CN101870894A - Method and biological plant for removing carbon dioxide, hydrogen sulfide and ammonia from methane by using microecology principle - Google Patents

Method and biological plant for removing carbon dioxide, hydrogen sulfide and ammonia from methane by using microecology principle Download PDF

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CN101870894A
CN101870894A CN200910049659A CN200910049659A CN101870894A CN 101870894 A CN101870894 A CN 101870894A CN 200910049659 A CN200910049659 A CN 200910049659A CN 200910049659 A CN200910049659 A CN 200910049659A CN 101870894 A CN101870894 A CN 101870894A
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hydrogen sulfide
ammonia
reactor
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carbon dioxide
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张扬
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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
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    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
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Abstract

The invention aims to utilize the principle of microecology, and utilize the characteristics that methane gas is insoluble, ammonia is soluble, and carbon dioxide and hydrogen sulfide gas are soluble under the alkaline condition. Blue-green algae can absorb the carbon dioxide dissolved in water and release oxygen through photosynthesis in the presence of nutritional components such as nitrogen and phosphorus; nitrobacteria and nitrite bacteria oxidize the ammonia dissolved in the water into nitrate ions so as to remove the ammonia under the aerobic condition; and under the condition of low oxygen concentration, thiobacteria can oxidize the hydrogen sulfide dissolved in the water into free sulphur so as to remove the hydrogen sulfide gas dissolved in the water. By utilizing the principle of microbial reactions, a method and a device for removing the carbon dioxide, hydrogen sulfide and ammonia from methane by means of the microecological reactions are established.

Description

Remove carbonic acid gas, hydrogen sulfide and ammonia method and biological device in the biogas with little ecological principle
One, technical field: B01D 53/84; C12P5/00
Utilize little ecological principle and microbial reaction to remove carbonic acid gas, hydrogen sulfide and ammonia method and biological device in the biogas.
Two, background technology:
Biogas is a kind of mixed gas, by methane, and carbonic acid gas, and small quantity of hydrogen, hydrogen sulfide, ammonia, the mixing inflammable gas that carbon monoxide etc. are formed.Usually, methane accounts for about 55%, and carbonic acid gas accounts for 40%, and is remaining by hydrogen, hydrogen sulfide, a small amount of gas composition such as carbon monoxide.The too high carbon dioxide content of ratio can reduce the combustion heat value of biogas, and high-load hydrogen sulfide forms severe corrosive solution after burning, to the metal parts formation corrosion of generating set and pipeline.The restriction that above-mentioned two shortcomings are serious the range of application of biogas, the function of present marsh gas purifying device is all more single, the structure more complicated, cost is higher, therefore generally have only the large-sized biogas facility just condition adopt.
Three, summary of the invention:
Inventive principle:
The objective of the invention is to utilize the principle of microecology, utilize the byproduct and the simple equipment of biogas fermentation, release a kind of easy, cheap, carbonic acid gas in the removal biogas that starting material are easy to get, the method and apparatus of hydrogen sulfide and ammonia.
The present invention is achieved in that biogas is a kind of mainly by methane, carbonic acid gas, and small quantity of hydrogen, hydrogen sulfide, ammonia, the mixing inflammable gas that carbon monoxide etc. are formed.Usually, methane accounts for about 55%, and carbonic acid gas accounts for 40%, and is remaining by hydrogen, hydrogen sulfide, a small amount of gas composition such as carbon monoxide.Methane gas is insoluble in water, and carbonic acid gas and hydrogen sulfide solution be alkalescence condition under soluble in water.Contain abundant being easy in the natural pond liquid after the fermentation, as nitrogen, phosphorus and other nutritive ingredients etc. by the nutritive ingredient of plant absorbing.Blue-green algae is a kind of prokaryotic micro-organisms of low grade, can survive in anoxybiotic water.Utilize inorganic nutrient salt such as nitrogen, phosphorus in the water simultaneously, be dissolved in the carbonic acid gas in the water and discharge oxygen by the photosynthesis absorption.Nitrobacteria and nitrite bacteria can be oxidized to nitrate ion with the free ammonia in the water under the condition of aerobic, and the form of the best nitrogen that nitrate ion is a blue-green algae can directly absorb.Simultaneously, under the condition that faint oxygen exists, a lot of thiobacteriums can be oxidized to dissolved hydrogen sulfide in the water free sulfur precipitation, thereby remove dissolved hydrogen sulfide in the water.The present invention is exactly a principle of utilizing the mentioned microorganism reaction, sets up the bio-reactor that a cover relies on microecosystem, removes carbonic acid gas, hydrogen sulfide and ammonia in the biogas.
Beneficial effect:
Because biogas contains a large amount of carbon dioxides, can reach 40% (V/V) usually, serious reduction the combustion heat value of biogas.Simultaneously, biogas contains a large amount of hydrogen sulfide, and the gas that produces severe corrosive when burning damages the pipeline and the generating set of metal.This has greatly limited and has used popularizing of marsh gas power generation.Present method is utilized the byproduct of biogas production and the microorganism that occurring in nature obtains easily, by the method for microecology, unites the carbonic acid gas that reduces in the biogas, the content of hydrogen sulfide and free ammonia.Present method principle is clear and definite, and implementing process is simple, simple in equipment, and the whole plant cost is cheap, the raw materials used byproduct that all produces from biogas fermentation, therefore suitable various types of methane-generating pits adopt, and purify the biogas that is produced and are used for the generating needs.
Four, description of drawings: see that accompanying drawing 1, microorganism marsh gas purifying equipment illustrate
1, intake ducting; 2, the gaseous diffuser of multiple exit; 3, by natural pond liquid be the meta-alkalescence nutritive medium of main preparation; 4, outlet pipe and pressure limiting valve; 5, be connected to the photosynthetic response solution of blue-green algae algae kind; 6, oxidation nitrator; 7, bioaffinity protruded packing; 8, water pump; 9, photosynthetic reactor; 10, oxygen emptying pressure limiting valve; 11, oxygen emptying pipe
Five, concrete embodiment:
Reactor R is by a plurality of scatterers 2 that scatter the gas of mouth, and the nutritive medium 3 of inner faint alkalescence and top have the outlet pipe of pressure limiting valve 4 and forms.
Biogas enters in the liquid 3 in the reactor R by a plurality of scatterers 2 that scatter mouthful are arranged along intake ducting 1.It is in order to increase the contact area of liquid 3 in biogas and the reactor R, to increase carbonic acid gas in the biogas, the solubleness of hydrogen sulfide and ammonia that scatterer 2 designs have a plurality of distributions mouths.Individual pressure limiting valve is arranged at reactor R top, can keep and keep certain pressure in the reactor R.Nutritive medium 3 in the reactor R is that the dilution of main adding small amounts of inorganic salt is formulated by the natural pond liquid behind the biogas fermentation, and adds an amount of yellow soda ash, keeps the weakly alkaline of nutritive medium 3 at pH 7.5-pH 8.5.Adding yellow soda ash makes nutritive medium 3 present the weakly alkaline dissolving power of liquid 3 for carbonic acid gas and hydrogen sulfide that can have additional nutrients.
The upper end of photosynthetic reactor 9 has pipeline to be connected with oxidation nitrator 6.Photosynthetic reactor 9 is made by transparent material, in have inoculation that blue-green algae algae kind is arranged.There is the filler 7 of bioaffinity oxidation nitrator 6 inside, thiobacteriums such as inoculation nitrobacteria and nitrite bacteria and thiobacillus denitrificans, thiobacillus thiooxidans on the filler.
When the ambient lighting condition is better, water pump 8 work, the saturated liquid 3 that carbonic acid gas and hydrogen sulfide is arranged and be dissolved with ammonia is entered photosynthetic reactor 9 through water pumps 8, owing to itself containing, the liquid 3 by the preparation of natural pond liquid enriches nitrogen, phosphorus nutrition element, and saturated carbon dioxide dissolved CO2 gas, very suitable blue algae growth.Blue-green algae consumes the carbonic acid gas in the nutritive medium 3 and discharges oxygen, reaction equation (a) by photosynthesis.A large amount of oxygen that photosynthesis produces enter specific container by pressure limiting valve 10 by pipeline 11 and recycle or emptying.At this moment, nutritive medium 3 is the state of the saturated oxygen of dissolving by the state-transition of the saturated carbonic acid gas of dissolving, contains the nutritive medium 3 that enriches oxygen and flows to naturally in the oxidation nitrator 6.The filler 7 epimeres growth of oxidation nitrator 6 has aerobic nitrobacteria and nitrite bacteria.Under the condition of hyperoxia, the free ammonia in the water is oxidized into nitrate ion, and the dissolved oxygen in the consume water, reaction equation (b); The consumption of the bacterium of filler 7 aerobic sections in peroxidation nitrator 6, the saturated oxygen of dissolved is consumed in the nutritive medium 3, nutritive medium 3 transfers hypoxia to, low oxygen area is formed at the bottom of filler 7 in oxidation nitrator 6, under the condition of hyperoxia or hypoxemia, thiobacillus denitrificans, thiobacillus thiooxidans, thiobacillus ferrooxidant, grate sulfur thiobacillus, thread thiobacterium, family name's sulphur Pseudomonas, distinguish that thiobacteriums such as sulphur Pseudomonas, Thiothrix can be oxidized to hydrogen sulfide simple substance S or SO 4 2-Thereby, the hydrogen sulfide in the biogas is removed.Reaction equation (c), (d).
Through above-mentioned circulation, nutritive medium 3 is dissolved with saturated carbonic acid gas when being come out by reactor R, and hydrogen sulfide and dissolving ammonia are consumed or transform, and reenter among the reactor R, continue carbonic acid gas, hydrogen sulfide and ammonia in the biogas in the dissolution reactor R.And continue to be pumped in the photosynthetic reactor 9 by water pump 8, repeat aforesaid circulation.And so forth, continuous carbonic acid gas, hydrogen sulfide and the ammonia in the biogas of absorption reactor thermally R top of total system.Nutrition in nutritive medium 3 is consumed light, or blue algae growth density is when too high, can be by adding new nutritive medium or discharging excessive blue-green algae and keep the stable of reaction and carry out.
6CO 2+6H 2O→C 6H 12O 6+6O 2 (a)
NH 3+2O 2→NO 3 -+H 2O+H + (b)
2H 2S+O 2→2S+2H 2O (c)
2S+3O 2+2H 2O→2H 2SO 4 (d)。
Figure of description
Figure B2009100496595D0000031
Figure one, microorganism marsh gas purifying equipment illustrate
1, intake ducting; 2, the gaseous diffuser of multiple exit; 3, by natural pond liquid be the meta-alkalescence nutritive medium of main preparation; 4, outlet pipe and pressure limiting valve; 5, be connected to the photosynthetic response solution of blue-green algae algae kind; 6, oxidation nitrator; 7, bioaffinity protruded packing; 8, water pump; 9, photosynthetic reactor; 10, oxygen emptying pressure limiting valve; 11, oxygen emptying pipe.

Claims (4)

1. one kind is utilized little ecological principle and microbial reaction to remove carbonic acid gas, hydrogen sulfide and ammonia method and biological device in the biogas, it is by gas reactor R, and transparent photosynthetic reactor is formed with the oxidation nitrator that multiporous biological affinity packing material is housed.It is characterized in that being full of by natural pond, fermentation back liquid in the reactor is main formulated nutritive medium, and makes solution be weakly alkaline by adding carbonate.Under illumination condition, algae utilizes nitrogen, the phosphorus composition in the nutritive medium, and absorbing carbon dioxide is emitted oxygen.Dissolved oxygen is utilized by aerobic bacteria and will have the ammonia and the hydrogen sulfide oxidation of going back ortho states in the solution.Obtain the solution removal carbonic acid gas, the effect of hydrogen sulfide and dissolved ammonia.
2. according to the described reactor R of claim (1), it is characterized in that it is the main nutritive medium that is mixed with that inside fills by natural pond, fermentation back liquid, and add an amount of carbonate and make its pH value present weakly alkaline.
3. according to the described photosynthetic reactor of claim (1), it is characterized in that: inoculation has the algae and the bacterium that can carry out photosynthetic response in the photosynthetic reactor, and these algae and bacterium can absorb carbon dioxide dissolved and emit oxygen.
4. according to the described oxidation nitrator of claim (1), it is characterized in that: be filled with the porous biocompatible material in the reactor, inoculation has nitrobacteria and denitrifying bacterium and thiobacterium etc.Above-mentioned bacterium can be converted into nitrate ion with ammonia under the condition of aerobic, hydrogen sulfide is oxidized to sulphur or oxysulfide.
CN2009100496595A 2009-04-21 2009-04-21 Method and biological plant for removing carbon dioxide, hydrogen sulfide and ammonia from methane by using microecology principle Expired - Fee Related CN101870894B (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002408A (en) * 2010-12-16 2011-04-06 哈尔滨工业大学 Marsh gas biological desulphurization energy-saving method
ES2372509A1 (en) * 2011-10-18 2012-01-23 Biogás Fuel Cell, S.A. System of simultaneous purification of biogas and industrial residual effluents through microalogs and bacteria. (Machine-translation by Google Translate, not legally binding)
CN102835261A (en) * 2012-09-17 2012-12-26 北京化工大学 Application of residual waste gas after biogas purification as gas fertilizer
WO2013034947A1 (en) * 2011-09-08 2013-03-14 Cellennium (Thailand) Company Limited Upgrading of biogas to marketable purified methane exploiting microalgae farming
CN104226671A (en) * 2013-06-11 2014-12-24 远东生物科技股份有限公司 Green treatment system and method for biological waste
CN104383804A (en) * 2014-12-02 2015-03-04 华中农业大学 CO2 absorption and storage utilization system and method adopting anaerobic fermentation biogas slurry as carrier
CN104548921A (en) * 2014-12-23 2015-04-29 北京伊普国际水务有限公司 Biological deodorization filling material and preparation method thereof
CN105623761A (en) * 2014-11-26 2016-06-01 成都中科能源环保有限公司 Method for biologically synthesizing natural gas from coke oven gas
CN105623766A (en) * 2014-11-26 2016-06-01 成都中科能源环保有限公司 Biological treatment method for combustible gas deoxidation and denitrification
WO2016109020A1 (en) * 2014-12-30 2016-07-07 Exxonmobil Upstream Research Company Algae-based method of inhibiting corrosion in offshore flexible pipes
CN106268290A (en) * 2016-09-28 2017-01-04 徐明好 The method for designing of a kind of gas disposal device and device thereof
CN107513442A (en) * 2017-10-10 2017-12-26 重庆大学 Indirect type Methane decarbonization method of purification and system based on microalgae photosynthetic carbon fixation principle
US10487636B2 (en) 2017-07-27 2019-11-26 Exxonmobil Upstream Research Company Enhanced methods for recovering viscous hydrocarbons from a subterranean formation as a follow-up to thermal recovery processes
CN110627214A (en) * 2019-08-15 2019-12-31 西安建筑科技大学 Device and method for improving toxic gas in pipeline
US11002123B2 (en) 2017-08-31 2021-05-11 Exxonmobil Upstream Research Company Thermal recovery methods for recovering viscous hydrocarbons from a subterranean formation
GB2592841A (en) * 2019-01-18 2021-09-15 Autichem Ltd Treatment of carbon dioxide containing materials with algae
US11142681B2 (en) 2017-06-29 2021-10-12 Exxonmobil Upstream Research Company Chasing solvent for enhanced recovery processes
US11261725B2 (en) 2017-10-24 2022-03-01 Exxonmobil Upstream Research Company Systems and methods for estimating and controlling liquid level using periodic shut-ins

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002408A (en) * 2010-12-16 2011-04-06 哈尔滨工业大学 Marsh gas biological desulphurization energy-saving method
WO2013034947A1 (en) * 2011-09-08 2013-03-14 Cellennium (Thailand) Company Limited Upgrading of biogas to marketable purified methane exploiting microalgae farming
ES2372509A1 (en) * 2011-10-18 2012-01-23 Biogás Fuel Cell, S.A. System of simultaneous purification of biogas and industrial residual effluents through microalogs and bacteria. (Machine-translation by Google Translate, not legally binding)
CN102835261A (en) * 2012-09-17 2012-12-26 北京化工大学 Application of residual waste gas after biogas purification as gas fertilizer
CN104226671B (en) * 2013-06-11 2018-02-09 远东生物科技股份有限公司 Green treatment system and method for biological waste
CN104226671A (en) * 2013-06-11 2014-12-24 远东生物科技股份有限公司 Green treatment system and method for biological waste
CN105623761B (en) * 2014-11-26 2019-09-20 成都中科能源环保有限公司 A kind of method of coke-stove gas biosynthesis natural gas
CN105623761A (en) * 2014-11-26 2016-06-01 成都中科能源环保有限公司 Method for biologically synthesizing natural gas from coke oven gas
CN105623766A (en) * 2014-11-26 2016-06-01 成都中科能源环保有限公司 Biological treatment method for combustible gas deoxidation and denitrification
CN105623766B (en) * 2014-11-26 2019-08-09 成都中科能源环保有限公司 A kind of bioremediation of fuel gas deoxidation, denitrogenation
CN104383804A (en) * 2014-12-02 2015-03-04 华中农业大学 CO2 absorption and storage utilization system and method adopting anaerobic fermentation biogas slurry as carrier
CN104383804B (en) * 2014-12-02 2016-07-06 华中农业大学 A kind of be carrier with anaerobic fermentation biogas slurry CO2Absorb and storage utilizes system and method
CN104548921A (en) * 2014-12-23 2015-04-29 北京伊普国际水务有限公司 Biological deodorization filling material and preparation method thereof
WO2016109020A1 (en) * 2014-12-30 2016-07-07 Exxonmobil Upstream Research Company Algae-based method of inhibiting corrosion in offshore flexible pipes
CN106268290A (en) * 2016-09-28 2017-01-04 徐明好 The method for designing of a kind of gas disposal device and device thereof
US11142681B2 (en) 2017-06-29 2021-10-12 Exxonmobil Upstream Research Company Chasing solvent for enhanced recovery processes
US10487636B2 (en) 2017-07-27 2019-11-26 Exxonmobil Upstream Research Company Enhanced methods for recovering viscous hydrocarbons from a subterranean formation as a follow-up to thermal recovery processes
US11002123B2 (en) 2017-08-31 2021-05-11 Exxonmobil Upstream Research Company Thermal recovery methods for recovering viscous hydrocarbons from a subterranean formation
CN107513442A (en) * 2017-10-10 2017-12-26 重庆大学 Indirect type Methane decarbonization method of purification and system based on microalgae photosynthetic carbon fixation principle
US11261725B2 (en) 2017-10-24 2022-03-01 Exxonmobil Upstream Research Company Systems and methods for estimating and controlling liquid level using periodic shut-ins
GB2592841A (en) * 2019-01-18 2021-09-15 Autichem Ltd Treatment of carbon dioxide containing materials with algae
CN110627214A (en) * 2019-08-15 2019-12-31 西安建筑科技大学 Device and method for improving toxic gas in pipeline

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