CN103773807A - Method for improving anaerobic methanogenesis efficiency by using nano magnetite - Google Patents

Method for improving anaerobic methanogenesis efficiency by using nano magnetite Download PDF

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CN103773807A
CN103773807A CN201310728818.0A CN201310728818A CN103773807A CN 103773807 A CN103773807 A CN 103773807A CN 201310728818 A CN201310728818 A CN 201310728818A CN 103773807 A CN103773807 A CN 103773807A
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magnetite
efficiency
nano magnetite
chain fatty
fatty acid
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CN103773807B (en
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郭荣波
杨智满
王传水
许晓辉
戴萌
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

The invention belongs to the field of biomass energy sources and relates to a method for improving anaerobic methanogenesis efficiency by using nano magnetite. The method takes a short-chain fatty acid as an electron donor and the nano magnetite is used as an electron carrier; under an anaerobic fermentation cultivation condition, the short-chain fatty acid is degraded so as to improve syntrophic oxidization methanogenesis efficiency of the system. With the adoption of the method, the energy source utilization efficiency of the short-chain fatty acid can be obviously improved. The method has important meanings on the improvement of the operation efficiency of a methanogenesis reactor and also has good economic benefits.

Description

A kind of method of utilizing nano magnetite to improve anaerobism product methane efficiency
Technical field
The invention belongs to biomass energy source domain, relate to a kind of method of utilizing nano magnetite to improve anaerobism product methane efficiency.
Background technology
Syntrophism is a kind of connected mutual benefit and collaboration behavior closely existing between different microorganisms kind, is to produce the essential integral part of the methane ecosystem.Syntrophism is produced in methane system and is had very important effect at anaerobically fermenting, and short chain fatty acid (as propionic acid, butyric acid) is converted into methane needs the kind indirect force between syntrophism bacterium and methanobacteria, and it is realized by electronics transmission between planting.
Produce in methane system in anaerobism, syntrophism relation is mainly present between syntrophism bacterium and methanobacteria.It is generally acknowledged, in product methane process, acidogenic fermentation bacterium transforms the short chain fatty acid (as propionic acid and butyric acid) that larger molecular organics (as carbohydrate and lipid) generates, and becomes substrate (acetic acid, hydrogen and the CO of methanobacteria through syntrophism degradation by bacteria 2).But under standard state, it is thermo-negative reaction that syntrophism bacterial oxidation short chain fatty acid becomes acetic acid, can not spontaneously carry out on thermodynamics.They need to set up syntrophism relation between methanobacteria, just can complete the conversion from short chain fatty acid to methane.Therefore, the step of oxidation short chain fatty acid product acetic acid is the rate-limiting step of producing in methane process.
For a long time, researchist thinks H always 2or formic acid can be used as kind between the carrier of electronics transmission complete short-chain fat acid degradation and produce methane process.But, due to H in solution 2or the impact of stirring in the restriction of the rate of diffusion of formic acid and fermenting process, the space length of syntrophism flora has limited organic efficient and rapid conversion to a great extent.Therefore, the syntrophism relation of this form has limited the speed of marsh gas fermentation processes greatly, causes biogas fermentation excessive cycle, has improved the running cost of biogas engineering.
In sum, in the urgent need to developing one not with H 2or the formic acid product methane process that is electron carrier, for breaking through thermodynamics obstacle in organic matter degradation process, ensure the efficient and operation fast of anaerobic digestion reaction vessel, significant.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing nano magnetite to improve anaerobism product methane efficiency.
For achieving the above object, the present invention adopts technical scheme to be:
A kind of method of utilizing nano magnetite to improve anaerobism product methane efficiency, using short chain fatty acid as electron donor, nano magnetite is as electron carrier, and under anaerobically fermenting culture condition, methane efficiency is produced in short chain fatty acid generation fast degradation and then raising system syntrophism oxidation.
Furtherly, using anaerobically digested sludge or rice soil as inoculum, short chain fatty acid adds in substratum as electron carrier successively as electron donor and nano magnetite, under the condition of pH=7.0 and 30-37 ℃, anaerobically fermenting produces methane.
Described substratum composition is: NaH 2pO 4h 2o1g/L, Na 2hPO 4h 2o0.55g/L, NaHCO 33g/L, CaCl 2275mg/L, NH 4cl310mg/L, MgCl 2330mg/L, KCl130mg/L, MnSO 46H 2o5mg/L, FeSO 47H 2o10mg/L, CuSO 45H 2o0.1mg/L, CoCl 25H 2o1mg/L, NiSO 428-42mg/L, ZnCl 21mg/L, H 3bO 30.1mg/L, Na 2moO 40.25mg/L, NiCl 2.6H 2o0.24mg/L and EDTA1mg/L.
In described every liter of substratum, add successively the electron donor of 1-10g, the inoculum of 1-4g magnetite and 10-20g.
Wherein, electron donor is propionic acid and/or butyric acid (propionic acid and butyric acid can be mixed by any ratio); Magnetite final concentration is 1-4g/L, and diameter is 5-50nm; Inoculum final concentration is 10-20g/L.
The present invention has advantages of:
1. the present invention utilizes nano magnetite to produce methane, has significantly improved the efficiency of energy utilization of short chain fatty acid, to maintaining the stable and high-speed cruising of methane-producing reactor and can significantly improving methane content in biogas component, and then has improved methane concentration.
2. adopt method of the present invention that short chain fatty acid (as propionic acid, butyric acid) is degraded rapidly, thereby solved this bottleneck problem of thermodynamical restriction that in anaerobic fermentation process, the acid degradation of the short-chain fat such as propionic acid, butyric acid exists.
Accompanying drawing explanation
The methanogenic performance figure of anaerobically digested sludge after the interpolation magnetite that Fig. 1 provides for the embodiment of the present invention.
The anaerobically digested sludge current-voltage response analysis figure that Fig. 2 provides for the embodiment of the present invention.
The methanogenic performance figure of rice soil after the interpolation magnetite that Fig. 3 provides for the embodiment of the present invention.
Embodiment
Following examples are detailed description of the present invention.
Embodiment 1
Utilize the magnetite colloidal solution of the synthetic 10nm of coprecipitation method according to prior art, stand-by.Selecting anaerobically digested sludge is inoculum, and electron donor is the mixture (mass ratio, 1:1) of propionic acid and butyric acid.
Anaerobically digested sludge, propionic acid and the butyric acid of the magnetite of above-mentioned final concentration 2g/L, final concentration 15g/L (each 5g/L) and 150mL substratum are joined with high pure nitrogen and purge and remove in the anaerobic reactor of oxygen residual in anaerobism bottle, anaerobically fermenting under pH=7.0, the air-proof condition of 37 ℃.
Meanwhile, not add magnetite (referring to Fig. 1) as a control group.
As shown in Figure 1, interpolation magnetite causes system methane production and improves 90% than not adding magnetite group, and methane generating rate improves 1.9 times, and the syntrophism microorganism species of enrichment has significant electrochemical activity (Fig. 2).
Culture medium prescription is:
NaH 2pO 4h 2o1g/L, Na 2hPO 4h 2o0.55g/L, NaHCO 33g/L, CaCl 2275mg/L, NH 4cl310mg/L, MgCl 2330mg/L, KCl130mg/L, MnSO 46H 2o5mg/L, FeSO 47H 2o10mg/L, CuSO 45H 2o0.1mg/L, CoCl 25H 2o1mg/L, NiSO 428-42mg/L, ZnCl 21mg/L, H 3bO 30.1mg/L, Na 2moO 40.25mg/L, NiCl 2.6H 2o0.24mg/L and EDTA1mg/L.
Anaerobically digested sludge character: pH, total solids (TS) and volatile suspended solid (VSS) are respectively 6.94,3.63 ± 1.30g/L and 11.75 ± 0.79g/L.
Embodiment 2
Utilize the magnetite colloidal solution of the synthetic 10nm of coprecipitation method according to prior art, stand-by.Selecting rice soil is inoculum, and electron donor is propionic acid.
The rice soil of the magnetite of above-mentioned final concentration 2g/L, final concentration 10g/L, propionic acid (5g/L) and substratum (30mL) are joined with high pure nitrogen and purge and remove in the anaerobic reactor of oxygen residual in anaerobism bottle, anaerobically fermenting under pH=7.0, the air-proof condition of 37 ℃.
Meanwhile, not add magnetite (referring to Fig. 3) as a control group.
As shown in Figure 3, interpolation magnetite causes system methane production and improves 7 times than not adding magnetite group, and methane generating rate improves 12 times.
Rice soil character: pH6.3, organic 20.1g/kg.
Embodiment 4
Utilize the magnetite colloidal solution of the synthetic 30nm of coprecipitation method according to prior art, stand-by.Selecting rice soil is inoculum, and electron donor is butyric acid.
Above-mentioned each material is joined in substratum, then be transferred to high pure nitrogen purge remove in the anaerobic reactor of oxygen residual in anaerobism bottle, in every liter of substratum, add successively the butyric acid of 8g, the rice soil of 3g magnetite and 20g.In reactor with anaerobically fermenting under pH=7.0, the air-proof condition of 37 ℃.

Claims (6)

1. a method of utilizing nano magnetite to improve anaerobism product methane efficiency, it is characterized in that: using short chain fatty acid as electron donor, nano magnetite is as electron carrier, under anaerobically fermenting culture condition, methane efficiency is produced in short chain fatty acid generation fast degradation and then raising system syntrophism oxidation.
2. by the method for utilizing nano magnetite to improve anaerobism product methane efficiency claimed in claim 1, it is characterized in that: using anaerobically digested sludge or rice soil as inoculum, short chain fatty acid adds in substratum as electron carrier successively as electron donor and nano magnetite, under the condition of pH=7.0 and 30-37 ℃, anaerobically fermenting produces methane.
3. by the method for utilizing nano magnetite to improve anaerobism product methane efficiency claimed in claim 2, it is characterized in that: described substratum composition is: NaH 2pO 4h 2o1g/L, Na 2hPO 4h 2o0.55g/L, NaHCO 33g/L, CaCl 2275mg/L, NH 4cl310mg/L, MgCl 2330mg/L, KCl130mg/L, MnSO 46H 2o5mg/L, FeSO 47H 2o10mg/L, CuSO 45H 2o0.1mg/L, CoCl 25H 2o1mg/L, NiSO 428-42mg/L, ZnCl 21mg/L, H 3bO 30.1mg/L, Na 2moO 40.25mg/L, NiCl 2.6H 2o0.24mg/L and EDTA1mg/L.
4. by the method for utilizing nano magnetite to improve anaerobism product methane efficiency claimed in claim 2, it is characterized in that:
Described electron donor is the short chain fatty acid such as propionic acid and/or butyric acid (1-10g/L).
5. by the method for utilizing nano magnetite to improve anaerobism product methane efficiency claimed in claim 2, it is characterized in that:
Described magnetite final concentration is 1-4g/L, and diameter is 5-50nm.
6. by the method for utilizing nano magnetite to improve anaerobism product methane efficiency claimed in claim 2, it is characterized in that:
Described inoculum final concentration is 10-20g/L.
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CN105731640A (en) * 2016-03-21 2016-07-06 浙江大学 Magnetite-enhanced biological electrode coupled UASB (upflow anaerobic sludge bed/blanket) apparatus and operation method
CN105755059A (en) * 2016-04-06 2016-07-13 同济大学 Method for improving synthesis concentration of carbon-chain biological extension product
CN107557395A (en) * 2017-10-25 2018-01-09 厦门大学 A kind of method for improving anaerobic methane production efficiency
CN108793402A (en) * 2018-07-16 2018-11-13 哈尔滨工业大学 A method of utilizing ferroferric oxide nano granules reinforced anaerobic reactor degradation phenol pollutant
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CN104762332A (en) * 2015-04-23 2015-07-08 合肥工业大学 Method for improving efficiency of blue-green algae or straw anaerobic methane production process
CN105731640A (en) * 2016-03-21 2016-07-06 浙江大学 Magnetite-enhanced biological electrode coupled UASB (upflow anaerobic sludge bed/blanket) apparatus and operation method
CN105755059A (en) * 2016-04-06 2016-07-13 同济大学 Method for improving synthesis concentration of carbon-chain biological extension product
CN107557395A (en) * 2017-10-25 2018-01-09 厦门大学 A kind of method for improving anaerobic methane production efficiency
CN107557395B (en) * 2017-10-25 2020-06-09 厦门大学 Method for improving anaerobic methanogenesis efficiency
CN108793402A (en) * 2018-07-16 2018-11-13 哈尔滨工业大学 A method of utilizing ferroferric oxide nano granules reinforced anaerobic reactor degradation phenol pollutant
CN110468023A (en) * 2019-07-31 2019-11-19 安徽环境科技集团股份有限公司 A kind of promotion anaerobic fermentation of organisms device
CN111302485A (en) * 2020-03-05 2020-06-19 北京师范大学 Biological nano-Fe-loaded material3O4Method for improving methane yield by using anaerobic granular sludge
CN111302485B (en) * 2020-03-05 2021-03-16 北京师范大学 Biological nano-Fe-loaded material3O4Method for improving methane yield by using anaerobic granular sludge
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