CN105854550A - Method and device for directly removing hydrogen sulfide from biogas by microorganisms - Google Patents

Method and device for directly removing hydrogen sulfide from biogas by microorganisms Download PDF

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Publication number
CN105854550A
CN105854550A CN201610298544.XA CN201610298544A CN105854550A CN 105854550 A CN105854550 A CN 105854550A CN 201610298544 A CN201610298544 A CN 201610298544A CN 105854550 A CN105854550 A CN 105854550A
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China
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tower
biogas
hydrogen sulfide
gas
desulfurizing tower
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Chinese (zh)
Inventor
宋燕民
巴国庆
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Shidai Taoyuan Environment Science And Technology Co Ltd Beijing
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Shidai Taoyuan Environment Science And Technology Co Ltd Beijing
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Priority to CN201610098990 priority
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Publication of CN105854550A publication Critical patent/CN105854550A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75Multi-step processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D47/00Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • B01D47/06Spray cleaning
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/52Hydrogen sulfide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84Biological processes
    • B01D53/85Biological processes with gas-solid contact
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10Working-up natural gas or synthetic natural gas
    • C10L3/101Removal of contaminants
    • C10L3/102Removal of contaminants of acid contaminants
    • C10L3/103Sulfur containing contaminants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/05Biogas
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/10Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

Abstract

The invention discloses a device for removing hydrogen sulfide from biogas. The device comprises a front washing tower, a main desulfurizing tower and an external reactor. The front washing tower is provided with a biogas inlet and an upper gas outlet, and the upper gas outlet is connected with a gas inlet of the main desulfurizing tower; the main desulfurizing tower is a biotrickling filter with the gas inlet and a lower liquid outlet; the height of the gas inlet is larger than accumulation height of liquid in the main desulfurizing tower; the reactor is connected with the lower liquid outlet of the main desulfurizing tower through a pipeline, the main desulfurizing tower comprises a plurality of liquid inlets and spraying devices from top to bottom, the liquid inlets are connected with the spraying devices, and culture solution in the reactor enters the spraying devices in the main desulfurizing tower through pumps and the liquid inlets. By the device for removing hydrogen sulfide from biogas, treatment of biogas with hydrogen sulfide concentration higher than 5000ppmv can be realized, the hydrogen sulfide concentration can be directly decreased to below 100ppmv to meet technical requirements of boilers and engines, and treatment cost is no more than 0.014yuan per cubic meter.

Description

A kind of apparatus and method utilizing microorganism directly to remove hydrogen sulfide in methane
Technical field
The invention belongs to biogas treatment field, be specifically related to a kind of utilize microorganism directly to remove hydrogen sulfide in methane A kind of apparatus and method removing hydrogen sulfide in methane of device.
Background technology
Biogas is the general designation of the mixed gas produced under organic anaerobic condition, and its Main Ingredients and Appearance is with methane (50%- 60%), carbon dioxide (40%-50%) be main, additionally possibly together with steam, hydrogen sulfide, ammonia, carbon monoxide, Hundreds of different foreign gas and the solid impurity such as nitrogen, oxygen, wherein hydrogen sulfide content is from 1000ppm (body Long-pending ratio) arrive 10000ppm.Hydrogen sulfide not only severe toxicity and also be inflammable and explosive composition.In National Fuel Gas standard The content requirement of hydrogen sulfide is less than 20mg/Nm3, and vehicle-mounted gas standard is 15mg/Nm3.Because fermentation raw material Characteristic, almost all of biogas all contains hydrogen sulfide and increasingly complex organic sulfur compounds.
Process for biogas relates generally to impurity component therein process and the process of hydrogen sulfide.At biogas Reason process needs consideration Cost Problems and biogas originally as sour gas, if according to the side of conventional removing solid particle Formula needs to introduce new energy consumption, therefore does not boost biogas and the most directly enter the solid impurity in biogas at present Row individual processing, but follow-up handle together in sweetening process.
China is biogas production big country, estimate annual various biogas generation amount more than 10,000,000,000 cubes, but owing to it is inflammable easily Quick-fried, impurity is more, the especially toxic component content such as hydrogen sulfide is the most higher, seriously constrains the utilization of biogas, one As the inspection shaft operation that frequently refers in report cause the dead situation of people and be typically all because caused by hydrogen sulfide poisoning, hydrogen sulfide Belong to nerve gas class, lethal rapidly, so biogas desulfurization is the only way of biogas utilization.
Along with the change that cleans of China's energy resource structure, biogas will undertake more importantly role.But the utilization of biogas Seriously receive the impact of wherein pollutant component, especially sulphur compound.Sulfur in biogas, based on hydrogen sulfide, vulcanizes Hydrogen is not only severe toxicity gas, and is also the Main Ingredients and Appearance forming air acidity gaseous contamination after burning.So biogas takes off Sulfur, is also the important means controlling acid gas emissions.
Common biogas desulfurization mode has a variety of, is divided into Physical and the big class of chemical method two in simple terms.At Physical Managing with physical absorption or be absorbed as main, the concentration of process is the most relatively low, and (condition is required relatively by special Physical Absorption method Height, such as low-temp methanol washing process), chemical method, based on chemical reaction, is typically directed to catalysis and a large amount of medicine Agent is lost, and processing cost is high.Tabulation conventional during general measurement desulfurization expense is the expense of every square gas, and chemical method leads to Often need the operating cost of 0.1-0.2 unit every side gas.
Biological desulphurization is the new method of the new removing hydrogen sulfide grown up in recent years, also known as biocatalytic desulfurization (letter Claim BDS), it is a kind of one utilizing aerobe removing biogas to contain the sulfide based on hydrogen sulfide at normal temperatures and pressures New technique.Its process is the aerobic antibacterial and sulfide generation oxidation reaction produced with nature, is become by Oxidation of Hydrogen Sulfide Elemental sulfur, sulfate or sulphite proceed to solid phase or aqueous phase, thus reach the purpose of desulfurization.BDS technology is from going out The most so far decades are had been developed in, so far still in the developmental research stage.Run due to system and rely primarily on biology Activity, so operating cost is the lowest, good operation stability.
Biological desulphurization purifies gas can be divided into three steps:
Dissolve: the moisture film contact stain thing of biogas and water or the surface of solids soluble in water or be the molecule in liquid phase or from Son, i.e. hydrogen sulfide are transferred to liquid phase by gas phase, and this step meets physical process Henry's law.
Absorption absorbs: in aqueous solution, odor pollutant is by microorganism adsorption, absorption.It is transferred to from water in microbial body, Water as absorbent is reproduced recovery, then goes to dissolve new odor pollutant.
Biodegradation: the odor pollutant of entrance microbial cell is divided as the energy or the nutrient of microbial life activity Solve and utilize, making pollutant be removed.
Enter the Organic substance oxidation Decomposition under desmoenzyme effect in microbial cell, carry out anabolism product simultaneously The microbial cell of tissue regeneration promoting.Biological desulfurizing technology includes Biological fitler method, biosorption process and biological island, three kinds System all belongs to open systems.
Current system is in during laboratory scale preferable for the process performance of gas, but is being applied to reality During scene, its disposal ability is not enough, and conventional bio-desulfurization device can be with concentration for the treatment of in the natural pond of about 3000ppm Gas, limited for its disposal ability of biogas more than this concentration, and flora cannot the environment of adjustment reaction device, shorter Time in lost efficacy, its reason is the microorganism in the hydrogen sulfide gas of high concentration inhibits reactor.High concentration vulcanizes In the presence of hydrogen, flora not only can be made to lose efficacy and form elemental sulfur, and it oxidation can form sulphuric acid further Salt, and this process is not observed when low concentration, it may there is no corresponding relation with the concentration of hydrogen sulfide, and mixed Enter oxygen and air can bring the risk in production, as follow-up NOx and nitrogen can be introduced.
Summary of the invention
For overcoming the defect that cannot process high concentration in existing biological desulfurizing technology, the invention provides a kind of removing natural pond The apparatus and method of hydrogen sulfide in gas.
Understand microbiostatic activity in the presence of the present invention is directed to prior art middle and high concentration hydrogen sulfide gas and cause flora Dead and that oxidation product is complicated defect provides the device of a kind of new removing hydrogen sulfide, and the present invention is by hydrogen sulfide It is stripped of the impurity affecting bacterial activity of the unknown by pretreatment, makes microorganism at suitable oxygen by process afterwards Concentration is reacted, so that oxidation product is the sulfate of solubility.
The device that the present invention provides includes preposition scrubbing tower, main desulfurizing tower and external reactor;
Described preposition scrubbing tower is provided with biogas entrance and upper gas outlet, the outlet of described upper gas and main desulfurization The gas feed of tower connects;
Described main desulfurizing tower, for dripping filter tower, described filter tower is provided with gas access and lower liquid outlet;Described gas Body entrance accumulates height higher than liquid in main desulfurizing tower;
Described reactor is connected by the lower liquid outlet of pipeline and main desulfurizing tower, and described main desulfurizing tower is from top to bottom Connect including some liquid-inlets and spray equipment, described liquid-inlet and spray equipment, the cultivation in described reactor Liquid enters the spray equipment in main desulfurizing tower by pump and liquid-inlet.
Preferably, described main desulfurizing tower built-in filler material is not stratified plastic filler (preferably PP class), earthfill rockfill concrete riprap RCC Type is Raschig ring, Pall ring or cascade ring, and its characteristic size is about 80mm, bottom grill support, and tower material is Fiberglass.Aforementioned structure can effectively prevent corrosion.
Described filling surface is growth of microorganism region, and the hydrogen sulfide in biogas enters microorganism by gas-liquid surface and lives Dynamic region, is obtained by microorganism, thus maintains the hydrogen sulfide lasting transport process from gas to liquid, finally realize natural pond The removal of hydrogen sulfide in gas.Preferably, the bottom spray in described main desulfurizing tower is intermittent duty, because gas feed Near desulfurization load higher, periodically turn on bottom spray and filler can be accumulated impurity and wash down, its control valve be for oneself Brake control valve.
The fermentation methane that the present invention processes is common biogas, and it both typically is from similar installation for fermenting, and pressure is relatively low, About 1-3kPa, and gas is messy, containing impurity such as more solid particles;Composition is more complicated, and main component has first Alkane accounts for 50%-60%, carbon dioxide about 40%-50%, hydrogen sulfide about 1000ppmv-10000ppmv, except this it Outward, other are also had not determine composition.
Described preposition scrubbing tower be filler be the packed tower of DG25 or DG50 dumped packing, following of described packed tower Ring liquid is fermentation biogas slurry supernatant.Aforesaid filler is generally plastics, preferably PP class plastics.In aforementioned filler tower, Circulating pump by water from top of tower drench, with biogas adverse current.The impurity that recirculated water generally uses under tap water cleans remains in Tower bottom, periodically discharges.
Described preposition scrubbing tower can use fermentation biogas slurry supernatant as circulation fluid, and described fermentation biogas slurry supernatant is not Only can be with gas washing, it is also possible to remove the hydrogen sulfide (reduction ratio reaches as high as 10%) in part biogas, and this process Reduce the hydrogen sulfide content of follow-up desulfurizing tower entrance so that its gas the most persistently processing high concentration becomes existing Real.
After preposition scrubbing tower washs, the hydrogen sulfide ratio in described biogas occurs in that reduction, and the content of hydrogen sulfide is Height can be down to below 9000ppmv from 10000ppmv, after this step process, although the concentration of hydrogen sulfide Reduced by only a part, but effectively avoid flora and lost efficacy.
Inventor finds, for the biogas after this step process, and resistance to for concentration of hydrogen sulfide of the strain of main desulfurizing tower Being significantly improved by property, hydrogen sulfide major part is sulfate radical by direct oxidation, thus avoid elemental sulfur precipitation and Deposition on reaction tower, so that this course of reaction can persistently be carried out.
Desulfurized effect for desulfurizing tower can be detected by the oxygen concentration table after tower, and this concentration may be used for adjusting Inclusion of air amount before whole tower.
Described external reactor is provided with Aeration tank, and described culture fluid directly mixes with the oxygen in air in Aeration tank Close.Utilizing air pump at this pond aeration, dissolved oxygen content in monitoring solution, so can reduce front end air simultaneously Mixed volume.When exposing in the case of oxygen amount meets reaction requirement, front end air can be stopped and being mixed into, natural pond after such desulfurization Gas oxygen content can be the lowest, and owing to not having being mixed into of nitrogen, biogas calorific value can't reduce because of desulfurization Calorific value.Aeration mode has two kinds, i.e. the direct aeration of blower fan and water pump injection type aeration.
It is generally acknowledged that in dripping filter tower, biogas has time enough and culture fluid mixing, even if requiring supplementation with oxygen, it also should When be by blast after oxygen or air are directly mixed with biogas drip filter tower in react, and without extra drum Enter oxygen containing culture fluid.The method of the present invention can significantly reduce the addition of nitrogen, because biogas is typically all after desulfurization Burning utilizes, so also effectively reducing the generation amount of NOx, this process the most effectively avoids answering of oxidation product Polygamy.Because the effect of the oxygen that front end air adds the most also is to dissolve, so the mode of aeration oxygen can accelerate biological bacteria Reaction.
Described external reactor is additionally provided with water pipe.Tap water can fill into this pond by aforementioned pipeline moisturizing.
Being provided with dividing plate in described external reactor, described reactor is separated into two top connection by this dividing plate from bottom Logical region, heating hot water and/or steam fill into wherein in a separated region.Because desulfurization bacterium environment need to maintain 25- 30 DEG C, steam or the hot water of heating directly fill in aforesaid marker space, and this Hybrid Heating mode can avoid volume Outer arrange one to corrosion require high heat exchanger.
Described external reactor also includes that feeding tube, described nutrient add external reactor by feeding tube.Battalion Support thing and automatically filled into system by dosing pump through feeding tube.
Between described preposition scrubbing tower and main desulfurizing tower, pipeline arranges air intake, and air is mixed in biogas by this entrance. Because desulfurization bacterium needs oxygen, can directly pass through blower fan (air pump) by inclusion of air biogas.The addition of air On the basis of methane quantity, for the 10% of its flow.For preventing biogas from leaking, after blower fan, set non-return valve.The stream of air pump Amount can be automatically adjusted according to biogas flow.In view of the effect of aeration, the air herein added can coordinate control in the lump System.
Preferably, the middle part of described filter tower is provided with and is divided into two-part dividing plate by dripping a filter tower, described dividing plate and dripping The top of filter tower is provided with gas passage, described gas dripping after filter tower desulfurization processes through gas through side from the bottom to top Passage is processed by the packed tower desulfurization of opposite side from top to bottom.Which can change the sharing of load in tower, at lifting After reason ability and desulfurization, biogas is given vent to anger by bottom, maintains easily.
Present invention also offers a kind of method removing hydrogen sulfide in methane, including:
1) biogas by circulation fluid be fermentation biogas slurry supernatant packed tower by preliminary purification;
2) biogas after preliminary purification enters and drips filter tower removing hydrogen sulfide, and the circulation fluid dripping filter tower is through air or oxygen Culture fluid after aeration, the pH value of described culture fluid is between 1.0-3.0;
3) desulfurization bacterium grows on filler, with the hydrogen sulfide in gas, supplementary oxygen and other a small amount of nutrients is Raw, hydrogen sulfide is changed into elemental sulfur or sulfate radical and inferior sulfate radical from gaseous state.
Preferably, described biogas mainly includes methane 50%-60%, carbon dioxide 40%-50%, hydrogen sulfide 1000ppmv-10000ppmv, preferred concentration is 5500-10000ppmv.
Preferably, the pH of described fermentation biogas slurry is 7.0-8.0.Although the solution providing similar pH can also play one Fixed effect, but with regard to its cost and system can be for seriality aspect, it obviously possesses excellent not as fermentation biogas slurry Gesture.
Preferably, the oxygen content in described culture fluid after air or oxygen aeration is 3-9mg/L.Due to hydrogen sulfide Concentration is higher, cannot process by traditional biological mode, and flora is all suppressed by serious, and uses the process of the application Mode, it is ensured that removal efficiency that hydrogen sulfide is good also ensures the survival of strain.
Preferably, described filter tower is respectively provided with several spray equipments from top to bottom, and the jet apparatus of its middle and upper part is normal Opening, the spray equipment of bottom is that filler is accumulated impurity and washes down by the unlatching selected.
Preferably, the biogas after described preliminary purification is mixed into the volume accounting air less than 10% or is mixed into and makes removing In the gas of hydrogen sulfide, oxygen content is not higher than the air of 0.5%.The flow of described air is the most controlled.
Preferably, described circulation fluid is from top is drenched, and general methane quantity and liquor capacity ratio is for 100:1.
Preferably, for flow 1000Nm3The biogas of/h, diameter 4 meters, the microorganism that filler is high 9 meters takes off Sulfur tower, directly can be reduced to below 200ppmv by the hydrogen sulfide of 5000ppmv.
Preferably, packed tower ratio of height to diameter is 2-3, preferably 2.55 ± 0.1.
Preferably, gas liquid ratio or volume ratio are 80-200, preferably 105 ± 5.
The strain in culture fluid in the present invention is aerobic strain, and most important of which flora is thiobacillus ferrooxidant Thiobacillusferrooxidans, T.f), it is a kind of gram negative bacteria, there is chemautotrophy, aerobic, addicted to acid, suitable In characteristics such as middle temperature environment, being widely present in the sour environment of Acid mine water and iron content or sulfur, it is for being a kind of weight The leaching microbacteria wanted, is used for biological ore dressing field.The present invention is different with traditional processing mode, is ensureing strain On the premise of survival, hydrogen sulfide is further oxidized to the soluble sulphates such as sulfate radical, makes relative in prior art It is sulfur simple substance with strain by Oxidation of Hydrogen Sulfide, thus realizes continuous desulfurization.
Preferably, when elemental sulfur generates when dripping formation accumulation in filter tower, it is mixed into air capacity by adjustment or aeration rate comes Accelerate it and be converted into acid group or the flushing of provisional increasing spray flux.
The present invention has a following advantage:
1, there is preposition scrubbing tower, which removes and may affect the impurity that follow-up desulfurization processes the place making desulfurizing tower Reason ability improves;
2, desulfurizing tower is with outside multifunctional reactor, and wherein heating temperature control, dosing etc. all access from outside Aeration tank;
3, using aerobic desulfurization bacterium, oxygen supply introduces in the way of the direct hybrid mode of air and outside aeration, Outside Aeration tank is effectively reduced the amount being directly mixed with air, and the nitrogen that simultaneously will not enter system is too much;
4, the hydrogen sulfide content of general Organic substance (referring mainly to agricultural zootechnical) fermentation methane is less than 5000ppmv, And the present invention can process the biogas higher than this limit, can directly hydrogen sulfide be dropped to by this method Below 100ppmv, meets the technical need of boiler, electromotor, and considers power consumption, water consumption and heat dissipation, the present invention's The processing cost of every cubic metre is less than 0.014 yuan.
Accompanying drawing explanation
Fig. 1 is the device of the removing hydrogen sulfide in methane gas of the present invention.
Detailed description of the invention
The following is embodiments of the invention, what it was used only as the present invention illustrates rather than restriction.
See Fig. 1,
The device that the present invention provides includes preposition scrubbing tower, main desulfurizing tower and reactor;
Described preposition scrubbing tower is provided with biogas entrance and upper gas outlet, the outlet of described upper gas and main desulfurization The gas feed of tower connects;
Described main desulfurizing tower, for dripping filter tower, described filter tower is provided with gas access, upper gas outlet and bottom liquid Body exports;Height is accumulated higher than liquid in main desulfurizing tower in described gas access;
Described reactor is connected by the lower liquid outlet of pipeline and main desulfurizing tower, and described main desulfurizing tower is from top to bottom Connect including some liquid-inlets and spray equipment, described liquid-inlet and spray equipment, the cultivation in described reactor Liquid enters the spray equipment in main desulfurizing tower by pump and liquid-inlet.
Described circulation fluid is from top is drenched, and general methane quantity and liquor capacity ratio is for 100:1.
Described bottom spray is intermittent duty, because adjacent gas inlets desulfurization load is higher, periodically turns on bottom spray Filler can be accumulated impurity to wash down, its control valve is autocontrol valve.
The fermentation methane that the present invention processes is common biogas, and it both typically is from similar installation for fermenting, and pressure is relatively low, About 1-3kPa, and gas is messy, containing impurity such as more solid particles;Composition is more complicated, and main component has first Alkane accounts for 50%-60%, carbon dioxide about 40%-50%, hydrogen sulfide about 5500ppmv-10000ppmv, except this it Outward, other are also had not determine composition.
Desulfurized effect for desulfurizing tower can be detected by the oxygen concentration table after tower, and this concentration may be used for adjusting Inclusion of air amount before whole tower.
Preferably, described external reactor is provided with Aeration tank, and described culture fluid is direct with in air in Aeration tank Oxygen mix.Utilizing air pump at this pond aeration, dissolved oxygen content in monitoring solution, so can reduce front end simultaneously The mixed volume of air.When exposing in the case of oxygen amount meets reaction requirement, front end air can be stopped and being mixed into, the most de- After sulfur, biogas oxygen content can be the lowest, and owing to not having being mixed into of nitrogen, biogas calorific value can't be because of desulfurization And reduce calorific value.Aeration mode has two kinds, i.e. the direct aeration of blower fan and water pump injection type aeration.
Preferably, described external reactor is provided with water pipe.Tap water can fill into this by aforementioned pipeline moisturizing Pond.
Preferably, being provided with dividing plate in described external reactor, described reactor is separated into two by this dividing plate from bottom The region of top UNICOM, heating hot water and/or steam fill into wherein in a separated region.Because desulfurization bacterium environment needs dimension Holding 25-30 DEG C, steam or the hot water of heating directly fill in aforesaid marker space, and this Hybrid Heating mode is permissible Avoid additionally arranging one and corrosion is required high heat exchanger.
Preferably, described external reactor also includes feeding tube, described nutrient by feeding tube add external instead Answer device.Nutrient is filled into system by dosing pump automatically through feeding tube.
Preferably, between described preposition scrubbing tower and main desulfurizing tower, pipeline arranges air intake, and air is mixed into by this entrance In biogas.Because desulfurization bacterium needs oxygen, can directly pass through blower fan (air pump) by inclusion of air biogas.Air Addition on the basis of methane quantity, for its flow 10% or be mixed into and make in the gas of removing hydrogen sulfide oxygen content not Air higher than 0.5%.For preventing biogas from leaking, after blower fan, set non-return valve.The flow of air pump can be according to biogas Flow is automatically adjusted.
Preferably, described preposition scrubbing tower be filler be the packed tower of DG25 or DG50 dumped packing, described filler The circulation fluid of tower is fermentation biogas slurry supernatant.Aforesaid filler is generally plastics.In aforementioned filler tower, circulating pump is by water From top of tower drenches, with biogas adverse current.The impurity that recirculated water generally uses under tap water cleans remains in tower bottom, fixed Phase discharges.Packed tower can use fermentation biogas slurry supernatant as circulation fluid, is possible not only to gas washing, it is also possible to removal portion Divide the hydrogen sulfide in biogas, and this process reduces the hydrogen sulfide content of follow-up desulfurizing tower entrance so that it is held for a long time The continuous gas processing high concentration becomes a reality, and in the gas after washing, concentration of hydrogen sulfide can be up to 5000- 7000ppmv, and occur without the problems such as flora inactivation and over oxidation.Because biogas slurry pH is generally about 8.0, tool Having alkalescence, the reaction of desulfurization and washing process are a competitive relation, therefore this area is not the most used as washing gas Body.
Preferably, the middle part of described filter tower is provided with and is divided into two-part dividing plate by dripping a filter tower, described dividing plate and dripping The top of filter tower is provided with gas passage, described gas dripping after filter tower desulfurization processes through gas through side from the bottom to top Passage is processed by the packed tower desulfurization of opposite side from top to bottom.This set-up mode can extend the time of staying of gas, enters The effect of one-step optimization desulfurization.
Present invention have the advantage that:
1, there is preposition scrubbing tower, which removes and may affect the impurity that follow-up desulfurization processes the place making desulfurizing tower Reason ability improves;
2, desulfurizing tower is with outside multifunctional reactor, and wherein heating temperature control, dosing etc. all access from outside Aeration tank;
3, using aerobic desulfurization bacterium, oxygen supply introduces in the way of the direct hybrid mode of air and outside aeration, Outside Aeration tank is effectively reduced the amount being directly mixed with air, and the nitrogen that simultaneously will not enter system is too much.
Hydrogen sulfide directly can be dropped to below 100ppm by the present invention, meets the technical need of boiler, electromotor, and Considering power consumption, water consumption, heat dissipation, the processing cost of every cubic metre of the present invention is less than 0.014 yuan.

Claims (11)

1. utilize microorganism directly to remove a device for hydrogen sulfide in methane, including preposition scrubbing tower, main desulfurizing tower With external reactor, it is characterised in that:
Described preposition scrubbing tower is provided with biogas entrance and upper gas outlet, the outlet of described upper gas and main desulfurization The gas feed of tower connects;
Described main desulfurizing tower, for dripping filter tower, described filter tower is provided with gas access and lower liquid outlet;Described gas Body entrance accumulates height higher than liquid in main desulfurizing tower;
Described external reactor is connected by the lower liquid outlet of pipeline and main desulfurizing tower, and described main desulfurizing tower is from upper Include under to that some liquid-inlets and spray equipment, described liquid-inlet and spray equipment connect, described external reactor Interior culture fluid enters the spray equipment in main desulfurizing tower by pump and liquid-inlet.
Device the most according to claim 1, it is characterised in that the described built-in filler of main desulfurizing tower is not stratified Plastic filler, wire feeding is Raschig ring, Pall ring or cascade ring, bottom grill support, and tower material is fiberglass.
Device the most according to claim 1, it is characterised in that described preposition scrubbing tower be filler be DG25 Or the packed tower of DG50 Pall ring filler in bulk, the circulation fluid of described packed tower is fermentation biogas slurry supernatant.
Device the most according to claim 1, it is characterised in that described external reactor is provided with Aeration tank, Described culture fluid is direct with the oxygen mix in oxygen or air in Aeration tank.
Device the most according to claim 1, it is characterised in that manage between described preposition scrubbing tower and main desulfurizing tower Road arranges air intake, and air is mixed in biogas by this entrance.
Device the most according to claim 1, it is characterised in that the middle part of described filter tower is provided with will drip filter Tower is divided into two-part dividing plate, described dividing plate and drip the top of filter tower and be provided with gas passage, described gas by down to On through side drip filter tower desulfurization process after processed by the packed tower desulfurization of opposite side from top to bottom through gas passage.
7. the method utilizing microorganism removing hydrogen sulfide in methane, including:
1) biogas by circulation fluid be fermentation biogas slurry supernatant packed tower by preliminary purification;
2) biogas after preliminary purification enters and drips filter tower removing hydrogen sulfide, and the circulation fluid dripping filter tower is through air or oxygen Culture fluid after aeration;
3) desulfurization bacterium grows on filler, with the hydrogen sulfide in gas, supplementary oxygen and other a small amount of nutrients is Raw, hydrogen sulfide is changed into elemental sulfur or sulfate radical and inferior sulfate radical from gaseous state.
Method the most according to claim 7, it is characterised in that if described filter tower is respectively provided with from top to bottom Dry spray equipment, the jet apparatus of its middle and upper part is normally opened, and the spray equipment of bottom is that filler is accumulated by the unlatching selected Impurity washes down.
9. according to the method described in claim 7 or 8, it is characterised in that the biogas after described preliminary purification is mixed into The volume accounting air less than 10% or be mixed into oxygen content in the gas making removing hydrogen sulfide and be not higher than the sky of 0.5% Gas.
10. according to the method described in claim 7 or 8, it is characterised in that described methane quantity and circulation fluid volume Ratio is for more than 100:1.
11. according to the method described in claim 7 or 8, it is characterised in that when elemental sulfur generates in dripping filter tower When forming accumulation, it is mixed into air capacity by adjustment or aeration rate accelerates it and is converted into acid group or provisional increasing spray Amount is rinsed.
CN201610298544.XA 2016-02-23 2016-05-06 Method and device for directly removing hydrogen sulfide from biogas by microorganisms Pending CN105854550A (en)

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CN205730824U (en) * 2016-02-23 2016-11-30 北京时代桃源环境科技有限公司 A kind of device utilizing microorganism directly to remove hydrogen sulfide in methane

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