CN110127918A - A kind of acidic flue gas washes Zero discharge treatment method and its device - Google Patents

A kind of acidic flue gas washes Zero discharge treatment method and its device Download PDF

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Publication number
CN110127918A
CN110127918A CN201810106012.0A CN201810106012A CN110127918A CN 110127918 A CN110127918 A CN 110127918A CN 201810106012 A CN201810106012 A CN 201810106012A CN 110127918 A CN110127918 A CN 110127918A
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flue gas
ammonia
wet scrubbing
acid
waste water
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CN110127918B (en
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杨本涛
魏进超
孙英
李俊杰
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Zhongye Changtian International Engineering Co Ltd
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Zhongye Changtian International Engineering Co Ltd
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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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • 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
    • B01D53/14—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 by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • 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
    • 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
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • 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
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultra-violet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents

Abstract

The present invention provides a kind of acidic flue gas washes Zero discharge treatment method, is filtered by acidity, removes the suspended matter in waste water；By flocculation sedimentation, metal ion is removed；Pass through the substances such as dried recovered fluorine chlorine, removing organic matter again；Or by-product containing ammonia is recycled by high-alkali ammonia-removal process, the substances such as fluorine chlorine are recycled by condensation-crystallization.Method of the invention can be effectively treated acidic cleaning waste water, realize the minimizing of heavy metal dangerous waste, ammonia nitrogen cleaning is administered and reuse, avoid elemental sulfur occluding device, the zero-emission of waste water, dust viscosity it is low, without paste bag phenomenon；Resource reclaim simultaneously reuses, and protects environment.

Description

A kind of acidic flue gas washes Zero discharge treatment method and its device
Technical field
The present invention relates to a kind of wastewater treatment methods, and in particular to a kind of processing method of acidic flue gas washes and its Device.Belong to protection of natural resources and environment field.
Background technique
Sulfur dioxide is one of main atmosphere pollution in China, nearly 20,000,000 tons of annual emissions, serious sulphur is caused to provide The air environmental pollutions such as source waste and acid rain, haze.As National Environmental laws and regulations and standard are increasingly stringent, titanium dioxide is realized The emission reduction and recycling of sulphur have become environment protection field and are badly in need of the key subjects broken through.Sulfuric acid is as important industrial chemicals, in industry It is widely used in production, and China's Sulphur ressource relative shortage, supply falls short of demand for a long time for sulfuric acid.Sulphur ressource in sulfur dioxide is become After carrying out for sulfuric acid, the situation of China's Sulphur ressource shortage can not only be effectively relieved, moreover it is possible to pollution of the sulfur dioxide to environment is reduced, Certain income is brought simultaneously for enterprise.
Predominantly use solid absorbent or liquid by low concentration dioxy the technique that Sulphur Dioxide is sulfuric acid at present Change sulphur absorption after, then by parsing make sulphur dioxide enrichment high-concentration sulfur dioxide, be used to prepare sulfuric acid.To guarantee sulfuric acid product The stability of matter and acid making system usually carries out washing impurity-removing to parsing gas using washing method, thereby produces a large amount of acid Property flue gas washing waste water.
It since resolution gas often contains a large amount of sulfur dioxide, can be dissolved into water in washing process, so that washing Waste water is generally in acidity.Since washes ingredient is vulnerable to sulfur dioxide flue gas, adsorbent and the influence for parsing technique, type It is more various, and since the impurity in resolution gas is often complex, concentration is high, this results in washes ingredient is especially multiple It is miscellaneous.
By early-stage study, determine that Wastewater from Acid Preparation predominantly contains elemental sulfur, suspended matter, metal, ammonia nitrogen, fluorine chlorine, organic dirt Contaminate the complicated waste water of object.But currently, the waste water is not effectively addressed, it there is no referential technology both at home and abroad.
Ammonia nitrogen is one of the major pollutants in water body, and ammonia nitrogen is to cause red tide and wawter bloom etc. rich to the main harm of environment Nutrient laden phenomenon, seriously threatens ecological safety.For the chemical precipitation method common at present of ammonia nitrogen removal method in waste water, stripping Method, chemical oxidization method, bioanalysis, membrane separation process, ion-exchange etc..Metal ion waste water largely discharge also can to environment and Human health causes significant damage, metal ion such as iron, copper, lead, zinc, cadmium, cobalt, nickel etc..Common metallic wastewater processing method There are chemical precipitation method, extraction, floatation, absorption method, ion-exchange and electrochemical deposition method etc..And chemical precipitation method is most Mature, most widely used method.Ammonia nitrogen is not only contained only but in actual industrial, in waste water or contains metal ion, two Person is often to coexist.Such as hydrometallurgy, plating, PCB (printed circuit board), Rare Earth Production, garbage loading embeading generation waste water. For the processing of the compound wastewater, although having carried out numerous studies at present, fail to obtain preferable treatment effect.As specially Sharp 103964612 B of CN report a kind of high COD, high salinity, high content of beary metal middle Low Concentration Ammonia Containing Wastewater processing Method, concrete operations are that wastewater pH is adjusted to 9-11, and the ammonium ion (NH4+) in waste water is made to be converted into volatile NH3；Gold Belong to ion to remove after flocculation sedimentation, filtering；To achieve the purpose that remove ammonia nitrogen and metal ion.For another example patent CN 102942280 A report a kind of solution complexing method of heavy metal ammino-complex in high-concentration ammonia nitrogenous wastewater, concrete operations be by Wastewater pH is adjusted to 9-11, so that ammonium ion is converted into amino molecule, and there are extra hydroxide ions；Pass through control input stripping The steam flow of tower controls the Temperature Distribution of stripper with steam pressure, and the temperature region for keeping liquid certain in stripper is protected Hold certain residence time, make heavy metal ammino-complex decompose, heavy metal ion in conjunction with hydroxide ion extra in waste water, Generate precipitating.
As described above, handling the high ammonia-nitrogen wastewater of metal ion in the prior art, solution is first adjusted to high alkalinity, So that metal ion all precipitates, ammonia nitrogen is then reprocessed.But in high-alkali condition, metal cation easily with ammonia nitrogen shape At stable complex compound, to reduce the removal rate of metal cation and ammonia nitrogen.In addition, solution is in high-alkali state, although energy Metal cation is precipitated, but since ammonia nitrogen in high alkalinity can be changed into free ammonia, is conducive to be precipitated from liquid phase, will lead to a large amount of Ammonia escape.However solution is adjusted to the whole precipitatings for compared with low alkalinity, being then unfavorable for metal cation.Effectively to solve above-mentioned lance Shield, realization metal cation and ammonia nitrogen effectively remove, and are badly in need of developing a kind of novel cleaning treatment technology.
Due to conventional waste water treatment process there are long flow path, equipment is more, operating cost is high the problems such as, it is contemplated that flue gas has Waste heat is able to achieve the dry feature of waste water, and drying forms dry ash after desulfurization wastewater is atomized, then is captured by cleaner Removal.It is small with simple process, occupied area, moreover it is possible to remove the dissolubility salinity that traditional chemical technique can not be handled, such as Cl- Deng realizing the zero-emission of waste water, increasingly obtain extensive concern.But utilize the technology of fume afterheat dry acidic washes Have not been reported, and current technology be applied to acidic cleaning waste water drying there is also various disadvantages.Such as patent CN 106145230 A report a kind of system with fume afterheat processing desulfurization wastewater, and concrete operations are to add waste water by spray Entering to spray column, then waste water is evaporated using the waste heat of flue gas, the waste water after having evaporated most of water enters thickener, It is discharged after last filters pressing.This method be only waste water is concentrated, and waste water is not implemented and is completely dried, and waste water without Other processing, direct evaporation drying.It is that there is also concentrate processing hardly possiblies, and can generate largely containing metal sludge in practical application. For another example 106630259 A of patent CN reports a kind of power plant's tail end wastewater Zero discharging system, is specifically by waste water first using alkali Liquid adjusts waste water and is greater than 10, then passes through after being separated by solid-liquid separation, and the waste water of low conductivity, which returns, is used for desulfurization, the waste water of high conductivity Acid readjustment pH to 6-7 is added, then passes sequentially through filtration system, atomization system, drying system, realizes the drying and zero-emission of waste water It puts.This method is conventional waste water dry treatment process, it is clear that cannot be directly used to the processing of acidic cleaning waste water.Such as the party Method directly waste water is adjusted to first it is high-alkali, can if not removing in advance due to often containing elemental sulfur in acidic cleaning waste water So that elemental sulfur dissolution is become sodium thiosulfate, is finally decomposed into sulphur when dry and equipment is caused to block.In addition, the above method exists When dry, waste water is adjusted to neutrality, then the ammonia nitrogen in waste water cannot be made to volatilize, ammonium sulfate or hydrogen sulfate easy to form when dry Ammonium increases the viscosity of dry ash, and deduster is caused to paste bag.Effectively to solve above-mentioned a series of problems, acidic cleaning waste water is realized Cleaning is administered and zero-emission, is badly in need of developing a kind of novel cleaning treatment technology for acidic cleaning waste water feature.
Summary of the invention
It is containing elemental sulfur, suspended matter, metal, ammonia nitrogen, fluorine chlorine, organic pollutant for acidic cleaning waste water in the prior art Complicated waste water the characteristics of；The present invention is the processing method proposed on the basis of numerous studies and engineering practice, provides one kind Acidic flue gas washes Zero discharge treatment method is filtered by acidity, removes the suspended matter in waste water；By flocculation sedimentation, Remove metal ion；Pass through the substances such as dried recovered fluorine chlorine, removing organic matter again；Or ammonia is contained by the recycling of high-alkali ammonia-removal process By-product recycles the substances such as fluorine chlorine by condensation-crystallization.Acidic cleaning waste water can be effectively treated in method of the invention, realize weight The minimizing of metal dangerous waste, ammonia nitrogen cleaning is administered and reuse, to avoid elemental sulfur occluding device, the zero-emission of waste water, dust viscous Spend it is low, without paste bag phenomenon；Resource reclaim simultaneously reuses, and protects environment.
In the treatment process of multi-pollutant flue gas, it is useless to generate a large amount of acidic cleanings for active carbon SRG gas scrubbing removal of impurities Water.Its complicated component, and be emerging waste water, both at home and abroad without referential technology.There is only the controls of independent pollutant Technology, such as ammonia nitrogen heavy metal compound wastewater processing technique, but there are ammonia nitrogens the problems such as volatile, processing is not thorough, more than flue gas The problems such as heated drying waste water easily pastes bag there are the dry incomplete, crystallized product of waste water.In addition, current wastewater treatment process is not It control effectively to elemental sulfur, there are the threats of elemental sulfur occluding device.This method is by moving waste water feature and pollutant Move law-analysing, it is determined that process route is, it can be achieved that the minimizing of heavy metal dangerous waste, ammonia nitrogen cleaning is administered and reuse, waste water Zero-emission avoids elemental sulfur occluding device.
The first embodiment provided according to the present invention provides a kind of acidic flue gas washes zero discharge treatment side Method.
A kind of acidic flue gas washes Zero discharge treatment method, method includes the following steps:
1) wet scrubbing: acidic flue gas is passed through into wet scrubbing by wet scrubbing device, it is useless to obtain acidic flue gas washing Water；
2) acid filtering: acidic flue gas washes is passed through into acid filter device and carries out acid filtering, obtains suspended matter Precipitating and clear liquid；
3) clear liquid flocculates: the clear liquid obtained in step 2) imports in flocculation deposition apparatus, mixed base is added, so that clear liquid Flocculation sedimentation obtains and contains metal sludge and brine waste；
4) processing of brine waste: the brine waste that step 3) is obtained is handled by following step:
Brine waste is mixed with lye 4a), is atomized by atomizer, flue is then delivered to, passes through cigarette Flue gas in feed channel is dried, and is then dusted processing by deduster, obtains crystal salt and flue gas containing ammonia.
Second of the embodiment provided according to the present invention provides a kind of acidic flue gas washes zero discharge treatment side Method.
A kind of acidic flue gas washes Zero discharge treatment method, method includes the following steps:
1) wet scrubbing: acidic flue gas is passed through into wet scrubbing by wet scrubbing device, it is useless to obtain acidic flue gas washing Water；
2) acid filtering: acidic flue gas washes is passed through into acid filter device and carries out acid filtering, obtains suspended matter Precipitating and clear liquid；
3) clear liquid flocculates: the clear liquid obtained in step 2) imports in flocculation deposition apparatus, mixed base is added, so that clear liquid Flocculation sedimentation obtains and contains metal sludge and brine waste；
4) processing of brine waste: the brine waste that step 3) is obtained is handled by following step:
4b) brine waste obtain by-product containing ammonia except ammonia treatment and remove ammonia waste water by high-alkali ammonia removal device；So After will except ammonia waste water by condensation-crystallization device by cooling, condensation process, obtain crystal salt and clean water.
Preferably, this method further include: 5) metal recovery: passing through metal recovery containing metal sludge for what step 3) obtained Device recycles metal.
Preferably, further including oxidation operation in step 3)；Specifically: the clear liquid that step 2) obtains is passed through into oxidation unit Oxidation processes are carried out, are then imported in flocculation deposition apparatus again, mixed base are added, by weak base flocculation sedimentation process, so that clearly Liquid flocculation sedimentation obtains and contains metal sludge and brine waste.
In the present invention, the oxidation processes are using chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, air oxidation Or one of medicament oxidation or a variety of.
Preferably, step 4b) in obtain clean water be recycled to wet scrubbing device.
Preferably, the acidic flue gas is SRG gas.SRG gas are as follows: multi-pollutant flue gas is inhaled by adsorption tower Attached processing has adsorbent in adsorption tower, and the adsorbent for having adsorbed pollutant parse obtaining by Analytic Tower.
Preferably, the adsorbent be solid or liquid, more preferably adsorbent be active carbon, molecular sieve, One of MOFs, ionic liquid, organic amine are a variety of.
Preferably, step 4a) in obtain flue gas containing ammonia be delivered to adsorption tower progress circular treatment.
Preferably, suspended matter described in step 2) is precipitated as carbon dust.Preferably, powdered carbon passes through powdered carbon recycling process It is recycled for synthesizing in bulky grain active carbon return adsorption tower.
In the present invention, in step 1), (such as 0.5-10% is dense for acid solution for solution that the wet scrubbing uses The dilute hydrochloric acid or dilute sulfuric acid or dilute phosphoric acid solution of degree.Concentration is, for example, 1wt%, 4wt%, 5wt% or 7wt%).
Preferably, the pH value of acid solution is 0~7, preferably 1~6, more preferably 2~5.
Preferably, the solution is dilute sulfuric acid or dilute hydrochloric acid or phosphoric acid,diluted.
Preferably, the volume flow ratio of SRG gas and acid solution is 1:10~100, preferably during wet scrubbing For 1:20~80, more preferable 1:30~60.
In the present invention, in step 2), acidity filtering specifically: utilize suspended matter self gravity settlement action or filter Interception function removes oil removal.Concentration of suspension is 0~100mg/L, preferably 1~80mg/L in clear liquid after acidity filtering, more excellent Select 2~50mg/L.
It in the present invention, include suspended matter, metal ion, ammonia nitrogen, fluorine chlorine, organic pollutant in acidic flue gas washes One of or it is a variety of.Preferably, one of the metal ion iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel, aluminium or a variety of.
In the present invention, in step 3), flocculation sedimentation specifically: mixed base is added in clear liquid, adjusts pH value to weak base Property, so that clear liquid weak base flocculation sedimentation, obtains and contains metal sludge and brine waste.
Preferably, adjusting the pH to 7-10, preferably 7.2-9, more preferably 7.5-8.5 of clear liquid.
Preferably, mixed base is the mixture or readily soluble hydroxide that readily soluble hydroxide and readily soluble carbonate form With the mixture of readily soluble bicarbonate composition；It is further preferred that mixed base is one of sodium hydroxide, potassium hydroxide, lithium hydroxide Or it is a variety of, with one of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus or a variety of mixtures.
In the present invention, step 4a) in, the atomization specifically: clear liquid and lye mixture will be mixed by atomizer Object is separated into small droplet, and partial size is 10~100 μm, preferably 15~80 μm, more preferable 20~50 μm.
Preferably, the lye is one of readily soluble hydroxide, readily soluble carbonate, readily soluble bicarbonate or more Kind, preferably sodium hydroxide.
Preferably, the additional amount of lye is 0~0.5 times of clear liquid amount, and preferably 0.01~0.25 times, more preferable 0.05 ~0.1 times.
In the present invention, step 4a) in dust removal process using dry method dust.Preferably electric precipitation, bag-type dust Or ceramic dedusting, preferred bag-type dust.
In the present invention, after dust removal process, crystal salt is discharged from the solid outlet of deduster.
In the present invention, step 4b) in, it is described to remove ammonia treatment specifically: to be added in the brine waste that step 3) obtains Highly basic；The pH of brine waste is adjusted to 10-14, preferably 10.5-13.5, more preferably 11-13；Ammonia is separated and is returned It receives, obtain by-product containing ammonia and removes ammonia waste water.
Preferably, the separation is using stripping except ammonia, UF membrane, steaming method are except one of ammonia or a variety of methods.
Preferably, the highly basic is one of sodium hydroxide, potassium hydroxide, lithium hydroxide or a variety of.
In the present invention, step 4b) in, the cooling, condensation process specifically: be adjusted to the temperature for removing ammonia waste water low Temperature makes to obtain crystal salt and clean water except the salt condensation-crystallization in ammonia waste water.
Preferably, the low temperature is 0-30 DEG C, preferably 5-25 DEG C, more preferably 10-20 DEG C.
Preferably, the crystal salt is one of sulfate, villaumite, villiaumite or a variety of.
In the present invention, the multi-pollutant flue gas is by SO2, NOx, dust, VOCs, one of heavy metal or a variety of The mixed flue gas of composition.
In the present invention, the multi-pollutant flue gas derives from steel, electric power, coloured, petrochemical industry, chemical industry or building material industry The complicated gas containing sulfur dioxide generated.
Preferably, the volume content of multi-pollutant sulfur dioxide in flue gas be 0.01%~1%, preferably 0.03%~ 0.8%, more preferable 0.05%~0.5%.
Preferably, the temperature of multi-pollutant flue gas be 100~200 DEG C, preferably 120~180 DEG C, more preferable 130~ 160℃。
The third embodiment provided according to the present invention provides a kind of acidic flue gas washes zero discharge treatment dress It sets.
A kind of acidic flue gas washes zero discharge treatment device or for side described in first or second kind embodiment The device of method, the device include wet scrubbing device, acid filter device, flocculation deposition apparatus, atomizer, flue and remove Dirt device.Acidic flue gas is delivered to the feed inlet of wet scrubbing device.The acid filtering dress of the liquid outlet connection of wet scrubbing device It sets.The liquid outlet of acid filter device is connected to flocculation deposition apparatus.The liquid outlet of flocculation deposition apparatus is connected to atomization Device.Atomizer is connected to flue.Flue is connected to deduster.
The 4th kind of embodiment provided according to the present invention provides a kind of acidic flue gas washes zero discharge treatment dress It sets.
A kind of acidic flue gas washes zero discharge treatment device, the device include wet scrubbing device, acid filtering dress It sets, flocculation deposition apparatus, high-alkali ammonia removal device and condensation-crystallization device.Acidic flue gas is delivered to the charging of wet scrubbing device Mouthful.The liquid outlet of wet scrubbing device connects acid filter device.It is heavy that the liquid outlet of acid filter device is connected to flocculation Shallow lake device.The liquid outlet of flocculation deposition apparatus is connected to high-alkali ammonia removal device.The liquid outlet of high-alkali ammonia removal device is connected to Condensation-crystallization device.
Preferably, the device includes oxidation unit, adsorption tower and Analytic Tower.Multi-pollutant flue gas passes through flue gas delivery pipe Road is delivered to adsorption tower.The adsorbent outlet of adsorption tower is connected to Analytic Tower.The SRG gas vent of Analytic Tower is connected by pipeline To the feed inlet of wet scrubbing device.The liquid outlet of wet scrubbing device connects acid filter device.Acid filter device Liquid outlet is connected to oxidation unit.The outlet of oxidation unit is connected to flocculation deposition apparatus.
Preferably, the device includes apparatus for recovering metal.The solid outlet of flocculation deposition apparatus is connected to metal recovery Device.
Preferably, the solid outlet of acid filter device is connected to the adsorbent entrance of adsorption tower.Condensation-crystallization device 7 Clean water out be connected to wet scrubbing device.
Preferably, atomizer is equipped with alkali liquor inlet.The gas vent of deduster is connected to the gas access of adsorption tower.
In the present invention, 1) acidic flue gas washes is filtered by acid, obtain suspended matter precipitating and clear liquid；2) it took Mixed base is added in supernatant after filter, the pH of waste water is adjusted to alkalescent, metal ion forms precipitating；Filtering is obtained containing gold Belong to the filter residue and brine waste of ion precipitation object；3) brine waste is added in bypass flue by atomizer, more than flue gas Heat realizes drying crystalline, meanwhile, a certain amount of lye is added into atomizer, adjusting waste water droplet is high alkalinity；4) after dry The crystal salt of generation is recycled using deduster, and is discharged from system.
In the present invention, 1) acidic flue gas washes is filtered by acid, obtain suspended matter precipitating and clear liquid；2) it took Mixed base is added in supernatant after filter, the pH of waste water is adjusted to alkalescent, metal ion forms precipitating；Filtering is obtained containing gold Belong to the filter residue and brine waste of ion precipitation object；3) carry out by high-alkali ammonia removal device except ammonia treatment, obtain by-product containing ammonia with Except ammonia waste water；4) it then will cool down except ammonia waste water is passed through by condensation-crystallization device, condensation process, and obtain crystal salt and cleaning Water.
The technical principle of technique:
1) acidic precipitation/acidity filtering: pass through gravity in acid condition using the easily settled property of suspended matter itself Effect and acid filter, realize that suspended matter is filtered in acidity.
2) waste water flocculation weak base precipitating: is adjusted to by alkalescent, pH≤10 using mixed base；Metal cation meeting and OH-、 CO3 2-Or HCO3 -Deng generation precipitation reaction, indissoluble substance is formed.And by additional flocculating agents, precipitating is settled, is realized in waste water The removal of metal cation, and the hardness of waste water is reduced simultaneously.
3) waste water atomization and alkali tune: since droplet is easily evaporated to dryness, using air compressor machine to waste water pressurization after, be atomized and be 10~100 μm of partial size improves waste water rate of drying.Simultaneously as high-alkali lower ammonia is easily escaped from waste water, workshop ring is caused Border deteriorates and the ammonia nitrogen rate of recovery is low.Purpose using atomization alkali tune is the waste water droplet after being atomized, in confined space reality PH >=10 are now quickly adjusted, realization mineralized nitrogen is free ammonia, while avoiding the escaping of ammonia caused by open type alkali tune.
4) crystallization recycling: solid is conventional inorganic salts mainly based on sulfate, villaumite, villiaumite after solution evaporation, can Removal may be recovered using filter dedusting material of the diameter less than 1 μm.Common dedusting material includes cloth bag, ceramics, metal film Deng.After waste water passes through acid filter and remove suspended substances, short grained acid droplet is become by atomizer, since partial size is small, Large specific surface area and mass transfer rate are high, can quickly contact and occur neutralization reaction with the lye after atomization, form alkali droplet, and It quickly absorbs flue gas heat and realizes drying crystalline.Due to eliminating heavy metal by weak base flocculation sedimentation, the crystallization after drying Salt is free of heavy metal, reduces the harmfulness of crystal salt, realizes fluorine chlorine harmlessness disposing.
5) powdered carbon recycling: activated carbon adsorption and desorption process can generate a large amount of activity due to chemical wear and mechanical loss Powdered carbon, a part of powdered carbon separate after being sized with the active carbon after desorption, and a part of powdered carbon can enter waste water with stripping gas.This Invention is based on powdered carbon granularmetric analysis and surface hydrophobicity characteristic, by rationally designing filter condition, in acid condition filtered wastewater In powdered carbon, and after drying with sieve lower powdered carbon and mix, for carrying out powdered carbon granulation, burning, landfill, realize the recycling of powdered carbon It utilizes, reduces operating cost.
6) ammonia nitrogen cleans recycling: after ammonia enters flue gas, a part and SO2In conjunction with becoming ammonium sulfite, a part with NOx occurs SCR and reacts to form nitrogen.Since ammonium sulfite is unstable, the ammonium sulfite of generation is easily regenerated in active carbon high-temp It is decomposed into ammonia and SO in the process2.Since ammonia is highly soluble in water, washes can be almost fully entered.The present invention is using mixed Alkali precipitation of heavy metals under weak base (7~9) is closed, except the technology of ammonia or recycling ammonia under high-alkali (11~14), can effectively avoid high-alkali The escape of ammonia caused by when precipitation of heavy metals and formation metal ammonia nitrogen stable comple, that realizes ammonia nitrogen cleans recycling or place Reason.
7) fluorine chlorine is innoxious: the fluorine chlorine in flue gas is easily tightly held by activated carbon, and is then desorbed at high temperature, and then enters washing In waste water.Since the solubility of fluorine villaumite in water is reduced with the reduction of temperature, this method is in heavy metal in waste water and ammonia After nitrogen is removed, the crystallization of fluorine villaumite is precipitated using solution temperature is reduced.It avoids and is precipitated jointly with heavy metal and ammonium salt is difficult The problem of crystallization, reduces the harmfulness of crystal salt, realizes fluorine chlorine harmlessness disposing.
In the present invention, after by wet scrubbing, the acidic cleaning waste water of generation includes the powdered carbon of suspended state, containing gold Belong to the waste water solution of ion；By the partially acidic washes by acid filtering, by the suspended matter (such as powdered carbon) in waste water It separates, obtains powdered carbon, which can be recycled by powdered carbon recycling process, for example, by using being granulated again Process obtains bulky grain active carbon, then loops to adsorption tower.In waste water after suspended matter is separated containing metal ion (or Metal salt), it is clear liquid；Clear liquid is passed through into flocculation sedimentation process, mixed base is added in clear liquid, so that the overwhelming majority in clear liquid Heavy metal ion all forms sediment, into metal sludge is contained, then carries out metal recovery to containing metal sludge, obtains pure Other purposes can be sold or be used for metal recovery object.The brine waste obtained after flocculation sedimentation process is containing Aqueous slkali is added in salt waste water, after atomization, is dried using the heat that smoke conveying duct comes out, passes through flocculation The metal ion that precipitation process does not precipitate crystallizes after passing through drying in brine waste, with chloride ion, the fluorine in waste water Ion, sulfate ion etc., by being added in brine waste, lye forms clear liquid and lye mixture passes through flue gas delivery pipe During the heat that road comes out is dried, volatilization is moisture, forms crystal salt.Volatilization is pollution-free substance. Other purposes can be sold or be used as to the crystal salt, generate economic value.The crystal salt is sulfate, villaumite, fluorine Salt.
In second of embodiment of the invention, after wet scrubbing, the acidic cleaning waste water of generation includes suspending Powdered carbon, the metal ion of state；By the partially acidic washes by acid filtering, by the suspended matter (i.e. powdered carbon) in waste water It separates, obtains powdered carbon, which can be recycled by powdered carbon recycling process, for example, by using being granulated again Process obtains bulky grain active carbon, then loops to adsorption tower.In waste water after suspended matter is separated containing metal ion (or Metal salt), it is clear liquid；Clear liquid after acidic cleaning removes COD in clear liquid by oxidation operation so that in clear liquid organic matter at Divide and largely reduces；Then by flocculation sedimentation, heavy metal ion therein is eliminated, metal ion, which enters, contains metal sludge, so Afterwards by metal recovery process, collection and enriched in metals, other purposes are sold or are used as.After flocculation sedimentation process Brine waste passes through high-alkali ammonia-removal process, removes the ammonia in brine waste, obtains by-product containing ammonia and removes ammonia waste water；By-product containing ammonia Object can sell, and generate economic value.Except ammonia waste water passes through condensation-crystallization, chloride ion, fluorine ion, sulfate ion are removed Deng；Obtain crystal salt and clean water；The crystal salt is sulfate, villaumite, villiaumite.Crystal salt can sell, and generate warp Ji value.The crystallization processes water of remainder is recycled to wet scrubbing process, can be recycled.
Using method of the invention, after multi-pollutant flue gas is using active carbon processing, active carbon may be implemented to recycle completely And it recycles.Sulfide in pollutant is recovered as sulfur byproduct species.Metal ion can largely pass through flocculation sedimentation work Sequence and metal recovery process are recycled, and remaining chloride ion, fluorine ion, sulfate ion etc. become crystal salt.To really It realizes the collaboration of multi-pollutant flue gas to administer, wastewater zero discharge does not generate the effect of secondary pollution, while also having recycled more pollutions Metal ion (or heavy metal ion) in object flue gas.Turn waste into wealth, reuses, save the cost, Resource recovery, protection ring Border.
In the present invention, the SRG gas refers to the enriched flue gas being discharged after desorber parsing.SRG gas (or be SRG flue gas) there is temperature height, dust-laden height, SO2The features such as content is high, moisture content is high, flue gas sundries complicated component.In this field In, SRG gas is also referred to as sulfur-rich gas；Relieving haperacidity is carried out for being delivered to acid making system.
Compared with prior art, method of the invention has following advantageous effects:
(1) method of the invention handles pickling flue gas washing waste water, is filtered by acidity, prevents powdered carbon from blocking；Prevent sulphur Colloid dissolves to form sodium thiosulfate, and decomposes when dry；
(2) acid filtered clear liquid is by flocculation sedimentation process, so that heavy metal forms heavy metal precipitation, prevents a huge sum of money Belong to and enter crystal salt, realizes dangerous waste minimizing；Meanwhile flocculation sedimentation process uses mixed base, guarantees mild alkaline conditions, ammonia is avoided to wave Hair and formation metal ammonia nitrogen complex compound；
(3) ammonia-containing water of flocculation sedimentation process is dry using the waste heat of flue gas in flue by atomizer；Using High-alkali atomization is conducive to recycle ammonia；Alkalinity is dry, prevents from forming the by-products such as highly viscous ammonium hydrogen sulfate；
(4) present invention uses mixed base precipitation of heavy metals under weak base (7~9), and ammonia or recycling are removed under high-alkali (11~14) The technology of ammonia, when can effectively avoid high-alkali precipitation of heavy metals caused by ammonia escape and form metal ammonia nitrogen stable comple, it is real Existing ammonia nitrogen cleans recycling or processing.
(5) since the solubility of fluorine villaumite in water is reduced with the reduction of temperature, this method is in heavy metal in waste water And after ammonia nitrogen is removed, the crystallization of fluorine villaumite is precipitated using solution temperature is reduced.It avoids and is precipitated jointly with heavy metal and ammonium The problem of salt difficulty crystallizes reduces the harmfulness of crystal salt, realizes fluorine chlorine harmlessness disposing.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of acidic flue gas washes Zero discharge treatment method of the present invention；
Fig. 2 is a kind of process flow chart of the second method of acidic flue gas washes zero discharge treatment of the present invention；
Fig. 3 is a kind of process flow chart of the third method of acidic flue gas washes zero discharge treatment of the present invention；
Fig. 4 is a kind of structural schematic diagram of acidic flue gas washes zero discharge treatment device of the present invention；
Fig. 5 is a kind of structural schematic diagram of second of device of acidic flue gas washes zero discharge treatment of the present invention.
Appended drawing reference: 1: wet scrubbing device；2: acid filter device；3: flocculation deposition apparatus；4: atomizer；5: dedusting Device；6: high-alkali ammonia removal device；7: condensation-crystallization device；8: apparatus for recovering metal；9: oxidation unit；10: adsorption tower；11: parsing Tower；L1: flue.
Specific embodiment
The first embodiment provided according to the present invention provides a kind of acidic flue gas washes zero discharge treatment side Method.
A kind of acidic flue gas washes Zero discharge treatment method, method includes the following steps:
1) wet scrubbing: acidic flue gas is passed through into wet scrubbing by wet scrubbing device 1, it is useless to obtain acidic flue gas washing Water；
2) acid filtering: acidic flue gas washes is passed through into acid filter device 2 and carries out acid filtering, obtains suspended matter Precipitating and clear liquid；
3) clear liquid flocculates: the clear liquid obtained in step 2) imports in flocculation deposition apparatus 3, mixed base is added, so that clearly Liquid flocculation sedimentation obtains and contains metal sludge and brine waste；
4) processing of brine waste: the brine waste that step 3) is obtained is handled by following step:
Brine waste is mixed with lye 4a), is atomized by atomizer 4, flue L1 is then delivered to, passes through Flue gas in flue is dried, and is then dusted processing by deduster 5, obtains crystal salt and flue gas containing ammonia.
Second of the embodiment provided according to the present invention provides a kind of acidic flue gas washes zero discharge treatment side Method.
A kind of acidic flue gas washes Zero discharge treatment method, method includes the following steps:
1) wet scrubbing: acidic flue gas is passed through into wet scrubbing by wet scrubbing device 1, it is useless to obtain acidic flue gas washing Water；
2) acid filtering: acidic flue gas washes is passed through into acid filter device 2 and carries out acid filtering, obtains suspended matter Precipitating and clear liquid；
3) clear liquid flocculates: the clear liquid obtained in step 2) imports in flocculation deposition apparatus 3, mixed base is added, so that clearly Liquid flocculation sedimentation obtains and contains metal sludge and brine waste；
4) processing of brine waste: the brine waste that step 3) is obtained is handled by following step:
4b) brine waste obtain by-product containing ammonia except ammonia treatment and remove ammonia waste water by high-alkali ammonia removal device 6； Then it will cool down except ammonia waste water is passed through by condensation-crystallization device 7, condensation process, and obtain crystal salt and clean water.
Preferably, this method further include: 5) metal recovery: passing through metal recovery containing metal sludge for what step 3) obtained Device 8 recycles metal.
Preferably, further including oxidation operation in step 3)；Specifically: the clear liquid that step 2) obtains is passed through into oxidation unit 9 carry out oxidation processes, are then imported in flocculation deposition apparatus 3 again, and mixed base is added, by weak base flocculation sedimentation process, so that Clear liquid flocculation sedimentation obtains and contains metal sludge and brine waste.
In the present invention, the oxidation processes are using chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, air oxidation Or one of medicament oxidation or a variety of.
Preferably, step 4b) in obtain clean water be recycled to wet scrubbing device 1.
Preferably, the acidic flue gas is SRG gas.SRG gas are as follows: multi-pollutant flue gas is carried out by adsorption tower 10 Adsorption treatment has adsorbent in adsorption tower 10, and the adsorbent for having adsorbed pollutant parse obtaining by Analytic Tower 11.
Preferably, the adsorbent be solid or liquid, more preferably adsorbent be active carbon, molecular sieve, One of MOFs, ionic liquid, organic amine are a variety of.
Preferably, step 4a) in obtain flue gas containing ammonia be delivered to adsorption tower 10 progress circular treatment.
Preferably, suspended matter described in step 2) is precipitated as carbon dust.Preferably, powdered carbon passes through powdered carbon recycling process For synthesize bulky grain active carbon return adsorption tower 10) in be recycled.
In the present invention, in step 1), (such as 0.5-10% is dense for acid solution for solution that the wet scrubbing uses The dilute hydrochloric acid or dilute sulfuric acid or dilute phosphoric acid solution of degree.Concentration is, for example, 1wt%, 4wt%, 5wt% or 7wt%).
Preferably, the pH value of acid solution is 0~7, preferably 1~6, more preferably 2~5.
Preferably, the solution is dilute sulfuric acid or dilute hydrochloric acid or dilute phosphoric acid solution.
Preferably, during wet scrubbing, the volume flow ratio of SRG gas and solution is 1:10~100, preferably 1: 20~80, more preferable 1:30~60.
In the present invention, in step 2), acidity filtering specifically: utilize suspended matter self gravity settlement action or filter Interception function removes oil removal.Concentration of suspension is 0~100mg/L, preferably 1~80mg/L in clear liquid after acidity filtering, more excellent Select 2~50mg/L.
It in the present invention, include suspended matter, metal ion, ammonia nitrogen, fluorine chlorine, organic pollutant in acidic flue gas washes One of or it is a variety of.Preferably, one of the metal ion iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel, aluminium or a variety of.
In the present invention, in step 3), flocculation sedimentation specifically: mixed base is added in clear liquid, adjusts pH value to weak base Property, so that clear liquid weak base flocculation sedimentation, obtains and contains metal sludge and brine waste.
Preferably, adjusting the pH to 7-10, preferably 7.2-9, more preferably 7.5-8.5 of clear liquid.
Preferably, mixed base is the mixture or readily soluble hydroxide that readily soluble hydroxide and readily soluble carbonate form With the mixture of readily soluble bicarbonate composition；It is further preferred that mixed base is one of sodium hydroxide, potassium hydroxide, lithium hydroxide Or it is a variety of, with one of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus or a variety of mixtures.
In the present invention, step 4a) in, the atomization specifically: clear liquid and lye mixture will be mixed by atomizer Object is separated into small droplet, and partial size is 10~100 μm, preferably 15~80 μm, more preferable 20~50 μm.
Preferably, the lye is one of readily soluble hydroxide, readily soluble carbonate, readily soluble bicarbonate or more Kind, preferably sodium hydroxide.
Preferably, the additional amount of lye is 0~0.5 times of clear liquid amount, and preferably 0.01~0.25 times, more preferable 0.05 ~0.1 times.
In the present invention, step 4a) in dust removal process using dry method dust.Preferably electric precipitation, bag-type dust Or ceramic dedusting, preferred bag-type dust.
In the present invention, after dust removal process, crystal salt is discharged from the solid outlet of deduster 5.
In the present invention, step 4b) in, it is described to remove ammonia treatment specifically: to be added in the brine waste that step 3) obtains Highly basic；The pH of brine waste is adjusted to 10-14, preferably 10.5-13.5, more preferably 11-13；Ammonia is separated and is returned It receives, obtain by-product containing ammonia and removes ammonia waste water.
Preferably, the separation is using stripping except ammonia, UF membrane, steaming method are except one of ammonia or a variety of methods.
Preferably, the highly basic is one of sodium hydroxide, potassium hydroxide, lithium hydroxide or a variety of.
In the present invention, step 4b) in, the cooling, condensation process specifically: be adjusted to the temperature for removing ammonia waste water low Temperature makes to obtain crystal salt and clean water except the salt condensation-crystallization in ammonia waste water.
Preferably, the low temperature is 0-30 DEG C, preferably 5-25 DEG C, more preferably 10-20 DEG C.
Preferably, the crystal salt is one of sulfate, villaumite, villiaumite or a variety of.
In the present invention, the multi-pollutant flue gas is by SO2, NOx, dust, VOCs, one of heavy metal or a variety of The mixed flue gas of composition.
In the present invention, the multi-pollutant flue gas derives from steel, electric power, coloured, petrochemical industry, chemical industry or building material industry The complicated gas containing sulfur dioxide generated.
Preferably, the volume content of multi-pollutant sulfur dioxide in flue gas be 0.01%~1%, preferably 0.03%~ 0.8%, more preferable 0.05%~0.5%.
Preferably, the temperature of multi-pollutant flue gas be 100~200 DEG C, preferably 120~180 DEG C, more preferable 130~ 160℃。
The third embodiment provided according to the present invention provides a kind of acidic flue gas washes zero discharge treatment dress It sets.
A kind of acidic flue gas washes zero discharge treatment device or for side described in first or second kind embodiment The device of method, the device include wet scrubbing device 1, acid filter device 2, flocculation deposition apparatus 3, atomizer 4, flue L1 and deduster 5.Acidic flue gas is delivered to the feed inlet of wet scrubbing device 1.The liquid outlet of wet scrubbing device 1 connects acid Property filter device 2.The liquid outlet of acid filter device 2 is connected to flocculation deposition apparatus 3.The liquid discharge of flocculation deposition apparatus 3 Mouth is connected to atomizer 4.Atomizer 4 is connected to flue L1.Flue L1 is connected to deduster 5.
The 4th kind of embodiment provided according to the present invention provides a kind of acidic flue gas washes zero discharge treatment dress It sets.
A kind of acidic flue gas washes zero discharge treatment device, the device include wet scrubbing device 1, acid filtering dress Set 2, flocculation deposition apparatus 3, high-alkali ammonia removal device 6 and condensation-crystallization device 7.Acidic flue gas is delivered to wet scrubbing device 1 Feed inlet.The liquid outlet of wet scrubbing device 1 connects acid filter device 2.The liquid outlet of acid filter device 2 is connected to Flocculation deposition apparatus 3.The liquid outlet of flocculation deposition apparatus 3 is connected to high-alkali ammonia removal device 6.The liquid of high-alkali ammonia removal device 6 Outlet is connected to condensation-crystallization device 7.
Preferably, the device includes oxidation unit 9, adsorption tower 10 and Analytic Tower 11.Multi-pollutant flue gas passes through flue gas Conveyance conduit L1 is delivered to adsorption tower 10.The adsorbent outlet of adsorption tower 10 is connected to Analytic Tower 11.The SRG gas of Analytic Tower 11 Outlet is connected to the feed inlet of wet scrubbing device 1 by pipeline.The acid filtering dress of the liquid outlet connection of wet scrubbing device 1 Set 2.The liquid outlet of acid filter device 2 is connected to oxidation unit 9.The outlet of oxidation unit 9 is connected to flocculation deposition apparatus 3。
Preferably, the device includes apparatus for recovering metal 8.The solid outlet of flocculation deposition apparatus 3 is connected to metal and returns Receiving apparatus 8.
Preferably, the solid outlet of acid filter device 2 is connected to the adsorbent entrance of adsorption tower 10.Condensation-crystallization dress The clean water out for setting 7 is connected to wet scrubbing device 1.
Preferably, atomizer 4 is equipped with alkali liquor inlet.The gas vent of deduster 5 is connected to the gas of adsorption tower 10 Entrance.
Embodiment 1
As shown in figure 4, a kind of acidic flue gas washes zero discharge treatment device or be used for first or second kind embodiment party The device of method described in case, the device include wet scrubbing device 1, acid filter device 2, flocculation deposition apparatus 3, atomizer 4, flue L1 and deduster 5.Acidic flue gas is delivered to the feed inlet of wet scrubbing device 1.The liquid of wet scrubbing device 1 Outlet connects acid filter device 2.The liquid outlet of acid filter device 2 is connected to flocculation deposition apparatus 3.Flocculation deposition apparatus 3 liquid outlet is connected to atomizer 4.Atomizer 4 is connected to flue L1.Flue L1 is connected to deduster 5.
Embodiment 2
Embodiment 1 is repeated, only the device includes oxidation unit 9, adsorption tower 10 and Analytic Tower 11.Multi-pollutant flue gas is logical It crosses smoke conveying duct L1 and is delivered to adsorption tower 10.The adsorbent outlet of adsorption tower 10 is connected to Analytic Tower 11.Analytic Tower 11 SRG gas vent is connected to the feed inlet of wet scrubbing device 1 by pipeline.The liquid outlet of wet scrubbing device 1 connects acid Property filter device 2.The liquid outlet of acid filter device 2 is connected to oxidation unit 9.The outlet of oxidation unit 9 is connected to flocculation Settler 3.The device includes apparatus for recovering metal 8.The solid outlet of flocculation deposition apparatus 3 is connected to apparatus for recovering metal 8. The solid outlet of acid filter device 2 is connected to the adsorbent entrance of adsorption tower 10.The clean water out of condensation-crystallization device 7 connects It is connected to wet scrubbing device 1.Atomizer 4 is equipped with alkali liquor inlet.The gas vent of deduster 5 is connected to the gas of adsorption tower 10 Entrance.
Embodiment 3
As shown in figure 5, a kind of acidic flue gas washes zero discharge treatment device, the device include wet scrubbing device 1, Acid filter device 2, flocculation deposition apparatus 3, high-alkali ammonia removal device 6 and condensation-crystallization device 7.Acidic flue gas is delivered to wet process and washes Wash the feed inlet of device 1.The liquid outlet of wet scrubbing device 1 connects acid filter device 2.The liquid of acid filter device 2 Outlet is connected to flocculation deposition apparatus 3.The liquid outlet of flocculation deposition apparatus 3 is connected to high-alkali ammonia removal device 6.The high-alkali ammonia that removes fills The liquid outlet for setting 6 is connected to condensation-crystallization device 7.
Embodiment 4
As shown in Figure 1, a kind of acidic flue gas washes Zero discharge treatment method, method includes the following steps:
1) wet scrubbing: acidic flue gas is passed through into wet scrubbing by wet scrubbing device 1, the wet scrubbing uses Solution be acid solution (i.e. dilute sulfuric acid), pH value 4；Obtain acidic flue gas washes；
2) acid filtering: acidic flue gas washes is passed through into acid filter device 2 and carries out acid filtering, utilizes suspended matter Self gravity settlement action or filter interception function remove oil removal；Obtain suspended matter precipitating and clear liquid；
3) clear liquid flocculates: the clear liquid obtained in step 2) imports in flocculation deposition apparatus 3, and sodium hydroxide and carbonic acid is added Sodium, adjusting pH is 8；So that clear liquid flocculation sedimentation, obtains and contains metal sludge and brine waste；
4) processing of brine waste: the brine waste that step 3) is obtained is handled by following step:
Brine waste is mixed with sodium hydroxide 4a), is atomized by atomizer 4, flue L1 is then delivered to, It is dried by the flue gas in flue, processing is then dusted by bag-type dust by deduster 5, is crystallized Salt and flue gas containing ammonia.
In the present embodiment, concentration of suspension is 1mg/L in clear liquid after peracidity filters.Clear liquid after acidic cleaning passes through Flocculation sedimentation eliminates heavy metal ion therein, and metal ion, which enters, contains metal sludge.Brine waste by flue into Row drying obtains crystal salt.Realize wastewater zero discharge.
Embodiment 5
As shown in Fig. 2, a kind of acidic flue gas washes Zero discharge treatment method, method includes the following steps:
1) wet scrubbing: acidic flue gas is passed through into wet scrubbing by wet scrubbing device 1, the wet scrubbing uses Solution be acid solution (i.e. dilute hydrochloric acid), pH value 4；Obtain acidic flue gas washes；
2) acid filtering: acidic flue gas washes is passed through into acid filter device 2 and carries out acid filtering, utilizes suspended matter Self gravity settlement action or filter interception function remove oil removal；Obtain suspended matter precipitating and clear liquid；
3) clear liquid flocculates: the clear liquid obtained in step 2) imports in flocculation deposition apparatus 3, and potassium hydroxide and carbonic acid is added Hydrogen potassium, adjusting pH is 8；So that clear liquid flocculation sedimentation, obtains and contains metal sludge and brine waste；
4) processing of brine waste: the brine waste that step 3) is obtained is handled by following step:
Sodium hydroxide 4b) is added in the brine waste that step 3) obtains；The pH of brine waste is adjusted to 12；To ammonia into Row separation and recycling obtain by-product containing ammonia and remove ammonia waste water.The separation uses UF membrane.Then the temperature of ammonia waste water will be removed 15 DEG C are adjusted to, makes to obtain crystal salt and clean water except the salt condensation-crystallization in ammonia waste water.The crystal salt is sulfate, chlorine Salt, villiaumite.
In the present embodiment, concentration of suspension is 1mg/L in clear liquid after peracidity filters.Clear liquid after acidic cleaning passes through Flocculation sedimentation eliminates heavy metal ion therein, and metal ion, which enters, contains metal sludge.Saliferous after flocculation sedimentation process is useless Water removes the ammonia in brine waste by high-alkali ammonia-removal process, obtains by-product containing ammonia and removes ammonia waste water；By-product containing ammonia can be with Sell, generates economic value.Except ammonia waste water passes through condensation-crystallization, chloride ion, fluorine ion are removed；Obtain crystal salt and cleaning Water；The crystal salt is sulfate, villaumite, villiaumite.Crystal salt can sell, and generate economic value.Realize waste water, exhaust gas Zero-emission.
Embodiment 6
It further include only oxidation operation in step 3) as shown in figure 3, repeating embodiment 4；Specifically: step 2) is obtained Clear liquid by oxidation unit 9 using electrochemical oxidation carry out oxidation processes, then imported in flocculation deposition apparatus 3 again, be added Mixed base, by weak base flocculation sedimentation process, so that clear liquid flocculation sedimentation, obtains and contain metal sludge and brine waste.This method Further include: 5) metal recovery: passes through apparatus for recovering metal 8 containing metal sludge for what step 3) obtained, recycle metal.Step 4a) The flue gas containing ammonia of middle acquisition is delivered to adsorption tower 10 and carries out circular treatment.
In the present embodiment, the clear liquid after acidic cleaning removes COD in clear liquid, so that organic in clear liquid by oxidation operation Object ingredient largely reduces；Then by flocculation sedimentation, heavy metal ion therein is eliminated.It is returned containing metal sludge by metal Knock off sequence, enrichment and recycling metal, directly generation economic value.Flue gas recirculation containing ammonia to adsorption tower after drying process is handled, Realize the zero-emission of waste water, exhaust gas.
Embodiment 7
Embodiment 5 is repeated, further includes only oxidation operation in step 3)；Specifically: the clear liquid that step 2) obtains is passed through Oxidation unit 9 carries out oxidation processes using electrochemical oxidation, is then imported in flocculation deposition apparatus 3 again, and mixed base is added, and passes through Weak base flocculation sedimentation process, so that clear liquid flocculation sedimentation, obtains and contain metal sludge and brine waste.This method further include: 5) golden Belong to recycling: passing through apparatus for recovering metal 8 containing metal sludge for what step 3) obtained, recycle metal.Step 4b) in obtain cleaning Water is recycled to wet scrubbing device 1.
In the present embodiment, the clear liquid after acidic cleaning removes COD in clear liquid, so that organic in clear liquid by oxidation operation Object ingredient largely reduces；Then by flocculation sedimentation, heavy metal ion therein is eliminated.It is returned containing metal sludge by metal Knock off sequence, enrichment and recycling metal, directly generation economic value.The clean water generated after condensation-crystallization processing is recycled to wet process and washes Device is washed, realizes recycling for water resource.
Embodiment 8
Embodiment 6 is repeated, the acidic flue gas is SRG gas.Multi-pollutant flue gas is carried out at absorption by adsorption tower 10 It manages, active charcoal in adsorption tower 10, the active carbon for having adsorbed pollutant parse obtaining by Analytic Tower 11.In step 2) The suspended matter is precipitated as carbon dust.Powdered carbon is inhaled by powdered carbon recycling process (being granulated again) for synthesizing bulky grain active carbon and returning Attached tower 10) in be recycled.It include suspended matter, metal ion, ammonia nitrogen, fluorine chlorine, organic pollutant in SRG gas.The metal Ionic iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel, aluminium.
In step 1), during wet scrubbing, the volume flow ratio of SRG gas and solution is 1:45.It is acid in step 2) Concentration of suspension is 1.8mg/L in clear liquid after filtering.By flocculation sedimentation process, wherein the heavy metal ion in brine waste contains Measure 6.7mg/L.
The high-sulfur gas generated in SRG gas treating process recycles sulfuric acid, remaining sulfur-bearing after Sulphur ressource chemical industry sequence Circulation of tail gas is to smoke conveying duct L1, then is focused on.Brine waste after flocculation sedimentation process is by adding alkali, mist The processes such as change, drying, dedusting become crystal salt, and crystal salt is can to sell, and generate economic benefit；Activity after hot recycling Charcoal obtains bulky grain active carbon and little particle active carbon by screening.The present embodiment fully achieves at multi-pollutant flue gas collaboration The advantage that reason, secondary pollution effectively control.Processing secondary pollution can be very good using method of the invention, turn waste into wealth, Recycling, wastewater zero discharge, save the cost, Resource recovery protect environment.
Embodiment 9
Embodiment 7 is repeated, the acidic flue gas is SRG gas.Multi-pollutant flue gas is carried out at absorption by adsorption tower 10 It manages, active charcoal in adsorption tower 10, the active carbon for having adsorbed pollutant parse obtaining by Analytic Tower 11.In step 2) The suspended matter is precipitated as carbon dust.Powdered carbon is inhaled by powdered carbon recycling process (being granulated again) for synthesizing bulky grain active carbon and returning It is recycled in attached tower 10.It include suspended matter, metal ion, ammonia nitrogen, fluorine chlorine, organic pollutant in SRG gas.The metal from Sub- iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel, aluminium.
In step 1), during wet scrubbing, the volume flow ratio of SRG gas and acid solution is 1:45.In step 2), Concentration of suspension is 1.8mg/L in clear liquid after acidity filtering.
The high-sulfur gas generated in SRG gas treating process recycles sulfuric acid after Sulphur ressource chemical industry sequence.Flocculation sedimentation work Sequence recycles most heavy metal ion, and it is useless to remove saliferous by high-alkali ammonia-removal process for the brine waste after flocculation sedimentation process Ammonia in water obtains by-product containing ammonia and removes ammonia waste water；By-product containing ammonia can sell, and generate economic value.Except ammonia is useless Water passes through condensation-crystallization, removes chloride ion, fluorine ion；Obtain crystal salt and clean water；The crystal salt be sulfate, villaumite, Villiaumite.Crystal salt can sell, and generate economic value.

Claims (13)

1. a kind of acidic flue gas washes Zero discharge treatment method, method includes the following steps:
1) wet scrubbing: acidic flue gas is passed through into wet scrubbing by wet scrubbing device (1), it is useless to obtain acidic flue gas washing Water；
2) acid filtering: acidic flue gas washes is passed through into acid filter device (2) and carries out acid filtering, it is heavy to obtain suspended matter Shallow lake and clear liquid；
3) clear liquid flocculates: the clear liquid obtained in step 2) imports in flocculation deposition apparatus (3), mixed base is added, so that clear liquid Flocculation sedimentation obtains and contains metal sludge and brine waste；
4) processing of brine waste: the brine waste that step 3) is obtained is handled by following step:
Brine waste is mixed with lye 4a), is atomized by atomizer (4), flue (L1) is then delivered to, passes through Flue gas in flue is dried, and is then dusted processing by deduster (5), obtains crystal salt and flue gas containing ammonia； Or
4b) brine waste obtain by-product containing ammonia except ammonia treatment and remove ammonia waste water by high-alkali ammonia removal device (6)；So After will except ammonia waste water by condensation-crystallization device (7) by cooling, condensation process, obtain crystal salt and clean water.
2. according to the method described in claim 1, it is characterized by: this method further include: 5) metal recovery: step 3) is obtained Containing metal sludge pass through apparatus for recovering metal (8), recycle metal；And/or
It further include oxidation operation in step 3)；Specifically: the clear liquid that step 2) obtains is carried out at oxidation by oxidation unit (9) Reason, then imports again in flocculation deposition apparatus (3), and mixed base is added, by weak base flocculation sedimentation process, so that clear liquid flocculation is heavy It forms sediment, obtains and contain metal sludge and brine waste.
3. according to the method described in claim 2, it is characterized by: the oxidation processes using chemical oxidation, electrochemical oxidation, One of ultraviolet catalytic oxidation, air oxidation or medicament oxidation are a variety of；And/or
Step 4b) in obtain clean water be recycled to wet scrubbing device (1).
4. method according to any one of claim 1-3, it is characterised in that: the acidic flue gas is SRG gas, SRG Gas are as follows: multi-pollutant flue gas carries out adsorption treatment by adsorption tower (10), has adsorbent in adsorption tower (10), has adsorbed pollution The adsorbent of object parse obtaining by Analytic Tower (11)；Preferably, the adsorbent be solid or liquid, it is more excellent Choosing be adsorbent be one of active carbon, molecular sieve, MOFs, ionic liquid, organic amine or a variety of；Preferably, step The flue gas containing ammonia obtained in 4a) is delivered to adsorption tower (10) and carries out circular treatment；And/or
Suspended matter described in step 2) is precipitated as carbon dust；Preferably, powdered carbon is by powdered carbon recycling process for synthesizing big Grain active carbon, which returns in adsorption tower (10), to be recycled.
5. method according to any of claims 1-4, it is characterised in that: in step 1), the wet scrubbing is adopted Solution is acid solution；Preferably, the pH value of acid solution is 0~7, preferably 1~6, more preferably 2~5；As excellent Choosing, the acid solution are dilute sulfuric acid or dilute hydrochloric acid；During wet scrubbing, the volume flow ratio of SRG gas and acid solution For 1:10~100, preferably 1:20~80, more preferable 1:30~60.
6. method according to any one of claims 1-5, it is characterised in that: in step 2), acidity filtering specifically: benefit Oil removal is removed with suspended matter self gravity settlement action or filter interception function, concentration of suspension in clear liquid after acidity filtering For 0~100mg/L, preferably 1~80mg/L, more preferable 2~50mg/L；And/or
It include one of suspended matter, metal ion, ammonia nitrogen, fluorine chlorine, organic pollutant or a variety of in acidic flue gas washes； Preferably, one of the metal ion iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel, aluminium or a variety of.
7. method according to claim 1 to 6, it is characterised in that: in step 3), flocculation sedimentation specifically: Mixed base is added in clear liquid, adjusts pH value to alkalescent, so that clear liquid weak base flocculation sedimentation, obtains useless containing metal sludge and saliferous Water；Preferably, adjusting the pH to 7-10, preferably 7.2-9, more preferably 7.5-8.5 of clear liquid；Preferably, mixed base is The mixing of the mixture or readily soluble hydroxide and readily soluble bicarbonate composition of readily soluble hydroxide and readily soluble carbonate composition Object；It is further preferred that mixed base is one of sodium hydroxide, potassium hydroxide, lithium hydroxide or a variety of, with sodium carbonate, potassium carbonate, carbon One of sour hydrogen sodium, saleratus or a variety of mixtures.
8. method according to any one of claims 1-7, it is characterised in that: step 4a) in, the atomization specifically: Clear liquid and lye mixture pass through atomizer and mixture are separated into small droplet, and partial size is 10~100 μm, preferably 15~80 μ M, more preferable 20~50 μm；Preferably, the lye is readily soluble hydroxide, in readily soluble carbonate, readily soluble bicarbonate It is one or more, preferably sodium hydroxide；Preferably, the additional amount of lye is 0~0.5 times of clear liquid amount, preferably 0.01 ~0.25 times, more preferable 0.05~0.1 times；And/or
Step 4a) in dust removal process using dry method dust, preferably electric precipitation, bag-type dust or ceramic dedusting, preferably Bag-type dust；After dust removal process, crystal salt is discharged from the solid outlet of deduster (5).
9. according to the method described in claim 8, it is characterized by: step 4b) in, it is described to remove ammonia treatment specifically: in step 3) highly basic is added in the brine waste obtained；The pH of brine waste is adjusted to 10-14, preferably 10.5-13.5, more preferably 11-13；Ammonia is carried out separation and recycling, by-product containing ammonia is obtained and removes ammonia waste water；Preferably, the separation is removed using stripping Ammonia, UF membrane steam method except one of ammonia or a variety of methods；Preferably, the highly basic is sodium hydroxide, potassium hydroxide, hydrogen One of lithia is a variety of；And/or
Step 4b) in, the cooling, condensation process specifically: low temperature will be adjusted to except the temperature of ammonia waste water, made except in ammonia waste water Salt condensation-crystallization, obtain crystal salt and clean water；Preferably, the low temperature be 0-30 DEG C, preferably 5-25 DEG C, more preferably It is 10-20 DEG C；Preferably, the crystal salt is one of sulfate, villaumite, villiaumite or a variety of.
10. the method according to any one of claim 4-9, it is characterised in that: the multi-pollutant flue gas is by SO2、 The mixed flue gas of one of NOx, dust, VOCs, heavy metal or a variety of compositions；And/or
The multi-pollutant flue gas contains titanium dioxide from what steel, electric power, coloured, petrochemical industry, chemical industry or building material industry generated The complicated gas of sulphur；Preferably, the volume content of multi-pollutant sulfur dioxide in flue gas is 0.01%~1%, preferably 0.03%~0.8%, more preferable 0.05%~0.5%；The temperature of multi-pollutant flue gas be 100~200 DEG C, preferably 120~ 180 DEG C, more preferable 130~160 DEG C.
11. a kind of acidic flue gas washes zero discharge treatment device or for any one of claim 1-10 the method Device, the device include wet scrubbing device (1), acid filter device (2), flocculation deposition apparatus (3), atomizer (4), flue gas Pipeline (L1) and deduster (5)；Acidic flue gas is delivered to the feed inlet of wet scrubbing device (1)；The liquid of wet scrubbing device (1) Body outlet connects acid filter device (2)；The liquid outlet of acid filter device (2) is connected to flocculation deposition apparatus (3)；Flocculation The liquid outlet of settler (3) is connected to atomizer (4), and atomizer (4) is connected to flue (L1), flue (L1) It is connected to deduster (5)；Or
The device includes wet scrubbing device (1), acid filter device (2), flocculation deposition apparatus (3), high-alkali ammonia removal device (6) With condensation-crystallization device (7)；Acidic flue gas is delivered to the feed inlet of wet scrubbing device (1)；The liquid of wet scrubbing device (1) Outlet connects acid filter device (2)；The liquid outlet of acid filter device (2) is connected to flocculation deposition apparatus (3)；Flocculation is heavy The liquid outlet of shallow lake device (3) is connected to high-alkali ammonia removal device (6), and the liquid outlet of high-alkali ammonia removal device (6) is connected to condensation Crystallization apparatus (7).
12. device according to claim 11, it is characterised in that: the device include oxidation unit (9), adsorption tower (10) and Analytic Tower (11)；Multi-pollutant flue gas is delivered to adsorption tower (10) by smoke conveying duct (L1), the absorption of adsorption tower (10) Agent outlet is connected to Analytic Tower (11)；The SRG gas vent of Analytic Tower (11) is connected to wet scrubbing device (1) by pipeline Feed inlet；The liquid outlet of wet scrubbing device (1) connects acid filter device (2)；The liquid outlet of acid filter device (2) It is connected to oxidation unit (9)；The outlet of oxidation unit (9) is connected to flocculation deposition apparatus (3)；And/or
The device includes apparatus for recovering metal (8)；The solid outlet of flocculation deposition apparatus (3) is connected to apparatus for recovering metal (8).
13. device according to claim 12, it is characterised in that: the solid outlet of acid filter device (2) is connected to suction The adsorbent entrance of attached tower (10)；The clean water out of condensation-crystallization device (7) is connected to wet scrubbing device (1)；And/or
Atomizer (4) is equipped with alkali liquor inlet；The gas vent of deduster (5) is connected to the gas access of adsorption tower (10).
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