CN103074380A - Method for improving anaerobic energy production efficiency of algae raw material through bacterial degradation biological pretreatment - Google Patents
Method for improving anaerobic energy production efficiency of algae raw material through bacterial degradation biological pretreatment Download PDFInfo
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- CN103074380A CN103074380A CN2012105675023A CN201210567502A CN103074380A CN 103074380 A CN103074380 A CN 103074380A CN 2012105675023 A CN2012105675023 A CN 2012105675023A CN 201210567502 A CN201210567502 A CN 201210567502A CN 103074380 A CN103074380 A CN 103074380A
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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
- Y02E50/10—Biofuels, e.g. bio-diesel
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention belongs to the field of biotechnology and renewable energy sources, and relates to a method for improving the anaerobic energy production efficiency of an algae raw material through bacterial degradation biological pretreatment. The method comprises the following steps: (1), the algae raw material is mixed with a nutritive salt solution to be inoculated to an anaerobic cellulose degrading bacteria seed solution which is cultivated in advance; (2), the seed solution is cultivated under the conditions of thermal insulation and opaque background, the bacterial degradation pretreatment is performed, hydrogen is synchronously produced, hydrolysis of cell walls is promoted, and hydrogen, hydrolysis product ethanol and volatile organic acid are obtained; and (3), after the bacterial degradation synchronous hydrogen production cultivation is finished, anaerobic inoculated sludge containing methanogens is inoculated in fermentation liquor, and accordingly hydrolysis product ethanol, volatile organic acid and algae cell residues after the bacterial degradation suffer anaerobic fermentation for methanogenesis. According to the invention, the algae biomass raw material is subjected to pretreatment through bacterial degradation so as to promote hydrolysis wall breaking of algae cells; and moreover, higher yield of hydrogen is simultaneously obtained in the process of anaerobic fermentation methanogenesis, thereby improving the energy conversion efficiency of the algae biomass raw material.
Description
Technical field
The invention belongs to biotechnology and renewable energy source domain, relate to the method that a kind of fungi degradation Biological Pretreatment improves algae raw material anaerobism production capacity efficient.
Background technology
Under the overall situation of energy and environment crisis, the energy of seeking cleaning, safety, Sustainable development has become the task of top priority.The use of renewable energy source can reduce the dependency to oil, reduces environmental pollution.Under this background, the development of biomass renewable energy source more and more is subject to social concerns, becomes the anti-risk important selection of the diversification of current realization energy sources and national energy strategy.The algae raw material is one of important biomass resource.Algae be of a great variety in the lower plant, extremely widely holophyte monoid distributes.Compare with other biological matter such as ligno-cellulosic materials (timber), algae has photosynthetic efficiency height, adaptive capacity to environment is strong, growth cycle is short, biological yield is high characteristics, algae grows in water simultaneously, does not take the agricultural land, and its breeding process can be realized automatization control.Eutrophic water body is administered by product and can be provided very abundant algae bio amount every year in addition, so algae is the good material of preparation biomass energy.Algae has been developed number of ways as the Energy resources crop, and wherein anaerobic digestion is a kind of energy-conserving and environment-protective, has an approach of development potentiality.
Anaerobic digestion is that organism is under anaerobic stablized by the Metabolic activity of microorganism, and the while is with the process of the γ-ray emissions such as hydrogen, methane and carbon dioxide.Anaerobic digestion generally can be divided into hydrolysis, acidifying, acetoxylation and 4 stages of methanation, relies on the acting in conjunction of multiple anerobe and facultative anaerobe.The microbe species that participates in metabolism is various, wherein relates to multiple biochemical reaction and materialization equilibrium process.The speed of organism anaerobic digestion depends on that the size of particle and microorganism are to the utilization of organic constituent in the substrate.If substrate contains the biological polymer of large amount of complex, such as lipid, Mierocrystalline cellulose, protein, then hydrolysis is rate-limiting step; For easy degraded raw material, such as the solvability carbohydrate, then acetoxylation and methanation are rate-limiting step.The lipid of algae and protein content are very high, and firm cell walls is the important factor that the restriction frustule is degraded.The cell walls of most of algaes contains Mierocrystalline cellulose.The cell walls internal layer of algae is generally the cellulose layer of playing a supporting role, and may be surrounded by other mucus, colloid, protein, lipid and sulfonation polysaccharide layer.Some algae kind also has three base layer structures, wherein contains insoluble, unhydrolyzed aliphatics biomacromolecule material (as: glue sheath), and chemistry and enzyme liberating are had very strong resistibility.The alga cells wall is carried out pre-treatment, can improve the efficient of subsequent biological treatment process.
Common cell wall breaking method mainly contains mechanical process, heat treating process and enzymolysis process.Mechanical process comprises grinding, high-pressure extrusion, ultrasonication etc.The alga cells wall is more firmer than general microorganism cells, need extra energy with mechanical process and heat treating process, and algae organism has loss to a certain degree in treating processes, affects follow-up biomass utilization, such as the methane production that reduces anaerobic digestion.Investigator (Schwede S is arranged, Kowalczyk A, Gerber M, Span is of different cell disruption techniques on mono digestion of algal biomass.World Renewable Energy Congress 2011-Sweden R.2011.Influence, 8-13 May 2011.LinK
Ping, Sweden.) adopt ultrasonication, high-pressure extrusion, microwave heating and four kinds of methods of hyperthermia drying that frustule is carried out pre-treatment after, studied organic matter degradation and aerogenesis situation in the frustule.The result shows that high-pressure extrusion, microwave heating and hyperthermia drying pre-treatment can improve the degradation efficiency of algae, but the organic matter that front two kinds of methods are processed in the rear algae has certain loss, thereby causes follow-up anaerobic gas generation rate to descend; And after the ultrasonication pre-treatment, the organic matter in the algae has larger loss, and gas production rate is lower than untreated algae.Compare with heat treating process with mechanical process, enzymolysis process has efficient height, the little advantage of loss; And when with enzymolysis process algae being carried out pre-treatment, the effect of enzyme has selectivity, can not destroy other component; But enzyme can not be reused, and use once namely to lose efficacy afterwards, so processing cost is higher.
Summary of the invention
The present invention carries out pre-treatment by the fungi degradation method to the algae bio raw material, promotes the hydrolysis broken wall of frustule, and in the methanogenic while of anaerobically fermenting, obtains the hydrogen of high yield, thereby has improved the energy conversion efficient of algae bio raw material.
The present invention carries out pre-treatment by the fungi degradation method to the algae raw material, and the advantage of the existing enzymolysis process of the method has again continuity, and cost is lower, and can directly be connected with the technology that subsequent anaerobic digestion obtains biomass energy.
For achieving the above object, the present invention is by the following technical solutions:
A kind of fungi degradation Biological Pretreatment improves the method for algae raw material anaerobism production capacity efficient, may further comprise the steps:
(1) the algae raw material is mixed with nutrient salt solution, access is cultured anaerobic cellulose degradation bacteria seed liquor in advance;
(2) insulation, lucifuge are cultivated, and carry out the fungi degradation pre-treatment and produce synchronously hydrogen, promote the hydrolysis of frustule wall, obtain hydrogen and hydrolysate ethanol and VFA;
(3) after fungi degradation produced synchronously hydrogen and cultivate to finish, access contained the anaerobism seed sludge of methanogen in the fermented liquid, thereby the frustule resistates behind hydrolysate ethanol and VFA and the fungi degradation is carried out anaerobic fermentation methane.
In the described step (1), the algae raw material is selected from the algae bio raw material of cellulose in any cell walls.
In the described step (1), the blending ratio of algae raw material and nutrient salt solution is 2～10g(dry weight): 1L, nutrient salt solution are every liter and comprise NH
4Cl, 1g; K
2HPO
4, 2g; KH
2PO
4, 3.3g; CaCl
2, 0.1g; MgCl
26H
2O, 0.2g; Yeast powder, 0.1g; FeSO
47H
2O, 1mg; MnCl
24H
2O, 1mg; ZnCl
2, 1mg; CuCl
22H
2O, 0.2mg; NaMoO
42H
2O, the aqueous solution of 1mg, pH=7.0.
In the described step (1), cellulose-degrading bacteria is clostridium, and wherein the volume ratio of cellulose-degrading bacteria seed liquor and nutrient salt solution is 1～10%.
In the described step (2), the temperature of insulation is 30～40 ℃ or 50～60 ℃.
In the described step (2), the time that lucifuge is cultivated is 0～5 day, and the pH scope should be controlled at 6.6～7.5 during cultivation.
In the described step (3), the anaerobism seed sludge is 0.2～2.1(VS/VS) with the inoculation ratio of algae raw material, and the inoculum size of anaerobism seed sludge is 3～5gVS/L, and described anaerobically fermenting is 50～60 ℃ of 30～40 ℃ of mesophilic digestions or thermophilic fermentations.
The present invention has following beneficial effect:
The present invention carries out pre-treatment by the fungi degradation method to the algae bio raw material, promotes the hydrolysis broken wall of frustule, and in the methanogenic while of anaerobically fermenting, obtains the hydrogen of high yield, thereby has improved the energy conversion efficient of algae bio raw material.
1, promote the hydrolysis broken wall of frustule with the fungi degradation method, its reaction has continuity, and inoculation liquid can recycle, so cost is lower.
2, after the fungi degradation pre-treatment, it remains in the product in the liquid phase, such as voltaile fatty acid, also can be by follow-up anaerobic digestion process utilization, and raw material availability is high.
3, significantly improved the output of hydrogen, and can obtain respectively comparatively pure hydrogen and methane, the energy conversion efficient of algae bio raw material is high.
Description of drawings
Fig. 1 is that algae raw material fungi degradation produces hydrogen and methanogenic technical process synchronously in the embodiment of the invention.
Fig. 2 is that algae raw material fungi degradation produces the methanogenic technical process of hydrogen subsequent anaerobic digestion synchronously in the embodiment of the invention.
Embodiment
Further specify the present invention below in conjunction with embodiment and accompanying drawing.
Embodiment 1
A kind of fungi degradation Biological Pretreatment improves the method for algae raw material anaerobism production capacity efficient:
(1) with for subsequent use behind grid algae (Scenedesmussubspicatus) the algae liquid process centrifugal concentrating.
Add the 500ml nutrient salt solution in concentrated algae liquid, access is cultured cellulose-degrading bacteria clostridium (Clostridium sp.) seed liquor in advance, and temperature is controlled at carries out pre-treatment about 55 ℃; The volume ratio of clostridium and nutrient salt solution is 5%.
Wherein the nutrient salt solution prescription is every liter and comprises NH
4Cl, 1g; K
2HPO
4, 2g; KH
2PO
4, 3.3g; CaCl
2, 0.1g; MgCl
26H
2O, 0.2g; Yeast powder, 0.1g; FeSO
47H
2O, 1mg; MnCl
24H
2O, 1mg; ZnCl
2, 1mg; CuCl
22H
2O, 0.2mg; NaMoO
42H
2O, the aqueous solution of 1mg; PH=7.0.
(2) insulation, lucifuge were cultivated after 20 hours, and TOC increases 284mg/L in the solution, and the total amount of ethanol and voltaile fatty acid is not significantly increased, and illustrates that the intracellular organic matter of grid algae enters in the solution, and cell hydrolysis shell-broken effect is obvious.
Embodiment 2
A kind of fungi degradation Biological Pretreatment improves the method for algae raw material anaerobism production capacity efficient, as shown in Figure 1:
(1) with for subsequent use behind chlorella (Chlorella vulgaris) the algae liquid process centrifugal concentrating.
(2) add the 500ml nutrient salt solution in concentrated algae liquid, access is cultured clostridium (Clostridium sp.) seed liquor in advance, accesses simultaneously anaerobic grain sludge, and temperature is controlled at carries out anaerobically fermenting about 55 ℃.
The nutrient salt solution prescription is as follows: NH
4Cl, 0.5g; K
2HPO
4, 1g; KH
2PO
4, 1.7g; CaCl
2, 0.05g; MgCl
26H
2O, 0.1g; Yeast powder, 0.05g; FeSO
47H
2O, 0.5mg; MnCl
24H
2O, 0.5mg; ZnCl
2, 0.5mg; CuCl
22H
2O, 0.1mg; NaMoO
42H
2O, 0.5mg; Water, 500ml; PH=7.0.
Anaerobic grain sludge is taken from anaerobic internal circulation reactor, contains active higher methanogen, and the frustule resistates behind hydrolysate ethanol and VFA and the fungi degradation is carried out anaerobic fermentation methane.Wherein, the inoculum size of anaerobic grain sludge is 3gVS/L, and mud is 2.0(VS/VS with the inoculation ratio of algae), the volume ratio of clostridium and nutrient salt solution is 5%; Adopt aforesaid treatment process, hydrogen yield is 10ml H
2/ g VS, methane production reach 403ml CH
4/ g VS.
Embodiment 3
A kind of fungi degradation Biological Pretreatment improves the method for algae raw material anaerobism production capacity efficient, as shown in Figure 2:
(1) with for subsequent use behind chlorella (Chlorella vulgaris) the algae liquid process centrifugal concentrating.
Add the 500ml nutrient salt solution in concentrated algae liquid, access is cultured clostridium (Clostridium sp.) seed liquor in advance, and temperature is controlled at carries out pre-treatment about 55 ℃.
(2) cultivate after 4 days, the access anaerobic grain sludge carries out anaerobically fermenting about 55 ℃.
The nutrient salt solution prescription is as follows: NH
4Cl, 0.5g; K
2HPO
4, 1g; KH
2PO
4, 1.7g; CaCl
2, 0.05g; MgCl
26H
2O, 0.1g; Yeast powder, 0.05g; FeSO
47H
2O, 0.5mg; MnCl
24H
2O, 0.5mg; ZnCl
2, 0.5mg; CuCl
22H
2O, 0.1mg; NaMoO
42H
2O, 0.5mg; Water, 500ml; PH7.0.
(3) after fungi degradation produces hydrogen cultivation end synchronously, access the anaerobism seed sludge that contains methanogen in fermented liquid, anaerobic grain sludge is taken from anaerobic internal circulation reactor, contains active higher methanogen, can stablize product methane under the condition of supplying with nutritive substance.The inoculum size of anaerobic grain sludge is 3gVS/L, and mud is 2.0(VS/VS with the inoculation ratio of algae), the volume ratio of clostridium and nutrient salt solution is 5%.
Adopt aforesaid treatment process, hydrogen yield is 54ml H
2/ g VS, methane production reach 395ml CH
4/ g VS.
Do not compare with carrying out the pretreated algae of fungi degradation, hydrogen yield slightly is improved among the embodiment 2, and that methane production increases is about 6%, and methane production slightly is improved among the embodiment 3, and hydrogen yield has improved 7 times.
Compare with pretreatment processs such as commonly used mechanical process, heat treating process, enzymolysis processs, adopt the fungi degradation method to promote the hydrolysis broken wall of frustule, its reaction has continuity, and inoculation liquid can recycle, and cost is lower; After the fungi degradation pre-treatment, it remains in the product in the liquid phase, such as voltaile fatty acid, also can be by follow-up anaerobic digestion process utilization, and raw material availability is high; Significantly improve through fungi degradation pre-treatment hydrogen output, and can obtain respectively comparatively pure hydrogen and methane, the energy conversion efficient of algae bio raw material is high.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (7)
1. a fungi degradation Biological Pretreatment improves the method for algae raw material anaerobism production capacity efficient, it is characterized in that: may further comprise the steps:
(1) the algae raw material is mixed with nutrient salt solution, access is cultured anaerobic cellulose degradation bacteria seed liquor in advance;
(2) insulation, lucifuge are cultivated, and carry out the fungi degradation pre-treatment and produce synchronously hydrogen, promote the hydrolysis of frustule wall, obtain hydrogen and hydrolysate ethanol and VFA;
(3) after fungi degradation produces hydrogen cultivation end synchronously, in fermented liquid, access the anaerobism seed sludge that contains methanogen, the frustule resistates behind hydrolysate ethanol and VFA and the fungi degradation is carried out anaerobic fermentation methane.
2. method according to claim 1, it is characterized in that: in the described step (1), the algae raw material is selected from the algae bio raw material of cellulose in the cell walls.
3. method according to claim 1, it is characterized in that: in the described step (1), the blending ratio of algae raw material and nutrient salt solution is dry weight 2～10g algae raw material: 1L nutrient salt solution, nutrient salt solution are every liter and comprise NH
4Cl, 1g; K
2HPO
4, 2g; KH
2PO
4, 3.3g; CaCl
2, 0.1g; MgCl
26H
2O, 0.2g; Yeast powder, 0.1g; FeSO
47H
2O, 1mg; MnCl
24H
2O, 1mg; ZnCl
2, 1mg; CuCl
22H
2O, 0.2mg; NaMoO
42H
2O, the aqueous solution of 1mg, pH=7.0.
4. method according to claim 1, it is characterized in that: in the described step (1), cellulose-degrading bacteria is clostridium, and wherein the volume ratio of cellulose-degrading bacteria seed liquor and nutrient salt solution is 1～10%.
5. method according to claim 1, it is characterized in that: in the described step (2), the temperature of insulation is 30～40 ℃ or 50～60 ℃.
6. method according to claim 1 is characterized in that: in the described step (2), the time that lucifuge is cultivated is 0～5 day, and the pH scope is 6.6～7.5 during cultivation.
7. method according to claim 1, it is characterized in that: in the described step (3), the anaerobism seed sludge is 0.2～2.1 with the inoculation ratio of algae raw material, VS/VS, the inoculum size of anaerobism seed sludge is 3～5 gVS/L, and described anaerobically fermenting is 50～60 ℃ of 30～40 ℃ of mesophilic digestions or thermophilic fermentations.
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| CN108315353A (en) * | 2018-03-10 | 2018-07-24 | 浙江大学 | The method of ocean bulk kelp and microalgae mixed fermentation continuous production hydrogen and methane |
| CN109266691A (en) * | 2018-09-18 | 2019-01-25 | 罗绍庆 | A kind of method of cassava grain stillage fermenting and preparing biological matter combustion gas |
| CN110129399A (en) * | 2019-05-14 | 2019-08-16 | 河南农业大学 | A method of promoting HAU-M1 photosynthetic bacteria group highly effective hydrogen yield using bead algal biomass |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108315353A (en) * | 2018-03-10 | 2018-07-24 | 浙江大学 | The method of ocean bulk kelp and microalgae mixed fermentation continuous production hydrogen and methane |
| CN109266691A (en) * | 2018-09-18 | 2019-01-25 | 罗绍庆 | A kind of method of cassava grain stillage fermenting and preparing biological matter combustion gas |
| CN109266691B (en) * | 2018-09-18 | 2021-12-07 | 罗绍庆 | Method for preparing biomass gas by fermenting cassava vinasse |
| CN110129399A (en) * | 2019-05-14 | 2019-08-16 | 河南农业大学 | A method of promoting HAU-M1 photosynthetic bacteria group highly effective hydrogen yield using bead algal biomass |
| CN110129399B (en) * | 2019-05-14 | 2022-05-27 | 河南农业大学 | Method for promoting HAU-M1 photosynthetic bacteria to efficiently produce hydrogen by utilizing chlorella biomass |
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