CN109179651A - A kind of quickly culturing anaerobic granule sludge and the method for efficiently producing propionic acid and valeric acid - Google Patents
A kind of quickly culturing anaerobic granule sludge and the method for efficiently producing propionic acid and valeric acid Download PDFInfo
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- CN109179651A CN109179651A CN201811186888.7A CN201811186888A CN109179651A CN 109179651 A CN109179651 A CN 109179651A CN 201811186888 A CN201811186888 A CN 201811186888A CN 109179651 A CN109179651 A CN 109179651A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/282—Anaerobic digestion processes using anaerobic sequencing batch reactors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2866—Particular arrangements for anaerobic reactors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/004—Apparatus and plants for the biological treatment of water, waste water or sewage comprising a selector reactor for promoting floc-forming or other bacteria
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
Abstract
The invention belongs to technical field of environmental microorganism, and in particular to a kind of quickly culturing anaerobic granule sludge and the method for efficiently producing propionic acid and valeric acid.This method uses Anaerobic Sequencing Bath Reactor, and using slaughterhouse cow dung as inoculum, using manual simulation's waste water, temperature is 37 DEG C, and pH maintains 5.6-6.0.By controlling reactor head CO2Concentration maintains 35% or more and does not use the means such as pH adjusting in fill phase, accelerates culture hydrolysis acidification anaerobic grain sludge in the reactor, and control microbial metabolism path.Anaerobic grain sludge of the invention was formed through 30 days or so, sludge volume index 15.6-25.8ml/gVSS, granulated average grain diameter 0.57-0.72mm.VFA yield (in terms of COD) reaches 0.72-0.81gCOD/gCOD in anaerobic hydrolysate, and propionic acid and valeric acid are major fermentation product, and content reaches 68%-73%.This method can speed up anaerobic grain sludge and form and improve the operating load of reactor for hydrolysis and acidification, produce sour efficiency, is a kind of process for being widely portable to Sewage Biological Treatment, has a good application prospect.
Description
Technical field
The present invention relates to technical field of environmental microorganism, and in particular to a kind of quickly culturing anaerobic granule sludge is simultaneously efficiently given birth to
The method for producing propionic acid and valeric acid.
Background technique
Anaerobic digestion techniques are microorganisms in the environment of anoxic, convert organic matter to a system of methane and carbon dioxide
Column process.It has many advantages, such as that low energy consumption, can generate resource product, in the neck such as high-concentration waste water and solid waste processing
It is used widely in domain.Anaerobic Digestion technology is broadly divided into three phases: hydrolysis, acidification and methane phase stage, generating
Volatile fatty acid (VFA), including acetic acid, propionic acid, butyric acid and valeric acid belong to short chain carboxy acid's class.These short chain carboxy acid's salts
It is the important raw materials for production of organic chemical industry's industry, added value is much larger than methane, in the synthesis of biological plastics, the life of bioenergy
It produces and the denitrogenation dephosphorizing etc. of waste water has a wide range of applications potentiality.Propose " carboxylic acid salt platform " in the world thus, at present
Anaerobic fermentation and acid production has become one of research direction of waste resource recovery.
Efficiently " carboxylic acid salt platform " not only needs higher carboxylate yield, less chemicals investment, but also ferments and produce
The control of object is equally particularly significant.Because the production of VFA must be combined with later use, different VFA components is for subsequent production
The type and quality of object have different influences.Since acetic acid chemical potential energy is lower, acetic acid type ferments the most during the fermentation
It is common, it does not often need especially to regulate and control to be obtained with the fermentation liquid that acetic acid is primary product.For example, with acetic acid type fermentation phase
Than being feed precursor using propionic acid and valeric acid, the polyhydroxyalkanoate of production has better material property and higher quotient
Industry value.But the research at present about the control of fermentation process product is actually rare, overwhelming majority research around by locating in advance
Reason technology or common fermentation method etc. promote VFA yield.Also being only limitted to acetic acid about the research of tunning regulation on a small quantity at present is
The fermentation system of primary product, and establish actually rare as the report of the fermentation system of primary product using propionic acid and valeric acid.Therefore,
It probes into and how to establish more anaerobic fermentation and acid production types and its process control, for producing, using fermentation VFA, establish complete
" carboxylic acid salt platform " has highly important practical significance.
Anaerobic grain sludge is formed by microorganism self-cohesion action, and sludge concentration in reactor can be improved, and increase has
Machine load, improves reaction efficiency to the greatest extent, simultaneously because having preferable settleability, it is easier to realize mud-water separation, energy
Shorten the sedimentation time and reduces sludge loss.But the starting time of anaerobic grain sludge is relatively long, increases in practical projects
Cost.In addition, current anaerobic grain sludge is more for methane phase process, since the period in acid-producing bacteria epoch is short, phase
Than in methane phase process, hydrolysis acidification granule sludge is more difficult to form stable granular sledge.Therefore, how quickly to cultivate
Hydrolysis acidification granule sludge simultaneously efficiently produces propionic acid and valeric acid for realizing that efficient " carboxylic acid salt platform " has great importance.And
Up to the present, there has been no the report researchs about this aspect in document.
Summary of the invention
1. goal of the invention
For being difficult to set up in current open system using propionic acid and valeric acid as primary product, anaerobic grain sludge starts slow etc.
Problem, the present invention provides a kind of quickly culturing anaerobic granule sludge production propionic acid and valeric acid is the method for major fermentation product.
2. technical solution
A kind of method that the present invention provides quickly culturing anaerobic granule sludge and efficiently produces propionic acid and valeric acid, including it is following
Aspect:
(1) reactor: the present invention uses Anaerobic Sequencing Bath Reactor (ASBR).The high 1.6m of reactor, diameter about 10cm,
Middle internal diameter 6.5cm, effective volume about 5.6L.
(2) inoculum: inoculum is derived from certain slaughterhouse cow dung, crosses 80 mesh screens and removes bulky grain residue, saves before being inoculated with
To 4 DEG C of refrigerators.
(3) artificial distribution's ingredient: culture granule sludge process uses artificial distribution, and main component includes:
C3H8NO2SCl·H2O 0.118g/L, yeast 0.05g/L, glucose 5.6g/L, dipotassium hydrogen phosphate 0.967g/L；Microelement:
NH4Cl 0.967g/L；K2HPO4·3H2O 0.25g/L；MgSO4·7H2O 0.111g/L；NaCl 0.039g/L；EDTA
0.066g/L；ZnCl20.00085g/L；CoCl2·6H2O 0.00083g/L；MnCl2·4H2O 0.00017g/L；NiCl2·
6H2O 0.0002g/L；CuCl2·2H2O 0.00067g/L；FeCl2·4H2O 0.0062g/L；Na2SeO30.00107g/L；
HBO30.000056g/L；(NH4)6Mo7O24·4H2O 0.0015g/L；NaWO4·2H2O 0.000044g/L；CaCl2·2H2O
0.125g/L.Other compositions and microelement isolated system save in plastic barrel in 4 DEG C in water distribution.Wherein other compositions are molten
Liquid is acidified to pH 2.0-2.5 with 2M HCL.
(4) it is carried out in reactor of the incubation of anaerobic grain sludge described in (1), takes seed sludge described in (2)
The reactor is added in 100-200ml, by adjusting, makes reactor influent COD 2.3-2.5g/L, cycle period setting 1h (into
Water: 1min；The stage of reaction: 52min；Precipitating: 6min；Draining: 1min), hydraulic detention time (HRT) 2h.
(5) reaction temperature is 37 DEG C in fermentation process, and pH maintains 5.6-6.0, but fill phase regulates and controls without pH.Instead
It answers and is passed through CO at the top of device2And N2Gaseous mixture guarantees reactor head space CO in operational process2Concentration account for the 35% of total gas content with
On, liquid is stirred by gas circulator in reactor, flow velocity 2.0-2.5L/min.
3. beneficial effects of the present invention
Present invention anaerobic hydrolysis-acidification granule sludge of fast culture in ASBR reactor is stable, solves tradition
Hydrolysis acidification pool takes up a large area, sludge content is low, particularly acid-producing bacteria growth rate is fast, should not form stable particle sludge
Etc. problems.Anaerobic grain sludge was formed through 30 days or so, and sludge volume index (SVI) is 15.6-25.8ml/gVSS, granulating
Average grain diameter 0.57-0.72mm.VFA concentration (in terms of COD) reaches as high as 2.05g/L in anaerobic hydrolysate, and VFA yield is (with COD
Meter) reach 0.72-0.81gCOD/gCOD.In anaerobic hydrolysate based on propionic acid and valeric acid, content reaches 68%-73%.The party
Method can quickly culturing anaerobic hydrolysis acidification granule sludge, and formed using propionic acid and valeric acid as the fermentation system of primary product, energy
It enough improves the operating load of reactor for hydrolysis and acidification, produce sour efficiency and operation stability, and reduce SVI, be that one kind can fit extensively
For the process of Sewage Biological Treatment, tunning can be used for synthesizing high added value biological plastics, have good application
Prospect.
Detailed description of the invention
Fig. 1 is hydrolysis acidification granule sludge photo (20 times of amplification).
Specific embodiment
It further elaborates below by way of specific embodiment to the present invention.
Instrument used in the present invention and material are commercially available.Wherein cow dung is derived from Beijing as inoculum and butchers
?.
Embodiment 1:
(1) cow dung uses 80 mesh net filtrations first, takes 150ml that ASBR reactor (1.6m, diameter is added as seed sludge
About 10cm, wherein internal diameter 6.5cm, effective volume about 5.6L).
(2) the glucose simulated wastewater that COD concentration is 2.5g/L is added into reactor by peristaltic pump, sets the circulating cycle
Phase is 1h (water inlet: 1min；The stage of reaction: 52min；Precipitating: 6min；Draining: 1min), HRT 2h.
(3) control reaction temperature is 37 DEG C, and stage of reaction pH maintains 6.0 or so, and fill phase is controlled without pH, into
PH is about 4.7 in system after the completion of the water stage.Reactor head is passed through 50%:50%CO with 200Nml/min2And N2Gaseous mixture,
Reactor head gas circulation, flow velocity 2.0L/min are passed through from reactor bottom in water inlet and the stage of reaction.
(4) pass through culture in 33 days, light yellow oval spherical granule sludge is generated in the visible reactor of naked eyes, sees Fig. 1 institute
Show.Mean particle size 0.58mm, SVI 15.7ml/gVSS.VFA mean concentration (in terms of COD) is in reactor water outlet
1.91gCOD/L, propionic acid and valeric acid account for the 69.2% of total VFA content, and water outlet VSS is 0.86g/L.
Embodiment 2:
(1) cow dung uses 80 mesh net filtrations first, takes 150ml that ASBR reactor (1.6m, diameter is added as seed sludge
About 10cm, wherein internal diameter 6.5cm, effective volume about 5.6L).
(2) the glucose simulated wastewater that COD concentration is 2.5g/L is added into reactor by peristaltic pump, sets the circulating cycle
Phase is 1h (water inlet: 1min；The stage of reaction: 52min；Precipitating: 6min；Draining: 1min), HRT 2h.
(3) control reaction temperature is 37 DEG C, and stage of reaction pH maintains 5.9 or so, and fill phase is controlled without pH, into
About 4.3 pH in system after the completion of the water stage.Reactor head is passed through 50%:50%CO with 200Nml/min2And N2Gaseous mixture,
Water inlet and the stage of reaction are passed through reactor head gas from reactor bottom and recycle, flow velocity 2.0L/min.
(4) reactor operation after a week, can be observed to stick on the reactor wall by sludge.By training in about 27 days altogether
It supports, light yellow oval spherical granule sludge is generated in the visible reactor of naked eyes.Mean particle size 0.64mm, SVI 17.3ml/
gVSS.VFA mean concentration (in terms of COD) is 1.83gCOD/L in reactor water outlet, and propionic acid and valeric acid account for total VFA content
70.6%, water outlet VSS are 0.92g/L.
Embodiment 3:
(1) cow dung uses 80 mesh net filtrations first, takes 150ml that ASBR reactor (1.6m, diameter is added as seed sludge
About 10cm, wherein internal diameter 6.5cm, effective volume about 5.6L).
(2) the glucose simulated wastewater that COD concentration is 2.5g/L is added into reactor by peristaltic pump, sets the circulating cycle
Phase is 1h (water inlet: 1min；The stage of reaction: 52min；Precipitating: 6min；Draining: 1min), HRT 2h.
(3) control reaction temperature is 37 DEG C, and stage of reaction pH maintains 5.8 or so, and fill phase is controlled without pH, into
About 4.6 pH in system after the completion of the water stage.Reactor head is passed through 50%:50%CO with 200Nml/min2And N2Gaseous mixture,
Water inlet and the stage of reaction are passed through reactor head gas from reactor bottom and recycle, flow velocity 2.0L/min.
(4) reactor operation after a week, can be observed to stick on the reactor wall by sludge.By training in about 30 days altogether
It supports, light yellow oval spherical granule sludge is generated in the visible reactor of naked eyes.Mean particle size 0.66mm, SVI 20.4ml/
gVSS.VFA mean concentration (in terms of COD) is 1.86gCOD/L in reactor water outlet, and propionic acid and valeric acid account for total VFA content
71.2%, water outlet VSS are 0.93g/L.
In the various embodiments described above, the particle size distribution of anaerobic grain sludge uses the KEYENCE configured with scale micro-
Mirror measurement；Volatile acid concentration in water sample is measured using Agilent gas chromatograph 7890A.
Claims (5)
1. a kind of quickly culturing anaerobic granule sludge and the method for efficiently producing propionic acid and valeric acid, it is characterised in that the method packet
Include following steps:
(1) present invention uses Anaerobic Sequencing Bath Reactor (ASBR), the high 1.6m of reactor, diameter about 10cm, wherein internal diameter
6.5cm, effective volume about 5.6L；
(2) inoculum is derived from certain slaughterhouse cow dung, crosses 80 mesh screens and removes bulky grain residue, saves before being inoculated with to 4 DEG C of refrigerators；
(3) culture granule sludge process uses artificial distribution, and main component includes: C3H8NO2SCl·H2O 0.118g/L, ferment
Female 0.05g/L, glucose 5.6g/L, dipotassium hydrogen phosphate 0.967g/L, microelement: NH4Cl 0.967g/L, K2HPO4·3H2O
0.25g/L, MgSO4·7H2O 0.111g/L, NaCl 0.039g/L, EDTA 0.066g/L, ZnCl20.00085g/L,
CoCl2·6H2O 0.00083g/L, MnCl2·4H2O 0.00017g/L, NiCl2·6H2O 0.0002g/L, CuCl2·2H2O
0.00067g/L, FeCl2·4H2O 0.0062g/L, Na2SeO30.00107g/L, HBO30.000056g/L, (NH4)6Mo7O24·4H2O 0.0015g/L, NaWO4·2H20 0.000044g/L, CaCl2·2H2O 0.125g/L, other in water distribution
Ingredient and microelement isolated system save, wherein other compositions solution is acidified to pH with 2M HCL in plastic barrel in 4 DEG C
2.0-2.5；
(4) it is carried out in the reactor of the culture of anaerobic grain sludge and fermentation process described in (1), takes inoculation described in (2) dirty
Mud 100-200ml is added the reactor, and adjusting reactor inlet COD concentration is 2.3-2.5g/L, cycle period set 1h (into
Water: 1min, the stage of reaction: 52min, precipitating: 6min, draining: 1min), hydraulic detention time (HRT) 2h；
(5) fermentation temperature is 37 DEG C, and stage of reaction pH is set as 5.6-6.0, but fill phase regulates and controls without pH, reactor top
Portion is passed through CO2And N2Gaseous mixture guarantees reactor head space CO in operational process2Concentration accounts for 35% or more of total gas content, reaction
Liquid is stirred by gas circulator in device, flow velocity 2.0-2.5L/min.
2. according to method described in right 1, which is characterized in that it uses Anaerobic Sequencing Bath Reactor (ASBR), the high 1.6m of reactor,
Diameter about 10cm, wherein internal diameter 6.5cm, effective volume about 5.6L, reactor influent COD are 2.3-2.5g/L, and cycle period is set
Determine 1h (water inlet: 1min, the stage of reaction: 52min, precipitating: 6min, draining: 1min), hydraulic detention time (HRT) 2h.
3. according to method described in right 1, which is characterized in that reaction temperature is 37 DEG C in fermentation process, and pH maintains 5.6-
6.0, but reactor fill phase regulates and controls without pH, and reactor head is passed through CO with 50%:50% ratio2And N2Gaseous mixture is protected
Demonstrate,prove reactor head space CO in operational process2Concentration accounts for 35% or more of total gas content, and liquid is recycled by gas in reactor
Pump is stirred, flow velocity 2.0-2.5L/min.
4. according to method described in right 1, which is characterized in that anaerobic hydrolysis-acidification granule sludge was formed through 30 days or so, sludge
Bulk index (SVI) is 15.6-25.8ml/gVSS, granulates average grain diameter 0.57-0.72mm.
5. according to method described in right 1, which is characterized in that VFA yield (in terms of COD) reaches 0.72- in anaerobic hydrolysate
0.81gCOD/gCOD, using propionic acid and valeric acid as primary product in anaerobic hydrolysate, content reaches 68%-73%, and methane production is only
0.015-0.019gCOD/gCOD。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337549A (en) * | 2021-05-17 | 2021-09-03 | 北京化工大学 | Method for preparing different polyhydroxyalkanoates by directional acidification of pig manure |
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| CN113337549A (en) * | 2021-05-17 | 2021-09-03 | 北京化工大学 | Method for preparing different polyhydroxyalkanoates by directional acidification of pig manure |
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Application publication date: 20190111 |