CN104662157A - Method for implementing zero emission biogas slurry in pure straw anaerobic digestion - Google Patents
Method for implementing zero emission biogas slurry in pure straw anaerobic digestion Download PDFInfo
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- CN104662157A CN104662157A CN201380047597.9A CN201380047597A CN104662157A CN 104662157 A CN104662157 A CN 104662157A CN 201380047597 A CN201380047597 A CN 201380047597A CN 104662157 A CN104662157 A CN 104662157A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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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
Abstract
Disclosed in the present invention is a method for implementing zero emission biogas slurry in pure straw anaerobic digestion, comprising (1) pretreating a pure straw feedstock; (2) adjusting the C/N of the pretreated straw, and feeding; (3) discharging fermentation residues from the anaerobic digestion reactor, and isolating biogas slurry therefrom; (4) performing an aerobic nitrification treatment on the biogas slurry outside the anaerobic digestion reactor; (5) refluxing 100% of the biogas slurry in the straw feeding process, after the aerobic treatment, to the anaerobic digestion system, and performing a denitrification treatment on the biogas slurry in the anaerobic digestion reactor. The method of the present invention combines the in vitro aerobic nitrification and in vivo denitrification of the biogas slurry, thereby effectively reducing the COD and ammonia nitrogen concentration of the biogas slurry, no additional carbon source needs to be added in the denitrification process, and the inhibitory effect of reusing the biogas slurry on the system is eliminated, thereby achieveing zero emission biogas slurry and 100% reuse, and avoiding secondary pollution; at the same time, completely replacing the straw with biogas slurry for feeding regulates water, thereby achieving significant water conservation, reducing operating costs and being capable of maintaining the long-term stable operation of the anaerobic digestion reactor.
Description
It is a kind of to realize the method and technology field that pure straw anaerobic digests biogas slurry zero-emission
The invention belongs to Solid Waste Treatment technical field, and in particular to a kind of to realize the method that pure straw anaerobic digests biogas slurry zero-emission.Background technology
China is traditional large agricultural country, stalk resource very abundant.In addition to a small amount of be used effectively, open incineration is still main disposal options, and ample resources is wasted when causing the Jiong of air pollution.The features such as stalk wet type anaerobic digestion techniques are with its low power consuming, high production capacity, the disposal of biogas slurry after engineer applied more and more widely, but digestion is obtained in recent years turns into one of subject matter of obstruction tangerine stalk anaerobic digestion techniques development.Traditional biogas engineering is equipped with biogas slurry and biogas residue storage pond, and floor space is big, and cost of investment is high and subsequent treatment is difficult, and a large amount of biogas slurry Chang Wuxu discharges cause serious secondary pollution.
The processing mode of current biogas slurry is concentrated mainly on is irrigated or foliage spray as organic fertilizer, therefrom extract nutriment and add other nutritional ingredients and high-efficient bacterial fertilizer and microbial bacterial agent is made, the processing such as physics, biology heel row is carried out to it and puts or is directly back to biogas slurry in terms of anaerobic digester system.Wherein biogas slurry backflow can substantially reduce biogas slurry discharge capacity, reduction processing cost of disposal, but directly backflow is easily caused the accumulation of the inhibiting substances such as COD in reactor, ammonia nitrogen, system is set not run steadily in the long term, and it is also extremely limited to the correlative study using pure tangerine stalk as the anaerobic digestion reaction vessel of raw material.
Patent CN102586333 proposes that by the method for part biogas slurry circulating and recovering to straw anaerobic digestive system to reduce biogas slurry discharge, but biogas slurry direct reuse easily causes the rise of system organic loading and part anaerobic reaction mortifier（Such as ammonia nitrogen）Accumulation, cause system to run steadily in the long term, and the complete emission reduction of biogas slurry can not be realized；Patent CN102503019 proposes to produce biological fermentation process after the waste liquid produced in the traditional industries such as sucrose, alcohol carries out the processing such as low-level oxidation and decolouring is back to former anaerobic digestion reaction vessel again, though alleviating because biogas slurry directly flows back to the impact caused by system, Aerobic Process for Treatment complex procedures and alcoholic fermentation industry is directed to.
The present invention proposes the external aerobic nitrification of biogas slurry being combined with internal denitrification, realizes the zero-emission and 100% reuse of pure stalk anaerobic fermentation biogas slurry.There is not been reported for the current research that biogas slurry progress similar process is digested to pure straw anaerobic.The content of the invention
The present invention is intended to provide a kind of by the way that the external aerobic nitrification of biogas slurry is combined with internal denitrification, the method for really realizing pure straw anaerobic digestion biogas slurry zero-emission and 100% reuse.Its object is to realize biogas slurry zero-emission and 100% reuse, it is to avoid secondary pollution；Biogas slurry is replaced to the regulation water in stalk fill process completely, significantly reduces water consumption, reduces operating cost；Anaerobic digestion reaction vessel can be maintained to run steadily in the long term simultaneously, improve production efficiency.
As shown in figure 1, realizing the method that pure straw anaerobic digests biogas slurry zero-emission the present invention relates to a kind of, its concrete technology includes
Following steps：
The rapid h of Walk are pre-processed to pure stalk
Stalk is subjected to stalk particle diameter 3cm after mechanical crushing, crushing, it is preferred that particle diameter lcm;Optionally, the stalk crushed is pre-processed, pretreatment mode includes but is not limited to biology, chemically or physically method, it is preferred that 12-24h can be soaked under mesophilic condition using 0.2-0.4% NaOH solution;
Walk rapid 2:C/N is adjusted to the stalk pre-processed, and fed
Adjust C N to the stalk that has pre-processed, it is optional, including the N sources such as addition urea；Biogas slurry and stalk are added in stable semicontinuous or continuous anaerobic digestion reaction vessel；
Step 3:Residues are discharged from anaerobic digestion reaction vessel, and therefrom isolate biogas slurry
In semicontinuous or continuous feeding and discharging system, the mixing discharging of corresponding amount can be discharged after charging daily, mixing discharging obtains biogas slurry and biogas residue by separation of solid and liquid, and described biogas residue separation, biogas slurry enters the lower Walk processing of row；
Walk rapid 4:Biogas slurry carries out aerobic nitrification processing outside anaerobic digestion reaction vessel and COD is removed
By continuous aeration 20-24h in isolated biogas slurry feeding aerobic aeration pond, biogas slurry carries out external nitration reaction.Ammonia nitrogen is completely converted into nitrite nitrogen and nitrate nitrogen, ammonia nitrogen removal frank is 100%, and nitration reaction formula is as follows by biogas slurry during aerobic aeration using nitrifier：
Nitrosomas
2NH4+ + 02 ► 2 Ν02' + 4Η+ + 2 Η20
Nitromonas
2 Ν02" ► 2 Ν03"
Meanwhile, part COD of the aerobic bacteria in consumption biogas slurry during own growth, COD clearances effectively reduce biogas slurry organic loading up to 50% ~ 60%；
Walk rapid 5:Biogas slurry carries out denitrification processing in anaerobic digestion reaction vessel
Being mixed with the tangerine stalk in step 1 for biogas slurry 100% after Aerobic Process for Treatment is added in stable semicontinuous or continuous anaerobic digestion reaction vessel, the C sources being dissolved in after being digested in itself using stalk in biogas slurry carry out denitrification, without additionally adding carbon source in denitrification process, anti-nitration reaction in biogas slurry body can be achieved, by NH4 +- N is changed into N2, anti-nitration reaction formula is as follows；Nitrate reduction bacterium
NCV+C are (in stalk） ^ N02- + C02 + H20
τ^ . ^ ί+3:τ ^ ήΑ, sub- Xiao's hydrochlorate reduction ι,τ^ eightτ τ ^
Ν02+ C is (in stalk） ► Ν2 + C02 + H2The 0 Chong Fu rapid 1-5 of Walk, the number of times repeated can carry out reasonable selection as needed.
In a preferred embodiment of the present invention, in Suo Shu Walk rapid 2, including to biogas slurry TS detecting step；It is preferred that, the biogas slurry TS after the separation of solid and liquid answers 0.5%, biogas slurry TS after separation is met above-mentioned condition if that should change separate mode if being unsatisfactory for.
In a preferred embodiment of the present invention, in described step 3, it is aerated in aeration process by increasing or reducing
Strength control aeration tank DO concentration；Also include reducing Na by dilution method after continuous aeration+The step of concentration；Optionally, including to the phegma TS after aeration, ammonia nitrogen and COD concentration detect, it is preferred that the aeration process and phegma meet the mg/L of DO 2.0;Biogas slurry TS 0.2%, the mg/L of COD 1500,1000 mg/L of mg/L, Na+ of ammonia nitrogen 10;Charging in another preferred embodiment of the present invention Zhong , Walk rapid 1 only includes the biogas slurry and stalk of backflow, not including extra water distribution.
In another preferred embodiment of the present invention, semicontinuous or continuous feeding and discharging system refers to traditional batch-type anaerobic digestion reaction vessel, including but not limited to CSTR, ASBR reactor, and the size shape of reactor does not influence the implementation of the present invention.
In a preferred embodiment of the present invention, the extracting mode of biogas slurry is separation of solid and liquid, and separation of solid and liquid includes but is not limited to plate-frame filtering, high speed centrifugation, the combination with one or more modes in filter separate mode.
In another preferred embodiment of the present invention, experimental raw involved in the present invention is pure crops tangerine stalk, is not mixed with any other fermentation raw material, including but not limited to corn stalk, wheat straw, straw or its combination.
In another preferred embodiment of the present invention, method of the invention continuously runs more than 300d, it is preferred that continuous operation more than 350d.
It is of the invention compared with existing pure stalk biogas slurry treatment technology, advantage is the external aerobic nitrification of biogas slurry being combined with internal denitrification, and specific course of reaction is as shown in Figure 2.Biogas slurry is during aerobic aeration, and ammonia nitrogen changes into nitrite nitrogen and nitrate nitrogen in the presence of nitrifier, and ammonia nitrogen removal frank is steadily in the long term 100%;Meanwhile, part COD of the aerobic bacteria in consumption biogas slurry during own growth, COD clearances effectively reduce biogas slurry organic loading up to 50% ~ 60%.Biogas slurry 100% reuse in tangerine stalk fill process after aerobic nitrification, nitrite nitrogen and nitrate nitrogen change into nitrogen discharge system in the presence of denitrifying bacteria, stalk can provide sufficient carbon source for denitrifying bacterium and carry out anti-nitration reaction in itself, without adding Additional carbon sources.Effectively reduction biogas slurry COD and ammonia nitrogen concentration of the invention, eliminate inhibitory action of the reuse of biogas slurry 100% to system, maintain anaerobic digestion reaction vessel to run steadily in the long term while biogas slurry zero-emission and 100% reuse is realized；Replace the regulation water in stalk charging completely with biogas slurry, realize significantly water saving：The hydraulic detention time digested in pure straw anaerobic（HRT in), unit reactor volume can using water wisely more than 50%, reduction operating cost.Brief description of the drawings
Fig. 1 realizes the method overall procedure schematic diagram that pure straw anaerobic digests biogas slurry zero-emission to be a kind of.
Fig. 2 is the external aerobic nitrification processing of biogas slurry and internal denitrification handling principle schematic diagram.Embodiment
With reference to explanation of the specific example to be Jin mono- Walk of the present invention.
Experimental provision used in this example is CSTR anaerobic digestion reaction vessels, and volume is 8L, and anaerobic fermentation raw material is corn stalk, and feeding load is that (TS is corn tangerine dry weight to 80 gTS/L）.Ju Ti Walk are suddenly as follows：
1. in stable semicontinuous anaerobic digestion experiment, 15.05g is crushed to the corn stalk that particle diameter is 0.3cm daily and pre-processed by NaOH solution immersion（NaOH powder and clear water addition are respectively the 0.2% and 600% of corn stalk dry weight, and NaOH solution concentration is 0.33%), processing time is ld.
2. it is to send into CSTR anaerobic digestion reaction vessels after 25 that the tangerine stalk after the completion of pretreatment is adjusted into C N, while the discharging 180mlo on the day of discharge
3. discharging is centrifuged by supercentrifuge under 8400 rpm rotating speed obtains upper strata biogas slurry about 80ml after 10 min, its TS=0.42% is determined, meets and requires.
4. volume 3L aerobic aeration pond is poured into after biogas slurry is extracted out.
5. the parameters in aeration tank are monitored, the mg/L of its DO=6.7.It is the mg/L of TS=0.17%, COD=1250 that parameters are found after continuous aeration 24h;Ammonia nitrogen=21.8mg/L; Na+=2051 mg/L;It was found that Na+Concentration over-standard, therefore biogas slurry, which is diluted, makes Na+ concentration reach requirement.
6. the stalk described in the biogas slurry 75ml and Walk rapid 1 after aeration is mixed, without supplement clear water, add in CSTR anaerobic fermentation systems, and discharge the discharging on the same day.
7. repeat 3 to 6 Walk.
, there is not the phenomenon that stalk digestion aerogenesis suppresses in this example 380d in laboratory continuous service, and pH is stable, and system operation is normal.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any change or replacement expected without creative work, should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be determined by the scope of protection defined in the claims.
Claims (1)
- Claims1. a kind of realize the method that pure straw anaerobic digests biogas slurry zero-emission, comprise the technical steps that：(1) pure stalk is pre-processed；(2) C/N is adjusted to the stalk pre-processed, and fed；(3) residues are discharged from anaerobic digestion reaction vessel, and therefrom isolate biogas slurry；(4) biogas slurry carries out aerobic nitrification processing outside anaerobic digestion reaction vessel and COD is removed；(5) biogas slurry after Aerobic Process for Treatment 100% is back in anaerobic digestion reaction vessel in straw fill process, and biogas slurry carries out denitrification processing in anaerobic digestion reaction vessel.Repeat 1-5 steps.2. a kind of realize the method that pure straw anaerobic digests biogas slurry zero-emission, its concrete technology comprises the following steps：Step 1:Pure stalk is pre-processedStalk is subjected to stalk particle diameter 3cm after mechanical crushing, crushing, it is preferred that particle diameter lcm;It is optional, including soak 12-24h under mesophilic condition using 0.2-0.4% NaOH solution stalk is pre-processed；Step 2:C/N is adjusted to the tangerine stalk pre-processed, and fedAdjust C N to the stalk that has pre-processed, it is optional, including the N sources such as addition urea；Biogas slurry and stalk are added in stable semicontinuous or continuous anaerobic digestion reaction vessel；Walk rapid 3:Residues are discharged from anaerobic digestion reaction vessel, and therefrom isolate biogas slurryIn semicontinuous or continuous feeding and discharging system, the mixing discharging of corresponding amount can be discharged after charging daily, mixing discharging obtains biogas slurry and biogas residue by separation of solid and liquid, and described biogas residue separation, biogas slurry is further processed；Walk rapid 4:Biogas slurry carries out aerobic nitrification processing outside anaerobic digestion reaction vessel and COD is removedBy continuous aeration 20-24h in isolated biogas slurry feeding aerobic aeration pond, biogas slurry carries out external nitration reaction.Ammonia nitrogen is completely converted into nitrite nitrogen and nitrate nitrogen, ammonia nitrogen removal frank is 100%, and nitration reaction formula is as follows by biogas slurry during aerobic aeration using nitrifier：Nitrosomas2NH4 + + 02 ► 2 Ν02' + 4Η+ + 2 Η20 simultaneously, and part COD of the aerobic bacteria in consumption biogas slurry during own growth, COD clearances effectively reduce biogas slurry organic loading up to 50% ~ 60%；Walk rapid 5:Biogas slurry carries out denitrification processing in anaerobic digestion reaction vesselThe of biogas slurry 100% after Aerobic Process for Treatment is mixed Yu the stalk in Walk rapid 1 and added in stable semicontinuous or continuous anaerobic digestion reaction vessel, the C sources being dissolved in after being digested in itself using stalk in biogas slurry carry out denitrification, without additionally adding carbon source in denitrification process, anti-nitration reaction in biogas slurry body can be achieved, NH-N are changed into N2, anti-nitration reaction formula is as follows； N03- +C is (in stalk）Capsule ^ N02- + C02 + H20 N02- + C(in stalk）Asia pin hydrochlorate reductionN2 + C02 + H20Chong Fu Walk rapid 1-5, more than 2 times.3. in a kind of method for realizing pure straw anaerobic digestion biogas slurry zero-emission according to claim 2, Suo Shu Walk rapid 2, including to biogas slurry TS detecting step；It is preferred that, the biogas slurry TS 0.5% after the separation of solid and liquid makes biogas slurry TS after separation meet above-mentioned condition if it is not satisfied, Tong is crossed into Yi Walk separation.4. in a kind of method for realizing pure straw anaerobic digestion biogas slurry zero-emission according to claim 2, Suo Shu Walk rapid 3, pass through in aeration process and increase or reduce aeration intensity control aeration tank DO concentration；Also include after continuous aeration rapid by dilution method reduction Na+ concentration Walk；Optionally, including to the phegma TS after aeration, ammonia nitrogen and COD concentration detect, it is preferred that the aeration process and phegma meet the mg/L of DO 2.0;Biogas slurry TS 0.2%, 1500 mg/L ammonia nitrogens of COD ^ 10 mg/L, Na+^ 1000 mg/L;5. a kind of charging realized in the method that pure straw anaerobic digests biogas slurry zero-emission, step 1 according to claim 2 only includes the biogas slurry and stalk of backflow, not including extra water distribution and/or other fermentation raw materials.6. a kind of method for realizing pure straw anaerobic digestion biogas slurry zero-emission according to claim 2, semicontinuous or continuous feeding and discharging system is selected from CSTR or ASBR reactors.7. a kind of method for realizing pure tangerine stalk anaerobic digestion biogas slurry zero-emission according to claim 2, separation of solid and liquid is selected from plate-frame filtering, centrifugation, the combination with one or more modes in filter separate mode.8. a kind of method for realizing pure straw anaerobic digestion biogas slurry zero-emission according to claim 2, described stalk is selected from corn tangerine, wheat straw, straw etc. or its combination.9. a kind of method for realizing pure straw anaerobic digestion biogas slurry zero-emission according to claim 2, methods described continuously runs more than 300d, it is preferred that continuous operation more than 350d.
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| PCT/CN2013/000856 WO2015006882A1 (en) | 2013-07-17 | 2013-07-17 | Method for implementing zero emission biogas slurry in pure straw anaerobic digestion |
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