CN102181486B - Method for promoting rapid preparation of methane from organic waste by utilizing exogenous hydrogen - Google Patents
Method for promoting rapid preparation of methane from organic waste by utilizing exogenous hydrogen Download PDFInfo
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- CN102181486B CN102181486B CN2011100609374A CN201110060937A CN102181486B CN 102181486 B CN102181486 B CN 102181486B CN 2011100609374 A CN2011100609374 A CN 2011100609374A CN 201110060937 A CN201110060937 A CN 201110060937A CN 102181486 B CN102181486 B CN 102181486B
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Abstract
The invention relates to a method for promoting the rapid preparation of methane from organic waste by utilizing exogenous hydrogen. The method comprises the following steps of: mixing sludge and domestic garbage in a weight ratio of 1:(2-4), wherein the content of volatile substances (VS) in the mixture is 20 to 65 percent, and the water content is 18 to 68 percent; and performing anaerobic fermentation reaction on the mixture for a period of 7 to 14 days at the temperature of between 35 and 37 DEG C and at the pH value of between 6.5 and 7.5, and introducing exogenous pure hydrogen under the pressure of between 1.1 and 5.5MPa from the bottom of the mixture in the second day of each period, wherein the maximum daily output of the methane can reach 3.65L/kg.d when the introducing amount is 50 to 150mL H2/kg VS, and is 2.81 times the yield of the methane when the hydrogen is not added. The concentration of the methane can be improved from 33.2 percent to 75.5 percent. The cost is low, the method is easy to operate, the problem of environmental pollution of municipal refuse and greenhouse gas is solved, and the clean energy is also provided, so that the method has good social benefit and economic benefit. The method can be widely applied to the rapid preparation of the methane from the organic waste in middle and small-sized landfill sites.
Description
Technical field
The present invention relates to a kind of external source hydrogen that utilizes and promote the quick methanogenic method of organic waste, belong to reclamation of solid wastes and pollution prevention technique field.
Background technology
Along with sustained economic development and resident living level steadily improve, China's domestic waste year generation has reached 1.5 hundred million tons, and (a day generation is 0.9～1.2kg) per capita, and every year is with 8～10% speed increment.The domestic rubbish disposal mode in the most of city of China is still take landfill as main, and rubbish can discharge a large amount of methane greenhouse gases in the landfill process, and content is up to 50～60%.At large-scale landfill yard, landfill gas can be collected by pipeline and special gas extractor, but for middle-size and small-size landfill yard, because aerogenesis is unstable, gas gross is few, comprehensive utilization value is not high, the methane gas that produces generally all directly enters atmosphere, has not only increased the weight of Greenhouse effect, and the today that lacks for the energy nowadays, biogas is not utilized effectively, and is a kind of very large waste.Therefore, the biogas output that how to improve middle-size and small-size household refuse landfill sites makes its effective utilization, is the important directions of present biogas utilization research.
The generation of methane derives from the anaerobically fermenting of rubbish, and this process is divided into three phases: hydrolysis, and produce hydrogen and produce acetic acid and produce methane phase.In anaerobic fermentation process, producing methane phase under the general condition is rate-limiting step, so methanogen is predominant bacteria in organism of fermentation.Methane finally utilizes acetic acid or H by methanogen
2/ CO
2For main matrix (also having formic acid, methyl alcohol and methylamine) is transformed.Wherein, utilize H
2/ CO
2The methane content that generates accounts for 1/3 of total methane production, and the methane content that (also can utilize methyl alcohol and methylamine) take acetic acid as matrix and generate accounts for 2/3 of total methane production.Refuse landfill landfill gas productive rate variation range is very large, and the productive rate of Accurate Prediction landfill gas is difficult to accomplish.The landfill gas productive rate that laboratory simulation obtains is 0～488L/kg/yr, and that field pilot test records is 13～37.5L/kg/yr, is 1～14L/kg/yr (being dried rubbish) and actual landfill yard records.
The method that improves the methane fermentation process efficiency is a lot, generally adopts following method: 1) add inoculum such as active sludge, organic fertilizer etc.; 2) ratio of adjusting inoculum and substrate, higher inoculum density can obviously improve factor of created gase; 3) add sodium ion, the metal ions such as calcium ion; 4) segmentation TPAD, and difference conditioned reaction parameter, such as pH, temperature.5) biogas refluxes.Contain more H with what hydrolysis, souring stage produced
2And CO
2Biogas introduce the methanation stage, for methanobacteria to H
2And CO
2Chemosynthesis sufficient basic substance is provided, this is introduced into, and I haven't seen you for ages increases by 30% methane content.6) temperature in raising methanation stage.Anaerobic process are usually higher to the requirement of temperature than aerobic processes, when the temperature of anaerobic process reaches respectively 35 ℃ and 55 ℃, the metabolic function of anaerobe reaches respectively the first peak value and the second peak value, can suitably the temperature in methanation stage be brought up to 35 ℃ or 55 ℃ thus, this both had been conducive to the growth and breeding of methanobacteria, improve the growing amount of methane, be conducive to again established methane and from reactor, parse in time.
Although the method for the raising methane production of having reported at present is a lot, have following problem: 1, facilitation effect is not obvious, and some additives only can increase the methane about 5-10% owing to running off or can't being evenly distributed; 2, complicated operation, wayward.Although the diphasic anaerobic fermentation can make the condition of producing methane phase be controlled to the best, but the parameter of regulating fermentation stage is a great engineering for day output large device or place, and the factor such as water ratio, temperature is affected greatly by extraneous weather condition, is difficult for manual control; 3, cost is higher, is not suitable for larger engineering, such as the metallic salt additive, because the amount that needs is large, therefore uses also not extensive.4, biogas refluxes and also has drawback.The H that forms previous stage
2With CO
2Be incorporated into the methanation stage, will cause H
2Wretched insufficiency.No matter can be found out by methanogenesis mechanism, be carbohydrate or lipoid substance, and protein is in forming the process of methane, H
2With CO
2Chemical combination all be to be undertaken by 4: 1 relation, but both produce in whole digestive process ratio but is not this ratio.CO
2The excessive decline that certainly will cause the pH value, thereby suppress the activity (top condition of methanobacteria is that pH value is neutral or summary meta-acid, meta-alkalescence) of methanobacteria, methane content is sharply reduced.
Summary of the invention
The objective of the invention is to disclose a kind of external source hydrogen that utilizes and promote the quick methanogenic method of organic waste.Specifically utilize the principle of biological excitation, find the additive that can effectively promote the methanogen floras activity, improve the activity of methanogen, make anaerobic digestion process continue to produce in large quantities methane gas, utilize for collecting, avoid discharging the Greenhouse effect that methane causes.
In order to achieve the above object, the present invention is large according to generation, the multi phase state coexistence, and the methanogenic requirement of keeping simultaneously the normal stabilization degradation process of rubbish will promoted, at first seek and a kind ofly can take into account domestic refuse anaerobic to produce methane speed fast, easily diffusion does not have restraining effect or the very little additive of restraining effect to other flora.Then test, find efficient raising to produce the operation scheme of methane effect.
The present invention is by replenishing an amount of external source pure hydrogen, makes it under the effect of methanobacteria and excessive CO
2Fully chemical combination reduces CO first
2Concentration improves the pH value, second increases the methanobacteria activity, strengthens the growing amount of methane, thereby has both avoided discharging the Greenhouse effect that methane causes, and the collecting methane resource utilization can be recycled again.
Concrete technology is:
At first, measure mud: domestic refuse=1: (2～4) weight ratio, mix, and to make volatile matter (VS) content of mixture be 20～65% weight percents,, water ratio is 18～68% weight percents; Then, said mixture is placed on 35～37 ℃ of temperature, carry out anaerobically fermenting 3-5 cycle of reaction under pH value 6.5～7.5 conditions, each cycle is 7～14 days, the external source pure hydrogen that at the second day in each cycle with pressure is 1.1～5.5MPa passes into from the mixture bottom, to promote organic substance decomposing in the mixture, improve methane production; The hydrogen intake is 50～150mL H
2During/kg VS (concentration of hydrogen this moment in system is 3～5%), reaction start time and aerogenesis peak can shift to an earlier date 4～7 days, compare conventional anaerobism and have saved the reaction domestication, and the whole anaerobic digestion cycle has shortened about 1/2.Continue to monitor gaseous fraction and the content in mixture top gas exit with gas chromatograph, when treating that the methane content fall per hour is no more than 1% in the gas of exit, stop to pass into of pure hydrogen, continue anaerobically fermenting, one-period finishes, and again repeats aforesaid operations, so periodically repeatedly passes into hydrogen, can routinely obtain maximum day output and reach the 3.65L/kg.d methane production, be not under the hydrogenated state 2.81 times of methane production; Methane concentration can bring up to 75.5% by 33.2%; Organic waste are converted into the energy conversion rate of methane and bring up to 2.93% by 1.04%.
The present invention has following advantage:
1. because the present invention has added hydrogen, anaerobically fermenting reaction start time and aerogenesis peak can shift to an earlier date 4～7 days, compare conventional anaerobism and have saved the reaction domestication, and the whole anaerobic digestion cycle can shorten about 1/2.And, gas production rate rises rapidly, reach very soon the aerogenesis peak, compare with the direct anaerobic digestion of organic waste, per day methane production can improve 2.81 times, methane concentration is also by bringing up to below 35% more than 75% simultaneously, and the minimum concentration that has satisfied the methane recycling requires (methane is 35% as the minimum concentration of combustion gas utilization, and minimum concentration is 40% when generating electricity and be used as).
2. because the anaerobic fermentation acid phase accumulates voltaile fatty acid easily, and it is excessive that the carbonic acid gas that produces the methane phase generation is compared hydrogen, therefore, the pH of reactive system easily is reduced to below 6.5, the methanogen activity is suppressed, therefore, the present invention makes it under the effect of methanobacteria by replenishing a certain amount of external source hydrogen, with excessive CO
2Fully chemical combination reduces CO
2Concentration, the activity of raising pH value and methanogen.
3. the CO that in anaerobic digestion process, generates
2Continuous discharging, except not causing the waste with hydrogen-gasified synthesizing methane gas, carbonic acid gas itself also is harmful to environment as greenhouse gases.Therefore, the present invention has reduced the discharging of carbon dioxide greenhouse gas first by added hydrogen, second takes full advantage of the carbonic acid gas of generation, makes organic waste can continue to produce efficiently methane, thereby has accelerated decomposition and the stabilization process of organic waste.
4. the methanogenic energy conversion rate of organic waste brought up to 2.93% by 1.04% before and after hydrogen of the present invention added.Therefore, cost that can be lower is realized the efficient output of methane.Simultaneously, organic waste are as raw material and the energy, and the introducing of hydrogen all improves its utilization ratio and energy conversion rate greatly, causes Greenhouse effect thereby avoided methane to discharge.
Description of drawings
Fig. 1 is process flow sheet of the present invention
Fig. 2 is that different content hydrogen of the present invention is to the impact effect figure of unit methane day output
Fig. 3 is that different content hydrogen of the present invention is to the impact effect figure of methane concentration
Fig. 4 is that hydrogen make-up of the present invention is to the impact effect figure of reaction system pH
Embodiment
See also accompanying drawing 1-4.
Be behind 50～60% the domestic refuse simple crushing, to take by weighing 12 parts of domestic refuse samples, every part of 0.070kg with water ratio.Prepare simultaneously water ratio and be 60～80% mud, also take by weighing 12 parts, every part of 0.030g.Domestic refuse and mud are respectively got 1 part of 200mL plastics testing bottle of packing into after fully mixing.This experiment is totally 12 parts of combined experiments samples, places respectively 12 assay flasks, is divided into 6 groups, every group of two Duplicate Samples.The VS content of combined experiments sample is about 20%, and water ratio is about 65%.Pass into nitrogen and make and do not contain other foreign gas in the assay flask, and be positioned over 37 ℃ of thermostatic chambers simulation anaerobically fermenting states after the sealing.Under 3.3MPa pressure, add respectively the pure H of 0,1,3,5,7,10mL from the assay flask lower end with injection needle tube
2(0mL's is blank group, in order to contrast; Because the VS content of sample is about 20%, so the pure H of 1～10mL
2Correspond respectively to 50,150,250,350 among Fig. 2-Fig. 4,500mLH
2/ kgVS).Seal after 24 hours and collect gas with row's saturated common salt water law, with each component and content thereof in the gas of gas Chromatographic Determination air outlet, the result is referring to Fig. 2 and Fig. 3.As seen from Figure 2, the sample of respectively organizing of hydrogenation all produces Zao that the methane peak occurs than blank group, high yield methane speed and methane production appear at behind the hydrogenation experimental group that hydrogen concentration in the mixture reaches 3%-5%, the maximum day output of methane can reach 3.65L/kgd, is not during hydrogenation 2.81 times of methane production.Can be got by Fig. 3, methane concentration can bring up to 75.5% by 33.2%.Be 4420kJ/g as the domestic refuse of experiment material and the mass-heat mechanical energy of mud mixture, H
2The mole thermodynamic energy be 242kJ/mol, CH
4A mole thermodynamic energy be 801kJ/mol, calculate the energy conversion rate of fermenting process with this, the Hydrogenation Experiment group is compared the energy conversion rate of blank group organic waste and is brought up to 2.93% by 1.04%.
See also accompanying drawing 4.
If the acid accumulation occurs rubbish anaerobic digestion process, namely pH descends, and then produces methane speed and greatly reduces, and the process of garbage decomposition also can slow down.Choose that the hydrogen addition is respectively 0,3mL and 5mL, all the other are identical with embodiment 1, (7-14 days) sampling solid-like in the one-period of reaction, with solid sample: water=1: 3 hybrid measurement pH the results are shown in Figure 4.PH by Fig. 4 system can find out that the pH of blank group has dropped to below 6.4, and so downward trend will suppress the activity of methanogen largely, hinders garbage decomposition and methane and produces.After adding hydrogen, anaerobic fermentation process pH is stabilized in 6.5～7.8, has effectively prevented the accumulation of voltaile fatty acid, is conducive to the existence of methanogen, thereby has kept the anaerobic digestion that organic waste continue, and has accelerated the stabilization process of its household refuse landfill sites.
Claims (1)
1. one kind is utilized external source hydrogen to promote the quick methanogenic method of organic waste, it is characterized in that: at first, measure mud: domestic refuse=1:(2～4) weight ratio, mix, and the VS content that makes the mixture that obtains is 20%～65% weight percent, water ratio is 18%～68% weight percent, and the mass-heat mechanical energy is 4420kJ/kg; Then, place 35～37 ℃ to be to carry out anaerobically fermenting 3-5 cycle of reaction under 6.5～7.5 conditions with the pH value in mixture, each cycle is 7～14 days, it is that the pure hydrogen of 1.1～5.5MPa passes into from mixture bottom that each cycle begins pressure from second day, and the hydrogen intake is 150～250mL H
2/ kg VS; Simultaneously, continue to monitor gaseous fraction and the content in mixture top gas exit with gas chromatograph; When treating that the methane content fall per hour is no more than 1% in the gas of exit, stop to pass into of pure hydrogen, continuing the anaerobically fermenting one-period finishes, again repeat aforesaid operations, so periodically repeatedly pass into the hydrogen anaerobically fermenting, can persistence obtaining maximum day output and reach the 3.65L/kgd methane production, is not under the hydrogenated state 2.81 times of methane production; Methane concentration can bring up to 75.5% by 33.2%; Organic waste are converted into the transformation efficiency of energy methane and bring up to 2.93% by 1.04%.
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| CN103205293A (en) * | 2012-01-16 | 2013-07-17 | 周鼎力 | Method for preparing combustion gas for vehicle and ship engines by kitchen garbage or/and organic waste |
| CN104651412A (en) * | 2015-02-05 | 2015-05-27 | 昆明理工大学 | Carbon dioxide and hydrogen biomethanation method |
| CN104926062B (en) * | 2015-07-07 | 2018-09-28 | 云南师范大学 | A kind of enrichment of hydrogen auxotype methanogen floras and acclimation method |
| CN105036500A (en) * | 2015-07-28 | 2015-11-11 | 同济大学 | Method for improving anaerobic digestion efficiency of organic wastes and content of methane in biogas |
| NO344851B1 (en) * | 2016-07-14 | 2020-06-02 | Zeg Power As | Method and device for upgrading of biogas and hydrogen production from anaerobic fermentation of biological material |
| CN106368673A (en) * | 2016-10-13 | 2017-02-01 | 中国石油化工股份有限公司 | Measuring method for water content and crude output of carbon dioxide flooding high water content oil reservoir producing well |
| CN108265081A (en) * | 2018-01-24 | 2018-07-10 | 中国石油大学(北京) | A kind of simple method for producing high quality biological methane |
| CN113481089A (en) * | 2021-07-28 | 2021-10-08 | 河南财政金融学院 | Two-phase anaerobic fermentation system for improving methane content in biogas |
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