CN109592834A - A kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system and method - Google Patents
A kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system and method Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/96—Methods for the preparation of sulfates in general
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/48—Methods for the preparation of nitrates in general
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- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- 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
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/101—Sulfur compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
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Abstract
The invention discloses a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system and method, which stores reclaiming system, Cl by coagulating sedimentation system, nanofiltration membrane system, sulfate evaporation and crystallization system, anion exchange system, nitrate evaporation crystal system, electrolyzer system, NaOH solution2Store metering injection system, H2Stocking system and flue gas reclaiming system composition.Present invention process system, by the integrated innovation of technique, realizes the resource reusing of sulfate, nitrate in waste water using desulphurization denitration waste water as raw material, while passing through oxidant Cl needed for electrolytic preparation flue gas desulfurization and denitrification2With NaOH absorbing liquid, smoke gas treatment expense is greatly reduced, furthermore this technique generates clean energy resource H simultaneously2, can be used as a kind of gas for domestic use source, it can be achieved that the economical and efficient of flue gas pollutant removes while realizing the resource utilization and wastewater zero discharge of flue gas desulfurization and denitrification waste water.
Description
Technical field
The invention belongs to field of industrial waste water treatment, and in particular to a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment
Process system and method.
Background technique
In recent years, flue gas wet process simultaneous SO_2 and NO removal technology obtains Demonstration Application on industrial boilers in China, Industrial Stoves,
Achieve preferable SO2, NOx control effect.But there is also some problems for the technology, such as absorb the processing handling problems of tail washings.
Wet process simultaneous SO_2 and NO removal technology can be broadly divided into oxidized form, reduced form, solvay-type three greatly according to the difference to NOx cutting mechanisms
Class, wherein oxidized form simultaneous SO_2 and NO removal technology is that one kind passes through on the basis of existing Wet Flue Gas Desulfurization Technique (mainly sodium alkali)
Oxidant, such as sodium hypochlorite are added, to realize SO in flue gas2, a kind of NOx smoke gas treatment technology for efficiently removing simultaneously, mesh
It is preceding to study and be most widely used.Since the absorbing liquid of wet process simultaneous SO_2 and NO removal technology is recycled, needs are saturated when reaching
When outlet, there can be a large amount of SO in solution4 2-、NO3 -、Cl-And Na+, it is a kind of high-salt wastewater, processing difficulty is very big.Mesh
Preceding enterprise is discharged into waste water processing station typically directly or after simple coagulating sedimentation for desulphurization denitration waste water, does not consider waste water
In a large amount of inorganic ions reuse and its influence to the waste water treatment system being discharged into.201711342100.2 disclosure of patent of invention
A kind of desulfurization wastewater Zero emission device, it is anti-using mechanical filter-redox for power plant desulfurization method of limestone-gypsum waste water
Membrane stack technique is answered, solid matter in waste water is separated and returns to desulphurization system, electrolysis wastewater generates Cl2And NaOH, wherein Cl2For electricity
Factory's cooling circulating water sterilization algae removal, NaOH is back to desulphurization system, but the patent of invention is not directed to only for power plant desulfurization wastewater
SO4 2-、NO3 -Resource reusing, and isolated solid reuse can make absorbing liquid solid concentration is excessively high to cause pipeline, spray nozzle clogging etc.
Risk.Patent of invention 201711315966.4,201810110709.5 etc. is disclosed for power plant desulfurization wastewater processing technique,
But it is not directed to SO simultaneously containing high concentration4 2-、NO3 -、Cl-And Na+The disposal of resources technology of waste water, and by wastewater treatment
The technology combined with exhaust-gas treatment.
As it can be seen that the research of existing smoke gas treatment waste water is mainly for power plant desulfurization wastewater, and to wet process simultaneous SO_2 and NO removal
The disposition of waste water is rarely reported, in particular for SO in desulphurization denitration waste water4 2-、NO3 -、Cl-Resource reusing and by waste water dis posal
The technical research application combined with smoke gas treatment has not been reported at present.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of smoke-gas wet desulfurization
Denitration wastewater recycling treatment process system.
Smoke-gas wet desulfurization denitration wastewater resource is carried out using above system another object of the present invention is to provide a kind of
Change the method for processing.
The object of the invention is achieved through the following technical solutions:
A kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system connects with flue gas desulfurization and denitrification system circulation
It connects；The smoke-gas wet desulfurization denitration wastewater recycling treatment process system includes coagulating sedimentation system, nanofiltration membrane system, sulfuric acid
Salt evaporation and crystallization system, anion exchange system, nitrate evaporation crystal system, electrolyzer system, NaOH solution store reuse
System, Cl2Store metering injection system, H2Stocking system and flue gas reclaiming system；
The coagulating sedimentation system, nanofiltration membrane system, anion exchange system, electrolyzer system and NaOH solution are stored back into
It is sequentially connected with system；The nanofiltration membrane system is also connect with sulfate evaporation and crystallization system；The anion exchange system is also
It is connect with nitrate evaporation crystal system；The electrolyzer system also with Cl2Store metering injection system and H2Stocking system connects
It connects；The sulfate evaporation and crystallization system, nitrate evaporation crystal system and Cl2Store metering injection system with flue gas reuse
System connection, the coagulating sedimentation system, flue gas reclaiming system, NaOH solution storage reclaiming system with flue gas desulfurization and denitrification system
System connection.
Preferably, the coagulating sedimentation system includes waste water pump, coagulative precipitation device, flocculant add-on system and clear water storage
Tank；The nanofiltration membrane system includes booster pump, nano filter membrance device, concentrated water storage tank and fresh water storage tank；The sulfate evaporative crystallization
System includes concentrated water pump and sulfate evaporated crystallization device；The anion exchange system include fresh water pump, anion-exchange column,
Nitrate wastewater storage tank and regenerated liquid add-on system；The nitrate evaporation crystal system includes brine pump and nitrate evaporation knot
Brilliant device；The electrolyzer system includes electrolytic cell；The NaOH solution storage reclaiming system includes lye pump, alkali storage tank and adds
Teat pipette；The Cl2Storing metering injection system includes Cl2Storage tank and Cl2Mixing weighing spraying system；The H2Stocking system packet
Containing H2Storage tank；The flue gas reclaiming system includes the first hot fume circulation pipe, the first cold flue gas circulation pipe, the second hot fume circulation
Pipe, the second cold flue gas circulation pipe and mixed pipe line；
The waste water pump, coagulative precipitation device, clear water storage tank, booster pump, nano filter membrance device, fresh water storage tank, fresh water pump, yin
Ion exchange column, electrolytic cell, lye pump, alkali storage tank, dosing pump are connected with flue gas desulfurization and denitrification system circulation；The coagulating sedimentation
Device is also connect with flocculant add-on system；The nano filter membrance device is also connect with concentrated water storage tank, the concentrated water storage tank, concentrated water pump
It is sequentially connected with sulfate evaporated crystallization device；The regenerated liquid add-on system, anion-exchange column, nitrate wastewater storage tank,
Brine pump and nitrate evaporation crystallization apparatus are sequentially connected；The electrolytic cell also with H2Storage tank and Cl2Storage tank connection, the Cl2Storage
Tank, Cl2Mixing weighing spraying system, mixed pipe line are sequentially connected；The first hot fume circulation pipe, sulfate evaporative crystallization dress
It sets, the first cold flue gas circulation pipe, mixed pipe line are connected by circulation；The second hot fume circulation pipe, nitrate evaporation crystallization apparatus,
Second cold flue gas circulation pipe, mixed pipe line are connected by circulation；The mixed pipe line is also connect with flue gas desulfurization and denitrification system.
The smoke-gas wet desulfurization denitration wastewater recycling treatment process system is for handling flue gas desulfurization and denitrification system
The desulphurization denitration waste water of discharge, water outlet discharge of the desulphurization denitration waste water Jing Guo flue gas desulfurization and denitrification system, subsequently into coagulation
Settling system carries out coagulating sedimentation, then crystallized by filtering and sulfate evaporative crystallization, anion exchange and nitrate evaporation,
The process such as electrolysis finally obtain the products such as vitriol, nitric acid salt crystal, chlorine, hydrogen and NaOH solution, complete useless
Recycling of water resource；The heat source that wherein sulfate evaporative crystallization and nitrate evaporation crystallization use is from factory's hot fume pipeline
And the hot fume without system for desulfuration and denitration processing, the hot fume enter mixed pipe line through factory's hot fume pipeline, then divide
Not Jin Ru the first hot fume circulation pipe and the second hot fume circulation pipe (temperature is generally at 120~250 DEG C), weight again after flue gas heat exchange
It newly is discharged into mixed pipe line, flue gas desulfurization and denitrification system is finally entered and is disposed, NaOH solution obtained is electrolysed and is back to flue gas
System for desulfuration and denitration, the chlorine being electrolysed are used to aoxidize the NO in flue gas.
Preferably, the mixed pipe line is also connect with the hot fume pipeline of factory.Hot fume from factory is as sulfuric acid
The heat source of salt evaporated crystallization device, nitrate evaporation crystallization apparatus is evaporated crystallization by the way of indirect heat exchange, exchanges heat it
Flue gas afterwards is discharged into mixed pipe line through the first cold flue gas circulation pipe or the second cold flue gas circulation pipe again, subsequently enters flue gas desulfurization
Denitrating system.
It is highly preferred that the electrolyzer system also includes NaCl add-on system, the electrolytic cell and NaCl add-on system connect
It connects.
It is highly preferred that the electrolytic cell is vertical diaphragm electrolytic cell.
It is highly preferred that being filled with anion exchange resin in the anion-exchange column.
It is highly preferred that the mixed pipe line and Cl2Mixing weighing spraying system is connected by chlorine pipeline, mixed pipe line
Caliber amplifies No.1 compared with chlorine pipeline caliber, to guarantee that gas mixing is uniform.
A method of smoke-gas wet desulfurization denitration wastewater recycling, including following step are realized using above-mentioned process system
It is rapid:
(1) waste water from flue gas desulfurization and denitrification system obtains the clear water of sulfur-bearing nitre after the processing of coagulating sedimentation system；
(2) clear water of sulfur-bearing nitre obtains after nanofiltration membrane system is handled containing SO4 2-Concentrated water and be free of SO4 2-Fresh water；Contain
SO4 2-Concentrated water after evaporative crystallization, obtain vitriol；
(3) SO is free of4 2-Fresh water after anion exchange system is handled, water after obtaining anion exchange and contain NO3 -It is useless
Water；Water after anion exchange obtains H after electrolyzer system is electrolysed2、Cl2And NaOH solution；
(4) contain NO3 -Waste water after evaporative crystallization, obtain nitric acid salt crystal.
Preferably, the method for realizing smoke-gas wet desulfurization denitration wastewater recycling using above-mentioned process system, including
Following steps:
(1) waste water from flue gas desulfurization and denitrification system is pumped into coagulative precipitation device by waste water, adds with from flocculant
The flocculant of adding system mixes in coagulative precipitation device, flocculates and precipitates, and obtains the clear water of sulfur-bearing nitre；
(2) clear water of sulfur-bearing nitre is pumped into nano filter membrance device by being pressurized, and contains SO through nano filter membrance device is isolated4 2-It is dense
Water and be free of SO4 2-Fresh water；Containing SO4 2-Concentrated water enter sulfate evaporation and crystallization system, through come from the first hot fume circulation pipe
Hot fume evaporative crystallization after, obtain vitriol；Flue gas after heat exchange is discharged into mixing through the first cold flue gas circulation pipe again
Pipeline subsequently enters flue gas desulfurization and denitrification system；
(3) SO is free of4 2-Fresh water enter and carry out anion exchange in anion-exchange column, the water after anion exchange into
Enter electrolyzer system, be electrolysed as electrolyte, obtains H2、Cl2And NaOH solution；H2、Cl2Respectively enter H2Storage tank and Cl2
Storage tank, NaOH solution enter alkali storage tank；
(4) it after anion exchange resin adsorption saturation, is regenerated using regenerated liquid, NO is contained after regeneration3 -Waste water give
Enter nitrate evaporation crystal system, after the hot fume evaporative crystallization from the second hot fume circulation pipe, obtains nitric acid salt crystal；
Flue gas after heat exchange is discharged into mixed pipe line through the second cold flue gas circulation pipe again, subsequently enters flue gas desulfurization and denitrification system.
Preferably, the mass concentration of sodium chloride is 10~25% in step (3) described electrolyte.
Preferably, in step (3), saturation NaCl solution can be also added into electrolyzer system, after anion exchange
Water and the mixed liquor of saturation NaCl solution are as electrolyte.
Preferably, step (3) anion exchange resin is Chioro-anion exchange resin, for removing NO3 -Ion.
Preferably, step (3) Cl2Oxidant as NOx pollutant in the flue gas in flue gas desulfurization and denitrification system
It uses, specifically: according to Cl2With NOx molar ratio be 0.3~2.0:1 ratio by Cl2Mixing weighing spraying system is injected into
NO is oxidized to NO soluble easily in water by mixed pipe line in mixed pipe line2, NO2Into the absorption tower of flue gas desulfurization and denitrification system,
It reacts in absorption tower with absorbent solution counter current contacting and to form nitrate and be dissolved in waste water, again through smoke-gas wet desulfurization denitration
Waste water reclaiming process system desulphurization denitration processing, until being discharged again through demisting after purifying smoke is up to standard.
Preferably, step (3) NaOH solution can enter in flue gas desulfurization and denitrification system through dosing pump, as absorbing liquid
It recycles.
Preferably, step (3) described hydrogen is alternatively arranged as a kind of gas for domestic use.
Preferably, step (4) described regenerated liquid is the sodium chloride solution or NaOH solution that mass concentration is 2~8%, more excellent
It is selected as the sodium chloride solution that mass concentration is 2~8%；Pass through the Cl of high concentration-Or OH-By the NO on ion exchange resin3 -It hands over
It changes, forms higher concentration NO3 -Waste water.
Preferably, the temperature of step (2) and (4) described hot fume is 120~250 DEG C.
System of the invention, the SO containing high concentration generated for flue gas desulfurization and denitrification4 2-、NO3 -、Cl-And Na+Waste water,
For the purpose of resource reusing, by coagulating sedimentation remove waste water in suspended matter and coloration, purified clear water enter nanofiltration membrane
System is separated into a small amount of concentrated water and a large amount of fresh water, passes through the ion selection index system of nanofiltration membrane, SO4 2-It is pooled to concentrated water, NO3 -、Cl-
Then enter fresh water；SO containing high concentration4 2-Concentrated water subsequently enter sulfate evaporation and crystallization system, using hot fume as heat source, between
The mode for connecing heat exchange flashes to vitriol, can be used as industrial chemicals sale, it is de- that the flue gas after exchanging heat reenters flue gas
Sulphur denitrating system is disposed；Enter Chioro-anion exchange resin by the fresh water that nanofiltration membrane system is separated, in fresh water
NO3 -With the Cl on resin-Ion exchange occurs to be removed, exchanges the Cl to get off-Enter electrolytic cell with fresh water；Work as ion
After exchanger resin saturation, is regenerated using certain density NaCl or NaOH solution, pass through the Cl of high concentration-Or OH-By ion
NO on exchanger resin3 -Exchange is got off, and higher concentration NO is formed3 -Waste water, subsequent higher concentration NO3 -Waste water enters nitrate evaporation knot
Crystallographic system system, using hot fume as heat source, flashes to nitric acid salt crystal by the way of indirect heat exchange, can be used as industrial chemicals sale,
Flue gas after heat exchange reenters flue gas desulfurization and denitrification system and is disposed；What is exchanged contains Cl-Water enter electrolytic cell
System prepares H using electrolysis method2、Cl2,NaOH.The H wherein generated2It is stored in H2Storage tank can be used as a kind of gas for domestic use source；
Cl2As gaseous oxidant, by Cl2Mixing weighing spraying system is injected into mixed pipe line, the Cl in mixed pipe line2By NO oxygen
It is melted into NO soluble easily in water2、N2O3；NaOH solution is back to flue gas desulfurization and denitrification system, for preparing absorbing liquid；It is final to realize
The resource utilization and wastewater zero discharge of flue gas desulfurization and denitrification waste water.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) present invention combines wastewater treatment and smoke gas treatment, in the recycling benefit for realizing flue gas desulfurization and denitrification waste water
While with wastewater zero discharge, smoke gas treatment expense is greatly reduced, realizes the removal of flue gas economical and efficient.
(2) present invention solves high saliferous industrial waste disposal problem, especially Cl containing high concentration-The disposition of waste water is difficult
Topic, in conjunction with gas pollution control, by using techniques such as coagulating sedimentation, nanofiltration, ion exchange, electrolysis, finally by harmful Cl-
Oxidant Cl needed for being converted into smoke gas treatment2, while NaOH solution needed for producing smoke gas treatment, it realizes waste treatment and waste and becomes
Waste be changed into values.
(3) present invention realizes the recycling reuse of sulfate and nitrate in waste water, by SO harmful in flue gas2、NOx
It is converted to useful raw material of industry sulfate and nitrate, while realizing pollutant removal, obtains preferable environment, economy
Benefit.
(4) method of operation of the present invention is flexible, applied widely, and it is useless to can be applied to the independent desulfurization of flue gas by technique adjustment
Water, flue gas desulfurization and denitrification waste water and all types of industries wastewater treatment are especially suitable for processing SO containing high concentration4 2-、NO3 -、Cl-Deng
Waste water.
Detailed description of the invention
Fig. 1 and Fig. 2 is that the structure of smoke-gas wet desulfurization denitration wastewater recycling treatment process system of the present invention is shown
It is intended to；
Wherein: 1- coagulating sedimentation system, 2- nanofiltration membrane system, 3- sulfate evaporation and crystallization system, 4- anion exchange system
System, 5- nitrate evaporation crystal system, 6- electrolyzer system, 7-NaOH solution store reclaiming system, 8-Cl2Store metered injection
System, 9-H2Stocking system, 10- flue gas reclaiming system, 11- flue gas desulfurization and denitrification system, 38- waste water, the first hot fume of 39- are followed
Endless tube, 40- the first cold flue gas circulation pipe, 37- the second hot fume circulation pipe, 28- the second cold flue gas circulation pipe, 41- purifying smoke,
42- vitriol, 43- contain SO4 2-Concentrated water, 44- nitric acid salt crystal, 46-H2, 47-Cl2, 48-NaOH solution, 50- is containing NO3 -
Waste water, 12- waste water pump, 13- coagulative precipitation device, 14- flocculant add-on system, 15- clear water storage tank, 16- booster pump, 17-
Nano filter membrance device, 18- concentrated water storage tank, 19- fresh water storage tank, 20- concentrated water pump, 21- sulfate evaporated crystallization device, 22- fresh water pump,
23- anion-exchange column, 24- nitrate wastewater storage tank, 25- regenerated liquid add-on system, 26- brine pump, 27- nitrate evaporation knot
Brilliant device, 29- electrolytic cell, 30- lye pump, 31- alkali storage tank, 32- dosing pump, 33-Cl2Storage tank, 34-Cl2Mixing weighing injection system
System, 35-H2Storage tank, 36- mixed pipe line, the water after 45- anion exchange, 51- factory hot fume pipeline.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Referring to Fig. 1, the present invention provides a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system, with flue gas
System for desulfuration and denitration (11) is connected by circulation；The smoke-gas wet desulfurization denitration wastewater recycling treatment process system includes that coagulation is heavy
Shallow lake system (1), nanofiltration membrane system (2), sulfate evaporation and crystallization system (3), anion exchange system (4), nitrate evaporation knot
Crystallographic system is united (5), electrolyzer system (6), NaOH solution store reclaiming system (7), Cl2Store metering injection system (8), H2Storage
System (9) and flue gas reclaiming system (10)；The coagulating sedimentation system (1), nanofiltration membrane system (2), anion exchange system
(4), electrolyzer system (6) and NaOH solution storage reclaiming system (7) are sequentially connected；The nanofiltration membrane system (2) is gone back and sulfuric acid
Salt evaporation and crystallization system (3) connection；The anion exchange system (4) also connect with nitrate evaporation crystal system (5)；It is described
Electrolyzer system (6) is gone back and Cl2Store metering injection system (8) and H2Stocking system (9) connection；The sulfate evaporative crystallization
System (3), nitrate evaporation crystal system (5) and Cl2Metering injection system (8) are stored to connect with flue gas reclaiming system (10)
It connects, the coagulating sedimentation system (1), flue gas reclaiming system (10), NaOH solution storage reclaiming system (7) and flue gas desulfurization are de-
Nitre system connects (11).
Specifically, to provide a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system as shown in Figure 2 by the present invention:
The coagulating sedimentation system includes waste water pump (12), coagulative precipitation device (13), flocculant add-on system (14) and clear water storage tank
(15)；The nanofiltration membrane system includes booster pump (16), nano filter membrance device (17), concentrated water storage tank (18) and fresh water storage tank (19)；
The sulfate evaporation and crystallization system includes concentrated water pump (20) and sulfate evaporated crystallization device (21)；The anion exchange system
System includes fresh water pump (22), anion-exchange column (23), nitrate wastewater storage tank (24) and regenerated liquid add-on system (25)；It is described
Nitrate evaporation crystal system includes brine pump (26) and nitrate evaporation crystallization apparatus (27)；The electrolyzer system includes electricity
It solves slot (29)；The NaOH solution storage reclaiming system includes lye pump (30), alkali storage tank (31) and dosing pump (32)；It is described
Cl2Storing metering injection system includes Cl2Storage tank (33) and Cl2Mixing weighing spraying system (34)；The H2Stocking system is H2
Storage tank (35)；The flue gas reclaiming system includes the first hot fume circulation pipe (39), the first cold flue gas circulation pipe (40), the second heat
Flue gas recirculation pipe (37), the second cold flue gas circulation pipe (28) and mixed pipe line (36)；
The flue gas desulfurization and denitrification system (11), coagulative precipitation device (13), clear water storage tank (15), increases waste water pump (12)
Press pump (16), nano filter membrance device (17), fresh water storage tank (19), fresh water pump (22), anion-exchange column (23), electrolytic cell (29),
Lye pump (30), alkali storage tank (31) and dosing pump (32) are connected by circulation；The coagulative precipitation device (13) is also added with flocculant
System (14) connection；The nano filter membrance device (17), concentrated water storage tank (18), concentrated water pump (20) and sulfate evaporated crystallization device
(21) it is sequentially connected；The regenerated liquid add-on system (25), anion-exchange column (23), nitrate wastewater storage tank (24), salt water
Pump (26) and nitrate evaporation crystallization apparatus (27) are sequentially connected；The electrolytic cell (29) is gone back and H2Storage tank (35) and Cl2Storage tank
(33) it connects；The Cl2Storage tank (33), Cl2Mixing weighing spraying system (34), mixed pipe line (36) are sequentially connected；Described first
Hot fume circulation pipe (39), sulfate evaporated crystallization device (21), the first cold flue gas circulation pipe (40), mixed pipe line (36) circulation
Connection；The second hot fume circulation pipe (37), the second cold flue gas circulation pipe (28), is mixed nitrate evaporation crystallization apparatus (27)
Pipeline (36) are closed to be connected by circulation；The mixed pipe line (36) also connect with factory's hot fume pipeline (51), the hot cigarette from factory
Gas is as sulfate evaporated crystallization device (21), the heat source of nitrate evaporation crystallization apparatus (27)；The mixed pipe line (36) with
Flue gas desulfurization and denitrification system (11) connection；
In above system, the waste water (38) from flue gas desulfurization and denitrification system (11) enters coagulative precipitation device through waste water pump
(13) coagulating sedimentation is carried out, subsequently into nanofiltration membrane system, what is obtained after nanofiltration membrane system is handled contains SO4 2-Concentrated water (43)
Obtained vitriol (42) through evaporative crystallization, the fresh water obtained after nanofiltration membrane system is handled through anion-exchange column (23) at
Reason obtains the water (45) after anion exchange and containing NO3 -Waste water (50), the water (45) after anion exchange is through electrolyzer system
H is obtained after electrolysis2(46)、Cl2(47) and NaOH solution (48)；Containing NO3 -Waste water (50) obtain nitric acid salt crystal through evaporative crystallization
(44)；Enter flue gas through mixed pipe line with the flue gas after sulfate evaporated crystallization device, the heat exchange of nitrate evaporation crystallization apparatus to take off
Sulphur denitrating system (11) purification, is purified flue gas (41).
In a preferred scheme, the electrolyzer system (6) also include NaCl add-on system, the electrolytic cell (29) with
The connection of NaCl add-on system.
Embodiment 1
The present embodiment is applied on ceramics factory's industrial furnace smoke is administered and its desulphurization denitration waste water reclaiming is handled, wherein
Ceramics factory's industrial furnace smoke particulate matter, SO2, NOx initial ejection concentration be respectively 58mg/m3、162mg/m3、135mg/m3。
A method of smoke-gas wet desulfurization denitration wastewater recycling, technique are realized using process system provided by the present application
System structure is as illustrated in fig. 1 and 2, comprising the following steps:
(1) waste water from flue gas desulfurization and denitrification system is pumped into coagulative precipitation device by waste water, adds with from flocculant
The flocculant of adding system mixes in coagulative precipitation device, flocculates and precipitates, and removes suspended matter, coloration etc. in waste water, processing
The clear water of sulfur-bearing nitre is obtained afterwards；
(2) clear water of sulfur-bearing nitre is pumped into nano filter membrance device by being pressurized, and contains SO through nano filter membrance device is isolated4 2-It is dense
Water and be free of SO4 2-Fresh water；Containing SO4 2-Concentrated water enter sulfate evaporation and crystallization system, through come from the first hot fume circulation pipe
Hot fume (250 DEG C) evaporative crystallization after, obtain vitriol；Flue gas after heat exchange is arranged again through the first cold flue gas circulation pipe
Enter mixed pipe line, subsequently enters flue gas desulfurization and denitrification system；
(3) SO is free of4 2-Fresh water enter and carry out anion exchange in anion-exchange column, the water after anion exchange with
The saturation NaCl solution of addition is hybridly prepared into the sodium chloride solution that mass concentration is 25%, into electrolyzer system, as electricity
Solution liquid is electrolysed, and H is obtained2、Cl2And NaOH solution；H2、Cl2Respectively enter H2Storage tank and Cl2Storage tank, NaOH solution enter alkali
Storage tank；
(4) after anion exchange resin adsorption saturation, use mass concentration for 8% NaCl solution as regenerated liquid into
Row regeneration, contains NO after regeneration3 -Waste water be sent into nitrate evaporation crystal system, through the hot fume from the second hot fume circulation pipe
After (250 DEG C) evaporative crystallization, nitric acid salt crystal is obtained；Flue gas after heat exchange is discharged into mixing tube through the second cold flue gas circulation pipe again
Road subsequently enters flue gas desulfurization and denitrification system；
Wherein, step (3) Cl2, according to Cl2With NOx molar ratio be 2.0:1 ratio by Cl2Mixing weighing injection system
System is injected into mixed pipe line, as the oxidant of NOx pollutant in flue gas, is oxidized to NO in mixed pipe line soluble easily in water
NO2, NO2Into the absorption tower of flue gas desulfurization and denitrification system, in absorption tower, NO2Shape is reacted with absorbent solution counter current contacting
It is dissolved in waste water at nitrate, purifying smoke discharges after demister demisting again；
Step (3) described NaOH solution enters in flue gas desulfurization and denitrification system through dosing pump, recycles as absorbing liquid；
Step (3) described hydrogen is alternatively arranged as a kind of gas for domestic use.
Finally, the present embodiment purifying smoke monitoring result: particulate matter, SO2, NOx emission concentration be respectively smaller than 30mg/m3、
10mg/m3、85mg/m3, ceramics factory's industrial furnace smoke qualified discharge is realized, and produce sulfuric acid using desulphurization denitration waste water
Salt, nitrate, H2、Cl2With NaOH product, the resource utilization and zero-emission of desulphurization denitration waste water are realized.
Embodiment 2
The present embodiment is applied in biomass boiler smoke gas treatment and its processing of desulphurization denitration waste water reclaiming, wherein biology
Matter boiler smoke particulate matter, SO2, NOx initial ejection concentration be respectively 38mg/m3、12mg/m3、311mg/m3。
A method of smoke-gas wet desulfurization denitration wastewater recycling, technique are realized using process system provided by the present application
System structure is as illustrated in fig. 1 and 2, comprising the following steps:
(1) waste water from flue gas desulfurization and denitrification system is pumped into coagulative precipitation device by waste water, adds with from flocculant
The flocculant of adding system mixes in coagulative precipitation device, flocculates and precipitates, and removes suspended matter, coloration etc. in waste water, processing
The clear water of sulfur-bearing nitre is obtained afterwards；
(2) clear water of sulfur-bearing nitre is pumped into nano filter membrance device by being pressurized, and contains SO through nano filter membrance device is isolated4 2-It is dense
Water and be free of SO4 2-Fresh water；Containing SO4 2-Concentrated water enter sulfate evaporation and crystallization system, through come from the first hot fume circulation pipe
Hot fume (250 DEG C) evaporative crystallization after, obtain vitriol；Flue gas after heat exchange is arranged again through the first cold flue gas circulation pipe
Enter mixed pipe line, subsequently enters flue gas desulfurization and denitrification system；
(3) SO is free of4 2-Fresh water enter and carry out anion exchange in anion-exchange column, the water after anion exchange with
The saturation NaCl solution of addition is hybridly prepared into the sodium chloride solution that mass concentration is 10%, into electrolyzer system, as electricity
Solution liquid is electrolysed, and H is obtained2、Cl2And NaOH solution；H2、Cl2Respectively enter H2Storage tank and Cl2Storage tank, NaOH solution enter alkali
Storage tank；
(4) after anion exchange resin adsorption saturation, use mass concentration for 2% NaOH solution as regenerated liquid into
Row regeneration, contains NO after regeneration3 -Waste water be sent into nitrate evaporation crystal system, through the hot fume from the second hot fume circulation pipe
After (250 DEG C) evaporative crystallization, nitric acid salt crystal is obtained；Flue gas after heat exchange is discharged into mixing tube through the second cold flue gas circulation pipe again
Road subsequently enters flue gas desulfurization and denitrification system；
Wherein, step (3) Cl2, according to Cl2With NOx molar ratio be 3.0:1 ratio by Cl2Mixing weighing injection system
System is injected into mixed pipe line, as the oxidant of NOx pollutant in flue gas, is oxidized to NO in mixed pipe line soluble easily in water
NO2, NO2Into the absorption tower of flue gas desulfurization and denitrification system, in absorption tower, NO2Shape is reacted with absorbent solution counter current contacting
It is dissolved in waste water at nitrate, purifying smoke discharges after demister demisting again；
Step (3) described NaOH solution enters in flue gas desulfurization and denitrification system through dosing pump, recycles as absorbing liquid；
Step (3) described hydrogen is alternatively arranged as a kind of gas for domestic use.
Finally, the present embodiment purifying smoke monitoring result: particulate matter, NOx emission concentration are respectively smaller than 20mg/m3、
149mg/m3, SO2Concentration of emission is 0mg/m3, biomass boiler flue gas qualified discharge is realized, and utilize desulphurization denitration waste water
Produce sulfate, nitrate, H2、Cl2With NaOH product, the resource utilization and zero-emission of desulphurization denitration waste water are realized.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system connects with flue gas desulfurization and denitrification system circulation
It connects, which is characterized in that the smoke-gas wet desulfurization denitration wastewater recycling treatment process system includes coagulating sedimentation system, nanofiltration
Membranous system, sulfate evaporation and crystallization system, anion exchange system, nitrate evaporation crystal system, electrolyzer system, NaOH are molten
Liquid stores reclaiming system, Cl2Store metering injection system, H2Stocking system and flue gas reclaiming system；
The coagulating sedimentation system, nanofiltration membrane system, anion exchange system, electrolyzer system and NaOH solution store reuse system
System is sequentially connected；The nanofiltration membrane system is also connect with sulfate evaporation and crystallization system；The anion exchange system also with nitre
The connection of hydrochlorate evaporation and crystallization system；The electrolyzer system also with Cl2Store metering injection system and H2Stocking system connection；Institute
State sulfate evaporation and crystallization system, nitrate evaporation crystal system and Cl2Store metering injection system with flue gas reclaiming system
Connection, the coagulating sedimentation system, flue gas reclaiming system, NaOH solution storage reclaiming system connect with flue gas desulfurization and denitrification system
It connects.
2. a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system according to claim 1, feature exist
In the coagulating sedimentation system includes waste water pump, coagulative precipitation device, flocculant add-on system and clear water storage tank；The nanofiltration
Membranous system includes booster pump, nano filter membrance device, concentrated water storage tank and fresh water storage tank；The sulfate evaporation and crystallization system includes concentrated water
Pump and sulfate evaporated crystallization device；The anion exchange system includes fresh water pump, anion-exchange column, nitrate wastewater storage
Tank and regenerated liquid add-on system；The nitrate evaporation crystal system includes brine pump and nitrate evaporation crystallization apparatus；It is described
Electrolyzer system includes electrolytic cell；The NaOH solution storage reclaiming system includes lye pump, alkali storage tank and dosing pump；It is described
Cl2Storing metering injection system includes Cl2Storage tank and Cl2Mixing weighing spraying system；The H2Stocking system includes H2Storage tank；Institute
Stating flue gas reclaiming system includes the first hot fume circulation pipe, the first cold flue gas circulation pipe, the second hot fume circulation pipe, the second cold smoke
Gas circulation pipe and mixed pipe line；
The waste water pump, coagulative precipitation device, clear water storage tank, booster pump, nano filter membrance device, fresh water storage tank, fresh water pump, anion
Exchange column, electrolytic cell, lye pump, alkali storage tank, dosing pump are connected with flue gas desulfurization and denitrification system circulation；The coagulative precipitation device
Also it is connect with flocculant add-on system；The nano filter membrance device is also connect with concentrated water storage tank, the concentrated water storage tank, concentrated water pump and sulphur
Hydrochlorate evaporated crystallization device is sequentially connected；The regenerated liquid add-on system, anion-exchange column, nitrate wastewater storage tank, salt water
Pump and nitrate evaporation crystallization apparatus are sequentially connected；The electrolytic cell also with H2Storage tank and Cl2Storage tank connection；The Cl2Storage tank,
Cl2Mixing weighing spraying system, mixed pipe line are sequentially connected；The first hot fume circulation pipe, sulfate evaporated crystallization device,
First cold flue gas circulation pipe, mixed pipe line are connected by circulation；The second hot fume circulation pipe, nitrate evaporation crystallization apparatus,
Two cold flue gas circulation pipes, mixed pipe line are connected by circulation；The mixed pipe line is also connect with flue gas desulfurization and denitrification system.
3. a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system according to claim 2, feature exist
In the electrolyzer system also includes NaCl add-on system, and the electrolytic cell is connect with NaCl add-on system.
4. a kind of realize smoke-gas wet desulfurization denitration wastewater recycling using the described in any item process systems of claims 1 to 33
Method, which comprises the following steps:
(1) waste water from flue gas desulfurization and denitrification system obtains the clear water of sulfur-bearing nitre after the processing of coagulating sedimentation system；
(2) clear water of sulfur-bearing nitre obtains after nanofiltration membrane system is handled containing SO4 2-Concentrated water and be free of SO4 2-Fresh water；Containing SO4 2-'s
Concentrated water obtains vitriol after evaporative crystallization；
(3) SO is free of4 2-Fresh water after anion exchange system is handled, water after obtaining anion exchange and contain NO3 -Waste water；
Water after anion exchange obtains H after electrolyzer system is electrolysed2、Cl2And NaOH solution；
(4) contain NO3 -Waste water after evaporative crystallization, obtain nitric acid salt crystal.
5. a kind of method for realizing smoke-gas wet desulfurization denitration wastewater recycling using process system as claimed in claim 4,
It is characterized in that, comprising the following steps:
(1) waste water from flue gas desulfurization and denitrification system is pumped into coagulative precipitation device by waste water, is with from flocculant addition
The flocculant of system mixes in coagulative precipitation device, flocculates and precipitates, and obtains the clear water of sulfur-bearing nitre；
(2) clear water of sulfur-bearing nitre is pumped into nano filter membrance device by being pressurized, and contains SO through nano filter membrance device is isolated4 2-Concentrated water and
Without SO4 2-Fresh water；Containing SO4 2-Concentrated water enter sulfate evaporation and crystallization system, through the heat from the first hot fume circulation pipe
After smoke evaporative crystallization, vitriol is obtained, the flue gas after heat exchange is discharged into mixed pipe line through the first cold flue gas circulation pipe again,
Subsequently enter flue gas desulfurization and denitrification system；
(3) SO is free of4 2-Fresh water enter and carry out anion exchange in anion-exchange column, the water after anion exchange enters electricity
Tank systems are solved, is electrolysed as electrolyte, obtains H2、Cl2And NaOH solution；H2、Cl2Respectively enter H2Storage tank and Cl2Storage tank,
NaOH solution enters alkali storage tank；
(4) it after anion exchange resin adsorption saturation, is regenerated using regenerated liquid, NO is contained after regeneration3 -Waste water be sent into nitre
Hydrochlorate evaporation and crystallization system obtains nitric acid salt crystal after the hot fume evaporative crystallization from the second hot fume circulation pipe, heat exchange
Flue gas afterwards is discharged into mixed pipe line through the second cold flue gas circulation pipe again, subsequently enters flue gas desulfurization and denitrification system.
6. a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system according to claim 5, feature exist
In step (3) anion exchange resin is Chioro-anion exchange resin.
7. a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system according to claim 5, feature exist
In step (4) described regenerated liquid is the sodium chloride solution or NaOH solution that mass concentration is 2~8%.
8. a kind of smoke-gas wet desulfurization denitration wastewater recycling treatment process system according to claim 5 or 6 or 7,
It is characterized in that, the mass concentration of sodium chloride is 10~25% in step (3) described electrolyte.
9. a kind of method of smoke-gas wet desulfurization denitration wastewater recycling according to claim 8, which is characterized in that step
(3) Cl2Oxidant as NOx pollutant in the flue gas in flue gas desulfurization and denitrification system uses；The NaOH solution warp
Dosing pump enters in flue gas desulfurization and denitrification system, recycles as absorbing liquid.
10. a kind of method of smoke-gas wet desulfurization denitration wastewater recycling according to claim 8, which is characterized in that step
Suddenly in (3), the addition saturation NaCl solution into electrolyzer system, by the mixing of water and saturation NaCl solution after anion exchange
Liquid is as electrolyte.
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