CN1618980A - Method and device for making hydrogen using sewage plant residual mud to produce anaerobic fermentation - Google Patents
Method and device for making hydrogen using sewage plant residual mud to produce anaerobic fermentation Download PDFInfo
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- CN1618980A CN1618980A CNA2003101161426A CN200310116142A CN1618980A CN 1618980 A CN1618980 A CN 1618980A CN A2003101161426 A CNA2003101161426 A CN A2003101161426A CN 200310116142 A CN200310116142 A CN 200310116142A CN 1618980 A CN1618980 A CN 1618980A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
A process for generating H2 from the residual mud of sewage treating works include using alkali to regulate the pH value of active mud to 12-13, stirring, pumping it into the reactor, filling N2 for displacing O2, and anaerobic fermenting at 20-55 deg.C for generating H2. Its apparatus is composed of alkali-treating reactor, anaerobic fermenting and hydrogene generating reactor, acidity control system and gas collecting system.
Description
Technical field
The invention belongs to the dispose of sewage technology of made from residual actived sludge hydrogen in treatment plant's biological treatment of Unareobic fermentation of utilizing, particularly a kind of by adding alkali pre-treatment mud and being controlled at the method for anaerobically fermenting hydrogen manufacturing under the alkaline condition.
The invention still further relates to the device of realizing aforesaid method.
Background technology
The world today is faced with two big challenging problems of energy shortage and environmental pollution.World energy sources about 80% is to rely on fossil oil at present, as oil, and Sweet natural gas and coal etc.Yet the deposit of these energy substances all is the deterioration that can cause global environment in very limited and the use.Therefore, seek a kind ofly to clean reproducible energy substance and replace fossil oil to become one of our times various countries research focus.Hydrogen is as a kind of extremely everybody concern of green energy resource of cleanliness without any pollution.Only produce water after its burning, do not discharge any pollution substance, and the combustion heat value height, can emit the heat of 142.35 kilojoules after every kg of hydrogen burning, be 2.75 times of gasoline, 3.9 times of alcohol, 4.5 times of coke.And hydrogen also is one of important material very in many industrial production.The acquisition mode of hydrogen roughly can be divided into two big class, i.e. physico-chemical process and biological processes at present.Wherein physico-chemical process mainly contains water electrolysis, water-gas conversion method and methane cracking process etc., and these methods itself need to consume a large amount of energy substances.Yet the hydrogen generation by biological process method need not to consume big energy, has economy and advantages of environment protection.Utilize organic ferment for hydrogen production in waste water or the solid waste, in degradation of organic substances, decontamination, obtain hydrogen, can reduce the hydrogen manufacturing cost and protect environment.What at present, hydrogen generation by biological process research was maximum is hydrogen manufacturing of photosynthetic organism method and the hydrogen manufacturing of fermentation using bacteria method.The research of adopting various organic waste waters and organic solid castoff to carry out fermentative hydrogen production is on the increase, comprising molasses containing waste water, brewing wastewater, plant amylum factory effluent, cellulose crystallite and city organic solid rubbish etc.
Along with the raising of people's Environmental awareness and the increasingly stringent of environmental legislation, there is increasing sewage work to come into operation or build, this will increase the input and the processing costs of sludge treatment significantly.But be rich in a large amount of organic substances in the residual active sludge, such as polyose, protein and lipoid material etc.These organism can carry out stabilization, innoxious and recycling treatment by the mode of energy recovery.Usually the processing of excess sludge is to adopt the methanogenic technology of anaerobically fermenting to carry out mostly.But the waste gas such as carbonic acid gas that the methane gas that this process produced and its burning back are produced all are the important factors that causes Global Greenhouse Effect.As everyone knows, hydrogen is a kind of important intermediate product in the sludge anaerobic fermenting process.Utilize the technology of sewage plant excess sludge ferment for hydrogen production not only can obtain clean energy, reasonably handle mud again simultaneously, for sludge treatment provides a kind of new approach.The gordian technique of obtaining hydrogen from the sludge fermentation process is how to keep higher hydrogen yield, and methanation reaction does not take place.The method of at present existing relevant excess sludge ferment for hydrogen production comprises by the biological reinforced method of the hydrogenogens (Clostridium bifermentans) that adds pure culture comes ferment for hydrogen production, in addition also by the mud heated and boiled being reached the method product hydrogen that mud melts born of the same parents and enrichment hydrogenogens.But the pH of these method fermentation culture all between 5.5～7.5, can not suppress the growth of hydrogen-consuming bacteria effectively, and the hydrogen that causes producing is promptly consumed again, thereby can't realize the purpose of the hydrogen manufacturing of continuously fermenting of mud.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing the hydrogen manufacturing of sewage plant excess sludge anaerobically fermenting, by born of the same parents being melted in the pre-treatment of mud alkali and being controlled at anaerobically fermenting under the condition of high pH, realized the hydrogen manufacturing of continuously fermenting of mud, thereby solved the problem of hydrogen consumption in the sludge fermentation hydrogen production process, helped the continuously ferment realization of hydrogen manufacturing of mud.
The method of utilizing the hydrogen manufacturing of sewage plant excess sludge anaerobically fermenting provided by the invention, active sludge is regulated initial pH=9.0～12.5 with alkali, charge into nitrogen to drive away oxygen wherein, 20～55 ℃ of controlled temperature carry out anaerobically fermenting and obtain hydrogen after 20～30 hours.
The present invention also can regulate pH=12.0～13.0 with alkali earlier with active sludge earlier, stir and carried out pre-treatment in 12～24 hours, pretreated mud is regulated initial pH=9.0～12.5 with acid or alkali again, charge into nitrogen to drive away oxygen wherein, and 20～55 ℃ of controlled temperature, carry out anaerobically fermenting and obtain hydrogen after 20～30 hours.It mainly is to play the effect that mud melts born of the same parents and enrichment hydrogenogens and suppresses the hydrogen-consuming bacteria growth that mud adds the alkali pre-treatment.
Aforesaid method is to carry out in an airtight container, after reaction finishes, opens the mud behind the container cleaning reaction, refills new mud and alkali, repeats operation steps.
The present invention adopts the anaerobically fermenting hydrogen-manufacturing reactor can produce biological hydrogen continuously, its step is that active sludge is regulated pH=12.0～13.0 with alkali earlier, stirred 12～24 hours, be continuously pumped into the anaerobically fermenting hydrogen-manufacturing reactor, and charge into nitrogen to drive away oxygen wherein, and control pH=9.5～10.0 in the anaerobically fermenting hydrogen-manufacturing reactor, temperature is 20～55 ℃, sludge retention time is 12～24 hours, can produce biological hydrogen continuously.
The alkali that the present invention adopts is NaOH, Ca (OH)
2Or/and KOH.
The anaerobically fermenting hydrogen-manufacturing reactor that the present invention adopts includes:
One mud transferpump and links to each other with pipeline between the airtight mud alkaline purification reactor, and this transferpump pumps into mud in the alkaline purification reactor.
After dirty alkaline purification reactor is finished the alkali pre-treatment, be delivered in the hydrogen-manufacturing reactor through the alkaline purification mud inlet of a pump mud that alkali is pretreated by the mud hydrogen-manufacturing reactor; This hydrogen-manufacturing reactor is a closed reactor, and is provided with sludge outlet after the hydrogen manufacturing, is used to discharge the mud of finishing hydrogen production reaction.
Mud alkaline purification reactor and sludge fermentation hydrogen-manufacturing reactor are equipped with the resistance to air loss agitator, and this agitator can be a mechanical stirrer, also can be gas circulation formula agitators.
The such as reaction acidity of hydrogen-manufacturing reactor among the present invention, by a pH electrode that places hydrogen-manufacturing reactor the acidity of hydrogen-manufacturing reactor mud is fed back to online pH switchboard (as adopting but be not limited to PHG-21D type industry pH/ORP meter), add alkali or acid by this switchboard control alkali jar and acid jar to hydrogen-manufacturing reactor, so that the mud in the hydrogen-manufacturing reactor reaches predetermined pH value.
The temperature of reaction of hydrogen-manufacturing reactor is controlled by a temperature controlling system (as adopting but be not limited to XMTD type digital display temperature controller) among the present invention, so that the temperature of reaction in the reactor reaches predetermined temperature value.
The hydrogen of hydrogen-manufacturing reactor output is collected in the hydrogen collecting apparatus by a gasometer.
Description of drawings
The synoptic diagram of figure-mud hydrogen-manufacturing reactor 1. of the present invention and technical process thereof;
Among the figure: 1-mud transferpump; 2-mud alkaline purification reactor; 3-mud hydrogen-manufacturing reactor; 4-hydrogen manufacturing fermentation back sludge outlet; 5-alkaline purification mud inlet; The 6-stirring system; The online pH switchboard of 7-; 8-sodium hydroxide; 9-hydrochloric acid; The 10-pH electrode; The 11-constant flow pump; The 12-fluid-tight; The 13-wet test meter; The 14-temperature controlling system.
Embodiment
By the following examples content of the present invention is illustrated in further detail.
Embodiment 1:
To be 10.36g/l residual active sludge 50ml directly regulate the cumulative volume of packing under the alkaline condition of initial pH=11.0 with NaOH with concentration is in the serum bottle of 125ml, to wherein towards pure nitrogen gas to drive away oxygen wherein, controlled temperature is 36 ℃, 150rpm, anaerobically fermenting just can obtain maximum product hydrogen rate after 24～30 hours be 9.13LH
2/ kg-TS or 16.23LH
2/ kg-VS.
Embodiment 2:
The residual active sludge 50ml that at first with concentration is 12.60g/l regulates pH=12.0 with NaOH, alkaline purification is 24 hours under the condition of room temperature, regulating the mud initial pH value then is 11.0, the cumulative volume of packing into is in the serum bottle of 125ml, to wherein towards pure nitrogen gas to drive away oxygen wherein, controlled temperature is 36 ℃, and 150rpm, anaerobically fermenting just can obtain maximum product hydrogen rate after 24～30 hours be 16.59LH
2/ kg-TS or 29.36LH
2/ kg-VS.
Embodiment 3:
See also Fig. 1.The residual active sludge that at first with concentration is 15.47g/l is with in the mud transferpump 1 input mud alkaline purification reactor 2, the pH=12.0 of mud in this reactor 2, handled 24 hours under the room temperature, get then and handle 2.5 liters in back mud, regulating the sludge pH value is 11.0, the cubic capacity of packing into is in 3 liters the airtight mud hydrogen-manufacturing reactor 3, and inflated with nitrogen is to drive away oxygen wherein in reactor 3.Controlled temperature is 36 ℃, through having obtained 379.93mlH after 24～30 hours the anaerobically fermenting reaction
2, producing the hydrogen rate is 12.28LH
2/ kg-TS or 21.53LH
2/ kg-VS.
Embodiment 4:
Long run test: the residual active sludge alkaline purification 12～24h under the condition of pH=12.0 that at first is 10～30g/l with concentration, be continuously pumped into volume and be in the ferment for hydrogen production reactor of 8.0 liters (effective volume is 6.0 liters) and carry out the anaerobic hydrogen-generating fermentation, pH in the controlling reactor is between 9.5～10.0, temperature is 36 ℃, sludge retention time is 24h, the average hydrogen that can produce 600～1000ml every day, the product hydrogen rate of acquisition is 8.68～11.59LH
2/ kg-TS or 16.73～21.51LH
2/ kg-VS.The content of hydrogen is more than 93% in the biogas that produces, and do not have methane and produce, in addition since the pH in the reactor between 9.3～9.8, so carbon dioxide content is also very micro-in the aerogenesis, that is to say to obtain the very high biological hydrogen as energy source of purity.
Claims (8)
1, a kind of method of utilizing the hydrogen manufacturing of sewage plant excess sludge anaerobically fermenting is regulated initial pH=9.0～12.5 with active sludge with alkali, charges into nitrogen driving away oxygen wherein, and 20～55 ℃ of controlled temperature, carries out anaerobically fermenting and obtains hydrogen after 20～30 hours.
2, the method for claim 1 is characterized in that, active sludge is regulated pH=12.0～13.0 with alkali earlier, stirs 12～24h, carries out anaerobically fermenting hydrogen manufacturing by claim 1 then.
3, method as claimed in claim 1 or 2 is characterized in that, described alkali is NaOH, Ca (OH)
2Or/and KOH.
4, method as claimed in claim 1 or 2 is characterized in that, described anaerobically fermenting is to produce in the hydrogen reactor to mud to charge into nitrogen.
5, a kind of method of utilizing the hydrogen manufacturing of sewage plant excess sludge anaerobically fermenting, active sludge is regulated pH=12.0～13.0 with alkali earlier, stir 12～24h, be continuously pumped in the anaerobically fermenting hydrogen-manufacturing reactor, charge into nitrogen with expeling oxygen wherein, and the pH=9.5 in the controlling reactor～10.0, temperature is 20～55 ℃, sludge retention time is 12～24h, can produce biological hydrogen continuously.
6, a kind of device of implementing the described method of claim 5 includes:
One mud transferpump links to each other with a mud alkaline purification pipe reactor;
One dirty alkaline purification reactor is connected to the alkaline purification mud inlet of mud hydrogen-manufacturing reactor by a pump;
The mud hydrogen-manufacturing reactor also is provided with sludge outlet after the hydrogen manufacturing;
Above-mentioned mud alkaline purification reactor and sludge fermentation hydrogen-manufacturing reactor are closed reactor;
Above-mentioned mud alkaline purification reactor and sludge fermentation hydrogen-manufacturing reactor are equipped with the resistance to air loss agitator;
One acidity control system is made up of an online pH switchboard, a pH electrode, an alkali jar and an acid jar, wherein:
PH electrode places in the hydrogen-manufacturing reactor, and the acidity in the reactor is fed back to online pH switchboard, adds alkali or acid by this switchboard control alkali jar and acid jar to hydrogen-manufacturing reactor, so that the mud in the hydrogen-manufacturing reactor reaches predetermined pH value;
One temperature controlling system places hydrogen-manufacturing reactor in it, so that the temperature of reaction in the reactor reaches predetermined temperature value;
One hydrogen collecting apparatus is used to collect the hydrogen of hydrogen-manufacturing reactor output.
7, device as claimed in claim 6 is characterized in that, the agitator of described mud alkaline purification reactor and the setting of sludge fermentation hydrogen-manufacturing reactor is mechanical stirrer or gas circulation formula agitator.
8, device as claimed in claim 6 is characterized in that, the inlet mouth of described hydrogen collecting apparatus is equipped with a gasometer.
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| CNB2003101161426A CN1273373C (en) | 2003-11-17 | 2003-11-17 | Method and device for making hydrogen using sewage plant residual mud to produce anaerobic fermentation |
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|---|---|---|---|
| CNB2003101161426A CN1273373C (en) | 2003-11-17 | 2003-11-17 | Method and device for making hydrogen using sewage plant residual mud to produce anaerobic fermentation |
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| CN1273373C CN1273373C (en) | 2006-09-06 |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100575495C (en) * | 2008-07-15 | 2009-12-30 | 同济大学 | The method of mineralized waste, percolate, changing food waste and producing methane by sludge and hydrogen |
| CN1990872B (en) * | 2005-12-27 | 2010-04-14 | 中国科学院海洋研究所 | Method of preparing hydrogen gas by using castoff of mariculture organic matter |
| CN101831462A (en) * | 2010-04-29 | 2010-09-15 | 中国科学院生态环境研究中心 | Anaerobic-fermentation hydrogen production method by pretreating and electrochemically strengthening sludge |
| CN101186931B (en) * | 2007-12-18 | 2011-11-02 | 华南理工大学 | Biological method for producing hydrogen by mixing sludge and organic garbage |
| CN102786196A (en) * | 2012-07-24 | 2012-11-21 | 北京工业大学 | Method capable of guaranteeing acid production of surplus sludge and improving dewatering performance of fermented sludge |
| CN102879296A (en) * | 2012-10-15 | 2013-01-16 | 环境保护部华南环境科学研究所 | Simulated measurement and calculation device and method for exhaust gas emission in urban sewerage system |
| CN101717790B (en) * | 2009-12-10 | 2013-02-13 | 同济大学 | Method for promoting sludge anaerobic fermentation to produce hydrogen in sewage plant |
| MD4204C1 (en) * | 2012-03-29 | 2013-09-30 | Государственный Университет Молд0 | Installation for anaerobic production of biohydrogen |
| CN105567741A (en) * | 2016-01-15 | 2016-05-11 | 复旦大学 | Method for improving excess activated sludge anaerobic fermentation hydrogen production efficiency |
| CN105861566A (en) * | 2016-05-18 | 2016-08-17 | 东北农业大学 | Method and device for producing hydrogen through pulsed power ultrasonic enhanced anaerobic biological fermentation |
| CN108249400A (en) * | 2018-02-26 | 2018-07-06 | 刘约翰 | A kind of specific function nonferrous materials equipment |
| CN109912154A (en) * | 2019-03-19 | 2019-06-21 | 哈尔滨工业大学 | A kind of microorganism electrolysis cell highly effective hydrogen yield and the method for inhibiting methane phase |
| CN110054379A (en) * | 2019-03-19 | 2019-07-26 | 哈尔滨工业大学 | Inhibit the method for methane phase during a kind of sludge substrate anaerobic digestion |
| CN113045034A (en) * | 2021-03-12 | 2021-06-29 | 桂林兴百利机械制造有限责任公司 | PLC system for sewage treatment and capable of being remotely and intelligently controlled and adjusted |
| CN113697949A (en) * | 2021-08-20 | 2021-11-26 | 中钢集团鞍山热能研究院有限公司 | Short-flow anaerobic reactor device and high-concentration organic wastewater pretreatment method |
| CN114560556A (en) * | 2021-12-31 | 2022-05-31 | 北京工业大学 | Method for promoting hydrolytic fermentation of excess sludge and simultaneously utilizing fermentation product in situ |
| CN117448132A (en) * | 2023-11-01 | 2024-01-26 | 哈尔滨工业大学 | High-load organic wastewater dark fermentation biological hydrogen production device and hydrogen production method |
-
2003
- 2003-11-17 CN CNB2003101161426A patent/CN1273373C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990872B (en) * | 2005-12-27 | 2010-04-14 | 中国科学院海洋研究所 | Method of preparing hydrogen gas by using castoff of mariculture organic matter |
| CN101186931B (en) * | 2007-12-18 | 2011-11-02 | 华南理工大学 | Biological method for producing hydrogen by mixing sludge and organic garbage |
| CN100575495C (en) * | 2008-07-15 | 2009-12-30 | 同济大学 | The method of mineralized waste, percolate, changing food waste and producing methane by sludge and hydrogen |
| CN101717790B (en) * | 2009-12-10 | 2013-02-13 | 同济大学 | Method for promoting sludge anaerobic fermentation to produce hydrogen in sewage plant |
| CN101831462A (en) * | 2010-04-29 | 2010-09-15 | 中国科学院生态环境研究中心 | Anaerobic-fermentation hydrogen production method by pretreating and electrochemically strengthening sludge |
| CN101831462B (en) * | 2010-04-29 | 2012-07-25 | 中国科学院生态环境研究中心 | Anaerobic-fermentation hydrogen production method by pretreating and electrochemically strengthening sludge |
| MD4204C1 (en) * | 2012-03-29 | 2013-09-30 | Государственный Университет Молд0 | Installation for anaerobic production of biohydrogen |
| CN102786196A (en) * | 2012-07-24 | 2012-11-21 | 北京工业大学 | Method capable of guaranteeing acid production of surplus sludge and improving dewatering performance of fermented sludge |
| CN102786196B (en) * | 2012-07-24 | 2014-03-05 | 北京工业大学 | Method capable of guaranteeing acid production of surplus sludge and improving dewatering performance of fermented sludge |
| CN102879296A (en) * | 2012-10-15 | 2013-01-16 | 环境保护部华南环境科学研究所 | Simulated measurement and calculation device and method for exhaust gas emission in urban sewerage system |
| CN105567741A (en) * | 2016-01-15 | 2016-05-11 | 复旦大学 | Method for improving excess activated sludge anaerobic fermentation hydrogen production efficiency |
| CN105861566A (en) * | 2016-05-18 | 2016-08-17 | 东北农业大学 | Method and device for producing hydrogen through pulsed power ultrasonic enhanced anaerobic biological fermentation |
| CN108249400A (en) * | 2018-02-26 | 2018-07-06 | 刘约翰 | A kind of specific function nonferrous materials equipment |
| CN109912154A (en) * | 2019-03-19 | 2019-06-21 | 哈尔滨工业大学 | A kind of microorganism electrolysis cell highly effective hydrogen yield and the method for inhibiting methane phase |
| CN110054379A (en) * | 2019-03-19 | 2019-07-26 | 哈尔滨工业大学 | Inhibit the method for methane phase during a kind of sludge substrate anaerobic digestion |
| CN113045034A (en) * | 2021-03-12 | 2021-06-29 | 桂林兴百利机械制造有限责任公司 | PLC system for sewage treatment and capable of being remotely and intelligently controlled and adjusted |
| CN113697949A (en) * | 2021-08-20 | 2021-11-26 | 中钢集团鞍山热能研究院有限公司 | Short-flow anaerobic reactor device and high-concentration organic wastewater pretreatment method |
| CN113697949B (en) * | 2021-08-20 | 2023-03-10 | 中钢集团鞍山热能研究院有限公司 | Short-process anaerobic reactor device and high-concentration organic wastewater pretreatment method |
| CN114560556A (en) * | 2021-12-31 | 2022-05-31 | 北京工业大学 | Method for promoting hydrolytic fermentation of excess sludge and simultaneously utilizing fermentation product in situ |
| CN117448132A (en) * | 2023-11-01 | 2024-01-26 | 哈尔滨工业大学 | High-load organic wastewater dark fermentation biological hydrogen production device and hydrogen production method |
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