CN110124490A - A kind of active carbon handles the method and device thereof of multi-pollutant flue gas and waste water reuse - Google Patents
A kind of active carbon handles the method and device thereof of multi-pollutant flue gas and waste water reuse Download PDFInfo
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- CN110124490A CN110124490A CN201810105832.8A CN201810105832A CN110124490A CN 110124490 A CN110124490 A CN 110124490A CN 201810105832 A CN201810105832 A CN 201810105832A CN 110124490 A CN110124490 A CN 110124490A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
A kind of method that active carbon handles multi-pollutant flue gas and waste water reuse, method includes the following steps: 1) more polluting the absorption of flue gas: multi-pollutant flue gas being 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 carries out wet scrubbing, obtains high-sulfur gas and acidic cleaning waste water；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 subsequent processing: then the clear liquid that step 5) is obtained obtains by flocculation sedimentation process by oxidation operation and contains metal sludge and brine waste.Method of the invention can be very good processing secondary pollution, turn waste into wealth, and reuse, save the cost, Resource recovery, protect environment.
Description
Technical field
The present invention relates to a kind of multi-pollutant flue gas processing methods, and in particular to a kind of active carbon processing multi-pollutant flue gas
And the method and device thereof of waste water reuse.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 active carbon processing
The method of multi-pollutant flue gas and waste water reuse, this method have that multi-pollutant collaboration processing, operating cost is low, equipment investment
It saves, the advantage that cleaning is administered, secondary pollution effectively controls.Processing secondary pollution can be very good using method of the invention,
Turn waste into wealth, reuse, save the cost, Resource recovery, protects environment.
Using method of the invention, after multi-pollutant flue gas is handled by active carbon, hot recycling is carried out to active carbon, is carried out
The recycling of active carbon.The SRG gas generated during hot recycling recycles Sulphur ressource by wet scrubbing；Wet scrubbing
The waste water of generation, by filtering, oxidation, flocculation sedimentation, except the techniques such as ammonia, crystallization become clean water, be recycled to wet scrubbing work
Sequence is reused.Method of the invention can realize that active carbon and the cleaning of process water Two-way Cycle administer multi-pollutant flue gas.
The first embodiment provided according to the present invention provides a kind of active carbon processing multi-pollutant flue gas and waste water again
The method utilized.
A kind of method that active carbon handles multi-pollutant flue gas and waste water reuse, 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) subsequent processing of clear liquid: then the clear liquid that step 5) is obtained passes through flocculation sedimentation process by oxidation operation
It obtains and contains metal sludge and brine waste.
Preferably, this method further include: 7) high-alkali ammonia-removal process: being added in the brine waste that step 6) obtains strong
Alkali obtains by-product containing ammonia and removes ammonia waste water.
Preferably, this method further include: 8) condensation-crystallization: the ammonia waste water that removes that step 7) is obtained passes through cooling, condensation,
Obtain crystal salt and clean water.Preferably, clean water is recycled to wet scrubbing device.
Preferably, this method further include: 9) metal recovery: passing through metal recovery containing metal sludge for what step 6) obtained
Process recycles metal.
In the present invention, the high-alkali ammonia-removal process specifically: highly basic is added in the brine waste that step 6) obtains；It will
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, is obtained
By-product containing ammonia and remove 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.
In the present invention, the condensation-crystallization specifically: low temperature is adjusted to except the temperature of ammonia waste water by what step 7) obtained,
Make 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, oxidation described in step 6) is using chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, sky
One of gas oxidation or medicament oxidation are a variety of.
In the present invention, flocculation sedimentation process described in step 6) specifically: be added in the clear liquid obtained in step 5)
The pH of clear liquid is adjusted to alkalescent by mixed base, by weak base flocculation sedimentation, is obtained and is contained 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.
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).
Preferably, highly basic described in step 7) is one of sodium hydroxide, potassium hydroxide, lithium hydroxide 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%.
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 uses active carbon to be handled specially active carbon to more pollutions in step 1)
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 of ammonia is sprayed within the unit time as contained NOx in flue gas stream in the unit time
0.8~2 times of mole, 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, the pH value of acid solution is 0~7, preferably 1~6, more preferably 2~5.
In the present invention, during wet scrubbing, the volume flow ratio of SRG gas and acid solution is 1:10~100, excellent
It is selected as 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。
Preferably, the crystal salt that step 8) obtains carries out dust removal process after being further dried at hot wind.
Preferably, the dust removal process uses dry method dust, preferably electric precipitation, bag-type dust, in ceramic dedusting
One kind, 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 side 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
Recycling unit, acid filter device, oxidation unit, flocculation deposition apparatus.Multi-pollutant flue gas is defeated by smoke conveying duct
It send to flue gas adsorption device.The active carbon of flue gas adsorption device, which is exported, is connected to active carbon hot recycling device by conveying device.
The SRG gas vent of active carbon hot recycling device is connected to wet scrubbing device by pipeline.The high-sulfur gas of wet scrubbing device
Body outlet is connected to Sulphur ressource makeup and sets.The wastewater outlet of wet scrubbing device is connected to acid filter device.Acidity filtering dress
The liquid outlet set is connected to oxidation unit.The outlet of oxidation unit is connected to flocculation deposition apparatus.
Preferably, the device further includes high-alkali ammonia removal device, condensation-crystallization device.The liquid outlet of flocculation deposition apparatus
It is connected to high-alkali ammonia removal device.The liquid outlet of high-alkali ammonia removal device is connected to condensation-crystallization device.Condensation-crystallization device it is clean
Water purification outlet is connected to wet scrubbing device.
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 device further includes apparatus for recovering metal.The solid outlet of flocculation deposition apparatus is connected to metal and returns
Receiving apparatus.
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.
The present invention proposes a kind of active carbon and the method that multi-pollutant flue gas is administered in the cleaning of process water Two-way Cycle, technique mistake
Journey is summarized as follows with technical principle:
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) 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.
E) 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.
F) 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.
G) 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.
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 after acidic cleaning removes COD in clear liquid, so that organic components largely reduce in clear liquid by oxidation operation；So
Afterwards by flocculation sedimentation, heavy metal ion therein is eliminated, metal ion, which enters, contains metal sludge, then passes through metal recovery
Other purposes are sold or are used as to process, collection and enriched in metals.Brine waste after flocculation sedimentation process is through excessively 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 can directly go out
It sells, generates economic value.Except ammonia waste water passes through condensation-crystallization, chloride ion, fluorine ion are removed；Obtain crystal salt and clean water；Institute
Stating crystal salt is sulfate, villaumite, villiaumite.Crystal salt can sell, and generate economic value.The crystallization processes of remainder
Water 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 to become crystal salt, nitrogen oxides has become nitrogen in resolving, organic
Object has become carbon dioxide by oxidation operation.It is administered to be truly realized the collaboration of multi-pollutant flue gas, wastewater zero discharge, no
The effect of secondary pollution is generated, while also having recycled the metal ion (or heavy metal ion) in multi-pollutant flue gas.Become useless
For treasured, recycling, wastewater zero discharge；Save the cost, Resource recovery protect 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 rationalizes stepwise disposal by powdered carbon recycling and washes, realizes active carbon and industry water
Two-way Cycle recycle, greatly reduce energy and material consumption.
(3) 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.
(4) present invention carries out Rational Classification separation to heavy metal and the lesser crystal salt material stream of harmfulness, avoids and adopts
The shortcomings that sludge quantity caused by conventional limestone method is big, complicated component.
(5) present invention couples the high-alkali technique except ammonia using mixed base weak base flocculation sedimentation, avoids high-alkali precipitation of heavy metals
When caused by ammonia escape and formed metal ammonia nitrogen stable comple, that realizes ammonia nitrogen cleans recycling or processing.
To sum up, the method that multi-pollutant flue gas is administered in active carbon and process water Two-way Cycle cleaning provided by the invention has more
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 the process flow chart for the method that a kind of active carbon of the present invention handles multi-pollutant flue gas and waste water reuse；
Fig. 2 is another technique stream for the method that a kind of active carbon of the present invention handles multi-pollutant flue gas and waste water reuse
Cheng Tu；
Fig. 3 is the structural schematic diagram for the device that a kind of active carbon of the present invention handles multi-pollutant flue gas and waste water reuse.
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: oxidation unit；7: flocculation deposition apparatus；8: high-alkali ammonia removal device；
9: condensation-crystallization device；10: screening plant；11: powdered carbon recycling unit；12: apparatus for recovering metal.
Specific embodiment
The first embodiment provided according to the present invention provides a kind of active carbon processing multi-pollutant flue gas and waste water again
The method utilized.
A kind of method that active carbon handles multi-pollutant flue gas and waste water reuse, 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) subsequent processing of clear liquid: then the clear liquid that step 5) is obtained passes through flocculation sedimentation process by oxidation operation
It obtains and contains metal sludge and brine waste.
Preferably, this method further include: 7) high-alkali ammonia-removal process: being added in the brine waste that step 6) obtains strong
Alkali obtains by-product containing ammonia and removes ammonia waste water.
Preferably, this method further include: 8) condensation-crystallization: the ammonia waste water that removes that step 7) is obtained passes through cooling, condensation,
Obtain crystal salt and clean water.Preferably, clean water is recycled to wet scrubbing device 3.
Preferably, this method further include: 9) metal recovery: passing through metal recovery containing metal sludge for what step 6) obtained
Process recycles metal.
In the present invention, the high-alkali ammonia-removal process specifically: highly basic is added in the brine waste that step 6) obtains；It will
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, is obtained
By-product containing ammonia and remove 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.
In the present invention, the condensation-crystallization specifically: low temperature is adjusted to except the temperature of ammonia waste water by what step 7) obtained,
Make 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, oxidation described in step 6) is using chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, sky
One of gas oxidation or medicament oxidation are a variety of.
In the present invention, flocculation sedimentation process described in step 6) specifically: be added in the clear liquid obtained in step 5)
The pH of clear liquid is adjusted to alkalescent by mixed base, by weak base flocculation sedimentation, is obtained and is contained 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.
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).
Preferably, highly basic described in step 7) is one of sodium hydroxide, potassium hydroxide, lithium hydroxide 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%.
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 uses active carbon to be handled specially active carbon to more pollutions in step 1)
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, the mole of ammonia is sprayed within the unit time as contained NOx in flue gas stream in the unit time
0.8~2 times of mole, 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, the pH value of acid solution is 0~7, preferably 1~6, more preferably 2~5.
In the present invention, during wet scrubbing, the volume flow ratio of SRG gas and acid solution is 1:10~100, excellent
It is selected as 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。
Preferably, the crystal salt that step 8) obtains carries out dust removal process after hot wind is further dried.
Preferably, the dust removal process uses dry method dust, preferably electric precipitation, bag-type dust, in ceramic dedusting
One kind, 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 side 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 dress
It sets the makeup of 3, Sulphur ressource and sets 4, acid filter device 5, oxidation unit 6, flocculation deposition apparatus 7.Multi-pollutant flue gas passes through flue gas
Conveyance conduit L1 is delivered to flue gas adsorption device 1.The active carbon of flue gas adsorption device 1, which is exported, is connected to activity by conveying device
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.Wet process
The high-sulfur gas vent of wash mill 3 is connected to Sulphur ressource makeup and sets 4.The wastewater outlet of wet scrubbing device 3 is connected to acidity
Filter device 5.The liquid outlet of acid filter device 5 is connected to oxidation unit 6.It is heavy that the outlet of oxidation unit 6 is connected to flocculation
Shallow lake device 7.
Preferably, the device further includes high-alkali ammonia removal device 8, condensation-crystallization device 9.The liquid of flocculation deposition apparatus 7
Outlet is connected to high-alkali ammonia removal device 8.The liquid outlet of high-alkali ammonia removal device 8 is connected to condensation-crystallization device 9.Condensation-crystallization dress
The clean water out for setting 9 is connected to wet scrubbing device 3.
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 device further includes apparatus for recovering metal 12.The solid outlet of flocculation deposition apparatus 7 is connected to metal
Recyclable device 12.
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 collaboration is administered and the device of wastewater zero discharge, which includes that flue gas is defeated
Pipeline L1, flue gas adsorption device 1, active carbon hot recycling device 2, wet scrubbing device 3, Sulphur ressource makeup is sent to set 4, acid filtering
Device 5, oxidation unit 6, flocculation deposition apparatus 7.Multi-pollutant flue gas is delivered to flue gas absorption dress by smoke conveying duct L1
Set 1.The active carbon of flue gas adsorption device 1, which is exported, is connected to active carbon hot recycling device 2 by conveying device.Active carbon hot recycling
The SRG gas vent of device 2 is connected to wet scrubbing device 3 by pipeline.The high-sulfur gas vent of wet scrubbing device 3 connects
4 are set to Sulphur ressource makeup.The wastewater outlet of wet scrubbing device 3 is connected to acid filter device 5.The liquid of acid filter device 5
Body outlet is connected to oxidation unit 6.The outlet of oxidation unit 6 is connected to flocculation deposition apparatus 7.The flue gas adsorption device 1 is
Adsorption tower, the active carbon hot recycling device 2 are Analytic Tower.
Embodiment 2
Embodiment 1 is repeated, only the device further includes high-alkali ammonia removal device 8, condensation-crystallization device 9.Flocculation deposition apparatus 7
Liquid outlet be connected to high-alkali ammonia removal device 8.The liquid outlet of high-alkali ammonia removal device 8 is connected to condensation-crystallization device 9.Condensation
The clean water out of crystallization apparatus 9 is connected to wet scrubbing device 3.
The device further includes screening plant 10, powdered carbon recycling unit 11.The active carbon of active carbon hot recycling device 2 exports
It is connected to screening plant 10.The bulky grain active carbon outlet of screening plant 10 is connected to flue gas adsorption device 1.Screening plant 10
Little particle active carbon exports, the solid outlet of acid filter device 5 is connected to powdered carbon recycling unit 11.Powdered carbon recycling unit
11 discharge port is connected to flue gas adsorption device 1.
Embodiment 3
Embodiment 2 is repeated, only the device further includes apparatus for recovering metal 12.The solid outlet of flocculation deposition apparatus 7 connects
It is connected to apparatus for recovering metal 12.The sulfur-containing tail gas outlet that Sulphur ressource makeup sets 4 is connected to smoke conveying duct L1.
Embodiment 4
As shown in Figure 1, a kind of method of active carbon processing multi-pollutant flue gas and waste water reuse, this method includes following
Step:
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, 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, specifically
Are as follows: sulfur byproduct species are converted by high-sulfur gas, sulfur byproduct species are sulfuric acid；
5) processing of acidic cleaning waste water: the acidic cleaning waste water that step 3) obtains passes through acid filtering, the solution of use
For acid solution, pH value 4；The volume flow ratio of SRG gas and solution is 1:50；Obtain clear liquid and powdered carbon；
6) subsequent processing of clear liquid: the clear liquid that step 5) is obtained is by electrochemical oxidation process, then through peroxidating
Sodium hydroxide and sodium carbonate are added in clear liquid, the pH of clear liquid is adjusted to 8, by weak base flocculation sedimentation, obtains and contains metal sludge
And brine waste.
The multi-pollutant flue gas is by SO2, dust, VOCs, the mixed flue gas in heavy metal.Two in multi-pollutant flue gas
The volume content of sulfur oxide is 0.3%；The temperature of multi-pollutant flue gas is 150 DEG C.
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 removes clear liquid by oxidation operation
Middle COD, so that organic components largely reduce in clear liquid；Then by flocculation sedimentation, heavy metal ion therein is eliminated, is led to
Flocculation sedimentation process is crossed, wherein the heavy metal ion content 7.2mg/L in brine waste；Brine waste reaches discharge standard, can
With direct emission, powdered carbon can be recycled and reused.
Embodiment 5
As shown in Fig. 2, repeating embodiment 4, only this method further include:
7) sodium hydroxide high-alkali ammonia-removal process: is added in the brine waste that step 6) obtains；By the pH tune of brine waste
It saves to 12；Ammonia is carried out separation and recycling, separation removes ammonia using stripping；It obtains by-product containing ammonia and removes ammonia waste water；
8) condensation-crystallization: 15 DEG C are adjusted to except the temperature of ammonia waste water by what step 7) obtained, keeps the salt removed in ammonia waste water cold
Condensation is brilliant, obtains crystal salt and clean water；The crystal salt is sulfate, villaumite, villiaumite.
The volume content of multi-pollutant sulfur dioxide in flue gas is 0.2%；The temperature of multi-pollutant flue gas is 160 DEG C.
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.Flocculation sedimentation process recycles most heavy metal ion, wadding
Brine waste after solidifying precipitation process 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 sell, and generate economic value.Except ammonia waste water passes through condensation-crystallization, chloride ion, fluorine are removed
Ion；Obtain crystal salt and clean water；The crystal salt is sulfate, villaumite, villiaumite.Crystal salt can sell, and generate
Economic value.
Embodiment 6
Embodiment 5 is repeated, only this method further include: 9) metal recovery: passed through what step 6) obtained containing metal sludge
Metal recovery process recycles metal.
Clean water is recycled to wet scrubbing device 3 in step 7).
Step 6) contains metal sludge by existing metals recovery processes by what weak base flocculation sedimentation obtained, can recycle
Metal values；Such as iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel, aluminium.
Embodiment 7
Embodiment 6 is repeated, only step 6) is aoxidized using ultraviolet catalytic, and hydroxide then is added in the clear liquid through peroxidating
The pH of clear liquid is adjusted to 9 by potassium and saleratus.
The high-alkali ammonia-removal process specifically: highly basic is added in the brine waste that step 6) obtains；By brine waste
PH is adjusted to 10；Ammonia is carried out separation and recycling, separation uses UF membrane；It obtains by-product containing ammonia and removes ammonia waste water.Step 7)
The highly basic of middle addition is potassium hydroxide.28 DEG C are adjusted to except the temperature of ammonia waste water by what step 7) obtained in step 8).
Embodiment 8
Repeat embodiment 6, only in step 2), active carbon after hot recycling by screening, obtain bulky grain active carbon and
Little particle active carbon.Bulky grain active carbon return step 1) flue gas adsorption device 1 in be recycled.Little particle active carbon passes through
Powdered carbon recycling process synthesize bulky grain active carbon return step 1) flue gas adsorption device 1 in be recycled or be used as fuel.
Sulphur ressource chemical industry sequence obtains sulfur byproduct species and sulfur-containing tail gas in step 4).Sulfur-containing tail gas is delivered to flue gas delivery pipe
Road L1, is recycled to step 1).
The powdered carbon obtained in step 5) is used to synthesize bulky grain active carbon return step 1 by powdered carbon recycling process)
Fuel is recycled or is used as in flue gas adsorption device 1.
In the present embodiment: the active carbon after hot recycling obtains bulky grain active carbon and little particle active carbon by screening.Greatly
Granular activated carbon return step 1) flue gas adsorption device 1 in be recycled.Little particle active carbon passes through powdered carbon recycling process
Synthesis bulky grain active carbon return step 1) flue gas adsorption device 1 in be recycled.The powdered carbon obtained in step 5) passes through charcoal
Powder recycling process be used for synthesize bulky grain active carbon return step 1) flue gas adsorption device 1 in be recycled.The present embodiment
Fully achieve multi-pollutant flue gas collaboration processing, the advantage that secondary pollution effectively controls.It can be fine using method of the invention
Processing secondary pollution, turn waste into wealth, reuse, wastewater zero discharge, save the cost, Resource recovery, protect environment.
Embodiment 9
Embodiment 6 is repeated, only the multi-pollutant flue gas is by SO2, NOx, dust, VOCs, the mixing in heavy metal
Flue gas.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 into unit time is in the unit time 1 times of the mole of contained NOx in flue gas stream.In step 1)
Multi-pollutant flue gas is handled using active carbon using adverse current.The hot recycling of step 2) is using Hot-blast Heating to 320 DEG C of progress
Heating.
The crystal salt obtained in step 8) is dusted after hot wind is further dried.
Claims (15)
1. a kind of method of active carbon processing multi-pollutant flue gas and waste water reuse, 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) subsequent processing of clear liquid: then the clear liquid that step 5) is obtained is obtained by oxidation operation by flocculation sedimentation process
Containing metal sludge and brine waste.
2. according to the method described in claim 1, it is characterized by: this method further include: 7) high-alkali ammonia-removal process: in step 6)
Highly basic is added in the brine waste of acquisition, obtain by-product containing ammonia and removes ammonia waste water；
8) condensation-crystallization: ammonia waste water is removed by cooling, condensation by what step 7) obtained, obtains crystal salt and clean water；Preferably
It is that clean water is recycled to wet scrubbing device (3)；And/or
9) metal recovery: pass through metal recovery process containing metal sludge for what step 6) obtained, recycle metal.
3. according to the method described in claim 2, it is characterized by: the high-alkali ammonia-removal process specifically: obtained in step 6)
Brine waste in highly basic is added；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 removes ammonia, film using stripping
Separation steams method except one of ammonia or a variety of methods；And/or
The condensation-crystallization specifically: be adjusted to low temperature except the temperature of ammonia waste water for what step 7) obtained, make to remove in ammonia waste water
Salt condensation-crystallization obtains crystal salt and clean water；Preferably, the low temperature be 0-30 DEG C, preferably 5-25 DEG C, more preferably
10-20℃；Preferably, the crystal salt is one of sulfate, villaumite, villiaumite or a variety of.
4. method according to any one of claim 1-3, it is characterised in that: oxidation described in step 6) is using chemistry
One of oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, air oxidation or medicament oxidation are a variety of；And/or
Flocculation sedimentation process described in step 6) specifically: mixed base is added in the clear liquid obtained in step 5), by clear liquid
PH is adjusted to alkalescent, by weak base flocculation sedimentation, obtains and contains metal sludge and brine waste；Preferably, adjusting clear liquid
PH to 7-10, preferably 7.2-9, 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 active carbon in step 2), after hot recycling
By screening, bulky grain active carbon and little particle active carbon are obtained；Bulky grain active carbon return step 1) flue gas adsorption device
(1) it is recycled in；Little particle active carbon by powdered carbon recycling process synthesize bulky grain active carbon return step 1) flue gas
Fuel is recycled or is used as in adsorbent equipment (1)；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.
7. method according to claim 1 to 6, 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
Highly basic described in step 7) is one of sodium hydroxide, potassium hydroxide, lithium hydroxide or a variety of.
8. method according to any one of claims 1-7, 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.
9. method according to claim 1 to 8, 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.
10. method according to claim 1 to 9, it is characterised in that: the hot recycling be using electric heating or
Hot-blast Heating heats the active carbon of adsorption saturation；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 DEG C；And/or
The solution that the wet scrubbing uses is acid solution；Preferably, the pH value of acid solution be 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.
11. method according to claim 1 to 10, it is characterised in that: the Sulphur ressource chemical industry sequence specifically:
Sulfur byproduct species are converted by high-sulfur gas, sulfur byproduct species are sulfuric acid, sulphur, liquid SO2, sulphite, in sulfate
It is one or more, more preferably sulfuric acid is converted by 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.
12. according to the method for claim 11, it is characterised in that: the acidity is filtered into 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 crystal salt that step 8) obtains carries out dust removal process after hot wind is further dried, preferably, the dust removal process
Using dry method dust, preferably one of electric precipitation, bag-type dust, ceramic dedusting, more preferable bag-type dust.
13. a kind of multi-pollutant flue gas cooperates with the device of improvement and wastewater zero discharge or for any one of claim 1-12 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), oxidation unit (6), flocculation deposition apparatus (7)；
Multi-pollutant flue gas is delivered to flue gas adsorption device (1) by smoke conveying duct (L1), the active carbon of flue gas adsorption device (1)
Outlet is connected to active carbon hot recycling device (2) by conveying device, and the SRG gas vent of active carbon hot recycling device (2) is logical
Piping is connected to wet scrubbing device (3), and the high-sulfur gas vent of wet scrubbing device (3) is connected to Sulphur ressource makeup and sets
(4), the wastewater outlet of wet scrubbing device (3) is connected to acid filter device (5), the liquid outlet of acid filter device (5)
It is connected to oxidation unit (6), the outlet of oxidation unit (6) is connected to flocculation deposition apparatus (7).
14. device according to claim 13, it is characterised in that: the device further includes high-alkali ammonia removal device (8), condensation knot
Brilliant device (9)；The liquid outlet of flocculation deposition apparatus (7) is connected to high-alkali ammonia removal device (8), the liquid of high-alkali ammonia removal device (8)
Body outlet is connected to condensation-crystallization device (9), and the clean water out of condensation-crystallization device (9) is connected to wet scrubbing device (3)；
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).
15. device described in 3 or 14 according to claim 1, it is characterised in that: the device further includes apparatus for recovering metal (12)；
The solid outlet of flocculation deposition apparatus (7) is connected to apparatus for recovering metal (12)；And/or
The sulfur-containing tail gas outlet that (4) are set in Sulphur ressource makeup is connected to smoke conveying duct (L1) or flue gas adsorption device (1)；Make
To be preferred, the flue gas adsorption device (1) is adsorption tower, and the active carbon hot recycling device (2) is Analytic Tower.
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