CN101109014A - Method for producing hydrogen by dark-light zymolysis couple - Google Patents
Method for producing hydrogen by dark-light zymolysis couple Download PDFInfo
- Publication number
- CN101109014A CN101109014A CNA2006100291553A CN200610029155A CN101109014A CN 101109014 A CN101109014 A CN 101109014A CN A2006100291553 A CNA2006100291553 A CN A2006100291553A CN 200610029155 A CN200610029155 A CN 200610029155A CN 101109014 A CN101109014 A CN 101109014A
- Authority
- CN
- China
- Prior art keywords
- fermentation
- hydrogen
- dark
- light
- fermented liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides a method for producing hydrogen by fermentation, in particular to a waste biomass clean and turning into hydrogen energy technology. The invention comprises the following steps: firstly taking the carbon-contained organic waste as the fermentation substrate, the pretreated mixture bacteria of natural livestock manure is dark fermented to get the fermentation liquid of hydrogen and organic acid. Then the photosynthetic bacteria are applied to anaerobicly ferment the fermentation liquid gotten from the above step to produce hydrogen. The invention has advantages of quick hydrogen production, high substrate conversion efficiency, low hydrogen producing cost and standard fermentation liquid emission.
Description
Technical field
The invention belongs to the bioenergy technical field.Be specifically related to utilize natural microbial group as the hydrogenogens source, with the carbon containing organic waste, especially abandoned biomass such as rubbish from cooking and ethanol fermentation waste water is a raw material, produces the clean preparation method of hydrogen by dark fermentation and light fermentation coupling.
Background technology
At present very limited as the reserves of the fossil oil (oil, Sweet natural gas and coal) of global economy artery, and the use of fossil energy is the major cause of environmental pollution and Greenhouse effect.The exploitation renewable and clean energy resource is imperative.
Hydrogen is compared with traditional energy, has energy density height (for 3 times of gasoline), thermal conductivity height, thermal transition efficient height, carries low cost and other advantages, can adopt the form of gas, liquid, solid or compound to store and transportation.Hydrogen only generates water as a kind of clean energy in combustion processes, do not produce greenhouse gases and other pollutents; And hydrogen or aerospace, the ideal fuels of electriclocomotive, modern city public transport.
The preparation of hydrogen at present mainly be adopt that hydrocarbon steam heavily steams, traditional hydrogen production process such as the electrolysis of the gasification of biomass and water or photoelectrolysis under the high temperature, wherein 96% hydrogen still is directed to fossil energy.These methods can't fundamentally be broken away from the dependence to fossil energy in hydrogen production process, also can't avoid the harm to environment.At occurring in nature, many microorganisms can be in its metabolic process be converted into hydrogen with the hydrogen proton of carbohydrate in the various biomass, this metabolic characteristic with microorganism is the bio-hydrogen production technology that the basis forms, have advantages such as normal temperature, normal pressure, energy consumption are low, environmental protection, will become the main stream approach of producing hydrogen future.
How reducing product hydrogen cost is the biological important topic that the hydrogen technology faces of producing.With the abandoned biomass is that raw material carries out biology product hydrogen, is not only and reduces biological important channel of producing the hydrogen cost, also significant to the development of environment protection and recycling economy.Dark anaerobically fermenting (dark fermentation) produces the hydrogen approach, is inoculum with natural mixed bacterial particularly, have hydrogen-producing speed fast, aspect technological design advantage such as fairly simple, receive much attention utilizing abandoned biomass to produce in the research of hydrogen.For example utilize the dark fermentation and hydrogen production of potato source mill waste water (Steven WVan, Sang-Eun Oh, Bruce E.Logan.Biohydrogen gas production from foodprocessing and domestic wastewaters.Int J Hydrogen energy30 (2005)), the distillery vinasse produce hydrogen (Yao-Ting Fan, and the dark fermentation and hydrogen production of abandoned biomass such as carbohydrate in the citric acid production wastewater and urban solid garbage Gao-sheng Zhang et al.Biohydrogen-productionfrom beer lees biomass by cow dung compost.Biomass and Bioenergy30 (2006)).These dark fermentation and hydrogen production results show, because the dark fermentation and hydrogen production process of biomass except producing hydrogen and carbonic acid gas, has also generated a large amount of organic acids based on acetate and butyric acid.Therefore, it is low only to adopt dark fermentation to make abandoned biomass be converted into the efficient Hen of hydrogen, produces hydrogen 140mlH as Steven W Van report potato factory waste water
2/ g-COD; Sang-Hyoum Kim report domestic refuse is produced hydrogen 122.9ml H
2If a large amount of organic acids are not employed in these dark fermented liquids of/g-COD., not only can cause the waste of resource, and can bring serious environmental to pollute.
Photosynthetic bacterium can high-level efficiency utilize low molecular organic acids, and they thoroughly are degraded to hydrogen and carbonic acid gas.Secretly-the light coupling produces hydrogen and not only can increase substantially the transformation efficiency of substrate to Hydrogen Energy, can also reduce the COD in the fermented liquid, reaches the cleaning emission standard.
In order to solve low, the hydrogen manufacturing cost height of the existing substrate conversion efficiency of existing dark fermentation and hydrogen production method, problems such as the organic acid that dark fermentation produces can not be utilized, environmental pollution, this area also needs the technology and the technology that provide new.
Summary of the invention
The purpose of this invention is to provide a kind of high-level efficiency utilizes the carbon containing organic waste to carry out the process for cleanly preparing and the technology of biological hydrogen production for substrate.
For achieving the above object, the invention provides a kind of dark-light fermentation coupling produces the method for hydrogen, this method may further comprise the steps:
(a) be fermentation substrate with the carbon containing organic waste, use mixed bacterial to carry out the dark fermentation, produce hydrogen and contain the organic acid fermented liquid through the natural compost of pretreated animal manure;
(b) with photosynthetic bacterium the organic acid fermented liquid that step (a) is produced is carried out the light anaerobically fermenting, produce hydrogen.
In a preferable embodiment, described pre-treatment is that boiling of the natural compost of animal manure handled 1-60 minute, is more preferred from 10-30 minute.
In another preferable embodiment, described animal manure is a cow dung.
In another preferable embodiment, described photosynthetic bacterium is selected from red bacterium of class ball or the red bacterium of pod membrane.
In a preferable embodiment, described carbon containing organic waste is selected from rubbish from cooking or fermentation organic waste water.In another preferable embodiment, described fermentation organic waste water is selected from citric acid fermentation waste liquid, ethanol fermentation.
In one embodiment, step (a) comprises the steps: and will be inoculated into by 10-150g/L through pretreated animal manure compost in described rubbish from cooking or the described fermentation organic waste water, under 30-40 ℃, normal pressure, carry out the dark fermentation, the pH value of fermented liquid is regulated and control to 3.0-7.5, and producing the whole process of hydrogen is 2-3 days.In embodiment preferred more, step (a) comprises the steps: the cow dung through pretreated natural compost is inoculated into by 60-80g/l in described rubbish from cooking or the described fermentation organic waste water, under 36-39 ℃, normal pressure, carry out the dark fermentation, the pH value of fermented liquid is regulated and control to 5.0-7.5, producing the whole process duration of hydrogen is 2-3 days, and stirring velocity is 100-500rpm/min.
In another embodiment, step (b) comprises the steps: photosynthetic bacterium to be inoculated in the fermented liquid of step (a) by the inoculum size of 2-8%, carries out the light fermentation and hydrogen production under 25-33 ℃, normal pressure, pH6.5-7.5, light intensity 2000-5000lux.In embodiment preferred more, step (b) comprises the steps: photosynthetic bacterium to be inoculated in the fermented liquid of step (a) by the inoculum size of 2-8%, anaerobically fermenting under 25-33 ℃, normal pressure, pH6.5-7.2, light intensity 2000-5000lux.
In another preferable embodiment, the starting point concentration of described rubbish from cooking is 10-40g/l-TS, 15-60g/l-COD, 10-30g/l-TOC.
In another preferable embodiment, the COD of described fermentation organic waste water is 10-70g/L.
In another preferable embodiment, in step (b), the light hydrogen production through anaerobic fermentation time length is 3-7 days.
The present invention compares with the dark fermentation and hydrogen production method of simple utilization, has the following advantages:
At first, the present invention gets up dark fermentation and light anaerobic fermentation of biological hydrogen manufacturing coupling, and this method hydrogen-producing speed is fast, substrate conversion efficiency is high, the hydrogen manufacturing cost is low.
Second, secretly-fermented liquid behind the light coupling fermentation and hydrogen production in, detect the only remaining butyric acid of residue organic acid, its remaining concentration very low (less than 1mM (0.008%)), the hidden danger of enriching the organic acid contaminate environment of having avoided dark fermentation to produce can realize utilizing the waste biomass clean to produce the purpose of hydrogen, after the thalline comprehensive utilization, fermented liquid reaches the cleaning emission standard, and this turns waste into wealth to sewage disposal and has played huge pushing effect.
The 3rd, the present invention's (as cow dung) mixing microorganisms by utilizing the natural compost of pretreated animal manure is as inoculum, thereby makes the product hydrogen total amount and the speed of dark fermentation that further raising arranged.
The 4th, method of the present invention is supplied with thalli growth and is changed into hydrogen for carbon source with abandoned biomass (as the rubbish from cooking in dining room, Maize Production alcoholic acid fermentation waste water etc.), thereby has reduced the cost of this method, has realized the recycling economy that turns waste into wealth.
Specific embodiments
Particularly, the invention provides a kind of the fermentation and produce the method for hydrogen, this method may further comprise the steps:
(a) be fermentation substrate with the carbon containing organic waste, use animal manure mixed bacterial to carry out the dark fermentation, produce hydrogen and contain the organic acid fermented liquid through pretreated natural compost;
(b) with photosynthetic bacterium step (a) gained is contained the organic acid fermented liquid and carry out the light anaerobically fermenting, produce hydrogen.
The present invention is that a kind of dark fermentation produces hydrogen and thereby the light anaerobically fermenting produces the method that the hydrogen coupling gets up to realize goal of the invention, particularly, is with the product of the dark fermenting process fermentation substrate as the light anaerobic fermentation process.
In dark fermenting process of the present invention (be step (a), be also referred to as " dark fermentation "), adopted the carbon containing organic waste as fermentation substrate.
The term that this specification sheets uses in the whole text " organic waste " have those skilled in the art the common implication of approval, it generally includes, but is not limited to: the food-processing waste residue; Rubbish from cooking or tankage; Farmland and orchard residue are as stalk, stubble, weeds, fallen leaves, fruit shell, tendril, branch and other agroforestry forest farm refuse particularly; Agriculture and forestry product processing fent, forest and sheet material scrap stock and wood sawdust etc.; Livestock, poultry and human excrement; Mud etc.Term " carbon containing " means and contains the available carbon source of microbial fermentation in the described organic waste, as carbohydrate such as carbohydrate, starch, Mierocrystalline celluloses." the carbon containing organic waste " that is applicable to the inventive method should contain a large amount of carbohydrate or main ingredient is a carbohydrate, preferred rubbish from cooking or fermentation organic waste water.
The term that this specification sheets uses in the whole text " rubbish from cooking " or " kitchen remaining years rubbish alive " can exchange, they have those skilled in the art the common implication of approval, specifically be meant in the course of processing of kitchen the just mixture of remaining rice, wheaten food, vegetables, various meat, grease, bone the like waste after the meal of food and drink places such as depleted mixture and dining room, dining room, restaurant, hotel.In a preferable embodiment, should be before being used for the inventive method with conventional means such as stirrer, pulverizer or device with described kitchen surplus (life) rubbish with the broken mixing of pigment, make fermented liquid.
The term that this specification sheets uses in the whole text " fermentation organic waste water (waste liquid) " has those skilled in the art institute implication of approval usually, specifically be meant with fermentation form produce produced in the process of various organic productss (specifically as ethanol, citric acid etc.) be rich in organic waste liquid or waste water.From convenient sources and abundance and the little equal angles consideration of waste liquid composition fluctuation, should adopt the waste liquid that produces from behind the industrial large scale fermentation, produce the waste liquid of citric acid generation, waste liquid that industrial fermentation production ethanol produces or the like as industrial fermentation.Yet, those skilled in the art also can understand after the technical scheme of having read the present invention's instruction fully, can also adopt the fermentation organic liquid waste in other sources, for example from waste liquid that laboratory ferment produced etc., they are also included within the scope of term of the present invention " fermentation organic waste water (waste liquid) ".
Generally speaking, be applicable to that the raw material of dark fermenting process of the present invention should contain a large amount of carbon source (as carbohydrate such as carbohydrate or starch), what have may also contain some nitrogenous sources.For the hydrogen generation efficiency that makes dark fermentation further improves, those skilled in the art can also add other suitable carbon sources, nitrogenous source and other nutrition source therein according to technique known.For example, carbon source can be starch, dextrin, glycerine, glucose, sucrose, inositol, N.F,USP MANNITOL etc.Nitrogenous source can be peptone, soyflour, meat extract, rice sugar, wheat skin, yeast powder, corn steep liquor and other organic or inorganic nitrogenous compound.In addition, also can suitably add some inorganic salts in the substratum, as metal-salts such as sodium-chlor, phosphoric acid salt such as dipotassium hydrogen phosphate and potassium primary phosphate, manganous sulfate, sal epsom, lime carbonate.
In an exemplary embodiment, can in rubbish from cooking or fermentation organic waste water, add: KH
2PO
41.5g/L, Na
2HPO
412H
2O 4.2g/L, L-glutamic acid 1g/L, yeast extract 2g/L, MgCL
20.18g/L, FeSO
40.1g/L, transfer its pH3.0-7.5.Those skilled in the art can carry out suitable adjusting to material and the content thereof that is added in the fermentation substrate.In a preferred embodiment, the concentration that is used for the fermented liquid of dark fermentation should be controlled in the following scope: 10-40g/l-TS (waste dry weight), 15-60g/l-COD (chemical oxygen demand (COD)), 10-30g/L-TOC (total organic carbon), total nitrogen 0.5-1.5g/L, total phosphorus 100-500mg/L, NH4
+60-120mg/L.The pH of fermented liquid should be adjusted in the 3.0-7.5 scope.Certainly, if the organic content in the used fermentation substrate (as wastewater from fermentation industry) is too high, then also can carry out suitable dilution to it.
In the process of dark fermentation, the present invention has adopted the animal manure of the pretreated natural compost of process as the flora that produces hydrogen.The term that this specification sheets uses in the whole text " animal manure (compost) ", " animal manure of natural compost " have the implication that those skilled in the art know and approve, it specifically is meant the fertile mixture of dunghill of livestocks such as ox, horse, sheep.In an exemplary embodiment, adopted the cow dung of natural compost (promptly piling up under the state of nature) in the open.In order to improve efficient and the speed that dark fermentation and hydrogen production produces acid, need before the dark fermentation, carry out pre-treatment by the animal manure to used natural compost, so that remove or kill the suction hydrogen bacterium (as methanobacteria) of non-spore state, and stay the product hydrogen acid-producing bacteria group of spore state.Preferred pretreating scheme is that the animal manure with natural compost boils 1-60 minute (preferred 10-30 minute) under 100 ℃.Then, the animal manure with the pretreated natural compost of described process is inoculated in the fermented liquid of aforesaid preparation in advance.Inoculum size can be carried out suitable adjusting or selection as the case may be by those skilled in the art, and it is usually in the 10-150g/L scope, preferably at 60-80g/L.
Dark fermentation can be carried out according to the routine techniques in this area, for example in the dark down fermentation of normal temperature (temperature range is 30-40 ℃, is preferably 37 ℃) normal pressure, mixing speed is 100-500rpm/min (as 300rpm/min), fermented liquid pH is controlled at about 3.0-7.5 all the time, is preferably 5.0-7.5.After 7-8 hour, just begin to receive hydrogen in the fermentation beginning, the waterpower time length of whole product hydrogen process is 2-3 days, for example about 50 hours.Dark fermentation has also produced low-molecular-weight organic acid (mainly be the organic acid that 1-6 carbon atom arranged, for example acetate, propionic acid, butyric acid, valeric acid, isopropylformic acid etc.) when producing hydrogen.
Then, dark is fermented secondary fermentation liquid is transferred in other containers or is carried out light anaerobically fermenting (or abbreviate as in the text " light fermentation ") in position.Before carrying out the light anaerobically fermenting, may need it suitably to be diluted according to organic acid concentration, so that being in the best of used photosynthetic bacterium, its organic acid concentration produces hydrogen concentration.Concrete Dilution ratio can be determined according to concrete photosynthetic bacterium by those skilled in the art.
In addition, before carrying out the light anaerobically fermenting, can also randomly carry out pre-treatment or allotment to the fermented liquid after the dark fermentation.For example, can be in fermented liquid the required nutritive element of some photosynthetic bacterium growths of restock.In an exemplary embodiment, (every liter of basic saline solution consists of MgSO can to replenish basic saline solution 40-60ml in every liter of fermented liquid
47H
2O 4g, CaCl
22H
2O 1.5g, FeSO
47H
2O 0.236g, Na
2EDTA 0.4g, liquid microelement 20ml), vitamin H liquid 1-2ml, phosphoric acid buffer 7.5ml, L-glutamic acid 1g regulates fermented liquid pH then to 6.5-7.2.Yet should be appreciated that such adjusting and replenishing is that those skilled in the art just can realize according to routine techniques and suitable experiment, and scope of the present invention is not limited to these specific substratum compositions or replenishes liquid and form.
Photosynthetic bacterium can thoroughly be degraded to hydrogen and carbonic acid gas with low molecular organic acids (organic acid that 1-6 carbon atom arranged).Can be used for photosynthetic bacterium of the present invention and include, but are not limited to the red bacterium of class ball, the red bacterium of pod membrane.Yet those skilled in the art can recognize that the present invention can also adopt other can utilize organic acid to carry out the purple nonsulfur bacteria of light fermentation and hydrogen production.They can be used for smooth anaerobically fermenting step of the present invention alone or in combination.
Before carrying out light anaerobically fermenting step, can earlier photosynthetic bacterium in the dark be cultivated in suitable medium in advance.This substratum can carry out appropriate selection and allotment according to concrete used photosynthetic bacterium kind by those skilled in the art.In an exemplary embodiment, used substratum contains 30mM oxysuccinic acid and 7mM L-glutamic acid.Pre-incubated temperature is about 25-33 ℃, and mixing speed is 200rpm/ minute, cultivates 20-28 hour under dark.Then, with the thalline inoculation liquid of this photosynthetic bacterium nutrient solution, be inoculated in the fermented liquid with the inoculum size of 2-10% as the light hydrogen production through anaerobic fermentation.In a preferred embodiment, the OD value of described photosynthetic bacterium is about 1.7-2.2, is more preferred from about 1.9.
The light hydrogen production through anaerobic fermentation can carry out according to the routine techniques in this area, the product hydrogen condition is that (temperature is about 25-33 ℃ to normal temperature, preferred 30 ℃), normal pressure, pH be controlled at 6.8-7.2 (preferred 7.0), light intensity is 2000-5000lux (being preferably 4000lux), hydraulic detention time is about 3-7 days.
After the light anaerobically fermenting finished, available ordinary method detected the content of the residue organic acid (as acetate, butyric acid etc.) in the fermented liquid.Because characteristics of the present invention are to make the organic acid concentration in the fermented liquid behind the light anaerobically fermenting reach direct emission standards, therefore also can be in the process of light anaerobically fermenting, constantly regulate by organic acid is carried out sampling analysis, form and culture condition to determine the suitableeest fermented liquid.In an embodiment preferred of the present invention, butyro-content is lower than 1mM, so this fermented liquid can directly discharge.
Of the present invention dark-the following feature that has that hydrogen is produced in light fermentation coupling:
(1) the dark mixed bacterial hydrogen-producing speed of the first step is very fast, can reach 679ml H
2/ l.h, and start the product hydrogen time for inoculating 7-8 hour just quick hydrogen, the H of producing in back
2Content accounts for mixed gas (CO
2And H
2) 60-70%, abundant acetate is arranged simultaneously, propionic acid, butyric acid, valeric acid, generations such as isopropylformic acid;
(2) second steps are during the light hydrogen production through anaerobic fermentation, and photosynthetic bacterium can efficiently change into the organic acid that the first step produces highly purified hydrogen (hydrogen content is 90-99%) and CO on a small quantity
2Dark-light fermentation coupling method like this produces hydrogen, lives with the kitchen remaining years that to produce hydrogen be example to rubbish, when rubbish from cooking fermented liquid starting point concentration is 30g/l-TS, can realize that every gram dry weight rubbish from cooking produces hydrogen and be up to 550ml (550ml H
2/ g-TS is equivalent to 304ml H
2/ g-COD), this utilizes the dark fermentation and hydrogen production report of solid waste (140-190ml H with present other investigators
2/ g-TS is equivalent to 110-140mlH
2/ g-COD) to compare, hydrogen output has increased about 250%, can realize simultaneously the fermented liquid behind the light hydrogen production through anaerobic fermentation is reached the cleaning discharging.Dark-light fermentation and hydrogen production technology like this can not only efficiently change into clean energy-Hydrogen Energy to abandoned biomass in domestic refuse and the fermentation organic waste water, and can eliminate the environmental pollution that organic acid brings in the waste water.
By the following examples content of the present invention is illustrated in further detail.
Embodiment one: with dining room rubbish from cooking biological hydrogen production
1, hydrogenogens group's pre-treatment: get the cow dung that natural compost is crossed, boil 15min at 100 ℃.
2, the configuration of the dark fermented liquid of dining room rubbish from cooking: directly fetch kitchen remaining years rubbish (mainly being the mixture that rice, green vegetables, pericarp and various meat and bone etc. are discarded by the dining room) alive from students' dining hall, survey its water content and be approximately 65%-70%, directly rubbish from cooking is added water then and blend mixing with stirrer.In the rubbish from cooking of mixing, add some nutritive elements: KH again
2PO
41.5g/L, Na
2HPO
412H
2O 4.2g/L, L-glutamic acid 1g/L, yeast extract 2g/L, MgCl
20.18g/L, FeSO
40.1g/L, transfer its pH 6.0.Survey the concentration of its kitchen remaining years that prepare garbage fermentation liquid alive, 30g/L-TS, 54.2g/L-COD, 25.2g/L-TOC, total nitrogen 1.04g/L, total phosphorus 200mg/L, NH4
+98.4mg/L COD: N: P is 260: 5: 1.
3, in the rubbish from cooking fermented liquid that configures, directly add the good natural cow dung of pre-treatment (adding 60g cow dung) by every liter of fermented liquid, carry out the dark fermentation.Whole dark fermenting process carries out in a volume is the glass reactor of 250ml (fermentating liquid volume is 150ml), and temperature is controlled in the 36-39 ℃ of scope, leaves standstill, and dark fermentation and hydrogen production produces acid under the normal pressure.
4, produce the process that hydrogen produces acid: behind fermentation beginning 7-8h, just begin to receive hydrogen, whole product hydrogen process is 50h, and maximum hydrogen-producing speed is 660ml/L.h, and hydrogen content is the 40%-68% of mixed gas.Every gram dry weight rubbish from cooking is produced hydrogen 213ml hydrogen (213mlH
2/ g-TS is equivalent to about 120mlH
2/ g-COD), every liter of such fermented liquid produces pure hydrogen 6.39L at dark fermenting process, produces main organic acid acetate and butyric acid simultaneously and is respectively 3.57g/L and 10.65g/L.
5. photosynthetic bacterium utilizes the fermented liquid after secretly fermenting to carry out the light hydrogen production through anaerobic fermentation
Dark fermented liquid is suitably diluted, and making its organic acid concentration is that the red bacterium of photosynthetic bacterium class ball (DSM158 is available from German bacterial classification database (http://www.dsmz.de)) utilizes the best hydrogen concentration acetate that produces of organic acid to be 35mM, and butyric acid is 50mM.The required nutritive element of some photosynthetic bacterium growths of restock in the good fermented liquid of dilution: (the basic salt of 1L is formed MgSO to replenish basic saline solution 50ml in the 1L fermented liquid
47H
2O 4g, CaCl
22H
2O1.5g, FeSO
4.7H
2O 0.236g, Na
2EDTA 0.4g, liquid microelement 20ml), vitamin H liquid 1ml, phosphoric acid buffer 7.5ml, L-glutamic acid 1g transfers fermented liquid pH to 7.0 then, distinguish packing 37ml fermented liquid again in the glass test tube of 38ml, add the cultured in advance photosynthetic bacteria liquid of 1ml again, at light intensity 4000lux, light hydrogen production through anaerobic fermentation under the condition that temperature is 30 ℃.Producing the hydrogen time length is about 7d, and the fermented liquid behind every liter of undiluted dark fermentation and hydrogen production can produce the pure hydrogen of 10.1L in the light anaerobically fermenting.After the light hydrogen production through anaerobic fermentation finishes, detect residue organic acid in the fermented liquid and be butyric acid and be less than 1mM (promptly 0.008%).
Secretly-and the light fermentation and hydrogen production integrates: the high energy of every gram dry weight rubbish from cooking changes into 550mlH
2/ g-TS, dark fermentation and hydrogen production top speed reaches 660mlH
2/ L.h, light anaerobically fermenting top speed in the 38ml reactor reaches 95ml H
2/ Lh.And behind the light hydrogen production through anaerobic fermentation, detecting the residue organic acid content is 0.008%, and after the thalline comprehensive utilization, fermented liquid is qualified discharge directly, does not bring environmental pollution.
The amplification that the surplus rubbish of embodiment second cook produces the H-H reaction volume
The moiety of mixed living flora of the cow dung that pre-treatment is good and the dark fermentation of domestic refuse and concentration thereof and embodiment one are identical, just fermentation reactor is enlarged and in the glass reactor of 5L, carry out, fermentating liquid volume is 3.5L, mixing speed is 450rpm/min, temperature is controlled in the 36-39 ℃ of scope, dark fermentation and hydrogen production under the normal pressure.
Inoculation back 7-8h begins to produce hydrogen.After beginning to produce hydrogen 15min, hydrogen content just accounts for more than 50% of mixed gas (H2 and CO2), and the highest accounting for mixed gas 65%, and when producing the hydrogen end, hydrogen content is not lower than 50%.Maximum hydrogen-producing speed is 679ml/Lh, the waterpower time length of whole product hydrogen process is 40h, when producing hydrogen, produced lot of organic acids, be respectively acetate, butyric acid, propionic acid and valeric acid, be respectively 4.54g/L, 5.38g/L, the every gram dry weight of 0.72g/L, 0.068g/L. rubbish from cooking product hydrogen 132ml (132mlH
2/ g-TS), every liter of so dark fermented liquid produces the about 4L of pure hydrogen.
After the suitable dilution of the fermented liquid behind the dark fermentation and hydrogen production of the first step, such according to embodiment one, replenish required trace element and the nitrogenous source of photosynthetic bacterium, and transfer pH to 7.0, the red bacterium DSM158 of the cultured in advance photosynthetic bacterium class ball bacterium liquid (glass reactor of 6L) in the light anaerobic fermentation tank of inoculation 5%, mixing speed 400rmp/min, all the other light anaerobically fermenting conditions are identical with embodiment one.Begin to produce hydrogen behind photosynthetic bacterium inoculation 5h, hydrogen content accounts for mixed gas (CO
2And H
2) more than 90%, through absorbing CO
2After device was handled, the time length that hydrogen purity reaches 99.99%. overall optical hydrogen production through anaerobic fermentation process was 5 days, calculated by the dark fermented liquid behind the dark fermentation and hydrogen production before the dilution, and in the light anaerobic fermentation process, every liter of dark fermented liquid produces hydrogen 8.12L.Residue organic acid butyric acid contains about 0.01% in the fermented liquid after detection light anaerobically fermenting finishes, and all the other organic acids are converted into hydrogen and tropina fully.
Secretly comprehensive-light coupling fermentation extended volume (3.5L) is produced hydrogen, and every gram dry weight rubbish from cooking changes into hydrogen 400ml H
2/ g-TS, the highest hydrogen-producing speed of dark fermentation reaches 679ml H
2/ Lh, in 6L light anaerobic fermentation reactor, light hydrogen production through anaerobic fermentation top speed reaches 40ml H
2/ Lh, after the thalline comprehensive utilization, fermented liquid can qualified discharge.Although behind dark-light fermentation coupling expansion fermentation and hydrogen production volume, the amount that every gram waste changes into hydrogen reduces to some extent than the small volume fermentation and hydrogen production of embodiment one that (this is main because the light fermentation reactor after enlarging haves much room for improvement in design, in order to avoid that the photosynthetic bacterium of fermentor tank inside is accepted illumination is inadequate, make nitrogenase catalysis produce hydrogen and lack energy, causing producing hydrogen stops too early, organic acid utilization is not thorough), but only adopt dark fermentation method that waste is changed into hydrogen (110-140ml H with other investigators
2/ g-COD is equivalent to 140-190mlH
2/ g-TS) compare, not only improved waste greatly and changed into the utilising efficiency of hydrogen (waste of the present invention changes into hydrogen and is up to 304ml H
2/ g-COD is equivalent to 550ml H
2/ g-TS), and after dark-light fermentation, the residue organic acid in the fermented liquid mostly is about 0.01% most, again after the thalline comprehensive utilization, and direct qualified discharge, the environment protection treating that helps sewage to turn waste into wealth.
The rubbish from cooking biological hydrogen production of embodiment three different starting point concentrations
The moiety that the good cow dung of pre-treatment is mixed living flora and the dark fermentation of domestic refuse and embodiment one, example two are identical, are that starting point concentration with the dark fermented liquid of rubbish from cooking changes 18g/l-TS into, 35.6g/l-COD, 20g/l-TOC, total nitrogen 0.92g/L, total phosphorus 0.45g/L, NH4
+98.1mg/L, and initial pH value is adjusted to 6.0, carries out in the glass reactor (fermentating liquid volume 180ml) of 250ml, all the other dark fermentation and hydrogen production conditions are identical with example one, two.Every batch of dark fermentation and hydrogen production time length is about 3 days, produces the hydrogen top speed and reaches 640mlH
2/ Lh, hydrogen content are up to (hydrogen and the carbonic acid gas) 68% that mixes gas content, and every gram dry weight rubbish from cooking is produced hydrogen 182ml hydrogen (182mlH
2/ g-TS), producing organic acid simultaneously and be mainly acetate and butyric acid, it is respectively 3.79g/L, butyric acid 4.98g/L.Its dark fermented liquid suitably is diluted to photosynthetic bacterium DSM158 utilizes acetate and butyro-optimum concn, and it is described to press embodiment one, replenish the required nutritive element of photosynthetic bacterium, adjust pH is 7.0, carries out the light fermentation and hydrogen production according to example one described smooth fermentation condition then.The whole process duration of light fermentation and hydrogen production is about 7 days, and the highest hydrogen-producing speed is 110ml/L.h, and the fermented liquid behind every liter of undiluted dark fermentation and hydrogen production produces hydrogen (the 8.12L H of 8.12L in the light fermentation and hydrogen production
2/ L), survey its light fermentation ends secondary fermentation liquid, only detect 0.008% butyric acid residue, after the thalline comprehensive utilization, fermented liquid is qualified discharge directly.
Secretly comprehensive-coupling of light fermentation and hydrogen production, producing the hydrogen result is 633mlH
2/ g-TS, 320 mlH
2/ g-COD has improved about 4 times than the dark fermentation and hydrogen production of independent use rubbish from cooking, and simultaneously last light fermentation waste water can qualified discharge.
The rubbish from cooking biological hydrogen production of embodiment four different initial pH value
Moiety that the cow dung that pre-treatment is good is mixed living flora and the rubbish from cooking of living is secretly fermented and concentration thereof and embodiment three are identical, the initial pH value of the dark fermented liquid of rubbish from cooking of just will living is adjusted to 3.5, and remaining dark fermentation and light fermentation and hydrogen production processing condition and example three are identical.The result is dark fermentation and hydrogen production, and whole product hydrogen process has continued 3 days, and the efficient that waste is converted into hydrogen is 147 mlH
2/ g-TS, organic acid mainly are acetate and butyric acid, are respectively 2.70g/L, and 3.99g/L. carries out the light fermentation and hydrogen production with dark fermented liquid, and the fermented liquid after every liter of undiluted dark fermentation ends is at light fermentation and hydrogen production 6.70L (6.70LH
2/ L), the test light fermentation and hydrogen production finishes the organic acid in the secondary fermentation liquid, and the residue organic acid is a butyric acid, and the butyric acid residue that is less than 1mM (0.007%) is arranged, and after the thalline comprehensive utilization, fermented liquid is qualified discharge directly.Hydrogen is produced in secretly comprehensive-light fermentation coupling, and every gram dry weight rubbish from cooking is produced hydrogen 520 mlH
2/ g-TS has improved more than 3 times than separately dark fermentation and hydrogen production.Compare with example three, dark fermented liquid initial pH value is 3.5 to be 6.0 o'clock than pH value, and product hydrogen total amount and waste transformation efficiency have all reduced by 1.2 times.
Five days hats of embodiment group corn fermentation is produced alcohol waste water and is used for hydrogen manufacturing
After 3 times of corn fermentation alcoholic acid waste liquid (available from sky hat group) 60.9g/l-COD dilutions, produce the substrate of acid as dark fermentation and hydrogen production, be inoculum with the good cow dung mixed bacterial of embodiment one described pre-treatment again, embodiment one according to the dark fermentation and hydrogen production of life rubbish from cooking adds corresponding trace element and nitrogenous source, transfer pH6.0, temperature is controlled in 36-39 ℃, dark fermentation and hydrogen production under the normal pressure.The product hydrogen time length of 35h, every liter of dark fermented liquid produces hydrogen 800ml H
2, produce acetate 5.4g/L, produce butyric acid 1.0g/L.
Produce hydrogen with carrying out photosynthetic fermentation coupling after 3 times of its dark fermented liquid dilutions, the fermented liquid liquid behind every liter of dark fermentation and hydrogen production produces pure hydrogen 7.69L in the light anaerobic fermentation process, remain the organic acid butyric acid less than 1mM (0.007%).Secretly comprehensive-light fermentation and hydrogen production technology, every liter of such corn fermentation alcohol waste water can produce hydrogen 20.8L hydrogen.
In sum, the present invention meets the Energy policy and the Environmental policy of national sustainable development strategy, shows that the mankind might realize turning waste into wealth fully, produces clean energy, and progressively substitute petroleum products, have broad application prospects and significant economic benefits and social benefit.
Although the invention describes concrete example, having a bit is significantly to those skilled in the art, promptly can do various variations and change to the present invention under the premise without departing from the spirit and scope of the present invention.Therefore, claims have covered all these changes within the scope of the present invention.It is for referencial use that this paper is all included in all publications, patent and the patent application that this paper quotes in.
Claims (11)
1. one kind ferments and produces the method for hydrogen, it is characterized in that this method may further comprise the steps:
(a) be fermentation substrate with the carbon containing organic waste, use mixed bacterial to carry out the dark fermentation, produce hydrogen and organic acid fermented liquid through the natural compost of pretreated animal manure;
(b) with photosynthetic bacterium step (a) gained organic acid fermentation liquid is carried out the light anaerobically fermenting, produce hydrogen.
2. the method for claim 1 is characterized in that, described pre-treatment is the natural compost of animal manure to be boiled handled 1-60 minute.
3. the method for claim 1 is characterized in that, described animal manure is a cow dung.
4. the method for claim 1 is characterized in that, described photosynthetic bacterium is selected from red bacterium of class ball or the red bacterium of pod membrane.
5. the method for claim 1, described carbon containing organic waste are selected from rubbish from cooking or fermentation organic waste water.
6. method as claimed in claim 5 is characterized in that, described fermentation organic waste water is selected from citric acid fermentation waste liquid or ethanol fermentation waste liquid.
7. method as claimed in claim 5, it is characterized in that, step (a) comprises the steps: and will be inoculated into by 10-150g/L through pretreated animal manure compost in described rubbish from cooking or the described fermentation organic waste water, under 30-40 ℃, normal pressure, carry out the dark fermentation, the pH value of fermented liquid is regulated and control to 3.0-7.5, and producing the whole process of hydrogen is 2-3 days.
8. the method for claim 1, it is characterized in that, step (b) comprises the steps: photosynthetic bacterium to be inoculated in the fermented liquid of step (a) by the inoculum size of 2-8%, carries out the light fermentation and hydrogen production under 25-33 ℃, normal pressure, pH6.5-7.5, light intensity 2000-5000lux.
9. method as claimed in claim 5 is characterized in that, the starting point concentration of described rubbish from cooking is 10-40g/l-TS, 15-60g/l-COD, 10-30g/l-TOC, total nitrogen 0.5-1.5g/L, total phosphorus 100-500mg/L, NH4
+60-120mg/L.
10. method as claimed in claim 5 is characterized in that, the COD of described fermentation organic waste water is 10-70g/l.
11. the method for claim 1 is characterized in that, in step (b), the light hydrogen production through anaerobic fermentation time length is 3-7 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100291553A CN101109014A (en) | 2006-07-20 | 2006-07-20 | Method for producing hydrogen by dark-light zymolysis couple |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100291553A CN101109014A (en) | 2006-07-20 | 2006-07-20 | Method for producing hydrogen by dark-light zymolysis couple |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101109014A true CN101109014A (en) | 2008-01-23 |
Family
ID=39041272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100291553A Pending CN101109014A (en) | 2006-07-20 | 2006-07-20 | Method for producing hydrogen by dark-light zymolysis couple |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101109014A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766571A (en) * | 2012-07-04 | 2012-11-07 | 中国环境科学研究院 | Biohydrogen production method and device adopting hydrophyte and animal manure light-dark cascade coupling |
| CN103146568A (en) * | 2013-03-19 | 2013-06-12 | 哈尔滨工业大学 | Dark-l fermentation integrated biological hydrogen production device |
| CN103484364A (en) * | 2013-09-17 | 2014-01-01 | 国家纳米科学中心 | Nanometer device for solar biological hydrogen production |
| CN103923946A (en) * | 2014-04-11 | 2014-07-16 | 河南农业大学 | Tubular multi-line circular light and dark alternating biological hydrogen production method and device |
| CN104004791A (en) * | 2014-05-16 | 2014-08-27 | 浙江工商大学 | Coupled two-phase anaerobic kitchen garbage strengthening treatment method combining microbial electrolysis cell and microbial cell and device |
| CN109301287A (en) * | 2018-09-06 | 2019-02-01 | 北京铂陆氢能科技开发有限公司 | It is a kind of can hydrogen-preparing hydrogen-storing organic liquid hydrogen storage technology electricity generation system |
| CN113981010A (en) * | 2021-12-01 | 2022-01-28 | 日照市海洋与渔业研究所 | Method for producing hydrogen by culturing marine photosynthetic bacteria through light-dark fermentation coupling |
| WO2023087972A1 (en) * | 2021-11-19 | 2023-05-25 | 河南农业大学 | Biological hydrogen-alkane co-production fermentation system and method with negative carbon emission |
-
2006
- 2006-07-20 CN CNA2006100291553A patent/CN101109014A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766571A (en) * | 2012-07-04 | 2012-11-07 | 中国环境科学研究院 | Biohydrogen production method and device adopting hydrophyte and animal manure light-dark cascade coupling |
| CN103146568A (en) * | 2013-03-19 | 2013-06-12 | 哈尔滨工业大学 | Dark-l fermentation integrated biological hydrogen production device |
| CN103484364A (en) * | 2013-09-17 | 2014-01-01 | 国家纳米科学中心 | Nanometer device for solar biological hydrogen production |
| CN103484364B (en) * | 2013-09-17 | 2015-07-15 | 北京纳米能源与系统研究所 | Nanometer device for solar biological hydrogen production |
| CN103923946A (en) * | 2014-04-11 | 2014-07-16 | 河南农业大学 | Tubular multi-line circular light and dark alternating biological hydrogen production method and device |
| CN103923946B (en) * | 2014-04-11 | 2016-09-07 | 河南农业大学 | A kind of tubular type multichannel circulation light and shade replaces the method and device of biological hydrogen production |
| CN104004791A (en) * | 2014-05-16 | 2014-08-27 | 浙江工商大学 | Coupled two-phase anaerobic kitchen garbage strengthening treatment method combining microbial electrolysis cell and microbial cell and device |
| CN109301287A (en) * | 2018-09-06 | 2019-02-01 | 北京铂陆氢能科技开发有限公司 | It is a kind of can hydrogen-preparing hydrogen-storing organic liquid hydrogen storage technology electricity generation system |
| WO2023087972A1 (en) * | 2021-11-19 | 2023-05-25 | 河南农业大学 | Biological hydrogen-alkane co-production fermentation system and method with negative carbon emission |
| CN113981010A (en) * | 2021-12-01 | 2022-01-28 | 日照市海洋与渔业研究所 | Method for producing hydrogen by culturing marine photosynthetic bacteria through light-dark fermentation coupling |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jarunglumlert et al. | Scaling-up bio-hydrogen production from food waste: Feasibilities and challenges | |
| Huesemann et al. | Biofuels from Microalgae: review of products, processes and potential, with special focus on Dunaliella sp. | |
| Dutta et al. | Evolution retrospective for alternative fuels: First to fourth generation | |
| CN102559499B (en) | Preparation method of methane dry fermentation compound bacterial preparation | |
| Liu et al. | Fermentative hydrogen production from macro-algae Laminaria japonica using anaerobic mixed bacteria | |
| CN101864362B (en) | Compound microbial bacterial preparation and application thereof | |
| CN101109014A (en) | Method for producing hydrogen by dark-light zymolysis couple | |
| CN102533609B (en) | Methane dry fermentation compound bacteria | |
| JP2008104452A (en) | Alcohol production system and alcohol production method | |
| CN101372666B (en) | Composite microbial preparation for methane tank and preparation thereof | |
| CN101864363B (en) | Complex bacterial preparation and application thereof | |
| Sayed et al. | Enhancement of ethanol production from synthetic medium model of hydrolysate of macroalgae | |
| CN104388484B (en) | A kind of method that microbial grease is produced using volatile fatty acid as fermenting raw materials | |
| Sriyod et al. | One-step multi enzyme pretreatment and biohydrogen production from Chlorella sp. biomass | |
| CN101948752B (en) | Composite bacterial agent for methane fermentation | |
| CN100532565C (en) | Method for co-producing hydrogen and methane by biomass and solid organic waste fermenting method | |
| CN103421850A (en) | Method used for producing bioethanol with Scenedesmusabundans | |
| CN104774879A (en) | Method for producing 1,3-propanediol through mixed bacterium fermentation glycerinum | |
| CN102433262A (en) | Complex microbial agent for low-temperature methane fermentation and preparation method thereof | |
| CN105803004A (en) | Method for low-temperature fermentation of biogas from agricultural waste | |
| Souvannasouk et al. | Bioconverters for biogas production from bloomed water fern and duckweed biomass with swine manure co-digestion | |
| CN102911882B (en) | Rhodosporidium kratochvilovae and application of same in preparation of carotenoid and single-cell protein | |
| Mia et al. | Enhancement of biogas production by cellulytic bacteria from bagasse using methanogenesis | |
| Antunes et al. | Microbial Biotechnology for Renewable and Sustainable Energy: The Current Status of Biogas, Biodiesel, and Bioethanol in Brazil | |
| CN101760479A (en) | Method for producing hydrogen through biomass fermentation and photosynthetic coupling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080123 |