CN101177694A - Method for steam-exploded straw hydrogen production by controlling temperature of fermentation process - Google Patents
Method for steam-exploded straw hydrogen production by controlling temperature of fermentation process Download PDFInfo
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- CN101177694A CN101177694A CNA2006101143385A CN200610114338A CN101177694A CN 101177694 A CN101177694 A CN 101177694A CN A2006101143385 A CNA2006101143385 A CN A2006101143385A CN 200610114338 A CN200610114338 A CN 200610114338A CN 101177694 A CN101177694 A CN 101177694A
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Abstract
The invention discloses a hydrogen production method by using steam-exploded straw fermentation and adjusting the temperature of the fermentation process. The method comprises the steps that: the steam-exploded straw is added with carbamide, KH2PO4, MgSO4 and water to obtain a steam-exploded straw culture medium; the butyric acid clostridium is inoculated in a seed culture medium and an anaerobic culture at 35 DEG C is conducted to logarithmic phase so as to obtain seed liquid; the steam-exploded straw is inoculated with the seed liquid and is deoxidized through introducing nitrogen; the obtained material is fermented for 6 to 12 hours under the temperature of 35 DEG C, then fast heated to 40 to 46 DEG C and maintained for 1 to 3 hours; the temperature of the obtained material is fast lowered to 35 DEG C to continuously ferment under constant temperature; the ferment lasts 22 to 36 hours, and then the temperature is heated once again to 40 to 46 DEG C and maintained for 1 to 3 hours; the temperature of the obtained material is lowered to 35 DEG C to ferment under constant temperature till no gas produces; the generated gas is separated to make pure hydrogen. By using the method, the temperatures are enhanced a plurality of times for a short time during fermentation process, which can promote substrate cellulose to be degraded; since the temperature enhancing time is shorter, the microorganism activity has a little effect and the hydrogen yield is greatly enhanced.
Description
Technical field
The invention belongs to the zymotechnique technical field, relate generally to the method that transformation temperature is regulated and control steam explosion stalk fermented product hydrogen in the fermenting process of utilizing.
Background technology
Along with development of human society, increasing to the demand of the energy, however tellurian fossil oil reserves are limited, and therefore, renewable energy source that must development of new is to satisfy the needs of human being's production and life.Hydrogen is a kind of cleaning, the energy efficiently, is the good substitute of fossil oil.Conventional hydrogen production process is as water electrolysis method and fossil feedstock pyrolysis method [Adnan M.Int J Hydrogen Energy, 2001:26:29-27; AyhanD.Energy Sources, 2002:24:59-68.], exist the energy consumption height, the product component complexity, shortcomings such as separation costs height can not fundamentally solve the energy and environmental problem.With reproducible biomass resource is raw material, relies on the direction and the focus of microbial fermentation hydrogen manufacturing becoming day by day research.
Stalk is that class source is very abundant, the recyclability resource that price is very cheap, and after the quick-fried processing of vapour, the part hemicellulose in the stalk is degraded, and cellulosic dense structure is destroyed, is easy to degrade and is utilized by Institute of Micro-biology.Clostridium butylicum (Clostridium butyricum) can utilize most lignocellulose hydrolyzates such as comprising glucose, wood sugar, cellobiose, be with the steam puffed stalk be the raw material desirable bacterial classification that carries out fermentation and hydrogen production (Hawkes FR.Int J Hydrogen Energy 2002,27:1339-1347.).Being in the fermentation process of substrate with the steam puffed stalk, adding cellulase Mierocrystalline cellulose and hemicellulose in the substrate are degraded to produce the small molecules soluble sugar that microorganism can utilize, is the key that improves the steam puffed stalk raw material availability.
The mode of utilizing steam explosion stalk fermented hydrogen manufacturing commonly used is a simultaneous saccharification and fermentation, is about to the steam puffed stalk raw material, and cellulase and bacterial classification place fermentor tank simultaneously, the fermentation of enzymolysis limit, limit (Chen Hongzhang, Li Zuohu.Use the method for steam puffed plant straw fermenting process of preparing hydrogen.National inventing patent, CN1500879A).But in the simultaneous saccharification and fermentation process, envrionment temperature is a major objective to satisfy microbial growth usually.When being hydrogenogens with C.butyricum, the temperature of fermentor tank remains on 35 ℃ of its optimum growth temperatures, and the optimum temperature of cellulase is 50 ℃, and optimum temperature difference between the two has 15 ℃, causes utilization ratio of raw materials to be difficult to improve.Therefore, be necessary to explore new fermentation mode to solve this contradiction.
Summary of the invention
The objective of the invention is at enzymolysis in the steam puffed stalk simultaneous saccharification and fermentation hydrogen production process and the inconsistent problem of leavening temperature, provide a kind of alternating temperature that carries out during the fermentation to stimulate, to satisfy the needs of cellulose degradation and microbial fermentation simultaneously, improve the novel method of cellulase hydrolysis rate and hydrogen yield.
The present invention utilizes steam puffed stalk preparation substratum to carry out clostridium butylicum (C.butyricum AS1.209) and produces the hydrogen fermentation, and fermentation initial stage temperature maintenance is the optimum temperuture of microorganism growth, 35 ℃.After fermentation proceeded to the regular hour, after after a while, rapidly the temperature with fermentor tank raise, and reached to help the temperature that cellulase plays a role and don't influences microbic activity, keep for some time after, be cooled to 35 ℃ rapidly.After for some time is proceeded in fermentation, repeat aforesaid operations once more.Through so repeatedly alternating temperature, reach cellulosic degraded in the promotion substrate, improve the purpose of substrate conversion efficiency and hydrogen generation efficiency.
Technical scheme of the present invention is as follows:
Provided by the inventionly carry out the method for steam explosion stalk fermented product hydrogen by the temperature of regulation and control in the fermenting process, its step is as follows:
(1) preparation steam puffed stalk substratum
In the steam puffed stalk raw material, add urea 0.05～0.3g/g-substrate, KH
2PO
40.03g/g-substrate, MgSO
40.015g/g-substrate and water obtain the steam puffed stalk substratum after the sterilization; Described substrate is meant the steam puffed stalk raw material;
Steam puffed stalk raw material in the steam puffed stalk substratum is 1: 3 with the solid-liquid proportion by weight of add liquid;
(2) preparation butyrate spindle bacillus seed liquid
Clostridium butylicum is inoculated in the butyrate spindle bacillus seed substratum, and 35 ℃ of anaerobism are cultured to logarithmic phase, make butyrate spindle bacillus seed liquid; Described clostridium butylicum is available from Chinese microbial preservation management committee common micro-organisms preservation center, and its preserving number is CGMCC AS1.209.
Described every liter of butyrate spindle bacillus seed substratum contains glucose 20g, yeast extract 3g, KH
2PO
40.2g, K
2HPO
41.6g, MgSO
47H
2O 0.2g, NaCl 0.1g, CaCl
20.01g, Na
2S9H
2O0.25g, NaMoO
42H
2O 0.01g, NaHCO
30.2g (NH
4)
2SO
43.0g;
(3) temperature-variable fermentation prepares hydrogen
In step (1) gained steam puffed stalk substratum, insert butyrate spindle bacillus seed liquid, inoculum size is 4～1,000,000,000 cell/g-substrates, add an amount of sterile distilled water again, making final solid-liquid mass parts ratio is 1: 5～1: 8, behind the uniform mixing, feed the nitrogen deoxygenation rapidly, place 35 ℃ to begin fermentation;
The fermentation beginning is after 6～12 hours, and rapid elevated temperature to 40～46 ℃ kept after 1～3 hour, is cooled to 35 ℃ of constant temperature rapidly and continues fermentation;
When fermentation proceeds to 22～36 hours, be increased to 40～46 ℃ once more rapidly, kept 1～3 hour, be cooled to 35 ℃ of ferment at constant temperature afterwards rapidly and produce to no longer including gas;
Collect the gas that produces with draining water gathering of gas law, the gas that produces is hydrogen and carbon dioxide mixture, after separating, obtains pure hydrogen.
Being prepared as follows of described steam puffed stalk material:
Straw is pulverized the length of 3～4cm, put into steam-explosion jar, airtight back feeds water vapor, makes tank pressure rise to 1.5MPa rapidly, and dimension is put pressure rapidly after pressing 10min, makes the steam puffed stalk material;
Described steam-puffed plant straw and stalk material is the quick-fried wheat stalk material of vapour wheat straw stalk, the quick-fried maize straw material of vapour, the quick-fried rice straw material of vapour or the quick-fried jowar stalk of vapour material.
Method of carrying out steam explosion stalk fermented product hydrogen by the temperature in the regulation and control fermenting process of the present invention, short period of time elevated temperature during the fermentation, to significantly promote cellulase hydrolysis, microbic activity will not but be had too big influence, thereby improve utilization ratio of raw materials and product output.
It is that substrate carries out in the process of clostridium butylicum fermentation that Fig. 1 has shown with the quick-fried maize straw of vapour, fermenting process is carried out the hydrogen output change curve of alternating temperature control and ferment at constant temperature; Alternating temperature is controlled to be fermentation to carry out behind the 10h temperature being increased to 45 ℃ of maintenance 2h, reduces afterwards and gets back to 35 ℃, continues ferment at constant temperature; After fermentation proceeds to 30h, be warming up to 45 ℃ once more and keep 2h, and then be reduced to 35 ℃ of ferment at constant temperature; As can be known, at fermentation short period of time at initial stage elevated temperature, microbic activity is under some influence, and lag period is elongated, but after the temperature reduction was got back to 35 ℃, hydrogen output increased sharply; After heating up for the second time, fermentation is under some influence, but increasing has rapidly for the second time appearred in hydrogen output subsequently, illustrates that elevated temperature has promoted cellulose degradation, and the required nutritive ingredient of microbial fermentation is replenished, and total hydrogen output significantly improves.
In a word, method of carrying out steam explosion stalk fermented product hydrogen by the temperature of regulation and control in the fermenting process of the present invention possesses following advantage:
The present invention is directed to enzymolysis and the inconsistent problem of leavening temperature in the steam puffed stalk simultaneous saccharification and fermentation hydrogen production process, provide a kind of alternating temperature that carries out during the fermentation to stimulate, to satisfy the needs of cellulose degradation and microbial fermentation simultaneously, can improve cellulase hydrolysis rate and hydrogen yield in the straw.
Description of drawings
Accompanying drawing 1 is for being that substrate carries out the comparison of test results synoptic diagram that temperature-variable fermentation and ferment at constant temperature prepare hydrogen with the quick-fried maize straw of vapour.
Embodiment
Embodiment 1. usefulness method provided by the invention is that raw material carries out temperature-variable fermentation and prepares hydrogen with the quick-fried maize straw of vapour, and concrete steps are as follows:
1, preparation steam puffed stalk material
The length of crushed stalk to 3～4cm, put into steam-explosion jar, airtight back feeds water vapor, makes tank pressure rise to 1.5MPa rapidly, after keeping 10min under this pressure, puts pressure rapidly, makes the steam puffed stalk material;
2, preparation butyrate spindle bacillus seed liquid
Clostridium butylicum (available from Chinese microbial preservation management committee common micro-organisms preservation center, its preserving number is CGMCC AS1.209) is inoculated in the clostridium butylicum substratum, and 35 ℃ of anaerobism are cultured to logarithmic phase, promptly make butyrate spindle bacillus seed liquid;
Described every liter of clostridium butylicum substratum contains glucose 20g, yeast extract 0.5g, KH
2PO
40.2g, K
2HPO
41.6g, MgSO
47H
2O 0.2g, NaCl 0.1g, CaCl
20.01g, Na
2S9H
2O 0.25g, NaMoO
4.2H
2O 0.01g, NaHCO
30.2g and (NH
4)
2SO
43.0g;
3, preparation steam puffed stalk substratum
In the steam puffed stalk raw material, add urea 0.2g/g-substrate, KH
2PO
40.03g/g-substrate, MgSO
40.015g/g-substrate and water, its solid-liquid proportion by weight is 1: 3, obtains the steam puffed stalk substratum after the sterilization; Described substrate is meant the steam puffed stalk raw material;
4, temperature-variable fermentation prepares hydrogen
The seed liquor that will be in logarithmic phase is inoculated in steam puffed stalk substratum (mixing), 400,000,000 cells of inoculum size/g-substrate, and in the steam puffed stalk substratum, suitably add sterile distilled water, making final solid-liquid mass parts ratio is 1: 6, after feeding the nitrogen deoxygenation rapidly, place 35 ℃ to begin fermentation;
After the fermentation beginning 8 hours, temperature of reactor is increased to 40 ℃ rapidly, keep 1 hour after, cool to 35 ℃ rapidly, continue ferment at constant temperature; After fermentation proceeds to 30 hours, be warming up to 40 ℃ once more rapidly, keep 1 hour after, be cooled to 35 ℃ rapidly, continue ferment at constant temperature and produce to no longer including gas;
Collect hydrogen and the carbonic acid gas that is produced with draining water gathering of gas law, after separating, obtain hydrogen.
Continuously fermented 78 hours, and had only hydrogen and carbonic acid gas in the tunning, wherein, hydrogen content is 44.5%, is the 78ml/g-substrate than producing the hydrogen rate, can get pure hydrogen after the separation.
Embodiment 2. usefulness method provided by the invention is that raw material ferments with the quick-fried broomcorn straw of vapour, and concrete steps are as follows:
Step 1,2 is with embodiment 1.
3, in the steam puffed stalk raw material, add urea 0.15g/g-substrate, KH
2PO
40.03g/g-substrate, MgSO
40.015g/g-substrate and water, its solid-liquid proportion by weight is 1: 3, obtains the steam puffed stalk substratum after the sterilization; Described substrate is meant the steam puffed stalk raw material;
4, the C.butyricum AS1.209 seed liquor and the substratum that will be in logarithmic phase mixes, 600,000,000 cells of inoculum size/g-substrate, and in substratum, suitably add sterile distilled water, making final solid-liquid mass parts ratio is 1: 5, after feeding the nitrogen deoxygenation rapidly, place 35 ℃ to begin fermentation.After the fermentation beginning 10 hours, temperature of reactor is increased to 45 ℃ rapidly, keep 1 hour after, cooling is got back to 35 ℃ rapidly, continues ferment at constant temperature under this temperature.After fermentation proceeds to 24 hours, be warming up to 45 ℃ once more rapidly, keep 1 hour after, be cooled to 35 ℃ rapidly and produce to no longer including gas.Collect hydrogen and the carbonic acid gas that is produced with draining water gathering of gas law, after separating, obtain hydrogen.
Continuously fermented 78 hours, and had only hydrogen and carbonic acid gas in the tunning, wherein, hydrogen content is 42.6%, is the 75ml/g-substrate than producing the hydrogen rate, can get pure hydrogen after the separation.
Embodiment 3. usefulness method provided by the invention is that raw material ferments with the quick-fried wheat straw of vapour, and concrete steps are as follows:
Step 1,2 is with embodiment 1.
3, in the steam puffed stalk raw material, add urea 0.18g/g-substrate, KH
2PO
40.03g/g-substrate, MgSO
40.015g/g-substrate and water, its solid-liquid proportion by weight is 1: 3, obtains the steam puffed stalk substratum after the sterilization; Described substrate is meant the steam puffed stalk raw material;
4, the C.butyricum AS1.209 seed liquor and the substratum that will be in logarithmic phase mixes, 800,000,000 cells of inoculum size/g-substrate, and in substratum, suitably add sterile distilled water, making final solid-liquid proportion by weight is 1: 7, after feeding the nitrogen deoxygenation rapidly, place 35 ℃ to begin fermentation.After the fermentation beginning 8 hours, temperature of reactor is increased to 43 ℃ rapidly, keep 2 hours after, cooling is got back to 35 ℃ rapidly, continues ferment at constant temperature.After fermentation proceeds to 30 hours, be warming up to 43 ℃ once more rapidly, keep 2 hours after, be cooled to 35 ℃ rapidly, continue ferment at constant temperature and produce to no longer including gas.Collect hydrogen and the carbonic acid gas that is produced with draining water gathering of gas law, after separating, obtain hydrogen.
Continuously fermented 78 hours, and had only hydrogen and carbonic acid gas in the tunning, wherein, hydrogen content is 43.8%, is the 74ml/g-substrate than producing the hydrogen rate, can get pure hydrogen after the separation.
Embodiment 4. usefulness method provided by the invention is that raw material ferments with the quick-fried maize straw of vapour, and concrete steps are as follows:
Step 1,2 is with embodiment 1.
3, in the steam puffed stalk raw material, add urea 0.2g/g-substrate, KH
2PO
40.03g/g-substrate, MgSO
40.015g/g-substrate and water, its solid-liquid proportion by weight is 1: 3, obtains the steam puffed stalk substratum after the sterilization; Described substrate is meant the steam puffed stalk raw material;
4, the C.butyricum AS1.209 seed liquor and the substratum that will be in logarithmic phase mixes, 1,000,000,000 cells of inoculum size/g-substrate, and in substratum, suitably add sterile distilled water, making final solid-liquid proportion by weight is 1: 6, after feeding the nitrogen deoxygenation rapidly, place 35 ℃ to begin fermentation.After the fermentation beginning 10 hours, temperature of reactor is increased to 45 ℃ rapidly, keep 2 hours after, cooling is got back to 35 ℃ rapidly, continues ferment at constant temperature.After fermentation proceeds to 35 hours, be warming up to 45 ℃ once more rapidly, keep 2 hours after, be cooled to 35 ℃ rapidly, continue ferment at constant temperature and produce to no longer including gas.Collect the gas that is produced with draining water gathering of gas law.
Continuously fermented 78 hours, and had only hydrogen and carbonic acid gas in the tunning, wherein, hydrogen content is 45.2%, is the 76ml/g-substrate than producing the hydrogen rate, can get pure hydrogen after the separation.
Claims (3)
1. one kind is carried out the method for steam explosion stalk fermented product hydrogen by the temperature of regulation and control in the fermenting process, and its step is as follows:
(1) preparation steam puffed stalk substratum
In the steam puffed stalk raw material, add urea 0.05～0.3g/g-substrate, KH
2PO
40.03g/g-substrate, MgSO
40.015g/g-substrate and water obtain the steam puffed stalk substratum after the sterilization; Described substrate is meant the steam puffed stalk raw material;
Steam puffed stalk raw material in the steam puffed stalk substratum and institute's liquid feeding body solid-liquid proportion by weight are 1: 3;
(2) preparation butyrate spindle bacillus seed liquid
Clostridium butylicum is inoculated in the butyrate spindle bacillus seed substratum, and 35 ℃ of anaerobism are cultured to logarithmic phase, make butyrate spindle bacillus seed liquid; Described clostridium butylicum is available from Chinese microbial preservation management committee common micro-organisms preservation center, and its preserving number is CGMCC AS1.209;
Described every liter of butyrate spindle bacillus seed substratum contains glucose 20g, yeast extract 3g, KH
2PO
40.2g, K
2HPO
41.6g, MgSO
47H
2O 0.2g, NaCl 0.1g, CaCl
20.01g, Na
2S9H
2O0.25g, NaMoO
42H
2O 0.01g, NaHCO
30.2g (NH
4)
2SO
43.0g;
(3) temperature-variable fermentation prepares hydrogen
In step (1) gained steam puffed stalk substratum, insert butyrate spindle bacillus seed liquid, inoculum size is 4～1,000,000,000 cell/g-substrates, add an amount of sterile distilled water again, making final solid-liquid proportion by weight is 1: 5～1: 8, behind the uniform mixing, feed the nitrogen deoxygenation rapidly, place 35 ℃ to begin fermentation;
The fermentation beginning is after 6～12 hours, and rapid elevated temperature to 40～46 ℃ kept after 1～3 hour, is cooled to 35 ℃ of constant temperature rapidly and continues fermentation;
When fermentation proceeds to 22～36 hours, be increased to 40～46 ℃ once more rapidly, kept 1～3 hour, be cooled to 35 ℃ of ferment at constant temperature afterwards rapidly and produce to no longer including gas;
Collect the gas that produces with draining water gathering of gas law, the gas that produces is hydrogen and carbon dioxide mixture, after separating, obtains pure hydrogen.
2. carry out the method for steam explosion stalk fermented product hydrogen by claim 1 is described by the temperature of regulation and control in the fermenting process, it is characterized in that, being prepared as follows of described steam puffed stalk material:
Straw is pulverized the length of 3～4cm, put into steam-explosion jar, airtight back feeds water vapor, makes tank pressure rise to 1.5MPa rapidly, and dimension is put pressure rapidly after pressing 10min, makes the steam-puffed plant straw and stalk material,
3. by claim 1 or 2 described methods of carrying out steam explosion stalk fermented product hydrogen by the temperature in the regulation and control fermenting process, it is characterized in that, described steam-puffed plant straw and stalk material is the quick-fried wheat stalk material of vapour wheat straw stalk, the quick-fried maize straw material of vapour, the quick-fried rice straw material of vapour or the quick-fried jowar stalk of vapour material.
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| CNB2006101143385A CN100562579C (en) | 2006-11-07 | 2006-11-07 | Carry out the method for steam explosion stalk fermented product hydrogen by the temperature in the regulation and control fermenting process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420554A (en) * | 2013-08-07 | 2013-12-04 | 大连理工大学 | Method for promoting residual sludge to produce methane by using iron rust |
| CN106350568A (en) * | 2016-08-25 | 2017-01-25 | 辽宁大学 | Method for synchronously degrading cellulose by multiple microorganisms and producing hydrogen by anaerobic fermentation organisms |
| CN117025691A (en) * | 2023-08-29 | 2023-11-10 | 中国科学院上海高等研究院 | Use and method of clostridium thermocutyrate in preparing hydrogen |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254544C (en) * | 2002-11-15 | 2006-05-03 | 中国科学院过程工程研究所 | Method for producing hydrogen gas using steam cracked plant fermentation straw |
| FI118012B (en) * | 2004-06-04 | 2007-05-31 | Valtion Teknillinen | Process for producing ethanol |
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2006
- 2006-11-07 CN CNB2006101143385A patent/CN100562579C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420554A (en) * | 2013-08-07 | 2013-12-04 | 大连理工大学 | Method for promoting residual sludge to produce methane by using iron rust |
| CN103420554B (en) * | 2013-08-07 | 2015-10-28 | 大连理工大学 | Iron rust is utilized to promote excess sludge methane phase method |
| CN106350568A (en) * | 2016-08-25 | 2017-01-25 | 辽宁大学 | Method for synchronously degrading cellulose by multiple microorganisms and producing hydrogen by anaerobic fermentation organisms |
| CN106350568B (en) * | 2016-08-25 | 2019-11-29 | 辽宁大学 | A kind of method of composite flora synchronous degradation cellulose and anaerobic fermentation of biological production hydrogen |
| CN117025691A (en) * | 2023-08-29 | 2023-11-10 | 中国科学院上海高等研究院 | Use and method of clostridium thermocutyrate in preparing hydrogen |
| CN117025691B (en) * | 2023-08-29 | 2024-03-01 | 中国科学院上海高等研究院 | Use and method of clostridium thermocutyrate in preparing hydrogen |
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