CN110124507A - A kind of method and device thereof of multi-pollutant flue gas cleaning treatment - Google Patents

A kind of method and device thereof of multi-pollutant flue gas cleaning treatment Download PDF

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CN110124507A
CN110124507A CN201810105823.9A CN201810105823A CN110124507A CN 110124507 A CN110124507 A CN 110124507A CN 201810105823 A CN201810105823 A CN 201810105823A CN 110124507 A CN110124507 A CN 110124507A
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flue gas
active carbon
pollutant
gas
clear liquid
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CN110124507B (en
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叶恒棣
魏进超
杨本涛
刘昌齐
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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
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • 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
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/70—Non-metallic catalysts, additives or dopants
    • B01D2255/702—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption 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
    • C02F1/001—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
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • C02F2001/007—Processes including a sedimentation step

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  • Environmental & Geological Engineering (AREA)
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Abstract

A kind of method of multi-pollutant flue gas cleaning treatment disposition, method includes the following steps: 1) mostly pollution flue gas absorption: multi-pollutant flue gas is handled using active carbon, obtains adsorption saturation active carbon；2) active carbon hot recycling: adsorption saturation active carbon is heated to high temperature, carries out hot recycling；3) SRG gas treatment: the SRG gas that active carbon hot recycling generates obtains high-sulfur gas and acidic cleaning waste water by wet scrubbing；4) high-sulfur gas treatment: the high-sulfur gas that step 3) obtains recycles Sulphur ressource by Sulphur ressource chemical industry sequence；5) acidic cleaning wastewater treatment: the acidic cleaning waste water that step 3) obtains obtains clear liquid and powdered carbon by acid filtering；6) clear liquid flocculates: lye is added in the clear liquid obtained in step 5), so that clear liquid flocculation sedimentation, obtains and contain metal sludge and brine waste.Processing secondary pollution can be very good using method of the invention, turn waste into wealth, reuse, save the cost, Resource recovery, protect environment.

Description

A kind of method and device thereof of multi-pollutant flue gas cleaning treatment
Technical field
The present invention relates to a kind of multi-pollutant flue gas processing methods, and in particular to a kind of multi-pollutant flue gas cleaning treatment Method and device thereof.Belong to protection of natural resources and environment field.
Background technique
In the industries such as conventional steel, electric power, coloured, petrochemical industry, chemical industry or building materials, since the raw material type used is more, Often generate multiple pollutant, such as SO2, NOx, dust, VOCs, heavy metal etc..Increasingly with national environmental protection regulation and standard Strictly, in addition to major pollutants, considered critical gradually is proposed to the discharge of all kinds of minor contaminants.Such as State Ministry of Environmental Protection 2012 issuing and implementation " steel sintering, pelletizing industrial air pollution object discharge standard " (GB28662-2012) increase NOx, The discharge standard of dioxin pollution object, fluoride.This makes smoke gas treatment technology by originally to dust, SO2Single Pollution object Improvement, become the comprehensive treatment to multiple pollutant, multi-pollutant gas pollution control technology put forward new requirements.
Currently, multi-pollutant flue gas processing method in a joint manner based on, such as SCR denitration+desulfurization.But such methods exist Multi-pollutant collaboration processing it is difficult, and the increase of multi-pollutant can growth process flow sharply, cause environmental unit to take up an area face The problems such as product is big, operating cost is high.The method generallyd use at present are as follows: multi-pollutant flue gas is handled with active carbon, it then will place The active carbon for having managed multi-pollutant flue gas is parsed, and is recycled, and this method can be very good multi-pollutant fume treatment Reach discharge standard；But the active carbon for having handled multi-pollutant flue gas is secondary by generation solid, waste water etc. in resolving Pollutant, this is a problem for perplexing the field always.
An urgent demand totally improved in face of the sharp contradiction and eco-environmental quality of industrial development and atmosphere pollution, needs It researches and develops that a kind of contaminant removal efficiency is high, multi-pollutant collaboration processing technique with low investment and safe operation, and realizes by-product Resource utilization.Active carbon smoke pollution emission control technique has abundant functional group and large specific surface area using active carbon Feature can remove SO simultaneously2, NOx, dust, VOCs, the pollutants such as heavy metal, after the active carbon of adsorption saturation can be by regeneration It is recycled, there is vast potential for future development.Active carbon Flue Gas Control Technology is developed so far existing more than 50 year, both at home and abroad in succession A series of technique is had developed, representative technique has Reinluft technique, Sumitomo technique and Westvaco technique.
Although active carbon Flue Gas Control Technology is able to achieve multi-pollutant collaboration removal, actually simply by absorption-solution Pollutant is enriched with by suction, there are problems that secondary pollution.Powdered carbon as adsorption-desorption process generates does not efficiently use, Stripping gas washes fails to be effectively treated, and the high-concentration sulfur dioxide flue gas generated after desorption carries out Sulphur ressource recycling rear molding The problems such as gas is not up to standard, it is serious to limit the popularization and application of active carbon Flue Gas Control Technology.Since active carbon flue gas controls skill Art is industrially used that the time is shorter at home, and the above problem of appearance is larger compared with new and processing difficulty, and there is no can borrow in the world The technology of mirror needs entirely autonomous innovation.
Summary of the invention
The present invention is the administering method proposed on the basis of numerous studies and engineering practice, provides a kind of multi-pollutant cigarette The method of gas cleaning treatment, this method have low multi-pollutant collaboration processing, operating cost, low equipment investment, cleaning improvement, two It is secondary to pollute the advantage effectively controlled.Processing secondary pollution can be very good using method of the invention, turn waste into wealth, repeat benefit With save the cost, Resource recovery protect environment.
A kind of method of multi-pollutant flue gas cleaning treatment disposition, method includes the following steps:
1) it pollutes the absorption of flue gas more: multi-pollutant flue gas is delivered to flue gas adsorption device by smoke conveying duct, Flue gas adsorption device is provided with active carbon, and multi-pollutant flue gas is handled using active carbon, obtains adsorption saturation active carbon；
2) hot recycling of active carbon: being delivered to active carbon hot recycling device for adsorption saturation active carbon, and adsorption saturation is living Property charcoal be heated to high temperature, carry out hot recycling；
3) processing of SRG gas: the SRG gas that active carbon hot recycling generates carries out wet process by wet scrubbing device and washes It washs, obtains high-sulfur gas and acidic cleaning waste water；
4) processing of high-sulfur gas: the high-sulfur gas that step 3) obtains recycles Sulphur ressource by Sulphur ressource chemical industry sequence；
5) processing of acidic cleaning waste water: the acidic cleaning waste water that step 3) obtains by acid filtering, obtain clear liquid and Powdered carbon；
6) clear liquid flocculates: lye is added in the clear liquid obtained in step 5), so that clear liquid flocculation sedimentation, obtains and contain metal Sludge and brine waste.
Preferably, this method further include: 7) metal recovery: passing through metal recovery containing metal sludge for what step 6) obtained Process recycles metal.
Preferably, this method further include: 8) brine waste crystallizes: alkali is added in the brine waste that step 6) obtains Liquid is atomized by atomizer, is dried in the clear liquid and lye mixture input smoke conveying duct after atomization by flue gas, so After crystallize, flue gas is dusted by deduster, obtain (retention) crystal salt.
Preferably, the active carbon after hot recycling obtains bulky grain active carbon and little particle is living by screening in step 2) Property charcoal.Bulky grain active carbon return step 1) flue gas adsorption device in be recycled.Little particle active carbon passes through powdered carbon resource Chemical industry sequence synthesize bulky grain active carbon return step 1) flue gas adsorption device in be recycled or be used as fuel.
Preferably, the powdered carbon obtained in step 5) is by powdered carbon recycling process for synthesizing the return of bulky grain active carbon Fuel is recycled or is used as in the flue gas adsorption device of step 1).
Preferably, the mode of the powdered carbon recycling process is to be granulated, burn or fill again.
In the present invention, Sulphur ressource chemical industry sequence obtains sulfur byproduct species and sulfur-containing tail gas in step 4).
Preferably, sulfur-containing tail gas is delivered to smoke conveying duct, it is recycled to step 1).
In the present invention, step 6) specifically: mixed base is added in the clear liquid obtained in step 5), by the pH tune of clear liquid Section obtains by weak base flocculation sedimentation to alkalescent 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.
In the present invention, the mixed base is containing OH-And CO3 2-The mixture of composition, or for containing OH-And HCO3 -Composition Mixture.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, 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%.
In the present invention, the temperature of multi-pollutant flue gas be 100~200 DEG C, preferably 120~180 DEG C, more preferable 130 ~160 DEG C.
In the present invention, multi-pollutant flue gas is handled using active carbon in step 1) specifically: active carbon is to mostly dirty Dye object flue gas is adsorbed, the pollutant in activated carbon adsorption multi-pollutant flue gas.
Preferably, described be adsorbed as using cross-flow absorption or counter current absorption.
In the present invention, in step 1), when containing NOx in multi-pollutant flue gas, ammonia is sprayed into flue gas adsorption device Gas.Preferably, the mole that the mole for spraying into ammonia within the unit time is contained NOx in flue gas stream in the unit time 0.8~2 times, preferably 0.9~1.5 times, more preferably 1.0~1.3 times.
In the present invention, the hot recycling is to be heated the active carbon of adsorption saturation using electric heating or Hot-blast Heating.
Preferably, the temperature of hot recycling be 250 DEG C~480 DEG C, preferably 300 DEG C~450 DEG C, more preferable 360 DEG C~ 430℃。
In the present invention, the solution that the wet scrubbing uses is acid solution (such as dilute salt of 0.5-10% concentration Acid or dilute sulfuric acid or dilute phosphoric acid solution.Concentration is, for example, 1wt%, 4wt%, 5wt% or 7wt%).Preferably, acid solution PH value be 0~7, preferably 1~6, more preferably 2~5.During wet scrubbing, the volume flow of SRG gas and acid solution Than for 1:10~100, preferably 1:20~80, more preferable 1:30~60.
In the present invention, the Sulphur ressource chemical industry sequence specifically: convert sulfur byproduct species, sulfur-bearing by-product for high-sulfur gas Object is sulfuric acid, sulphur, liquid SO2, sulphite, one of sulfate or a variety of, more preferably convert sulphur for high-sulfur gas Acid.
It in the present invention, include suspended matter, metal ion, ammonia nitrogen, fluorine chlorine, organic dirt in the acidic flue gas washes Contaminate one of object or a variety of.Preferably, one of the metal ion iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel, aluminium or It is a variety of.
In the present invention, the acidity is filtered into is gone using suspended matter self gravity settlement action or filter interception function Oil removal.Concentration of suspension is 0~100mg/L, preferably 1~80mg/L, more preferable 2~50mg/ in clear liquid after acidity filtering L。
In the present invention, the atomization is that clear liquid and lye mixture pass through atomizer and mixture are separated into small droplet, Its partial size is 10~100 μm, preferably 15~80 μm, more preferable 20~50 μm.In atomization process, exhaust gas volumn and clear liquid and lye are mixed Closing object atomization quantity ratio is 1000:1~2000:1, preferably 1500:1~1800:1.
Preferably, the clear liquid and lye mixture after atomization are inputted in smoke conveying duct and are dried specifically: will In clear liquid after atomization and lye mixture input smoke conveying duct, be dried by the flue gas in smoke conveying duct and Then the partial fume is dusted processing by deduster by crystallization, crystal salt is discharged from the solid outlet of deduster, obtains Crystal salt.Preferably, the clear liquid after atomization and lye mixture can use the flue gas in smoke conveying duct and be dried Processing；Also it can use the bypass that smoke conveying duct separates, the flue gas in the bypass separated using smoke conveying duct is carried out It is dried, the mixed gas process for the flue gas and clear liquid and lye mixture in bypass for then separating smoke conveying duct Deduster, crystal salt are solid, and crystal salt is discharged from the solid outlet of deduster.
In the present invention, lye described in step 8) 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.Lye additional amount is 0~0.4 times of brine waste additional amount, preferably 0.1~0.25 Times.
In the present invention, dust removal process described in step 8) uses dry method dust.Preferably electric precipitation, bag-type dust, pottery One of porcelain dedusting, more preferable bag-type dust.
Second of the embodiment provided according to the present invention provides a kind of collaboration of multi-pollutant flue gas and administers and waste water zero-emission The device put.
A kind of collaboration of multi-pollutant flue gas is administered and the device of wastewater zero discharge or for described in the first embodiment The device of method, the device include smoke conveying duct, flue gas adsorption device, active carbon hot recycling device, wet scrubbing device, Sulphur ressource makeup sets, acid filter device, flocculation deposition apparatus.Multi-pollutant flue gas is delivered to flue gas by smoke conveying duct Adsorbent equipment.The active carbon of flue gas adsorption device, which is exported, is connected to active carbon hot recycling device by conveying device.Active carbon heat The SRG gas vent of regenerating unit is connected to wet scrubbing device by pipeline.The high-sulfur gas vent of wet scrubbing device connects Sulphur ressource makeup is connected to set.The wastewater outlet of wet scrubbing device is connected to acid filter device.The liquid of acid filter device Outlet is connected to flocculation deposition apparatus.
Preferably, the device further includes atomizer, deduster, apparatus for recovering metal.The liquid discharge of flocculation deposition apparatus Mouth is connected to atomizer.The outlet of atomizer is connected to deduster.
Preferably, atomizer is equipped with alkali liquor inlet.The solid outlet of flocculation deposition apparatus is connected to metal recovery dress It sets.
Preferably, the device further includes screening plant, powdered carbon recycling unit.The active carbon of active carbon hot recycling device Outlet is connected to screening plant.The bulky grain active carbon outlet of screening plant is connected to flue gas adsorption device.Screening plant it is small Granular activated carbon exports, the solid outlet of acid filter device is connected to powdered carbon recycling unit.Powdered carbon recycling unit goes out Material mouth is connected to flue gas adsorption device.
Preferably, the gas vent of deduster is connected to flue gas adsorption device.The solid outlet of deduster recycles crystallization Salt.
Preferably, the sulfur-containing tail gas outlet that Sulphur ressource makeup is set is connected to smoke conveying duct or flue gas absorption dress It sets.
Preferably, the flue gas adsorption device is adsorption tower, the active carbon hot recycling device is Analytic Tower.
A kind of method of multi-pollutant flue gas cleaning treatment disposition of the invention, technical process and technical principle are sketched such as Under:
a)SO2Recycling and deep purifying: based on activated carbon surface functional group is abundant and the biggish feature of specific surface area, Low concentration SO in flue gas2Gas cleaning is realized by active carbon selective absorption, the active carbon of adsorption saturation passes through reasonable heat Desorption obtains the higher high concentration SO of purity2.High concentration SO2Can respectively by oxidation, reduction, concentration, absorb with sulfuric acid, sulphur, Liquid SO2, sulfate recycled.Fail then to return to active carbon air inlet by the tail gas of effective recycling, it is de- to carry out circulation It removes, realizes SO2Recycling and deep purifying.
B) NOx is innoxious: since active carbon has strong reducing property, the nitrogen oxides in flue gas can occur in activated carbon surface Non-SCR reaction is converted into nitrogen.In addition, active carbon have surface functional group abundant, in the case that ammonia there are, can pass through SCR reaction occurs for surface catalysis, is nitrogen by conversion of nitrogen oxides.Both the above approach can make conversion of nitrogen oxides Harmless nitrogen realizes the innoxious governance of NOx.
C) dioxin is innoxious: dioxin is attracted in active carbon first and realizes gas cleaning, then can be in activity Cracking is occurred by the catalytic action of active carbon during charcoal thermal desorption and is converted into innocuous substance, the experimental results showed that desorbing 400 DEG C of 1.5h or more are kept in tower, so that it may thoroughly decompose.
D) 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.
E) minimizing containing solid waste of heavy metal: after heavy metal is tightly held by activated carbon, the overwhelming majority can enter desorption by desorption Then gas is washed purification and enters washes.Each pollutant characteristic of this method reasonable analysis is combined by stepwise disposal and is mixed Alkali (OH-And CO3 2-) weak base flocculation sedimentation heavy metal, greatly reducing heavy metal sewage sludge amount i.e. reduces dangerous solid waste amount.
F) waste water cleans evaporative crystallization: after waste water passes through acid filter and remove suspended substances, becoming little particle by atomizer Acid droplet, since partial size is small, large specific surface area and mass transfer rate are high, quickly can contact and occur with the lye after atomization Neutralization reaction forms alkali droplet, and quickly absorbs flue gas heat and realize drying crystalline.Due to being gone by weak base flocculation sedimentation In addition to heavy metal, the crystal salt after drying is free of heavy metal, reduces the harmfulness of crystal salt, realizes fluorine chlorine harmlessness disposing.
G) 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, atomization returns to flue under high-alkali (11~14), can effectively avoid high alkali precipitation weight The escape of ammonia caused by when metal and formation metal ammonia nitrogen stable comple, meanwhile, the ammonia of high-alkali precipitation can be used for active carbon Catalytic denitration, that realizes ammonia nitrogen cleans recycling.
In the present invention, the active carbon of pollutant has been adsorbed by making after active carbon hot recycling device (such as Analytic Tower) It obtains the pollutant of former absorption on the activated carbon to enter in parsing gas, the active carbon of adsorption saturation has become fresh active carbon again (active carbon that adsorption tower absorption pollutant can be used for).The active carbon that analytically tower emits is generated due to mechanical loss Big carbon content active powder, is sieved, bulky grain active carbon return step 1 by screening plant) flue gas adsorption device in recycle Use, little particle active carbon by powdered carbon recycling process synthesize bulky grain active carbon return step 1) flue gas adsorption device in It is recycled or is used as fuel；So that active carbon is recycled, is recycled.
In the present invention, gas is parsed, that is, SRG gas, by wet scrubbing, so that subsidiary one in SRG gas Part powdered carbon can enter in waste water with stripping gas, and metal ion also is soluble in water.Sulfurous gas is still gaseous state, collects high-sulfur Gas recycles Sulphur ressource by Sulphur ressource chemical industry sequence, and remaining extremely least a portion of sulfur-containing tail gas is delivered to smoke conveying duct, then It is handled by adsorption tower.Realize the zero-emission of polluted gas.
In the present invention, after by wet scrubbing, the acidic cleaning waste water of generation include the powdered carbon of suspended state, metal from Son；By the partially acidic washes by acid filtering, the suspended matter (i.e. powdered carbon) in waste water is separated, obtains charcoal Powder, the part powdered carbon can be recycled by powdered carbon recycling process, obtain bulky grain for example, by using granulating working procedure again Active carbon then loops to adsorption tower.Contain metal ion (or metal salt) in waste water after suspended matter is separated, is clear Liquid；Clear liquid is passed through into flocculation sedimentation process, mixed base is added in clear liquid, so that most heavy metal ion in clear liquid are all Sediment is formed, into metal sludge is contained, then metal recovery is carried out to containing metal sludge, obtains pure metal recovery object, It can sell or be used for other purposes.The brine waste obtained after flocculation sedimentation process adds in brine waste Enter aqueous slkali, after atomization, is dried in input smoke conveying duct using the waste heat of argon gas, passes through flocculation sedimentation process Metal ion, chloride ion, fluorine ion, sulfate ion for not precipitating etc. crystallize after passing through drying in brine waste, Generate metallic crystal salt；Other purposes can be sold or be used as to the metallic crystal salt, generate economic value.It is useless in saliferous During lye formation clear liquid and lye mixture are added in water by being dried in smoke conveying duct, metal ion, The formation such as chloride ion, fluorine ion, sulfate ion crystallization, is collected by deduster, recycles crystal salt.
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 metal ion becomes crystal salt, and nitrogen oxides becomes in resolving Nitrogen, organic matter have become carbon dioxide in resolving.It is administered to be truly realized the collaboration of multi-pollutant flue gas, waste water Zero-emission does not generate the effect of secondary pollution, at the same also recycled the metal ion in multi-pollutant flue gas (or heavy metal from Son).Turn waste into wealth, reuse, save the cost, Resource recovery, protects environment.
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) present invention is rationally designed for multi-pollutant reapective features in flue gas, realizes the depth of each pollutant Purification or recycling or harmless treatment/disposition.
(2) present invention is directed to washing active carbon Wastewater Pollutant characteristic, to heavy metal and the lesser crystal salt object of harmfulness The shortcomings that mass flow carries out Rational Classification separation, avoids, complicated component big using sludge quantity caused by conventional limestone method.
(3) present invention is atomized the technique of high alkali collection ammonia using the coupling of mixed base weak base flocculation sedimentation, avoids high alkali precipitation The escape of ammonia caused by when heavy metal and formation metal ammonia nitrogen stable comple, that realizes ammonia nitrogen cleans recycling.Alkalinity simultaneously Formation hydrogen sulfate ammonia is made when evaporation solution can avoid HF, HCl escape corrosion pipeline caused by acid solution evaporation and acidic crystallization The problems such as big at crystal salt viscosity.
(4) it uses active carbon as adsorbent in the present invention, flue gas need to be controlled in lower temperature, flue proposed by the present invention Dry technology is not only able to achieve " zero-emission " and the Ammonia recovery of washes, moreover it is possible to while realizing the cooling of flue gas, effectively The usage amount for reducing cooling wind or condensed water realizes the effective distribution and calling of thermal energy.
(5) when Sulphur ressource chemical industry skill fails to be effectively treated high-concentration sulfur dioxide, the dioxy of low concentration can be generated Change sulphur tail gas, since the present invention is process object with middle low-concentration sulfur dioxide, tail gas can return to smoke absorption, without new Increase vent gas treatment facility, cost of investment can be greatly reduced.
To sum up, the method for multi-pollutant flue gas cleaning treatment provided by the invention disposition have multi-pollutant collaboration processing, Operating cost is low, low equipment investment, cleans improvement, the advantage that secondary pollution effectively controls.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of the method for multi-pollutant flue gas cleaning treatment disposition of the present invention；
Fig. 2 is a kind of another process flow chart of the method for multi-pollutant flue gas cleaning treatment disposition of the present invention；
Fig. 3 is a kind of structural schematic diagram of the device of multi-pollutant flue gas cleaning treatment disposition of the present invention.
Appended drawing reference: L1: smoke conveying duct；1: flue gas adsorption device；2: active carbon hot recycling device；3: wet scrubbing Device；4: Sulphur ressource makeup is set；5: acid filter device；6: flocculation deposition apparatus；7: atomizer；8: deduster；9: metal returns Receiving apparatus；10: screening plant；11: powdered carbon recycling unit.
Specific embodiment
A kind of method of multi-pollutant flue gas cleaning treatment disposition, method includes the following steps:
1) it pollutes the absorption of flue gas more: multi-pollutant flue gas is delivered to flue gas adsorption device by smoke conveying duct L1 1, flue gas adsorption device 1 is provided with active carbon, and multi-pollutant flue gas is handled using active carbon, obtains adsorption saturation activity Charcoal；
2) hot recycling of active carbon: being delivered to active carbon hot recycling device 2 for adsorption saturation active carbon, and adsorption saturation is living Property charcoal be heated to high temperature, carry out hot recycling；
3) processing of SRG gas: the SRG gas that active carbon hot recycling generates carries out wet process by wet scrubbing device 3 and washes It washs, obtains high-sulfur gas and acidic cleaning waste water；
4) processing of high-sulfur gas: the high-sulfur gas that step 3) obtains recycles Sulphur ressource by Sulphur ressource chemical industry sequence；
5) processing of acidic cleaning waste water: the acidic cleaning waste water that step 3) obtains by acid filtering, obtain clear liquid and Powdered carbon；
6) clear liquid flocculates: lye is added in the clear liquid obtained in step 5), so that clear liquid flocculation sedimentation, obtains and contain metal Sludge and brine waste.
Preferably, this method further include: 7) metal recovery: passing through metal recovery containing metal sludge for what step 6) obtained Process recycles metal.
Preferably, this method further include: 8) brine waste crystallizes: alkali is added in the brine waste that step 6) obtains Liquid is atomized by atomizer (4), is done in the clear liquid and lye mixture input smoke conveying duct L1 after atomization by flue gas It is dry, it then crystallizes, flue gas is dusted by deduster 8, obtains (retention) crystal salt.
Preferably, the active carbon after hot recycling obtains bulky grain active carbon and little particle is living by screening in step 2) Property charcoal.Bulky grain active carbon return step 1) flue gas adsorption device 1 in be recycled.Little particle active carbon passes through powdered carbon resource Chemical industry sequence synthesize bulky grain active carbon return step 1) flue gas adsorption device 1 in be recycled or be used as fuel.
Preferably, the powdered carbon obtained in step 5) is by powdered carbon recycling process for synthesizing the return of bulky grain active carbon Fuel is recycled or is used as in the flue gas adsorption device 1 of step 1).
Preferably, the mode of the powdered carbon recycling process is to be granulated, burn or fill again.
In the present invention, Sulphur ressource chemical industry sequence obtains sulfur byproduct species and sulfur-containing tail gas in step 4).
Preferably, sulfur-containing tail gas is delivered to smoke conveying duct L1, it is recycled to step 1).
In the present invention, step 6) specifically: mixed base is added in the clear liquid obtained in step 5), by the pH tune of clear liquid Section obtains by weak base flocculation sedimentation to alkalescent 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.
In the present invention, the mixed base is containing OH-And CO3 2-The mixture of composition, or for containing OH-And HCO3 -Composition Mixture.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, 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%.
In the present invention, the temperature of multi-pollutant flue gas be 100~200 DEG C, preferably 120~180 DEG C, more preferable 130 ~160 DEG C.
In the present invention, multi-pollutant flue gas is handled using active carbon in step 1) specifically: active carbon is to mostly dirty Dye object flue gas is adsorbed, the pollutant in activated carbon adsorption multi-pollutant flue gas.
Preferably, described be adsorbed as using cross-flow absorption or counter current absorption.
In the present invention, it in step 1), when containing NOx in multi-pollutant flue gas, is sprayed into flue gas adsorption device (1) Ammonia.Preferably, mole that the mole for spraying into ammonia within the unit time is contained NOx in flue gas stream in the unit time 0.8~2 times of amount, preferably 0.9~1.5 times, more preferably 1.0~1.3 times.
In the present invention, the hot recycling is to be heated the active carbon of adsorption saturation using electric heating or Hot-blast Heating.
Preferably, the temperature of hot recycling be 250 DEG C~480 DEG C, preferably 300 DEG C~450 DEG C, more preferable 360 DEG C~ 430℃。
In the present invention, the solution that the wet scrubbing uses is acid solution (such as dilute salt of 0.5-10% concentration Acid or dilute sulfuric acid or dilute phosphoric acid solution.Concentration is, for example, 1wt%, 4wt%, 5wt% or 7wt%).Preferably, acid solution PH value be 0~7, preferably 1~6, more preferably 2~5.During wet scrubbing, the volume flow of SRG gas and acid solution Than for 1:10~100, preferably 1:20~80, more preferable 1:30~60.
In the present invention, the Sulphur ressource chemical industry sequence specifically: convert sulfur byproduct species, sulfur-bearing by-product for high-sulfur gas Object is sulfuric acid, sulphur, liquid SO2, sulphite, one of sulfate or a variety of, more preferably convert sulphur for high-sulfur gas Acid.
It in the present invention, include suspended matter, metal ion, ammonia nitrogen, fluorine chlorine, organic dirt in the acidic flue gas washes Contaminate one of object or a variety of.Preferably, one of the metal ion iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel, aluminium or It is a variety of.
In the present invention, the acidity is filtered into is gone using suspended matter self gravity settlement action or filter interception function Oil removal.Concentration of suspension is 0~100mg/L, preferably 1~80mg/L, more preferable 2~50mg/ in clear liquid after acidity filtering L。
In the present invention, the atomization is that clear liquid and lye mixture pass through atomizer and mixture are separated into small droplet, Its partial size is 10~100 μm, preferably 15~80 μm, more preferable 20~50 μm.
Preferably, the clear liquid and lye mixture after atomization are inputted in smoke conveying duct L1 and are dried specifically: By in the clear liquid and lye mixture input smoke conveying duct L1 after atomization, carried out by the flue gas in smoke conveying duct L1 Then the partial fume is dusted processing, solid outlet of the crystal salt from deduster 8 by deduster 8 by dry and crystallization Discharge obtains crystal salt.
In the present invention, lye described in step 8) 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.
In the present invention, dust removal process described in step 8) uses dry method dust.Preferably electric precipitation, bag-type dust, pottery One of porcelain dedusting, more preferable bag-type dust.
Second of the embodiment provided according to the present invention provides a kind of collaboration of multi-pollutant flue gas and administers and waste water zero-emission The device put.
A kind of collaboration of multi-pollutant flue gas is administered and the device of wastewater zero discharge or for described in the first embodiment The device of method, the device include smoke conveying duct L1, flue gas adsorption device 1, active carbon hot recycling device 2, wet scrubbing Device 3, Sulphur ressource makeup set 4, acid filter device 5, flocculation deposition apparatus 6.Multi-pollutant flue gas passes through smoke conveying duct L1 is delivered to flue gas adsorption device 1.The active carbon of flue gas adsorption device 1, which is exported, is connected to active carbon hot recycling by conveying device Device 2.The SRG gas vent of active carbon hot recycling device 2 is connected to wet scrubbing device 3 by pipeline.Wet scrubbing device 3 High-sulfur gas vent be connected to Sulphur ressource makeup set 4.The wastewater outlet of wet scrubbing device 3 is connected to acid filter device 5. The liquid outlet of acid filter device 5 is connected to flocculation deposition apparatus 6.
Preferably, the device further includes atomizer 7, deduster 8, apparatus for recovering metal 9.The liquid of flocculation deposition apparatus 6 Body outlet is connected to atomizer 7.The outlet of atomizer 7 is connected to deduster 8.Deduster 8 is arranged on smoke conveying duct L1.
Preferably, atomizer 7 is equipped with alkali liquor inlet.The solid outlet of flocculation deposition apparatus 6 is connected to metal recovery Device 9.
Preferably, the device further includes screening plant 10, powdered carbon recycling unit 11.Active carbon hot recycling device 2 Active carbon outlet is connected to screening plant 10.The bulky grain active carbon outlet of screening plant 10 is connected to flue gas adsorption device 1.Sieve The little particle active carbon outlet of separating device 10, the solid outlet of acid filter device 5 are connected to powdered carbon recycling unit 11.Powdered carbon The discharge port of recycling unit 11 is connected to flue gas adsorption device 1.
Preferably, the sulfur-containing tail gas outlet that Sulphur ressource makeup sets 4 is connected to smoke conveying duct L1 or flue gas absorption Device 1.
Preferably, the flue gas adsorption device 1 is adsorption tower, the active carbon hot recycling device 2 is Analytic Tower.
Embodiment 1
As shown in figure 3, a kind of multi-pollutant flue gas cooperates with the device of improvement and wastewater zero discharge or for the first implementation The device of method described in scheme, the device include smoke conveying duct L1, flue gas adsorption device 1, active carbon hot recycling device 2,4, acid filter device 5, flocculation deposition apparatus 6 are set in wet scrubbing device 3, Sulphur ressource makeup.Multi-pollutant flue gas passes through cigarette Letter shoot road L1 is delivered to flue gas adsorption device 1.The active carbon of flue gas adsorption device 1, which is exported, is connected to work by conveying device Property charcoal hot recycling device 2.The SRG gas vent of active carbon hot recycling device 2 is connected to wet scrubbing device 3 by pipeline.It is wet The high-sulfur gas vent of method wash mill 3 is connected to Sulphur ressource makeup and sets 4.The wastewater outlet of wet scrubbing device 3 is connected to acid Property filter device 5.The liquid outlet of acid filter device 5 is connected to flocculation deposition apparatus 6.The flue gas adsorption device 1 is to inhale Attached tower, the active carbon hot recycling device 2 are Analytic Tower.
Embodiment 2
Embodiment 1 is repeated, only the device further includes atomizer 7, deduster 8, apparatus for recovering metal 9.Flocculation sedimentation dress The liquid outlet for setting 6 is connected to atomizer 7.The outlet of atomizer 7 is connected to deduster 8.Deduster 8 is arranged in flue gas delivery pipe On road L1.Atomizer 7 is equipped with alkali liquor inlet.The solid outlet of flocculation deposition apparatus 6 is connected to apparatus for recovering metal 9.The dress Set further includes screening plant 10, powdered carbon recycling unit 11.The active carbon outlet of active carbon hot recycling device 2 is connected to screening dress Set 10.The bulky grain active carbon outlet of screening plant 10 is connected to flue gas adsorption device 1.The little particle active carbon of screening plant 10 It exports, the solid outlet of acid filter device 5 is connected to powdered carbon recycling unit 11.The discharge port of powdered carbon recycling unit 11 connects It is connected to flue gas adsorption device 1.The sulfur-containing tail gas outlet that Sulphur ressource makeup sets 4 is connected to smoke conveying duct L1 or flue gas absorption Device 1.
Embodiment 3
As shown in Figure 1, a kind of method of multi-pollutant flue gas cleaning treatment disposition, method includes the following steps:
1) it pollutes the absorption of flue gas more: multi-pollutant flue gas is delivered to flue gas adsorption device by smoke conveying duct L1 1, flue gas adsorption device 1 is provided with active carbon, and multi-pollutant flue gas is handled using cross-flow absorption using active carbon, inhaled Attached saturated activity charcoal；
2) hot recycling of active carbon: being delivered to active carbon hot recycling device 2 for adsorption saturation active carbon, and adsorption saturation is living Property charcoal by electric heating to 400 DEG C, carry out hot recycling；
3) processing of SRG gas: the SRG gas that active carbon hot recycling generates carries out wet process by wet scrubbing device 3 and washes It washs, the solution that wet scrubbing uses is dilute sulfuric acid, pH value 5；The volume flow ratio of SRG gas and dilute sulfuric acid is 1:40, is obtained High-sulfur gas and acidic cleaning waste water；
4) processing of high-sulfur gas: the high-sulfur gas that step 3) obtains recycles Sulphur ressource by Sulphur ressource chemical industry sequence；Sulphur money Source chemical industry sequence obtains sulfur byproduct species and sulfur-containing tail gas；Sulfur-containing tail gas is delivered to smoke conveying duct L1, is recycled to step 1)；
5) processing of acidic cleaning waste water: the acidic cleaning waste water that step 3) obtains by acid filtering, obtain clear liquid and Powdered carbon；The powdered carbon of acquisition by powdered carbon recycling process be used for synthesize bulky grain active carbon return step 1) flue gas adsorption device Fuel is recycled or is used as in 1；
6) clear liquid flocculates: sodium hydroxide and sodium carbonate being added in the clear liquid obtained in step 5), the pH of clear liquid is adjusted To 8, by weak base flocculation sedimentation, obtains and contain metal sludge and brine waste.
The mode of the powdered carbon recycling process is to be granulated again.The multi-pollutant flue gas is by SO2, dust, VOCs, again Mixed flue gas in metal.The volume content of multi-pollutant sulfur dioxide in flue gas is 0.3%；The temperature of multi-pollutant flue gas is 150℃。
In the present embodiment, concentration of suspension is 1mg/L in clear liquid after peracidity filters.It is produced in SRG gas treating process Raw high-sulfur gas recycles completely after Sulphur ressource chemical industry sequence；Clear liquid after acidic cleaning eliminates it by flocculation sedimentation In heavy metal ion, can be recycled and reused with direct emission, powdered carbon.
Embodiment 4
As shown in Fig. 2, repeating embodiment 1, only this method further include: 7) metal recovery: by step 6) obtain containing gold Belong to sludge and pass through metal recovery process, recycles metal.
This method further include: 8) brine waste crystallizes: lye is added in the brine waste that step 6) obtains, passes through atomization Device (4) atomization, clear liquid and lye mixture after atomization input in smoke conveying duct (L1) to be dried by flue gas, is then tied Crystalline substance, flue gas are dusted by deduster 8, obtain (retention) crystal salt.
Potassium hydroxide and saleratus are added in step 6), the pH of clear liquid is adjusted to 9, by weak base flocculation sedimentation, is obtained Metal sludge and brine waste must be contained.
Multi-pollutant flue gas is handled using active carbon by counter current absorption in step 1), and in step 2), hot recycling is By Hot-blast Heating to 380 DEG C, the active carbon after hot recycling obtains bulky grain active carbon and little particle active carbon by screening. Bulky grain active carbon return step 1) flue gas adsorption device 1 in be recycled.Little particle active carbon passes through powdered carbon resource engineering chemistry Sequence synthesize bulky grain active carbon return step 1) flue gas adsorption device 1 in be recycled.The powdered carbon obtained in step 5) passes through Powdered carbon recycling process be used for synthesize bulky grain active carbon return step 1) flue gas adsorption device 1 in be recycled.The charcoal The mode of powder recycling process is to be granulated again.
The solution that wet scrubbing uses in step 3) is dilute hydrochloric acid, pH value 4；The volume flow of SRG gas and dilute sulfuric acid Than for 1:20；
Sulphur ressource chemical industry sequence obtains sulfuric acid and sulfur-containing tail gas in step 4)；Sulfur-containing tail gas is delivered to smoke conveying duct L1, It is recycled to step 1).
Sodium hydroxide is added in the clear liquid that step 8) obtains, the additional amount of sodium hydroxide is 0.08 times of clear liquid amount；It is logical Atomizer (4) atomization is crossed, is dried in the clear liquid and lye mixture input smoke conveying duct L1 after atomization, then ties Crystalline substance is dusted by deduster 8, obtains crystal salt；The deduster 8 is bag filter.Dioxy in multi-pollutant flue gas The volume content for changing sulphur is 0.2%；The temperature of multi-pollutant flue gas is 160 DEG C.
In the present embodiment, concentration of suspension is 1.8mg/L in clear liquid after peracidity filters.By flocculation sedimentation process, The wherein heavy metal ion content 6.7mg/L in brine waste.
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.Bulky grain active carbon return step 1) flue gas adsorb dress It sets in 1 and is recycled.Little particle active carbon by powdered carbon recycling process synthesize bulky grain active carbon return step 1) flue gas It is recycled in adsorbent equipment 1.The powdered carbon obtained in step 5) is by powdered carbon recycling process for synthesizing bulky grain active carbon Return step 1) flue gas adsorption device 1 in be recycled.The present embodiment fully achieves multi-pollutant flue gas collaboration and handles, is secondary Pollute the advantage effectively controlled.Processing secondary pollution can be very good using method of the invention, turn waste into wealth, repeat benefit With wastewater zero discharge, save the cost, Resource recovery protect environment.
Embodiment 5
Embodiment 4 is repeated, only the multi-pollutant flue gas is by SO2, NOx, dust, VOCs, the mixing in heavy metal Flue gas.In step 1), ammonia is sprayed into flue gas adsorption device 1；When the mole for spraying into ammonia in unit time is the unit 1 times of the mole of contained NOx in interior flue gas stream.

Claims (14)

1. a kind of method of multi-pollutant flue gas cleaning treatment disposition, method includes the following steps:
1) it pollutes the absorption of flue gas more: multi-pollutant flue gas is delivered to flue gas adsorption device by smoke conveying duct (L1) (1), flue gas adsorption device (1) is provided with active carbon, and multi-pollutant flue gas is handled using active carbon, and it is living to obtain adsorption saturation Property charcoal；
2) hot recycling of active carbon: being delivered to active carbon hot recycling device (2) for adsorption saturation active carbon, by adsorption saturation activity Charcoal is heated to high temperature, carries out hot recycling；
3) processing of SRG gas: the SRG gas that active carbon hot recycling generates carries out wet scrubbing by wet scrubbing device (3), Obtain high-sulfur gas and acidic cleaning waste water；
4) processing of high-sulfur gas: the high-sulfur gas that step 3) obtains recycles Sulphur ressource by Sulphur ressource chemical industry sequence；
5) processing of acidic cleaning waste water: the acidic cleaning waste water that step 3) obtains obtains clear liquid and powdered carbon by acid filtering；
6) clear liquid flocculates: lye is added in the clear liquid obtained in step 5), so that clear liquid flocculation sedimentation, obtains and contain metal sludge And brine waste.
2. according to the method described in claim 1, it is characterized by: this method further include:
7) metal recovery: pass through metal recovery process containing metal sludge for what step 6) obtained, recycle metal；And/or
8) brine waste crystallizes: lye is added in the brine waste that step 6) obtains, is atomized by atomizer (4), after atomization Clear liquid and lye mixture input smoke conveying duct (L1) in be dried by flue gas, then crystallize, flue gas passes through dedusting Device (8) is dusted, while obtaining crystal salt.
3. method according to claim 1 or 2, it is characterised in that: in step 2), the active carbon after hot recycling is through being sieved Point, obtain bulky grain active carbon and little particle active carbon；Bulky grain active carbon return step 1) flue gas adsorption device (1) in follow Ring uses；Little particle active carbon by powdered carbon recycling process synthesize bulky grain active carbon return step 1) flue gas adsorption device (1) fuel is recycled or is used as in；And/or
The powdered carbon obtained in step 5) is used to synthesize bulky grain active carbon return step 1 by powdered carbon recycling process) flue gas Fuel is recycled or is used as in adsorbent equipment (1)；Preferably, the mode of the powdered carbon recycling process is to be granulated, fire again It burns or fills.
4. method according to any one of claim 1-3, it is characterised in that: Sulphur ressource chemical industry sequence is contained in step 4) Sulphur by-product and sulfur-containing tail gas；Preferably, sulfur-containing tail gas is delivered to smoke conveying duct (L1), it is recycled to step 1)；And/or
Step 6) specifically: mixed base is added in the clear liquid obtained in step 5), the pH of clear liquid is adjusted to alkalescent, is passed through Weak base flocculation sedimentation obtains and contains metal sludge and brine waste；Preferably, adjusting the pH to 7-10, preferably 7.2- of clear liquid 9, more preferably 7.5-8.5.
5. according to the method described in claim 4, it is characterized by: the mixed base is containing OH-And CO3 2-The mixture of composition, Or for containing OH-And HCO3 -The mixture of composition；Preferably, mixed base is that readily soluble hydroxide and readily soluble carbonate form The mixture of mixture or readily soluble hydroxide and readily soluble bicarbonate composition；It is further preferred that mixed base is sodium hydroxide, hydrogen-oxygen Change potassium, one of lithium hydroxide or a variety of, with one of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus or a variety of Mixture.
6. method according to any one of claims 1-5, 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.
7. method according to claim 1 to 6, it is characterised in that: multi-pollutant flue gas is using work in step 1) Property charcoal is handled specially active carbon and is adsorbed to multi-pollutant flue gas, the pollution in activated carbon adsorption multi-pollutant flue gas Object；Preferably, described be adsorbed as using cross-flow absorption or counter current absorption；And/or
In step 1), when containing NOx in multi-pollutant flue gas, ammonia is sprayed into flue gas adsorption device (1)；Preferably, The mole that ammonia is sprayed within the unit time is in the unit time 0.8~2 times of the mole of contained NOx in flue gas stream, Preferably 0.9~1.5 times, more preferably 1.0~1.3 times.
8. method according to any one of claims 1-7, it is characterised in that: the hot recycling is using electric heating or heat Wind, which heats, heats the active carbon of adsorption saturation；Preferably, the temperature of hot recycling is 250 DEG C~480 DEG C, preferably 300 DEG C ~450 DEG C, more preferable 360 DEG C~430 DEG C；And/or
The solution that the wet scrubbing uses is acid solution；Preferably, the pH value of solution is 0~7, preferably 1~6, more Preferably 2~5；During wet scrubbing, the volume flow ratio of SRG gas and acid solution is 1:10~100, preferably 1:20 ~80, more preferable 1:30~60.
9. method according to claim 1 to 8, it is characterised in that: the Sulphur ressource chemical industry sequence specifically: will High-sulfur gas is converted into sulfur byproduct species, and sulfur byproduct species are sulfuric acid, sulphur, liquid SO2, sulphite, one in sulfate Kind is a variety of, more preferably converts sulfuric acid for high-sulfur gas；And/or
In the acidic flue gas washes include one of suspended matter, metal ion, ammonia nitrogen, fluorine chlorine, organic pollutant 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.
10. according to the method described in claim 9, it is characterized by: the acidity be filtered into it is heavy using suspended matter self gravity Drop effect or filter interception function remove oil removal, and concentration of suspension is 0~100mg/L in clear liquid after acidity filtering, and preferably 1 ~80mg/L, more preferable 2~50mg/L；And/or
The atomization is that clear liquid and lye mixture pass through atomizer and mixture are separated into small droplet, and partial size is 10~100 μ M, preferably 15~80 μm, more preferable 20~50 μm；Preferably, the clear liquid and lye mixture after atomization input flue gas delivery pipe It is dried in road (L1) specifically: by the clear liquid and lye mixture input smoke conveying duct (L1) after atomization, pass through Flue gas in smoke conveying duct (L1) is dried and crystallizes, and is then dusted the partial fume by deduster (8) Processing, crystal salt are discharged from the solid outlet of deduster (8), obtain crystal salt.
11. according to the method described in claim 10, it is characterized by: lye described in step 8) is readily soluble hydroxide, easily One of molten carbonate, readily soluble bicarbonate are a variety of, preferably sodium hydroxide；Preferably, the additional amount of lye is clear 0~0.5 times of liquid measure, preferably 0.01~0.25 times, more preferable 0.05~0.1 times；And/or
Dust removal process described in step 8) uses dry method dust, preferably one of electric precipitation, bag-type dust, ceramic dedusting, More preferable bag-type dust.
12. a kind of multi-pollutant flue gas cooperates with the device of improvement and wastewater zero discharge or for any one of claim 1-11 institute State the device of method, the device include smoke conveying duct (L1), flue gas adsorption device (1), active carbon hot recycling device (2), Wet scrubbing device (3), Sulphur ressource makeup set (4), acid filter device (5) and flocculation deposition apparatus (6)；Multi-pollutant flue gas It is delivered to flue gas adsorption device (1) by smoke conveying duct (L1), the active carbon outlet of flue gas adsorption device (1) passes through conveying Device is connected to active carbon hot recycling device (2), and the SRG gas vent of active carbon hot recycling device (2) is connected to by pipeline Wet scrubbing device (3), the high-sulfur gas vent of wet scrubbing device (3) are connected to Sulphur ressource makeup and set (4), wet scrubbing dress The wastewater outlet for setting (3) is connected to acid filter device (5), and the liquid outlet of acid filter device (5) is connected to flocculation sedimentation Device (6).
13. device according to claim 12, it is characterised in that: the device further includes atomizer (7), deduster (8), gold Belong to recyclable device (9)；The liquid outlet of flocculation deposition apparatus (6) is connected to atomizer (7), and the outlet of atomizer (7) is connected to Deduster (8), deduster (8) are arranged on smoke conveying duct (L1)；Preferably, atomizer (7) is equipped with alkali liquor inlet； The solid outlet of flocculation deposition apparatus (6) is connected to apparatus for recovering metal (9)；And/or
The device further includes screening plant (10), powdered carbon recycling unit (11)；The active carbon of active carbon hot recycling device (2) goes out Mouth is connected to screening plant (10), and the bulky grain active carbon outlet of screening plant (10) is connected to flue gas adsorption device (1), is sieved The little particle active carbon outlet of device (10), the solid outlet of acid filter device (5) are connected to powdered carbon recycling unit (11), The discharge port of powdered carbon recycling unit (11) is connected to flue gas adsorption device (1).
14. device according to claim 12 or 13, it is characterised in that: the sulfur-containing tail gas outlet of (4) is set in Sulphur ressource makeup It is connected to smoke conveying duct (L1) or flue gas adsorption device (1)；Preferably, the flue gas adsorption device (1) is absorption Tower, the active carbon hot recycling device (2) are Analytic Tower.
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CN114053839A (en) * 2020-08-05 2022-02-18 中冶长天国际工程有限责任公司 Method and system for cleaning and treating cyanogen-containing SRG gas and purifying hot blast stove tail gas
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