CN104862346A - Method for increasing yield of short chain fatty acid produced with excess sludge through enzyme and alkali combined pretreatment - Google Patents
Method for increasing yield of short chain fatty acid produced with excess sludge through enzyme and alkali combined pretreatment Download PDFInfo
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- CN104862346A CN104862346A CN201510217054.8A CN201510217054A CN104862346A CN 104862346 A CN104862346 A CN 104862346A CN 201510217054 A CN201510217054 A CN 201510217054A CN 104862346 A CN104862346 A CN 104862346A
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
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- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/52—Propionic acid; Butyric acids
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Abstract
The invention belongs to the technical field of environment protection, and relates to a method for increasing the yield of short chain fatty acid produced with excess sludge through enzyme and alkali combined pretreatment. Precipitated concentrated sludge is obtained after excess sludge stands at 4 DEG Cfor 24 h, proteinase k is added into the concentrated sludge till the concentration of proteinase k ranges from 0.018 U/gVSS to 0.022U/gVSS, the concentrated sludge is hydrolyzed for 22 h to 26 h under 35 DEG Cto 37 DEG Cwith the stirring speed of 120 rpm, then, 10% of anaerobic granular sludge is inoculated, the pH of the sludge is adjusted to range from 9.5 to 10.5, fermentation is carried out for 4 days to 6 days in a reactor under 35 DEG Cto 37 DEG Cat the stirring speed of 120 rpm, short chain fatty acid mixed liquid which mainly contains acetic acid, propionic acid and butyric acid is obtained, and the mixed liquid can serve as a chemical material with high additive value and a methanogenesis matrix. The hydrolysis rate of sludge is increased because the proteinase k is added; the generation of short chain fatty acid is inhibited due to the alkaline condition, but because more than two pretreatment manners are combined, strict anaerobe, particularly clostridium, in acid production microorganisms is enriched, the proportion of facultative microorganisms is reduced, and the acid production rate and the acid production quantity of substrate are increased.
Description
Technical field
The invention belongs to environmental protection technical field, relate to a kind of enzyme alkali combined pretreatment and improve the method that excess sludge produces short chain fatty acid.
Background technology
End 2013, sewage work above county level of China has reached more than 3500, has supervened a large amount of excess sludges, and the total generation of national mud reaches 3,000 ten thousand tons (in water ratio 80 %), expects the year two thousand twenty sludge yield and can break through 6,000 ten thousand tons.Owing to containing large amount of organic matter in mud, the energy of mud, recycling are subject to the extensive attention of investigators.Due to the social demand of Sustainable development and the support on policy of government, nowadays the emphasis of solid waste disposal turns to recycling from Environmental capacity.Along with the through engineering approaches application of the anaerobic digestion reaction vessel nineties, Anaerobic Digestion solid waste is paid close attention to widely.Under anaerobic condition, mud can be nearly all other forms by microbial transformation.In anaeroic digestor, there is multiple microbial population decomposing organic waste, not only can obtain biogas, also can produce some other organic compound being rich in energy simultaneously.The short chain fatty acid that anaerobic sludge digestion process produces can produce the clean energies such as biogas as substrate, again can as the organic carbon source of biological carbon and phosphorous removal
Recent study persons propose the method that many raising mud produces short chain fatty acid, main on anaerobic digestion three-stage theory basis, sludge hydrolytic speed is improved and suppresses methane phase to improve the amount that mud produces short chain fatty acid by physics, chemistry or biological means, but the preprocessing means power consumptions such as existing thermokalite associating, ultrasonic wave are higher, the product acid anaerobic sludge population simultaneously obtained easily changes, and along with activity reduction working time, make reactor stable not.
In mud, acid-producing microorganisms can be divided into strictly anaerobic bacterium and facultative anaerobe according to the tolerance degree of oxygen, have document point out wherein facultative anaerobe under anaerobic activity comparatively strictly anaerobic bacterium is low, the present invention can tame the more strictly anaerobic bacterium especially fusobacterium with enrichment by the combined pretreatment of Proteinase K and alkaline condition, make microbiological paper method more stable, thus obtain the output of higher short chain fatty acid.
Summary of the invention
The present invention will solve excess sludge and produce the technical problem that short chain fatty acid efficiency is not high, produce acid system instability, thering is provided a kind of by improving high-efficiency fermenting bacterium-fusobacterium (strictly anaerobic bacterium) ratio in anaerobic fermentation process, significantly can promote that excess sludge produces the method for short chain fatty acid.
Research of the present invention shows, excess sludge can significantly improve the proteolysis in mud after Proteinase K pre-treatment, provides abundant water-soluble organic substrate for the fusobacterium product that can be with protein substrate is sour.Meanwhile, excess sludge, after initial alkaline pH pre-treatment, can improve the ratio of strictly anaerobic bacterium in microorganism (especially fusobacterium) further, and promotes mud dissolving, is hydrolyzed and continues generation short chain fatty acid.Therefore, Proteinase K pre-treatment and initial basic pH conditions combined action can be utilized to improve excess sludge hydrolysis, produce sour efficiency.
The enzyme alkali combined pretreatment that the present invention proposes improves the method that excess sludge produces short chain fatty acid, and concrete steps are as follows:
(1) for raw material after concentrating so that sewage treatment plant residual active sludge is standing, in thickened sludge, add Proteinase K to proteinase K concentration is 0.004-0.04 U/gVSS;
(2) step (1) products therefrom is hydrolyzed reaction, 30-40 DEG C, stir speed (S.S.) is be hydrolyzed 2-48h in reactor under 100-200rpm condition; In hydrolysate, inoculate anaerobic grain sludge, the inoculum size of anaerobic grain sludge is the 8-15% of thickened sludge quality;
(3) carry out the pre-treatment of mud alkalescence to step (2) products therefrom, adjustment initial pH value is 8-12;
(4) sludge anaerobic fermentation and acid production is carried out to step (3) products therefrom, 30-40 DEG C, stir speed (S.S.) continue under being 100-200rpm condition anaerobically fermenting 1-12 days produce short chain fatty acid.
In the present invention, the time that described excess sludge leaves standstill is 24h, and temperature is 4 DEG C.
In the present invention, described sludge protein enzyme K concentration is 0.018-0.022 U/gVSS.
In the present invention, the time of hydrolysis reaction described in step (2) is 22-26h.
In the present invention, described in step (2), the temperature of hydrolysis reaction is 35-37 DEG C.
In the present invention, described in step (2), the stir speed (S.S.) of hydrolysis reaction is 120rpm.
In the present invention, described in step (2), the inoculum size of anaerobic grain sludge is 10% of thickened sludge quality.
In the present invention, the pretreated initial pH value of the alkalescence of mud described in step (3) is 9.5-10.5.
In the present invention, described in step (4), the temperature of sludge anaerobic fermentation and acid production is 35-37 DEG C, and stir speed (S.S.) is 120rpm, and fermentation time is 4-6 days.
What the present invention proposed utilizes Proteinase K pre-treatment and initial basic pH conditions combined action to improve the method that mud produces short chain fatty acid, the excess sludge produced with sewage work is for raw material, by Proteinase K pre-treatment, control the proportion of composing that initial basic pH conditions changes microorganism in described mud, by the mud organic substance of the non-aqueous state in mud, as protein and polysaccharide etc. are more converted into short chain fatty acid.
The invention has the beneficial effects as follows:
(1) under Proteinase K pre-treatment and initial alkaline condition combined action, mud produces the output of methane and is significantly higher than that above either party acts solely on the short chain fatty acid that mud produces in both.
(2) more simple alkaline purification does not need to maintain reactor alkaline condition always, does not therefore need on-line monitoring pH and saves the consumption of alkali, having saved cost.
(3) Proteinase K pre-treatment and initial basic pH conditions combined action can improve the proportion of the especially fusobacterium of strictly anaerobic bacterium in mud preferably, optimize conditional parameter and the technological parameter of producing short-chain fat acid phase of sludge hydrolytic, acidifying, the product short chain fatty acid amount of excess sludge can be significantly improved, especially acetic acid, for methane phase afterwards or dephosphorization provide the substrate of more easily degrading, simultaneously domestication and enrichment after microflora more stable.
(4) utilize the excess sludge of urban wastewater treatment firm to produce short chain fatty acid, achieve sludge reduction, stabilization, resource utilization and reduce the object of mud organic substance contaminate environment.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
For promoting that excess sludge produces short chain fatty acid efficiency, the present invention, through repeatedly repetition test, finds to adopt following the present invention to improve with enzyme alkali combined pretreatment the method that excess sludge produces short chain fatty acid, can significantly improve short-chain fat acid yield.
Embodiment 1
Excess sludge after concentrated by 13.2 liters on average joins in 11 identical 2 liters of reactors that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0-0.04U/g VSS, temperature be 35-37 DEG C, stir speed (S.S.) is 120rpm Water Under solution 2-28h, recording best enzyme concn is 0.018-0.022U/g VSS, time is 22-26h, and the solvability COD of acquisition mostly is 250.97 mg COD/g VSS most.Following examples 2-8 all chooses preferably hydrolysising condition: proteinase K concentration is 0.018-0.022U/g VSS, and the time is 22-26h, and temperature is 35-37 DEG C, and stir speed (S.S.) is 120rpm.
Embodiment 2
1.2 liters of excess sludges are joined in the reactor of 2 liters that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0.018-0.022U/g VSS, be 35-37 DEG C in temperature, stir speed (S.S.) is 120rpm Water Under solution 22-26h, add the anaerobic grain sludge that volume percent is 10%, adjustment initial pH value is 8.5-9.5, anaerobically fermenting 1-3 days, the output of short chain fatty acid is 250.47 mg COD/g VSS, measured by 16S rRNA oligonucleotide probe fluorescence in situ hybridization, its fusobacterium proportion is 28%.
Embodiment 3
1.2 liters of excess sludges are joined in the reactor of 2 liters that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0.018-0.022U/g VSS, be 35-37 DEG C in temperature, stir speed (S.S.) is 120rpm Water Under solution 22-26h, add the anaerobic grain sludge that volume percent is 10%, adjustment initial pH value is 9.5-10.5, anaerobically fermenting 1-3 days, the output of short chain fatty acid is 292.49 mg COD/g VSS, measured by 16S rRNA oligonucleotide probe fluorescence in situ hybridization, its fusobacterium proportion is 32%.
Embodiment 4
1.2 liters of excess sludges are joined in the reactor of 2 liters that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0.018-0.022U/g VSS, be 35-37 DEG C in temperature, stir speed (S.S.) is 120rpm Water Under solution 22-26h, add the anaerobic grain sludge that volume percent is 10%, adjustment initial pH value is 10.5-11.5, anaerobically fermenting 1-3 days, the output of short chain fatty acid is 154.08 mg COD/g VSS, measured by 16S rRNA oligonucleotide probe fluorescence in situ hybridization, its fusobacterium proportion is 25%.
Embodiment 5
1.2 liters of excess sludges are joined in the reactor of 2 liters that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0.018-0.022U/g VSS, be 35-37 DEG C in temperature, stir speed (S.S.) is 120rpm Water Under solution 22-26h, add the anaerobic grain sludge that volume percent is 10%, adjustment initial pH value is 8.5-9.5, anaerobically fermenting 4-6 days, the output of short chain fatty acid is 267.27 mg COD/g VSS, measured by 16S rRNA oligonucleotide probe fluorescence in situ hybridization, its fusobacterium proportion is 30%.
Embodiment 6
1.2 liters of excess sludges are joined in the reactor of 2 liters that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0.018-0.022U/g VSS, be 35-37 DEG C in temperature, stir speed (S.S.) is 120rpm Water Under solution 22-26h, add the anaerobic grain sludge that volume percent is 10%, adjustment initial pH value is 9.5-10.5, anaerobically fermenting 4-6 days, the output of short chain fatty acid is 352.91 mg COD/g VSS, measured by 16S rRNA oligonucleotide probe fluorescence in situ hybridization, its fusobacterium proportion is 42%.
Embodiment 7
1.2 liters of excess sludges are joined in the reactor of 2 liters that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0.018-0.022U/g VSS, be 35-37 DEG C in temperature, stir speed (S.S.) is 120rpm Water Under solution 22-26h, add the anaerobic grain sludge that volume percent is 10%, adjustment initial pH value is 10.5-11.5, anaerobically fermenting 4-6 days, the output of short chain fatty acid is 314.03 mg COD/g VSS, measured by 16S rRNA oligonucleotide probe fluorescence in situ hybridization, its fusobacterium proportion is 36%.
Embodiment 8
1.2 liters of excess sludges are joined in the reactor of 2 liters that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0.018-0.022U/g VSS, be 35-37 DEG C in temperature, stir speed (S.S.) is 120rpm Water Under solution 22-26h, add the anaerobic grain sludge that volume percent is 10%, adjustment initial pH value is 8.5-9.5, anaerobically fermenting 7-10 days, the output of short chain fatty acid is 238.86 mg COD/g VSS, measured by 16S rRNA oligonucleotide probe fluorescence in situ hybridization, its fusobacterium proportion is 26%.
Embodiment 9
1.2 liters of excess sludges are joined in the reactor of 2 liters that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0.018-0.022U/g VSS, be 35-37 DEG C in temperature, stir speed (S.S.) is 120rpm Water Under solution 22-26h, add the anaerobic grain sludge that volume percent is 10%, adjustment initial pH value is 9.5-10.5, anaerobically fermenting 7-10 days, the output of short chain fatty acid is 300.82 mg COD/g VSS, measured by 16S rRNA oligonucleotide probe fluorescence in situ hybridization, its fusobacterium proportion is 34%.
Embodiment 10
1.2 liters of excess sludges are joined in the reactor of 2 liters that (reactor material is synthetic glass, working volume 1.5L, internal diameter 100mm, high 260mm, in cylinder shape), in reactor, add Proteinase K to concentration is 0.018-0.022U/g VSS, be 35-37 DEG C in temperature, stir speed (S.S.) is 120rpm Water Under solution 22-26h, add the anaerobic grain sludge that volume percent is 10%, adjustment initial pH value is 10.5-11.5, anaerobically fermenting 7-10 days, the output of short chain fatty acid is 341.25 mg COD/g VSS, measured by 16S rRNA oligonucleotide probe fluorescence in situ hybridization, its fusobacterium proportion is 38%.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (9)
1. enzyme alkali combined pretreatment improves the method that excess sludge produces short chain fatty acid, it is characterized in that concrete steps are as follows:
(1) for raw material after concentrating so that sewage treatment plant residual active sludge is standing, in thickened sludge, add Proteinase K to proteinase K concentration is 0.004-0.04 U/gVSS;
(2) step (1) products therefrom is hydrolyzed reaction, 30-40 DEG C, stir speed (S.S.) is be hydrolyzed 2-48h in reactor under 100-200rpm condition; In hydrolysate, inoculate anaerobic grain sludge, the inoculum size of anaerobic grain sludge is the 8-15% of thickened sludge quality;
(3) carry out the pre-treatment of mud alkalescence to step (2) products therefrom, adjustment initial pH value is 8-12;
(4) sludge anaerobic fermentation and acid production is carried out to step (3) products therefrom, 30-40 DEG C, stir speed (S.S.) continue under being 100-200rpm condition anaerobically fermenting 1-12 days produce short chain fatty acid.
2. enzyme alkali combined pretreatment according to claim 1 improves the method that excess sludge produces short chain fatty acid, it is characterized in that, the time that described excess sludge leaves standstill is 24h, and temperature is 4 DEG C.
3. enzyme alkali combined pretreatment according to claim 1 improves the method that excess sludge produces short chain fatty acid, and it is characterized in that, described sludge protein enzyme K concentration is 0.018-0.022 U/gVSS.
4. enzyme alkali combined pretreatment according to claim 1 improves the method that excess sludge produces short chain fatty acid, and it is characterized in that, the time of hydrolysis reaction described in step (2) is 22-26h.
5. enzyme alkali combined pretreatment according to claim 1 improves the method that excess sludge produces short chain fatty acid, and it is characterized in that, described in step (2), the temperature of hydrolysis reaction is 35-37 DEG C.
6. enzyme alkali combined pretreatment according to claim 1 improves the method that excess sludge produces short chain fatty acid, and it is characterized in that, described in step (2), the stir speed (S.S.) of hydrolysis reaction is 120rpm.
7. enzyme alkali combined pretreatment according to claim 1 improves the method that excess sludge produces short chain fatty acid, and it is characterized in that, described in step (2), the inoculum size of anaerobic grain sludge is 10% of thickened sludge quality.
8. enzyme alkali combined pretreatment according to claim 1 improves the method that excess sludge produces short chain fatty acid, it is characterized in that, the pretreated initial pH value of the alkalescence of mud described in step (3) is 9.5-10.5.
9. enzyme alkali combined pretreatment according to claim 1 improves the method that excess sludge produces short chain fatty acid, it is characterized in that, described in step (4), the temperature of sludge anaerobic fermentation and acid production is 35-37 DEG C, and stir speed (S.S.) is 120rpm, and fermentation time is 4-6 days.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105177061A (en) * | 2015-09-23 | 2015-12-23 | 江南大学 | Method for increasing acid production of municipal sludge through fermentation by adding external source protease |
| CN107245448A (en) * | 2017-08-03 | 2017-10-13 | 盐城工学院 | A kind of methane production equipment and its system |
| CN108753883A (en) * | 2018-05-29 | 2018-11-06 | 郑州大学 | A kind of low-intensity ultrasonic strengthened enzymolysis sludge method for extracting proteins |
| WO2021020964A1 (en) | 2019-07-26 | 2021-02-04 | Haskoningdhv Nederland B.V | Production of fatty acids from a sieve fraction of activated sludge from treated wastewater |
| CN113278573A (en) * | 2021-07-21 | 2021-08-20 | 同济大学 | Continuous directional high-value biotransformation method for strengthening urban wet garbage open system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105177061A (en) * | 2015-09-23 | 2015-12-23 | 江南大学 | Method for increasing acid production of municipal sludge through fermentation by adding external source protease |
| CN107245448A (en) * | 2017-08-03 | 2017-10-13 | 盐城工学院 | A kind of methane production equipment and its system |
| CN108753883A (en) * | 2018-05-29 | 2018-11-06 | 郑州大学 | A kind of low-intensity ultrasonic strengthened enzymolysis sludge method for extracting proteins |
| WO2021020964A1 (en) | 2019-07-26 | 2021-02-04 | Haskoningdhv Nederland B.V | Production of fatty acids from a sieve fraction of activated sludge from treated wastewater |
| NL2023573B1 (en) * | 2019-07-26 | 2021-02-18 | Haskoningdhv Nederland Bv | Production of fatty acids from a sieve fraction of activated sludge from treated wastewater |
| CN113278573A (en) * | 2021-07-21 | 2021-08-20 | 同济大学 | Continuous directional high-value biotransformation method for strengthening urban wet garbage open system |
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