CN101979610B - Method for improving efficiency of preparing hydrogen from vinegar residue by anaerobic fermentation - Google Patents
Method for improving efficiency of preparing hydrogen from vinegar residue by anaerobic fermentation Download PDFInfo
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- CN101979610B CN101979610B CN2010105232774A CN201010523277A CN101979610B CN 101979610 B CN101979610 B CN 101979610B CN 2010105232774 A CN2010105232774 A CN 2010105232774A CN 201010523277 A CN201010523277 A CN 201010523277A CN 101979610 B CN101979610 B CN 101979610B
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Abstract
The invention provides a method for improving the efficiency of preparing hydrogen from vinegar residue by anaerobic fermentation, belongs to the technical field of biological engineering, and in particular relates to an ultrasonic pretreatment method for improving the efficiency of preparing the hydrogen from the vinegar residue by the anaerobic fermentation. The method comprises the following steps of: (1) weighing a crushed vinegar residue sample, adding 0.2 to 2.0 percent solution of hydrochloric acid according to a solid-liquid ratio of 8:60-140 and stirring; ultrasonically treating at the initial temperature of below 30 DEG C and at the ultrasonic power of between 400 and 900W for 3 to 15 minutes; and adjusting the pH to be 6.5 after the ultrasonic treatment is finished; and (2) preparing hydrogen by the anaerobic fermentation: weighing the pretreated active sludge and adding into an anaerobic fermentation tank, adjusting the pH to be 6.5, blowing the air in a fermentation bottle with nitrogen gas and culturing at the temperature of 37 DEG C at constant temperature for 72 hours. The method for improving the efficiency of preparing the hydrogen from the vinegar residue by the anaerobic fermentation is simple to operate and easy to popularize, and can improve the pretreatment effect of cellulose type raw materials such as the vinegar residue and the like and the efficiency of preparing the hydrogen by fermentation.
Description
Technical field
The present invention relates to a kind of method that improves the poor anaerobically fermenting hydrogen manufacturing of vinegar, belong to technical field of bioengineering.
Background technology
Vinegar is poor to be to utilize grain raw material to produce the tankage of vinegar.The aboundresources that China's vinegar is poor, as the annual vinegar of producing discharging in Zhenjiang, Jiangsu poor up to 3,000 ten thousand tons about.Vinegar is poor acid big, rotten slow, is the big difficult point that urban environmental hygiene is administered.In order to reduce environmental pollution, realize the comprehensive utilization of resource, be necessary that poor utilization is studied to vinegar.
At present, the application that is pickled with grains or in wine on feed resource, culture medium of edible fungus and plant soil-less culturing matrix of vinegar is modal.Though it is poor that these methods can be disposed some vinegar to a certain extent, to the poor drying of vinegar the time, there is the big problem of power consumption.Is is its a large amount of residue landfill on earth or utilizing aspect culture medium of edible fungus and plant soil-less culturing matrix? If landfill, then contaminate environment has been wasted resource again.How does this utilize again if utilize again? These have shown that all the poor processing of these vinegar is not optimal treatment process.
In recent years, people had carried out vinegar and had been pickled with grains or in wine in direct burning the research of aspects such as fermentation of generating matter energy gas and thermo-cracking.It all has certain big advantage, can realize the poor extensive minimizing of vinegar, subtract appearanceization, innoxious, recycling like direct burning, preferably resolves poor society, environment and the energy problem of causing of vinegar; The hydrogen of its generation of hydrogen production through anaerobic fermentation is pollution-free energy source, and the waste that the fermentation back produces can be used as fertilizer; Thermo-cracking can be converted into biomass waste and be prone to store, is prone to transportation, liquid fuel that energy is high.Thereby,, all be the direction that is worthy to be popularized still from the comprehensive utilization angle of development of resources no matter from solving the angle of environmental pollution.In order to utilize vinegar poor, tackle these the latest developments and carry out more deep research.
Summary of the invention
To bacterial classification in the poor anaerobically fermenting of vinegar can not DIRECT UTILIZATION OF CELLULOSE this on the one hand, the purpose of this invention is to provide a kind of method and make bacterial classification can better utilize Mierocrystalline cellulose during the fermentation, for the development that promotes the poor anaerobically fermenting of vinegar provides theoretical foundation.
The objective of the invention is to improve that the method for the poor anaerobically fermenting hydrogen manufacturing of vinegar realizes, comprise the steps: through ultrasonic pretreatment
(1) the poor pre-treatment of vinegar: the poor sample of vinegar that takes by weighing a certain amount of pulverizing; According to the feed liquid mass ratio is that 8:60 ~ 140 adding mass concentrations are 0.2 ~ 2.0% hydrochloric acid soln, stirs, under 30 ℃ of initial temperatures; Ultrasonic time 3 ~ 15min, the ultrasonic power 400 ~ 900W of processing; Ultrasonic end is regulated pH to 6.5 with 1mol/L NaOH solution; With the poor anaerobic fermentation tank that drops into of pretreated vinegar;
(2) active sludge pre-treatment and anaerobically fermenting: take by weighing a certain amount of active sludge, the mass ratio of the poor sample of active sludge and pretreated vinegar is: active sludge/vinegar sample=1:0.5 ~ 2 that are pickled with grains or in wine; Regulate the pH to 11.0 of active sludge with NaOH solution, leave standstill 1.5h after, transfer pH to 6.5; Water is supplied certain volume then, in fermentation flask, charges into high pure nitrogen, behind the remaining oxygen, places 37 ℃ of constant temperature culture 72h then in the purging fermentation flask;
(3) with drainage aerogenesis is collected.
The present invention combines ultrasonic technology and s.t., has destroyed cellulosic structure significantly, has improved anaerobically fermenting hydrogen manufacturing.During with respect to simple s.t., the hydrogen that fermentation produces has improved 41.5%.
Ultrasonic pretreatment is as the method for a kind of effective increase anaerobism hydrogen manufacturing,, safety simple because of it, waits advantage easily and fast, will in the development of industrial sectorization, be widely used.
Embodiment
It is CO that the present invention adopts gas chromatographic analysis fermentation gas composition to the gas of collecting
2, H
2, CH
4Adopt the SP2000 gas chromatograph, thermal conductivity detector (TCD).Condition determination: PorapakQ6 foot stainless steel packed column (80/100Mesh), 35 ℃ of column temperature constant temperature; N
2Gas is carrier gas, flow velocity 20ml/min; Detector current and temperature are respectively 60mA, 100 ℃; Sampler is not shunted, 50 ℃ of sample introduction temperature.Quantitative with external standard method: the standard scrubbed gas with equal volume injects chromatographic column as external standard, obtains the standard reference color spectrogram.Then under the same conditions, testing sample is detected, obtain its color atlas.In color atlas, show identical RT with a kind of gas,, can calculate each gas-phase product concentration in the biogas according to peak area to be standard with volume standard gas.
The poor Hengshun Soy and Vinegar Factory, Zhenjiang that all takes from of vinegar among the present invention, through 120 ℃ of high-temperature sterilizations sterilizations, natural air drying, pulverized be encapsulated in the plastics bag behind 80 mesh sieves subsequent use.TS (total solids content), VS (volatility solid content) are respectively in this vinegar of mensuration is poor: 29.87%, 94.42%; Mud is taken near the sewage work the Jiangsu University of Zhenjiang.Mud after fetching is sealed in 4
.In the refrigerator of degree, during fermentation as the source of mixing the hydrogenogens kind.
Embodiment one:
(1) the poor pre-treatment of vinegar: the poor sample of vinegar that takes by weighing the 8g pulverizing is in the high pin beaker of several clean 250ml, under 30 ℃ of initial temperatures, by 2.0% hydrochloric acid solution and stirring that adds 60mL.Be ultrasonic 3min under the 900W at ultrasonic power then.Ultrasonic end, immediately with the cold water cooling, stirring and evenly mixing is regulated pH to 6.5 with HCl or the NaOH solution of 1mol/L.
(2) active sludge pre-treatment and anaerobically fermenting hydrogen manufacturing: take by weighing mud 16g, transfer pH to 11.0, wait leave standstill 1.5h after, again its pH is transferred to 6.5.Be settled to 200ml with tap water then, silicagel pad on the pad is tightened screw-cap.In fermentation flask, charge into high pure nitrogen through the conduit on the bottle cap, behind the remaining oxygen, clamp conduit in the purging fermentation flask, place water-bath to carry out 37 ℃ of constant temperature culture 72h then.With poor fermentation of vinegar as controlled trial without any processing, with drainage aerogenesis is collected, after the fermentation ends, carry out the gas-phase product composition analysis.
(3) gas phase compositional analysis: the fermentation gas composition is CO
2, H
2, CH
4Deng, its content is used gas chromatography determination.Adopt the SP2000 gas chromatograph, thermal conductivity detector (TCD).Condition determination: PorapakQ6 foot stainless steel packed column (80/100Mesh), 35 ℃ of column temperature constant temperature; N
2Gas is carrier gas, flow velocity 20ml/min; Detector current and temperature are respectively 60mA, 100 ℃; Sampler is not shunted, 50 ℃ of sample introduction temperature.Quantitative with external standard method: the standard scrubbed gas with equal volume injects chromatographic column as external standard, obtains the standard reference color spectrogram.Then under the same conditions, testing sample is detected, obtain its color atlas.In color atlas, show identical RT with a kind of gas,, can calculate each gas-phase product concentration in the biogas according to peak area to be standard with volume standard gas.Having recorded the hydrogen yield is 36～41%.
Embodiment two:
(1) the poor pre-treatment of vinegar: the poor sample of vinegar that takes by weighing the 8g pulverizing is in the high pin beaker of several clean 250ml, and under 30 ℃ of initial temperatures, adding 100mL concentration is respectively 0.2% hydrochloric acid solution and stirring, is ultrasonic 5min under the 700W at ultrasonic power then.Ultrasonic end, immediately with the cold water cooling, stirring and evenly mixing is regulated pH to 6.5 with HCl or the NaOH solution of 1mol/L.
(2) active sludge pre-treatment and anaerobically fermenting hydrogen manufacturing: take by weighing mud 4g, transfer pH to 11.0, wait leave standstill 1.5h after, again its pH is transferred to 6.5.Be settled to 200ml with tap water then, silicagel pad on the pad is tightened screw-cap.In fermentation flask, charge into high pure nitrogen through the conduit on the bottle cap, behind the remaining oxygen, clamp conduit in the purging fermentation flask, place water-bath to carry out 37 ℃ of constant temperature culture 72h then.With poor fermentation of vinegar as controlled trial without any processing, with drainage aerogenesis is collected, after the fermentation ends, carry out the gas-phase product composition analysis.
(3) gas phase compositional analysis: the fermentation gas composition is CO
2, H
2, CH
4Deng, its content is used gas chromatography determination.Adopt the SP2000 gas chromatograph, thermal conductivity detector (TCD).Condition determination: PorapakQ6 foot stainless steel packed column (80/100Mesh), 35 ℃ of column temperature constant temperature; N
2Gas is carrier gas, flow velocity 20ml/min; Detector current and temperature are respectively 60mA, 100 ℃; Sampler is not shunted, 50 ℃ of sample introduction temperature.Quantitative with external standard method: the standard scrubbed gas with equal volume injects chromatographic column as external standard, obtains the standard reference color spectrogram.Then under the same conditions, testing sample is detected, obtain its color atlas.In color atlas, show identical RT with a kind of gas,, can calculate each gas-phase product concentration in the biogas according to peak area to be standard with volume standard gas.Having recorded the hydrogen yield is 13～41%.
Embodiment three:
(1) the poor pre-treatment of vinegar: the poor sample of vinegar that takes by weighing the 8g pulverizing is in the high pin beaker of several clean 250ml; Under 30 ℃ of initial temperatures; The concentration that adds 100mL is 0.8% hydrochloric acid solution and stirring, is supersound process 15min under the condition of 400W at ultrasonic power then.Ultrasonic end, immediately with the cold water cooling, stirring and evenly mixing is regulated pH to 6.5 with HCl or the NaOH solution of 1mol/L.
(2) anaerobically fermenting hydrogen manufacturing: take by weighing mud 8g, transfer PH to 11.0, wait leave standstill 1.5h after, again its pH is transferred to 6.5.Be settled to 200ml with tap water then, silicagel pad on the pad is tightened screw-cap.In fermentation flask, charge into high pure nitrogen through the conduit on the bottle cap, behind the remaining oxygen, clamp conduit in the purging fermentation flask, place water-bath to carry out 37 ℃ of constant temperature culture 72h then.With poor fermentation of vinegar as controlled trial without any processing, with drainage aerogenesis is collected, after the fermentation ends, carry out the gas-phase product composition analysis.
(3) gas phase compositional analysis: the fermentation gas composition is CO
2, H
2, CH
4Deng, its content is used gas chromatography determination.Adopt the SP2000 gas chromatograph, thermal conductivity detector (TCD).Condition determination: PorapakQ6 foot stainless steel packed column (80/100Mesh), 35 ℃ of column temperature constant temperature; N
2Gas is carrier gas, flow velocity 20ml/min; Detector current and temperature are respectively 60mA, 100 ℃; Sampler is not shunted, 50 ℃ of sample introduction temperature.Quantitative with external standard method: the standard scrubbed gas with equal volume injects chromatographic column as external standard, obtains the standard reference color spectrogram.Then under the same conditions, testing sample is detected, obtain its color atlas.In color atlas, show identical RT with a kind of gas,, can calculate each gas-phase product concentration in the biogas according to peak area to be standard with volume standard gas.Having recorded the hydrogen yield is 17～45%.
Embodiment four:
(1) the poor pre-treatment of vinegar: the poor sample of vinegar that takes by weighing the 8g pulverizing is in the high pin beaker of several clean 250ml; Under 30 ℃ of initial temperatures; Adding 140mL concentration is 0.6% hydrochloric acid solution and stirring, is difference supersound process 10min under the 700W at ultrasonic power then.Ultrasonic end, immediately with the cold water cooling, stirring and evenly mixing is regulated pH to 6.5 with HCl or the NaOH solution of 1mol/L.
(2) anaerobically fermenting hydrogen manufacturing: take by weighing mud 6g, transfer PH to 11.0, wait leave standstill 1.5h after, again its pH is transferred to 6.5.Be settled to 200ml with tap water then, silicagel pad on the pad is tightened screw-cap.In fermentation flask, charge into high pure nitrogen through the conduit on the bottle cap, behind the remaining oxygen, clamp conduit in the purging fermentation flask, place water-bath to carry out 37 ℃ of constant temperature culture 72h then.With poor fermentation of vinegar as controlled trial without any processing, with drainage aerogenesis is collected, after the fermentation ends, carry out the gas-phase product composition analysis.
(3) gas phase compositional analysis: the fermentation gas composition is CO
2, H
2, CH
4Deng, its content is used gas chromatography determination.Adopt the SP2000 gas chromatograph, thermal conductivity detector (TCD).Condition determination: PorapakQ6 foot stainless steel packed column (80/100Mesh), 35 ℃ of column temperature constant temperature; N
2Gas is carrier gas, flow velocity 20ml/min; Detector current and temperature are respectively 60mA, 100 ℃; Sampler is not shunted, 50 ℃ of sample introduction temperature.Quantitative with external standard method: the standard scrubbed gas with equal volume injects chromatographic column as external standard, obtains the standard reference color spectrogram.Then under the same conditions, testing sample is detected, obtain its color atlas.In color atlas, show identical RT with a kind of gas,, can calculate each gas-phase product concentration in the biogas according to peak area to be standard with volume standard gas.Recorded hydrogen yield 13～44%.
Comparative Examples: with poor the fermentation as controlled trial of vinegar without any processing (ultrasonication and s.t.), other conditions are collected aerogenesis with drainage with embodiment 1, after the fermentation ends, carry out the gas-phase product composition analysis.Recorded hydrogen yield 10～25%.
Claims (1)
1. improve the method for the poor anaerobically fermenting hydrogen manufacturing of vinegar, comprise the steps:
(1) the poor pre-treatment of vinegar: the poor sample of vinegar that takes by weighing a certain amount of pulverizing; According to the feed liquid mass ratio is that 8:60 ~ 140 adding mass concentrations are 0.2 ~ 2.0% hydrochloric acid soln, stirs, under 30 ℃ of initial temperatures; Ultrasonic time 3 ~ 15min, the ultrasonic power 400 ~ 900W of processing; Ultrasonic end is regulated pH to 6.5 with 1mol/L NaOH solution; With the poor anaerobic fermentation tank that drops into of pretreated vinegar;
(2) active sludge pre-treatment and anaerobically fermenting: take by weighing a certain amount of active sludge, the mass ratio of the poor sample of active sludge and pretreated vinegar is: active sludge/vinegar sample=1:0.5 ~ 2 that are pickled with grains or in wine; Regulate the pH to 11.0 of active sludge with NaOH solution, leave standstill 1.5h after, transfer pH to 6.5; Water is supplied certain volume then, in fermentation flask, charges into high pure nitrogen, behind the remaining oxygen, places 37 ℃ of constant temperature culture 72h then in the purging fermentation flask;
(3) with drainage aerogenesis is collected.
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| CN104928322A (en) * | 2015-06-04 | 2015-09-23 | 江苏大学 | Method for increasing production of hydrogen by anaerobic fermentation of vinegar residue by adding metal trace element |
| 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 |
| CN110093377B (en) * | 2019-05-23 | 2023-02-07 | 太原理工大学 | Pretreatment method for improving dissolution efficiency of available organic matters in vinegar residue and anaerobic methane production potential of organic matters |
| CN113005057B (en) * | 2021-02-22 | 2022-06-07 | 江苏大学 | Method for culturing thermophilic bacteria by using vinegar residue and application of thermophilic bacteria to municipal sludge high-temperature biological drying |
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| JP2005324173A (en) * | 2004-05-17 | 2005-11-24 | Takuma Co Ltd | Method and apparatus for treating sludge |
| CN101649331A (en) * | 2009-09-15 | 2010-02-17 | 江苏大学 | Comprehensive treatment method of vinegar residues |
| CN101831463A (en) * | 2010-06-04 | 2010-09-15 | 中国科学院青岛生物能源与过程研究所 | Method for preparing biogas by two-phase anaerobic fermentation of oil-extracted algae slag |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005324173A (en) * | 2004-05-17 | 2005-11-24 | Takuma Co Ltd | Method and apparatus for treating sludge |
| CN101649331A (en) * | 2009-09-15 | 2010-02-17 | 江苏大学 | Comprehensive treatment method of vinegar residues |
| CN101831463A (en) * | 2010-06-04 | 2010-09-15 | 中国科学院青岛生物能源与过程研究所 | Method for preparing biogas by two-phase anaerobic fermentation of oil-extracted algae slag |
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