CN101445810A - Method for preparing hydrogen by fermenting biologically pretreated straw - Google Patents
Method for preparing hydrogen by fermenting biologically pretreated straw Download PDFInfo
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Abstract
The invention provides a method for preparing hydrogen by fermenting biologically pretreated straw, wherein, trichoderma is utilized to carry out biological pretreatment on straw, the biologically pretreated straw is mixed with un-treated straw, and then the hydrogen is prepared by fermenting the mixed straw and hydrogen sludge. As the method utilizes the crop straw as the raw material, the resource of the straw is rich and the price of the straw is low, thereby effectively solving the problem concerning the resource of biological hydrogen preparation; meanwhile, the method also overcomes the defect that when conventional straw fiber material is used in the hydrogen preparation process, the efficiency is low; and the method has the advantages of simplicity, high efficiency, energy conservation, low cost, and the like, and can improve the hydrogen yield rate by 50 percent to 120 percent.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogen, particularly a kind of method of using the Biological Pretreatment stalk fermentation to prepare hydrogen.
Background technology
Hydrogen Energy is a kind of new and renewable sources of energy of cleaning fully.Hydrogen can directly be used as fuel, also can utilize electrochemical reaction to be directly changed into electric energy by fuel cell, is used for generating and communications and transportation etc., and hydrogen also can be used as the intermediate carrier of the various energy.Hydrogen acts as a fuel when being used for communications and transportation, heat energy and power generation; characteristics with high-level efficiency, high benefit; and the reaction product of hydrogen is water and heat; be the clean energy and the sustainability energy truly, this sustainable use, environment protection, reduction atmospheric pollution and alleviate aspects such as Greenhouse effect and will produce revolutionary impact for the energy.Because conventional fossil energy is exhausted day by day, the mass-producing utilization of hydrogen just becomes the selection that a kind of worth emphasis is considered.
At present, mainly be to utilize hydrogen producing in next life such as fossil oil, nuclear energy and renewable energy source.It is reported that present 90% hydrogen energy source all derives from the conversion of primary energy source (coal, oil and natural gas).Though traditional preparation process technology process efficiency height, technology maturation, its facility investment is big, has also brought environmental hazard more or less when quickening primary energy consumption.It is wide that bio-hydrogen production technology has raw material sources, mild condition, and energy consumption is little, and cost is low, and plurality of advantages such as green non-pollution for the Sustainable development of Hydrogen Energy has brought hope, thereby receive much concern.What most researchers adopted both at home and abroad all is the material of degrading easily, as glucose, sucrose, starch, milk, short chain fatty acid and waste water main raw material (Fang HH etc. as the research of product hydrogen, Effect of pH on hydrogen production fromglucose by a mixed culture.Bioresource Technology, 2002,82:87-93; Shina HS etc., Hydrogen production from food waste in anaerobic mesophilic andthermophilic acidogenesis.International Journal of Hydrogen Energy, 2004,29:1355-1363).It is infeasible economically to be with glucose, sucrose that raw material prepares hydrogen, and produces with the waste water raw material in the research of hydrogen, and main purpose is the purification of waste water, and hydrogen is a byproduct, and there are problems such as factor of created gase is low in its process.
In China, the stalk annual production reaches 700,000,000 tons, and utilizing agricultural crop straw finally to obtain hydrogen as starting material is an imagination that initiative spirit is courageously arranged, and it makes 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, generally needs by pre-treatment, and then utilizes hydrogen production through anaerobic fermentation.Fan Yaoting provides a kind of method of utilizing sour pretreated straw fermentation and hydrogen production, and this method mainly may further comprise the steps: 1. with crushed stalk, place container, add certain density hydrochloric acid soln respectively according to a certain percentage, mix; 2. boil 30min; 3. the stalk that will handle places another container, regulates pH to neutral, adds a certain amount of anaerobic sludge and water, sealing; 4. said vesse being placed can ferment under the temperature (35 ℃) makes hydrogen.This method is pointed out simultaneously, undressed stalk can not be produced hydrogen mud by middle temperature basically and utilize, yet after the employing acid treatment, its hydrogen production potential has obtained huge lifting (Mao-Lin Zhang etc., Enhanced biohydrogenproduction from cornstalk wastes with acidification pretreatment by mixedanaerobic cultures.Biomass and Bioenergy, in Press).Rohit Datar provides another kind of employing pretreated straw to prepare the method for hydrogen, and this method mainly may further comprise the steps: 1. stalk is shredded, adopt water or sulfuric acid liquid to soak 2 hours; 2. the stalk after will soaking places steam-explosion jar to carry out the quick-fried pre-treatment of vapour; 3. the hydrolyzed solution that the quick-fried back of vapour is obtained is regulated pH to neutral, adds a certain amount of anaerobic sludge and water, sealing; 4. said vesse being placed can ferment under the temperature (35 ℃) makes hydrogen (RohitDatar etc., Hydrogen production from the fermentation of corn stover biomasspretreated with a steam-explosion process.International Journal of HydrogenEnergy, in press).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.
As mentioned above, pertinent literature has been reported some stalks through pre-treatment, and anaerobically fermenting prepares the method for hydrogen then.Yet above-mentioned pretreatment process needs high-temperature and high-pressure conditions, and the use of preprocessing process acid is simultaneously had higher requirement to equipment, might pollute, and therefore from large-scale application one segment distance is arranged still.
Summary of the invention
The objective of the invention is to widen the biological hydrogen production raw material sources, overcome the deficiency of stalk fibre fermenting raw materials product hydrogen difficulty and existing acid, the quick-fried pretreated straw biological fermentation product of vapour hydrogen process, thereby provide a kind of efficient, energy-conservation use Biological Pretreatment stalk fermentation to prepare the method for hydrogen.
Technical scheme of the present invention is as follows:
A kind of method of using the Biological Pretreatment stalk fermentation to prepare hydrogen, this method adopts wood mould, preferred Trichodermareesei, after more preferably Trichodermareesei Rut C30 (Trichoderma reesei Rut C30) carries out Biological Pretreatment to stalk, the stalk of Biological Pretreatment is mixed with untreated stalk, carry out fermenting process of preparing hydrogen with producing hydrogen mud then.
Aforesaid method specifically comprises the steps:
(1) Biological Pretreatment
In solid-state fermentation reactor, stalk is mixed with nutrient salt solution, add the mould Biological Pretreatment of carrying out of wood;
(2) fermentation makes hydrogen
The stalk and the untreated stalk of Biological Pretreatment in the step (1) are mixed in proportion, join in the product hydrogen reactor with producing hydrogen mud then, carry out anaerobically fermenting after stirring, make hydrogen.
In aforesaid method, the temperature of Biological Pretreatment is 25-32 ℃, and the time is 4-8 days; The stalk of Biological Pretreatment and the blending ratio of untreated stalk are 1:1-9; Fermentation time is 24-96 hour; When temperature was produced hydrogen mud in described product hydrogen mud adopts, described leavening temperature was 35 ℃; Produce hydrogen mud when described product hydrogen mud adopts high temperature, described leavening temperature is 50-58 ℃.Described stalk is selected from one or several in broomcorn straw, wheat stalk, straw, maize straw and other straw.Described nutrient salt solution comprises 1.6% ammonium sulfate, 0.6% magnesium sulfate heptahydrate and 0.3% potassium primary phosphate.
Use Biological Pretreatment stalk fermentation provided by the invention prepares the method for hydrogen, also comprises adopting draining water gathering of gas law to collect prepared hydrogen, adopts gas chromatographic analysis hydrogen composition.
The invention has the advantages that:
1. use stalk as raw material, prepare hydrogen, solved the problem of environmental pollution while renewable energy resources that crop straw burning causes, thereby proposed a kind of new way of stalk comprehensive utilization by anaerobically fermenting.
2. the present invention uses resourceful fermenting straw raw material to prepare hydrogen, has solved the problem of biological hydrogen production process insufficient raw material.
3. compare with the untreated stalk fermentation of direct employing, hydrogen yield improved 50-120% when the present invention adopted the stalk fermentation of aforesaid Biological Pretreatment to prepare hydrogen, and preprocessing process need not High Temperature High Pressure and strong acid treatment, energy-conserving and environment-protective simultaneously.
The stalk fermentation of use Biological Pretreatment provided by the invention prepares the method for 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.Technology is simply efficient, and is energy-conservation, and cost is low, has good economy, society, environment and ecological benefits, suits to utilize technology to be applied as stalk resource.
Embodiment
Further set forth the present invention below in conjunction with embodiment, but these embodiment only limit to illustrate the present invention, and can not limit the scope of the invention.
Embodiment 1
Use the broomcorn straw and the middle temperature product hydrogen sludge fermentation of Biological Pretreatment to prepare hydrogen, step is as follows:
(1) Biological Pretreatment
At first, in solid-state fermentation reactor, the solid-to-liquid ratio according to 1/2.5 adds nutrient salt solution (1.6% ammonium sulfate, 0.6% magnesium sulfate heptahydrate, 0.3% potassium primary phosphate) in broomcorn straw, stir.
Then, with conventional PDA substratum Trichodermareesei Rut C30 is carried out slant culture, inoculation Trichodermareesei Rut C30 cultivates for 28 ℃ and promptly obtained Trichodermareesei Rut C30 seed liquor in 4 days in seed culture medium.Seed culture medium is that 5% wheat is poor, 0.5% glucose, and 0.8% ammonium sulfate, pH 6.2.
At last, the inoculum size with 10% is inoculated in above-mentioned Trichodermareesei seed liquor in the solid-state fermentation reactor, and leavening temperature is 25 ℃, ferments 8 days, makes the broomcorn straw of Biological Pretreatment.
(2) fermentation makes hydrogen
The broomcorn straw and the untreated broomcorn straw of Biological Pretreatment in the above-mentioned steps (1) are pressed 1: 9 mixed, produce hydrogen mud with middle temperature then and join in the product hydrogen reactor, carry out anaerobically fermenting after stirring, leavening temperature is 35 ℃, fermentation time is 72 hours, makes hydrogen.Adopt conventional draining water gathering of gas law to collect prepared hydrogen, adopt conventional gas chromatographic analysis hydrogen composition.
The consumption of temperature product hydrogen mud is 12000mg VS/L in described, and promptly the volatile solid of the mud of every liter of reactor interpolation (being called for short VS) amount is 12000mg.
Middle temperature in the present embodiment is produced hydrogen mud and is taken from temperature product hydrogen reactor in the extensive stirring-type, also can make by the following method, 1. gets an amount of sewage sludge, in 100 ℃ of processing 30 minutes, places reactor then, and anaerobism is cultivated; 2. be raw material with sucrose, every day, feed loading maintained 1000-3000mgCOD/l.d, and pH maintains 5.5-6.5, and temperature maintenance is at 35 ℃, and hydraulic detention time was controlled at about 1-2 days; 3. move 1-2 month continuously, constant to COD clearance and product hydrogen, be considered as sludge acclimatization and finish, temperature is produced hydrogen mud in the acquisition.
Produce the hydrogen sludge fermentation with untreated broomcorn straw of direct employing and middle temperature and compare, adopting as mentioned above, the broomcorn straw hydrogen yield of Biological Pretreatment improves 50%.
Embodiment 2
Use the maize straw and the high temperature product hydrogen sludge fermentation of Biological Pretreatment to prepare hydrogen, step is as follows:
(1) Biological Pretreatment
At first, in solid-state fermentation reactor, the solid-to-liquid ratio according to 1/2.5 adds nutrient salt solution (1.6% ammonium sulfate, 0.6% magnesium sulfate heptahydrate, 0.3% potassium primary phosphate) in maize straw, stir.
Then, with conventional PDA substratum Trichodermareesei Rut C30 is carried out slant culture, inoculation Trichodermareesei Rut C30 cultivates for 28 ℃ and promptly obtained Trichodermareesei Rut C30 seed liquor in 4 days in seed culture medium.Seed culture medium is that 5% wheat is poor, 0.5% glucose, and 0.8% ammonium sulfate, pH 6.2.
At last, the inoculum size with 10% is inoculated in above-mentioned Trichodermareesei seed liquor in the solid-state fermentation reactor, and leavening temperature is 30 ℃, ferments 6 days, makes the maize straw of Biological Pretreatment.
(2) fermentation makes hydrogen
The maize straw and the untreated maize straw of Biological Pretreatment in the above-mentioned steps (1) are pressed the 1:5 mixed, produce hydrogen mud with high temperature then and join in the product hydrogen reactor, carry out anaerobically fermenting after stirring, leavening temperature is 55 ℃, fermentation time is 96 hours, makes hydrogen.Adopt conventional draining water gathering of gas law to collect prepared hydrogen, adopt conventional gas chromatographic analysis hydrogen composition.
The consumption that described high temperature produces hydrogen mud is 15000mg VS/L, and promptly the volatile solid of the mud of every liter of reactor interpolation (being called for short VS) amount is 15000mg.
High temperature in the present embodiment produces hydrogen mud and takes from extensive high temperature product hydrogen reactor, also can make by the following method, 1. gets an amount of sewage sludge, in 100 ℃ of processing 30 minutes, places reactor then, and anaerobism is cultivated; 2. be raw material with sucrose, every day, feed loading maintained 1000-3000mg COD/l.d, and pH maintains 5.5-6.5, and temperature maintenance is at 53-56 ℃, and hydraulic detention time was controlled at about 1-2 days; 3. move 1-2 month continuously, constant to COD clearance and product hydrogen, be considered as sludge acclimatization and finish, obtain high temperature and produce hydrogen mud.
Produce the hydrogen sludge fermentation with untreated maize straw of direct employing and high temperature and compare, adopting as mentioned above, the maize straw hydrogen yield of Biological Pretreatment improves 120%.
Embodiment 3
Use the wheat stalk and the high temperature product hydrogen sludge fermentation of Biological Pretreatment to prepare hydrogen, step is as follows:
(1) Biological Pretreatment
At first, in solid-state fermentation reactor, the solid-to-liquid ratio according to 1/2.5 adds nutrient salt solution (1.6% ammonium sulfate, 0.6% magnesium sulfate heptahydrate, 0.3% potassium primary phosphate) in wheat stalk, stir.
Then, with conventional PDA substratum Trichodermareesei Rut C30 is carried out slant culture, inoculation Trichodermareesei Rut C30 cultivates for 28 ℃ and promptly obtained Trichodermareesei seed liquor RutC30 in 4 days in seed culture medium.Seed culture medium is that 5% wheat is poor, 0.5% glucose, and 0.8% ammonium sulfate, pH 6.2.
At last, the inoculum size with 10% is inoculated in above-mentioned Trichodermareesei seed liquor in the solid-state fermentation reactor, and leavening temperature is 32 ℃, ferments 4 days, makes the wheat stalk of Biological Pretreatment.
(2) fermentation makes hydrogen
The wheat stalk and the untreated wheat stalk of Biological Pretreatment in the above-mentioned steps (1) are pressed the 1:1 mixed, produce hydrogen mud with high temperature then and join in the product hydrogen reactor, carry out anaerobically fermenting after stirring, leavening temperature is 50 ℃, fermentation time is 72 hours, makes hydrogen.Adopt conventional draining water gathering of gas law to collect prepared hydrogen, adopt conventional gas chromatographic analysis hydrogen composition.
The consumption that described high temperature produces hydrogen mud is 18000mg VS/L, and promptly the volatile solid of the mud of every liter of reactor interpolation (being called for short VS) amount is 18000mg.
It is identical with embodiment 2 that high temperature in the present embodiment produces the source of hydrogen mud.
Produce the hydrogen sludge fermentation with untreated wheat stalk of direct employing and high temperature and compare, adopting as mentioned above, the wheat stalk hydrogen yield of Biological Pretreatment improves 65%.
Embodiment 4
Use the stalk mixture and the high temperature product hydrogen sludge fermentation of straw, wheat stalk and the maize straw of Biological Pretreatment to prepare hydrogen, step is as follows:
(1) Biological Pretreatment
At first, in solid-state fermentation reactor, the solid-to-liquid ratio according to 1/2.5 adds nutrient salt solution (1.6% ammonium sulfate, 0.6% magnesium sulfate heptahydrate, 0.3% potassium primary phosphate) in above-mentioned stalk mixture, stir.
Then, with conventional PDA substratum Trichodermareesei Rut C30 is carried out slant culture, inoculation Trichodermareesei Rut C30 cultivates for 28 ℃ and promptly obtained Trichodermareesei Rut C30 seed liquor in 4 days in seed culture medium.Seed culture medium is that 5% wheat is poor, 0.5% glucose, and 0.8% ammonium sulfate, pH 6.2.
At last, the inoculum size with 10% is inoculated in above-mentioned Trichodermareesei seed liquor in the solid-state fermentation reactor, and leavening temperature is 28 ℃, ferments 5 days, makes the stalk mixture of Biological Pretreatment.
(2) fermentation makes hydrogen
The stalk mixture and the untreated stalk mixture of Biological Pretreatment in the above-mentioned steps (1) are pressed the 1:3 mixed, produce hydrogen mud with high temperature then and join in the product hydrogen reactor, carry out anaerobically fermenting after stirring, leavening temperature is 58 ℃, fermentation time is 24 hours, makes hydrogen.Adopt conventional draining water gathering of gas law to collect prepared hydrogen, adopt conventional gas chromatographic analysis hydrogen composition.
In the described stalk mixture, the blending ratio of straw, wheat stalk, maize straw is 2:1:7.
It is identical with embodiment 2 with consumption that described high temperature produces the source of hydrogen mud.
Produce the hydrogen sludge fermentation with untreated stalk mixture of direct employing and high temperature and compare, adopting as mentioned above, the stalk mixture hydrogen yield of Biological Pretreatment improves 85%.
Embodiment 5
The stalk mixture of the straw of use Biological Pretreatment, wheat stalk, maize straw, broomcorn straw, green grass stalk and high temperature produce the hydrogen sludge fermentation and prepare hydrogen, and step is as follows:
(1) Biological Pretreatment
At first, in solid-state fermentation reactor, the solid-to-liquid ratio according to 1/2.5 adds nutrient salt solution (1.6% ammonium sulfate, 0.6% magnesium sulfate heptahydrate, 0.3% potassium primary phosphate) in above-mentioned stalk mixture, stir.
Then, with conventional PDA substratum Trichodermareesei Rut C30 is carried out slant culture, inoculation Trichodermareesei Rut C30 cultivates for 28 ℃ and promptly obtained Trichodermareesei Rut C30 seed liquor in 4 days in seed culture medium.Seed culture medium is that 5% wheat is poor, 0.5% glucose, and 0.8% ammonium sulfate, pH 6.2.
At last, the inoculum size with 10% is inoculated in above-mentioned Trichodermareesei seed liquor in the solid-state fermentation reactor, and leavening temperature is 30 ℃, ferments 7 days, makes the stalk mixture of Biological Pretreatment.
(2) fermentative processing makes hydrogen
The stalk mixture and the untreated stalk mixture of Biological Pretreatment in the above-mentioned steps (1) are pressed the 1:7 mixed, produce hydrogen mud with high temperature then and join in the product hydrogen reactor, carry out anaerobically fermenting after stirring, leavening temperature is 55 ℃, fermentation time is 72 hours, makes hydrogen.Adopt conventional draining water gathering of gas law to collect prepared hydrogen, adopt conventional gas chromatographic analysis hydrogen composition.
In the described stalk mixture, the blending ratio of straw, wheat stalk, maize straw, broomcorn straw, green grass stalk is 1:3:1:3:2.
It is identical with embodiment 2 with consumption that described high temperature produces the source of hydrogen mud.
Produce the hydrogen sludge fermentation with untreated stalk mixture of direct employing and high temperature and compare, adopting as mentioned above, the stalk mixture hydrogen yield of Biological Pretreatment improves 105%.
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 (9)
1. method of using the Biological Pretreatment stalk fermentation to prepare hydrogen, it is characterized in that, described method adopts wood mould, preferred Trichodermareesei, after more preferably Trichodermareesei Rut C30 carries out Biological Pretreatment to stalk, the stalk of Biological Pretreatment is mixed with untreated stalk, carry out fermenting process of preparing hydrogen with producing hydrogen mud then.
2. method according to claim 1 is characterized in that described method comprises the steps:
(1) Biological Pretreatment
In solid-state fermentation reactor, stalk is mixed with nutrient salt solution, add the mould Biological Pretreatment of carrying out of wood;
(2) fermentation makes hydrogen
The stalk and the untreated stalk of Biological Pretreatment in the step (1) are mixed in proportion, join in the product hydrogen reactor with producing hydrogen mud then, carry out anaerobically fermenting after stirring, make hydrogen.
3. method according to claim 1 and 2 is characterized in that, the temperature of described Biological Pretreatment is 25-32 ℃, and the time is 4-8 days.
4. according to each described method in the claim 1 to 3, it is characterized in that the stalk of described Biological Pretreatment and the blending ratio of untreated stalk are 1:1-9.
5. according to each described method in the claim 1 to 4, it is characterized in that the fermentation time of described hydrogen is 24-96 hour.
6. according to each described method in the claim 1 to 5, it is characterized in that described product hydrogen mud is that middle temperature is produced hydrogen mud, described leavening temperature is 35 ℃; Perhaps described product hydrogen mud is that high temperature produces hydrogen mud, and described leavening temperature is 50-58 ℃.
7. according to each described method in the claim 1 to 6, it is characterized in that described stalk is selected from one or several in broomcorn straw, wheat stalk, straw, maize straw and other straw.
8. method according to claim 2 is characterized in that, described nutrient salt solution comprises 1.6% ammonium sulfate, 0.6% magnesium sulfate heptahydrate and 0.3% potassium primary phosphate.
9. according to each described method in the claim 1 to 9, it is characterized in that described method also comprises the hydrogen that adopts the draining water gathering of gas law collection to make.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174584A (en) * | 2011-01-28 | 2011-09-07 | 华南理工大学 | Combined biological hydrogen production method by adopting sludge and fibers of recovered waste paper |
| CN102031276B (en) * | 2009-09-28 | 2012-11-14 | 中国科学院过程工程研究所 | Method for producing hydrogen by fermenting organism and alkali mat composite pretreated straw fiber raw erial at two steps |
| CN104531766A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院成都生物研究所 | Method and device for generating hydrogen by virtue of micro oxygen fermentation of straws |
| CN105803002A (en) * | 2016-05-16 | 2016-07-27 | 南京林业大学 | Method for preparing hydrogen by virtue of xylose |
| CN107012195A (en) * | 2017-06-12 | 2017-08-04 | 北京中农富源生物工程技术有限公司 | A kind of method using agricultural crop straw as fermenting raw materials hydrogen manufacturing |
| CN109028123A (en) * | 2018-07-10 | 2018-12-18 | 哈尔滨锅炉厂有限责任公司 | Coal dust-biomass boiler steam coupling transformation method |
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2007
- 2007-11-27 CN CN2007101781817A patent/CN101445810B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031276B (en) * | 2009-09-28 | 2012-11-14 | 中国科学院过程工程研究所 | Method for producing hydrogen by fermenting organism and alkali mat composite pretreated straw fiber raw erial at two steps |
| CN102174584A (en) * | 2011-01-28 | 2011-09-07 | 华南理工大学 | Combined biological hydrogen production method by adopting sludge and fibers of recovered waste paper |
| CN104531766A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院成都生物研究所 | Method and device for generating hydrogen by virtue of micro oxygen fermentation of straws |
| CN104531766B (en) * | 2014-12-16 | 2018-10-12 | 中国科学院成都生物研究所 | A kind of method and device of stalk micro-aerobe fermentation production hydrogen |
| CN105803002A (en) * | 2016-05-16 | 2016-07-27 | 南京林业大学 | Method for preparing hydrogen by virtue of xylose |
| CN105803002B (en) * | 2016-05-16 | 2019-06-21 | 南京林业大学 | A method of hydrogen is prepared using xylose |
| CN107012195A (en) * | 2017-06-12 | 2017-08-04 | 北京中农富源生物工程技术有限公司 | A kind of method using agricultural crop straw as fermenting raw materials hydrogen manufacturing |
| CN107012195B (en) * | 2017-06-12 | 2022-07-12 | 北京中农富源生物工程技术有限公司 | Method for producing hydrogen by fermenting crop straws as raw materials |
| CN109028123A (en) * | 2018-07-10 | 2018-12-18 | 哈尔滨锅炉厂有限责任公司 | Coal dust-biomass boiler steam coupling transformation method |
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