CN106975342A - A kind of biological desulphurization system and biological flue gas sulfur method - Google Patents
A kind of biological desulphurization system and biological flue gas sulfur method Download PDFInfo
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- CN106975342A CN106975342A CN201710330537.8A CN201710330537A CN106975342A CN 106975342 A CN106975342 A CN 106975342A CN 201710330537 A CN201710330537 A CN 201710330537A CN 106975342 A CN106975342 A CN 106975342A
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
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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
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/95—Specific microorganisms
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- 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
Abstract
The present invention relates to a kind of biological desulphurization system and biological flue gas sulfur method, the system includes absorptive unit, biological respinse unit and the separative element being sequentially connected, and loop is provided between separative element and absorptive unit；Biological respinse unit includes biological reaction apparatus, ORP detectors, aerator and pH detectors, and aerator, ORP detectors, pH detectors are connected with biological reaction apparatus respectively.Methods described includes：(1) absorbed using absorbing liquid and contain H2H in S biological flue gas2S；(2) carry out being passed through air and/or oxygen in biological oxidation, biological oxidation process, and control ORP to be 450~300mV, obtain the mixed liquor containing sulphur simple substance；(3) carry out after separation of solid and liquid, collect sulphur simple substance, liquid phase is back in the absorbing liquid.Alkali regeneration is realized, disposal ability is up to more than 3g/ (Ld), and desulfurization degree is up to more than 98.8%.
Description
Technical field
The present invention relates to field of environment engineering, more particularly to a kind of biological desulphurization system and biological flue gas sulfur method.
Background technology
Often contain substantial amounts of hydrogen sulfide (H in the biological flue gas such as natural gas, biogas2S) gas.H2S, which is that one kind is colourless, smelly
The poisonous gas of egg flavor, and with certain corrosivity.Unstable chemcial property, it is inflammable in atmosphere, and filled in air
Burning generation sulfur dioxide (SO when sufficient2), it is converted into secondary pollution.Hydrogen sulfide is to not only to drilling equipment and delivery pipe
Line has very strong corrosiveness, and its combustion product sulfur dioxide is the major reason that acid rain is produced again.In recent years, although
China's economic development is swift and violent, but the environmental problem caused by economic development is increasingly valued by people.At home
Under the trend for advocating low-carbon economy and increasingly strict environment protection emission requirement energetically outside, desulfurization process is carried out to natural gas and seemed
More and more important and necessity.
At present, a variety of processing H are had built up both at home and abroad2The method of S gases.Taken off according to its faintly acid and strong reducing property
Sulphur can be divided into Physical, chemical method, bioanalysis.Physical and chemical method development are more early, comparative maturity.Bioanalysis desulfurization
It is a kind of new sulfur removal technology grown up the eighties in last century, the H in the gas such as natural gas, biogas2S is inhaled by alkali lye first
Receive, then, using microbiological treatment absorbing liquid, by H2S is converted into elemental sulfur.Biological desulphurization has low energy consumption, high efficiency, equipment
Simply, the advantages of not producing secondary pollution, is extremely potential desulfurization new method, causes and more and more grind both at home and abroad
Study carefully.It is agricultural chemicals and medicine life with good bioaffinity and hydrophily and the biological sulphur yardstick of generation is in nanoscale
The optimal raw material of production.
CN106381183A discloses a kind of methane bio-desulfurization device, including desulfurizing tower, biooxidation reactions device, sulphur content
From device, the bottom of desulfurizing tower is connected with the bottom of biooxidation reactions device, is provided with biooxidation reactions device and sulphur separator
The pipeline of connection, biooxidation reactions device is connected with desulfurizing tower top by pipeline；Logical pressure is provided with biooxidation reactions device
The entry and exit of contracting air.Under doctor solution is through the spray head spray at the top of desulfurizing tower, hydrogen sulfide containing biogas is from desulfurizing tower bottom
Air inlet pipe be blown into, fully contacted with circulation fluid in the filler in the middle part of desulfurizing tower, circulation fluid is in alkalescence, by hydrogen sulfide from biogas
Middle selective absorbing comes out, and the doctor solution for absorbing hydrogen sulfide enters in biooxidation reactions device, biooxidation reactions device in the presence of de-
Sulphur microorganism, by oxidation by the sulphur hydrogen radical ionic oxide formation in doctor solution into elemental sulfur.There is following defect in this technique：
(1) a large amount of solid sulfurs are carried when the liquid in reactor squeezes into absorption tower, the effective volume of alkali lye is smaller, to reach relatively good
Assimilation effect be necessarily required to enlargement discharge, this adds increased energy consumption；(2) it is an aeration environment in reactor, entrainment of oxygen
The liquid of gas can enter absorption tower, and the biogas after purification is contained oxygen, reduce the calorific value of biogas and produce hidden peril of explosion；
(3) interval separation sulphur is accomplished by doing settling tank greatly in order to be able to be separated to more sulphur, and needs to configure more liquid,
Equipment cost and operating cost are added, and separation process can take substantial amounts of liquid out of, can influence the operation of system stable and continuous.
H2S changes into S0It is a sulphur oxidizing process, the microorganism of conventional energy sulfur oxide compound can be divided into 3 classes：Thread sulphur
Bacterium, photosynthetic sulfur bacteria and colorless sulfur bacteria.
H2S is passed through in carbonate alkali lye, there is following reaction：
Further, HS-In the presence of sulfur oxidizing bacterium, simple substance S is generated0And SO4 2-.However, material generation skewed popularity with
ORP is closely related.ORP can be changed by adjusting aeration quantity.Under limited oxygen condition, ORP is very low, at this moment in system predominantly
Following reaction：
2HS-+O2→2S0+2OH- (3)
And work as in system under excess oxygen, SO4 2-Generation increase, it is as follows：
HS-+2O2→SO4 2-+H+ (4)
From (3) and (4) as can be seen that generating S in limited oxygen condition0While, there is OH-Release, and as it was previously stated,
Equipment disclosed in CN106381183A deposits deficiency in design, and bacterial activity is not high enough.Accordingly, it would be desirable to design more efficient
Biological desulfurization apparatus and technique.
The content of the invention
In view of problems of the prior art, i.e., the bacterium used in existing biological desulfurizing technology is low pH Low-salinities tolerance
Bacterium, this biological desulphurization system has absorbability low, high to equipment requirement, and strain activity is unstable to wait not enough, this hair
It is bright to develop a kind of high-alkali biological flue gas high-performance bio desulphurization system of high salt with alkali regeneration cycle.Utilize thermophilic salt basophilic sulphur
Sulfide formation elemental sulfur in oxidation bacteria removing absorbing liquid.
For up to above-mentioned purpose, the present invention is adopted the following technical scheme that：
In a first aspect, the present invention provides a kind of biological desulphurization system, including absorptive unit, the biological respinse list being sequentially connected
Member and separative element, are provided with loop between the separative element and the absorptive unit；The biological respinse unit includes life
Thing reaction unit, ORP detectors, aerator and pH detectors, the aerator, ORP detectors, pH detectors respectively with
Biological reaction apparatus is connected.
It should be noted that on loop, the liquid outlet of separative element is connected with the inlet of absorptive unit.Aerator
It is connected with the air inlet of biological reaction apparatus, ORP detectors, pH detectors are arranged on to detect inside biological reaction apparatus
The position of reaction solution.
Absorptive unit of the present invention preferably includes absorption tower.
Preferably, gas outlet, feeding port and air inlet are sequentially provided with from top to bottom in the absorptive unit.
Preferably, the top of the absorptive unit is provided with the spray equipment for connecting the loop.
Preferably, the spray equipment is located between the gas outlet and the horizontal position of the air inlet.
The top of absorptive unit of the present invention is connected by the loop with the separative element.
Separative element of the present invention includes sedimentary deposit tank.
The biological desulphurization system also includes device for absorbing tail gas, and the device for absorbing tail gas goes out with the absorptive unit
Connected between gas port by gas piping.
Exemplarily, the workflow of system of the present invention is：Containing H2S biological flue gas is passed through absorption by air inlet
Contacted in unit with alkaline absorption solution, absorb major part H2S, obtained reaction solution enter biological respinse unit, while air and/
Or oxygen is passed through biological respinse unit from oxygen intake, basophilic vulcanization bacterium carry out after biooxidation reactions will generation S simple substance and
OH-, gained mixed liquor enters separative element, and isolated S simple substance contains OH simultaneously-Liquid phase through loop to be back to absorption single
Member, realizes circulation.Through absorbing H2Biological flue gas after S can absorb remaining H by device for absorbing tail gas2Directly discharged after S.
In addition to periodic collection S simple substance and supplement nutrient solution, it is not necessary to which artificial operation can maintain continuously running for system.
Second aspect, the present invention provides a kind of biological flue gas sulfur method, and methods described comprises the following steps：
(1) absorption of hydrogen sulfide gas：Absorbed using absorbing liquid and contain H2H in S biological flue gas2S, obtains reaction solution；Its
In, the absorbing liquid contains the cell culture fluid and buffering pair of thermophilic salt basophilic sulfur oxidizing bacterium；
(2) biological oxidation：Will reaction solution obtained by step (1) be passed through in biological oxidation, biological oxidation process air and/
Or oxygen, and control ORP be -450~-300mV, such as -300mV, -330mV, -350mV, -380mV, -400mV, -
420mV, -435mV or -450mV etc., obtain the mixed liquor containing sulphur simple substance；
(3) separation of sulphur simple substance：Mixed liquor containing sulphur simple substance obtained by step (2) is carried out after separation of solid and liquid, sulphur is collected
Simple substance, liquid phase is back in the absorbing liquid.
SO in system under excess oxygen4 2-Concentration gradually accumulate, increase solution osmotic pressure, while discharging H+So that pH
Reduction, influences H2S absorption, causes the desulphurizing activated reduction of thermophilic salt basophilic sulfur oxidizing bacterium.The present invention is tieed up by adjusting aeration quantity
SO can be avoided in the range of -450~-300mV by holding ORP4 2-Accumulation and pH reduce and the suppression of thermophilic salt basophilic sulfur oxidizing bacterium made
With so as to improve the yield of desulfuration efficiency and sulphur simple substance.
Step (1) absorption of the present invention is carried out in absorptive unit.
Step (1) the thermophilic salt basophilic sulfur oxidizing bacterium of the present invention preferably includes sulphur alkali vibrios.Sulphur alkali vibrios
(Thialkalivibrio versutus) D301 belongs to the class of colorless sulfur bacteria one.The multipotency sulphur alkali vibrios D301 is in 2013
It is deposited in China Committee for Culture Collection of Microorganisms's common micro-organisms center (Chaoyang District, Beijing City North Star west on November 25, in
The institute 3 of road 1, Institute of Microorganism, Academia Sinica, 100101), it is referred to as CGMCC, and deposit number is CGMCC8497.
Multipotency sulphur alkali vibrios is a kind of chemautotrophy arcuation microorganism of thermophilic salt basophilic, is initially from saline-alkali environment in Gram-negative
In soil in separate, be resistant to higher pH and salinity.Sulphur alkali vibrios can utilize thiosulfate, sulfide etc.
Low sulfur compounds are used as electron donor, O2As electron acceptor, and utilize CO2It is used as carbon source.When using low sulfur compounds as
During electron donor, S particles are had in extracellular accumulation.
Preferably, step (1) it is described buffering to including：NaHCO3-Na2CO3、NaHCO3-NaOH、Na2CO3-NaOH、
KHCO3-K2CO3, KHCO3- KOH, K2CO3In-KOH any one or at least two combination.
Preferably, also include after the step (1)：
(1 ') H is absorbed2Biological flue gas after S is expelled directly out after carrying out tail gas absorption by alkali lye.
Preferably, the tail gas absorption is carried out in device for absorbing tail gas.
Preferably, the alkali lye includes NaOH solution, NaHCO3Or Ca (OH)2Any one in solution or at least two
Combination.
Preferably, H is absorbed2Biological flue gas after S is passed through the tail gas absorption from the absorptive unit through gas piping
Device.
Step (2) the of the present invention biological oxidation is carried out preferably in biological reaction apparatus.
The ORP of step (2) the of the present invention reaction solution is preferably kept between -400~-350mV.
Preferably, the ORP that step (2) passes through reaction solution described in ORP detector monitors.
Preferably, the Na of step (2) described reaction solution+Concentration is maintained between 0.5~4M, such as 0.5M, 0.8M, 1M,
1.2M, 1.5M, 1.8M, 2M, 2.2M, 2.5M, 2.8M, 3M, 3.2M, 3.5M, 3.8M or 4M etc., preferably 1~2M.
Preferably, the pH of step (2) described reaction solution be 7.5~11.5, such as 7.5,8,8.5,9,9.5,10,10.5,
11st, 11.2 or 11.5 etc., preferably 9~10.
Preferably, the pH that step (2) passes through reaction solution described in pH detector monitors.
Preferably, reaction solution overflow obtained by step (1) enters the biological reaction apparatus.
The separation of step (3) the of the present invention sulphur simple substance is carried out in sedimentary deposit tank.
Preferably, the mixed liquor overflow containing sulphur simple substance obtained by step (2) enters the sedimentary deposit tank.
Preferably, the mode of step (3) separation of solid and liquid includes natural subsidence.Under gravity, sulfur granules are settled quickly
To separative element bottommost.The sulfur granules of this method formation are highly convenient for separation, have saved time, manpower, energy consumption etc..Will not be right
The even running of system produces interference.
Preferably, step (3) described liquid phase is back to the mode of the absorbing liquid and specifically included：The liquid phase is pumped into back
The liquid phase is sprayed by spray equipment behind road, the liquid phase is imported the suction after being contacted with the gas in the absorption plant
Receive liquid.
As currently preferred technical scheme, the biological flue gas sulfur method comprises the following steps：
(1) absorption of hydrogen sulfide gas：Absorbing liquid is filled in absorptive unit, the absorbing liquid contains thermophilic salt basophilic sulphur oxygen
Change bacterium cell culture fluid and buffering pair, it is described buffering to including：NaHCO3-Na2CO3、NaHCO3-NaOH、Na2CO3-NaOH、
KHCO3-K2CO3, KHCO3- KOH, K2CO3In-KOH any one or at least two combination, H will be contained2S biological flue gas leads to
Enter the absorbing liquid, absorb H2S, obtains reaction solution；
(1 ') H is absorbed2Biological flue gas after S is passed through tail gas through the gas piping from the gas outlet of the absorptive unit and inhaled
NaOH solution, NaHCO are filled with receiving apparatus, the device for absorbing tail gas3Or Ca (OH)2In solution any one or at least
Two kinds of combination, further absorbs H2It is expelled directly out after S；
(2) biological oxidation：Reaction solution overflow obtained by step (1) enters biological reaction apparatus and carries out biological oxidation, while by sky
Gas and/or oxygen are passed through the biological reaction apparatus, by the ORP of reaction solution described in ORP detector monitors, control ORP for-
450~-300mV, the Na of the reaction solution+Concentration is maintained between 0.5~4M, passes through reaction solution described in pH detector monitors
PH, pH are maintained between 7.5~11.5, and the mixed liquor containing sulphur simple substance is obtained after reaction；
(3) separation of sulphur simple substance：Mixed liquor overflow containing sulphur simple substance obtained by step (2) enters after sedimentary deposit tank, separation of solid and liquid,
Sulphur simple substance is collected, the liquid phase will be sprayed by spray equipment after the liquid phase pump entry loop, the liquid phase is absorbed with described
The absorbing liquid is imported after gas contact in device.
Biological desulphurization system of the present invention and biological flue gas sulfur method can be used for house refuse, anaerobic digestion of kitchen wastes
H in the biogas of generation, natural gas, industrial waste gas2S removing.
Compared with prior art, the present invention at least has the advantages that：
(1) absorbing liquid of the present invention absorbs hydrogen sulfide in absorptive unit, consumes hydroxyl, and obtained sulfide enters biological
Reaction member, by controlling ORP value, biological oxidation formation elemental sulfur and hydroxyl, hydroxyl is back to suction from separative element again
Receive unit and enter next circulation, so that whole system realizes regeneration hydroxy, circulation, it is ensured that thermophilic salt basophilic sulphur oxidation
Bacterium continues, stable high desulfurization activity, and disposal ability can reach more than 3g/ (Ld), and final desulfurization degree is up to more than 98.8%；
(2) present invention is practically free of sulphur list by being set between separative element and absorptive unit in loop, phegma
Matter, the systemic hydrogen sulfide of unit volume can be more, and do not bring oxygen into, overcome CN106381183A and recycle efficiency
The poor defect of low, security, substantially reduces energy consumption；
(3) the interval separation process compared to CN106381183A, the present invention realizes continuous desulfurization, time saving and energy saving, from
Dynamicization degree is greatly improved, and equipment cost and operating cost are lower.
Brief description of the drawings
Fig. 1 is the schematic diagram of biological desulphurization system in the embodiment of the present invention；
Mark is illustrated as in figure：10- absorption towers, 20- bioreactors, 30- sedimentary deposit tanks, 101- gas outlets, 21-ORP inspections
Survey device, 22-pH detectors, 23- aerators, 40- tail gas absorption tanks, 41- spray equipments
Fig. 2 is H in the embodiment of the present invention 32SO in S clearances, absorptivity and reaction solution4 2-Concentration with system operation when
Between change curve；
Fig. 3 is H in the embodiment of the present invention 42SO in S clearances, absorptivity and reaction solution4 2-Concentration with system operation when
Between change curve.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.But following realities
The simple example that example is only the present invention is applied, the scope of the present invention, protection model of the invention is not represented or limit
Enclose and be defined by claims.
Embodiment 1
A kind of biological desulphurization system, including absorption tower 10, bioreactor 20 and the sedimentary deposit tank 30 being sequentially connected, in addition to
Tail gas absorption tank, is provided with loop, tail gas absorption tank 40 and the gas outlet 101 on absorption tower connect between sedimentary deposit tank 30 and absorption tower 10
Connect, bioreactor 20 is connected with pH meter 21 and ORP detectors 22, bioreactor 20 is connected with aerator 23.
A kind of biological flue gas sulfur method：
1) biogas that pig manure fermentation is produced, after testing, H in biogas2S content is up to 22.5g/m3, using flow velocity as 600L/h
This biogas is passed through the absorbing liquid in absorption tower 10, absorbing liquid contains the cell culture fluid and NaHCO of sulphur alkali vibrios3-Na2CO3It is slow
Punching pair, absorbs H2S, obtains reaction solution；
1 ') H is absorbed2Biogas after S is passed through in the tail gas absorption tank 40 from gas outlet 101 through the gas piping
NaOH solution, further absorbs H2It is expelled directly out after S；
2) step 1) gained reaction solution overflow enters bioreactor 20, while oxygen is passed through, it is anti-by ORP detector monitors
The ORP of liquid is answered, it is -300mV, the Na of reaction solution to control ORP+Concentration maintains 0.5M, by being reacted described in pH detector monitors
The pH of liquid, pH, which are maintained, obtains the mixed liquor containing sulphur simple substance after 7.5, reaction；
3) step 2) gained the mixed liquor overflow containing sulphur simple substance enter sedimentary deposit tank 40, after settlement, collect sulphur simple substance, upper strata
The liquid phase is sprayed by spray equipment 41 after liquid pump entry loop, upper liquid is imported after being contacted with the gas in absorption tower and absorbs
Liquid.
Embodiment 2
A kind of biological flue gas sulfur method, device is same as Example 1：
1) biogas that pig manure fermentation is produced, after testing, H in biogas2S content is up to 22.5g/m3, using flow velocity as 600L/h
This biogas is passed through the absorbing liquid in absorption tower 10, absorbing liquid contains the cell culture fluid and NaHCO of sulphur alkali vibrios3- NaOH delays
Punching pair, absorbs H2S, obtains reaction solution；
1 ') H is absorbed2Biogas after S is passed through in the tail gas absorption tank 40 from gas outlet 101 through the gas piping
NaOH solution, further absorbs H2It is expelled directly out after S；
2) step 1) gained reaction solution overflow enters bioreactor 20, while oxygen is passed through, it is anti-by ORP detector monitors
The ORP of liquid is answered, it is -450mV, the Na of reaction solution to control ORP+Concentration maintains 4M, passes through reaction solution described in pH detector monitors
PH, pH, which is maintained, obtains the mixed liquor containing sulphur simple substance after 11.5, reaction；
3) step 2) gained the mixed liquor overflow containing sulphur simple substance enter sedimentary deposit tank 40, after settlement, collect sulphur simple substance, upper strata
The liquid phase is sprayed by spray equipment 41 after liquid pump entry loop, upper liquid is imported after being contacted with the gas in absorption tower and absorbs
Liquid.
Embodiment 3
A kind of biological flue gas sulfur method, device is same as Example 1：
1) biogas that pig manure fermentation is produced, after testing, H in biogas2S content is up to 22.5g/m3, using flow velocity as 600L/h
This biogas is passed through the absorbing liquid in absorption tower 10, absorbing liquid contains the cell culture fluid and NaHCO of sulphur alkali vibrios3- NaOH delays
Punching pair, absorbs H2S, obtains reaction solution；
1 ') H is absorbed2Biogas after S is passed through in the tail gas absorption tank 40 from gas outlet 101 through the gas piping
NaOH solution, further absorbs H2It is expelled directly out after S；
2) step 1) gained reaction solution overflow enters bioreactor 20, while oxygen is passed through, it is anti-by ORP detector monitors
The ORP of liquid is answered, it is -380mV, the Na of reaction solution to control ORP+Concentration maintains 2M, passes through reaction solution described in pH detector monitors
PH, pH, which is maintained, obtains the mixed liquor containing sulphur simple substance after 9.5, reaction；
3) step 2) gained the mixed liquor overflow containing sulphur simple substance enter sedimentary deposit tank 40, after settlement, collect sulphur simple substance, upper strata
The liquid phase is sprayed by spray equipment 41 after liquid pump entry loop, upper liquid is imported after being contacted with the gas in absorption tower and absorbs
Liquid.
Fig. 2 is H in the embodiment of the present invention 32SO in S absorptivities, the clearance of sulfide and reaction solution4 2-Concentration with being
The change curve for run time of uniting.
Embodiment 4
A kind of biological flue gas sulfur method, device is same as Example 1：
1) by H2S contents are up to 44.5g/m3Natural gas absorbing liquid in absorption tower 10 is passed through by 600L/h of flow velocity, inhale
Receive cell culture fluid and NaHCO that liquid contains sulphur alkali vibrios3- NaOH bufferings pair, absorb H2S, obtains reaction solution；
1 ') H is absorbed2Natural gas after S is passed through in the tail gas absorption tank 40 from gas outlet 101 through the gas piping
NaOH solution, further absorbs H2It is expelled directly out after S；
2) step 1) gained reaction solution overflow enters bioreactor 20, while oxygen is passed through, it is anti-by ORP detector monitors
The ORP of liquid is answered, it is -380mV, the Na of reaction solution to control ORP+Concentration maintains 2M, passes through reaction solution described in pH detector monitors
PH, pH, which is maintained, obtains the mixed liquor containing sulphur simple substance after 9.5, reaction；
3) step 2) gained the mixed liquor overflow containing sulphur simple substance enter sedimentary deposit tank 40, after settlement, collect sulphur simple substance, upper strata
The liquid phase is sprayed by spray equipment 41 after liquid pump entry loop, upper liquid is imported after being contacted with the gas in absorption tower and absorbs
Liquid.
Fig. 3 is H in the embodiment of the present invention 42SO in S absorptivities, the removal rate of sulfide and reaction solution4 2-Concentration with being
The change curve for run time of uniting.
Embodiment 5
A kind of biological flue gas sulfur method, device is same as Example 1：
1) by H2S contents are up to 44.5g/m3Natural gas absorbing liquid in absorption tower 10 is passed through by 600L/h of flow velocity, inhale
Receive cell culture fluid and NaHCO that liquid contains sulphur alkali vibrios3- NaOH bufferings pair, absorb H2S, obtains reaction solution；
1 ') H is absorbed2Natural gas after S is passed through in the tail gas absorption tank 40 from gas outlet 101 through the gas piping
NaOH solution, further absorbs H2It is expelled directly out after S；
2) step 1) gained reaction solution overflow enters bioreactor 20, while oxygen is passed through, it is anti-by ORP detector monitors
The ORP of liquid is answered, it is -395mV, the Na of reaction solution to control ORP+Concentration maintains 1.0M, by being reacted described in pH detector monitors
The pH of liquid, pH, which are maintained, obtains the mixed liquor containing sulphur simple substance after 10.0, reaction；
3) step 2) gained the mixed liquor overflow containing sulphur simple substance enter sedimentary deposit tank, after settlement, collect sulphur simple substance, upper liquid
It is pumped into behind loop and the liquid phase is sprayed by spray equipment 41, upper liquid is imported after being contacted with the gas in absorption tower and absorb
Liquid.
Comparative example 1
With apparatus and method processing disclosed in CN106381183A embodiment and the identical biogas of embodiment 1, bacterium
Plant and use Thiobacillus ferrooxidans, nutrient solution is the nutrient solution of Thiobacillus ferrooxidans.
Comparative example 2
With apparatus and method processing disclosed in CN106381183A embodiment and the identical biogas of embodiment 1, bacterium
Plant same as Example 1, be sulphur alkali vibrios, nutrient solution is same as Example 1.
Comparative example 3
With differing only in for embodiment 1：Strain replaces with Thiobacillus ferrooxidans, while nutrient solution replaces with oxidation Asia
The nutrient solution of iron Thiobacillus.
Comparative example 4
With differing only in for embodiment 1：Step 2) ORP be -500mV.
Comparative example 5
With differing only in for embodiment 1：Step 2) ORP be -200mV.
The disposal ability of each embodiment and comparative example, final desulfurization degree, the yield of desulfurization finished product sulphur simple substance, operating cost
Arrange in table 1.Wherein, disposal ability is referred to：Continuous operation 10 days of reactor, the absorbing liquid of unit volume is averagely daily de-
Sulfur content, unit is g/ (Ld), and desulfurization degree refers to H in the gas that system is discharged2S content accounts for before processing H2The hundred of S content
Divide ratio.
Table 1
As shown in table 1, the disposal ability of comparative example 1~5, final desulfurization degree, the yield of desulfurization finished product sulphur simple substance are remote
Less than embodiment 1, comparative examples 1 and comparative example 1~5, it can be seen that biological desulphurization system of the invention, thermophilic salt basophilic sulphur
There is synergy between oxidation bacteria and ORP, specifically, loop is arranged between separative element and absorptive unit, rather than
In CN106381183A between absorptive unit and biological respinse unit, the basophilic characteristic of thermophilic salt basophilic sulfur oxidizing bacterium is dexterously utilized
The high-efficiency desulfurization system of alkali regeneration cycle is formed, and changes in biological desulphurization system, thermophilic salt basophilic sulfur oxidizing bacterium and ORP three and appoints
Meaning one can all reduce the overall efficiency of system and method for the present invention.
Comparative examples 1 and comparative example 2, then vs comparative examples 3 and comparative example 1, it can be seen that in strain (either oxygen
Change ferrous Thiobacillus or thermophilic salt basophilic sulfur oxidizing bacterium) and nutrient solution all same in the case of, equipment of the invention is handling energy
It is substantially better than device disclosed in CN106381183A in power, desulfuration efficiency, the advantage of system of the invention in design is very prominent.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of biological desulphurization system, including absorptive unit, biological respinse unit and the separative element being sequentially connected, its feature exist
In provided with loop between the separative element and the absorptive unit；
The biological respinse unit includes biological reaction apparatus, ORP detectors, aerator and pH detectors, the aeration dress
Put, ORP detectors, pH detectors are connected with biological reaction apparatus respectively.
2. the system as claimed in claim 1, it is characterised in that the absorptive unit includes absorption tower；
Preferably, gas outlet, feeding port and air inlet are sequentially provided with from top to bottom in the absorptive unit；
Preferably, the top of the absorptive unit is provided with the spray equipment for connecting the loop；
Preferably, the spray equipment is located between the gas outlet and the horizontal position of the air inlet.
3. system as claimed in claim 1 or 2, it is characterised in that the top of the absorptive unit passes through the loop and institute
State separative element connection.
4. the system as described in any one of claims 1 to 3, it is characterised in that the separative element includes sedimentary deposit tank.
5. the system as described in any one of Claims 1 to 4, it is characterised in that the biological desulphurization system also includes tail gas and inhaled
Connected between the gas outlet of receiving apparatus, the device for absorbing tail gas and the absorptive unit by gas piping.
6. a kind of biological flue gas sulfur method, it is characterised in that methods described comprises the following steps：
(1) absorption of hydrogen sulfide gas：Absorbed using absorbing liquid and contain H2H in S biological flue gas2S, obtains reaction solution；Wherein,
The absorbing liquid contains the cell culture fluid and buffering pair of thermophilic salt basophilic sulfur oxidizing bacterium；
(2) biological oxidation：Reaction solution obtained by step (1) is carried out to be passed through air and/or oxygen in biological oxidation, biological oxidation process
Gas, and control ORP to be -450~-300mV, obtain the mixed liquor containing sulphur simple substance；
(3) separation of sulphur simple substance：Mixed liquor containing sulphur simple substance obtained by step (2) is carried out after separation of solid and liquid, sulphur simple substance is collected,
Liquid phase is back in the absorbing liquid.
7. method as claimed in claim 6, it is characterised in that step (1) absorption is carried out in absorptive unit；
Preferably, step (1) the thermophilic salt basophilic sulfur oxidizing bacterium includes sulphur alkali vibrios；
Preferably, step (1) it is described buffering to including：NaHCO3-Na2CO3、NaHCO3-NaOH、Na2CO3-NaOH、KHCO3-
K2CO3, KHCO3- KOH, K2CO3In-KOH any one or at least two combination；
Preferably, also include after the step (1)：
(1 ') H is absorbed2Biological flue gas after S is expelled directly out after carrying out tail gas absorption by alkali lye；
Preferably, the tail gas absorption is carried out in device for absorbing tail gas；
Preferably, the alkali lye includes NaOH solution, NaHCO3Or Ca (OH)2In solution any one or at least two group
Close；
Preferably, H is absorbed2Biological flue gas after S is passed through the tail gas absorption from the gas outlet of the absorptive unit through gas piping
Device.
8. method as claimed in claims 6 or 7, it is characterised in that step (2) described biological oxidation is in biological reaction apparatus
Carry out；
Preferably, the ORP of step (2) described reaction solution is maintained between -400~-350mV；
Preferably, the ORP that step (2) passes through reaction solution described in ORP detector monitors；
Preferably, the Na of step (2) described reaction solution+Concentration is maintained between 0.5~4M, preferably 1~2M；
Preferably, the pH of step (2) described reaction solution is 7.5~11.5, preferably 9~10；
Preferably, the pH that step (2) passes through reaction solution described in pH detector monitors；
Preferably, reaction solution overflow obtained by step (1) enters the biological reaction apparatus.
9. the method as described in any one of claim 6~8, it is characterised in that the separation of step (3) described sulphur simple substance is in deposition
Carried out in tank；
Preferably, the mixed liquor overflow containing sulphur simple substance obtained by step (2) enters the sedimentary deposit tank；
Preferably, the mode of step (3) separation of solid and liquid includes natural subsidence；
Preferably, step (3) described liquid phase is back to the mode of the absorbing liquid and specifically included：After the liquid phase pump entry loop
The liquid phase is sprayed by spray equipment, the liquid phase is imported the absorption after being contacted with the gas in the absorption plant
Liquid.
10. the method as described in any one of claim 6~9, it is characterised in that comprise the following steps：
(1) absorption of hydrogen sulfide gas：Absorbing liquid is filled in absorptive unit, the absorbing liquid contains thermophilic salt basophilic sulfur oxidizing bacterium
Cell culture fluid and buffering pair, it is described buffering to including：NaHCO3-Na2CO3、NaHCO3-NaOH、Na2CO3-NaOH、
KHCO3-K2CO3, KHCO3- KOH, K2CO3In-KOH any one or at least two combination, H will be contained2S biological flue gas leads to
Enter the absorbing liquid, absorb H2S, obtains reaction solution；
(1 ') H is absorbed2Biological flue gas after S is passed through tail gas absorption dress from the gas outlet of the absorptive unit through the gas piping
Put, NaOH solution, NaHCO are filled with the device for absorbing tail gas3Or Ca (OH)2Any one in solution or at least two
Combination, further absorb H2It is expelled directly out after S；
(2) biological oxidation：Reaction solution overflow obtained by step (1) enters biological reaction apparatus and carries out biological oxidation, at the same by air and/
Or oxygen is passed through the biological reaction apparatus, by the ORP of reaction solution described in ORP detector monitors, control ORP for -450~-
300mV, the Na of the reaction solution+Concentration is maintained between 0.5~4M, passes through the pH of reaction solution described in pH detector monitors, pH
Maintain between 7.5~11.5, the mixed liquor containing sulphur simple substance is obtained after reaction；
(3) separation of sulphur simple substance：Mixed liquor overflow containing sulphur simple substance obtained by step (2) enters after sedimentary deposit tank, separation of solid and liquid, collects
Sulphur simple substance, will spray the liquid phase by spray equipment after the liquid phase pump entry loop, makes the liquid phase and the absorption plant
In gas contact after import the absorbing liquid.
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| CN110652864A (en) * | 2019-10-10 | 2020-01-07 | 南京清源生物工程有限公司 | For treating H2Biological desulfurization treatment device and process of S |
| CN114130173A (en) * | 2021-12-08 | 2022-03-04 | 厦门理工学院 | Hydrogen sulfide gas absorption method |
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