CN102604701A - Methane biodesulfurization method - Google Patents
Methane biodesulfurization method Download PDFInfo
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- CN102604701A CN102604701A CN2012100752447A CN201210075244A CN102604701A CN 102604701 A CN102604701 A CN 102604701A CN 2012100752447 A CN2012100752447 A CN 2012100752447A CN 201210075244 A CN201210075244 A CN 201210075244A CN 102604701 A CN102604701 A CN 102604701A
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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
- 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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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
Technical field
The invention belongs to the biogas desulfurization technical field, be specifically related to a kind of methane bio-desulfurization method.
Background technology
Biogas fermentation raw material such as livestock and poultry cultivation waste, high-concentration industrial organic waste water, municipal effluent plant excess sludge, crop material and organic waste etc. all are biomass class materials; Contain a considerable amount of organosulfurs or inorganic sulfur; In anaerobic digestion process, be converted to hydrogen sulfide; Therefore the hydrogen sulfide that all contains some amount in the biogas is as with the chicken manure being the hydrogen sulfide that contains 5000ppm in the biogas after the fermenting raw materials approximately.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 through after burning, and hydrogen sulfide can be converted into sulfur oxide (SO
x) and be discharged in the air, cause topsoil.Therefore, in order to reach the target of safe utilization and environment protection, must carry out desulfurization to biogas before use and handle.
At present, the hydrogen sulfide in methane removal methods mainly contains physico-chemical processes and biological process.The physico-chemical processes sweetening process is to generate sulfide 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 or with the hydrogen sulfide reaction basically; Be that electron acceptor(EA) is oxidized to elemental sulfur with hydrogen sulfide (sulfide) again with oxygen, make the regeneration of sorbent material or sweetening agent.Energy consumption is high because the physical chemistry sulfur method exists, processing costs is expensive, shortcomings such as sludge disposal difficulty, and biological desulphurization has received generally favor in recent years.
Biological desulphurization is meant that the biological oxidation that utilizes thiobacterium is oxidized to elemental sulfur with the hydrogen sulfide in the biogas, further is oxidized to sulfurous acid and sulfuric acid, thus the technology that sulphur is removed from biogas.With respect to physico-chemical processes, biological desulphurization has does not need oxygenant or catalyzer, do not produce the characteristics of chemical sludge, so is 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 purpose of this invention is to provide a kind of methane bio-desulfurization method, have and be convenient to control, simple to operate, the characteristics that desulfuration efficiency is high.
A kind of methane bio-desulfurization method of the present invention; The spray header of circulation fluid through the thionizer top that contains desulfurizing bacteria sprays and descends; 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 that contains in the circulation fluid through biological oxidation with the hydrogen sulfide oxidation removal in the biogas; Wherein, in every cubic metre circulation fluid, add 2.0～2.5L natural pond liquid every day.
Effective flora in the circulation fluid is to be master's desulfurization flora with thiobacillus ferrooxidant and thiobacillus thiooxidans; These two kinds of bacterium are has a liking for acid, aerobic type bacterium; Sulfide or elemental sulfur to go back ortho states are energy derive, are nitrogenous source with the ammonium nitrogen, are carbon source with the carbonic acid gas.
Wherein, Natural pond liquid preferably prepares according to following method: the feces of livestock and poultry acidifying that in hydrolysis acidification pool, is hydrolyzed, and the residence time is 4 days, the feed liquid behind the acidication pumps into anaerobic fermentation tank; Leavening temperature is 35～38 ℃; Feed liquid stopped in fermentor tank 35 days, fully discharged behind the aerogenesis, was natural pond liquid.
The total solids level of the feed liquid behind the acidication is preferably 6～8%.
The feeding manner that feed liquid behind the acidication pumps into anaerobic fermentation tank is preferably intermittent charging, and the anaerobic fermentation tank type is preferably the full-mixing type anaerobic fermentor tank.
The total solids level of natural pond liquid is preferably 2～5%, and pH is preferably 8.0～8.5.
Being in operation needs through controlling the vigor that some parameters guarantee the desulfurization flora, and these parameters comprise the temperature of circulation fluid, pH, the aeration rate of circulation fluid and the nutritive substance that need add.
The circulation fluid temperature is preferably 28～30 ℃.When Fig. 2 is the circulation fluid differing temps and the changing trend diagram of thionizer outlet biogas concentration, visible by figure, the concentration of hydrogen sulfide when the temperature of circulation fluid is 28～30 ℃ in the biogas is minimum, and sweetening effectiveness is best.
Circulation fluid pH is preferably 1.5～2.5.Thiobacillus ferrooxidant and thiobacillus thiooxidans all are wtih, so pH should be controlled in the lower scope.
The desulfurization bacterial classification is aerobic type bacterial classification; So should guarantee that competent oxygen is arranged in its living environment, aeration comprises two aspects, the one, aeration in the circulation fluid in cyclic water tank; Dissolved oxygen content in the circulation fluid is reached capacity, to guarantee the necessary oxygen of desulfurization bacterial classification life; The 2nd, in inlet pipe, feed the air capacity account for biogas flow 10%, make after the desulfurization in the biogas surplus oxygen level between 1.2～1.5%, there is competent 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 the required trace element of growth to wait other nutritive substance in addition in the liquid of natural pond, so the interpolation of natural pond liquid has been played very remarkable influence to sweetening effectiveness.As shown in Figure 3, once add natural pond liquid curve and be meant that every day, 16:30 added 2L/m in circulation fluid
3Natural pond liquid, secondary add natural pond liquid curve be meant every day 7:30 and 19:30 in circulation fluid, add 1L/m at twice respectively
3Natural pond liquid, the change conditions of hydrogen sulfide in methane concentration is as shown in the figure.Visible by once adding natural pond liquid curve, concentration of hydrogen sulfide begins to reduce after natural pond liquid adds, and reaches minimum after 9 hours, explains that natural pond liquid has tangible influence to the activity of desulfurization.And two curve contrasts can be known, same natural pond liquid addition, and the effect of adding at twice is better than once.
The invention has the advantages that:
(1) significant desulfurization effect.Can the concentration of hydrogen sulfide in the biogas be reduced to below the 200ppm by 5000ppm, desulfuration efficiency reaches more than 96%, has significantly reduced the influence of hydrogen sulfide to follow-up relevant device.
(2) parameter is easy to control.Regulate the air intake valve of the water back in the cyclic water tank, can reach the effect of Control Circulation liquid temp; Aeration rate can be adjusted through the valve of regulating on the pipeline; The interpolation of nutritive substance can be adjusted according to the flow of circulation fluid at any time.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 need not to add other material; And aerating system and recycle system equipment are simple, stable, the electricity charge that only need energy supply to use.
Description of drawings
Fig. 1 is the structural representation of methane bio-desulfurization device;
Fig. 2 is the influence trend map of the temperature of circulation fluid to sweetening effectiveness;
Fig. 3 adds the change curve of thionizer exit, front and back hydrogen sulfide in methane concentration for natural pond liquid;
Among the 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 is further specified.
Embodiment 1:
This desulfurizer comprises thionizer 1, and thionizer 1 bottom and top are provided with inlet pipe 2 and escape pipe 3 respectively, are filled with elastic filler 4 in the tower; The top of elastic filler 4 is provided with spray header 5; One side of thionizer 1 is provided with cyclic water tank 6, and cyclic water tank 6 is 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 links to each other with thionizer 1 bottom, and the top of cyclic water tank 6 is provided with moisturizing pipeline 9 and adds pipeline 10 with nutritive medium, 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 the cyclic water tank 6, and biogas is blown into from inlet pipe 2, and biogas fully combines at elastic filler 4 places with circulation fluid, realizes biological desulphurization, and the control method and the controlling valu of parameters are following:
Temperature: the circulation fluid temperature controlling is to realize that through the time of the logical steam in the control water back 11 temperature is controlled between 28～30 ℃.
Aeration rate: in inlet pipe 2 He in the cyclic water tank 6, feed air in certain amount respectively, feed the air of biogas flow 10% in the inlet pipe, the oxygen concentration of the circulation fluid of cyclic water tank then should reach 7.0mg/L.The size of air flow is regulated through pipeline valve.
Nutritive substance: added natural pond liquid every day at interval in 12 hours at twice in cyclic water tank, addition is that each every cubic metre circulation fluid adds 1L natural pond liquid.
PH: detect the pH of circulation fluid every day, it is maintained between 1.5～2.5.
Used natural pond liquid prepares according to following method: the feces of livestock and poultry acidifying that in hydrolysis acidification pool, is hydrolyzed, and the residence time is 4 days, the total solids level of the feed liquid behind the acidication is 8%; Feed liquid behind the acidication pumps into anaerobic fermentation tank, and feeding manner is intermittent charging, and the anaerobic fermentation tank type is the full-mixing type anaerobic fermentor tank; Leavening temperature is 35～38 ℃; Feed liquid stopped in fermentor tank 35 days, fully discharged behind the aerogenesis, was natural pond liquid.
The correlation parameter of natural pond liquid is that total solids level is 2～5%, and pH is 8.0～8.5, and several kinds to influential substances content of mikrobe such 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 surplus oxygen level is 1.2% in the biogas after the desulfurization.
Claims (9)
1. methane bio-desulfurization method; It is characterized in that the spray header of circulation fluid through the thionizer top that contains desulfurizing bacteria sprays and descend; 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 that contains in the circulation fluid through biological oxidation with the hydrogen sulfide oxidation removal in the biogas; Wherein, in every cubic metre circulation fluid, add 2.0～2.5L natural pond liquid every day.
2. methane bio-desulfurization method according to claim 1; It is characterized in that natural pond liquid prepares according to following method: the feces of livestock and poultry acidifying that in hydrolysis acidification pool, is hydrolyzed, the residence time is 4 days, the feed liquid behind the acidication pumps into anaerobic fermentation tank; Leavening temperature is 35～38 ℃; Feed liquid stopped in fermentor tank 35 days, fully discharged behind the aerogenesis, was natural pond liquid.
3. methane bio-desulfurization method according to claim 2 is characterized in that the total solids level of the feed liquid behind the acidication is 6～8%.
4. methane bio-desulfurization method according to claim 2 is characterized in that the feeding manner that feed liquid behind the acidication pumps into anaerobic fermentation tank is intermittent charging, and the anaerobic fermentation tank type is the full-mixing type anaerobic fermentor tank.
5. methane bio-desulfurization method according to claim 1, the total solids level that it is characterized in that natural pond liquid is 2～5%, pH is 8.0～8.5.
6. methane bio-desulfurization method according to claim 1 is characterized in that the circulation fluid temperature is 28～30 ℃.
7. methane bio-desulfurization method according to claim 1 is characterized in that circulation fluid pH is 1.5～2.5.
8. methane bio-desulfurization method according to claim 1 is characterized in that circulation fluid carries out aeration before spray, reach capacity dissolved oxygen content.
9. methane bio-desulfurization method according to claim 1 is characterized in that in the sweetening process, feeds the air of biogas flow 10% in the inlet pipe.
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Cited By (7)
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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 |
| 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 |
| 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 |
| CN111040818A (en) * | 2019-12-25 | 2020-04-21 | 常州合全药业有限公司 | Device and method for denitrifying and desulfurizing methane |
| CN111892964A (en) * | 2020-08-17 | 2020-11-06 | 温州嘉伟环保科技有限公司 | Biogas biological desulfurization equipment and method for anaerobic fermentation of kitchen waste |
| 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 |
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| 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 |
| CN111040818A (en) * | 2019-12-25 | 2020-04-21 | 常州合全药业有限公司 | Device and method for denitrifying and desulfurizing methane |
| CN111892964A (en) * | 2020-08-17 | 2020-11-06 | 温州嘉伟环保科技有限公司 | Biogas biological desulfurization equipment and method for anaerobic fermentation of kitchen waste |
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| CN102604701B (en) | 2014-03-26 |
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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. |