CN102031276A - Method for producing hydrogen by fermenting organism and alkali mat composite pretreated straw fiber raw erial at two steps - Google Patents
Method for producing hydrogen by fermenting organism and alkali mat composite pretreated straw fiber raw erial at two steps Download PDFInfo
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Abstract
The invention belongs to the technical field of renewable energy sources and particularly relates to a method for producing hydrogen by fermenting an organism and alkali composite pretreated straw fiber raw material at two steps. The method comprises the following steps of: (1) crushing the straw fiber raw material and mixing the crushed raw material with a nutritive salt solution to obtain a mixture; (2) introducing a thermophile bacteria seed solution into the mixture and carrying out the first-step anaerobic fermentation to produce hydrogen gas; (3) mixing fermentation residue, water and sodium hydroxide according to the proportion for alkali pretreatment, pre-treating the residue and washing to be neutral to obtain a compound pretreated straw fiber; and (4) mixing the obtained compound pretreated straw fiber with the nutritive salt solution, introducing the thermophile bacteria seed solution into the mixture and carrying out the second-step anaerobic fermentation to produce hydrogen gas. Compared with the traditional method for producing the hydrogen by pre-treating the straw with alkali, the method for producing hydrogen by fermenting the composite pretreated straw fiber at two steps ensures that the hydrogen-producing level is improved by 75 percent, the utilization rate of the raw material is improved to 70 percent from 40 percent and the expense for the alkali pretreatment is reduced by 40 percent.
Description
Technical field
The invention belongs to field of renewable energy technology, particularly, the present invention relates to the method for a kind of biology, the compound pretreated straw fibrous material of alkali two-step fermentation product hydrogen.
Background technology
Enter 21 century, the exploitation of renewable energy source becomes worldwide focus, utilizes the abandoned biomass renewable energy resources to become the important channel of the reply energy and ecocrisis.Hydrogen can directly be used as fuel, also can be directly changed into electric energy by electrochemical reaction by fuel cell, is used for communications and transportation etc.Hydrogen has the energy density height as energy carrier, and outstanding advantage such as green non-pollution is a green regenerative energy sources truly.
It is reported that present 90% hydrogen all derives from the conversion of primary energy source (coal, oil and natural gas), but its facility investment is big, has also brought environmental hazard more or less when quickening primary energy consumption.With the organic waste is raw material, prepares hydrogen by microbial fermentation, and the renewable energy resources when administering environment become one of hydrogen gas production approach that has potentiality.
At present, adopt biological method to prepare hydrogen and utilize the raw material of degraded easily mostly, as (.Biohydrogen production:prospects and limitations topractical application.International Journal of Hydrogen Energy such as David B.Levin such as glucose, sucrose and waste water, 2004,29:173-185).The stalk fibre waste is a huge resource, utilizes agricultural crop straw to make as starting material and obtains cheap hydrogen and realize that industrialization becomes possibility.Yet stalk fibre raw material mix complexity is difficult to directly be utilized by hydrogenogens.Fan Yaoting provides a kind of method of utilizing sour pretreated straw fermentation and hydrogen production, this method is earlier with crushed stalk, adding certain density hydrochloric acid soln mixing then boils, regulate pH to neutral, adding anaerobic sludge and water can ferment and make hydrogen (.Efficient conversion of wheat straw wastes intobiohydrogen gas by cow dung compost.Bioresource Technology such as Fan Yao Ting, 2006,97:500-505).Chen Hongzhang (CN1254544C, the method for use steam puffed plant straw fermenting process of preparing hydrogen) also provides a kind of steam explosion stalk fermented method for preparing hydrogen of using, and different is that the inoculum that adopts in the fermenting process is acetobutyl bacteria and Rhodopseudomonas spheroides.Above-mentioned fermentation and hydrogen production process uses pre-treatment, also will use cellulase sometimes, fibre composition being converted into the sugar of solubility, thereby is produced hydrogen by the hydrogenogens utilization.
(CN 200710071696 for Wang Aijie, the method of the composite degraded cellulose fermentation and hydrogen production of a kind of bacterial classification) a kind of method of composite bacteria fermentation and hydrogen production is disclosed, cellulose degradation hydrogenogens and highly effective hydrogen yield bacterium are inoculated in to carry out anaerobically fermenting in the cellulosic material, can obtain a large amount of hydrogen.Clostridium thermocellum is a kind of bacterium of fiber degradation efficiently, can prepare hydrogen (.Hydrogen production byClostridium thermocellum 27405 from cellulosic biomass substrates.InternationalJournal of Hydrogen Energy 2006 such as David B.Levin by the direct fermentation fibrous material, 31:1496-1503), yet, when the natural untreated straw refuse of fermentation, produce the hydrogen level well below pure cellulosic substrate.
The pre-treatment of tradition alkali can be removed part xylogen in the stalk fibre raw material, improve the fibrous material accessibility, thereby improve Clostridium thermocellum fermentation fibrous material the process transformation efficiency (.Production ofethanol from various pure and natural cellulosic biomass by Clostridium thermocellumstrains SS21 and SS22.Process Biochemistry 1998 such as K.Sudha Rani, 33:435-440).Yet traditional alkali preprocessing process also becomes by product with soluble sugar, part hemicellulose and cellulose conversion, and by product will produce toxic action to microorganism on the one hand, be unfavorable for follow-up fermentation; On the other hand, traditional alkali pre-treatment has also reduced the raw material availability of fermenting process.
As mentioned above, prior art has reported that some stalk fibre raw material anaerobic fermentations prepare the method for hydrogen, but to the requirement of preprocessing process and cellulase all than higher, this has improved product hydrogen process cost undoubtedly, preprocessing process will cause that also the generation of toxic byproduct and the reduction of raw material availability are arranged, and directly there is the low deficiency of hydrogen generation efficiency in fibrous material thermophilic fermentation product hydrogen methods, has hindered the practical application of producing the hydrogen process greatly.
Summary of the invention
The present inventor has proposed the method for a kind of biology, the compound pretreated straw fibrous material of alkali two-step fermentation product hydrogen in order to address the above problem.
Method according to biology of the present invention, the compound pretreated straw fibrous material of alkali two-step fermentation produce hydrogen may further comprise the steps:
1) broken stalk fibre raw material mixes broken raw material to obtain mixture with nutrient salt solution;
2) insert the thermophile bacteria seed liquor in mixture, carry out the first step anaerobic fermentation to produce hydrogen, the stalk fibre raw material obtains fermentation residue after Biological Pretreatment, and the ferment for hydrogen production process also is the straw biological preprocessing process, and fermentation residue is the Biological Pretreatment stalk;
3) above-mentioned Biological Pretreatment stalk, water and sodium hydroxide are pressed 10-20: 200: 1 mixed, to place 15min-3d down for 55-120 ℃ and carry out the alkali pre-treatment, the pre-treatment residue filters, is washed to neutrality, obtains compound pretreated straw;
The compound pretreated straw that 4) will obtain is mixed with nutrient salt solution, inserts the thermophile bacteria seed liquor in mixture, carries out the second step hydrogen production through anaerobic fermentation.
The method according to this invention, compound pre-treatment are Biological Pretreatment and alkali pre-treatment, and described the first step fermentation and hydrogen production process is again simultaneously to adopt the Biological Pretreatment process of thermophile bacteria to stalk.Described two-step fermentation is the first step fermentation and hydrogen production and the second step fermentation and hydrogen production process.Preferably, wherein, in step 2) and step 4) in, the blending ratio of described stalk and nutritive medium is 5-50g: 1L.
The method according to this invention, wherein, every liter of described nutrition saline solution comprises (NH
4)
2SO
4, 1.3g; KH
2PO
4, 1.5g; K
2HPO
43H
2O, 3.8g; CaCl
2, 0.013g; FeSO
4, 1.25mg; Yeast powder, 5g; MgCl
26H
2O, 1.41g; Halfcystine, 0.5g.
The method according to this invention, wherein, described thermophile bacteria is a Clostridium thermocellum, be thermophilic clostridium saccharolyticum perhaps: Clostridium thermocellum is pressed 0-10: 10 mixed bacteria liquid, the inoculum size of described thermophile bacteria seed liquor are 5-20%v.
The method according to this invention, wherein, in step 2) or 4) in, in described fermentation and hydrogen production process, temperature is controlled to be 55-60 ℃, and the time is 2-5 days, and pH is 6.5-7.5.
The method according to this invention, wherein, described stalk fibre raw material is to be selected from broomcorn straw, wheat stalk, straw, the maize straw one or several, wherein, any two kinds blending ratio is 0-10: 0-10.
The method that biology of the present invention, the compound pretreated straw fibrous material of alkali two-step fermentation produce hydrogen specifically comprises the steps:
1) raw material crushing and mixing
Collect the stalk fibre raw material, adopt the plant pulverizer to be crushed to below the particle diameter 15mm, will join in producing hydrogen reactor after a certain amount of solid material and the nutrient salt solution mixing, wherein solid straws concentration is 5-50g/L, and every liter of nutrient salt solution comprises (NH
4)
2SO
4, 1.3g; KH
2PO
4, 1.5g; K
2HPO
43H
2O, 3.8g; CaCl
2, 0.013g; FeSO
4, 1.25mg; Yeast powder, 5g; MgCl
26H
2O, 1.41g; Halfcystine, 0.5g.
2) the first step fermentation and hydrogen production and Biological Pretreatment
Obtain anaerobic environment with producing the hydrogen reactor inflated with nitrogen in the step 1), the inoculum size with 5-20% inserts the thermophile bacteria seed liquor then, carries out the first step anaerobically fermenting after stirring, and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 55-60 ℃, the time is 2-5 days, and pH is 6.5-7.5.The fermentation and hydrogen production process is again simultaneously the Biological Pretreatment process to stalk, and fermentation residue is the Biological Pretreatment stalk.
3) alkali pre-treatment
Is 10-20 with sodium hydroxide by mass ratio with Biological Pretreatment stalk, water: mix at 200: 1, place 15min-3d down at 55-120 ℃ and carry out the alkali pre-treatment, the pre-treatment residue filters, is washed to neutrality, obtains compound pretreated straw.
4) fermentation of second step makes hydrogen
Produce in the hydrogen reactor joining after compound pretreated straw and the nutrient salt solution mixing, making compound pretreated straw concentration is 5-50g/L, inflated with nitrogen obtains anaerobic environment, and the inoculum size with 5-20% inserts the thermophile bacteria seed liquor then, carries out the second step anaerobically fermenting and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 55-60 ℃, the time is 2-5 days, and pH is 6.5-7.5.
The method of aforesaid a kind of compound pretreated straw fibrous material two-step fermentation hydrogen producing, it can be independent Clostridium thermocellum (Clostridiumthermocellum) that wherein said fermentation makes the thermophile bacteria seed liquor that is used to inoculate in the hydrogen step, and also can be thermophilic clostridium saccharolyticum (Thermoanaerobacteriumthermosaccharolyticum): Clostridium thermocellum be pressed 0-10: 10 mixed bacteria liquid.The preparation of described Clostridium thermocellum bacterium seed liquor is that Clostridium thermocellum is inoculated in DSM 122 substratum, cultivates 2-4 days for 55 or 60 ℃, obtains the bacterium seed liquor.The preparation of described thermophilic clostridium saccharolyticum bacterium seed liquor is that thermophilic clostridium saccharolyticum is inoculated in DSM 61 substratum, cultivates 1-2 days for 60 ℃, obtains the bacterium seed liquor.Described DSM 122 and DSM 61 are conventional substratum, preparation according to a conventional method, and its detailed composition and compound method are seen German DSMZ website (www.dsmz.de).
Described stalk fibre raw material is selected from one or several in broomcorn straw, wheat stalk, straw, the maize straw, and wherein, any two kinds blending ratio is 0-10: 0-10.
In sum, the invention provides the method for a kind of biology, the compound pretreated straw fibrous material of alkali two-step fermentation product hydrogen, this method is produced hydrogen by thermophile bacteria direct fermentation stalk fibre raw material earlier, this process is again the straw biological preprocessing process simultaneously, fermentation residue is the Biological Pretreatment stalk, the Biological Pretreatment stalk is mixed with sodium hydroxide solution and carry out the alkali pre-treatment, obtain compound pretreated straw, compound pretreated straw is carried out the second step fermenting process of preparing hydrogen again.
The advantage of producing the method for hydrogen according to biology of the present invention, the compound pretreated straw fibrous material of alkali two-step fermentation is:
1, stalk fermentation prepares hydrogen, has solved the environmental problem of crop straw burning in the time of the renewable energy resources, thereby has proposed a kind of stalk resource new way, has on the industry utility value widely;
2, the method for producing hydrogen, i.e. " the first step Fa Jiaochanqing ﹠amp according to a kind of biology of the present invention, the compound pretreated straw fibrous material of alkali two-step fermentation; Biological Pretreatment-alkali pre-treatment-second step fermentation and hydrogen production " process; the advantage applies that described compound pre-treatment two-step fermentation produces the hydrogen process exists: 1. the first step fermenting process utilizes soluble sugar and easy degradation of fibers component product hydrogen in the stalk; avoided direct alkali preprocessing process soluble sugar and easily degradation of fibers component loss, improved raw material availability; 2. alkali pre-treatment delignification process forms the by product that fermenting bacteria is had inhibition with soluble sugar and easy degradation of fibers component hydrolysis easily, and the first step fermentation and hydrogen production has utilized said components, has therefore reduced by product formation; 3. the first step fermentation and hydrogen production is again the Biological Pretreatment process, has partially opened the fiber complex construction, thereby has improved follow-up alkali preprocessing process efficient, therefore produces the hydrogen level in the second step fermentation and hydrogen production process and is largely increased; 4. thermophile bacteria Biological Pretreatment process has reduced the treatment capacity of alkali preprocessing process, has therefore reduced alkali pre-treatment expense.Adopt above-mentioned compound pretreated straw two-step fermentation to produce hydrogen, produce the hydrogen level and improve 75%, raw material availability brings up to 70%, alkali pre-treatment expense reduction by 40% from 40%.
In sum, the method for biology provided by the invention, the compound pretreated straw fibrous material of alkali fermenting process of preparing hydrogen is stalk because of it uses raw material, and aboundresources is cheap, efficiently solves the problem of biological hydrogen production process insufficient raw material; Compound pre-treatment two-step fermentation process has improved product hydrogen level and raw material availability, has reduced the pre-treatment cost, makes the present invention be suitable for more using.Technology of the present invention is simply efficient, and is energy-conservation, and cost is low, has good economy, society, environment and ecological benefits, is suitable for utilizing technology to be applied as stalk resource.
Embodiment
Further set forth the present invention below in conjunction with preferred embodiment, but these embodiment only limit to illustrate the present invention, and can not limit the scope of the invention.
Embodiment 1 alkali pretreated straw fermentation and hydrogen production
Use maize straw (taking from suburb, Daxing, Beijing), Clostridium thermocellum DSM No.7072 (buying from German DSMZ) to pass through alkali pretreated straw fibrous material fermentation and hydrogen production process, step is as follows:
(1) raw material crushing and alkali pre-treatment
Collect the stalk fibre raw material, adopt the plant pulverizer to be crushed to below the particle diameter 15mm, with stalk, water and the sodium hydroxide mixed according to 10: 200: 1, place 3d down for 55 ℃, washing residue obtains the alkali pretreated straw to neutral.
(2) raw material mixes
To join in producing hydrogen reactor after a certain amount of alkali pretreated straw and the nutrient salt solution mixing, wherein alkali pretreated straw concentration is 10g/L, and every liter of nutrient salt solution comprises (NH
4)
2SO
4, 1.3g; KH
2PO
4, 1.5g; K
2HPO
43H
2O, 3.8g; CaCl
2, 0.013g; FeSO
4, 1.25mg; Yeast powder, 5g; MgCl
26H
2O, 1.41g; Halfcystine, 0.5g.
(3) fermentation makes hydrogen
Inoculum size with 10% inserts the thermophile bacteria seed liquor, carries out the first step anaerobically fermenting after stirring, and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 55 ℃, the time is 4 days, and pH is 7.5.
Described thermophile bacteria seed liquor is that Clostridium thermocellum DSM No.7072 is inoculated in DSM 122 substratum with 10% inoculum size, cultivates for 55 ℃ to obtain in 4 days.
Adopt the method for alkali pretreated straw fibrous material fermentation and hydrogen production as mentioned above, hydrogen yield (the hydrogen producing amount of unit mass stalk) reaches 65ml H
2/ g-stalk, raw material availability are 38%.
Embodiment 2 alkali pretreated straw fermentation and hydrogen productions
Use maize straw and broomcorn straw (to take from suburb, Daxing, Beijing, its blending ratio is 10: 10), by alkali pretreated straw fibrous material fermentation and hydrogen production process, step is as follows for Clostridium thermocellum DSM No.7072 and clostridium thermosaccharolyticum DSM No.869 (buying from German DSMZ):
(1) raw material crushing and alkali pre-treatment
Collect the stalk fibre raw material, adopt the plant pulverizer to be crushed to below the particle diameter 15mm, with stalk, water and the sodium hydroxide mixed according to 12: 200: 1, place 15min down for 120 ℃, washing residue obtains the alkali pretreated straw to neutral.
(2) raw material mixes
To join in producing hydrogen reactor after a certain amount of alkali pretreated straw and the nutrient salt solution mixing, wherein alkali pretreated straw concentration is 10g/L, and the nutrient salt solution composition is with embodiment 1.
(3) fermentation makes hydrogen
Inoculum size with 20% inserts the thermophile bacteria seed liquor, carries out anaerobically fermenting after stirring, and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 55 ℃, the time is 5 days, and pH is 7.2.
Described thermophile bacteria seed liquor is A bacterium seed liquor and B bacterium seed liquor equal proportion mixed solution.Described A bacterium seed liquor is that Clostridium thermocellum DSM No.7072 is inoculated in DSM 122 substratum with 10% inoculum size, cultivates for 55 ℃ to obtain in 4 days.Described B bacterium seed liquor is that Clostridium thermocellum DSM No.869 is inoculated in DSM 61 substratum with 10% inoculum size, cultivates for 60 ℃ to obtain in 1 day.
Adopt the method for alkali pretreated straw fibrous material fermentation and hydrogen production as mentioned above, hydrogen yield reaches 74mlH
2/ g-stalk, raw material availability reaches 40%.
Embodiment 3 biologies, alkali pretreated straw fermentation and hydrogen production
Use maize straw, Clostridium thermocellum DSM No.7072 produces the hydrogen process by compound pretreated straw fibrous material two-step fermentation, and step is as follows:
(1) raw material crushing and mixing
Collect stalk, adopt the plant pulverizer to be crushed to below the particle diameter 15mm, will join in producing hydrogen reactor after a certain amount of stalk and the nutrient salt solution mixing, wherein stalk concentration is 10g/L, and the nutritive salt composition is with embodiment 1.
(2) the first step fermentation and hydrogen production and Biological Pretreatment
Inoculum size with 10% inserts the thermophile bacteria seed liquor, carries out the first step anaerobically fermenting after stirring, and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 55 ℃, the time is 4 days, and pH is 7.5.The fermentation and hydrogen production process is again simultaneously the Biological Pretreatment process to stalk, and fermentation residue is the Biological Pretreatment stalk.
(3) alkali pre-treatment
With Biological Pretreatment stalk, water and sodium hydroxide be to mix at 10: 200: 1 by mass ratio, place 3d down at 55 ℃ and carry out the alkali pre-treatment, the pre-treatment residue filters, is washed to neutrality, obtains compound pretreated straw.
The fermentation of (4) second steps makes hydrogen
Produce in the hydrogen reactor joining after a certain amount of compound pretreated straw and the nutrient salt solution mixing, wherein compound pretreated straw concentration is 10g/L, and the nutritive salt composition is with embodiment 1.Insert the thermophile bacteria seed liquor with 10% inoculum size then, carry out the second step anaerobically fermenting and make hydrogen.Produce the hydrogen process temperature and be controlled to be 55 ℃, the time is 4 days, and pH is 7.5.
Thermophile bacteria seed liquor described in step (2) and (4) is with embodiment 1.
Adopt compound as mentioned above pretreated straw fibrous material two-step fermentation to produce the method for hydrogen, hydrogen yield reaches 115ml H
2/ g-stalk, raw material availability are 68%.
Embodiment 4 biologies, alkali pretreated straw fermentation and hydrogen production
Use maize straw and broomcorn straw (take from suburb, Daxing, Beijing, its blending ratio is 10: 10), Clostridium thermocellum DSM No.7072 and clostridium thermosaccharolyticum DSM No.869 (purchase) to pass through from German DSMZ
Biological, alkali pretreated straw fermentation and hydrogen productionProcess, step is as follows:
(1) raw material crushing and mixing
Concrete steps are with embodiment 3.
(2) the first step fermentation and hydrogen production and Biological Pretreatment
Inoculum size with 20% inserts the thermophile bacteria seed liquor, carries out the first step anaerobically fermenting after stirring, and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 55 ℃, the time is 5 days, and pH is 7.2.Collect fermentation residue and promptly obtain the Biological Pretreatment stalk.
(3) alkali pre-treatment
With Biological Pretreatment stalk, water and sodium hydroxide be to mix at 12: 200: 1 by mass ratio, place 15min down at 120 ℃ and carry out the alkali pre-treatment, the pre-treatment residue filters, is washed to neutrality, obtains compound pretreated straw.
The fermentation of (4) second steps makes hydrogen
Produce in the hydrogen reactor joining after a certain amount of compound pretreated straw and the nutrient salt solution mixing, wherein compound pretreated straw concentration is 10g/L, the nutritive salt composition is with embodiment 1, inserts the thermophile bacteria seed liquor with 20% inoculum size then, carries out the second step anaerobically fermenting and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 55 ℃, the time is 5 days, and pH is 7.2.
Thermophile bacteria seed liquor described in step (2) and (4) is with embodiment 2.
Adopt compound as mentioned above pretreated straw fibrous material two-step fermentation to produce the method for hydrogen, hydrogen yield reaches 131ml H
2/ g-stalk, raw material availability are 70%.
Embodiment 5 biologies, alkali pretreated straw fermentation and hydrogen production
(its blending ratio is 10: 10: 10: 10 to use broomcorn straw, wheat stalk, straw and maize straw, wherein wheat straw is taken from the rural area, Hebei, straw is taken from Hunan Rural Areas, Chinese sorghum and maize straw and taken from suburb, Daxing, Beijing), Clostridium thermocellum DSM No.7072 produces the hydrogen process by compound pretreated straw fibrous material two-step fermentation, and step is as follows:
(1) raw material crushing and mixing
Concrete steps are with embodiment 3, and different is that wherein stalk concentration is 50g/L.
(2) the first step fermentation and hydrogen production and Biological Pretreatment
Inoculum size with 5% inserts the thermophile bacteria seed liquor, carries out the first step anaerobically fermenting after stirring, and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 60 ℃, the time is 2 days, and pH is 6.5.Collect fermentation residue and promptly obtain the Biological Pretreatment stalk.
(3) alkali pre-treatment
With Biological Pretreatment stalk, water and sodium hydroxide be to mix at 20: 200: 1 by mass ratio, place 45min down at 100 ℃ and carry out the alkali pre-treatment, the pre-treatment residue filters, is washed to neutrality, obtains compound pretreated straw.
The fermentation of (4) second steps makes hydrogen
Produce in the hydrogen reactor joining after a certain amount of compound pretreated straw and the nutrient salt solution mixing, wherein compound pretreated straw concentration is 5g/L, and the nutritive salt composition is with embodiment 1.Insert the thermophile bacteria seed liquor with 8% inoculum size then, carry out the second step anaerobically fermenting and make hydrogen.Produce the hydrogen process temperature and be controlled to be 55 ℃, the time is 4 days, and pH is 7.5.
Described thermophile bacteria seed liquor is that Clostridium thermocellum DSM No.7072 is inoculated in DSM 122 substratum with 10% inoculum size, cultivates for 55 ℃ to obtain in 4 days.
Adopt compound as mentioned above pretreated straw fibrous material two-step fermentation to produce the method for hydrogen, hydrogen yield reaches 87ml H
2/ g-stalk, raw material availability are 63%.
Embodiment 6 biologies, alkali pretreated straw fermentation and hydrogen production
(its blending ratio is 10: 10: 10 to use broomcorn straw, wheat stalk and maize straw, the stalk source place is with embodiment 5), Clostridium thermocellum DSM No.4150 and thermophilic clostridium saccharolyticum DSM No.572 (buying from German DSMZ) produce the hydrogen process by compound pretreated straw fibrous material two-step fermentation, and step is as follows:
(1) raw material crushing and mixing
Concrete steps are with embodiment 3, and different is that wherein stalk concentration is 50g/L.
(2) the first step fermentation and hydrogen production and Biological Pretreatment
Inoculum size with 15% inserts the thermophile bacteria seed liquor, carries out the first step anaerobically fermenting after stirring, and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 60 ℃, the time is 5 days, and pH is 6.5.Collect fermentation residue and promptly obtain the Biological Pretreatment stalk.
(3) alkali pre-treatment
With Biological Pretreatment stalk, water and sodium hydroxide be to mix at 20: 200: 1 by mass ratio, place 25min down at 120 ℃ and carry out the alkali pre-treatment, the pre-treatment residue filters, is washed to neutrality, obtains compound pretreated straw.
The fermentation of (4) second steps makes hydrogen
Produce in the hydrogen reactor joining after a certain amount of compound pretreated straw and the nutrient salt solution mixing, wherein compound pretreated straw concentration is 5g/L, the nutritive salt composition is with embodiment 1, inserts the thermophile bacteria seed liquor with 20% inoculum size then, carries out the second step anaerobically fermenting and makes hydrogen.Produce the hydrogen process temperature and be controlled to be 60 ℃, the time is 2 days, and pH is 7.
Described thermophile bacteria seed liquor is that A bacterium seed liquor and B bacterium seed liquor were by 10: 5 proportioning concentrations, described A bacterium seed liquor is that Clostridium thermocellum DSM No.4150 is inoculated in DSM 122 substratum with 10% inoculum size, cultivate for 55 ℃ and obtained in 2 days, obtain A bacterium seed liquor, described B bacterium seed liquor is that Clostridium thermocellum DSM No.572 is inoculated in DSM 61 substratum with 10% inoculum size, cultivates for 60 ℃ to obtain in 1 day.
Adopt compound as mentioned above pretreated straw fibrous material two-step fermentation to produce the method for hydrogen, hydrogen yield reaches 93ml H
2/ g-stalk, raw material availability are 64%.
Embodiment 7 biologies, alkali pretreated straw fermentation and hydrogen production
(its blending ratio is 10: 10: 10 to use broomcorn straw, straw and maize straw, the stalk source place is with embodiment 5), Clostridium thermocellum DSM No.4150 and thermophilic clostridium saccharolyticum DSM No.869 produce the hydrogen process by compound pretreated straw fibrous material two-step fermentation, and step is as follows:
(1) raw material crushing and mixing
Concrete steps are with embodiment 3, and different is that wherein the stalk fibre material concentration is 15g/L.
(2) the first step fermentation and hydrogen production and Biological Pretreatment
Concrete steps are produced the hydrogen process temperature and are controlled to be 60 ℃ with embodiment 4, and the time is 3 days, and pH is 7.0.
(3) alkali pre-treatment
Concrete steps are with embodiment 4, different is Biological Pretreatment stalk, water and sodium hydroxide be to mix at 20: 200: 1 by mass ratio, place 1d down at 80 ℃ and carry out the alkali pre-treatment.
The fermentation of (4) second steps makes hydrogen
Concrete steps are with embodiment 4, and different is that compound pretreated straw concentration is 20g/L, and the inoculum size with 15% inserts the thermophile bacteria seed liquor.Produce the hydrogen process temperature and be controlled to be 60 ℃, the time is 5 days.
Described thermophile bacteria seed liquor is A bacterium seed liquor and the B bacterium seed liquor mixed solution by 10: 5 mixed, described A bacterium seed liquor is that Clostridium thermocellum DSM No.4150 is inoculated in DSM 122 substratum with 10% inoculum size, cultivate for 60 ℃ and obtained in 2 days, described B bacterium seed liquor is that Clostridium thermocellum DSM No.869 is inoculated in DSM 61 substratum with 10% inoculum size, cultivates for 60 ℃ to obtain in 2 days.
Adopt compound as mentioned above pretreated straw fibrous material two-step fermentation to produce the method for hydrogen, hydrogen yield reaches 107ml H
2/ g-stalk, raw material availability are 66%.
Embodiment 8 biologies, alkali pretreated straw fermentation and hydrogen production
(its blending ratio is 10: 5: 10: 5 to use broomcorn straw, straw, maize straw and wheat stalk, the source place is with embodiment 5), Clostridium thermocellum DSM No.7072 and thermophilic clostridium saccharolyticum DSM No.572 produce the hydrogen process by compound pretreated straw fibrous material two-step fermentation, and step is as follows:
(1) raw material crushing and mixing
Concrete steps are with embodiment 3.
(2) the first step fermentation and hydrogen production and Biological Pretreatment
Concrete steps are with embodiment 4, and different is to produce the hydrogen process temperature to be controlled to be 55 ℃, and the time is 5 days, and pH is 6.5.
(3) alkali pre-treatment
Concrete steps are with embodiment 6, and different is to place 1.5d down at 70 ℃ to carry out the alkali pre-treatment.
The fermentation of (4) second steps makes hydrogen
Concrete steps are with embodiment 4, and different is that compound pretreated straw concentration is 30g/L.
Described thermophile bacteria seed liquor is with embodiment 4, and different is that clostridium thermosaccharolyticum is DSM No.572.
Adopt compound as mentioned above pretreated straw fibrous material two-step fermentation to produce the method for hydrogen, hydrogen yield reaches 122ml H
2/ g-stalk, raw material availability are 68%.
Described DSM 122 of above embodiment 1-6 and DSM 61 substratum are conventional substratum, preparation according to a conventional method, and its detailed composition and compound method are seen German DSMZ website (www.dsmz.de).
In sum, compare with adopting traditional alkali pre-treatment forced fermentation product hydrogen process, the compound pretreated straw two-step fermentation of biology, the alkali that adopts the present invention to propose produces hydrogen, and hydrogen yield improves 75%, and raw material availability brings up to 70% from 40%.The Biological Pretreatment process soluble substance in part stalk and the stalk of having degraded simultaneously, not only avoided of the loss of this part material at traditional alkali preprocessing process, improved raw material availability, and reduce the treatment capacity about 40% of follow-up alkali preprocessing process, so alkali pre-treatment cost reduces about 40%.
Below in conjunction with embodiment the present invention has been done to specify, it should be appreciated by those skilled in the art that all within the scope of the present invention according to all variants, modification, alternative and the equivalent of embodiment of the present invention.
Claims (6)
1. the method that biology, the compound pretreated straw fibrous material of alkali two-step fermentation produce hydrogen is characterized in that, said method comprising the steps of:
1) broken stalk fibre raw material mixes broken raw material to obtain mixture with nutrient salt solution;
2) insert the thermophile bacteria seed liquor in mixture, carry out the first step anaerobic fermentation to produce hydrogen, the fermentation residue of stalk fibre raw material after Biological Pretreatment is the Biological Pretreatment stalk;
3) above-mentioned Biological Pretreatment stalk, water and sodium hydroxide are pressed 10-20: 200: 1 mixed, to place 15min-3d down for 55-120 ℃ and carry out the alkali pre-treatment, the pre-treatment residue filters, is washed to neutrality, obtains compound pretreated straw;
The compound pretreated straw that 4) will obtain is mixed with nutrient salt solution, inserts the thermophile bacteria seed liquor in mixture, carries out the second step hydrogen production through anaerobic fermentation.
2. the method for claim 1 is characterized in that, in step 2) and step 4) in, the blending ratio of described stalk and nutritive medium is 5-50g: 1L.
3. the method for claim 1 is characterized in that, every liter of described nutrition saline solution comprises (NH
4)
2SO
4, 1.3g; KH
2PO
4, 1.5g; K
2HPO
43H
2O, 3.8g; CaCl
2, 0.013g; FeSO
4, 1.25mg; Yeast powder, 5g; MgCl
26H
2O, 1.41g; Halfcystine, 0.5g.
4. the method for claim 1 is characterized in that, described thermophile bacteria is a Clostridium thermocellum, and perhaps be thermophilic clostridium saccharolyticum: Clostridium thermocellum is 0-10: 10 mixed bacteria liquid, the inoculum size of described thermophile bacteria seed liquor are 5-20%v.
5. the method for claim 1 is characterized in that, in step 2) or 4) in, in described fermentation and hydrogen production process, temperature is controlled to be 55-60 ℃, and the time is 2-5 days, and pH is 6.5-7.5.
6. method according to claim 1 is characterized in that, described stalk fibre raw material is to be selected from broomcorn straw, wheat stalk, straw, the maize straw one or several, and wherein, any two kinds blending ratio is 0-10: 0-10.
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