CN102002408A - Marsh gas biological desulphurization energy-saving method - Google Patents
Marsh gas biological desulphurization energy-saving method Download PDFInfo
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- CN102002408A CN102002408A CN2010105914716A CN201010591471A CN102002408A CN 102002408 A CN102002408 A CN 102002408A CN 2010105914716 A CN2010105914716 A CN 2010105914716A CN 201010591471 A CN201010591471 A CN 201010591471A CN 102002408 A CN102002408 A CN 102002408A
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- marsh gas
- nitrobacteria
- desulfurization
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- thiobacillus denitrificans
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Abstract
The invention provides a marsh gas biological desulphurization energy-saving method, which relates to a marsh gas desulphurization method. The invention solves the problems that the biological desulphurization process in the prior art is not easy to control, the conditions and requirements are harsh, and sulfureted hydrogen can be easily and directly converted into sulfur oxides by germs, so the sulfur oxide can not be easily discharged from a system. The method comprises the following steps of: 1. adding thiobacillus denitrificans and nitrobacteria into nutrient fluid, then spraying the nutrient fluid onto filling materials and culturing the filling materials until biomembranes are formed; and 2. completing the process after the marsh gas is in contact and reacts with the biomembranes. The biological desulphurization energy-saving method in the invention is easy to control, has slack condition requirements and solves the problem that the sulfureted hydrogen can be easily and directly converted into the sulfur oxides by the germs to be released to the marsh gas again, the desulphurization efficiency can achieve higher than 95 percent when the sulfureted hydrogen content in the marsh gas is between 1000 and 4000mg/L, in addition, elemental sulfur can be recovered, the thiobacillus denitrificans and the nitrobacteria are symbiotic systems, the self-sufficiency effect is realized basically through the marsh gas, and the energy-saving effect is realized.
Description
Technical field
The present invention relates to a kind of biogas desulfurization method.
Background technology
Along with the widespread use of agriculture and industry waste Anaerobic Microbiological Treatment Technology, biogas is as a kind of reproducible biomass energy, in fossil energy deficient day by day today, more and more is subjected to people's attention and attention.Under the standard state, the main component of biogas is methane (50% to 70%) and carbonic acid gas (30% to 40%), and contains a spot of carbon monoxide, hydrogen, hydrogen sulfide, oxygen and nitrogen etc.Hydrogen sulfide in the biogas results from the degradation process of protein and other sulfocompounds. so concentration of hydrogen sulfide depends on the charging situation of biogas generator. and between 0.1% and 2%, change.Concentration of hydrogen sulfide is too high, and to be biogas use one of maximum limiting factor as combustion gas because hydrogen sulfide has very strong corrosive nature to combustion powered equipment and metallic conduit, thereby and can cause the wearing and tearing of the rotten boost engine of lubricating oil; In addition, biogas is after the process burning, and hydrogen sulfide can be converted into sulfur oxide (SO
X) and be discharged in the air, cause topsoil.Therefore, before the biogas burning utilizes, must remove hydrogen sulfide wherein.
Biogas desulfurization mode commonly used has chemical method and biological process.The method that chemical desulfurization adopts dry oxidation iron to absorb is usually passed through sweetening agent bed, the H in the biogas with biogas at normal temperatures
2S contacts with activated ferric oxide, generates ironic sulfide, and the sweetening agent that contains sulfide then contacts with airborne oxygen, and when water existed, the sulfide of iron was converted into ferric oxide and elemental sulfur again.This desulfurization regeneration process is capable of circulation carries out repeatedly, is covered by sulphur or other impurity and till losing activity until most of space on ferric oxide desulfurizer surface.Chemical desulfurization need use sweetening agent, and when hydrogen sulfide in methane content was higher, sweetening agent was changed frequent, not only increases cost, and the comparison difficulty that operates.Inactivation get sweetening agent if improper conduct oneself well to put easily cause secondary pollution.
So-called biological desulphurization is exactly under suitable temperature, humidity, nutrient and little oxygen condition, and the metabolism by desulfurizing bacteria is with H
2S is converted into elemental sulfur.Reaction process is:
H
2S+2O
2→H
2SO
4
2H
2S+O
2→2S+2H
2O
The exercising result of desulfurization microorganism species is with the H in the biogas
2The S gas reforming is the effect that reaches biogas desulfurization behind elemental sulfur and the dilute sulphuric acid.Shortcoming: process is wayward, and the conditional request harshness is difficult for getting rid of from system thereby hydrogen sulfide can be converted into sulfur oxide by bacterium easily.
Summary of the invention
The present invention seeks to exist process wayward in order to solve existing biological desulphurization, the conditional request harshness is difficult for getting rid of from system thereby hydrogen sulfide is converted into sulfur oxide by bacterium easily, and the power-economizing method of a kind of methane bio-desulfurization that provides.
The power-economizing method of methane bio-desulfurization carries out according to the following steps: one, adding thiobacillus denitrificans and nitrobacteria in nutritive medium, be sprayed onto then on the filler, is 27～28 ℃ in temperature, and the pH value is to cultivate for 2 weeks under 6.7～7.3 the condition, forms microbial film; Two, biogas contacts with microbial film and reacts, and promptly finishes methane bio-desulfurization; Wherein the volume ratio of thiobacillus denitrificans and nitrobacteria is 2: 1 in the step 1; Every 1L of nutritive medium is by the Na of 5g in the step 1
2S
2O
35H
2The K of O, 1g
2HPO
4, 1g KNO
3, 1g NaHCO
3, 0.2g MgSO
47H
2The NH of O, 1g
4The NaNO of Cl, 4g
2, 0.5g FeSO
47H
2The distilled water of O and surplus is formed; Filler adopts two-layer polyurethane foam filler in the step 1, is respectively flexible PU foam packing layer and hard polyurethane foams packing layer, and the thickness ratio is 2: 1.
Microorganism in the microbial film that forms among the present invention is thiobacillus denitrificans and nitrobacteria, and these two kinds of bacteriums are syntaxial system; Under aerobic or anaerobic condition, thiobacillus denitrificans utilizes oxygen or nitrate as the electron acceptor(EA) H that can degrade
2S, nitrate (NO
3 -) under the nitrobacteria effect, can from the nitrification of ammonia, obtain; Thiobacillus denitrificans can be simultaneously with H
2S is oxidized to elemental sulfur or vitriol and is nitrogen with nitrate reduction; The syntaxial system that thiobacillus denitrificans and nitrobacteria are formed does not need the artificial air that adds in thionizer again, and by utilizing oxygen and the ammonia that contains in the biogas, the microorganism system in the microbial film can reach self-sufficient completely.
The power-economizing method of methane bio-desulfurization among the present invention, its operational outfit is an one, made things convenient for and made and use, easy to control, conditional request is loose, and it is safe and reliable, simple to operate, thereby avoided hydrogen sulfide to be converted into the difficult problem of getting rid of of sulfur oxide by bacterium from system easily, controlled the interior temperature of tower in the sweetening process automatically, it is few to produce the biological sludge amount, non-secondary pollution, when the content of hydrogen sulfide in methane was 1000～4000mg/L, desulfuration efficiency can reach more than 95%, and can reclaim elemental sulfur; Thiobacillus denitrificans and nitrobacteria are syntaxial system, rely on biogas to reach self-sufficiency substantially, realize energy-conservation; Adopt soft, hard double-deck filler, the existence and the breeding of suitable more microbe colony.
Description of drawings
Fig. 1 is the synoptic diagram of operational outfit in the power-economizing method of embodiment one methane bio-desulfurization, wherein 1 expression biogas import, 2 expression methane outlets, 3 expression biogas gas blowers, 4 expression discharge outlets, 5 expression ball valves, 6 expression gas monitors, 7 expression nozzles, 8 expression thermal insulation layers, 9 expression supports, 10 expression heating tubes, the ventilative dividing plate of 11 expressions, 12 expression hard polyurethane foams fillers, 13 expression flexible PU foam fillers, 14 expression temperature probes, 15 expression transfer limes, 16 expression reflux pumps, 17 expression wire mesh demisters.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: in conjunction with shown in Figure 1, the power-economizing method of present embodiment methane bio-desulfurization carries out according to the following steps: one, add thiobacillus denitrificans and nitrobacteria in nutritive medium, be sprayed onto on the filler then, in temperature is 27～28 ℃, the pH value is to cultivate for 2 weeks under 6.7～7.3 the condition, forms microbial film; Two, biogas contacts with microbial film and reacts, and promptly finishes methane bio-desulfurization; Wherein the volume ratio of thiobacillus denitrificans and nitrobacteria is 2: 1 in the step 1; Every 1L of nutritive medium is by the Na of 5g in the step 1
2S
2O
35H
2The K of O, 1g
2HPO
4, 1g KNO
3, 1g NaHCO
3, 0.2g MgSO
47H
2The NH of O, 1g
4The NaNO of Cl, 4g
2, 0.5g FeSO
47H
2The distilled water of O and surplus is formed; Filler adopts two-layer polyurethane foam filler in the step 1, is respectively flexible PU foam packing layer and hard polyurethane foams packing layer, and the thickness ratio is 2: 1.
The surface-area of polyurethane foam filler is 2400m in the present embodiment step 1
2/ m
3, porosity is 97%, has reticulated structure, microorganism can be closely knit thereon and propagation rapidly, forms microbial film.
Form microbial film in the present embodiment step 1, the microorganism in the microbial film is thiobacillus denitrificans and nitrobacteria, and these two kinds of bacteriums are syntaxial system; Under aerobic or anaerobic condition, thiobacillus denitrificans utilizes oxygen or nitrate as the electron acceptor(EA) H that can degrade
2S, nitrate (NO
3 -) under the nitrobacteria effect, can from the nitrification of ammonia, obtain; Thiobacillus denitrificans can be simultaneously with H
2S is oxidized to elemental sulfur or vitriol and is nitrogen with nitrate reduction; The syntaxial system that thiobacillus denitrificans and nitrobacteria are formed does not need the artificial air that adds in thionizer again, and by utilizing oxygen and the ammonia that contains in the biogas, the microorganism system in the microbial film can reach self-sufficient completely.
H in biogas
2S is converted to by thiobacillus denitrificans after the S simple substance, and the nutritive medium that is flowed downward is shed to reactor bottom under the shearing action that flows, and the valve of bottom drain is regularly opened discharging S; The cycle of discharging S simple substance be 2 days once.
In nutritive medium, add thiobacillus denitrificans and nitrobacteria in the present embodiment step 1, be sprayed onto on the filler then, this process circulation is carried out, it is for the microbial film that partly comes off is beaten to the operational outfit top by reflux pump that circulation behind the formation microbial film is sprayed, reflect in the flow process in opposite directions at nutritive medium (wherein containing two kinds of biologies) and biogas like this, contact is better, reacts more thorough.
The process of present embodiment methane bio-desulfurization, when the content of hydrogen sulfide in methane was 1000～4000mg/L, desulfuration efficiency can reach more than 95%; When desulfuration efficiency has obvious decline, illustrate that two kinds of bacteriums have not been in the remarkable advantages status, need to change fresh nutritive medium this moment.
The power-economizing method of the methane bio-desulfurization of present embodiment, its operational outfit can be in conjunction with shown in Figure 1, and as seen, the lower end side of equipment has biogas inlet 1, and discharge outlet 4 is arranged at the bottom, and there is methane outlet 2 on the top; Biogas import 1 lower end forms the nutritive medium section; Place flexible PU foam filler 13 and hard polyurethane foams filler 12 in the thionizer, establish support 9 between the two-layer filler; Ventilative dividing plate 11 is established in flexible PU foam filler 13 bottoms, hard polyurethane foams filler 12 tops are provided with nutritive medium nozzle 7, the upper end of transfer lime 15 of band reflux pump 16 is passed a sulphur tower wall and is connected with nozzle 7, and its lower end is passed the thionizer wall and submerged in the nutritive medium of bottom; Tower is indoor temperature probe 14; Thionizer peripheral hardware thermal insulation layer 8 is established heating tube 10 in the thermal insulation layer; Establish wire mesh demister 17 between nutritive medium nozzle 7 and the methane outlet 2; On methane outlet 2 and the discharge outlet 4 ball valve 5 is set respectively; Establish biogas gas blower 3 on the biogas import pipeline section 1;
At methane outlet 2 gas monitor is set, the concentration of back hydrogen sulfide in methane is handled in monitoring in real time; Ventilative dividing plate 11 plays uniform gas and supports filler; Wire mesh demister 17, the air-flow that can avoid rising is brought the mist that produces into methane outlet pipe and gas equipment.
Embodiment two: what present embodiment and embodiment one were different is to add thiobacillus denitrificans and nitrobacteria in the step 1 in nutritive medium, be sprayed onto on the filler then, in temperature is 27 ℃, and the pH value is to cultivate for 2 weeks under 6.7 the condition, forms microbial film.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is to add thiobacillus denitrificans and nitrobacteria in the step 1 in nutritive medium, be sprayed onto on the filler then, in temperature is 28 ℃, and the pH value is to cultivate for 2 weeks under 7.3 the condition, forms microbial film.Other step and parameter are identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is to add thiobacillus denitrificans and nitrobacteria in the step 1 in nutritive medium, be sprayed onto on the filler then, in temperature is 27.5 ℃, and the pH value is to cultivate for 2 weeks under 7.0 the condition, forms microbial film.Other step and parameter are identical with embodiment one.
Embodiment five: the power-economizing method of present embodiment methane bio-desulfurization carries out according to the following steps: one, add thiobacillus denitrificans and nitrobacteria in nutritive medium, be sprayed onto on the filler then, in temperature is 28 ℃, and the pH value is to cultivate for 2 weeks under 7.0 the condition, forms microbial film; Two, biogas contacts with microbial film and reacts, and promptly finishes methane bio-desulfurization; Wherein the volume ratio of thiobacillus denitrificans and nitrobacteria is 2: 1 in the step 1; Every 1L of nutritive medium is by the Na of 5g in the step 1
2S
2O
35H
2The K of O, 1g
2HPO
4, 1g KNO
3, 1g NaHCO
3, 0.2g MgSO
47H
2The NH of O, 1g
4The NaNO of Cl, 4g
2, 0.5g FeSO
47H
2The distilled water of O and surplus is formed; Filler adopts two-layer polyurethane foam filler in the step 1, is respectively flexible PU foam packing layer and hard polyurethane foams packing layer, and the thickness ratio is 2: 1.
When the content of present embodiment hydrogen sulfide in methane was 3000mg/L, desulfuration efficiency can reach 98.95%.
Claims (2)
1. the power-economizing method of a methane bio-desulfurization, the power-economizing method that it is characterized in that methane bio-desulfurization carries out according to the following steps: one, add thiobacillus denitrificans and nitrobacteria in nutritive medium, be sprayed onto on the filler then, in temperature is 27～28 ℃, the pH value is to cultivate for 2 weeks under 6.7～7.3 the condition, forms microbial film; Two, biogas contacts with microbial film and reacts, and promptly finishes methane bio-desulfurization; Wherein the volume ratio of thiobacillus denitrificans and nitrobacteria is 2: 1 in the step 1; Every 1L of nutritive medium is by the Na of 5g in the step 1
2S
2O
35H
2The K of O, 1g
2HPO
4, 1g KNO
3, 1g NaHCO
3, 0.2g MgSO
47H
2The NH of O, 1g
4The NaNO of Cl, 4g
2, 0.5g FeSO
47H
2The distilled water of O and surplus is formed; Filler adopts two-layer polyurethane foam filler in the step 1, is respectively flexible PU foam packing layer and hard polyurethane foams packing layer, and the thickness ratio is 2: 1.
2. the power-economizing method of a kind of methane bio-desulfurization according to claim 1, it is characterized in that adding thiobacillus denitrificans and nitrobacteria in the step 1 in nutritive medium, be sprayed onto then on the filler, is 27.5 ℃ in temperature, the pH value is to cultivate for 2 weeks under 7.0 the condition, forms microbial film.
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| CN2010105914716A CN102002408A (en) | 2010-12-16 | 2010-12-16 | Marsh gas biological desulphurization energy-saving method |
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| CN2010105914716A CN102002408A (en) | 2010-12-16 | 2010-12-16 | Marsh gas biological desulphurization energy-saving method |
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Cited By (6)
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| CN102614774A (en) * | 2012-04-06 | 2012-08-01 | 哈尔滨工业大学 | Biological treatment system of sludge odor and method for treating sludge odor by utilizing same |
| CN104129852A (en) * | 2014-06-20 | 2014-11-05 | 浙江工商大学 | Method and reaction device for reducing H2S inner sources of garbage landfill |
| JP2018130705A (en) * | 2017-02-17 | 2018-08-23 | 国立研究開発法人農業・食品産業技術総合研究機構 | Deodorization and nitrogen removal method |
| EP3228377A4 (en) * | 2014-12-02 | 2018-08-29 | Beijing Institute of Spacecraft System Engineering | Detoxification device for toxic gas |
| CN108479376A (en) * | 2018-03-22 | 2018-09-04 | 上海梅思泰克环境股份有限公司 | The method for fixing Thiobacillus as carrier using polyurethane foamed material |
| 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614774A (en) * | 2012-04-06 | 2012-08-01 | 哈尔滨工业大学 | Biological treatment system of sludge odor and method for treating sludge odor by utilizing same |
| CN104129852A (en) * | 2014-06-20 | 2014-11-05 | 浙江工商大学 | Method and reaction device for reducing H2S inner sources of garbage landfill |
| EP3228377A4 (en) * | 2014-12-02 | 2018-08-29 | Beijing Institute of Spacecraft System Engineering | Detoxification device for toxic gas |
| JP2018130705A (en) * | 2017-02-17 | 2018-08-23 | 国立研究開発法人農業・食品産業技術総合研究機構 | Deodorization and nitrogen removal method |
| CN108479376A (en) * | 2018-03-22 | 2018-09-04 | 上海梅思泰克环境股份有限公司 | The method for fixing Thiobacillus as carrier using polyurethane foamed material |
| CN108479376B (en) * | 2018-03-22 | 2020-09-29 | 上海梅思泰克环境股份有限公司 | Method for fixing thiobacillus by using polyurethane foam material as carrier |
| 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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Application publication date: 20110406 |