CN101259475A - Method for using chloromethane to inhibit methane discharging of consumer waste filling field - Google Patents
Method for using chloromethane to inhibit methane discharging of consumer waste filling field Download PDFInfo
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- CN101259475A CN101259475A CNA2008100367015A CN200810036701A CN101259475A CN 101259475 A CN101259475 A CN 101259475A CN A2008100367015 A CNA2008100367015 A CN A2008100367015A CN 200810036701 A CN200810036701 A CN 200810036701A CN 101259475 A CN101259475 A CN 101259475A
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Abstract
A method for restraining the methane discharge at a living garbage landfill field by using methyl chloride relates to a method which can stop the generation of the methane gas in the process of the anaerobic digestion of living garbage. Firstly, the methyl chloride of technical grade sold in the market is used as a depressor for the methane generating flora of the living garbage; then, each ton of living garbage is added with 5 to 25g of the methyl chloride and the water containing rate of the living garbage is 50 to 80 percent; then the methyl chloride is uniformly sprayed in the living garbage during the normal operation of the landfill field; finally, a measurement on the volatilization acid of the percolate of the living garbage is carried out; simultaneously the gas is collected by using a method of discharging the saturated salt water; a gas chromatography is used for detecting each component and content in the gas; the total capacity of the volatilization acid is 0.94 to 1.18g/kg; the ratio of monoprop to acetic acid is 0.73 to 1.24; the methane restraining effect can reach 100 percent. The invention has the low cost and the simple operation, which avoids the greenhouse effect caused by releasing the methane; and carries out control on the metabolizing of acid generating flora simultaneously when restraining the methane, which promotes the stabilization course of the landfill field.
Description
Technical field
The present invention relates to a kind of method that can stop the generation of methane gas in the domestic refuse anaerobic digestion process, belong to reclamation of solid wastes and pollution prevention technique field.
Background technology
Methane in the atmosphere is a kind of CO of being only second to
2Important greenhouse gases.The discharge capacity of the annual methane in the whole world reaches 5.35 * 10
8T, the methane content that produces by mankind's activity is 3.75 * 10
8T.According to estimates, the contribution of methane will reach 50% to the year two thousand thirty, become No.1 greenhouse gases.As seen, the discharge capacity of control methane is very important to the effect that suppresses greenhouse effects.At present, minimizing CO is all being sought in the whole world
2The measure of discharging, but the attention for methane is not enough, therefore cause the methane generating capacity to increase, and can cause the problem of the minimizing of those chemical substances that its content reduces neither be very clear, reduce discharge of methane and become extremely urgent problem with methane reaction.China produces 1.5 hundred million tons of domestic wastes per year, has built up 375 of house refuse sanitary filling fields (wherein most of is middle-size and small-size landfill yard), is using the thousands of seats in stockyard, and the landfill house refuse is estimated as 1,000,000,000 tons, and the methane of annual discharging is about millions of tons.Estimate that will there be 1000 middle-size and small-size house refuse sanitary filling fields in China in 10 years of future, day landfill house refuse is more than 500,000 tons, and day is discharged nearly ten thousand tons in methane.At large-scale landfill yard, these gases can be collected by pipeline and special gas collecting apparatus, but, at middle-size and small-size landfill yard, because the instability and the gas gross of aerogenesis are few, the value of comprehensive utilization is not high, and therefore the methane gas that produces generally all is discharged in the atmosphere, increase the concentration of methane in the air, cause the generation of greenhouse effects.
The stabilization procedures of refuse landfill is finished by the microbe symbiotic body, comprising many bacteriums and some intermediate steps are arranged.In this process, the metabolic process of different microorganisms influences each other, and mutual restriction forms the complicated ecosystem.The anaerobic degradation process of complex organic compound can roughly be divided into three phases: hydrolysis stage, product acid phase and product methane phase, and the task in each stage is all finished by specific microorganism species---hydrolysed ferment bacterial flora, acid-producing bacteria group and methanogen floras.Therefore; the anaerobic organism metabolic process is the process of material being connected and transmitting by microorganism; want to stop the generation of methane gas; methanogen floras must be suppressed; many people can't form the characteristics that gemma carries out self-protection according to methanogen in adverse circumstances; adopt methods such as heating, microwave, ultraviolet that methanogen is killed, but its complicated operation, be not suitable for the inhibition of methanogen in the place such as household refuse landfill sites.
Though the methanogen inhibition method of having reported at present is a lot, has following problem: 1, the inhibition effect is undesirable, and the methane that some microbial inhibitors only can suppress about 50% produces; 2, valid density is too high, and ammonia nitrogen and aliphatic acid report can effectively suppress the generation of methane in the landfill yard environment, and 3000ppm is above just to produce effect but its concentration will reach at least; 3, have and suppress effect and lower inhibition concentration preferably, but inapplicable and refuse landfill, such as anthraquinone class inhibitor, because its solubility is extremely low, be difficult to diffuse in the solid phase that methanogen floras is assembled in the rubbish; Coban, lasalocid can also produce stronger inhibitory action to hydrolysis bacterium and acid-producing bacteria when suppressing methanogen, be unfavorable for the stabilisation of landfill yard.
Summary of the invention
The objective of the invention is to disclose a kind of methanogenic method in the domestic refuse anaerobic digestion process that can suppress in the landfill yard.It specifically is the principle of utilizing biologic specificity to suppress, find the inhibitor that can effectively suppress the methanogen floras activity, the activity that suppresses methanogen in the landfill yard, make anaerobic digestion process no longer produce methane gas, but organic carbon is changed in the liquid phase, again the liquid phase of collecting is focused on, avoided discharging the greenhouse effects that methane causes.
In order to achieve the above object, the present invention is big according to the consumer waste filling and embedding amount, the multi phase state coexistence, and to when suppressing, keep the requirement of the normal stabilisation degradation process of landfill yard, at first seek and a kind ofly can take into account low, the easy diffusion of the effective inhibition concentration of household refuse landfill sites methane, other flora is not had inhibitory action or the very little inhibitor of inhibitory action.Experimentize then, find and suppress methane outstanding effect proportioning.
The present invention has found the chloromethane that comprises carrene, chloroform and tetrachloromethane as the methanogen floras inhibitor, it can be suppressed the activity of methanogen in the anaerobic digestion process as the additive of house refuse, make anaerobic digestion process no longer produce methane gas, but organic carbon is forwarded in the liquid phase, the liquid phase of collecting can be focused on like this, avoided discharging the greenhouse effects that methane causes.
Concrete technology is: at first, with commercially available technical grade chloromethane as house refuse methanogen floras inhibitor; Then, measure according to adding 5～25g chloromethane in the house refuse per ton, the moisture content of house refuse is 50～80% percentage by weights; Then, in the landfill yard routine work, equably chloromethane is sprayed to house refuse; The anaerobic reaction of beginning household refuse landfill sites behind the adding chloromethane, the percolate of house refuse is carried out the measurement of total volatile acid amount (VFA), collect gas with row's saturated common salt water law simultaneously, with each component and the content thereof in the gas Chromatographic Determination gas, total volatile acid amount is 0.94～1.18g/kg, propionic acid/acetate ratio is 0.73～1.24, and methane suppresses effect and reaches 100%.
The present invention has following advantage
1. chloromethane of the present invention has the advantages that to methanogen selectivity suppresses, and has guaranteed the efficient inhibition effect of extremely low concentration.By the metabolic pathway of methanogen as can be known: the acidylate methyl is transferred to tetrahydrochysene sarcine purine co-factor, generates CH
3Generate methyl coenzyme M (CH with (HS-CoM) reaction behind the-TPSPt
3-S-CoM), be reduced to methane by methyl coenzyme reductase demethylation at last, in the whole enzymatic process, methyl is all as fixed group, combine with tetrahydrochysene sarcine purine co-factor and coenzyme M respectively, and the chloroform in the chloromethane has and similar structure of methyl and active stronger hydrocarbon key, therefore, with well-known halogen (fluorine, chlorine, bromine, iodine) to the toxic comparison of bacterium, extremely low concentration chloromethane of the present invention is realized methanogen inhibitory action efficiently by competitive substrate is suppressed.
2. chloromethane of the present invention produces acid to system and has no side effect, and sour flora metabolic pathway is changed, improved propionic acid/acetate ratio, because propionic acid is difficult to be converted into methane, and is mainly propionic acid and acetate in the volatile acid, therefore, the generation of anaerobic digestion process methane has been blocked in the propionic acid/raising of acetate ratio, make house refuse maintain anaerobic digestion, prevent the acid-producing bacteria group because of inhibition influences the landfill yard stabilisation producing acid phase, guaranteed the landfill yard stabilisation continue carry out.
3. because the addition of chloromethane is to add 5～25mg by per kilogram rubbish (moisture content is 50～80%) to carry out, therefore, realizing that the landfill yard methanogen floras efficiently suppresses simultaneously, the cost of increase is very low.
4. chloromethane is added middle-size and small-size landfill yard, focus on behind the leachate collection that can produce, avoided the harm of the methane that produces in the landfill process, avoided discharging the greenhouse effects that methane causes, have positive social benefit environment.
Description of drawings
Fig. 1 is a process chart of the present invention
The chloromethane of Fig. 2 different content suppresses methane effect curve figure
The chloroform of Fig. 3 different content is to landfill yard stabilizing influence curve map
The specific embodiment
Embodiment 1
See also accompanying drawing 1,2 and 3.
Be behind 50～80% the house refuse simple crushing, to take by weighing 50g and put into the 150mL serum bottle moisture content.Then chloroform is diluted with water to the solution that chloroform content is 0.1% percentage by weight, the ratio that adds the 20mg chloromethane according to every kg house refuse, the aqueous solution of weighing 1g chloroform also adds in the serum bottle, the anaerobic state of simulation household refuse landfill sites, collect gas with row's saturated common salt water law, use the content of methane in the gas Chromatographic Determination gas and the composition and the content of volatile acid again, and the ratio that produces methane of the blank assay by inhibition group and the unconstrained dose rate that is inhibited, the result sees also Fig. 2 and Fig. 3.The main inhibition effect of chloroform (formal name used at school chloroform) under this concentration of investigating among the embodiment 1.When chloroform content during at 20mg/kg, methane is suppressed fully, suppresses effect near best.Total acid concentration is on the low side, illustrates that the chloroform of high concentration is influential to the stabilisation of landfill yard but as shown in Figure 3.
Embodiment 2
Change chloroform into carrene, add the metering of 5～25mg carrene according to every kg house refuse then, all the other are identical with embodiment 1.As shown in Figure 2, the highest inhibiting rate is 80%, because carrene mainly is to rely on the height of content of Cl element to realize suppressing, and does not have the specific substrate of chloroform to suppress, and it is poor therefore to suppress effect than chloroform.
Embodiment 3
Change chloroform into tetrachloromethane (also claiming carbon tetrachloride), add the metering of 5～25mg carbon tetrachloride according to every kg house refuse then, promptly carbon tetrachloride content is 5～25mg/kg, and all the other are identical with embodiment 1.As shown in Figure 2, the highest inhibiting rate is 90%, because carbon tetrachloride mainly is to rely on the height of content of Cl element to realize suppressing, and does not have the specific substrate of chloroform to suppress, and it is poor therefore to suppress effect than chloroform.
Embodiment 4
The content of chloroform is 5～25mg/kg, and all the other are identical with embodiment 1.Propionic acid in the percolate/acetate ratio is 0.73～1.24, and total volatile acid amount is 0.94～1.18g/kg.This has illustrated that the chloroform of high concentration has improved the concentration of propionic acid to acid-producing bacteria group's metabolic regulation effect, by the variation of total volatile acid (VFA) content as can be known chloroform concentration when being lower than 20mg/kg, can ignore acid-producing bacteria group inhibitory action, to the stabilisation of landfill yard total come have certain facilitation.
Claims (2)
1, suppress the method for household refuse landfill sites discharge of methane with chloromethane, it is characterized in that: at first, with commercially available technical grade chloromethane as house refuse methanogen floras inhibitor; Then, measure according to adding 5～25g chloromethane in the house refuse per ton, the moisture content of house refuse is 50～80% percentage by weights; Then, in the landfill yard routine work, equably chloromethane is sprayed to house refuse; At last, the percolate of house refuse is carried out the measurement of volatile acid, collect gas with row's saturated common salt water law simultaneously, with each component and the content thereof in the gas Chromatographic Determination gas, total volatile acid amount is 0.94～1.18g/kg, propionic acid/acetate ratio is 0.73～1.24, and methane suppresses effect can reach 100%.
2, according to the method with chloromethane inhibition household refuse landfill sites discharge of methane of claim 1, it is characterized in that: chloromethane wherein is carrene, chloroform and tetrachloromethane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174402A (en) * | 2011-01-31 | 2011-09-07 | 中国科学院过程工程研究所 | Method for preparing microbial agent for hydrolyzing and acidifying lignocellulose |
| CN102826732A (en) * | 2012-08-28 | 2012-12-19 | 清华大学 | Landfill methane depth control technology based on dissimilatory iron reduction |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2147647C (en) * | 1992-10-22 | 1999-06-01 | James Martin Odom | Anthraquinone inhibition of methane production in methanogenic bacteria |
| CN100502662C (en) * | 2007-04-30 | 2009-06-24 | 同济大学 | Additives for eliminating activity of methane bacteria used in house refuse buried field |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174402A (en) * | 2011-01-31 | 2011-09-07 | 中国科学院过程工程研究所 | Method for preparing microbial agent for hydrolyzing and acidifying lignocellulose |
| CN102174402B (en) * | 2011-01-31 | 2012-11-21 | 中国科学院过程工程研究所 | Method for preparing microbial agent for hydrolyzing and acidifying lignocellulose |
| CN102826732A (en) * | 2012-08-28 | 2012-12-19 | 清华大学 | Landfill methane depth control technology based on dissimilatory iron reduction |
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