CN103922554A - Method for promoting anaerobic digestion of sludge through microbial electrical mediation - Google Patents
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Abstract
The invention discloses a method for promoting anaerobic digestion of sludge through microbial electrical mediation, and relates to a method for fast generating methane from organic waste biomass and at the method is used for solving the technical problems that the existing sludge anaerobic fermentation technology is difficult in sludge floc wall breakage, organic matters in sludge microbial cells is difficult to fully release to a liquid phase, and the utilization rate of organic matters of the sludge and the recovery rate of methane are low. The method comprises the following steps: I, pretreating sludge; II, performing the function microbial acclimation of an anode electrolysis flora; III, promoting the anaerobic digestion of sludge through microbial electrical mediation. According to the method, protons in a system can be more quickly converted by means of the electric mediation action of a microbial catalytic electrolysis system, complicated organic acid ingredients can be effectively converted in an electronic manner so as to eliminate the inhibition role of acid accumulation in the system, and the anaerobic digestion of sludge and the speed and yield of the generated methane can be effectively promoted. The method belongs to the fields of promoting sludge to generate methane through microbial electrolysis.
Description
Technical field
The present invention relates to a kind of quick methanogenic method of organic waste biomass.
Background technology
The potential hazard of municipal sludge to environment and high processing costs thereof make the minimizing of mud and resource utilization become the problem of world wide extensive concern, one of most important mode realizing its resource utilization and utilize excess sludge to produce methane, anaerobic digestion process is the most feasible current sludge stabilizing technique, compared with other biochemical methods, the advantage of anaerobic digestion process comprises that (1) treatment effect is good, the organism that can degrade to greatest extent in mud; (2) dehydration property of digested sludge is good, can greatly reduce sludge volume, realizes minimizing and the stabilization of mud; (3) can supervene high energy biogas, technique entirety energy consumption is low.
Due to the special property of mud, existing sludge anaerobic zymotechnique ubiquity organic matter in mud flco broken wall difficulty, sludge microbe cell and is difficult to fully be released into the problems such as liquid phase, the organic utilization ratio of mud and methane recovery are low, and be difficult to have breakthrough by regulate and control operation and operation optimization merely, therefore, how mechanism, to improve sludge anaerobic fermenting process creatively, improving mud utilization ratio and methane production, is wide concerned problem.
Summary of the invention
The object of the invention is to solve and organicly in mud flco broken wall difficulty that existing sludge anaerobic zymotechnique exists, sludge microbe cell be difficult to fully be released into liquid phase, the organic utilization ratio of mud and the low technical problem of methane recovery, provide the mediation of a kind of microorganism electricity to promote the method for anaerobic sludge digestion.
The mediation of microorganism electricity promotes the method for anaerobic sludge digestion to carry out according to following steps:
One, sludge pretreatment: conditioning of mud concentration, to 14000mg/L, utilizes double-frequency ultrasound to sludge pretreatment 10min, with sodium hydroxide solution conditioning of mud pH value be 10, then refrigerate stand-by;
Two, anode electrolysis flora functional microorganism domestication: using single chamber MEC reactor as microorganism electrolysis anaerobic acclimation device, fixing additional 0.6～0.9V micro voltage is added at electrode two ends, under 30 DEG C of conditions, cultivate, the single chamber MEC reactor start-up stage, 24h is one-period, and change a subculture at interval of 24h, change after substratum at single chamber MEC reactor, in reaction chamber, continue to pass into 20min purity and be 99.998% nitrogen and remove residual oxygen, be under the condition of 30 DEG C at acclimation temperature, carry out sequence batch (domestication, detect series connection 10? more than in the circuit of resistance, electric current reaches 2.0mA, complete domestication, obtain the microorganism electrode with anode function flora,
Three, the mediation of microorganism electricity promotes anaerobic sludge digestion: taking the microorganism electrode in step 2 as anode, being coated with platinum carbon cloth is negative electrode, by two electrodes with negative electrode underlying, the form of putting on anode is inserted in anaerobic digestion reaction vessel, then pretreated mud in step 1 is joined to anaerobic digestion reaction vessel, and add the fresh sludge that accounts for cumulative volume 10% as inoculum, in step 1, the volume ratio of pretreated mud and fresh sludge is 10 ﹕ 1, nitrogen 10min exposes to the sun, sealing anaerobic digestion reaction vessel, 0.8V micro voltage is added at electrode two ends, 35 DEG C～38 DEG C of controlled fermentation temperature, magnetic agitation speed 100rpm/min, ferment 5～20 days, complete the process that the mediation of microorganism electricity promotes anaerobic sludge digestion.
Described in step 1, utilizing double-frequency ultrasound is to carry out being equipped with in the groove type ultrasonic instrument that frequency is the ultrasonic generator of 28kHz and 40kHz to sludge pretreatment, and the acoustic density of ultrasonic pretreatment is 0.25～1.0kW/L.
In step 3, electric two interpole gaps are 0.5～5cm.
In step 3, electrode position is to put on anode, negative electrode underlying.
Principle of the present invention:
Because the biodegradability of excess sludge is low, anaerobic digestion completely needs considerable time, the residence time of 20～30d only can be removed 30%～50% volatile solid (VSS), sewage sludge solid cell decomposes and the interior biomacromolecule of born of the same parents is hydrolyzed to small molecules, is the rate-limiting step of anaerobic digestion.The treatment time of traditional anaerobic digestion process is long, and producing methane process is the process that methanogen floras and fermentation and acid hydrogenogens group cooperate with each other.Anode electronics transmits bacterium and has similar ecological niche to methanogen, and the inventive method is the born of the same parents' exoelectron that is attached to electrode surface to be transmitted to bacterium construct in traditional anaerobism methane-producing reactor.This class born of the same parents exoelectron propagation function bacterium has the ability of efficient degradation of organic substances, and complex substrate directly can be degraded to electronics and carbonic acid gas.By above putting the embedded structure of anode underlying negative electrode, first ensure that methanogen preferentially utilizes the suitableeest substrates such as acetic acid, in volatile acid more than remaining C3 and short period of time, the complexity organic matter of degraded not yet in effect is at positive column, top biological decomposition; Under additional boosting voltage, all kinds of organic acids of the effective degraded of anode function flora are also delivered to bottom negative electrode by bioelectronics, direct in conjunction with producing hydrogen by electronics and proton under the catalyst action of cathode surface.This process can, by regulating impressed voltage realize the acceleration of electron transfer process and the further consumption of proton, reduce acid the inhibition, utilizes microorganism electrocatalysis to produce hydrogen and provides sufficient hydrogen substrate for hydrogen nutrition methanogen.
Beneficial effect of the present invention: the mediation of microorganism electricity promotes in the method for anaerobic sludge digestion, transform faster the proton in system by the electric mediation of biocatalysis electrolytic system, effectively transform complicated Determination of Organic Acids with electronic form simultaneously, the restraining effect of acid accumulation in elimination system, anaerobic sludge digestion be can effectively promote, methanogenic speed and output improved.After pretreated residue anaerobically fermenting 24h, organic acid reaches 4000mg COD/L, within the 3rd day, is promoted to 6000mg COD/L, and starts to produce methane under microorganism electronics mediation, and stable rear peak methane-producing rate is 0.138m
3cH
4/ m
3/ d, improves 3 times than traditional anaerobic fermentation process, and VSS clearance improves 10～20%.
The inventive method is used for promoting anaerobic sludge digestion.
The technique that the present invention proposes is by biocatalysis electrolytic system and anaerobic system coupling, transform faster proton by biocatalysis electrolytic system, effectively transform complicated Determination of Organic Acids with electronic form, microorganism electrolysis system can effectively improve the methanogenic speed of mud and output simultaneously.Bioelectrochemistry technology be combined with traditional technology can science avoid novel process and conventional process techniques transformation and existing utility conflicting between equipment replacement, can be to sludge treatment effect and the larger promoter action of energy gain generation by technique local improvement on the basis that retains original process facility under prior art system.
Brief description of the drawings
Fig. 1 is the device schematic diagram that microorganism electricity of the present invention mediation promotes anaerobic sludge digestion, and in figure, 1 represents anode, and 2 represent negative electrode, and 3 represent external circuit, and 4 represent thief hole, and 5 represent agitator, and 6 represent gas collector;
Fig. 2 is embodiment mono-and contrast experiment one methane accumulation volume and the graph of a relation of fermentation time; Wherein
represent methane accumulation volume in contrast experiment one and the relation curve of fermentation time;
with
represent respectively the methane accumulation volume of two groups of parallel laboratory tests in embodiment mono-and the relation curve of fermentation time.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the mediation of present embodiment microorganism electricity promotes the method for anaerobic sludge digestion to carry out according to following steps:
One, sludge pretreatment: conditioning of mud concentration, to 14000mg/L, utilizes double-frequency ultrasound to sludge pretreatment 10min, with sodium hydroxide solution conditioning of mud pH value be 10, then refrigerate stand-by;
Two, anode electrolysis flora functional microorganism domestication: using single chamber MEC reactor as microorganism electrolysis anaerobic acclimation device, fixing additional 0.6～0.9V micro voltage is added at electrode two ends, under 30 DEG C of conditions, cultivate, the single chamber MEC reactor start-up stage, 24h is one-period, and change a subculture at interval of 24h, change after substratum at single chamber MEC reactor, in reaction chamber, continue to pass into 20min purity and be 99.998% nitrogen and remove residual oxygen, be under the condition of 30 DEG C at acclimation temperature, carry out sequence batch (domestication, detect series connection 10? more than in the circuit of resistance, electric current reaches 2.0mA, complete domestication, obtain the microorganism electrode with anode function flora,
Three, the mediation of microorganism electricity promotes anaerobic sludge digestion: taking the microorganism electrode in step 2 as anode, being coated with platinum carbon cloth is negative electrode, by two electrodes with negative electrode underlying, the form of putting on anode is inserted in anaerobic digestion reaction vessel, then pretreated mud in step 1 is joined to anaerobic digestion reaction vessel, and add the fresh sludge that accounts for cumulative volume 10% as inoculum, in step 1, the volume ratio of pretreated mud and fresh sludge is 10 ﹕ 1, nitrogen 10min exposes to the sun, sealing anaerobic digestion reaction vessel, 0.8V micro voltage is added at electrode two ends, 35 DEG C～38 DEG C of controlled fermentation temperature, magnetic agitation speed 100rpm/min, ferment 5～20 days, complete the process that the mediation of microorganism electricity promotes anaerobic sludge digestion.
In present embodiment step 2, the anode of microorganism electrolysis anaerobic acclimation device is the carbon brush that carbon fiber and titanium silk form.
Embodiment two: what present embodiment was different from embodiment one is double-frequency ultrasound described in step 1 is to carry out being equipped with in the groove type ultrasonic instrument of ultrasonic generator that frequency is 28kHz and 40kHz to sludge pretreatment, and the acoustic density of ultrasonic pretreatment is 0.25～1.0kW/L.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from one of embodiment one or two is that in step 2, additional 0.8V micro voltage is added at electrode two ends.Other is identical with one of embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is that in step 2 microorganism electrolysis anaerobic acclimation device, negative electrode is painting platinum carbon cloth prepared by conductive carbon cloth.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is that in step 3, leavening temperature is 37 DEG C.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that in step 3, fermentation time is 6 days.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is that in step 3, fermentation time is 7 days.Other is identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different from one of embodiment one to seven is that in step 3, fermentation time is 8 days.Other is identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is that in step 3, electric two interpole gaps are 0.5～5cm.Other is identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different from one of embodiment one to nine is that in step 3, electrode position is to put on anode, negative electrode underlying.Other is identical with one of embodiment one to nine.
Adopt following examples and contrast experiment to verify beneficial effect of the present invention:
Embodiment mono-: the mediation of the present embodiment microorganism electricity promotes the method for anaerobic sludge digestion, specifically carries out according to following steps:
One. measure 800ml excess sludge, it is natural subsidence 24h under 4 DEG C of conditions in temperature that excess sludge is put into container, the supernatant liquor of draining, regulate concentration to 14000mg/L the mud water obtaining, utilize double-frequency ultrasound (frequency is housed is in the groove type ultrasonic instrument of ultrasonic generator of 28kHz and 40kHz and carry out, energy density 0.5kW/L) to sludge pretreatment 10min, be that 10 rear refrigerations are stand-by with sodium hydroxide solution conditioning of mud pH.
Two. utilize the polycarbonate synthetic glass single chamber MEC reactor that volume is 30ml, the anodal carbon brush anode that connects of accessory power supply in circuit, negative pole connects painting platinum carbon cloth negative electrode, the additional 0.8V micro voltage in electrode two ends, under 30 DEG C of conditions, cultivate, the nutrient solution that is single carbon source with sodium acetate after 24 hours is changed domestication device solution, and sequence batch (is tamed one week, in testing circuit, connect 10? load in electric current reach 2.0mA and be and tame successfully above.
Three. to tame successful microorganism anode in step 2 as anode, being coated with platinum carbon cloth is negative electrode, by two electrodes with negative electrode underlying, the form of putting on anode is inserted in the glass anaerobic digestion reaction vessel of 700ml, getting pretreated mud 500ml in step 1 adds in reactor, and the fresh excess sludge that adds 50ml is as inoculum, expose to the sun nitrogen 10min to drive away the dissolved oxygen in mud, sealing anaerobic digestion reaction vessel, electrode two ends apply 0.8V micro voltage, 35 DEG C～38 DEG C of controlled fermentation temperature, magnetic agitation speed 100rpm/min, ferment 20 days, complete the anaerobic digestion process of microorganism electricity mediation catalysis.
Wherein mud used is taken from the peaceful sewage work in Harbin.
Contrast experiment one:
This contrast experiment, for not applying the method for the electric anaerobic sludge digestion mediating of microorganism, specifically carries out according to the following steps:
One. measure 800ml excess sludge, it is natural subsidence 24h under 4 DEG C of conditions in temperature that excess sludge is put into container, the supernatant liquor of draining, regulate concentration to 14000mgVSS/L the mud water obtaining, utilize double-frequency ultrasound (frequency is housed is in the groove type ultrasonic instrument of ultrasonic generator of 28kHz and 40kHz and carry out, energy density 0.5kW/L) to sludge pretreatment 10min, be that 10 rear refrigerations are stand-by with sodium hydroxide solution conditioning of mud pH.
Two. getting in step 1 pretreated mud 500ml, to add cumulative volume be in the glass anaerobic digestion reaction vessel of 700ml, and the fresh excess sludge that adds 50ml is as inoculum, expose to the sun nitrogen 10min to drive away the dissolved oxygen in mud, sealed reactor, 35 DEG C～38 DEG C of controlled fermentation temperature, magnetic agitation speed 100rpm/min, ferments 20 days, completes the anaerobic sludge digestion process without microorganism electricity mediation catalysis.
Wherein the mud that uses is taken from the peaceful sewage work in Harbin.
In embodiment mono-, within the 24th hour, microorganism electrocatalysis accelerating system is continuing to make volatile acid concentration reach 4100mg COD/L under micro voltage, increase by 20%, the 3 day accelerating system volatile acid production peak than contrast experiment's one volatile acid accumulation volume and can reach 6500mg COD/L, start to produce methane simultaneously.Fig. 2 is embodiment mono-and contrast experiment one methane accumulation volume and the graph of a relation of fermentation time, and in embodiment mono-, after the stable product of mud methane, the highest methane production reaches 0.138m as seen from the figure
3cH
4/ m
3reactor/d, increases 3 times than traditional anaerobic fermentation process.10 days (10 to 20 days) Promotion systems of aerogenesis finally add up methane production and improve 3 times than traditional anaerobically fermenting, and VSS clearance improves 10-20%.
Claims (9)
1. the mediation of microorganism electricity promotes the method for anaerobic sludge digestion, it is characterized in that the mediation of microorganism electricity promotes the method for anaerobic sludge digestion to carry out according to following steps:
One, sludge pretreatment: conditioning of mud concentration, to 14000mg/L, utilizes double-frequency ultrasound to sludge pretreatment 10min, with sodium hydroxide solution conditioning of mud pH value be 10, then refrigerate stand-by;
Two, anode electrolysis flora functional microorganism domestication: using single chamber MEC reactor as microorganism electrolysis anaerobic acclimation device, fixing additional 0.6～0.9V micro voltage is added at electrode two ends, under 30 DEG C of conditions, cultivate, the single chamber MEC reactor start-up stage, 24h is one-period, and change a subculture at interval of 24h, change after substratum at single chamber MEC reactor, in reaction chamber, continue to pass into 20min purity and be 99.998% nitrogen and remove residual oxygen, be under the condition of 30 DEG C at acclimation temperature, carry out sequence batch (domestication, detect series connection 10? more than in the circuit of resistance, electric current reaches 2.0mA, complete domestication, obtain the microorganism electrode with anode function flora,
Three, the mediation of microorganism electricity promotes anaerobic sludge digestion: taking the microorganism electrode in step 2 as anode, being coated with platinum carbon cloth is negative electrode, by two electrodes with negative electrode underlying, the form of putting on anode is inserted in anaerobic digestion reaction vessel, then pretreated mud in step 1 is joined to anaerobic digestion reaction vessel, and add the fresh sludge that accounts for cumulative volume 10% as inoculum, in step 1, the volume ratio of pretreated mud and fresh sludge is 10 ﹕ 1, nitrogen 10min exposes to the sun, sealing anaerobic digestion reaction vessel, 0.8V micro voltage is added at electrode two ends, 35 DEG C～38 DEG C of controlled fermentation temperature, magnetic agitation speed 100rpm/min, ferment 5～20 days, complete the process that the mediation of microorganism electricity promotes anaerobic sludge digestion.
2. microorganism electricity mediates the method that promotes anaerobic sludge digestion according to claim 1, it is characterized in that double-frequency ultrasound described in step 1 is to carry out being equipped with in the groove type ultrasonic instrument of ultrasonic generator that frequency is 28kHz and 40kHz to sludge pretreatment, the acoustic density of ultrasonic pretreatment is 0.25～1.0kW/L.
3. described microorganism electricity mediates the method that promotes anaerobic sludge digestion according to claim 1, it is characterized in that in step 2, fixing additional 0.8V micro voltage is added at electrode two ends.
4. described microorganism electricity mediates the method that promotes anaerobic sludge digestion according to claim 1, it is characterized in that in step 3, leavening temperature is 37 DEG C.
5. described microorganism electricity mediates the method that promotes anaerobic sludge digestion according to claim 1, it is characterized in that in step 3, fermentation time is 6 days.
6. described microorganism electricity mediates the method that promotes anaerobic sludge digestion according to claim 1, it is characterized in that in step 3, fermentation time is 7 days.
7. described microorganism electricity mediates the method that promotes anaerobic sludge digestion according to claim 1, it is characterized in that in step 3, fermentation time is 8 days.
8. described microorganism electricity mediates the method that promotes anaerobic sludge digestion according to claim 1, it is characterized in that in step 3, electric two interpole gaps are 0.5～5cm.
9. the method that promotes anaerobic sludge digestion according to described microorganism electricity mediation described in claim 1,2,3,4,5,6,7 or 8, is characterized in that in step 3, electrode position is to put on anode, negative electrode underlying.
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| CN112939393B (en) * | 2021-03-05 | 2023-10-03 | 太原理工大学 | Device for realizing caproic acid production and synchronous separation of sludge by electrofermentation without electron donor |
| CN112960880A (en) * | 2021-03-12 | 2021-06-15 | 桂林理工大学 | Method for improving methane production of anaerobic co-digestion waste oil and sludge based on carbon cloth addition |
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