CN106222206A - Cyanophyceae harmlessness disposing and recycling processing method - Google Patents
Cyanophyceae harmlessness disposing and recycling processing method Download PDFInfo
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- CN106222206A CN106222206A CN201610701973.7A CN201610701973A CN106222206A CN 106222206 A CN106222206 A CN 106222206A CN 201610701973 A CN201610701973 A CN 201610701973A CN 106222206 A CN106222206 A CN 106222206A
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- 241000192700 Cyanobacteria Species 0.000 title claims abstract description 87
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 238000003672 processing method Methods 0.000 title claims abstract description 19
- 241000195493 Cryptophyta Species 0.000 claims abstract description 94
- 239000003053 toxin Substances 0.000 claims abstract description 89
- 231100000765 toxin Toxicity 0.000 claims abstract description 89
- 108700012359 toxins Proteins 0.000 claims abstract description 89
- 238000000855 fermentation Methods 0.000 claims abstract description 79
- 230000004151 fermentation Effects 0.000 claims abstract description 72
- 238000006731 degradation reaction Methods 0.000 claims abstract description 36
- 230000015556 catabolic process Effects 0.000 claims abstract description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005728 strengthening Methods 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
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- 238000000354 decomposition reaction Methods 0.000 claims abstract description 6
- 241000894006 Bacteria Species 0.000 claims description 83
- 239000000463 material Substances 0.000 claims description 70
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- 238000011081 inoculation Methods 0.000 claims description 29
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 10
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- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
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- 235000002247 Aspergillus oryzae Nutrition 0.000 claims description 3
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 3
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- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
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- 235000013305 food Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- DIDLWIPCWUSYPF-UHFFFAOYSA-N microcystin-LR Natural products COC(Cc1ccccc1)C(C)C=C(/C)C=CC2NC(=O)C(NC(CCCNC(=N)N)C(=O)O)NC(=O)C(C)C(NC(=O)C(NC(CC(C)C)C(=O)O)NC(=O)C(C)NC(=O)C(=C)N(C)C(=O)CCC(NC(=O)C2C)C(=O)O)C(=O)O DIDLWIPCWUSYPF-UHFFFAOYSA-N 0.000 description 3
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- 241001465754 Metazoa Species 0.000 description 1
- 241000192710 Microcystis aeruginosa Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 208000006454 hepatitis Diseases 0.000 description 1
- 231100000283 hepatitis Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 230000000696 methanogenic effect Effects 0.000 description 1
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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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- 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
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Abstract
The present invention relates to a kind of cyanophyceae harmlessness disposing and recycling processing method, including the first step, cyanophyceae breaking cellular wall and decomposition;Second step, the multi-stage degradation of Algae toxins;3rd step, strengthening acidifying;4th step, dry fermentation methane production.Present invention achieves harmlessness disposing and the resource of cyanophyceae, processing speed is high, and Algae toxins residual is low, and it is high to produce its biogas potentiality.
Description
Technical field
The present invention relates to a kind of cyanophyceae harmlessness disposing and recycling processing method, by harmlessness disposing by eutrophication
Water body cyanophyceae is fermented realizes biogas energy and biogas residue fertilizer, belongs to environmental protection and technical field of new energies.
Background technology
According to the applicant understood, the lake in the current world existing more than 40% is contaminated;The lake pollution situation of China
Even more serious, it is Heavyeutrophication that the lake of existing 66% is in more than Eutrophication Status, and 44%.Due to water body nitrogen, phosphorus
Exceed standard, the body eutrophication such as lake, cause breakout of water bloom.Wawter bloom main species is poisonous cyanophyceae, constitutes the cyanophyceae group of wawter bloom
Body grow in a large number after mortality again, give out during decomposition and make us insufferable stench, polluted water and air, simultaneously a large amount of
Consume the oxygen dissolved in water, often result in large quantities of Fish death by suffocation, seriously destroy the ecosystems such as lake.In cyanophyceae
Algae toxins is referred to as emerging pollutant, is strong rush cancer material, and people, animal are drunk and produced the water that poison cyanophyceae pollutes and can be poisoned or extremely
Dying, therefore drinking water source and aquatic product quality are affected bigger by blue-green alga bloom.Blue-green Algae Fast Growth is frequent, has had a strong impact on lake
Etc. landscape value and resident living.
" wawter bloom " in lake is two hang-ups of the domestic and international water environment protection of puzzle.In the past, controlled in minimizing wawter bloom
During reason lake, the most also used salvaging measure artificial, mechanical, but owing to the toxicity of cyanophyceae causes it to be difficult to directly
As feed conversion;Cause serious secondary pollution after Fu Laning, and employing is buried and taken a large amount of land resource.Therefore salvage
The huge blue alga biomass of results is one all the time a difficult problem to be solved.
Current researcher is thought treat eutrophic water algae dialectically, and algae is Water, phosphorus
Maximum enrichment person, algae efficient absorption and substantial amounts of nitrogen, phosphorus and organic pollution in polluted-water of dissolving in eutrophication water,
If being drawn off just to play the effect purified water.When water body breaks out wawter bloom, its alga cells quantity is often beyond 100
Hundred million.It was found that the standing crop biomass dry weight of Dianchi Lake cyanophyceae is about more than 10000 tons, it is clear that the algae and water such as lake are
Water, the maximum enrichment person of phosphorus, be also huge resources bank.The most how to utilize this potential resource of algae
Storehouse, is allowed to resource, has both realized administering lake eutrophication, and realizing again turning waste into wealth will be following lake treatment and water ecology
The developing direction repaired.
Use anaerobic fermentation technology that algae and water is processed, while producing biogas energy, carry to agricultural production
For high-quality and efficient organic fertilizer resource, promote pollution-free food production and agricultural sustainable development, the most both solved eutrophication lake
Pool breaks out the huge Biomass disposal difficulties of bloom blue algae, can be translated into again clean energy resource, reaches to improve environment, and increases
Add the purpose of economy, society and ecological benefits.
But, the maximum bottleneck that blue algae resource utilizes is the Algae toxins that contains hazardous substance.Algae toxins in cyanophyceae, predominantly
Ring-type heptapeptide hepatotoxin, ring-type five hepatotoxin, that toxicity is bigger is mainly MC-LR, MC-RR, MC-YR etc. several.If warp
It often is exposed to the water containing above-mentioned toxin, skin carcinoma, hepatitis and hepatocarcinoma can be caused, even result in death.With containing Algae toxins
Cyanophyceae directly uses soil, and Algae toxins can contaminated soil, subsoil water the most also can be enriched in crop body, if the mankind acquire
The crop being contaminated by microcystin, is difficult to effectively degrade Algae toxins at food processing process.Use Algae toxins content
High cyanophyceae biogas residue, blue alga organic fertilizer etc., can enter human body by food chain, thus produce physiology, biochemistry and genetoxic.
Therefore, the harmlessness disposing to algal toxin degradation is the precondition of its recycling.
The innoxious guardian technique of cyanophyceae is: be suitable for processing the cyanophyceae that dry matter content is high, Algae toxins initial value is high,
And Algae toxins residual quantity is low after requirement process.In prior art, in (2009), Han Shiqun etc. (2009), Yang Hong etc. such as Hu Ping
(2013) in the research that (list of references is shown in the table 1 in detailed description of the invention) is removed about blue algae toxin, respectively with cyanophyceae+work
Property mud, cyanophyceae+activated sludge, the fermentation process of cyanophyceae+fermenting mixture remove Algae toxins in cyanophyceae.Said method can be located
The cyanophyceae dry matter content of reason is relatively low, and respectively 5.96%, 4.24%, 3.4%;Accessible initial Algae toxins (MC-LR, MC-
RR) relatively low, respectively 244~366 μ g/kg, 510~1410 μ g/kg, 26.98~41.8 μ g/kg.After degraded, Algae toxins
Residual quantity is respectively < 5 μ g/kg, < 5 μ g/kg, 1.86 μ g/kg.Additionally, application number CN200810194451.8, publication number
CN101418316A, entitled a kind of cyanophyceae and the Chinese invention patent application of mud producing marsh gas through mixed anaerobic fermentation, Algae toxins
Initial value is 244~366 μ g/kg, Algae toxins residual quantity < 5 μ g/kg after process.As can be seen here, these methods reported are only
After being suitable for processing the cyanophyceae that dry matter content is low, Algae toxins initial value is low, and process, Algae toxins residual quantity is all higher than both at home and abroad
Algae toxins limit index (< 1 μ g/kg) in drinking water, they are all unsuitable for processing dry matter content height, Algae toxins initial value height
Cyanophyceae, and residual Algae toxins exceed standard.
About the existing numerous studies of algal toxin degradation bacterium, but currently mainly concentrate on the screening of algal toxin degradation bacterium, kind
The aspects such as qualification and algal toxin degradation effect, and produce about cyanophyceae in the production process of biogas and add algal toxin degradation bacterium artificially
The application aspect of agent has no report;Especially with regard to adding the complex of iron content and charcoal, Algae toxins is catalyzed two grades of falls
Research in terms of solution has no report;Additionally, the multi-stage degradation about anaerobic fermentation stage interpolation algal toxin degradation microbial inoculum does not appears in the newspapers
Road.
It is that fermentation is short big (per dry matter gas production) with product its biogas potentiality for demurrage that cyanophyceae produces the core technology of biogas,
It is directly connected to the application efficiency of equipment and the height of economic benefit.In prior art, (list of references is shown in detailed description of the invention
Table 2), Xu Rui (2007), use Dian Chi cyanophyceae+activated sludge to produce biogas method, result of study shows that cyanophyceae produces its biogas potentiality and is
345mL/gTS.Zhang Jianhong (2013), uses the batch fermentation process for producing biogas of Dian Chi cyanophyceae+blue algae fermentation residue, and result shows
Showing that demurrage is 29 days, it is 255mL/gTS that cyanophyceae produces its biogas potentiality.Zhao Ming magnitude (2013) uses Taihu Lake cyanophyceae+methane phase
Grain mud produces biogas method, and it is 120.5mL/gTS that result shows that cyanophyceae produces its biogas potentiality.Han Shiqun etc. (2009) use Taihu Lake blue
Algae+activated sludge produces biogas method, and result shows that demurrage is 90 days, and it is 850mL/gTS that cyanophyceae produces its biogas potentiality.Wang Zhenyu etc.
(2008), using Taihu Lake cyanophyceae+activated sludge to produce biogas method, result shows that demurrage is 16 days, and cyanophyceae produces its biogas potentiality and is
530mL/gTS.Song Wei (2009), uses the Taihu Lake dry fermentation method of cyanophyceae, and demurrage is 42 days, and cyanophyceae produces its biogas potentiality and is
352.31mL/gTS。
In anaerobic fermentation research, VFAs content is the hallmark parameters that organic matter degradation process conditions are good and bad, its content and first
Alkane yield is proportionate.Li Yuxiang etc. (2009), ether acid blue algae is object of study, by optimizing cyanophyceae anaerobic fermentation and acid production bar
Part, uses alkaline Pretreatment improve target product volatile fatty acid (VFAs) concentration and the degradation rate of substrate organic matter and turn
Rate, result shows: demurrage is 15 days, and VFAs concentration is 5.60g/L.Wang Zhenyu etc. (2008), research Taihu Lake cyanophyceae anaerobism
Some indexs during fermentation methane production, result shows that its demurrage is 16 days, VFAs concentration 0.2~4.58g/L.Different fermentations
(2005) researchs such as material and Different treatments affect the concentration of volatile fatty acid, Zhang Bo show that rubbish from cooking biogas is sent out
15 days demurrages of ferment, VFAs concentration 24.3g/L.Shi Feng etc. (2008), research shows biogas fermentation demurrage 12 of municipal sludge
My god, VFAs concentration 3.92g/L.Horiuchi J (2002) research shows 35 days demurrages of biogas fermentation of municipal refuse+pig manure,
VFAs concentration 6.7g/L.
Summary of the invention
The technical problem to be solved is: overcome the problem that prior art exists, it is provided that a kind of cyanophyceae is innoxious
Disposing and recycling processing method, processing speed is high, and Algae toxins residual is low, and it is high to produce its biogas potentiality.
The technical scheme that the present invention solves its technical problem is as follows:
A kind of cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, comprise the following steps:
The first step, cyanophyceae breaking cellular wall and decomposition:
Take target cyanophyceae material, wherein inoculating cell wall degraded composite bacteria agent capable and protein degradation composite bacteria agent capable, then
It is stirred aerobe fermentation 2~3 days;Described cell wall degradation composite bacteria agent capable is by aspergillus niger, white thin,tough silk bulbil bacterium and Neurospora crassa
Constituting, described protein degradation composite bacteria agent capable is made up of bacillus and aspergillus oryzae;
Second step, first, second grade of degraded of Algae toxins:
S1, the first order degraded of Algae toxins:
Take first step gained material, in this material, inoculate Algae toxins high-efficiency degradation composite bacteria agent, then stir aerobic
Ferment 1~2 days;Described Algae toxins high-efficiency degradation composite bacteria agent is by Rhodopseudomonas antibacterial, rhizobium sp and antibacterial
Paucibacter sp. is constituted;
S2, the second level catalytic degradation of Algae toxins:
Take S1 gained material, in this material, add carbon-nitrogen ratio regulator;Then aerobe fermentation 1~2 days it are stirred;Described carbon
Nitrogen is powdery than regulator, and is formed by Zero-valent Iron, ferroso-ferric oxide, charcoal mixing;
3rd step, strengthening acidifying:
Take second step S2 gained material, in this material inoculation strengthening acidifying composite bacteria agent capable, be then stirred aerobe fermentation 1~
2 days;Described strengthening acidifying composite bacteria agent capable is by photosynthetic bacteria, lactic acid bacteria, bacillus bifidus, product propionibacterium antibacterial, shuttle shape spore bar
Campylobacter bacteria and Streptococcus antibacterial are constituted;
The third level degraded of the 4th step, dry fermentation methane production and Algae toxins:
Use Zymolysis Equipment, utilize the 3rd step gained material to carry out anaerobic dry fermentation and produce biogas, come with this process simultaneously
Becoming the third level degraded of Algae toxins, fermentation time is 5-9 days;Afterwards, from Zymolysis Equipment, biogas residue, biogas slurry are discharged for following resource
Change and utilize.
The key point of technique scheme is as follows:
(1) there is cell wall and be difficult to breaking cellular wall and the high feature of protein content in cyanophyceae, needs first to solve breaking cellular wall, albumen
The problem of matter degraded.Through going deep into practical studies repeatedly, inventor has drawn previously described cell wall degradation composite bacteria agent capable
With protein degradation composite bacteria agent capable, cyanophyceae can be carried out breaking cellular wall and decomposition, thus lay the foundation for subsequent process steps.
(2) blue algae toxin always hinders the technical bottleneck that biogas slurry, biogas residue cyanophyceae Fertilizer Transformed utilize, through the deepest
Entering practical studies, inventor has drawn previously described multi-stage degradation step, uses inventor after deliberation in the first order is degraded
The Algae toxins high-efficiency degradation composite bacteria agent drawn, can efficient degradation Algae toxins;In degrading in the second level, fe is at sour environment
The hydrogen of lower generation can promote next stage methane production, can provide electron donor, catalysis Algae toxins fall to microorganism simultaneously
Solve;In the third level is degraded, anaerobic fermentation is used to degrade further Algae toxins.After this multi-stage degradation, final gained natural pond can be made
Algae toxins residual quantity in slag and biogas slurry is less than 1 μ g/kg, meets the limitation requirement of Algae toxins in national drinking water standard.
(3) through going deep into practical studies repeatedly, inventor draws previously described strengthening acidification step before dry fermentation,
The strengthening acidifying composite bacteria agent capable using inventor to draw after deliberation carries out strengthening acidifying to gained material, can be effectively improved material
Produce its biogas potentiality.
Using the preceding solution of above-mentioned key point, processing speed is high, and Algae toxins residual is low, and it is high to produce its biogas potentiality,
Guarantee to realize the harmlessness disposing of cyanophyceae and resource.
The technical scheme that the present invention is the most perfect is as follows:
Preferably, described cell wall degradation composite bacteria agent capable, protein degradation composite bacteria agent capable, strengthening acidifying composite bacteria agent capable are respectively
Can grow with cyanophyceae for culture medium culturing;Described Algae toxins high-efficiency degradation composite bacteria agent can be with blue algae toxin as sole carbon source
Culture medium on cultivate growth.
Preferably, at cell wall degradation composite bacteria agent capable, protein degradation composite bacteria agent capable, Algae toxins high-efficiency degradation composite bacteria
In agent, strengthening acidifying composite bacteria agent capable, the quantity of every kind of bacterium is respectively greater than or equal to 1 × 108cfu/mL。
Preferably, in the first step, before inoculation, first the pH value of target cyanophyceae material is adjusted to 6.5~8.5;During inoculation, cell
The inoculum concentration of wall degraded composite bacteria agent capable and protein degradation composite bacteria agent capable is respectively the 0.1%-2% weight hundred of cyanophyceae material gross weight
Proportion by subtraction;Fermentation temperature is 20 DEG C-45 DEG C.
Preferably, in second step S1, before inoculation, first the pH value of this material is adjusted to 6.5~8.5;During inoculation, Algae toxins is high
The 0.1%-0.5% percentage by weight that inoculum concentration is this material gross weight of effect degraded composite bacteria agent capable;Fermentation temperature is 20 DEG C-45
℃;
In second step S2, before inoculation, first the pH value of this material is adjusted to 3.5~6.5;The addition of carbon-nitrogen ratio regulator is
The 3%-10% percentage by weight of this material gross weight;Fermentation temperature is 20 DEG C-45 DEG C.
Preferably, in second step S2, in described carbon-nitrogen ratio regulator, Zero-valent Iron, ferroso-ferric oxide, the weight hundred of charcoal
Proportion by subtraction is 27%~45%:22%~30%:25%~51%.
Preferably, in the 3rd step, before inoculation, first the pH value of this material is adjusted to 3.5~6.5;During inoculation, strengthening acidifying is multiple
Close the 0.1%-1% percentage by weight that inoculum concentration is this material gross weight of microbial inoculum;Fermentation temperature is 20 DEG C-45 DEG C.
Preferably, in the 4th step, before dry fermentation methane production, first, use charcoal by the 3rd step gained material
Carbon-nitrogen ratio regulation is to 20~30:1 weight ratios, and is regulated to 20% percentage by weight by the moisture content of this material;Secondly, adopt
By pH adjusting agent, the pH value of this material is adjusted to 6~8, described pH adjusting agent by through 560 DEG C-750 DEG C calcinings attapulgites and
Na2CO3Constitute;Again, by 5%~15% percentage by weight inoculation biogas slurry of the 3rd step gained material gross weight;Is produced from natural pond in dry fermentation
During gas, fermentation temperature is 20 DEG C-45 DEG C.
Forming it is highly preferred that described charcoal is fired through anaerobism by biomass, described biomass include straw, phragmites communis, wood
Bits;Or, in described pH adjusting agent, attapulgite and Na2CO3Ratio be 15%-45%:55%-85% percentage by weight;
Or, inoculation biogas slurry used is fresh biogas slurry.
Preferably, in the 4th step, described Zymolysis Equipment includes the fermentation tank with sludge pump and spray equipment, during fermentation,
By sludge pump, the fermentation liquid of fermenter base is extracted out, then the spray equipment of fermented tank top sprays into fermentation tank.
Due to submerged fermentation liquid enrichment microorganism, this preferred version can make fermentation raw material be evenly distributed, increase microorganism with
The contact surface of raw material.
Compared with prior art, present invention achieves harmlessness disposing and the resource of cyanophyceae, processing speed is high, Algae toxins
Remain low, and it is high to produce its biogas potentiality.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.But the invention is not restricted to given example.
The cyanophyceae harmlessness disposing used when the present invention is embodied as and recycling processing method, including:
The first step, cyanophyceae breaking cellular wall and decomposition:
Take target cyanophyceae material, wherein inoculating cell wall degraded composite bacteria agent capable and protein degradation composite bacteria agent capable, then
It is stirred aerobe fermentation 2~3 days;Cell wall degradation composite bacteria agent capable is made up of aspergillus niger, white thin,tough silk bulbil bacterium and Neurospora crassa,
Protein degradation composite bacteria agent capable is made up of bacillus and aspergillus oryzae;
Specifically, before inoculation, first the pH value of target cyanophyceae material is adjusted to 6.5~8.5;During inoculation, cell wall degradation
The inoculum concentration of composite bacteria agent capable and protein degradation composite bacteria agent capable is respectively the 0.1%-2% percentage by weight of cyanophyceae material gross weight;
Fermentation temperature is 20 DEG C-45 DEG C.
Second step, first, second grade of degraded of Algae toxins:
S1, the first order degraded of Algae toxins:
Take first step gained material, in this material, inoculate Algae toxins high-efficiency degradation composite bacteria agent, then stir aerobic
Ferment 1~2 days;Algae toxins high-efficiency degradation composite bacteria agent is by Rhodopseudomonas antibacterial, rhizobium sp and antibacterial
Paucibacter sp. is constituted;
Specifically, before inoculation, first the pH value of this material is adjusted to 6.5~8.5;During inoculation, Algae toxins efficient degradation is multiple
Close the 0.1%-0.5% percentage by weight that inoculum concentration is this material gross weight of microbial inoculum;Fermentation temperature is 20 DEG C-45 DEG C.
S2, the second level catalytic degradation of Algae toxins:
Take S1 gained material, in this material, add carbon-nitrogen ratio regulator;Then aerobe fermentation 1~2 days it are stirred;Carbon-nitrogen ratio
Regulator is powdery, and is formed by Zero-valent Iron, ferroso-ferric oxide, charcoal mixing;
Specifically, before inoculation, first the pH value of this material is adjusted to 3.5~6.5;The addition of carbon-nitrogen ratio regulator is for being somebody's turn to do
The 3%-10% percentage by weight of material gross weight;Fermentation temperature is 20 DEG C-45 DEG C;In carbon-nitrogen ratio regulator, Zero-valent Iron, four oxidations
Three-iron, the percentage by weight of charcoal are 27%~45%:22%~30%:25%~51%.
3rd step, strengthening acidifying:
Take second step S2 gained material, in this material inoculation strengthening acidifying composite bacteria agent capable, be then stirred aerobe fermentation 1~
2 days;Strengthening acidifying composite bacteria agent capable is by photosynthetic bacteria, lactic acid bacteria, bacillus bifidus, product propionibacterium antibacterial, Clostridium
Antibacterial and Streptococcus antibacterial are constituted;
Specifically, before inoculation, first the pH value of this material is adjusted to 3.5~6.5;During inoculation, strengthening acidifying composite bacteria agent capable
The 0.1%-1% percentage by weight that inoculum concentration is this material gross weight;Fermentation temperature is 20 DEG C-45 DEG C.
The third level degraded of the 4th step, dry fermentation methane production and Algae toxins:
Use Zymolysis Equipment, utilize the 3rd step gained material to carry out anaerobic dry fermentation and produce biogas, come with this process simultaneously
Becoming the third level degraded of Algae toxins, fermentation time is 5-9 days;Afterwards, from Zymolysis Equipment, biogas residue, biogas slurry are discharged for following resource
Change and utilize;
Specifically, before dry fermentation methane production, first, charcoal is used the carbon-nitrogen ratio of the 3rd step gained material to be adjusted
Save to 20~30:1 weight ratios, and the moisture content of this material is regulated to 20% percentage by weight;Secondly, pH regulator is used
The pH value of this material is adjusted to 6~8 by agent, and pH adjusting agent is by through 560 DEG C-750 DEG C attapulgites calcined and Na2CO3Constitute;Again
Secondary, by 5%~15% percentage by weight inoculation biogas slurry of the 3rd step gained material gross weight;When dry fermentation methane production, fermentation temperature
Degree is 20 DEG C-45 DEG C.
Charcoal is fired through anaerobism by biomass and is formed, and biomass include straw, phragmites communis, wood flour;In pH adjusting agent, concavo-convex
Rod soil and Na2CO3Ratio be 15%-45%:55%-85% percentage by weight;Inoculation biogas slurry used is fresh biogas slurry.
Zymolysis Equipment includes the fermentation tank with sludge pump and spray equipment, during fermentation, by sludge pump by fermenter base
Fermentation liquid extract out, then the spray equipment of fermented tank top sprays into fermentation tank.
In technique scheme, cell wall degradation composite bacteria agent capable, protein degradation composite bacteria agent capable, strengthening acidifying composite bacteria agent capable
Can grow with cyanophyceae for culture medium culturing respectively;Algae toxins high-efficiency degradation composite bacteria agent can be with blue algae toxin as sole carbon source
Culture medium on cultivate growth.
At cell wall degradation composite bacteria agent capable, protein degradation composite bacteria agent capable, Algae toxins high-efficiency degradation composite bacteria agent, intensified acid
Changing in composite bacteria agent capable, the quantity of every kind of bacterium is respectively greater than or equal to 1 × 108cfu/mL。
It should be noted that in research process, it is multiple that the acquisition process of above-mentioned each composite bacteria agent capable is respectively as follows: cell wall degradation
Close microbial inoculum and protein degradation composite bacteria agent capable respectively from naturally rotten cyanophyceae screening and separating obtain;Algae toxins efficient degradation is multiple
Closing microbial inoculum is to carry out screening and separating acquisition by the culture medium with blue algae toxin as sole carbon source;Strengthening acidifying composite bacteria agent capable is
From the cyanophyceae of acidifying, screening and separating obtains.Method owing to using during screening and separating is existing mature technology hands
Section, concrete operating process that so here is omitted.
In the specific implementation, both each composite bacteria agent capable used by the present invention can be obtained as above-mentioned acquisition process, it is also possible to adopt
The each composite bacteria agent capable obtained used by the present invention is compounded, it is also possible to use commercially available bacterial strain to train with microorganism contained in commercially available live bacteria agent etc.
The microorganism supported compounds each composite bacteria agent capable obtained used by the present invention, and make the quantity of every kind of bacterium be respectively greater than or equal to 1 ×
108Cfu/mL.
Embodiment 1 Algae toxins efficient degradation
Algae toxins has strong carcinogenesis, and the Algae toxins of cyanophyceae is the bottleneck problem of its recycling.Use three
The technical solution of the present invention of level algal toxin degradation step, the Algae toxins residual quantity being effectively reduced in biogas residue, biogas slurry.
The target cyanophyceae material that the present embodiment uses, its dry matter content (TS%) is high, more than 14%, its Algae toxins content
The highest, Algae toxins MC-RR concentration is 8705.87 μ g/kg, and MC-LR concentration is 573.40 μ g/kg, far above existing document report
The target blue algae content of toxins in road.
After the present embodiment uses technical solution of the present invention to process target cyanophyceae material, Algae toxins clearance reaches
More than 99.99%, in biogas residue, biogas slurry, Algae toxins content is 0.84 μ g/kg, less than 1 μ g/kg, meets in national drinking water standard
The limitation requirement of Algae toxins, and report (as shown in table 1) far below existing document.
The Algae toxins treatment effect contrast of table 1 different disposal method
As can be seen here, technical solution of the present invention is entirely capable of dry matter content (TS%) is high and Algae toxins content is the highest
Cyanophyceae carry out harmlessness disposing.
Embodiment 2 produces its biogas potentiality
Determine that the key factor of blue algae fermentation efficiency and economic benefit is fermentation demurrage and produces its biogas potentiality (unit dry
Matter gas production).Refer to the process cycle demurrage, as the inventive method has all performed once to the 4th step from the first step, be one
In the individual process cycle, its length is length demurrage.Demurrage is the shortest, and the time of shared equipment is the shortest, and production efficiency is more
High.Produce its biogas potentiality and determine the efficiency of fermented material product biogas, produce the highest then efficiency of its biogas potentiality the highest.
The present embodiment average out to demurrage about 14 days, is shorter than other processing methods of existing document report, can be abundant
Utilize Zymolysis Equipment, be particularly suitable for cyanophyceae break out greatly period needed for efficient, quickly dispose.Meanwhile, the present embodiment product biogas is dived
Power 878.34mL/gTS produces its biogas potentiality (as shown in table 2) far above the cyanophyceae having been reported.
The different cyanophyceae of table 2 and the fermentation demurrage of processing method and product its biogas potentiality contrast
Embodiment 3 produces volatile fatty acid VFAs
In microbiological anaerobic sweat, a kind of indispensable nutrition is not only by volatile fatty acid (VFAs)
Point, and be for methanogenic raw material.In anaerobic fermentation research, VFAs content is the mark that organic matter degradation process conditions are good and bad
Will parameter, its content is proportionate with methane production.
The present embodiment is before dry fermentation methane production will enter the aerogenesis stage, containing more VFAs in material, although its
Content is less than self containing fatty rubbish from cooking, but other Taihu Lake blue algae fermentation techniques reported far above existing document
(as shown in table 3).As can be seen here, technical solution of the present invention can make Taihu Lake cyanophyceae will enter the aerogenesis stage at dry fermentation methane production
The more volatile fatty acid of Shi Hanyou (VFAs), it is thus possible to make Taihu Lake cyanophyceae possess higher product its biogas potentiality (such as embodiment 2
Result is confirmed).
Volatile fatty acid (VFAs) contrast that table 3 different materials produces in biogas fermentation
Note: VS is volatile solid.
From embodiment 1 to 3, the present invention solves the key problem of cyanophyceae harmlessness disposing recycling, the most in fact
The efficient degradation of existing Algae toxins and low-residual, it is achieved the high efficiency (short demurrage) of biogas fermentation and high yield its biogas potentiality.
In addition to the implementation, the present invention can also have other embodiments.All employing equivalents or equivalent transformation shape
The technical scheme become, all falls within the protection domain of application claims.
Claims (10)
1. cyanophyceae harmlessness disposing and a recycling processing method, is characterized in that, comprises the following steps:
The first step, cyanophyceae breaking cellular wall and decomposition:
Taking target cyanophyceae material, inoculating cell wall degraded composite bacteria agent capable and protein degradation composite bacteria agent capable, then stir wherein
Aerobic fermentation 2~3 days;Described cell wall degradation composite bacteria agent capable is made up of aspergillus niger, white thin,tough silk bulbil bacterium and Neurospora crassa,
Described protein degradation composite bacteria agent capable is made up of bacillus and aspergillus oryzae;
Second step, first, second grade of degraded of Algae toxins:
S1, the first order degraded of Algae toxins:
Take first step gained material, in this material inoculate Algae toxins high-efficiency degradation composite bacteria agent, be then stirred aerobe fermentation 1~
2 days;Described Algae toxins high-efficiency degradation composite bacteria agent is by Rhodopseudomonas antibacterial, rhizobium sp and antibacterial
Paucibacter sp. is constituted;
S2, the second level catalytic degradation of Algae toxins:
Take S1 gained material, in this material, add carbon-nitrogen ratio regulator;Then aerobe fermentation 1~2 days it are stirred;Described carbon-nitrogen ratio
Regulator is powdery, and is formed by Zero-valent Iron, ferroso-ferric oxide, charcoal mixing;
3rd step, strengthening acidifying:
Taking second step S2 gained material, in this material, inoculation strengthening acidifying composite bacteria agent capable, is then stirred aerobe fermentation 1~2 days;
Described strengthening acidifying composite bacteria agent capable is by photosynthetic bacteria, lactic acid bacteria, bacillus bifidus, product propionibacterium antibacterial, Clostridium
Antibacterial and Streptococcus antibacterial are constituted;
The third level degraded of the 4th step, dry fermentation methane production and Algae toxins:
Use Zymolysis Equipment, utilize the 3rd step gained material to carry out anaerobic dry fermentation and produce biogas, complete algae with this process simultaneously
The third level degraded of toxin, fermentation time is 5-9 days;Afterwards, from Zymolysis Equipment, biogas residue, biogas slurry are discharged for following resourceization profit
With.
The most according to claim 1, cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, described cell wall degradation
Composite bacteria agent capable, protein degradation composite bacteria agent capable, strengthening acidifying composite bacteria agent capable can grow with cyanophyceae for culture medium culturing respectively;Described
Algae toxins high-efficiency degradation composite bacteria agent can cultivate growth in the culture medium with blue algae toxin as sole carbon source.
The most according to claim 1, cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, multiple at cell wall degradation
Close in microbial inoculum, protein degradation composite bacteria agent capable, Algae toxins high-efficiency degradation composite bacteria agent, strengthening acidifying composite bacteria agent capable, every kind of bacterium
Quantity is respectively greater than or equal to 1 × 108cfu/mL。
The most according to claim 1, cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, in the first step, and inoculation
Before, first the pH value of target cyanophyceae material is adjusted to 6.5~8.5;During inoculation, cell wall degradation composite bacteria agent capable and protein degradation are multiple
The inoculum concentration closing microbial inoculum is respectively the 0.1%-2% percentage by weight of cyanophyceae material gross weight;Fermentation temperature is 20 DEG C-45 DEG C.
The most according to claim 1, cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, in second step S1, connects
Before Zhong, first the pH value of this material is adjusted to 6.5~8.5;During inoculation, the inoculum concentration of Algae toxins high-efficiency degradation composite bacteria agent is this thing
The 0.1%-0.5% percentage by weight of material gross weight;Fermentation temperature is 20 DEG C-45 DEG C;
In second step S2, before inoculation, first the pH value of this material is adjusted to 3.5~6.5;The addition of carbon-nitrogen ratio regulator is this thing
The 3%-10% percentage by weight of material gross weight;Fermentation temperature is 20 DEG C-45 DEG C.
The most according to claim 5, cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, in second step S2, and institute
Stating in carbon-nitrogen ratio regulator, Zero-valent Iron, ferroso-ferric oxide, the percentage by weight of charcoal are 27%~45%:22%~30%:
25%~51%.
The most according to claim 1, cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, in the 3rd step, and inoculation
Before, first the pH value of this material is adjusted to 3.5~6.5;During inoculation, the inoculum concentration of strengthening acidifying composite bacteria agent capable is this material gross weight
0.1%-1% percentage by weight;Fermentation temperature is 20 DEG C-45 DEG C.
The most according to claim 1, cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, in the 4th step, dry
Before fermentation methane production, first, charcoal is used to regulate the carbon-nitrogen ratio of the 3rd step gained material to 20~30:1 weight ratios, and
The moisture content of this material is regulated to 20% percentage by weight;Secondly, use pH adjusting agent that the pH value of this material is adjusted to 6
~8, described pH adjusting agent is by through 560 DEG C-750 DEG C attapulgites calcined and Na2CO3Constitute;Again, by the 3rd step gains
5%~15% percentage by weight inoculation biogas slurry of material gross weight;When dry fermentation methane production, fermentation temperature is 20 DEG C-45 DEG C.
The most according to claim 8, cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, described charcoal is by giving birth to
Material is fired through anaerobism and is formed, and described biomass include straw, phragmites communis, wood flour;Or, in described pH adjusting agent, attapulgite
And Na2CO3Ratio be 15%-45%:55%-85% percentage by weight;Or, inoculation biogas slurry used is fresh biogas slurry.
The most according to claim 8, cyanophyceae harmlessness disposing and recycling processing method, is characterized in that, in the 4th step, described
Zymolysis Equipment includes the fermentation tank with sludge pump and spray equipment, during fermentation, by sludge pump by the fermentation liquid of fermenter base
Extract out, then the spray equipment of fermented tank top sprays into fermentation tank.
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Application publication date: 20161214 |