Background technology
At present limited as the ore fuel reserves of main body, and produce CO during burning
2With the oxide compound of nitrogen, sulphur etc., in a single day these materials are discharged in the atmosphere, all are the atmospheric polluting materials that influences environment for human survival.In order to impel economy and harmonious development, implement the sustainable development strategy, need seek the new way of rational use of energy.Exploitation is also transferred to use other reproducible new forms of energy and is built consensus at world wide, and this just makes hydrogen become the consistent desirable development object of generally acknowledging of various countries scientific research personnel.
Hydrogen only produces water when burning, be a kind of clean energy that can realize zero emission.As the 21st century people a kind of energy that can utilize, its position is very important.Occurring in nature does not almost have hydrogen to exist.Traditional hydrogen production process has water electrolysis method, conversion method for synthesis gas, conversion of natural gas method etc., and these method power consumptions are excessive, and the cost of hydrogen manufacturing is very high.Therefore, the microorganism that utilization can be produced hydrogen comes hydrogen manufacturing, is a kind of pollution-free and cost-effective good method.
Biological hydrogen production is to be put forward by M.Mickelson and C.H.Werkman in 1938.Can produce the microorganism of hydrogen, according to the required energy derive of microorganism growth, can be divided into two big classes substantially: a class is to utilize the non-photosynthesizing microorganism of organism growth (generating bacterium to call anaerobic type hydrogen in the following text), anaerobic type hydrogen generates bacterium and utilizes organism existence usually, and organism is resolved into organic acid, H
2, CO
2Another kind of is the photosynthetic microorganism (to call photosynthetic bacterium in the following text) that utilizes the luminous energy growth, and photosynthetic bacterium utilizes organic acid existence usually, and organic acid is resolved into H
2, CO
2This two big class hydrogen generates bacterium, all is that anaerobic type hydrogen generates bacterium.Utilize research that photosynthetic bacterium passes through organic acid hydrogen manufacturing 70, the eighties just formed an individual system.Because the raw material sources organic acid has limited the large-scale industrialization biological hydrogen production.
(bacterial species that participates in fermentation reaction is different) can produce the characteristics of hydrogen after international scientific circle was utilized organic matter fermentation, seeking more economic biological hydrogen production method always.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing industrial organic waste water to prepare hydrogen, can handle waste water efficiently, a large amount of simultaneously preparation hydrogen.
The method for preparing hydrogen that another object of the present invention provides, both may command environmental pollutions can be turned waste into wealth again, produce new forms of energy, and reduce the hydrogen manufacturing cost greatly, and its cost is well below traditional industrial hydrogen production method.
For achieving the above object, technical solution of the present invention provides a kind of method of utilizing the industrial organic waste water biological hydrogen production, and this method comprises:
(1) preparation utilizes the nutrient solution of industrial organic waste water biological hydrogen production
Industrial organic waste water is placed airtight transparent vessel, and the air with in nitrogen or the carbon dioxide displacement container adds fermented liquid for biologically producing hydrogen at ambient temperature and carries out fermentation reaction, obtains utilizing the nutrient solution of industrial organic waste water biological hydrogen production;
(2) preparation utilizes the fermented liquid of industrial organic waste water biological hydrogen production
The nutrient solution of (1) preparation moved under the condition of anaerobic proceed room temperature in the hydrogen-manufacturing reactor and ferment, add industrial organic waste water simultaneously and ferment, fermenting process carries out under oxygen free condition, obtains utilizing the fermented liquid of industrial organic waste water biological hydrogen production.
(3) utilize industrial organic waste water to prepare hydrogen
Under the condition of anaerobic, allow industrial organic waste water flow into continuously to fill in the hydrogen-manufacturing reactor of fermented liquid of (2) preparation, in 15~55 ℃ temperature range, carry out ferment for hydrogen production, preparation hydrogen that so just can be a large amount of.
(4) extract hydrogen
The hydrogen that (3) are prepared in hydrogen-manufacturing reactor is by gas separation unit, to obtain pure hydrogen.
The described method of utilizing the industrial organic waste water biological hydrogen production, the COD concentration of its industrial organic waste water is in 1000~150000mg/L scope.
The described method of utilizing the industrial organic waste water biological hydrogen production, the temperature of reaction that wherein prepares hydrogen is preferably 25~35 ℃.
The described method of utilizing the industrial organic waste water biological hydrogen production, when caliber was φ 20cm, described industrial organic waste water flowed in the hydrogen-manufacturing reactor continuously with the speed of 0.02~0.15cm/s.
The described method of utilizing the industrial organic waste water biological hydrogen production, wherein the fermentation reaction time when preparation utilizes the nutrient solution of industrial organic waste water biological hydrogen production and fermented liquid all is 2~4 months.
Basic point of departure of the present invention is: under the condition of anaerobic, industrial organic waste water produces hydrogen by the effect of bacterium, by gas separation unit, can obtain 99.5% pure hydrogen.
The characteristics of present method are, in airtight transparent vessel, add the fermented liquid for biologically producing hydrogen (publication number: CN1276430A), use general hydrogen producer that we develop, under normal temperature, normal pressure, carry out fermentation reaction, obtain utilizing the hydrogen of industrial organic waste water preparation.
Utilize the inventive method, the industrial organic waste water of numerous species can be sent into continuously in the general biological hydrogen production equipment commonly used, handled, promptly make hydrogen serially, turn waste into wealth.
The hydrogen of the inventive method preparation owing to be to use general hydrogen producer, carries out fermentation reaction under normal temperature, normal pressure, make industrial biological hydrogen preparing become possibility and economical and effective.The fermented liquid for biologically producing hydrogen that uses present method preparation with utilize anaerobic activated sludge (Chinese patent application 92114474.1) to carry out organic waste water fermentation method biological hydrogen production to compare, do not contain the methane that consumes hydrogen in the fermented liquid that the present invention obtains and generate anaerobic bacteriums such as bacterium, therefore, recover hydrogen in a large number.Utilize fermented liquid that the present invention obtains in preparation hydrogen process, its meta-bolites is simple, is H
2, CO
2, acetate, butyric acid, acetate, butyric acid can directly be recycled.
Above-mentioned reaction all can at room temperature be carried out, and with the difference in place or season, temperature of reaction can change thereupon, is generally 15~55 ℃, in most cases is 25~35 ℃.In above-mentioned reaction, the concentration of COD can change within a large range in the industrial organic waste water, and for example, concentration is greatly then difficult relatively on the possible operation, and simple in the little operation of concentration, but hydrogen capacity is not restricted.The concentration of COD all makes hydrogen serially in the general industrial organic waste water in the method in 1000~150000mg/L scope.Industrial organic waste water flows into the speed in the hydrogen-manufacturing reactor continuously, when caliber is φ 20cm, is controlled at 0.02~0.15cm/s as required.
The present invention can make industrial organic waste water produce hydrogen by fermentation using bacteria.Utilize hydrogen production process provided by the invention, both may command environmental pollutions can be turned waste into wealth again, produce new forms of energy, and reduce the hydrogen manufacturing cost greatly, its cost is well below traditional industrial hydrogen production method, raw material sources are extensive, and meta-bolites is simple, have the practicality that hydrogen is produced in industry.
The applicant's achievement in research meets the Energy policy and the Environmental policy of national sustainable development strategy, shows that the mankind can cultivate the high-efficiency cleaning energy fully from the soil.Have broad application prospects remarkable economic efficiency and social benefit.