CN1506465A - Method for Biological Hydrogen Production Using Industrial Organic Wastewater - Google Patents

Method for Biological Hydrogen Production Using Industrial Organic Wastewater Download PDF

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Publication number
CN1506465A
CN1506465A CNA021560242A CN02156024A CN1506465A CN 1506465 A CN1506465 A CN 1506465A CN A021560242 A CNA021560242 A CN A021560242A CN 02156024 A CN02156024 A CN 02156024A CN 1506465 A CN1506465 A CN 1506465A
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hydrogen
industrial organic
hydrogen production
organic wastewater
fermentation
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CNA021560242A
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刘光臻
张永芳
沈建权
陈申
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

本发明涉及一种氢气的制备方法,特别涉及一种利用工业有机废水,通过微生物的作用,制备氢气的方法;该方法是在一般制氢设备中,以工业有机废水为原料,于无氧的条件下,加入生物制氢发酵液进行发酵制氢。本方法是在常温、常压下制备氢气,制氢成本低廉,不但制备了清洁能源氢气,还处理了工业有机废水。本发明原料来源广泛,代谢产物单纯,具有工业产氢的实用性。The present invention relates to a method for preparing hydrogen, in particular to a method for preparing hydrogen by using industrial organic waste water through the action of microorganisms; Under certain conditions, biohydrogen production fermentation liquid is added to carry out fermentation hydrogen production. The method prepares hydrogen at normal temperature and normal pressure, and the cost of hydrogen production is low. It not only prepares clean energy hydrogen, but also treats industrial organic waste water. The invention has wide sources of raw materials, simple metabolites and practicability for industrial hydrogen production.

Description

Utilize the method for industrial organic waste water biological hydrogen production
Technical field
The present invention relates to a kind of preparation method of hydrogen, particularly a kind of method of utilizing industrial organic waste water to prepare hydrogen.
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.
Embodiment
Embodiment 1
With COD concentration is the beer brewery water of 12500mg/L, flow into continuously with 1680 liters/day speed in the hydrogen-manufacturing reactor of 700 liters of useful volumes and carry out ferment for hydrogen production, fermenting process carries out under oxygen free condition, and the fermentation reaction temperature is 34 ℃, can produce 4.0m every day like this 3Hydrogen.
Embodiment 2
With COD concentration is the beer waste water of 17000mg/L, flow into continuously with 1680 liters/day speed in the hydrogen-manufacturing reactor of 700 liters of useful volumes and carry out ferment for hydrogen production, fermenting process carries out under oxygen free condition, and the fermentation reaction temperature is 32 ℃, can produce 5.1m every day like this 3Hydrogen.

Claims (5)

1.一种利用工业有机废水生物制氢的方法,其特征在于,该方法包括:1. A method for utilizing industrial organic waste water to produce hydrogen, characterized in that the method comprises: (1)制备利用工业有机废水生物制氢的培养液(1) Preparation of culture medium for biohydrogen production from industrial organic wastewater 将工业有机废水置于密闭透明容器中,用氮气或二氧化碳气体置换容器中的空气,在室温条件下加入生物制氢发酵液进行发酵反应,得到利用工业有机废水生物制氢的培养液;Put industrial organic wastewater in a closed transparent container, replace the air in the container with nitrogen or carbon dioxide gas, add bio-hydrogen production fermentation liquid at room temperature to carry out fermentation reaction, and obtain a culture liquid for bio-hydrogen production using industrial organic wastewater; (2)制备利用工业有机废水生物制氢的发酵液(2) Preparation of fermentation broth for biological hydrogen production from industrial organic wastewater 将(1)制备的培养液在无氧的条件下移入制氢反应器中继续进行室温发酵,同时加入工业有机废水进行发酵,发酵过程在无氧条件下进行,得到利用工业有机废水生物制氢的发酵液。Transfer the culture solution prepared in (1) into the hydrogen production reactor under anaerobic conditions to continue fermentation at room temperature, and at the same time add industrial organic wastewater for fermentation. The fermentation process is carried out under anaerobic conditions to obtain biological hydrogen production using industrial organic wastewater of fermentation broth. (3)利用工业有机废水制备氢气(3) Hydrogen production from industrial organic wastewater 在无氧的条件下,让工业有机废水连续地流入盛有(2)制备的发酵液的制氢反应器中,在15~55℃的温度范围内进行发酵制氢,这样就可大量的制备氢气。Under anaerobic conditions, let industrial organic wastewater flow continuously into the hydrogen production reactor filled with the fermentation liquid prepared in (2), and carry out fermentation hydrogen production in the temperature range of 15-55°C, so that a large amount of hydrogen can be produced hydrogen. (4)提取氢气(4) extract hydrogen 将(3)于制氢反应器中制备的氢气,通过气体分离装置,以获得纯氢气。(3) The hydrogen produced in the hydrogen production reactor is passed through a gas separation device to obtain pure hydrogen. 2.如权利要求1所述的利用工业有机废水生物制氢的方法,其特征在于,所述工业有机废水的COD浓度在1000~150000mg/L范围内。2. The method for biological hydrogen production using industrial organic wastewater according to claim 1, characterized in that the COD concentration of the industrial organic wastewater is in the range of 1000-150000 mg/L. 3.如权利要求1所述的利用工业有机废水生物制氢的方法,其特征在于,其中制备氢气的反应温度优选为25~35℃。3. The method for biological hydrogen production from industrial organic wastewater according to claim 1, wherein the reaction temperature for hydrogen production is preferably 25-35°C. 4.如权利要求1所述的利用工业有机废水生物制氢的方法,其特征在于,当管径为φ20cm时,所述工业有机废水以0.02~0.15cm/s的速度连续地流入制氢反应器中。4. The method for biological hydrogen production using industrial organic wastewater according to claim 1, characterized in that, when the pipe diameter is φ20cm, the industrial organic wastewater flows into the hydrogen production reaction continuously at a speed of 0.02-0.15cm/s device. 5.如权利要求1所述的利用工业有机废水生物制氢的方法,其特征在于,其中在制备利用工业有机废水生物制氢的培养液和发酵液时的发酵反应时间均为2~4个月。5. The method for biological hydrogen production from industrial organic wastewater as claimed in claim 1, wherein the fermentation reaction time is 2 to 4 hours when preparing the culture liquid and fermentation liquid for biological hydrogen production from industrial organic wastewater. moon.
CNA021560242A 2002-12-11 2002-12-11 Method for Biological Hydrogen Production Using Industrial Organic Wastewater Pending CN1506465A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1321174C (en) * 2005-09-28 2007-06-13 哈尔滨工业大学 Continuous flow culture of industrialized biohydrogen-producing bacteria and strengthening method of biohydrogen-producing system
CN100549180C (en) * 2005-12-30 2009-10-14 逢甲大学 Method for promoting anaerobic bio-hydrogen production
CN101270368B (en) * 2008-05-19 2010-12-29 哈尔滨工业大学 Method for biohydrogen production by cascade utilization of organic wastewater

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1321174C (en) * 2005-09-28 2007-06-13 哈尔滨工业大学 Continuous flow culture of industrialized biohydrogen-producing bacteria and strengthening method of biohydrogen-producing system
CN100549180C (en) * 2005-12-30 2009-10-14 逢甲大学 Method for promoting anaerobic bio-hydrogen production
CN101270368B (en) * 2008-05-19 2010-12-29 哈尔滨工业大学 Method for biohydrogen production by cascade utilization of organic wastewater

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