CN102604701B - Methane biodesulfurization method - Google Patents

Methane biodesulfurization method Download PDF

Info

Publication number
CN102604701B
CN102604701B CN201210075244.7A CN201210075244A CN102604701B CN 102604701 B CN102604701 B CN 102604701B CN 201210075244 A CN201210075244 A CN 201210075244A CN 102604701 B CN102604701 B CN 102604701B
Authority
CN
China
Prior art keywords
circulation fluid
methane
natural pond
biogas
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210075244.7A
Other languages
Chinese (zh)
Other versions
CN102604701A (en
Inventor
董泰丽
宫亚斌
吴军宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Minhe Biological Technology Co., Ltd.
Original Assignee
SHANDONG MINHE BIOLOGICAL TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHANDONG MINHE BIOLOGICAL TECHNOLOGY Co Ltd filed Critical SHANDONG MINHE BIOLOGICAL TECHNOLOGY Co Ltd
Priority to CN201210075244.7A priority Critical patent/CN102604701B/en
Publication of CN102604701A publication Critical patent/CN102604701A/en
Application granted granted Critical
Publication of CN102604701B publication Critical patent/CN102604701B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Landscapes

  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Treatment Of Sludge (AREA)

Abstract

The invention belongs to the technical field of methane desulfurization, and particularly relates to a methane biodesulfurization method. The methane biodesulfurization method comprises the following steps that: a circulating liquid containing desulfurizing bacteria is sprayed down by a spraying head at the top part of a desulfurization tower, methane is blown into a gas inlet pipe from the lower part of the desulfurization tower, and is fully contacted with the circulating liquid in the middle filler, the desulfurizing bacteria contained in the circulating liquid oxidizes and removes hydrogen sulfide in the methane by the action of biological oxidation, wherein 2.0-2.5L methane liquid is added into each cubic meter of circulating liquid every day. The methane biodesulfurization method has the characteristics that the control is convenient, the operation is simple, and the desulfurization efficiency is high.

Description

Methane bio-desulfurization method
Technical field
The invention belongs to biogas desulfurization technical field, be specifically related to a kind of methane bio-desulfurization method.
Background technology
Biogas fermentation material as animal waste, high-concentration industrial organic waste water, municipal effluent plant excess sludge, crop material and organic waste etc. be all biomass class material, contain a considerable amount of organosulfurs or inorganic sulfur, in anaerobic digestion process, be converted to hydrogen sulfide, therefore in biogas, all contain the hydrogen sulfide of some amount, as take, approximately contain the hydrogen sulfide of 5000ppm in the biogas of chicken manure after fermenting raw materials.Hydrogen sulfide not only has very strong corrosive nature to combustion powered equipment and metallic conduit, thereby also can cause the wearing and tearing of the rotten boost engine of lubricating oil.Biogas is after burning, and hydrogen sulfide can be converted into sulfur oxide (SO x) and be discharged in air, cause topsoil.Therefore,, in order to reach the target of safe utilization and environment protection, must to biogas, carry out desulfurization processing before use.
At present, hydrogen sulfide in methane removal methods mainly contains physico-chemical processes and biological process.Physico-chemical processes sweetening process is with sorbent material (as: arsyl compound, iron chelate, iron trichloride etc.) or sweetening agent (as: iron system, zinc system, copper system, calcium based compound etc.) adsorption of hydrogen sulfide substantially or reacts generation sulfide with hydrogen sulfide, take oxygen as electron acceptor(EA) is oxidized to elemental sulfur by hydrogen sulfide (sulfide) again, make sorbent material or desulfurizer regeneration.Because physical chemistry sulfur method exists the shortcomings such as energy consumption is high, processing costs is expensive, sludge disposal difficulty, biological desulphurization has been subject to generally favor in recent years.
Biological desulphurization refers to and utilizes the biological oxidation of thiobacterium that the Oxidation of Hydrogen Sulfide in biogas is become to elemental sulfur, is further oxidized to sulfurous acid and sulfuric acid, thus the technique that sulphur is removed from biogas.With respect to physico-chemical processes, biological desulphurization has not aerobic agent or catalyzer, does not produce the feature of chemical sludge, is therefore generally favored.And also there is following shortcoming in the biological process sulfur removal technology of current stage: desulfuration efficiency is low, operational conditions is difficult to control, running cost is higher.
Summary of the invention
The object of this invention is to provide a kind of methane bio-desulfurization method, have and be convenient to control, simple to operate, the feature that desulfuration efficiency is high.
A kind of methane bio-desulfurization method of the present invention, the circulation fluid that contains desulfurizing bacteria through the spray header spray at thionizer top and under, biogas is blown into from the inlet pipe of thionizer bottom, in the filler at middle part, fully contact with circulation fluid, the desulfurizing bacteria containing in circulation fluid removes the Oxidation of Hydrogen Sulfide in biogas through biological oxidation, wherein, in the circulation fluid of every cubic metre, add 2.0～2.5L natural pond liquid every day.
Effective flora in circulation fluid is that to take thiobacillus ferrooxidant and thiobacillus thiooxidans be main desulfurization flora, these two kinds of bacterium are has a liking for acid, aerobic type bacterium, sulfide or the elemental sulfur of reduction-state of take is energy derive, take ammonium nitrogen as nitrogenous source, take carbonic acid gas as carbon source.
Wherein, natural pond liquid preferably prepares in accordance with the following methods: the feces of livestock and poultry acidifying that is hydrolyzed in hydrolysis acidification pool, the residence time is 4 days, feed liquid after acidication pumps into anaerobic fermentation tank, leavening temperature is 35～38 ℃, feed liquid stops 35 days in fermentor tank, fully after aerogenesis, discharges, and is natural pond liquid.
The total solids level of the feed liquid after acidication is preferably 6～8%.
The feeding manner that feed liquid after acidication pumps into anaerobic fermentation tank is preferably intermittent charging, and anaerobic fermentation tank type is preferably full-mixing type anaerobic fermentor tank.
The total solids level of natural pond liquid is preferably 2～5%, pH and is preferably 8.0～8.5.
Be in operation and need guarantee by controlling some parameters the nutritive substance that the vigor of desulfurization flora, these parameters comprise the temperature of circulation fluid, the pH of circulation fluid, aeration rate and need add.
Circulation fluid temperature is preferably 28～30 ℃.When Fig. 2 is circulation fluid differing temps and the changing trend diagram of thionizer outlet biogas concentration, as seen from the figure, the concentration of hydrogen sulfide when the temperature of circulation fluid is 28～30 ℃ in biogas is minimum, and sweetening effectiveness is best.
Circulation fluid pH is preferably 1.5～2.5.Thiobacillus ferrooxidant and thiobacillus thiooxidans are all acidophilic bacteria, therefore pH should be controlled in lower scope.
Desulphurization Strains is aerobic type bacterial classification, therefore should guarantee has sufficient oxygen, aeration to comprise two aspects in its living environment, the one, to aeration in the circulation fluid in cyclic water tank, dissolved oxygen content in circulation fluid is reached capacity, to guarantee the Desulphurization Strains necessary oxygen of living; The 2nd, in inlet pipe, pass into the air capacity that accounts for biogas flow 10%, make after desulfurization in biogas remaining oxygen level between 1.2～1.5%, there is sufficient oxygen to utilize when guaranteeing bacterial classification reduction-sulfurization hydrogen.
Ammonia-nitrogen content in the liquid of natural pond is 5000mg/L, for desulfurizing bacteria provides abundant nitrogenous source, has in addition required other nutritive substances such as trace element of growth in the liquid of natural pond, therefore the interpolation of natural pond liquid has been played impact very significantly to sweetening effectiveness.As shown in Figure 3, once add natural pond liquid curve and refer to that every day, 16:30 added 2L/m in circulation fluid 3natural pond liquid, secondary add natural pond liquid curve refer to every day 7:30 and 19:30 in circulation fluid, add 1L/m respectively at twice 3natural pond liquid, the change conditions of hydrogen sulfide in methane concentration is as shown in the figure.From once adding natural pond liquid curve, concentration of hydrogen sulfide starts to reduce after natural pond liquid adds, and after 9 hours, reaches minimum, illustrates that natural pond liquid has obvious impact to the activity of desulfurization.And two curve comparisons are known, same natural pond liquid addition, the effect of adding is at twice than once good.
The invention has the advantages that:
(1) significant desulfurization effect.Concentration of hydrogen sulfide in biogas can be down to below 200ppm by 5000ppm, desulfuration efficiency reaches more than 96%, has significantly reduced the impact of hydrogen sulfide on follow-up relevant device.
(2) parameter is easy to control.Regulate the air intake valve of the water back in cyclic water tank, can reach the effect of controlled circulation liquid temp; Aeration rate can be by regulating the valve on pipeline to adjust; The interpolation of nutritive substance can be adjusted at any time according to the flow of circulation fluid.The cooperation adjustment of various parameters has guaranteed the stability of sweetening effectiveness.
(3) running cost is cheap.The natural pond liquid that nutritive substance mainly adopts fermentation to produce, without adding other material; And aerating system and recycle system equipment are simple, stable, the electricity charge that only need energy supply to use.
Accompanying drawing explanation
Fig. 1 is the structural representation of methane bio-desulfurization device;
Fig. 2 is the affect trend map of the temperature of circulation fluid on sweetening effectiveness;
Fig. 3 is the change curve of thionizer exit hydrogen sulfide in methane concentration before and after natural pond liquid adds;
In figure: 1, thionizer 2, inlet pipe 3, escape pipe 4, elastic filler 5, spray header 6, cyclic water tank 7, circulation fluid rising pipe 8, circulation fluid water inlet pipe 9, moisturizing pipeline 10, nutritive medium add pipeline 11, water back.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described.
Embodiment 1:
This desulfurizer comprises thionizer 1, thionizer 1 bottom and top arrange respectively inlet pipe 2 and escape pipe 3, in tower, be filled with elastic filler 4, the top of elastic filler 4 is provided with spray header 5, one side of thionizer 1 is provided with cyclic water tank 6, on cyclic water tank 6, be provided with circulation fluid rising pipe 7 and circulation fluid water inlet pipe 8, wherein, circulation fluid rising pipe 7 is connected with spray header 5, circulation fluid water inlet pipe 8 is connected with thionizer 1 bottom, the top of cyclic water tank 6 is provided with moisturizing pipeline 9 and nutritive medium adds pipeline 10, and cyclic water tank 6 covers are connected with water back 11.
Spray header 5 sprays in thionizer 1 come from the circulation fluid in cyclic water tank 6, and biogas is blown into from inlet pipe 2, and biogas and circulation fluid, in the elastic filler abundant combination in 4 places, are realized biological desulphurization, and control method and the controlling valu of parameters are as follows:
Temperature: the control of circulation fluid temperature is to realize by controlling the time of the logical steam in water back 11, and temperature is controlled between 28～30 ℃.
Aeration rate: pass into a certain amount of air respectively in inlet pipe 2 and in cyclic water tank 6, pass into the air of biogas flow 10% in inlet pipe, the oxygen concentration of the circulation fluid of cyclic water tank should reach 7.0mg/L.The size of air flow regulates by pipeline valve.
Nutritive substance: every day, natural pond liquid was added in 12 hours at twice in interval in cyclic water tank, the circulation fluid that addition is each every cubic metre adds 1L natural pond liquid.
PH: detect the pH of circulation fluid every day, it is maintained between 1.5～2.5.
Natural pond used liquid is prepared in accordance with the following methods: the feces of livestock and poultry acidifying that is hydrolyzed in hydrolysis acidification pool, the residence time is 4 days, the total solids level of the feed liquid after acidication is 8%, feed liquid after acidication pumps into anaerobic fermentation tank, and feeding manner is intermittent charging, and anaerobic fermentation tank type is full-mixing type anaerobic fermentor tank, leavening temperature is 35～38 ℃, feed liquid stops 35 days in fermentor tank, fully after aerogenesis, discharges, and is natural pond liquid.
The correlation parameter of natural pond liquid is that total solids level is that 2～5%, pH is 8.0～8.5, several to the influential substances content of microorganism as following table:
Index Content (mg/L)
Ammonia nitrogen 5128
Trace element 0.011
CODcr 482
TP (total phosphorus) 482
TN (total nitrogen) 2018
Organic 2860
Humic acids 2018
The hydrogen sulfide of the present embodiment air inlet mouth of pipe is 5273ppm, and the mouth of pipe hydrogen sulfide of giving vent to anger is 96ppm, and desulfuration efficiency is 98.2%, and in the biogas after desulfurization, remaining oxygen level is 1.2%.

Claims (1)

1. a methane bio-desulfurization method, the circulation fluid that it is characterized in that containing desulfurizing bacteria through the spray header spray at thionizer top and under, biogas is blown into from the inlet pipe of thionizer bottom, in the filler at middle part, fully contact with circulation fluid, the desulfurizing bacteria containing in circulation fluid removes the Oxidation of Hydrogen Sulfide in biogas through biological oxidation, and wherein, add 2.0～2.5L natural pond liquid every day in the circulation fluid of every cubic metre, add at twice in circulation fluid, add 1L/m at every turn 3; Circulation fluid carries out aeration before spray, passes into the air of biogas flow 10% in inlet pipe;
Natural pond liquid prepares in accordance with the following methods: the feces of livestock and poultry acidifying that is hydrolyzed in hydrolysis acidification pool, and the residence time is 4 days, the feed liquid after acidication pumps into anaerobic fermentation tank, leavening temperature is 35～38 ℃, feed liquid stops 35 days in fermentor tank, fully after aerogenesis, discharges, and is natural pond liquid;
The total solids level of the feed liquid after acidication is 6～8%;
The feeding manner that feed liquid after acidication pumps into anaerobic fermentation tank is intermittent charging, and anaerobic fermentation tank type is full-mixing type anaerobic fermentor tank;
The total solids level of natural pond liquid is that 2～5%, pH is 8.0～8.5;
Circulation fluid temperature is 28～30 ℃;
Circulation fluid pH is 1.5～2.5.
CN201210075244.7A 2012-03-21 2012-03-21 Methane biodesulfurization method Active CN102604701B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210075244.7A CN102604701B (en) 2012-03-21 2012-03-21 Methane biodesulfurization method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210075244.7A CN102604701B (en) 2012-03-21 2012-03-21 Methane biodesulfurization method

Publications (2)

Publication Number Publication Date
CN102604701A CN102604701A (en) 2012-07-25
CN102604701B true CN102604701B (en) 2014-03-26

Family

ID=46522481

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210075244.7A Active CN102604701B (en) 2012-03-21 2012-03-21 Methane biodesulfurization method

Country Status (1)

Country Link
CN (1) CN102604701B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104152203B (en) * 2014-08-31 2017-02-08 广西大学 Method for purifying and preparing high-purity biomass methane by using biogas slurry
CN108358418A (en) * 2016-01-09 2018-08-03 充烜金 A kind of excreta recycling system
CN110064295A (en) * 2019-03-11 2019-07-30 昆明理工大学 A kind of biogas oxygen-enriched combusting-biogas slurry denitrating system and method
CN112342066A (en) * 2019-08-09 2021-02-09 长沙蓝熙环保科技有限公司 Anaerobic biological desulfurization method and device for biogas
CN110551612A (en) * 2019-09-25 2019-12-10 农业部沼气科学研究所 Method for biogas fermentation stirring and biogas desulfurization

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1986819A (en) * 2006-12-18 2007-06-27 同济大学 Time-controllable greenhouse marsh gas fermentation process and system
CN101073745A (en) * 2007-03-29 2007-11-21 南京大学 Method for removing sulfur-dioxide in smoke by bamboo-carbon filler biological drip filtering tower
CN101732985A (en) * 2010-01-29 2010-06-16 北京德青源农业科技股份有限公司 Methane-desulfurizing device
CN101984026A (en) * 2010-11-09 2011-03-09 浙江大学 Integrated methane biological desulphurization device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100261266A1 (en) * 2007-12-28 2010-10-14 Yasuhiko Nagamori Biological desulfurization apparatus
JP5072612B2 (en) * 2008-01-16 2012-11-14 株式会社東芝 Start-up method of biological desulfurization equipment

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1986819A (en) * 2006-12-18 2007-06-27 同济大学 Time-controllable greenhouse marsh gas fermentation process and system
CN101073745A (en) * 2007-03-29 2007-11-21 南京大学 Method for removing sulfur-dioxide in smoke by bamboo-carbon filler biological drip filtering tower
CN101732985A (en) * 2010-01-29 2010-06-16 北京德青源农业科技股份有限公司 Methane-desulfurizing device
CN101984026A (en) * 2010-11-09 2011-03-09 浙江大学 Integrated methane biological desulphurization device

Also Published As

Publication number Publication date
CN102604701A (en) 2012-07-25

Similar Documents

Publication Publication Date Title
Toledo-Cervantes et al. Photosynthetic biogas upgrading to bio-methane: Boosting nutrient recovery via biomass productivity control
Sialve et al. Anaerobic digestion of microalgae as a necessary step to make microalgal biodiesel sustainable
Angelidaki et al. A mathematical model for dynamic simulation of anaerobic digestion of complex substrates: focusing on ammonia inhibition
Liamleam et al. Electron donors for biological sulfate reduction
US7811455B2 (en) Removal of ammonia from fermentation effluent and sequestration as ammonium bicarbonate and/or carbonate
CN102942973B (en) Method and system for combined air stripping biogas slurry depth treatment and biogas purification and desulfurization
CN102604701B (en) Methane biodesulfurization method
Naegele et al. Effects of temperature, pH and O2 on the removal of hydrogen sulfide from biogas by external biological desulfurization in a full scale fixed-bed trickling bioreactor (FBTB)
US20120021477A1 (en) Method for the Fixation of CO2 and for Treating Organic Waste by Coupling an Anaerobic Digestion System and a Phytoplankton Microorganism Production System
NL1039442C2 (en) Biomass conversion methods and systems.
CN101805689A (en) Apart-shaped anaerobic digester for producing biogas
CN102583930A (en) Livestock excrement biogas generation method and livestock excrement biogas generation system
CN101984026B (en) Integrated methane biological desulphurization device
CN106396112A (en) Composite system used for purifying high ammonia nitrogen pig breeding biogas slurry via algae-bacterium symbiosis/ecological floating bed combined technology
CN108821429A (en) A kind of apparatus system and its processing method of sulfate wastewater treatment
Sobhi et al. Selecting the optimal nutrients recovery application for a biogas slurry based on its characteristics and the local environmental conditions: A critical review
CN101234831A (en) Waste water denitrogenation and marsh gas desulfurization coupling technique
Yang et al. Transformations, inhibition and inhibition control methods of sulfur in sludge anaerobic digestion: a review
CN103319061A (en) Method for improving comprehensive effect of anaerobic digestion treatment of breeding manure
Cheng Anaerobic digestion for biogas production
CN104911133A (en) Pseudomonas aeruginosa and application
CN102276118A (en) Method for simultaneously removing nitrogen in waste water and sulfur in sewage gas
CN102010768A (en) Biogas anaerobe desulfuration device and method thereof
Liu et al. Integration of algae cultivation to anaerobic digestion for biofuel and bioenergy production
CN106467352A (en) A kind of for the foul smell resource reutilization of sludge organism drying technique with the method for deodorization

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
C56 Change in the name or address of the patentee
CP01 Change in the name or title of a patent holder

Address after: South Gate Road Penglai city 265600 Shandong city of Yantai province 2-3

Patentee after: Shandong Minhe Biological Technology Co., Ltd.

Address before: South Gate Road Penglai city 265600 Shandong city of Yantai province 2-3

Patentee before: Shandong Minhe Biological Technology Co., Ltd.