CN105561755B - A kind of clean flue gas biological desulphurization method of denitration and device - Google Patents
A kind of clean flue gas biological desulphurization method of denitration and device Download PDFInfo
- Publication number
- CN105561755B CN105561755B CN201410533038.5A CN201410533038A CN105561755B CN 105561755 B CN105561755 B CN 105561755B CN 201410533038 A CN201410533038 A CN 201410533038A CN 105561755 B CN105561755 B CN 105561755B
- Authority
- CN
- China
- Prior art keywords
- biological desulphurization
- flue gas
- denitration
- sulfide
- hydrogen sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention belongs to field of environmental biotechnology, in particular it relates to a kind of clean flue gas biological desulphurization method of denitration and device.The present invention is combined by denitrification, sulfate reduction, methane phase, sulphur oxidation production four biological respinses of elemental sulfur and sulfide stripping/hydrogen sulfide absorption, sulfureous in flue gas oxide is collected and is converted into the sulphur of high-purity, conversion of nitrogen oxides is nitrogen, and regeneration of absorption solution, save the consumption of alkali and water.In addition, processing procedure does not generate solid waste and waste water, secondary pollution is not generated.
Description
Technical field
The invention belongs to field of environmental biotechnology, in particular it relates to which a kind of clean flue gas biological desulphurization takes off
Nitre method and device.
Background technology
Containing a large amount of sulfur and nitrogen oxides in the flue gas that the fuel combustions such as coal generate, these oxides are air
Major pollutants.Flue gas sulfur and nitrogen oxides have been classified as the main monitor control index of Air Pollution Control by country.At present,
People have been presented for a variety of flue gas desulfurization and denitration methods, and Part Methods have been achieved with industrial applications.However, these methods are still deposited
In serious secondary pollution problem, generate substantial amounts of difficult waste liquid and give up admittedly, such as high sulfate-containing wastewater and calcium sulfate are consolidated
Body etc..In actual production, since processing cost is high or cannot handle, these discarded objects often only with stacking and landfill etc.
Simple processing method disposal.A kind of flue gas desulfurization and denitration technique for cleaning non-secondary pollution is urgently developed in atmosphere pollution.
Due to sulfureous in flue gas oxide easily with water react generation sulfuric acid, see reaction equation 1-2, thus flue gas desulfurization frequently with
The methods of washing, alkali cleaning, wherein limestone-gypsum method are most ripe, the most widely used methods of flue gas oxysulfide removing.
The principle of limestone-gypsum method is to utilize lime stone and the sulfuric acid of oxysulfide generation and the solid sulphuric acid of sulfurous acid reaction generation
Calcium (gypsum), is shown in reaction equation 3.The desulfurated plaster of calcium salt method flue gas desulfurization generation is calcium sulfate hydrate, with natural gypsum property
There are significant differences, and recycling difficulty is larger, and of high cost, majority of case is disposed in a manner of stacking.
SO2+H2O→H2SO3 (1)
SO3+H2O→H2SO4 (2)
Limestone-gypsum method absorbs oxysulfide, easily fouling and clogging with lime white, influences the continuous operation of equipment.For
Overcome the problems, such as this, the Dual alkali using soda Dual alkali as representative is developed.Soda Dual alkali is with NaOH or Na2CO3Solution
Absorb the SO in flue gasx, then again with lime stone or lime treatment regeneration of absorption solution NaOH or Na2CO3, see formula 4 and 5.Though
So, soda Dual alkali solves the problems, such as limestone-gypsum method fouling for the Dual alkali of representative, but still generates substantial amounts of half
Hydrated calcium sulfate, it is also necessary to gypsum, solid waste processing cost higher could be made through processing.Flue gas desulfurization generates a large amount of de-
Sulphur gypsum problem is still unresolved.
Research shows that it is by sulfate and sulfurous acid by biological respinse to solve the intractable most effective approach of desulfurated plaster
Salt is converted into elemental sulfur and recycles, and principle is that sulfate and sulphite are first reduced to sulfide by sulfate reducing bacteria, then by
Sulfur oxidizing bacterium is oxidized to elemental sulfur, sees formula 6 and 7.
2HS-+O2→2S0+OH- (7)
Based on above-mentioned principle, flue gas biological desulphurization method is developed, and absorbs oxysulfide first with organic wastewater,
Oxysulfide is converted into sulfate and sulphite, by the sulfate reduction of microorganism by sulphur in anaerobic reactor
Hydrochlorate and sulphite are reduced to sulfide, and the water outlet of sulfur compound enters in aerobic reactor, and list is oxidized to by sulfur oxidizing bacterium
Matter sulphur (CN 2010105553188, CN200510076816).However, above-mentioned flue gas biological desulphurization technical process is aobvious there are two
Work problem：First, high sulfate-containing wastewater category is most difficult to processing one of waste water, is field of waste water treatment research hotspot, sulfate reduction
The sulfide of generation has anaerobic digestion strong inhibition effect, and sulfureous in flue gas oxide is absorbed into waste water, adds waste water
Intractability and cost.As Chinese patent CN201220477214 and CN201110133900 are directed to high-sulfate waste water difficulty
The problem of reason, proposes solution method.Also, the gas-liquid absorbed due to the limitation of sulphates content in waste water, flue gas oxysulfide
Than relatively low, absorbent dosage is big, high energy consumption.2nd, in wastewater treatment system containing substantial amounts of organic matter, in aerobic sulphur oxidation process
Elemental sulfur is not only generated, but also generates a large amount of sludge, forms sulphur and mud mixture, sulfur content is low, cost recovery.Example
As Chinese patent CN200910077456 proposes halogenated hydrocarbons, alkyl or aryl disulphide or alkylnaphthalene and Naphtha solvent
The method for extracting sulphur, however, this method not only there is it is of high cost the problem of, but also can generate intractable containing organic solvent
Waste water.Since sulphur economic value is relatively low, so the sulphur mud mixture of low sulphur content does not have recovery value.Cause
This, existing flue gas biological desulphurization method can not achieve cost-effective sulphur recovery.
In addition, flue gas biological desulphurization is dramatically different with sulfate wastewater treatment, flue gas pollutant is gaseous state oxysulfide, no
Containing organic matter.Ideally, oxysulfide should be converted into elemental sulfur by flue gas biological desulphurization, do not generated any waste water and given up
Gas.Since sulfate reducing bacteria needs electron donor to complete sulfate reduction, so flue gas biological desulphurization wants additional organic
Object, but the type and quantity of organic matter may be selected, is controllable.The absorbing liquid of flue gas biological desulphurization is answered renewable and can cycled
It utilizes, so as to reduce the water consumption of flue gas biological desulphurization, avoids discharge of wastewater, avoid generating secondary pollution, flue gas biological desulphurization
It is also differ in that with sulfate wastewater treatment, nitrate nitrogen can be contained in absorbing liquid, and sulfate wastewater contains ammonium nitrogen.
During flue gas biological desulphurization, while oxysulfide absorbs, nitrogen oxides can also be absorbed, and can realize flue gas
Biological synchronized desulfuring and denitrifying.It is consequently formed the absorbing liquid of containing sulfate and nitrate nitrogen, anaerobic denitrifying and sulfate reduction
There are substrate competition relations.Flue gas biological desulphurization technique needs to consider the collaboration processing of sulfate and nitrate nitrogen, is set by technique
Meter can solve the problems, such as that denitrification and sulfate reduction are vied each other, and establish flue gas biology synchronized desulfuring and denitrifying.
The content of the invention
The purpose of the invention is to provide a kind of cleaning flue gases biological desulphurization denitrating technique, to realize this technology mesh
Mark, the present invention use following technical solution：
The cleaning flue gases biological desulphurization method of denitration of the present invention, comprises the following steps：
(1) flue gas biological desulphurization coproduction elemental sulfur：
(1-1) absorbs the sulfur and nitrogen oxides in flue gas with weak lye, forms acid absorption rich solution；
(1-2) adds organic matter to acid absorb of step (1-1) in rich solution, form acid mixed solution, mixed using acidity
Liquid acidifying is closed, sulfide is converted into hydrogen sulfide by stripping；
The hydrogen sulfide gas that (1-3) stripping generates is absorbed by lye, and the sulfur compound rich solution of generation is aoxidized by biological sulphur
Reaction is converted into elemental sulfur；
(2) denitrification joint sulfate reduction：
(2-1) supplementary carbon source into the absorption rich solution after step (1-2) stripping hydrogen sulfide, it is anti-by simultaneous oxygen denitrification
Should, will absorb nitrate-nitrogen reduction in rich solution is nitrogen；
The absorption rich solution of (2-2) after step (2-1) denitration is by anaerobism sulfate reduction, by sulfuric acid therein
Salt and sulphite are reduced to sulfide；
(2-3) makes the waste water after step (2-2) sulfate reduction be reacted by anaerobic methane production, and remaining organic matter is turned
Turn to methane；
The waste water of (2-4) after the reaction of step (2-3) anaerobic methane production carries out aerobic reaction, removes carbon source.
Specifically, cleaning flue gases biological desulphurization method of denitration of the present invention, comprises the following steps：
(1) flue gas biological desulphurization coproduction elemental sulfur：
(1-1) absorbs the sulfur and nitrogen oxides in flue gas with weak lye, forms acid absorption rich solution；
(1-2) adds organic matter to acid absorb of step (1-1) in rich solution, form acid mixed solution, acid mixed solution
It into sulfide stripping tower, is acidified using acid mixed solution, sulfide is converted into hydrogen sulfide by stripping；
The hydrogen sulfide gas that (1-3) stripping generates is absorbed by the hydrogen sulfide absorption tower of the liquid containing soda ash, the sulfur compound of generation
Rich solution is sent into biological sulphur oxidation reactor and is converted into elemental sulfur；
(2) denitrification joint sulfate reduction：
The absorption rich solution of (2-1) after step (1-2) stripping hydrogen sulfide enters in simultaneous oxygen denitrification reactor, supplements carbon
Source, will absorb nitrate-nitrogen reduction in rich solution is nitrogen；
The absorption rich solution of (2-2) after step (2-1) denitration enters anaerobism sulfate reduction device, by sulfate and
Sulphite is reduced to sulfide；
(2-3) makes the waste water after step (2-2) sulfate reduction enter anaerobic methane production reactor for treatment, has remaining
Machine object is converted into methane；
The waste water of (2-4) after the reaction of step (2-3) anaerobic methane production enters aerobic aeration pond, removes carbon source.
The present invention absorbs the sulfur and nitrogen oxides in flue gas with weak lye, forms acid absorption rich solution.To absorb
Suitable organic matter is added in rich solution, nitrate nitrogen in rich solution will be first absorbed and is converted into nitrogen, then be by sulfate reduction therein
Sulfide.Rich solution is absorbed using acidity to be acidified, and sulfide is converted into hydrogen sulfide, using the method for gas stripping by the sulphur of conversion
Change hydrogen migration to gas phase, hydrogen sulfide absorption is converted back into sulfide again with soda ash liquid, the separating-purifying of sulfide is completed, makes vulcanization
Object is separated with organic matter.Sulfide after purification is converted into elemental sulfur by chemoautotroph sulfur oxidizing bacterium, is centrifuged through precipitation
To biological sulphur.Since sulfide is free from foreign meter, so Recovered sulphur purity is high, wanting for commodity sulphur is can reach without processing
It asks.It absorbs rich solution to handle through denitrification and sulfate reduction, nitrogen oxides and oxysulfide absorb the nitrate nitrogen and sulfuric acid to be formed
Salt is substantially completely removed.But denitrification and sulfate reduction cannot degradable organic matters, it is therefore desirable to pass through again
Cross anaerobic methane production processing residual organic substances are degradable for methane and carbon dioxide.Denitrification, sulfate reduction, methane phase
Three reactions can produce alkali, and smoke absorption liquid can be regenerated, recycled, and flue gas biological desulphurization denitration water be greatly decreased, alkali disappears
Consumption.
Cleaning flue gases biological desulphurization method of denitration according to the present invention to realize recycling for intermediate product, reaches clear
The environmentally friendly purpose of clean flue gas, preferably, nitrogen made from the step (2-1) enter gas collection and processing system, warp
For the inertia circulating carried between step (1-2) hydrogen sulfide stripping and step (1-3) hydrogen sulfide absorption after purification pressurization.It is described
The return of waste water step (1-2) of sulfur compound participates in hydrogen sulfide conversion after step (2-2) anaerobism sulfate reduction.It is described
Waste water after (2-4) aerobic reaction enters buffer pool as the weak lye in step (1-1), absorb oxysulfide in flue gas and
Nitrogen oxides.
Cleaning flue gases biological desulphurization method of denitration according to the present invention, step (1-1) described weak lye are 0.2~0.5M's
NaHCO3Solution.
The step (1-1) during sulfur and nitrogen oxides are absorbed, need to make acidity by controlling gas liquid ratio
The pH value for absorbing rich solution is down to 4.0~5.0.Oxysulfide, which absorbs, to form sulfuric acid and sulfurous acid can reduce pH value, control sulphur oxidation
Object uptake makes the pH value of rich solution be down to 4.0~5.0, is conducive to sulfide stripping.
Cleaning flue gases biological desulphurization method of denitration according to the present invention, the organic matter of step (1-2) described addition is ethyl alcohol,
Lactic acid or one or more of lactate or glucose.
The NaHCO that lye in step (1-3) of the present invention is 0.2~0.5M of concentration3.Generation in step (1-3)
The finished product sulphur of purity >=99% can be further made in elemental sulfur after precipitation and centrifugation.
Step (2-1) the of the present invention carbon source is ethyl alcohol, lactic acid or one or more of lactate and glucose.
The pH value of step (2-4) the of the present invention aerobic reaction>7.0.Sulfate reduction generate waste water after stripping, into
Enter aerobic tank processing.The carbon source of sulfide of the water inlet of aerobic tank containing stripping remnants and sulfate reduction remnants, these substances
Oxidation production acid can reduce the pH value of aerobic tank and, it is necessary to mend alkali aerobic tank pH be kept to stablize.In addition, aerobic tank water outlet is directly used in cigarette
Gas sulphur oxide absorbs, and higher ph is maintained to be conducive to absorb.
Biology sulphur oxidation reaction of the present invention and oxygen anti-nitration reaction, anaerobism sulfate reduction and methane phase
Using the existing bacterial strain that can carry out above-mentioned reaction, anaerobism and oxygen it is preferable to use municipal sewage plant are become reconciled for reaction
Oxygen activity sludge.
The device based on above-mentioned cleaning flue gases biological desulphurization method of denitration of this offer, including flue gas biological desulphurization coproduction
Elemental sulfur system combines sulfate reduction system with denitrification；
The flue gas biological desulphurization coproduction elemental sulfur system include smoke absorption tower 1, mixing tank 2, sulfide stripping tower 7,
Hydrogen sulfide absorption tower 8 and biological sulphur oxidation reactor 9；
The denitrification joint sulfate reduction system includes and oxygen denitrification reactor 3, anaerobism sulfate reduction
Device 4, anaerobic methane production reactor 5 and aerobic aeration pond 6；
The smoke absorption tower 1 is sequentially connected with mixing tank 2, sulfide stripping tower 7, hydrogen sulfide absorption tower 8 and biological sulphur
Oxidation reactor 9；
Described and oxygen denitrification reactor 3 and sulfide stripping tower 7, and be sequentially connected with anaerobism sulfate reduction device 4,
Anaerobic methane production reactor 5 and aerobic aeration pond 6.
Cleaning flue gases biological desulphurization denitrification apparatus according to the present invention, it is preferable that sulfide stripping tower 7 and hydrogen sulfide absorption
Gas flow cycle is equipped between tower 8；Described and oxygen denitrification reactor 3 is further connected with gas collection and processing system
12, the connection gas collection and processing system 12 are communicated in gas stream between sulfide stripping tower 7 and hydrogen sulfide absorption tower 8
Logical circuit.
It is further preferred that the anaerobism sulfate reduction device 4 is connected with mixing tank 2.
Preferably, the aerobic aeration pond 6 is connected another step by buffer pool 14 with smoke absorption tower 1.
Biology sulphur oxidation reactor 9 of the present invention is also further sequentially connected with sulphur sedimentation basin 10 and sulphur centrifuge
11, for purifying sulphur.
Advantages of the present invention is：Compared with prior art, technique provided by the invention converts the oxysulfide in flue gas
For elemental sulfur, and high-purity elemental sulfur is can obtain through simple physical method, be truly realized sulphur recovery；It is anti-using biology
Nitrification, anaerobism sulfate reduction and methane phase reaction production alkali effect, realize regeneration of absorption solution and recycle；Sulphur oxygen in flue gas
Compound and nitrogen oxides are separately converted to elemental sulphur and nitrogen, and sulfur recovery rate thoroughly solves cigarette higher than 90%
Desulfurization denitration secondary pollution problem, realizes cleaning flue gases biological desulphurization denitration.
Description of the drawings
Fig. 1 is cleaning flue gases biological desulphurization denitrating technique flow chart of the present invention.
Fig. 2 is the handling result to different sulfoxide concentration simulated flue gas.
Fig. 3 is the handling result to different sulfur and nitrogen oxides scale modeling flue gases.
Fig. 4 is the handling result of true flue gas.
Reference numeral
1st, smoke absorption tower 2, mixing tank 3 and oxygen denitrification reactor
4th, anaerobism sulfate reduction device 5, anaerobic methane production reactor
6th, aerobic aeration pond 7, sulfide stripping tower 8, hydrogen sulfide absorption tower
9th, biological sulphur oxidation reactor 10, sulphur sedimentation basin 11, sulphur centrifuge
12nd, gas collection and processing system 13, methane recovery system 14, buffer pool
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the embodiment invented is without being limited thereto.
1 cleaning flue gases biological desulphurization denitrating technique flow of embodiment
As shown in Figure 1, the cleaning flue gases biological desulphurization denitrification integral process of the present invention is mainly by smoke absorption, sulfide
Stripping/hydrogen sulfide absorption and oxygen denitrification, anaerobism sulfate reduction, anaerobic methane production, micro- oxygen sulphur oxidation production elemental sulfur, sulphur
Recycling and aerobic aeration tank composition.Concrete technology flow process is as follows：
1) with 0.2~0.5M NaHCO3For absorbing liquid, absorbed in absorption tower 1 and wait to locate by what dedirt and cooling were handled
The sulfur and nitrogen oxides in flue gas are managed, by controlling gas liquid ratio, the pH value of absorption rich solution are made to be down to 4.0~5.0.
2) absorb rich solution and anaerobism sulfate reduction device 4 flows back and is mixed to form acid mixed solution in mixing tank 2, mix
It closes liquid and enters sulfide stripping tower 7, sulfide is converted into hydrogen sulfide by stripping, and pH is increased to 5.5~6.0.
3) the H 2 S-containing gas hydrogen absorption tower 8 that cures that stripping generates absorbs, and the sulfur compound rich solution of generation is sent into life
Elemental sulfur is converted into object sulphur oxidation reactor 9.The elemental sulfur of generation is through precipitating (sulphur sedimentation basin 10) and centrifuging (sulphur
Centrifuge 11) the finished product sulphur of purity >=99% is made.The waste liquid that centrifugation generates is returned in biological sulphur oxidation reactor 9.Anaerobism
The sulfide that sulfate reduction generates is aoxidized through sulfide stripping/hydrogen sulfide absorption, chemautotrophy sulfur oxidizing bacterium, is eventually converted into
Elemental sulfur.
4) the absorption rich solution handled through stripping, into carbon such as simultaneous oxygen denitrification reactor 3, supplement ethyl alcohol, lactic acid, glucose
Source is stirred, and is absorbed nitrate nitrogen in rich solution and is reduced nitrogen, nitrogen enters gas collection and processing system 12, purification pressurization
The inertia circulating carried being used as afterwards between sulfide stripping/hydrogen sulfide absorption；The gas collection and processing system 12, can be with
Include gas holder, filter device and pressue device etc..
5) the absorption rich solution after denitration process enters anaerobism sulfate reduction device 5, sulfate and sulphite
Sulfide is reduced to, sulfur compound waste liquid enters the outer circulation of anaerobism sulfate reduction device, is back to step 2).
6) due to anaerobism sulfate reduction cannot degradable carbon source, anaerobism sulfate reduction water outlet enters anaerobic methane production
Reactor 5 is handled, and remaining organic matter is converted into methane, the methane of generation enters methane recovery system 13.
7) by denitrification, anaerobism sulfate reduction and methane phase reaction, the sulfate and nitrate nitrogen quilt in rich solution are absorbed
Removing, additional carbon are totally consumed completely.Since three above biological respinse produces alkali, anaerobic methane production reactor 5
Water outlet pH value is gone up to 7.0 or so.
8) aerobic aeration pond 6 is entered by the circulation fluid of denitrification, anaerobism sulfate reduction and methane phase reaction treatment
Except possible remaining a small amount of additional carbon, NaHCO is added as needed3Solution, adjustment pH value to 7.5.
9) circulation fluid handled through aerobic aeration completes regeneration, into buffer pool 14, again acts as smoke absorption liquid, is pumped
Enter smoke absorption tower, cycled into next time.
The pH test points of the system：The absorption rich solution of smoke absorption tower 1, sulfide stripping tower 7 and hydrogen sulfide absorption tower 8,
And in oxygen denitrification reactor 3 and aerobic aeration tank 6, anaerobism sulfate reduction device 4 and anaerobic methane production reactor 5 go out
Water.
The pH point of adjustment of the system is aerobic aeration tank 6.
Oxysulfide absorption, hydrogen sulfide stripping, hydrogen sulfide absorption principle are acid-base neutralization, detection aerobic aeration pond 6, cigarette
The absorption rich solution of aspiration tower 1, sulfide stripping tower 7 and hydrogen sulfide absorption tower 8 pH value everywhere can not only control absorption or blow
It is de-, the absorption of oxysulfide and hydrogen sulfide or stripping amount can also be calculated indirectly.And oxygen denitrification reactor 3, anaerobism sulfate
Reduction reactor 4, anaerobic methane production reactor 5 are three main reactions of the present invention, and bioactivity is affected by pH value, therefore
Need on-line checking pH value.
The waste water that sulfate reduction generates is after stripping, into aerobic tank processing.The water inlet of aerobic tank contains stripping remnants
Sulfide and sulfate reduction remnants carbon source, these substances oxidation production acid can reduce the pH value of aerobic tank, it is necessary to mend alkali guarantor
Hold aerobic tank pH stabilizations.In addition, aerobic tank water outlet is directly used in the absorption of sulfureous in flue gas oxide, higher ph is maintained to be conducive to inhale
It receives.Therefore, the pH point of adjustment of system is located at aerobic aeration pond.
2 present invention of embodiment is to the treatment effect of different sulfoxide concentration simulated flue gas
Simulated flue gas：SOxConcentration is (with SO2Meter) for 500,1000,2000,3000,4000mg/Nm3(Stage1~5).
Gas flow rate：1.0Nm3/h。
Absorb lean solution：With 0.2M NaHCO3Solution tune pH to 7.5.
Hydrogen sulfide absorption liquid：Na2CO3Solution.
Supplementary carbon source：Control system adds ethyl alcohol automatically according to the difference in pH absorbed between lean solution and rich solution.
Biological sulphur oxidation reactor is any strainDenitrifying bacterium is derived from municipal sewage plant denitrification sludge, inoculation
In simultaneous oxygen denitrification reactor；It is another take municipal sewage plant anaerobic sludge be inoculated in respectively anaerobism sulfate reduction device and
Methane-producing reactor.
Gas liquid ratio is adjusted, controls and absorbs rich solution pH for 4.0~5.0.
Remaining experiment condition is set with reference to embodiment 1.
As shown in Figure 2, simulated flue gas is through handling SO for experimental resultxRemoval efficiency>99%, SOxConcentration is down to<40mg/Nm3。
Sulfur recovery rate (recycles ratio) in the form of elemental sulfur>90%.After measured, sulfur purity>99%.The water outlet of aerobic aeration pond
COD concentration<20mg/m3.It is computed, alkali average consumption (in terms of NaOH) is 43.5g/kg SO2, it is theoretical consumption
3.5%.
This example demonstrates that the present invention can efficient removal oxysulfide, the overwhelming majority is converted into elemental sulfur, and obtains
Effectively recycling.Processing procedure generates outer draining, and not only water is small, but also COD concentration can be discharged directly less than discharge standard.Alkali disappears
Consumption is only the 3.5% of theoretical consumption.It can be seen that the present invention be it is a kind of do not generate secondary pollution, it is water-saving, save medicament
Cleaning flue gases sulfur removal technology.
3 present invention of embodiment is to the treatment effect of different sulfur and nitrogen oxides scale modeling flue gases
Simulated flue gas：SOxConcentration is (with SO2Meter) 2000mg/Nm3, NOxConcentration is (with NO2Meter) 50,100,200,400mg/
Nm3(Stage 1~4).
Other process conditions are same as Example 2.
Experimental result is as shown in Figure 3.Simulated flue gas is through handling SOxConcentration is down to<10mg/Nm3, SOxRemoval efficiency>99%.
Due to NOxInclude being insoluble in the NO of water, NOxRelatively low removal efficiency is 50~70%.Flue gas is after biological desulphurization denitrogenation processing, NOx
Concentration is down to 200mg/Nm3Hereinafter, the removal efficiency for the nitrate nitrogen that nitrogen oxides generates after being absorbed is 100%.Sulfur recovery rate, sulphur
The indexs such as sulphur purity, outer draining COD are similar to Example 2, are respectively>90%th,>98%th,<20mg/m3。
This example demonstrates that the present invention also has certain denitration ability while flue gas desulfurization, although NOxRemoval efficiency
It is not high, but still available for NOxThe relatively low fume treatment of content, and realize qualified discharge.During flue gas desulfurization and denitrification, still have
Do not generate secondary pollution, it is water-saving, save medicament characteristic.The present invention is a kind of cleaning flue gases biological desulphurization denitrating technique.
Embodiment 4 is using different carbon source as the operational effect of electron donor simulated flue gas biological desulphurization denitration
Simulated flue gas：SOxConcentration is (with SO2Meter) 2000mg/Nm3, NOxConcentration is (with NO2Meter) 500mg/Nm3。
Respectively using ethyl alcohol, lactic acid, sodium lactate, glucose, mixed carbon source to add carbon source.
Mixed carbon source：Ethyl alcohol：Lactic acid：Glucose=5:2:1
Other process conditions are same as Example 2.
The experimental results showed that ethyl alcohol, lactic acid, sodium lactate, glucose can serve as the carbon source of flue gas biological desulphurization denitration,
It is shown in Table 1.Using carbon source consumption as index, ethyl alcohol experimental group is often to handle 1Nm3The consumption of simulated flue gas is minimum.With aerobic tank
It intakes as index, the effluent COD concentration of mixed carbon source experimental group is minimum.
The consumption of 1 different carbon source of table and aerobic tank influent COD
This example demonstrates that the present invention can select the one of which such as ethyl alcohol, lactic acid, sodium lactate, glucose as carbon source,
Can use ethyl alcohol, lactic acid and glucose group into mixed carbon source.The effect of ethyl alcohol single carbon source and mixed carbon source is best.
5 cleaning flue gases biological desulphurization denitrating technique of embodiment is to the treatment effect of true flue gas
Flue gas：SOxConcentration is (with SO2Meter) 1,000~2,000mg/Nm3, NOxConcentration is (with NO2Meter) 400~500mg/Nm3,
Have been subjected to cooling, dust removal process.
Mixed carbon source：Ethyl alcohol：Lactic acid：Glucose=5:2:1
Other process conditions are same as Example 2.
Experimental result is as shown in Figure 4.Flue gas SO after processingxConcentration<20mg/Nm3, NOxConcentration is (with NO2Meter)<180mg/
Nm3。SOxAnd NOxRemoval efficiency is respectively>95% He>62%.Draining COD concentration outside aerobic aeration pond<30mg/L, total nitrogen<10mg/
L reaches direct discharge standard.Alkali average consumption (in terms of NaOH) is 45.2g/kg SO2, it is the 3.6% of theoretical consumption.
It is computed, absorbs the sulfate removal rate of rich solution>95%, sulfur recovery rate>90%, sulfur purity>95%.It absorbs rich
The nitrate nitrogen removal efficiency of liquid is 100%.
This example demonstrates that the present invention can be used for actual flue gas desulfurization and denitrification, processed flue gas reaches national discharge
Standard.What is more important, oxysulfide are converted into high-purity elemental sulfur by a series of biological respinses and recycle, nitrogen oxidation
Object is converted into nitrogen.Using regenerating biological reaction absorbing liquid, save>95% quantity of alkali consumption, reduces medicament and water consumption.
Do not generate solid waste in processing procedure, COD and total nitrogen concentration are less than the most stringent of discharge standard of country in the waste water of generation.
Therefore, the present invention is a kind of water-saving, section alkali, the cleaning flue gases biological desulphurization denitrating technique of non-secondary pollution.
Certainly, the present invention without deviating from the spirit and substance of the present invention, can also be familiar with there are many embodiment
Those skilled in the art can disclosure according to the present invention make various corresponding changes and modification, but these it is corresponding change and
Deformation should all belong to the protection domain of appended claims of the invention.
Claims (14)
1. a kind of cleaning flue gases biological desulphurization method of denitration, comprises the following steps：
(1) flue gas biological desulphurization coproduction elemental sulfur：
(1-1) absorbs the sulfur and nitrogen oxides in flue gas with weak lye, forms acid absorption rich solution；
(1-2) adds organic matter to acid absorb of step (1-1) in rich solution, form acid mixed solution, utilize acid mixed solution
Acidifying, sulfide are converted into hydrogen sulfide by stripping；
The hydrogen sulfide gas that (1-3) stripping generates is absorbed by lye, and the sulfur compound rich solution of generation passes through biological sulphur oxidation reaction
It is converted into elemental sulfur；
(2) denitrification joint sulfate reduction：
(2-1) supplementary carbon source into the absorption rich solution after step (1-2) stripping hydrogen sulfide, by and oxygen anti-nitration reaction,
It is nitrogen that nitrate-nitrogen reduction in rich solution, which will be absorbed,；
The absorption rich solution of (2-2) after step (2-1) denitration by anaerobism sulfate reduction, by sulfate therein and
Sulphite is reduced to sulfide；
(2-3) makes the waste water after step (2-2) sulfate reduction be reacted by anaerobic methane production, and remaining organic matter is converted into
Methane；
The waste water of (2-4) after the reaction of step (2-3) anaerobic methane production carries out aerobic reaction, removes carbon source.
2. cleaning flue gases biological desulphurization method of denitration according to claim 1, which is characterized in that step (2-1) system
The nitrogen obtained enters gas collection and processing system, for step (1-2) hydrogen sulfide stripping and step (1-3) after purified pressurization
Inertia circulating carried between hydrogen sulfide absorption.
3. cleaning flue gases biological desulphurization method of denitration according to claim 1, which is characterized in that the step (2-2) is detested
The return of waste water step (1-2) of sulfur compound participates in hydrogen sulfide conversion after oxygen sulfate reduction.
4. cleaning flue gases biological desulphurization method of denitration according to claim 1, which is characterized in that (2-4) is aerobic anti-
Waste water after answering enters buffer pool as the weak lye in step (1-1), absorbs the sulfur and nitrogen oxides in flue gas.
5. cleaning flue gases biological desulphurization method of denitration according to claim 1, which is characterized in that step (1-1) is described weak
Lye is the NaHCO of 0.2~0.5M3Solution.
6. cleaning flue gases biological desulphurization method of denitration according to claim 1, which is characterized in that the step (1-1) is logical
Control gas liquid ratio is crossed, the acid pH value for absorbing rich solution is made to be down to 4.0~5.0.
7. cleaning flue gases biological desulphurization method of denitration according to claim 1, which is characterized in that step (1-2) is added
Organic matter is ethyl alcohol, lactic acid or one or more of lactate or glucose.
8. cleaning flue gases biological desulphurization method of denitration according to claim 1, which is characterized in that step (2-1) described carbon
Source is ethyl alcohol, lactic acid or one or more of lactate and glucose.
9. cleaning flue gases biological desulphurization method of denitration according to claim 1, which is characterized in that step (2-4) is described good
The pH value of oxygen reaction is 7.0~7.5.
10. a kind of device based on cleaning flue gases biological desulphurization method of denitration described in claim 1, which is characterized in that including
Flue gas biological desulphurization coproduction elemental sulfur system combines sulfate reduction system with denitrification；
The flue gas biological desulphurization coproduction elemental sulfur system includes smoke absorption tower (1), mixing tank (2), sulfide stripping tower
(7), hydrogen sulfide absorption tower (8) and biological sulphur oxidation reactor (9)；
The denitrification joint sulfate reduction system includes and oxygen denitrification reactor (3), anaerobism sulfate reduction device
(4), anaerobic methane production reactor (5) and aerobic aeration pond (6)；
The smoke absorption tower (1) is sequentially connected with mixing tank (2), sulfide stripping tower (7), hydrogen sulfide absorption tower (8) and life
Object sulphur oxidation reactor (9)；
Described and oxygen denitrification reactor (3) is connected with sulfide stripping tower (7), and is sequentially connected with anaerobism sulfate reduction
Device (4), anaerobic methane production reactor (5) and aerobic aeration pond (6).
11. device according to claim 10, which is characterized in that sulfide stripping tower (7) and hydrogen sulfide absorption tower (8) it
Between be equipped with gas flow cycle；Described and oxygen denitrification reactor (3) is further connected with gas collection and processing system (12),
The gas collection and processing system (12) are communicated in the gas stream between sulfide stripping tower (7) and hydrogen sulfide absorption tower (8)
Logical circuit.
12. device according to claim 10, which is characterized in that the anaerobism sulfate reduction device (4) and batch mixing
Tank (2) is connected.
13. device according to claim 10, which is characterized in that the aerobic aeration pond (6) by buffer pool (14) with
Smoke absorption tower (1) is connected.
14. device according to claim 10, which is characterized in that the biology sulphur oxidation reactor (9) is also further suitable
Secondary connection sulphur sedimentation basin (10) and sulphur centrifuge (11).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410533038.5A CN105561755B (en) | 2014-10-10 | 2014-10-10 | A kind of clean flue gas biological desulphurization method of denitration and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410533038.5A CN105561755B (en) | 2014-10-10 | 2014-10-10 | A kind of clean flue gas biological desulphurization method of denitration and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105561755A CN105561755A (en) | 2016-05-11 |
| CN105561755B true CN105561755B (en) | 2018-05-22 |
Family
ID=55872717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410533038.5A Active CN105561755B (en) | 2014-10-10 | 2014-10-10 | A kind of clean flue gas biological desulphurization method of denitration and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105561755B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277459A (en) * | 2016-08-31 | 2017-01-04 | 河北源清环保科技有限公司 | Desulfuration processing method and processing means to waste water |
| CN108201777A (en) * | 2018-02-05 | 2018-06-26 | 郑兴华 | A kind of flue gas desulfurization technique |
| CN109607734A (en) * | 2018-12-31 | 2019-04-12 | 南京格洛特环境工程股份有限公司 | A kind of low-temperature denitration medicament and preparation method thereof |
| CN111422986B (en) * | 2020-04-10 | 2021-08-10 | 北京交通大学 | Autotrophic and heterotrophic coupling sewage deep denitrification device and method based on sulfur cycle |
| CN115254865A (en) * | 2022-08-25 | 2022-11-01 | 中原环保股份有限公司 | Method for treating denitrogenated gas in denitrification filter |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795739B (en) * | 2011-05-27 | 2014-12-24 | 中国科学院过程工程研究所 | Device and method for comprehensively treating acidic sulfate organic waste water based on biological desulfurization |
| CN102989272A (en) * | 2012-12-04 | 2013-03-27 | 天津大学 | Method and device for synchronously removing sulfur dioxide and nitric oxide by flue gas biological method |
-
2014
- 2014-10-10 CN CN201410533038.5A patent/CN105561755B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105561755A (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105561755B (en) | A kind of clean flue gas biological desulphurization method of denitration and device | |
| CN105032152B (en) | A kind of technique of chemical absorbing combination microbiological fuel cell synchronous flue gas desulfurization denitration | |
| US3377271A (en) | Process for the treatment of waste-containing waters | |
| CN104860474B (en) | Method for carbon sequestration and biological treatment of sulfur-containing waste alkali liquor | |
| CN102795739B (en) | Device and method for comprehensively treating acidic sulfate organic waste water based on biological desulfurization | |
| CN102309919B (en) | Combined treatment method for waste gas containing sulfur compounds | |
| CN111377575B (en) | Treatment method of high-sulfate high-COD organic wastewater | |
| CN109095732B (en) | Process for preparing high-purity magnesium hydroxide based on magnesium-method desulfurization wastewater | |
| CN107537293A (en) | A kind of closed cycle bacterial desulfurization and the method for reclaiming elemental sulfur | |
| CN110745989B (en) | Activated carbon flue gas purification acid-making wastewater zero-discharge process and system | |
| CN100571849C (en) | A kind of treatment process of discharged doctor solution of HPF desulfurization system of coke-oven plant | |
| CN110643403A (en) | Chemical absorption combined biological removal hydrogen sulfide and sulfur resource technology in methane | |
| CN104801166A (en) | Method and device for cooperative flue gas desulfurization and sewage organic matter degradation and denitrification | |
| CN113461284A (en) | Municipal sludge treatment method for nitrate-enhanced pyrohydrolysis | |
| CN109052850A (en) | A kind of standard processing method of petroleum and the high sulfur-containing waste lye of coal chemical industry | |
| Guimerà et al. | Optimization of SO2 and NOx sequential wet absorption in a two-stage bioscrubber for elemental sulphur valorisation | |
| CN107961653A (en) | A kind of dual alkali scrubbing FGD process modified technique and system | |
| CN102908893A (en) | Method for flue gas desulfurization and byproduct polymeric ferric sulfate production by using steel pickling waste liquor | |
| CN105174581B (en) | A kind of sulfur Gas Fields produced water treatment technique | |
| CN208857099U (en) | The system for handling biomass pyrolytic water | |
| CN103043779B (en) | Flue gas desulfurization waste liquid treatment and activated sludge reduction treatment method | |
| CN108975616A (en) | Handle the system and method for biomass pyrolytic water | |
| CN105984892A (en) | Calcium sulfate biological treatment regeneration method based on biological desulphurization | |
| CN106582246A (en) | Carbide slag wet-method flue gas simultaneous desulfurization and denitrification process | |
| CN207755960U (en) | A kind of dual alkali scrubbing FGD process improvement system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |