CN101157938B - Method for relieving restriction of sulfate reduction to anaerobic digestion methane production process - Google Patents
Method for relieving restriction of sulfate reduction to anaerobic digestion methane production process Download PDFInfo
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- CN101157938B CN101157938B CN2007101319917A CN200710131991A CN101157938B CN 101157938 B CN101157938 B CN 101157938B CN 2007101319917 A CN2007101319917 A CN 2007101319917A CN 200710131991 A CN200710131991 A CN 200710131991A CN 101157938 B CN101157938 B CN 101157938B
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- anaerobic digestion
- sulfate reduction
- sulfate
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- methane production
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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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- Treatment Of Sludge (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention relates to a method for removing the sulfate reduction inhibition of anaerobic digestion marsh gas production, pertaining to the offal biological treatment technical field. The content of the invention is to add nitrilotriacetic acid or a sodium salt thereof to an anaerobic digestion reactor to act with trace metal element and then form dissoluble chelate, thus avoiding hydrogen sulfide produced by sulfate reduction in the reactor forming precipitate with metal ion, therefore raising the biological exploitability of trace metal element and providing sufficient nutrition for methanogen, leading trace metal element to predominate in competition with sulfate reducing bacteria and then convert fermentation substrate into marsh gas more thoroughly and solving the problem of environmental pollution of degradable things in offal containing sulfate. Owing to the extreme micro-amount of nitrilotriacetic acid, the method is not only convenient to be manipulated with high efficiency, but also low in cost which leads the invention to be extensively applicable in engineering practice.
Description
Technical field
A kind of method of removing sulfate reduction to the anaerobic digestion methane production process inhibition, relate to a kind of by in anaerobic reactor, adding micro-complexon I or its sodium salt inhibition sulfate reduction, thereby organism is converted into the method for biogas to greatest extent, belongs to waste biologic treating technique field.
Background technology
In the anaerobic digestion process of sulfur-bearing hydrochlorate abandoned biomass (as: organic composition in municipal sludge, high concentrated organic wastewater, the municipal garbage etc.), sulfate concentration is to the digestion reaction important influence.Too high usually can the inhibition of sulfate concentration produced the methane process, causes biogas output to descend and even do not produce biogas, simultaneously, follows also original a large amount of hydrogen sulfide of vitriol to produce.
Micro-metals nickel, cobalt, molybdenum, zinc, manganese, copper etc. are the necessary nutritive elements of the synthetic thalline of methanogen, also are simultaneously the important composition compositions of the enzyme that catalytic methane forms in the thalline body.There is report to think, above-mentioned micro-metals very easily reacts with the hydrogen sulfide that sulfate-reducing process produces, and generates insoluble precipitated metal, causes it not utilized by methanogen, influence methanogen growth and active, thereby suppress the producing methane through anaerobic fermentation process.
Therefore, in actual anaerobic digestion reaction vessel (when especially handling the waste of sulfur-bearing hydrochlorate), usually need to add in a large number above-mentioned micro-metals and produce carrying out smoothly of methane process to keep fermentation.The growth and breeding, the releasing hydrogen sulfide that how to suppress sulphate reducing bacteria are the key that improves sulfur-bearing hydrochlorate waste anaerobic digestion biogas output to the influence of producing the methane process.
Summary of the invention
The purpose of this invention is to provide a kind of method that sulfate reduction suppresses anaerobic digestion methane production process of removing,, improve the bioavaliability of the necessary micro-metals of methanogen in the reactor, promote biogas output by suppressing sulfate reduction.This method has characteristics such as biogas output obviously improves, expense is low, workable.
Technical scheme of the present invention: by in anaerobic digestion reaction vessel, adding complexon I or its sodium salt inhibition sulfate reduction, thereby improve the bioavaliability of the essential micro-metals of methanogen, thereby the raising biogas output, making more substrate conversion is methane, described method is:
The addition of additive complexon I or its sodium salt is 10-100 μ M; Additive initially adds in fermentation, or adds at ferment middle; The initial pH of anaerobic digestion is 6.5-7.5, and temperature is 30-35 ℃, and initial sludge concentration is 5-8gVSS/L, and COD: N: P is 200: 5: 1.
In the anaerobic reactor of handling sulfur-bearing hydrochlorate waste, by the reduction of inhibition vitriol, thereby the bioavaliability that improves the essential micro-metals of methanogen is the key that promotes methane production.The present invention is in the anaerobic digestion reaction vessel of handling sulfur-bearing hydrochlorate waste, add an amount of complexon I or its sodium salt, suppress the reduction of vitriol and the generation of hydrogen sulfide, reduce or eliminate the amount of the micro-metals that exists with precipitation forms, for methanogen provides necessary nutrition and promotes its growth and breeding, and then improve biogas output.
The inventive method is particularly useful for: SO
4 2-Concentration is no more than 5000mg/L, or COD: SO
4 2-＞0.9 the waste water or the anaerobic digestion methane production of abandoned biomass.Compare with common anaerobic methane production gas process, methane production can improve 35-159%, and the sulfate reduction rate reduces 38-96%.
Beneficial effect of the present invention: compare with method with prior art, the selected sequestrant of the present invention is complexon I or its sodium salt, can obviously eliminate the disadvantageous effect of sulfate reduction to anaerobic digestion, and multiple micro-metals is had chelate effect preferably; Can significantly improve the necessary micro-Fe of methanogen, the biological utilisation of Co and Ni, thus the growth of promotion methanogen improves the utilization ratio to substrate, improves the biogas output of anaerobic digestion greatly simultaneously, and good application prospects is arranged; Only need once add, easy and simple to handle, quick; Can reduce the dosage of trace element greatly, cost saving.Key point of the present invention is by adding the bioavaliability that complexon I or its sodium salt improve the essential micro-metals of methanogen, remove the disadvantageous effect that sulfate reduction brings, promote anaerobism to produce methane, theoretical foundation is abundant, improved organic transformation efficiency in the waste greatly, the quantity discharged of having subdued pollutent.Compare with the control experiment of not adding complexon I or its sodium salt, methane production can improve 35-159%, and the sulfate reduction rate reduces 38-96%.
Embodiment
Case of comparative examples
Product methane content and sulfate reduction rate with the common anaerobically fermenting of handling similar waste water and waste are contrast.
Embodiment 1
The substrate abandoned biomass is in acetate, concentration is 7g/L, COD concentration is 4500mg/L, temperature is 30-35 ℃, and COD: N: P is 200: 5: 1, and initial sludge concentration is 5gVSS/L, initial pH is 6.5, sulfate concentration is 1700mg/L, and the addition of complexon I is 10 μ M, and the fermentation initial stage adds.Under identical experiment condition and measuring method, during fermentation ends, in the same old way methane production and sulfate reduction rate is respectively 0.24m
3/ kgCOD and 48%, and add in the test of complexon I, methane production and sulfate reduction rate are respectively 0.36m
3/ kgCOD and 22%, methane production has improved 50%, and the sulfate reduction rate has reduced by 54%.
Embodiment 2
The substrate abandoned biomass is in acetate, concentration is 7g/L, COD concentration is 4500mg/L, temperature is 30-35 ℃, and COD: N: P is 200: 5: 1, and initial sludge concentration is 5gVSS/L, initial pH is 6.5, sulfate concentration is 650mg/L, and the addition of complexon I is 10 μ M, and added on the 5th day the fermentation back.Under identical experiment condition and measuring method, during fermentation ends, in the same old way methane production and sulfate reduction rate is respectively 0.39m
3/ kgCOD and 24%, and add in the test of complexon I, methane production and sulfate reduction rate are respectively 1.01m
3/ kgCOD and 1%, methane production has improved 159%, and the sulfate reduction rate has reduced by 96%.
Embodiment 3
The substrate abandoned biomass is in acetate, concentration is 10g/L, COD concentration is about 6900mg/L, temperature is 30-35 ℃, and COD: N: P is 200: 5: 1, and initial sludge concentration is 8gVSS/L, initial pH is 7.0, sulfate concentration is 4300mg/L, and the addition of complexon I is 100 μ M, and the fermentation initial stage adds.Under identical experiment condition and measuring method, during fermentation ends, in the same old way methane production and sulfate reduction rate is respectively 0.20m
3/ kgCOD and 32%, and add in the test of complexon I, methane production and sulfate reduction rate are respectively 0.28m
3/ kgCOD and 20%, methane production has improved 40%, and the sulfate reduction rate has reduced by 38%.
Embodiment 4
The substrate abandoned biomass is in acetate, concentration is 15g/L, COD concentration is about 9800mg/L, temperature is 30-35 ℃, and COD: N: P is 200: 5: 1, and the initial stage sludge concentration is 6gVSS/L, initial pH is 7.5, sulfate concentration is 460mg/L, and the addition of complexon I is 50 μ M, and the fermentation initial stage adds.Under identical experiment condition and measuring method, during fermentation ends, in the same old way methane production and sulfate reduction rate is respectively 0.26m
3/ kgCOD and 95%, and add in the test of complexon I, methane production and sulfate reduction rate are respectively 0.35m
3/ kgCOD and 23%, methane production has improved 35%, and the sulfate reduction rate has reduced by 76%.
Claims (2)
1. remove the method that sulfate reduction suppresses anaerobic digestion methane production process for one kind, it is characterized in that by in anaerobic digestion reaction vessel, adding complexon I or its sodium salt inhibition sulfate reduction, thereby improve the bioavaliability of the essential micro-metals of methanogen, thereby raising biogas output, making more substrate conversion is methane, and described method is:
The addition of additive complexon I or its sodium salt is 10-100 μ M; Additive initially adds in fermentation, or adds at ferment middle; The initial pH of anaerobic digestion is 6.5-7.5, and temperature is 30-35 ℃, and initial sludge concentration is 5-8gVSS/L;
The substrate abandoned biomass is in acetate, and concentration is 7-15g/L, and COD concentration is 4500-9800mg/L, and control COD: N: P is 200: 5: 1.
2. method according to claim 1 is characterized in that being applicable to: SO
4 2-Concentration is no more than 5000mg/L, or COD:SO
4 2-＞0.9 the waste water or the anaerobic digestion methane production of abandoned biomass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101319917A CN101157938B (en) | 2007-09-11 | 2007-09-11 | Method for relieving restriction of sulfate reduction to anaerobic digestion methane production process |
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| CN2007101319917A CN101157938B (en) | 2007-09-11 | 2007-09-11 | Method for relieving restriction of sulfate reduction to anaerobic digestion methane production process |
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| CN101157938A CN101157938A (en) | 2008-04-09 |
| CN101157938B true CN101157938B (en) | 2010-06-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106587558B (en) * | 2016-12-26 | 2020-06-19 | 同济大学 | Method for promoting anaerobic digestion of high-solid-content sludge to produce biogas and reducing content of hydrogen sulfide by alkaline fermentation |
| CN108503024B (en) * | 2018-04-12 | 2021-03-26 | 江南大学 | Method for promoting advanced treatment effect of sulfate radical-containing high-carbon-nitrogen-ratio wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0241999B1 (en) * | 1986-04-16 | 1991-08-21 | Biothane Systems International B.V. | Anaerobic purification of waste water containing sulphate and organic material |
| US6329192B1 (en) * | 1985-10-18 | 2001-12-11 | Cp Kelco U.S., Inc. | Reticulated cellulose and methods of microorganisms for the production thereof |
| WO2005005773A2 (en) * | 2003-07-14 | 2005-01-20 | The Energy Research Institute | A process for enhanced recovery of crude oil from oil wells using novel microbial consortium |
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2007
- 2007-09-11 CN CN2007101319917A patent/CN101157938B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6329192B1 (en) * | 1985-10-18 | 2001-12-11 | Cp Kelco U.S., Inc. | Reticulated cellulose and methods of microorganisms for the production thereof |
| EP0241999B1 (en) * | 1986-04-16 | 1991-08-21 | Biothane Systems International B.V. | Anaerobic purification of waste water containing sulphate and organic material |
| WO2005005773A2 (en) * | 2003-07-14 | 2005-01-20 | The Energy Research Institute | A process for enhanced recovery of crude oil from oil wells using novel microbial consortium |
Non-Patent Citations (4)
| Title |
|---|
| 康风先.硫酸盐还原－甲烷发酵两步厌氧法处理含高浓度硫酸盐有机废水可行性研究.工业水处理13 1.1993,13(1),13-16. |
| 康风先.硫酸盐还原-甲烷发酵两步厌氧法处理含高浓度硫酸盐有机废水可行性研究.工业水处理13 1.1993,13(1),13-16. * |
| 莫文英.硫酸盐对不同浓度有机废水厌氧消化的影响.环境污染与防治15 3.1993,15(3),5-8. |
| 莫文英.硫酸盐对不同浓度有机废水厌氧消化的影响.环境污染与防治15 3.1993,15(3),5-8. * |
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