CN105817129A - Device and method for removing hydrogen sulfide in marsh gas with microorganisms - Google Patents

Device and method for removing hydrogen sulfide in marsh gas with microorganisms Download PDF

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Publication number
CN105817129A
CN105817129A CN201610298870.0A CN201610298870A CN105817129A CN 105817129 A CN105817129 A CN 105817129A CN 201610298870 A CN201610298870 A CN 201610298870A CN 105817129 A CN105817129 A CN 105817129A
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tower
gas
hydrogen sulfide
biogas
desulfurizing tower
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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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    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention discloses a device for removing hydrogen sulfide in marsh gas with microorganisms. The device comprises a front-arranged washing tower, a main desulfurizing tower and an external-arranged reaction vessel. A marsh gas entrance and an upper gas outlet are formed in the front-arranged washing tower, and the upper gas outlet is divided into a plurality of branches in the gas flow direction, and is connected with gas inlets of the main desulfurizing tower; the main desulfurizing tower is a trickling filtration tower, and a plurality of gas entrances, a plurality of upper gas outlets and a plurality of lower liquid outlets are formed in the trickling filtration tower; the trickling filtration tower internally comprises a plurality of packing layers, and the gas entrances and the packing layers are correspondingly arranged; the reaction vessel is connected with the lower liquid outlets of the main desulfurizing tower through a pipe, the main desulfurizing tower comprises a plurality of liquid inlets and spraying devices from top to bottom, the liquid inlets are formed in the tops and middles of the packing layers, and are connected with the spraying devices, dand culture solutions in the reaction vessel enter the main desulfurizing tower through a pump and the liquid inlets. According to the device, marsh gas with the hydrogen-sulfide concentration of 5,000 ppmv can be treated, and the concentration of hydrogen sulfide can be directly reduced below 100 ppmv.

Description

A kind of apparatus and method utilizing microorganism removing hydrogen sulfide in methane
Technical field
The invention belongs to biogas treatment field, be specifically related to the apparatus and method of a kind of device removing hydrogen sulfide in methane utilizing microorganism removing hydrogen sulfide in methane.
Background technology
Biogas is the general designation of the mixed gas produced under organic anaerobic condition, its Main Ingredients and Appearance is based on methane (50%-60%), carbon dioxide (40%-50%), additionally possibly together with hundreds of different foreign gas and solid impurities such as steam, hydrogen sulfide, ammonia, carbon monoxide, nitrogen, oxygen, wherein hydrogen sulfide content is from 1000ppm (volume ratio) to 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 the characteristic of fermentation raw material, 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.Owing to biogas treatment process needs to consider that Cost Problems and biogas are originally as sour gas, if needing to introduce new energy consumption according to the mode of conventional removing solid particle, therefore biogas is not boosted at present and the most directly the solid impurity in biogas is carried out individual processing, but follow-up handle together in sweetening process.
China is biogas production big country, estimate that annual various biogas generation amount is more than 10,000,000,000 cubes, but owing to it is inflammable and explosive, impurity is more, the especially toxic component content such as hydrogen sulfide is the most higher, seriously constraining the utilization of biogas, the inspection shaft operation frequently referred in general report causes the dead situation of people and is typically all because caused by hydrogen sulfide poisoning, hydrogen sulfide belongs 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 receives the impact of wherein pollutant component, especially sulphur compound.Sulfur in biogas is based on hydrogen sulfide, and hydrogen sulfide is not only severe toxicity gas, and is also the Main Ingredients and Appearance forming air acidity gaseous contamination after burning.So biogas desulfurization, it also it is 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.Physical processes with physical absorption or is absorbed as main, and the concentration of process is the most relatively low, and (condition is required higher by special Physical Absorption method, such as low-temp methanol washing process), chemical method, based on chemical reaction, is typically directed to catalysis and a large amount of drug out loss, and processing cost is high.Tabulation conventional during general measurement desulfurization expense typically requires the operating cost of 0.1-0.2 unit every side gas for the expense of every square gas, chemical method.
Biological desulphurization is the new method of the new removing hydrogen sulfide grown up in recent years, also known as biocatalytic desulfurization (being called for short BDS), is a kind of a kind of new technique utilizing aerobe removing biogas to contain the sulfide based on hydrogen sulfide at normal temperatures and pressures.Its process is the aerobic antibacterial and sulfide generation oxidation reaction produced with nature, Oxidation of Hydrogen Sulfide becomes elemental sulfur, sulfate or sulphite proceed to solid phase or aqueous phase, thus reaches the purpose of desulfurization.BDS technology has been developed in decades, so far still in the developmental research stage so far from appearance.Run due to system and rely primarily on biological activity, so operating cost is the lowest, good operation stability.
Biological desulphurization purifies gas can be divided into three steps:
Dissolving: the moisture film contact stain thing of biogas and water or the surface of solids is soluble in water or be that the molecule in liquid phase or ion, i.e. hydrogen sulfide are transferred to liquid phase by gas phase, this step meets physical process Henry's law.
Absorption absorbs: in aqueous solution, odor pollutant is by microorganism adsorption, absorption.Being transferred to from water in microbial body, the water as absorbent is reproduced recovery, then goes to dissolve new odor pollutant.
Biodegradation: the odor pollutant of entrance microbial cell is decomposed as the energy or the nutrient of microbial life activity and utilizes, and makes pollutant be removed.
Enter the Organic substance oxidation Decomposition under desmoenzyme effect in microbial cell, carry out anabolism simultaneously and produce new microbial cell.Biological desulfurizing technology includes that Biological fitler method, biosorption process and biological island, three kinds of systems all belong to open systems.
Current system is in during laboratory scale preferable for the process performance of gas, but when being applied to the scene of reality, its disposal ability is not enough, conventional bio-desulfurization device can be with concentration for the treatment of at the biogas of about 3000ppm, limited for its disposal ability of biogas more than this concentration, and flora cannot the environment of adjustment reaction device, lost efficacy in the short period of time, its reason is the microorganism in the hydrogen sulfide gas of high concentration inhibits reactor.In the presence of high concentration hydrogen sulfide gas, flora not only can be made to lose efficacy and form elemental sulfur, and it oxidation can form sulfate further, and this process is not observed when low concentration, it may there is no corresponding relation with the concentration of hydrogen sulfide, and it is mixed into oxygen and air can bring the risk in production, as introduced follow-up NOx and nitrogen.
Summary of the invention
For overcoming sulfur method in prior art cannot process the defect of high concentration, the invention provides a kind of apparatus and method removing hydrogen sulfide in methane.
The present invention is directed in the presence of prior art middle and high concentration hydrogen sulfide gas can microbiostatic activity cause the defect that flora is dead and oxidation product is complicated to provide the device of a kind of new removing hydrogen sulfide, hydrogen sulfide is stripped of the impurity affecting bacterial activity of the unknown by the present invention by pretreatment, by process, microorganism is reacted in suitable oxygen concentration afterwards, 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, described upper gas outlet along gas flow be divided into some branch roads and and main desulfurizing tower gas feed connect described main desulfurizing tower for drip a filter tower, described filter tower is provided with some gas accesses, upper gas outlet and lower liquid outlet;Including some packing layers in described filter tower, described gas access is arranged corresponding to packing layer;
Described reactor is connected by the lower liquid outlet of pipeline and main desulfurizing tower, described main desulfurizing tower includes some liquid-inlets and spray equipment from top to bottom, described liquid-inlet is positioned at top and the middle part of packing layer, described liquid-inlet and spray equipment connect, and the culture fluid in described reactor 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, and wire feeding is Raschig ring or Pall ring, and its characteristic size is about 80mm, bottom grill support, and tower material is fiberglass.Aforementioned structure can effectively prevent corrosion.
Preferably, the gas inlet of described gas access is according to gas differential pressure in the tower of packing layer or according to the oxygen content distribution of differing heights gas in tower.
Preferably, the middle part of described filter tower is provided with and is divided into two-part dividing plate by dripping filter tower, the top of described dividing plate and a filter tower is provided with gas passage, and described gas is processed by the packed tower desulfurization of opposite side through gas passage from top to bottom through dripping after filter tower desulfurization processes of side from the bottom to top.Which can change the sharing of load in tower, and after promoting disposal ability and desulfurization, biogas is given vent to anger by bottom, maintains easily.
Preferably, bottom in described main desulfurizing tower spray is intermittent duty, because adjacent gas inlets desulfurization load is higher, periodically turns on bottom spray and filler can be accumulated impurity and wash down, and its control valve is autocontrol valve.Blasted the removal efficiency that can realize improving hydrogen sulfide to the full extent by filler segmentation and segmentation, due to each section of concurrent working, and the hydrogen sulfide of bottom persistently removes through top again, thus the efficiency of bulk devulcanization also improves.
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 methane to account for 50%-60%, carbon dioxide about 40%-50%, hydrogen sulfide about 1000ppmv-10000ppmv, in addition, also has other not determine composition.
Described preposition scrubbing tower be filler be the packed tower of DG25 or DG50 dumped packing, the circulation fluid of described packed tower for 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, described fermentation biogas slurry supernatant is possible not only to gas washing, the hydrogen sulfide in part biogas (reduction ratio reaches as high as 10%) can also be removed, and this process reduces the hydrogen sulfide content of follow-up desulfurizing tower entrance, its gas the most persistently processing high concentration is become a reality, in gas after washing, concentration of hydrogen sulfide can be up to 5000-7000ppmv, and occurs without the problems such as flora inactivation and over oxidation.Because biogas slurry pH is generally about 8.0, having alkalescence, the reaction of desulfurization and washing process are a competitive relation, therefore this area is not the most used as washing gas.
After preposition scrubbing tower washs, hydrogen sulfide ratio in described biogas occurs in that reduction, and the content of hydrogen sulfide is the highest can be down to below 9000ppmv, 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, the strain of main desulfurizing tower significantly improves for the toleration of concentration of hydrogen sulfide, hydrogen sulfide major part is sulfate radical by direct oxidation, thus avoid the precipitation of elemental sulfur and the 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 tower.
Described external reactor is provided with Aeration tank, and described culture fluid is direct with the oxygen mix in air in Aeration tank.Utilizing air pump at this pond aeration, dissolved oxygen content in monitoring solution, so can reduce the mixed volume of front end air simultaneously.When exposing in the case of oxygen amount meets reaction requirement, can stop front end air and be mixed into, after such desulfurization, biogas oxygen content can be the lowest, and owing to not having being mixed into of nitrogen, biogas calorific value can't reduce calorific value because of desulfurization.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 should also be as being by reacting in blasting a filter tower after oxygen or air directly being mixed with biogas, and without additionally blasting oxygen containing culture fluid.The method of the present invention can significantly reduce the generation amount of NOx, and in waste gas, the content of nitrogen also significantly reduces, and this process the most effectively avoids the complexity of oxidation product.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 the reaction of biological bacteria.
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 the region of Liang Ge top UNICOM by this dividing plate from bottom, and 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 be avoided additionally arranging one and corrosion is required high heat exchanger.
Described external reactor also includes that feeding tube, described nutrient add external reactor by feeding tube.Nutrient is filled into system by dosing pump automatically 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 is 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 flow of air pump can be automatically adjusted according to biogas flow.
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 the culture fluid after air or oxygen aeration, and the pH value of described culture fluid is between 1.0-3.0;
3) desulfurization bacterium grows on filler, makes a living with the hydrogen sulfide in gas, supplementary oxygen and other a small amount of nutrients, from gaseous state, hydrogen sulfide is changed into elemental sulfur or sulfate radical and inferior sulfate radical.
Preferably, described biogas mainly includes methane 50%-60%, carbon dioxide 40%-50%, hydrogen sulfide 1000ppmv-10000ppmv.
Although the solution of pH providing the biogas slurry that is similar to ferment can also play certain effect, but with regard to its cost and system can be for seriality aspect, it obviously possesses advantage not as fermentation biogas slurry.
Preferably, the oxygen content in described culture fluid after air or oxygen aeration is 3-9mg/L.Owing to concentration of hydrogen sulfide is higher, cannot process in a traditional way, flora is all suppressed by serious, and uses the processing mode of the application, 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 normally opened, and 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 oxygen content in the gas making removing hydrogen sulfide and 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 bacterial desulfurization tower of high 9 meters of filler, directly the hydrogen sulfide of 5000ppmv can be reduced to below 200ppmv.
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, most important of which flora is thiobacillus ferrooxidant Thiobacillusferrooxidans, T.f), it it is a kind of gram negative bacteria, have chemautotrophy, aerobic, addicted to acid, be suitable to the characteristics such as middle temperature environment, being widely present in the sour environment of Acid mine water and iron content or sulfur, it is to be a kind of important leaching microbacteria, is used for biological ore dressing field.The present invention is different with traditional processing mode, on the premise of ensureing strain survival, hydrogen sulfide is further oxidized to the soluble sulphates such as sulfate radical, and relative to using strain to be sulfur simple substance by Oxidation of Hydrogen Sulfide in prior art, it can realize producing continuously.
Preferably, when elemental sulfur generates when dripping formation accumulation in filter tower, it is mixed into air capacity by adjustment or aeration rate accelerates it and is converted into acid group.
The present invention has a following advantage:
1, there is preposition scrubbing tower, which removes and may affect the impurity of follow-up desulfurization process and the disposal ability of desulfurizing tower is improved;
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, and 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, directly hydrogen sulfide can be dropped to below 100ppmv by this method, meet the technical need of boiler, electromotor, and considering power consumption, water consumption and heat dissipation, the processing cost of every cubic metre of the present invention is less than 0.015 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, described upper gas outlet along gas flow be divided into some branch roads and and main desulfurizing tower gas feed connect described main desulfurizing tower for drip a filter tower, described filter tower is provided with some gas accesses, upper gas outlet and lower liquid outlet;Including some packing layers in described filter tower, described gas access is arranged corresponding to packing layer;
Described reactor is connected by the lower liquid outlet of pipeline and main desulfurizing tower, described main desulfurizing tower includes some liquid-inlets and spray equipment from top to bottom, described liquid-inlet is positioned at top and the middle part of packing layer, described liquid-inlet and spray equipment connect, and the culture fluid in described reactor 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, and it can also be between 40-150:1.
Described bottom spray is for intermittent duty, because adjacent gas inlets desulfurization load is higher, periodically turns on bottom spray and filler can be accumulated impurity and wash down, and 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 methane to account for 50%-60%, carbon dioxide about 40%-50%, hydrogen sulfide about 1000ppmv-10000ppmv, in addition, also has other 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 tower.
Optionally, described external reactor is provided with Aeration tank, and described culture fluid is direct with the oxygen mix in air in Aeration tank.Utilizing air pump at this pond aeration, dissolved oxygen content in monitoring solution, so can reduce the mixed volume of front end air simultaneously.When exposing in the case of oxygen amount meets reaction requirement, can stop front end air and be mixed into, after such desulfurization, biogas oxygen content can be the lowest, and owing to not having being mixed into of nitrogen, biogas calorific value can't reduce calorific value because of desulfurization.Aeration mode has two kinds, i.e. the direct aeration of blower fan and water pump injection type aeration.
Optionally, described external reactor is provided with water pipe.Tap water can fill into this pond by aforementioned pipeline moisturizing.
Optionally, being provided with dividing plate in described external reactor, described reactor is separated into the region of Liang Ge top UNICOM by this dividing plate from bottom, and 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 be avoided additionally arranging one and corrosion is required high heat exchanger.
Optionally, described external reactor also includes that feeding tube, described nutrient add external reactor by feeding tube.Nutrient is filled into system by dosing pump automatically through feeding tube.
Optionally, 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 is 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 flow of air pump can be automatically adjusted according to biogas flow.
Optionally, described preposition scrubbing tower be filler be the packed tower of DG25 or DG50 dumped packing, the circulation fluid of described packed tower for fermentation biogas slurry supernatant.Aforesaid filler is generally 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.Packed tower can use fermentation biogas slurry supernatant as circulation fluid, it is possible not only to gas washing, the hydrogen sulfide in part biogas can also be removed, and this process reduces the hydrogen sulfide content of follow-up desulfurizing tower entrance, its gas the most persistently processing high concentration is become a reality, in gas after washing, concentration of hydrogen sulfide can be up to 5000-7000ppmv, and occurs without the problems such as flora inactivation and over oxidation.Because biogas slurry pH is generally about 8.0, having alkalescence, the reaction of desulfurization and washing process are a competitive relation, therefore this area is not the most used as washing gas.
Optionally, the middle part of described filter tower is provided with and is divided into two-part dividing plate by dripping filter tower, the top of described dividing plate and a filter tower is set to gas passage, and described gas is processed by the packed tower desulfurization of opposite side through gas passage from top to bottom through dripping after filter tower desulfurization processes of side from the bottom to top.
Optionally, the pressure reduction distribution of the gas inlet packing layer as required of described gas access.Owing to pressure drop there are differences, the reasonable layout of gas can be realized according to pressure drop.
Present invention have the advantage that:
1, there is preposition scrubbing tower, which removes and may affect the impurity of follow-up desulfurization process and the disposal ability of desulfurizing tower is improved;
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, and 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 98ppm by the present invention, meets the technical need of boiler, electromotor, and considers power consumption, water consumption, heat dissipation, and the processing cost of every cubic metre of the present invention is less than 0.015 yuan.

Claims (11)

1. utilize a device for microorganism removing hydrogen sulfide in methane, including preposition scrubbing tower, main desulfurizing tower and external reactor, it is characterised in that:
Described preposition scrubbing tower is provided with biogas entrance and upper gas outlet, and the outlet of described upper gas is divided into some branch roads and the gas feed connection of main desulfurizing tower along gas flow;
Described main desulfurizing tower, for dripping filter tower, described filter tower is provided with some gas accesses and lower liquid outlet;Including some packing layers in described filter tower, described gas access is arranged corresponding to packing layer;
Described reactor is connected by the lower liquid outlet of pipeline and main desulfurizing tower, described main desulfurizing tower includes some liquid-inlets and spray equipment from top to bottom, described liquid-inlet is positioned at top and the middle part of packing layer, described liquid-inlet and spray equipment connect, culture fluid in described reactor is entered external reactor described in the spray equipment in main desulfurizing tower by pump and liquid-inlet and is connected by the lower liquid outlet of pipeline and main desulfurizing tower, described main desulfurizing tower includes some liquid-inlets and spray equipment from top to bottom, described liquid-inlet and spray equipment connect, culture fluid in described external reactor 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, and wire feeding is Raschig ring or Pall 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 the packed tower of DG25 or DG50 Pall ring filler in bulk, the circulation fluid of described packed tower for 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 between described preposition scrubbing tower and main desulfurizing tower, pipeline arranges air intake, and air is mixed in biogas by this entrance.
Device the most according to claim 1, it is characterized in that, the middle part of described filter tower is provided with and is divided into two-part dividing plate by dripping filter tower, the top of described dividing plate and a filter tower is set to gas passage, and described gas is processed by the packed tower desulfurization of opposite side through gas passage from top to bottom through dripping after filter tower desulfurization processes of side from the bottom to top.
7. the 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 the culture fluid after air or oxygen aeration;
3) desulfurization bacterium grows on filler, and from gaseous state, hydrogen sulfide is changed into elemental sulfur or sulfate radical and inferior sulfate radical.
Method the most according to claim 7, it is characterised in that in several spray equipments that described filter tower is respectively provided with from top to bottom, the jet apparatus on top is normally opened, the spray equipment of bottom is that filler is accumulated impurity and washes down by the unlatching selected.
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 is mixed into oxygen content in the gas making removing hydrogen sulfide and is not higher than the air of 0.5%.
10. according to the method described in claim 7 or 8, it is characterised in that described methane quantity and circulation fluid volume ratio are 40-200:1, preferably 100:1.
11. according to the method described in claim 7 or 8, it is characterised in that when elemental sulfur generates when dripping formation accumulation in filter tower, be mixed into air capacity by adjustment or aeration rate accelerates it and is converted into sulfate radical.
CN201610298870.0A 2016-05-06 2016-05-06 Device and method for removing hydrogen sulfide in marsh gas with microorganisms Pending CN105817129A (en)

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Publication number Priority date Publication date Assignee Title
CN108893146A (en) * 2018-09-17 2018-11-27 陕西黑猫焦化股份有限公司 A kind of device using hydrogen sulfide gas in biological desulfurization removing coal gas
CN108993132A (en) * 2018-09-21 2018-12-14 无锡惠联资源再生科技有限公司 Material filling type biomass marsh gas desulfurizer
CN112210409A (en) * 2020-10-30 2021-01-12 岳阳县枫树湾畜牧有限公司 Biogas biological desulfurization device and desulfurization method
FR3112967A1 (en) * 2020-08-03 2022-02-04 Veolia Water Solutions & Technologies Support Process for the purification and deodorization of a gaseous effluent and installation for the implementation of such a process.

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CN104152203A (en) * 2014-08-31 2014-11-19 广西大学 Method for purifying and preparing high-purity biomass methane by using biogas slurry
CN205730825U (en) * 2016-05-06 2016-11-30 北京时代桃源环境科技有限公司 A kind of device utilizing microorganism removing hydrogen sulfide in methane

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Publication number Priority date Publication date Assignee Title
CN101234280A (en) * 2007-11-07 2008-08-06 中山大学 Absorption-biological treatment method for malodorous gas
CN102921293A (en) * 2011-08-12 2013-02-13 中国石油天然气股份有限公司 Method for processing foul gas through using biological combined technology
CN104152203A (en) * 2014-08-31 2014-11-19 广西大学 Method for purifying and preparing high-purity biomass methane by using biogas slurry
CN205730825U (en) * 2016-05-06 2016-11-30 北京时代桃源环境科技有限公司 A kind of device utilizing microorganism removing hydrogen sulfide in methane

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108893146A (en) * 2018-09-17 2018-11-27 陕西黑猫焦化股份有限公司 A kind of device using hydrogen sulfide gas in biological desulfurization removing coal gas
CN108993132A (en) * 2018-09-21 2018-12-14 无锡惠联资源再生科技有限公司 Material filling type biomass marsh gas desulfurizer
FR3112967A1 (en) * 2020-08-03 2022-02-04 Veolia Water Solutions & Technologies Support Process for the purification and deodorization of a gaseous effluent and installation for the implementation of such a process.
CN112210409A (en) * 2020-10-30 2021-01-12 岳阳县枫树湾畜牧有限公司 Biogas biological desulfurization device and desulfurization method
CN112210409B (en) * 2020-10-30 2021-07-20 岳阳县枫树湾畜牧有限公司 Biogas biological desulfurization device and desulfurization method

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