CN103074380B - 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 PDF

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CN103074380B
CN103074380B CN201210567502.3A CN201210567502A CN103074380B CN 103074380 B CN103074380 B CN 103074380B CN 201210567502 A CN201210567502 A CN 201210567502A CN 103074380 B CN103074380 B CN 103074380B
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raw material
algae
hydrogen
salt solution
anaerobic
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CN103074380A (en
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吕凡
季佳琪
何品晶
毛斌
邵立明
吴铎
柴丽娜
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Tongji University
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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
    • 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
    • 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
    • Y02P20/59—Biological synthesis; Biological purification

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

A kind of fungi degradation Biological Pretreatment improves the method for algae raw material anaerobism capacity efficiency
Technical field
The invention belongs to biotechnology and field of renewable energy, relate to a kind of method that fungi degradation Biological Pretreatment improves algae raw material anaerobism capacity efficiency.
Background technology
Under the overall situation of energy and environment crisis, seek cleaning, safety, Sustainable development the energy become the task of top priority.The use of renewable energy source can reduce the dependency to oil, reduces environmental pollution.In this context, the development of biomass renewable energy source is more and more subject to social concerns, becomes current and realizes energy sources diversification and the strategic anti-risk important selection of national energy.Algae raw material is one of important biomass resource.Algae is of a great variety in lower plant, a distribution holophyte monoid extremely widely.With other biological matter as compared with ligno-cellulosic materials (timber), algae has the advantages that photosynthetic efficiency is high, adaptive capacity to environment is strong, growth cycle is short, biological yield is high, algae grows in water simultaneously, do not take agricultural land, its breeding process can realize Automated condtrol.In addition eutrophic water body administers the algae bio amount that by product can provide very abundant every year, and therefore algae is the good material of preparation biomass energy.Algae has been developed number of ways as Energy resources crop, and wherein anaerobic digestion is a kind of energy-conserving and environment-protective, has the approach of development potentiality.
Anaerobic digestion is that organism is under anaerobic stablized by the Metabolic activity of microorganism, simultaneously with the process that the gas such as hydrogen, methane and carbon dioxide produces.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 participating 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 substrate.If the biological polymer of substrate containing large amount of complex, as lipid, Mierocrystalline cellulose, protein, then hydrolysis is rate-limiting step; For raw material of easily degrading, as 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 restriction frustule is degraded.The cell walls of most of algae 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 sulfonate polysaccharide layer.Some algae kind also has three base layer structures, wherein containing insoluble, unhydrolyzed aliphatics biomacromolecule material (as: glue sheath), has very strong resistibility to chemistry and enzyme liberating.Pre-treatment is carried out to alga cells wall, the efficiency of subsequent biological treatment process can be improved.
Common cell wall breaking method mainly contains mechanical process, heat treating process and enzymolysis process.Mechanical process comprises grinding, high-pressure extrusion, ultrasonication etc.Alga cells wall is more firmer than general microorganism cells, extra energy is needed with mechanical process and heat treating process, and algae organism has loss to a certain degree in treating processes, affect follow-up biomass utilization, such as reduce the methane production of anaerobic digestion.There is investigator (Schwede S, 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 hyperthermia drying four kinds of methods to carry out pre-treatment to frustule after, have studied organic matter degradation and aerogenesis situation in frustule.Result shows that high-pressure extrusion, microwave heating and hyperthermia drying pre-treatment can improve the degradation efficiency of algae, but the organic matter after the process of first two method in algae has certain loss, thus causes follow-up anaerobic gas generation rate to decline; And after ultrasonication pre-treatment, the organic matter in algae has larger loss, and gas production rate is lower than untreated algae.Compare with heat treating process with mechanical process, enzymolysis process have efficiency high, lose little advantage; And when carrying out pre-treatment with enzymolysis process to algae, the effect of enzyme has selectivity, can not destroy other component; But enzyme can not be reused, use and once namely lost efficacy afterwards, therefore processing cost is higher.
Summary of the invention
The present invention carries out pre-treatment by fungi degradation method to algae bio raw material, promotes the hydrolysis broken wall of frustule, and anaerobically fermenting is methanogenic while, obtains the hydrogen of high yield, thus improve the efficient energy conversion of algae bio raw material.
The present invention carries out pre-treatment by fungi degradation method to algae raw material, the advantage of the existing enzymolysis process of the method, and have continuity again, cost is lower, and directly can 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:
Fungi degradation Biological Pretreatment improves a method for algae raw material anaerobism capacity efficiency, comprises the following steps:
(1) algae raw material is mixed with nutrient salt solution, access cultured anaerobic cellulose degradation bacteria seed liquor in advance;
(2) be incubated, lucifuge cultivates, carry out fungi degradation pre-treatment synchronously produce hydrogen, promote the hydrolysis of frustule wall, obtain hydrogen and hydrolysate ethanol and VFA;
(3) fungi degradation synchronously produces after hydrogen cultivates and terminate, and in fermented liquid, access is containing the anaerobism seed sludge of methanogen, thus the frustule resistates after hydrolysate ethanol and VFA and fungi degradation is carried out anaerobically fermenting methane phase.
In described step (1), algae raw material is selected from the algae bio raw material of cellulose in any cell walls.
In described step (1), the blending ratio of algae raw material and nutrient salt solution is 2 ~ 10g(dry weight): 1L, nutrient salt solution is often 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 2the aqueous solution of O, 1mg, pH=7.0.
In 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 described step (2), the temperature of insulation is 30 ~ 40 DEG C or 50 ~ 60 DEG C.
In described step (2), the time that lucifuge is cultivated is 0 ~ 5 day, and during cultivation, pH scope should control 6.6 ~ 7.5.
In described step (3), anaerobism seed sludge is 0.2 ~ 2.1(VS/VS with the inoculation ratio of algae raw material), the inoculum size of anaerobism seed sludge is 3 ~ 5gVS/L, and described anaerobically fermenting is mesophilic digestion 30 ~ 40 DEG C or thermophilic fermentation 50 ~ 60 DEG C.
The present invention has following beneficial effect:
The present invention carries out pre-treatment by fungi degradation method to algae bio raw material, promotes the hydrolysis broken wall of frustule, and anaerobically fermenting is methanogenic while, obtains the hydrogen of high yield, thus improve the efficient energy conversion of algae bio raw material.
1, promote the hydrolysis broken wall of frustule by fungi degradation method, its reaction has continuity, and inoculation liquid can recycle, and therefore cost is lower.
2, after fungi degradation pre-treatment, its product residual in the liquid phase, as voltaile fatty acid, also can be utilized by follow-up anaerobic digestion process, raw material availability is high.
3, significantly improve the output of hydrogen, and can obtain comparatively pure hydrogen and methane respectively, the efficient energy conversion of algae bio raw material is high.
Accompanying drawing explanation
Fig. 1 is that in the embodiment of the present invention, algae raw material fungi degradation synchronously produces hydrogen and methanogenic technical process.
Fig. 2 is that in the embodiment of the present invention, algae raw material fungi degradation synchronously produces the methanogenic technical process of hydrogen subsequent anaerobic digestion.
Embodiment
The present invention is further illustrated 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 capacity efficiency:
(1) by for subsequent use after centrifugal concentrating for grid algae (Scenedesmussubspicatus) algae liquid.
In concentrated algae liquid, add 500ml nutrient salt solution, access cultured cellulose-degrading bacteria clostridium (Clostridium sp.) seed liquor in advance, temperature controls to carry out pre-treatment at about 55 DEG C; The volume ratio of clostridium and nutrient salt solution is 5%.
Wherein nutrient salt solution formula comprises NH for often liter 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 2the aqueous solution of O, 1mg; PH=7.0.
(2) after insulation, lucifuge cultivate 20 hours, in solution, TOC increases 284mg/L, 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 solution, and cell hydrolysis shell-broken effect is obvious.
Embodiment 2
Fungi degradation Biological Pretreatment improves a method for algae raw material anaerobism capacity efficiency, as shown in Figure 1:
(1) by for subsequent use after centrifugal concentrating for chlorella (Chlorella vulgaris) algae liquid.
(2) in concentrated algae liquid, add 500ml nutrient salt solution, access cultured clostridium (Clostridium sp.) seed liquor in advance, access anaerobic grain sludge, temperature controls to carry out anaerobically fermenting at about 55 DEG C simultaneously.
Nutrient salt solution formula 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 takes from anaerobic internal circulation reactor, containing active higher methanogen, the frustule resistates after hydrolysate ethanol and VFA and fungi degradation is carried out anaerobically fermenting methane phase.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 treatment process as above, hydrogen yield is 10ml H 2/ g VS, methane production reaches 403ml CH 4/ g VS.
Embodiment 3
Fungi degradation Biological Pretreatment improves a method for algae raw material anaerobism capacity efficiency, as shown in Figure 2:
(1) by for subsequent use after centrifugal concentrating for chlorella (Chlorella vulgaris) algae liquid.
In concentrated algae liquid, add 500ml nutrient salt solution, access cultured clostridium (Clostridium sp.) seed liquor in advance, temperature controls to carry out pre-treatment at about 55 DEG C.
(2) cultivate after 4 days, access anaerobic grain sludge, carries out anaerobically fermenting at about 55 DEG C.
Nutrient salt solution formula 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) fungi degradation synchronously produces after hydrogen cultivates and terminate, and in fermented liquid, access is containing the anaerobism seed sludge of methanogen, and anaerobic grain sludge takes from anaerobic internal circulation reactor, containing active higher methanogen, can stablize methane phase under the condition of supply 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 treatment process as above, hydrogen yield is 54ml H 2/ g VS, methane production reaches 395ml CH 4/ g VS.
With do not carry out compared with the pretreated algae of fungi degradation, in embodiment 2, hydrogen yield slightly improves, and methane production increase about 6%, and in embodiment 3, methane production slightly improves, and hydrogen yield improves 7 times.
Compared with the conventional pretreatment process such as mechanical process, heat treating process, enzymolysis process, adopt 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 fungi degradation pre-treatment, its product residual in the liquid phase, as voltaile fatty acid, also can be utilized by follow-up anaerobic digestion process, raw material availability is high; Significantly improve through fungi degradation pre-treatment hydrogen output, and can obtain comparatively pure hydrogen and methane respectively, the efficient energy conversion of algae bio raw material is high.
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 (3)

1. fungi degradation Biological Pretreatment improves a method for algae raw material anaerobism capacity efficiency, it is characterized in that: comprise the following steps:
(1) algae raw material is mixed with nutrient salt solution, access cultured anaerobic cellulose degradation bacteria seed liquor in advance;
(2) be incubated, lucifuge cultivates, carry out fungi degradation pre-treatment synchronously produce hydrogen, promote the hydrolysis of frustule wall, obtain hydrogen and hydrolysate ethanol and VFA;
(3) fungi degradation synchronously produces after hydrogen cultivates and terminate, and in fermented liquid, access is containing the anaerobism seed sludge of methanogen, and the frustule resistates after hydrolysate ethanol and VFA and fungi degradation is carried out anaerobically fermenting methane phase;
In 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, and nutrient salt solution is often 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 2the aqueous solution of O, 1mg, pH=7.0;
In 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 described step (3), 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 mesophilic digestion 30 ~ 40 DEG C or thermophilic fermentation 50 ~ 55 DEG C;
In described step (2), the temperature of insulation is 30 ~ 40 DEG C or 50 ~ 55 DEG C.
2. method according to claim 1, is characterized in that: in described step (1), algae raw material is selected from the algae bio raw material of cellulose in cell walls.
3. method according to claim 1, is characterized in that: in described step (2), and the time that lucifuge is cultivated is 0 ~ 5 day, and during cultivation, pH scope is 6.6 ~ 7.5.
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