CN100357174C - Heat treatment-fermented hy drogen-generating method by preparing hydrogen from residual sludge for sewage treatment plant - Google Patents
Heat treatment-fermented hy drogen-generating method by preparing hydrogen from residual sludge for sewage treatment plant Download PDFInfo
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- CN100357174C CN100357174C CNB2005100664287A CN200510066428A CN100357174C CN 100357174 C CN100357174 C CN 100357174C CN B2005100664287 A CNB2005100664287 A CN B2005100664287A CN 200510066428 A CN200510066428 A CN 200510066428A CN 100357174 C CN100357174 C CN 100357174C
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/33—Wastewater or sewage treatment systems using renewable energies using wind energy
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The present invention relates to a heat treatment-fermented integrated technology and an operation method for preparing hydrogen from residual sludge of a sewage treatment plant. The integrated technology is mainly composed of three parts of sludge conditioning, preheating treatment and anaerobic fermentation. The operation method comprises that concentration /pH of the excess sludge is firstly regulated, then, the excess sludge is preheated, and finally, hydrogen is generated through anaerobic fermentation. Organic substances in the sludge are released by proper heat treatment, the methanation in an anaerobic digestion of sludge process is effectively suppressed, and thus, the hydrogen is stably generated. When the excess sludge is preprocessed for 0.5 hour at a temperature of 121 DEG C and the pressure of 1.5 normal atmosphere, then, the anaerobic fermentation is carried out, the hydrogen production rate can reach 19.42 ml/gVS, and the maximum concentration of the hydrogen in biological gas can reach 47.0%. Besides, the amount of the sludge is reduced in different extent, and the dewatering performance is improved. The present invention is suitable for processing excess sludge in the sewage treatment plant, and biomass energy contained in organic substances in sludge is recovered in a hydrogen energy mode.
Description
Technical field
The present invention relates to a kind of biological hydrogen production integrated technique and working method, is to utilize sewage treatment plant residual active sludge after conditioning and hot pre-treatment, carries out integrated technique and working method that anaerobically fermenting is produced hydrogen again.
Background technology
At present, the energy mainly relies on fossil oil, but this energy reserve is limited, and is non-renewable, and when burning produces CO
2With NO, NO
2, SO
2Deng nitrogen, sulfur oxide, these materials are discharged in the atmosphere, can the severe contamination air.In order to realize the strategy of sustainable development, promote the coordinated development of economy and environment, develop reproducible clean energy, be the task of top priority.Renewable energy source has sun power, water energy, wind energy, biomass energy, Hydrogen Energy etc.Wherein Hydrogen Energy receives much concern owing to its hydrogen has plurality of advantages, is considered to 21 century ideal cleaning new energy.
Hydrogen is the abundantest element of content in the universe, and it is present on the earth in a large number with the form of water, and reserves are very abundant.The combustion heat value height of hydrogen, the heat that can emit 142.35 kJ after the burning of every kg of hydrogen is 3 times of oil, 3.9 times of alcohol, 4.5 times of coke.Hydrogen is in combustion processes, and except that discharging huge energy, the refuse of generation has only water, can not cause environmental pollution, thereby be otherwise known as " clean fuel ", is real free of contamination " green energy resource "; As clean energy, hydrogen is widely used in space industry, chemical engineering industry; As basic raw material for chemical industry, also be widely used in industries such as petrochemical complex, chemical pharmacy, electronic industry and metallic high temperature processing in addition.
Hydrogen production process commonly used at present mainly comprises pure water electrolytic process, water-gas conversion method, methane cracking process and pyrolysis oil, Sweet natural gas.These methods need consume a large amount of electric power or mineral wealth, and production cost is generally higher.Biological hydrogen production is to utilize microorganism to carry out enzymic catalytic reaction at normal temperatures and pressures to produce hydrogen, and its substrate mainly is renewable resourcess (in addition, in various organic waste, the content of this class material is also very high) such as various carbohydrate, protein, and cost is lower.
Biological hydrogen production is to be put forward by M.Mickelson and C.H.Werkman in 1938.Biological hydrogen production mainly contains hydrogen production with photosynthetic bacteria and fermenting bacteria produces two kinds of methods of hydrogen, and they produce hydrogen by the metabolic process of photosynthetic bacterium and fermenting bacteria respectively.From psychological need, hydrogen production with photosynthetic bacteria all needs light, thereby can not in the dark carry out, and fermenting bacteria does not need light.On energetics, it is very favourable that fermenting bacteria produces hydrogen, and they can obtain than photosynthetic bacterium more freedom energy from the reaction of producing hydrogen, and the enzymatic product H-H reaction of hydrogen does not need ATP.It is higher that fermenting bacteria produces speed, and for example, the speed that Enterobacter aerogens transforming glucose produces hydrogen is up to 17mmol/g stem cell h, and the hydrogen-producing speed of photosynthetic bacteria is then much lower, and (great majority are 5mmolH
2/ g stem cell h).In addition, the product hydrogen substrate that fermentation and hydrogen production utilized is the product of reproducible photosynthesis of plant, is a kind of indirect utilization of sun power, and its substrate is reproducible.Fermenting bacteria produces hydrogen and not only can utilize organic waste water and the various solid waste that is rich in organic matter to produce hydrogen, also can handle waste simultaneously effectively.Thereby, compare with utilizing photosynthetic bacterium, utilize fermenting bacteria to produce hydrogen and have clear superiority.
In recent years, people have studied the feasibility material of fermentation and hydrogen production, and the material that as a rule can be used for fermentation and hydrogen production should be to possess following several characteristics: the carbohydrate content height; Aboundresources, cheapness; Has higher energy transformation ratio etc.At present, the matrix of being utilized in the fermentation and hydrogen production research is extensive, comprising:
1, simple carbohydrate, as glucose, sucrose, starch etc.;
2, be rich in the organic waste water of carbohydrate, as molasses containing waste water, sugar production wastewater, brewing wastewater and starch production wastewater etc.;
3, organic solid or semi-solid waste are as municipal wastes, agricultural solid residue, Mierocrystalline cellulose and excess sludge, animal waste etc.
Along with Chinese society economy and development of urbanization, the generation of municipal effluent and quantity thereof are in continuous growth, and these sewage must could discharge through certain processing, otherwise pollute the environment, destroy the eubiosis.Biological process (as activated sludge process, biomembrance process etc.) has also produced a large amount of excess sludges when disposing of sewage, these mud are essential through suitable processing and disposal, otherwise can cause secondary pollution to environment.According to statistics, in whole construction costs of sewage work, the expense that is used to handle mud accounts for 20～50%, have in addition up to 70%.Therefore, sludge treatment is an important component part in the Sewage treatment systems.Excess sludge mainly is biomass, wherein is rich in a large amount of organic substances, such as polyose, and protein and fats etc.These organism can be by with the mode that reclaims the energy in addition stabilization, innoxious and recycling effectively.Anaerobic digestion is the method for sludge treatment of using always, and this method can reduce the volume and the quality of mud, and with the biomass energy in the form recovery mud of methane.And hydrogen only is a kind of mesostate in the anaerobic sludge digestion process, and is unstable usually, can be utilized by hydrogen-consuming bacterias such as methanobacterias very soon.Therefore, obtain stable hydrogen generation efficiency, need to solve two key issues: the one, the molten born of the same parents of mud; The 2nd, suppress hydrogen-consuming bacteria.
Summary of the invention
The integrated technique that the object of the present invention is to provide a kind of physics and biotechnology to organically combine can utilize excess sludge hydrogen manufacturing expeditiously.The present invention is in order to solve sewage treatment plant residual sludge treatment, handling problems, simultaneously with the biomass energy in the form recovery mud of hydrogen.
A kind of thermal treatment of mud hydrogen manufacturing-fermentation and hydrogen production integrated approach, it is made up of sludge conditioning, thermal pretreatment and anaerobically fermenting three parts; Working method is that excess sludge is carried out concentration/pH regulator earlier, carries out hot pre-treatment then, produces hydrogen by anaerobically fermenting at last.
The thermal treatment of described mud hydrogen manufacturing-fermentation and hydrogen production integrated approach, it is that the excess sludge that will take from Sewage treatment systems concentrates, and regulates concentration to DS 3～20 g/L, regulates its pH value to 4.5～9.5, carries out hot pre-treatment then; Hot pretreatment temperature is 60～200 ℃, and pressure is 1～1.5 standard atmospheric pressure (atm), and the treatment time is 0.25～1.0 hour.
The thermal treatment of described mud hydrogen manufacturing-fermentation and hydrogen production integrated approach, its be with hot pre-treatment mud through heat exchanger, regulate its temperature to 40～50 ℃, carry out hydrogen production through anaerobic fermentation then.The temperature of anaerobically fermenting is 36～38 ℃, and the hydrogen production through anaerobic fermentation time is 10～40 hours.
Characteristic feature of an invention of the present invention is, is to make raw material with sewage treatment plant residual mud, with mud nurse one's health, physics pre-treatment and anaerobically fermenting be integrated in the technology and carry out efficient hydrogen manufacturing.Sludge concentration is regulated and can be made sludge concentration be controlled at optimum range to reduce the volume of energy consumption and subsequent reactor; It is better that the sludge pH value is regulated when can make the hot pre-treatment of mud effect; Hot pre-treatment can make mud melt born of the same parents, discharges organic matter and kills hydrogen-consuming bacteria; Anaerobically fermenting can be produced hydrogen.
Positively effect of the present invention is: the present invention has potential distinct economic, social benefit and environmental benefit, have huge market and potentiality at aspects such as clean energy production, waste resource regeneration, sludge treatment, disposal, the maximum hydrogen production potential that experimental results show that excess sludge reaches more than 19.42 ml/gVS, excess sludge is behind thermal treatment, anaerobically fermenting, its dehydration property be improved significantly, sludge quantity reduces.
Description of drawings
Fig. 1 is the inventive method schema.
Embodiment
The object of the present invention is achieved like this: the inventive method may further comprise the steps:
1) excess sludge of Sewage treatment systems at first enters mud equalizing tank 1, by precipitating to concentrate sludge concentration is adjusted to 3-20g/L, and then the sludge pH value is adjusted to 4.5～9.5.
2) mud after conditioning enters hot pretreatment pool 3 then through heat exchanger 2 preheatings, and hot pretreatment temperature is 60～200 ℃, and pressure is 1-1.5 atm, and pretreatment time is 0.25～1.0 hour (h).
3) enter heat exchanger 4 through the pretreated mud of heat and make the mud temperature reduce to 40～50 ℃, it is stirred, enter then in the fermentor tank 5, under middle temperature (36～38 ℃) condition, carry out anaerobically fermenting with agitator.The biogas for preparing in the hydrogen-manufacturing reactor, by gas separator 6 separate, purifying, obtain pure hydrogen.
4) mud is discharged fermentor tank 5 behind anaerobically fermenting, and a part of mud (about 10%) is back in the fermentor tank 5 as kind of mud, and excess sludge can be directly used in anaerobic digestion.
5) in heat exchanger 4, the heat of mud is delivered in heat-transfer medium-water, and this medium circulation is carried out pre-heating temperature elevation to mud to heat exchanger 2, and heat energy is fully used.
Embodiment 1:
The excess sludge that to take from Sewage treatment systems is adjusted to DS 9.93 g/L (VS 6.23g/L) the following pre-treatment of 80 ℃, 1 standard atmospheric pressure (atm) 1 hour, under room temperature, be cooled to 50～60 ℃ then, with mechanical stirrer hot pre-treatment mud is stirred, getting 150 ml pre-treatment mud joins in the anaerobic fermentation tank of 310ml, with high purity nitrogen (99.99%) to mud bubbling 2 minutes, displacement and get rid of the fermentor tank gas phase and liquid phase in oxygen, sealing then, place the airbath shaking table, lucifuge stirs insulation (140～150 rpm * 37.0 ± 1.0 ℃).The peak concentration of hydrogen reaches 50.2% in the biological hydrogen that obtains behind anaerobically fermenting, and biogas does not equally detect methane yet.The hydrogen of mud produced to fall and reach maximum (7.67 ml/gVS) about 17 hour, and after this consumption hydrogen take place.
Embodiment 2:
The concentration adjustment of excess sludge is arrived DS 11.71 g/L (VS 7.81 g/L), and pre-treatment is 0.5 hour under 121 ℃, 1.5 standard atmospheric pressures (atm), and operation after this is identical with embodiment 1.The peak concentration of hydrogen is 47.0% in the biogas that obtains behind anaerobically fermenting, does not detect methane and exists.The hydrogen productive rate of mud reaches maximum (19.42 ml/gVS) about 32 hours, after this owing to the growth of hydrogen-consuming bacteria, the hydrogen of fermentor tank gas phase begins to be consumed.
Claims (1)
1, a kind of thermal treatment-fermentation and hydrogen production method with the hydrogen manufacturing of sewage treatment plant residual mud is characterized in that, is made up of sludge conditioning, thermal pretreatment and anaerobically fermenting three parts; Be that excess sludge is carried out concentration/pH regulator earlier, carry out hot pre-treatment then, produce hydrogen by anaerobically fermenting at last;
The excess sludge that is about to take from Sewage treatment systems concentrates, and regulates concentration to 3～20g/L, regulates its pH value to 4.5～9.5, carries out hot pre-treatment then; Hot pretreatment temperature is 60～200 ℃, and pressure is 1～1.5 standard atmospheric pressure, and the treatment time is 0.25～1.0 hour;
Hot pre-treatment mud through heat exchanger, is regulated its temperature to 40～50 ℃, carry out hydrogen production through anaerobic fermentation then; The temperature of anaerobically fermenting is 36～38 ℃, and the hydrogen production through anaerobic fermentation time is 10～40 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759336B (en) * | 2009-12-18 | 2011-07-27 | 北京工业大学 | Two grade alkaline hydrolysis and acidification device for processing residual activated sludge |
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| CN101063152B (en) * | 2007-05-25 | 2011-05-11 | 东莞科创未来能源科技发展有限公司 | Kitchen residual garbage normal temperature anaerobic fermentation method |
| CN101134684B (en) * | 2007-07-27 | 2010-09-29 | 东莞科创未来能源科技发展有限公司 | Method for producing hydrogen and methane by kitchen waste diphasic anaerobic fermentation |
| CN101717790B (en) * | 2009-12-10 | 2013-02-13 | 同济大学 | Method for promoting sludge anaerobic fermentation to produce hydrogen in sewage plant |
| CN101880115B (en) * | 2010-02-03 | 2012-12-26 | 王鹤立 | Method for supplementing denitrifying carbon source by utilizing excess sludge ethanol-type fermentation |
| 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 |
| CN102351391B (en) * | 2011-09-13 | 2013-06-19 | 大连力达环境工程有限公司 | Dewatered sludge anaerobic digestion pretreatment process and system |
| CN103172229B (en) * | 2013-03-14 | 2014-11-26 | 杨顺生 | Pre-treatment method for eliminating or reducing siloxane and color material in biogas |
| CN105018535A (en) * | 2014-12-17 | 2015-11-04 | 宇星科技发展(深圳)有限公司 | Method for producing hydrogen by using excess sludge |
| CN104762330B (en) * | 2015-04-16 | 2018-02-13 | 浙江工商大学 | A kind of apparatus and method for improving excess sludge electrochemistry hydrogen generation efficiency |
| CN105755049B (en) * | 2015-12-11 | 2020-04-07 | 清华大学 | Method for preparing hydrogen by fermenting with xylose as substrate |
| CN109368986A (en) * | 2018-12-06 | 2019-02-22 | 齐鲁工业大学 | It is a kind of to promote excess sludge digestion production H using charcoal2The method of yield |
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Patent Citations (3)
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Cited By (1)
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