CN102517368A - Method for preparing biogas by degrading coal with microorganisms - Google Patents

Method for preparing biogas by degrading coal with microorganisms Download PDF

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CN102517368A
CN102517368A CN2011104201966A CN201110420196A CN102517368A CN 102517368 A CN102517368 A CN 102517368A CN 2011104201966 A CN2011104201966 A CN 2011104201966A CN 201110420196 A CN201110420196 A CN 201110420196A CN 102517368 A CN102517368 A CN 102517368A
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coal
biogas
sample
substratum
white
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苏现波
龚红梅
郭红玉
林晓英
夏大平
徐影
吴昱
陈鑫
常天俊
潘文维
于洪飞
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Henan University of Technology
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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
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Abstract

The invention relates to technology for preparing biogas by degrading coal with microorganisms. The technology is suitable for any environment with oxygen or without oxygen. Under the condition of room temperature (15 to 35 DEG C), biologic methane can be ensured to be continuously generated without activating a strain in a way of raising temperature, so the development cost is effectively reduced; the adopted white-rot fungi is highly adaptive to the environment and is low in cost, so the technology has the feasibility of project development; and different types of colonies can be more effectively used and the effect of the colonies can be improved, so the degradation rate of a coal body is increased, and the yield of biological methane is improved.

Description

A kind of microbiological deterioration coal that utilizes is to produce the method for biogas
Technical field
The present invention relates to a kind of microbiological deterioration coal that utilizes to produce the method for biogas.
Background technology
Coal bed methane is claimed coal-seam gas again, is a kind of novel clean energy, also is the important potential energy of taking over of China.Through the cbm exploration exploitation course in surplus 30 years, realized in the U.S. that large-scale commercial applications melts and sent out that the whole America methane output broke through 600 billion cubic meters in 2007.China is after the difficult exploration of having experienced year surplus in the of 20; At present realized local commercial development in basin, Qinshui, the coalfield, the east of a river in Shanxi; Indicate that this clear energy sources is about to become the important supplement of China's primary energy source, will the improvement of China's energy structure be played a driving role.
Coal-seam gas has bigger margin in the world, yet according to the research of Leix, Lip river not etc., the productive life of a bite typical case coal bed gas well is about about 7-8, and in addition, the consumption of coal-seam gas is also increasing year by year.Therefore, how exploratory development goes out more potential coal bed gas resource, is the focus that present people pay close attention to.Conventional coal-bed gas exploitation mode is mainly water filling pressure break exploiting coal bed methane and the new gas injection pressure break exploiting coal bed methane that proposes.Yet because technical limitation, mostly present minable coal seam is permeable coal seam and shallow coal seam, and this available coal-seam gas also faces exhaustion.Therefore, seeking new coal-bed gas exploitation mode is the challenge that present various countries face.
Coal is converted into coal-seam gas to strengthen the enrichment degree of coal-seam gas in the coal seam, and the exploitation of being convenient to conventional coal-seam gas also is the novel method that addresses this problem.The eighties in 20th century; Lot of domestic and international scholar finds the mikrobe coal of can degrading under laboratory condition; Along with going deep into of research, the increasing laboratory evidence proof coal generation methane that can be degraded by microorganisms, promptly coal can be converted into the biogenesis coal-seam gas under certain conditions.Traditional coal-mining technique tends to produce the worked-out section; The residual coal of coal mine gob accounts for the 30-50% of its total resources; Be if can carry out in-situ treatment by microbe inoculation, then can be made this part residual coal be converted into methane by the resource of exploiting again; The realization biology is adopted residual coal, forms new coal-seam gas bioengineering field.In addition, there is CO in the formation of the biological methane in coal seam 2The reduction approach has become common recognition, therefore, can inject CO to the coal seam 2The forced mathane output is simultaneously with CO 2Inject the coal seam (like coal seam, deep or thin seam) that also can not adopt under the present economic technology condition, can also realize reduction of greenhouse gas discharge.
Summary of the invention
The object of the present invention is to provide a kind of microbiological deterioration coal that utilizes to produce the method for biogas, so that residual coal in the present worked-out section is made full use of.
The technical scheme that the present invention adopts is following:
A kind of microbiological deterioration coal that utilizes is to produce the method for biogas, and step is following:
1) the purpose district is carried out the collection of geology, mining basic data, and take coal sample and water sample, and institute's water sampling is carried out anaerobic bacteria flora detect;
2) under purpose district original temperature, pH and salinity condition; Environment in the biological methane output of experiment lab simulation; Utilize coal sample to carry out the experiment of oxygen free condition system biogas sample; Methane content with unit mass coal output is a standard, confirms that optimal culture medium prescription is with contained bacterial classification in enrichment culture pit water and the coal;
Wherein, purpose district original temperature is basically between 15-35 ℃.
Oxygen free condition can be through filling N in reaction flask 2Keep.
Substratum is the methanogen enrichment medium.
3) in the experiment of laboratory sample, design the sample of aerophil-anerobes combined degradation pattern simultaneously: in coal sample, add white-rot fungi bacterium liquid, water sample and substratum simultaneously, confirm the adding proportion that each material is best;
This step sample research is in order to do contrast with complete anaerobic bacterial fermentation sample, with the contribution of clear and definite aerophil to coal body degraded and methane output.With step 2) under the identical temperature, pH, Eh condition, add white-rot fungi bacterium liquid and in reaction flask, (mix) not filling N with coal body with certain proportion with bacterium liquid form 2, utilize remaining O in the whiterot fungi consumption reaction bottle 2, for follow-up anaerobic bacterial fermentation provides oxygen-free environment.Also utilize simultaneously the good degradation capability of whiterot fungi, for the output of follow-up methane provides a large amount of small-molecule substances to coal.Follow-up anerobes only need add water sample and substratum gets final product, and is convenient to carry out in order to test, and can water sample, substratum be added with white-rot fungi bacterium liquid.
4) confirming to adopt the anaerobic bacteria flora fermentation according to the oxygen situation that contains in purpose district still is the mode of aerophil-anerobes combined ferment, according to laboratory sample experimental result, confirms the dosage of substratum and white-rot fungi bacterium liquid;
5) the purpose district is produced biogas: if aerobic environment adds white-rot fungi bacterium liquid in the purpose district, the CO of monitoring reaction output in advance through boring 2Gas concentration is after treating in the purpose district to form oxygen-free environment, with step 2) in the substratum confirmed mixes with purpose district institute water sampling, inject the worked-out section, seal well head, monitor the variation of output gaseous constituent and concentration; In this process, according to output concentration, the quantum of output of methane and carbonic acid gas, adjustment adds the amount of white-rot fungi and pit water and substratum, the residual coal of farthest degrading; If oxygen-free environment omits the step that adds white-rot fungi, directly inject the operation of substratum and purpose district institute water sampling;
6) treat that methane concentration reaches degree capable of using, the biogas extraction after will transforming through ground coal-seam gas extraction mode utilizes.
Described in the step 1) institute's water sampling being carried out anaerobic bacteria flora detects to indigenous microorganism in the pit water being separated counting and carrying out physiological and biochemical property and identify.
The purpose district is carried out the collection of geology, mining basic data; Specifically can pass through coal petrology, coal chemistry, isotopic geochemistry, water geology and gas chromatographic technique research; Analyze petrology, chemical constitution and coal and the gaseous carbon isotopics of institute's coal sampling, find out purpose district quality of groundwater and underground water ambient condition.
Concrete, coal sample can be taken a sample by wire line coring, and water sample is extracted sampling out by drill hole.
Described anaerobic bacteria flora is anaerobically fermenting bacterium, anaerobic cellulose decomposer, sulphate reducing bacteria and methanogen.
In the step 3), when interpolation white-rot fungi bacterium liquid experimentizes, design no coal blank to eliminate the interference of substratum aerogenesis.
Described white-rot fungi bacterium liquid is that whiterot fungi is inoculated in the bacterium liquid that was obtained in 3 days in 35 ℃ of constant temperature culture in the PDA seed culture medium.
In the step 5), whiterot fungi bacterium liquid dosage serves as with reference to injecting the worked-out section with addition in the sample experiment.White-rot fungi and the adding proportion first time that only contains the pit water of methanogen enrichment medium are reference with the sample experiment.Adjust based on monitoring result then, can repeatedly add when being necessary.
In the step 6), specifically can set up ground coal bed gas well extraction device, the biogas after transforming extracted out utilize.
A kind of microbiological deterioration coal that utilizes provided by the invention is to produce the method for biogas; Mainly be to utilize mikrobe to the effective degraded of coal and the ability of conversion; Abundant residues coal in the worked-out section is converted into biological methane, develops and utilizes with ground coal-bed gas exploitation mode.On the one hand; Original bacterial classification in the worked-out section (being beneficial to the flora of biogas output) is carried out in-situ enrichment targetedly; Can select different aerogenesis patterns according to different initial environment (aerobic, anaerobic) simultaneously, also can be through repeating to add nutritive substance, to dilute harmful meta-bolites concentration and flora is carried out enrichment once more; Make its repeatedly the residual coal of Degradation and Transformation with the biological methane of output, to reach the purpose of effectively utilizing residual coal.
The present invention has following advantage with respect to prior art:
1) the present invention is applicable to any environment, and aerobic, anaerobic all can.Can adopt aerophil (white-rot fungi) and anerobes combined degradation coal body.The characteristic of white-rot fungi aerobic degradation can consume oxygen in the worked-out section in advance, and produces material such as great amount of carbon dioxide, is that anaerobic bacteria flora is created growing environment, to ensure the output of biological methane; Simultaneously; White-rot fungi has also been created a large amount of small-molecule substances for methanogen to effective degraded of coal body macromolecular structure (comprising xylogen, Mierocrystalline cellulose etc.); With auxiliary anaerobic bacteria flora synthesising biological methane gas, increase the coal body transformation efficiency, improve the concentration of biological methane.
2) white-rot fungi has good flexibility to environment, and cost is lower, has the feasibility of engineering development.
3) the present invention all can guarantee the lasting output of biological methane under room temperature (15 ℃～35 ℃) situation, need not to consider to activate bacterial classification with heating mode, thereby effectively reduces cost of development.
4) the present invention selective and carry out targetedly bacterial classification repeatedly enrichment, add, can effectively utilize dissimilar floras more, and improve its action effect, increase the coal body degradation rate, improve biological methane quantum of output.
Description of drawings
Fig. 1 is that microbiological deterioration coal of the present invention is to produce the method flow block diagram of biogas.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment: a kind of microbiological deterioration coal that utilizes is to produce the method for biogas, and concrete steps are following:
(1) data collection is taked coal sample and water sample simultaneously, and institute's water sampling is carried out anaerobic bacteria flora detect.
(2) originate as bacterial classification with dug up mine well water appearance; In the anaerobism glove box; Substratum with methanogen, hydrogen-producing acetogenic bacteria, anaerobic cellulose decomposer and sulphate reducing bacteria separates counting, with clear and definite wherein indigenous microorganism kind; And carry out selectivity and cultivate, concrete used culture medium prescription is following:
1) anaerobic hydrogen-generating acetogen substratum:
Glucose 25g, Tryptones 3g, Carnis Bovis seu Bubali cream 2.5g, yeast water 1.5g, NaCl 5g, K 2HPO 41g, MgCl 20.4g, FeSO 47H 2O 0.3g, L-halfcystine 0.5g, pH 7.0-7.2
2) anaerobic cellulose decomposer substratum:
Sulfate of ammoniac 3g, two hypophosphite monohydrate hydrogen dipotassium 1g, sal epsom 0.58g, NaCl 1g ,Zero(ppm) water 1000ml, pH 7.0-7.2.Every pipe inserts filter paper a slice, and other adds reductive agent L-halfcystine and redox indicator resazurin.
3) methanogen enrichment medium
Ammonium chloride 1g, three water potassium hydrogenphosphate 0.4g, sodium-chlor 40g, yeast extract paste 1g, 0.1% resazurin 1ml, magnesium chloride 0.1g, Tryptones 1g, halfcystine 0.5g, zero(ppm) water 1000ml.
4) methanogen isolation medium
NH 4Cl 1g, MgCl 21g, K 2HPO 40.4g, KH 2PO 40.4g, Tryptones 2g, yeast extract 1g, liquid microelement 10ml, vitamin solution 10ml, 0.2% resazurin 1ml, zero(ppm) water 1000ml, pH 6.8-7.0.
5) anaerobic sulfate reducer substratum
Sodium.alpha.-hydroxypropionate 3.5g, k 2HPO 40.5g, Na 2SO 40.5g, MgSO 47H 2O 2.0g, NH 4Cl 1.0g, FeSO47H2O 0.5g, CaCl2 0.1g, yeast extract paste 1.0g, resazurin (0.1%) 1mL, zero(ppm) water 1000ml, pH 6.8-7.0.
6) basic anaerobic culture medium
Peptone? 20g, Shi peptone? 1.5g, beef extract? 1.15g, Yeast extract? 10g, glucose? 3g, potassium dihydrogen phosphate? 2.5g, sodium? 3g, soluble starch? 5g, L-cysteine Acid? 0.3g, Sodium thioglycollate? 0.3g, Agar? 15g, distilled water? 1000ml.
7) whiterot fungi is used the PDA substratum
Yam 60g, glucose 6g, peptone 1.5g, zero(ppm) water 1000ml.
8) liquid microelement
Nitrilotriacetic acid 1.5g, MnSO 42H 2O 0.5g, MgSO 47H 2O 3.0g, FeSO 47H 2O 0.1g, NaCl 1g, CoCl 26H 2O 0.1g, CaCl 22H 2O 0.1g, CuSO 45H 2O 0.01g, ZnSO 47H 2O 0.1g, H 3BO 30.01g, Al (SO 4) 20.01g, NiCl 26H 2O 0.02g, Na 2MoO 40.01g, zero(ppm) water 1000ml.
9) vitamin solution
Vitamin H 2mg, folic acid 2mg, B6 10mg, B2 5mg, B1 5mg, nicotinic acid 5mg, VA 5mg, B12 0.1g, para-amino benzoic acid 5mg, Thioctic Acid 5mg, zero(ppm) water 1000ml.
(3) process of the biological methane output of experiment lab simulation; With coal sample (powdery; Cross 60 mesh sieves) mix with pit water and methanogen enrichment medium mass ratio with 1:10:2; Be about 7 at initial pH, Eh cultivates under 0 left and right sides condition, attemperation is 35 ℃, in constant incubator, cultivates; Utilize draining water gathering of gas law to collect gas; Utilize gc analysis gaseous constituent and CH 4Content is: methane: carbonic acid gas: nitrogen gas concn is than being 14:3:1.
(4) white-rot fungi bacterium liquid (in the white-rot fungi inoculation PDA substratum, the bacterium liquid that constant temperature culture obtained after 3 days under 35 ℃ of conditions) is mixed with coal dust, pit water and the methanogen enrichment medium mass ratio with 1:1:10:2.
(5) confirming to adopt the anaerobic bacteria flora fermentation according to the oxygen situation that contains in purpose district still is aerophil-the detest mode of aerophil combined ferment; According to laboratory sample experiment achievement; Confirm the substratum dosage: this example need employing aerophil-detest the mode of aerophil combined ferment, the material dosage is with reference to step 4).
(6) the purpose district is produced biogas: add white-rot fungi bacterium liquid in advance in the purpose district, the CO of monitoring reaction output through boring 2And O 2Gas concentration, after treating in the purpose district to form oxygen-free environment,, inject the purpose district through well head with substratum and the ratio thorough mixing of purpose district institute water sampling with 1:10, the sealing well head is monitored the variation of output gaseous constituent and concentration; In this process, according to output concentration, the quantum of output of methane and carbonic acid gas, adjustment adds the amount of white-rot fungi and pit water, the residual coal of farthest degrading;
(7) treat that methane concentration reaches 30% after, the biogas extraction after will transforming through ground coal-seam gas extraction mode utilizes.
The foregoing description is the preferred embodiment of the present invention, but embodiment of the present invention is not restricted to the described embodiments, and other the change that any the present invention of not deviating from did all should be the substitute mode of equivalence, is included within protection scope of the present invention.

Claims (5)

1. one kind is utilized the microbiological deterioration coal to produce the method for biogas, it is characterized in that step is following:
1) the purpose district is carried out the collection of geology, mining basic data, and take coal sample and water sample, and institute's water sampling is carried out anaerobic bacteria flora detect;
2) under purpose district original temperature, pH and salinity condition; Environment in the biological methane output of experiment lab simulation; Utilize coal sample to carry out the experiment of oxygen free condition system biogas sample; Methane content with unit mass coal output is a standard, confirms that optimal culture medium prescription is with contained bacterial classification in enrichment culture pit water and the coal;
3) in the experiment of laboratory sample, design the sample of aerophil-anerobes combined degradation pattern simultaneously: in coal sample, add white-rot fungi bacterium liquid, water sample and substratum simultaneously, confirm the adding proportion that each material is best;
4) confirming to adopt the anaerobic bacteria flora fermentation according to the oxygen situation that contains in purpose district still is the mode of aerophil-anerobes combined ferment, according to laboratory sample experimental result, confirms the dosage of substratum and white-rot fungi bacterium liquid;
5) the purpose district is produced biogas: if aerobic environment adds white-rot fungi bacterium liquid in the purpose district, the CO of monitoring reaction output in advance through boring 2Gas concentration is after treating in the purpose district to form oxygen-free environment, with step 2) in the substratum confirmed mixes with purpose district institute water sampling, inject the worked-out section, seal well head, monitor the variation of output gaseous constituent and concentration; In this process, according to output concentration, the quantum of output of methane and carbonic acid gas, adjustment adds the amount of white-rot fungi and pit water and substratum, the residual coal of farthest degrading; If oxygen-free environment omits the step that adds white-rot fungi, directly inject the operation of substratum and purpose district institute water sampling;
6) treat that methane concentration reaches degree capable of using, the biogas extraction after will transforming through ground coal-seam gas extraction mode utilizes.
2. the microbiological deterioration coal that utilizes as claimed in claim 1 is to produce the method for biogas; It is characterized in that, described in the step 1) institute's water sampling is carried out anaerobic bacteria flora and detect to indigenous microorganism in the pit water being separated counting and carrying out physiological and biochemical property and identify.
3. the microbiological deterioration coal that utilizes as claimed in claim 2 is characterized in that to produce the method for biogas described anaerobic bacteria flora is anaerobically fermenting bacterium, anaerobic cellulose decomposer, sulphate reducing bacteria and methanogen.
4. the microbiological deterioration coal that utilizes as claimed in claim 1 is characterized in that to produce the method for biogas, in the step 3), when interpolation white-rot fungi bacterium liquid experimentizes, designs no coal blank to eliminate the interference of substratum aerogenesis.
5. the microbiological deterioration coal that utilizes as claimed in claim 4 is characterized in that to produce the method for biogas described white-rot fungi bacterium liquid is that whiterot fungi is inoculated in the bacterium liquid that is obtained after 3 days in 35 ℃ of constant temperature culture in the PDA substratum.
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CN103045652A (en) * 2012-11-14 2013-04-17 山西晋城无烟煤矿业集团有限责任公司 Method for converting brown coal into methane by utilizing microorganism
US20150329876A1 (en) * 2012-12-19 2015-11-19 Commonwealth Scientific And Industrial Research Orginasation Nutrient combination, process and system for enhancing biogenic methane production from a carbonaceous material
WO2016001479A1 (en) * 2014-07-01 2016-01-07 Eino Elias Hakalehto A method and apparatus for treating lignite with microbes to reduce the environmental hazards associated with its combustion
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CN110652847B (en) * 2019-11-14 2024-01-19 河南理工大学 Device and method for disposing carbon dioxide in industrial waste gas based on coal mine goaf
CN113652335A (en) * 2021-09-16 2021-11-16 河南理工大学 Method for preparing biological methane based on in-situ reservoir condition by coal anaerobic fermentation
CN113652335B (en) * 2021-09-16 2024-03-29 河南理工大学 Method for preparing biological methane based on in-situ reservoir condition coal anaerobic fermentation

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Application publication date: 20120627