to charging
Middle salt content is relatively low therefore needs to larger energy consumption, and the effect of wastewater treatment is not satisfactory in a word, therefore is badly in need of a kind of desulfurization
System can improve current sodium sulfite problem of oxidation and the subsequent processing problem of desulfurization wastewater.
Invention content
The problem of present invention proposes a kind of novel desulphurization system to improve sodium sulfite oxidation, especially by will be existing
Tower internal oxidition in desulfurizing tower is designed as special setting oxidizing tower outside tower and is aided with the shape that ozone carries out similar desulfurizing tower vapour-liquid contact
Formula is aoxidized to improve desulfurization effect, and design is optimized to subsequent desulfurization wastewater treatment system.
The present invention provides a kind of desulphurization systems, and including desulfurizing tower and oxidizing tower, wherein desulfurizing tower includes being located at tower body
The gas inlet of lower end side and desulfurization fume positioned at tower body top export, and the gas inlet and flue gas intake pipeline connect
It connects, there is desulfurization nozzle between gas inlet and desulfurization fume outlet, the desulfurization nozzle is included positioned at opposing lower end
Doctor solution circulation nozzle and the fresh desulfurization nozzle for liquid positioned at upper end, desulfurization tower bottom connection doctor solution discharge pipe are described
Doctor solution discharge pipe is divided into two, and one is connect with doctor solution circulation nozzle by doctor solution circulation line, secondly with oxidation
Tower upper end is connected by doctor solution pipeline to be oxidized, and the oxidizing tower has the ozone import positioned at tower body side, in ozone
Import upper end has the doctor solution nozzle to be oxidized being connect with doctor solution pipeline to be oxidized, and the ozone import is defeated by ozone
Pipeline is sent to be connect with ozone generating-device, oxidizing tower lower end is provided with oxidation sweetening liquid storage tank, oxidation sweetening liquid storage tank lower end tool
Have and arrange mouth outside oxidation doctor solution.
Preferably, it is additionally provided with oxidation fan on the oxidation sweetening liquid storage tank.
Preferably, oxidizing tower top is provided with spilling gas vent, the spilling gas vent and flue gas intake pipeline
Connection.
Preferably, it is additionally provided between spilling gas vent and doctor solution nozzle to be oxidized and overflows gas treatment nozzle.
Preferably, mouth is arranged outside the oxidation sweetening liquid to connect with desulfurizing waste water processing device.
Preferably, the desulfurizing waste water processing device includes ultrafiltration apparatus.
Preferably, the penetrating fluid outlet of ultrafiltration apparatus is connect with the spilling gas treatment nozzle.
Preferably, the desulfurizing waste water processing device includes sequentially connected neutralization precipitation device, reduction apparatus, ultrafiltration
Device, enrichment facility, two-stage dialyzer.
Preferably, the doctor solution circulation nozzle of the opposing lower end and between the fresh desulfurization nozzle for liquid of upper end also
Equipped with regenerative sulfur binding nozzle for liquid, the regenerative sulfur binding nozzle for liquid is connect with regenerative sulfur binding liquid pipe line, the regenerative sulfur binding liquid
Water outlet of the pipeline respectively with the sodium hydroxide outlet of two-stage dialyzer and enrichment facility is connect.
Preferably, the two-stage dialyzer includes level-one dialyzer and two level dialyzer, and the level-one dialyzer is double
Pole film and cation-exchange membrane form two Room bipolar membrane electrodialysis devices, and the two level electric dialyzator for Bipolar Membrane and negative and positive from
Three Room bipolar membrane electrodialysis devices of proton exchange composition.
The present invention is included the following steps using the sulfur removal technology of above-mentioned desulphurization system：
（1）Flue gas from flue gas delivery pipe line enters desulfurizing tower from desulfurizing tower lower end, with the hydroxide from upside down ejection
The contact of sodium solution vapour-liquid carries out desulfurization, and flue gas after desulfurization is discharged into remaining processing sequences from tower top.
The present invention devises multi-stage spray in desulfurizing tower, and every grade of spray is using separate sources and the hydroxide of various concentration
Sodium solution.Wherein with respect to low side using the desulfuration solution after desulfurization, containing unreacted sodium hydroxide, it is relatively high-end using compared with
The sodium hydroxide solution of high concentration, such as fresh sodium hydroxide solution, the sodium hydroxide generated in follow-up desulfurization wastewater processing
Solution.It various concentration and is from upstream to the desulfuration solution of downstream enrichment successively and ensure that the desulfurization effect of flue gas.It may be noted that
It is that the flue gas that the present invention applies should be flue gas after denitration, when containing NOX in flue gas, influences the desulfurization effect of the present invention.Institute
With the remaining processing sequences of the flue gas after denitration desulfurization can with when direct emission.
（2）Solution is pumped into oxidizing tower upper end and is sprayed downward through nozzle after desulfurization, with the ozone being passed through from oxidizing tower lower end
Vapour-liquid is contacted to be aoxidized to desulfuration solution, and it is defeated that spilling gas vent of the gas through tower top after vapour-liquid contact is back to flue gas
Pipeline is sent, the doctor solution after oxidation enters the oxidation sweetening liquid storage tank of oxidation tower bottom.Gas after vapour-liquid contact is from spilling
The doctor solution sprayed with overflowing gas treatment nozzle is also needed to carry out vapour-liquid before gas vent discharge to contact.
Existing desulfurizing tower generally carries out sodium sulfite oxidation by the way of tower internal oxidition, and oxidation effectiveness is poor, this
This method is abandoned in invention, by the way of tower external oxidation, an oxidizing tower is specifically separately provided, after sodium base desulfurizer desulfurization
Solution is passed through from upper end, is aoxidized with being contacted with the ozone entered from oxidizing tower lower end progress vapour-liquid, straight compared to by ozone
The mode in solution to be oxidized is connected, vapour-liquid contact is fully and path is longer, therefore with higher oxidation effectiveness, into one
Step improves desulfurization effect.In addition to this, what is be difficult to avoid that during being contacted due to ozone and desulfuration solution vapour-liquid causes shakiness
Fixed sodium sulfite decomposites sulfur dioxide again, for this purpose, the present invention is provided at the top of oxidizing tower overflows gas vent, from
The oxygen generated in the gas of outlet discharge containing the sulfur dioxide and unreacted ozone, the ozone decomposed that decompose again, will
It is back to flue gas intake pipeline other than guaranteeing desulfurization effect, and ozone and oxygen are passed through the dioxy that can cause in flue gas
Change sulphur and be direct oxidation into sulfur trioxide, what is made it easier to is desulfurized agent absorption.Certainly, for cost consideration, it is undesirable to excessive
Ozone and the sulfur dioxide that decomposes return into desulfurizing tower, therefore select one layer of desulfurization to be set to spray in oxidizing tower upper end
Mouth, due to overflow gas flow it is little, do not need to the desulfuration solutions at different levels used in desulfurizing tower, here present invention employs
Ultrafiltration apparatus treated penetrating fluid is as desulfuration solution herein in subsequent wastewater treatment, can also be higher, economical it is complete
Into desulfurization task herein.
（3）Desulfurization wastewater in oxidation sweetening liquid storage tank enters neutralization precipitation device, by adding solid sodium hydroxide tune
PH to 9-10 is saved, by most of heavy metal ion generation hydroxide precipitation such as Mg2+, Zn2+, Cu2+, Cr3+ in waste water
It is moved out.Using excessive sodium hydroxide neutralizer at this, the removal rate of above-mentioned ion on the one hand ensure that, on the other hand
The hydrogen ion generated in follow-up electrodialysis can be neutralized.
(4) supernatant liquor in neutralization precipitation device is passed through in anaerobism sulfate reduction device, is adopted in reduction apparatus
H2S is generated with sulfate reducing bacteria reduction part of sulfuric acid root so that the metal ions such as remaining Hg2+, Pb2+, Cr3+ in waste water
Sulfide precipitation is generated to remove.And for the H2S gases of collection, colourless sulphur can be used in CSB biooxidation reactions devices
Bacterium (CSB) biological oxidation sulfide generates elemental sulfur.
(5) supernatant liquor in anaerobism sulfate reduction device is passed through in ultrafiltration membrane to remove the solid in waste water
Grain object.Ultrafiltration membrane or ceramic membrane of organic material etc. may be used in ultrafiltration, and the average pore size of film is 1-100nm, particularly preferred
For PVDF tubular ultra-filtration membranes.A penetrating fluid part for imurity-removal can preferably be applied to oxidation with desulfurization is carried out
Top of tower is used to overflow the processing of gas.
（6）It is concentrated being further passed through in enrichment facility by the penetrating fluid of ultrafiltration membrane.In this step, at concentration
Reason can generate high-concentration waste water, and the salinity in waste water is made to reach more than 15wt%, preferably reaches 20wt%-25wt%.Concentration dress
Conventional ED ionic membranes, evaporation concentrator, reverse osmosis membrane can be selected by putting, and preferably using reverse osmosis membrane filtration, generated
Fresh water can be generated while high-concentration waste water and is able to reuse.Preferred reverse osmosis membrane is cellulose acetate film and polyamide reverse osmosis
Thoroughly, aperture 0.5-10nm, particularly preferred 0.5-1nm.Most preferably use polyamide reverse osmose membrane.
（7）Waste water after concentration is passed through in level-one electric dialyzator, wherein level-one electric dialyzator is Bipolar Membrane and cation
Exchange membrane forms two Room bipolar membrane electrodialysis devices, and level-one dialyzer forms two Room pair for Bipolar Membrane and cation-exchange membrane here
Pole membrane electrodialysis device carries out reuse to generate sodium hydroxide, and its hydrogen ion generated can be neutralized in aforementioned neutralization precipitation device
The excessive sodium hydrate of addition.In the apparatus, control current density is 50-80mA/cm2, and control water outlet pH is 7-8.
（8）By level-one electric dialyzator, treated that waste water continues to be passed through in two level electric dialyzator, and two level electric dialyzator is double
Three Room bipolar membrane electrodialysis devices of pole film and anions and canons exchange membrane composition.In the electric dialyzator there is sour room to generate bronsted lowry acids and bases bronsted lowry
Room generates lye, and two Room are passed through pure water.The sodium hydroxide and enrichment facility that level-one electric dialyzator and two level electric dialyzator are generated
It is passed through in desulfurizing tower for desulfurization after the water mixing of generation, and the sulfuric acid that sour room generates carries out acid recovery.In two-stage electric dialyzator
In, for the cation-exchange membrane used for indefinite valence state cation-exchange membrane, anion-exchange membrane is univalent anion exchange membrane,
The component of indefinite valence state cation-exchange membrane is polyacrylonitrile and sulfonic acid, the component of univalent anion exchange membrane for butadiene-styrene rubber and
Polyaniline.The component of anode plate is titanium ruthenium alloy；The component of cathode plate is titanium ruthenium alloy.In the apparatus, current density is controlled
For 40-100mA/cm2.After two-stage electrodialysis process, salt content can reduce 80-95% to desulfurization wastewater, and obtain by-product sulphur
Acid and sodium hydroxide, wherein acid concentration is up to 10wt%-20wt%, and alkali concn is up to 8wt%-15wt%.Wherein, sodium hydroxide can be with
, due to excessive concentration, the water generated with enrichment facility can be selected with desulfurization is carried out（And external water source）Mix laggard
Enter desulfurizing tower and carry out desulfurization.
（9）It will be arranged outside waste water by the processing of two-stage electric dialyzator.
Compared with the prior art, the present invention has the advantage that：
1. relative to traditional desulfurization method, the present invention is using setting special oxidation tower mode outside tower to desulfuration solution and ozone vapour
Liquid contacts, hence it is evident that improves the oxidation effectiveness of sodium sulfite, and prevents the spilling of sulfur dioxide in vapor-liquid contacting process.
2. desulfurization wastewater is optimized processing in the present invention, various heavy metal ion in waste water can be removed, it can also
Material consumption and the energy consumption of entire processing procedure are reduced using ultrafiltration, reverse osmosis and twin-stage electrodialysis plant, reduces flue gas desulfurization
The salt content of waste water, while the alkali and water that generate can be used into guild, improve the recycling of whole system.
Description of the drawings
The present invention is further described in conjunction with the accompanying drawings and embodiments：
Fig. 1 is the concrete structure of inventive desulfurization tower and oxidizing tower.
Fig. 2 is the embodiment of the desulphurization system of the present invention.
1- desulfurizing towers, 2- gas inlets, the fresh desulfurization nozzle for liquid of 3-1-, 3-2- doctor solution circulation nozzles, 3-3- regeneration are de-
Sulphur nozzle for liquid, 4- oxidizing towers, 5-1- doctor solutions nozzle to be oxidized, 5-2- spilling gas treatment nozzles, 6- oxidation fans, 7- are smelly
Oxygengenerating plant, 8- ozone imports, 9- overflow gas vent, 10- oxidation sweetening liquid storage tanks, and 11- oxidation sweetenings liquid arranges mouth outside.
Specific embodiment
It is further details of explanation to the present invention presently in connection with drawings and examples.The attached drawing is simplified schematic diagram, only with
Illustration illustrates the essential structure of the present invention, therefore it only shows composition related to the present invention.
As shown in Figure 1, a kind of desulphurization system is present embodiments provided, including desulfurizing tower 1 and oxidizing tower 4, wherein desulfurization
Tower 1 includes the gas inlet 2 positioned at tower body lower end side and the desulfurization fume positioned at tower body top exports, the gas inlet
2 connect with flue gas intake pipeline, have desulfurization nozzle, the desulfurization nozzle packet between gas inlet and desulfurization fume outlet
Include the doctor solution circulation nozzle 3-2 and the fresh desulfurization nozzle for liquid 3-1 positioned at upper end positioned at opposing lower end, the connection of desulfurization tower bottom
Doctor solution discharge pipe, the doctor solution discharge pipe are divided into two, and one is followed with doctor solution circulation nozzle by doctor solution
Endless tube road connects, secondly being connect with oxidizing tower upper end by doctor solution pipeline to be oxidized, the oxidizing tower, which has, is located at tower body
The ozone import 8 of side has the doctor solution nozzle 5- to be oxidized being connect with doctor solution pipeline to be oxidized in 8 upper end of ozone import
1, the ozone import 8 is connect by ozone feed-line with ozone generating-device 7, and it is de- that 4 lower end of oxidizing tower is provided with oxidation
There is row's mouth 11 outside oxidation sweetening liquid to be connect with desulfurizing waste water processing device for sulphur liquid storage tank 10, oxidation sweetening liquid storage tank lower end..Oxygen
Change and be additionally provided with oxidation fan 6 on doctor solution storage tank.Oxidizing tower top, which is provided with, overflows gas vent 9, the spilling gas
Outlet 9 is connect with flue gas intake pipeline.Overflowing spilling gas is additionally provided between gas vent and doctor solution nozzle to be oxidized
Handle nozzle 5-2.
Fig. 2 gives the armamentarium of desulphurization system provided in this embodiment, in addition to desulfurizing tower shown in FIG. 1 and again
Also there are sequentially connected neutralization precipitation device, reduction apparatus, ultrafiltration apparatus, enrichment facility, level-one dialyzer, two except raw tower
Grade dialyzer and crystallization apparatus.Wherein, the penetrating fluid outlet of ultrafiltration apparatus is connect with the spilling gas treatment nozzle 5-1 in Fig. 1.
Caused by level-one dialyzer, two level dialyzer the water discharge pipe line of sodium hydroxide outlet and enrichment facility connection after again with again
Raw doctor solution pipeline connection, the end of regenerative sulfur binding liquid pipe line connection and doctor solution circulation nozzle in desulfurizing tower 1 and 3-2 are fresh de-
Regenerative sulfur binding nozzle for liquid 3-3 connections between sulphur nozzle for liquid 3-1.Solid sodium hydroxide is set to add in mouth on neutralization precipitation device
To facilitate the addition of sodium hydroxide.Anaerobism sulfate reduction is used in reduction apparatus.And PVDF tubular types surpass in ultrafiltration apparatus
Filter membrane, a penetrating fluid part are back to oxidizing tower, connect to overflow gas with the spilling gas treatment nozzle 5-2 at the top of oxidizing tower
The processing of body.Enrichment facility is connected after ultrafiltration apparatus, enrichment facility uses aromatic polyamides reverse osmosis membrane filtration.After enrichment facility
Level-one electric dialyzator and two level dialyzer are connected, level-one dialyzer is two Room Bipolar Membrane electricity of Bipolar Membrane and cation-exchange membrane composition
Dialyzer carries out reuse to generate sodium hydroxide, and two level electric dialyzator is Bipolar Membrane and three Room of anions and canons exchange membrane composition
Bipolar membrane electrodialysis device.In the electric dialyzator there is sour room to generate bronsted lowry acids and bases bronsted lowry room and generate lye.The cation-exchange membrane is
Indefinite valence state cation-exchange membrane, anion-exchange membrane be univalent anion exchange membrane, the group of indefinite valence state cation-exchange membrane
It is divided into polyacrylonitrile and sulfonic acid, the component of univalent anion exchange membrane is butadiene-styrene rubber and polyaniline.The component of anode plate is titanium
Ruthenium alloy；The component of cathode plate is titanium ruthenium alloy.The sodium hydroxide that two-stage dialyzer generates is generated by pipeline and enrichment facility
Water connect back to for desulfurizing tower 1, the specific regenerative sulfur binding nozzle for liquid 3-3 connected in desulfurizing tower 1.
Sulfur removal technology using desulphurization system in the present embodiment includes the following steps：
(1) flue gas from flue gas delivery pipe line enters desulfurizing tower from desulfurizing tower lower end, with the hydroxide from upside down ejection
The contact of sodium solution vapour-liquid carries out desulfurization, and flue gas after desulfurization enters remaining processing sequences after demister is dehydrated.
（2）Solution is pumped into oxidizing tower upper end and is sprayed downward through nozzle after desulfurization, with the ozone being passed through from oxidizing tower lower end
Vapour-liquid is contacted to be aoxidized to desulfuration solution, and it is defeated that spilling gas vent of the gas through tower top after vapour-liquid contact is back to flue gas
Pipeline is sent, the doctor solution after oxidation enters the oxidation sweetening liquid storage tank of oxidation tower bottom.Gas after vapour-liquid contact is from spilling
The doctor solution sprayed with overflowing gas treatment nozzle is also needed to carry out vapour-liquid before gas vent discharge to contact.
（3）Desulfurization wastewater in oxidation sweetening liquid storage tank enters neutralization precipitation device, by adding solid sodium hydroxide tune
PH to 9-10 is saved, by most of heavy metal ion generation hydroxide precipitation such as Mg2+, Zn2+, Cu2+, Cr3+ in waste water
It is moved out.
(4) supernatant liquor in neutralization precipitation device is passed through in anaerobism sulfate reduction device, is adopted in reduction apparatus
H2S is generated with sulfate reducing bacteria reduction part of sulfuric acid root so that the metal ions such as remaining Hg2+, Pb2+ generate sulphur in waste water
Compound precipitates to remove.
(5) supernatant liquor in anaerobism sulfate reduction device is passed through in ultrafiltration membrane to remove the solid in waste water
Grain object.
（6）It is concentrated being further passed through in reverse osmosis membrane apparatus by the penetrating fluid of ultrafiltration membrane.
（7）Waste water after concentration is passed through in level-one electric dialyzator, wherein level-one electric dialyzator is Bipolar Membrane and cation
Exchange membrane forms two Room bipolar membrane electrodialysis devices, and level-one dialyzer forms two Room pair for Bipolar Membrane and cation-exchange membrane here
Pole membrane electrodialysis device carries out reuse to generate sodium hydroxide.
（8）By level-one electric dialyzator, treated that waste water continues to be passed through in two level electric dialyzator, and two level electric dialyzator is double
Three Room bipolar membrane electrodialysis devices of pole film and anions and canons exchange membrane composition.In the electric dialyzator there is sour room to generate bronsted lowry acids and bases bronsted lowry
Room generates lye, and two Room are passed through pure water.The sodium hydroxide and enrichment facility that level-one electric dialyzator and two level electric dialyzator are generated
It is passed through in desulfurizing tower for desulfurization after the water mixing of generation, and the sulfuric acid that sour room generates carries out acid recovery.
Desulfurization, so2 concentration in flue gas 3000ppm carry out power-plant flue gas using this system, and arranged from desulfurization column overhead
The so2 concentration in flue gas gone out decreases below 9ppm, and desulfurization degree is up to 99.8%.And to the oxidation sweetening liquid of oxidizing tower lower end outside
The desulfurization wastewater of row's mouth discharge is detected, and the inferior sulfate radical content contained is less than 5%, and in addition to this, Ca2+ is in waste water
1000mg/L, Mg2+ 3500mg/L, SiO2 10mg/L, mercury 0.3mg/L, chromium 4mg/L, lead 3-4mg/L, zinc 5-
6mg/L is nearly no detectable heavy metal ion in last draining.
The foregoing is merely highly preferred embodiment of the present invention, are not intended to restrict the invention.It is all the present invention principle and
Any modification, equivalent substitution, improvement and etc. done within spirit, should be included within the scope of the present invention.
Claims (10)
1. a kind of recycling flue gas desulphurization system, including desulfurizing tower and oxidizing tower, wherein desulfurizing tower includes being located at tower body lower end
The gas inlet of side and desulfurization fume positioned at tower body top export, and the gas inlet connect with flue gas intake pipeline,
There is desulfurization nozzle between gas inlet and desulfurization fume outlet, the desulfurization nozzle includes the desulfurization positioned at opposing lower end
Liquid circulation nozzle and the fresh desulfurization nozzle for liquid positioned at upper end, desulfurization tower bottom connection doctor solution discharge pipe, the desulfurization
Liquid discharge pipe is divided into two, and one is connect with doctor solution circulation nozzle by doctor solution circulation line, secondly on oxidizing tower
End is connected by doctor solution pipeline to be oxidized, and the oxidizing tower has the ozone import positioned at tower body side, in ozone import
Upper end has the doctor solution nozzle to be oxidized being connect with doctor solution pipeline to be oxidized, and the ozone import passes through ozone delivery pipe
Line is connect with ozone generating-device, and oxidizing tower lower end is provided with oxidation sweetening liquid storage tank, and oxidation sweetening liquid storage tank lower end has oxygen
Change and arrange mouth outside doctor solution.
2. system according to claim 1, it is characterised in that be additionally provided with oxidation wind on the oxidation sweetening liquid storage tank
Machine.
3. system according to claim 1, it is characterised in that oxidizing tower top is provided with spilling gas vent, and described overflows
Go out gas vent to connect with flue gas intake pipeline.
4. system according to claim 3, it is characterised in that overflowing between gas vent and doctor solution nozzle to be oxidized
It is additionally provided with and overflows gas treatment nozzle.
5. system according to claim 3, it is characterised in that mouth is arranged outside the oxidation sweetening liquid and is handled with desulfurization wastewater
Device connects.
6. system according to claim 5, it is characterised in that the desulfurizing waste water processing device includes ultrafiltration apparatus.
7. system according to claim 6, it is characterised in that penetrating fluid outlet and the spilling gas of ultrafiltration apparatus
Handle nozzle connection.
8. system according to claim 5, it is characterised in that the desulfurizing waste water processing device includes sequentially connected
Neutralization precipitation device, reduction apparatus, ultrafiltration apparatus, enrichment facility, two-stage dialyzer.
9. system according to claim 5, it is characterised in that the doctor solution circulation nozzle of the opposing lower end and be located at
Regenerative sulfur binding nozzle for liquid, the regenerative sulfur binding nozzle for liquid and regenerative sulfur binding liquid are additionally provided between the fresh desulfurization nozzle for liquid of upper end
Pipeline connects, and the regenerative sulfur binding liquid pipe line is arranged respectively with the water of the sodium hydroxide outlet of two-stage dialyzer and enrichment facility
Outlet connection.
10. system according to claim 8, it is characterised in that the two-stage dialyzer includes level-one dialyzer and two level is oozed
Parser, the level-one dialyzer forms two Room bipolar membrane electrodialysis devices for Bipolar Membrane and cation-exchange membrane, and described two
Grade electric dialyzator is Bipolar Membrane and three Room bipolar membrane electrodialysis devices of anion and cation exchange membrane composition.
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Cited By (1)
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| CN112996755A (en) * | 2018-11-01 | 2021-06-18 | 苏特沃克技术有限公司 | System and method for removing monovalent anionic species from wastewater |
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Application publication date: 20180622 |