CN108330090A - For the preparation method and purposes of the composite biological agent of pig manure waste medium temperature biogas fermentation high-content volatile fatty acid - Google Patents

For the preparation method and purposes of the composite biological agent of pig manure waste medium temperature biogas fermentation high-content volatile fatty acid Download PDF

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CN108330090A
CN108330090A CN201810203727.8A CN201810203727A CN108330090A CN 108330090 A CN108330090 A CN 108330090A CN 201810203727 A CN201810203727 A CN 201810203727A CN 108330090 A CN108330090 A CN 108330090A
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vitamin
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sodium
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郑涛
孙娟
陈琳
周政忠
袁浩然
何明阳
李东
刘晓风
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Changzhou University
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Abstract

The present invention relates to the composite biological agents and preparation method thereof for pig manure waste medium temperature biogas fermentation high-content volatile fatty acid.The composite biological agent of the present invention contains methanogen, medium temperature syntrophism acetic acid oxidation bacteria, medium temperature syntrophism propionic acid oxidation bacteria, medium temperature syntrophism butyric acid oxidized bacterium, trace element and vitamin.This composite biological agent can make pig manure be that the acidification marsh gas fermenting system of raw material quickly and effectively restores normal gas producing, and continuous and steady operation.The present invention also provides the preparation methods of above-mentioned composite biological agent, by pig manure inoculum and pig manure under raw material in the medium 37 DEG C of anaerobic conditions, increase sodium acetate, sodium propionate and butyric acid sodium content step by step and optimizes enrichment, ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, yeast powder, sodium acetate, sodium propionate and sodium butyrate are added after concentrating again, are then encapsulated Cord blood and are prepared into liquid composite biological agent.Can be further, 37 DEG C of anaerobism, which are dried, after being mixed with auxiliary material is made solid union biological agent.

Description

For the compound life of pig manure waste medium temperature biogas fermentation high-content volatile fatty acid The preparation method and purposes of object preparation
Technical field
The present invention relates to waste biofermentation techniques, and in particular to is directed to pig manure waste medium temperature biogas fermentation high-content The preparation method of the composite biological agent of volatile fatty acid, belongs to technical field of biological fermentation.
Background technology
In recent years, China's pig breeding industry is rapidly developed, and 2012~2016 years live pigs are delivered for sale all about 690,000,000. Feeding live pig produces the fecaluria excreta of enormous amount, and pig manure solid content is high, containing high-enriched organics, nitrogen, phosphorus, pathogenic bacteria With pathogenic microorganism etc..Unprocessed or processing can then not cause many environmental problems in qualified discharge to environment.Livestock and poultry are supported It grows prevention and cure of pollution work to relatively lag behind, Pollution from livestock and poultry is on the rise, and Pollution from livestock and poultry has become Chinese environmental pollution Key factor source.
Anaerobic digestion techniques are to handle the effective way of pig manure, and the biomass of pig manure can be converted to methane energy by it The pollution of environment to realize the recycling of resource and the energy, and is reduced in source.From energy angle preliminary budget, 1 ton of dry pig manure phase When in 0.3 ton or so of coal.Meanwhile anaerobic digestion can eliminate 90% or more poultry egg parasitoid, Escherichia coli etc., substantially Innoxious requirement can be reached, and be enriched the biological renewable energy for being easy to utilize, thus, anaerobic digestion methane production is pig The important means of excrement recovery energy.
In anaerobic digestion process, heavy-duty service easily accumulates a large amount of volatile fatty acid (VFA), for a long time, VFA Concentration by one of the important parameter as effective control anaerobic digester system.The concentration of VFA is under the conditions of system unstability, reflection The coupled action of sour generation and consumption, their accumulation can directly result in the reduction of pH, eventually lead to the collapse of reaction system, Thus many scholars think that the stability of volatile acid concentration and system has certain correlation.In fact, inhibition of the VFA to methane Be free VFA concentration has substantial connection with pH, its accumulation can indirectly be reflected by the variation of pH, but pH and and basic species Matter (ammonia) is related, and alkaline matter is related with the protein content in raw material, and when methanogen is to the tolerance of VFA can With by taming raising.
Usually it is the pH value of regulating system to the restoration methods of the marsh gas fermenting system of acidification, but is usually to add a large amount of stones The addition of the alkaline matters such as ash, ammonium hydrogen carbonate, potassium hydroxide, sodium hydroxide, these alkaline matters can influence the fermentation system later stage Efficiency, and if fermentation system when severe acidification, even if if pH is adjusted to neutrality system by these alkaline matters not It can restore aerogenesis, can only discharge or renewed vaccination of reloading greatly starts.However, restarting takes time and effort consumption object, and need compared with Long time domestication ability normal gas producing, this is undoubtedly prodigious loss for the engineering of anaerobic digestion gas production.Therefore, it is necessary to Develop a kind of restorative that can quickly and effectively restore to be acidified marsh gas fermenting system.
Invention content
Of the existing technology it is a primary object of the present invention to overcome the problems, such as, present invention firstly provides a kind of acidification biogas Fermentation system restores the composite biological agent of aerogenesis, and composite biological agent is mainly used for causing aerogenesis to reduce or stop production because of acidification The pig manure of gas is the anaerobic fermentation system of raw material, may make the system recovery value normal gas producing being acidified, a large amount of without addition Alkaline matter or discharging are reloaded greatly, and can guarantee the continuous-stable aerogenesis of marsh gas fermenting system.In addition, the present invention also provides one Kind restores the preparation method of the composite biological agent of aerogenesis, foundation this method for the acidification marsh gas fermenting system that pig manure is raw material It can make to obtain liquid composite biological agent and solid union biological agent.
In order to solve the above-mentioned technical problem, the invention is realized by the following technical scheme.
The present invention first provides a kind of liquid compound bio restoring aerogenesis for the acidifying fermentation system that pig manure is raw material Preparation, said preparation mainly contain methanogen, medium temperature syntrophism acetic acid oxidation bacteria, medium temperature syntrophism propionic acid oxidation bacteria, medium temperature syntrophism fourth Acid oxidase bacterium, trace element and vitamin.
Wherein, the methanogen include but not limited to methanimicrococcus, methanococcoides, methanohalobium、halomethanococcus、methanocella、methanolinea、methanocalculus、 Methanospirillum, methanocorpusculum etc. the Pseudomonas can be used alone or using mixing Pseudomonas.
The medium temperature syntrophism acetic acid oxidation bacteria including but not limited to SAOB Clostridium ultunense, Thermacetogenium phaeum、Tepidanaerobacter acetatoxydans Re1、 The Pseudomonas can be used alone or used by Thermoanaerobacteraceae and Thermotoga lettingae etc. Mix Pseudomonas.
The medium temperature syntrophism propionic acid oxidation bacteria including but not limited to Smithella propionica, Syntrophobacter fumaroxidans and Pelotomaculum thermopropionicum etc., can be by the Pseudomonas It is used alone or using mixing Pseudomonas.
The medium temperature syntrophism butyric acid oxidized bacterium is including but not limited to Syntrophomonas wolfei subsp.Methylbutyratica subsp、Syntrophomonas cellicola、Syntrophomonas erecta、 Syntrophomonas erecta subsp. sporosyntropha subsp, Syntrophomonas sapovorans and Syntrophomonas palpitatica etc. the Pseudomonas can be used alone or using mixing Pseudomonas.
The trace element is iron content (Fe), the compound of cobalt (Co), nickel (Ni), molybdenum (Mo), tungsten (W) and selenium (Se), packet It includes but does not limit to ferrous sulfate, cobalt chloride, nickel chloride, sodium molybdate, sodium tungstate and sodium selenate.
The vitamin is containing niacin, p-aminobenzoic acid, vitamin B6 (including but not limited to pyridoxine), vitamin B7 (including but not limited to biotin), folic acid, vitamin B2 (including but not limited to riboflavin), thiamine.
Preferably, in the liquid biological preparation, the methanogen, medium temperature syntrophism acetic acid oxidation bacteria, medium temperature syntrophism third Acid oxidase bacterium and medium temperature syntrophism butyric acid oxidized bacterium total cell concentration at least 1 × 109A/mL, and methane backeria, medium temperature syntrophism acetic acid oxygen Change bacterium, medium temperature syntrophism propionic acid oxidation bacteria and medium temperature syntrophism butyric acid oxidized bacterium cell quantity ratio, is preferably 1:1:1:1.
Preferably, in the liquid biological preparation, the concentration of a concentration of 0.5~5mg/L of iron, cobalt in the trace element For 0.1~1mg/L, a concentration of 0.2~2mg/L of nickel, a concentration of 0.1~1mg/L of molybdenum, tungsten a concentration of 0.01~ A concentration of 0.01~0.1mg/L of 0.1mg/L, selenium.
Preferably, in the liquid biological preparation, Nicotinic is 0.01~0.05mg/L, to amino in the vitamin Concentration of benzoic acid be 0.01~0.03mg/L, a concentration of 0.05~0.1mg/L of vitamin B6, vitamin B7 a concentration of 0.001~ 0.005mg/L, folic acid concentration are 0.001~0.005mg/L, a concentration of 0.005~0.01mg/L of vitamin B2, thiamine concentration For 0.005~0.01mg/L.
In addition, as an improvement of the present invention, for ease of long-term preservation, the present invention is above-mentioned for the acid that pig manure is raw material Change marsh gas fermenting system restore aerogenesis liquid composite biological agent in, in addition to contain methanogen, medium temperature syntrophism acetic acid oxidation bacteria, Other than medium temperature syntrophism propionic acid oxidation bacteria, medium temperature syntrophism butyric acid oxidized bacterium, trace element and vitamin, can also contain ammonium chloride, Magnesium sulfate, potassium chloride, calcium chloride, yeast powder, sodium acetate, sodium propionate and sodium butyrate, their preferred content is respectively 0.5~ 1.0g/L, 0.5~1.0g/L, 0.8~1.0g/L, 0.2~0.5g/L, 2~5g/L, 10~15g/L, 8~10g/L, 7~ 10g/L。
The present invention second provides a kind of solid union biology restoring aerogenesis for the acidifying fermentation system that pig manure is raw material Preparation, said preparation mainly contain methanogen, medium temperature syntrophism acetic acid oxidation bacteria, medium temperature syntrophism propionic acid oxidation bacteria, medium temperature syntrophism fourth Acid oxidase bacterium, trace element and vitamin.
Wherein, the methanogen methanogen include but not limited to methanimicrococcus, methanococcoides、 methanohalobium、halomethanococcus、methanocella、 Methanolinea, methanocalculus, methanospirillum, methanocorpusculum etc., can will be described Pseudomonas is used alone or using mixing Pseudomonas.
The medium temperature syntrophism acetic acid oxidation bacteria including but not limited to SAOB Clostridium ultunense, Thermacetogenium phaeum、Tepidanaerobacter acetatoxydans Re1、 The Pseudomonas can be used alone or used by Thermoanaerobacteraceae and Thermotoga lettingae etc. Mix Pseudomonas.
The medium temperature syntrophism propionic acid oxidation bacteria including but not limited to Smithella propionica, Syntrophobacter fumaroxidans and Pelotomaculum thermopropionicum etc., can be by the Pseudomonas It is used alone or using mixing Pseudomonas.
The medium temperature syntrophism butyric acid oxidized bacterium is including but not limited to Syntrophomonas wolfei subsp.Methylbutyratica subsp、Syntrophomonas cellicola、Syntrophomonas erecta、 Syntrophomonas erecta subsp. sporosyntropha subsp, Syntrophomonas sapovorans and Syntrophomonas palpitatica etc. the Pseudomonas can be used alone or using mixing Pseudomonas.
The trace element is iron content (Fe), the compound of cobalt (Co), nickel (Ni), molybdenum (Mo), tungsten (W) and selenium (Se), packet It includes but does not limit to ferrous sulfate, cobalt chloride, nickel chloride, sodium molybdate, sodium tungstate and sodium selenate.
The vitamin is containing niacin, p-aminobenzoic acid, vitamin B6 (including but not limited to pyridoxine), vitamin B7 (including but not limited to biotin), folic acid, vitamin B2 (including but not limited to riboflavin), thiamine.
Preferably, in the liquid biological preparation, the methanogen, medium temperature syntrophism acetic acid oxidation bacteria, medium temperature syntrophism third Acid oxidase bacterium and medium temperature syntrophism butyric acid oxidized bacterium total cell concentration at least 1 × 109A/g, and methane backeria, medium temperature syntrophism acetic acid oxygen Change bacterium, medium temperature syntrophism propionic acid oxidation bacteria and medium temperature syntrophism butyric acid oxidized bacterium cell quantity ratio, is preferably 1:1:1:1.
Preferably, in the solid-state biological agent, a concentration of 0.5~5mg/kg of iron in the trace element, cobalt it is dense Degree be 0.1~1mg/kg, a concentration of 0.2~2mg/kg of nickel, a concentration of 0.1~1mg/kg of molybdenum, tungsten a concentration of 0.01~ A concentration of 0.01~0.1mg/kg of 0.1mg/kg, selenium.
Preferably, and in the solid-state biological agent, in the vitamin Nicotinic be 0.01~0.05mg/kg, A concentration of 0.01~0.03mg/kg of p-aminobenzoic acid, a concentration of 0.05~0.1mg/kg of vitamin B6, vitamin B7 are a concentration of 0.001~0.005mg/kg, folic acid concentration are 0.001~0.005mg/kg, a concentration of 0.005~0.01mg/ of vitamin B2 Kg, a concentration of 0.005~0.01mg/kg of thiamine.
In addition, as an improvement of the present invention, for ease of long-term preservation, the present invention is above-mentioned for the acid that pig manure is raw material Change in the solid union biological agent that marsh gas fermenting system restores aerogenesis, in addition to containing medium temperature syntrophism acetic acid oxidation bacteria, medium temperature syntrophism Propionic acid oxidation bacteria, medium temperature syntrophism butyric acid oxidized bacterium, trace element can also contain ammonium chloride, magnesium sulfate, chlorine with other than vitamin It is respectively 0.5~1.0g/kg, 0.5 to change potassium, calcium chloride, yeast powder, sodium acetate, sodium propionate and sodium butyrate, their preferred content ~1.0g/kg, 0.8~1.0g/kg, 0.2~0.5g/kg, 2~5g/kg, 10~15g/kg, 8~10g/kg, 7~10g/kg.
Third of the present invention provides a kind of above-mentioned liquid for restoring aerogenesis for the acidification marsh gas fermenting system that pig manure is raw material The preparation method of composite biological agent, this method comprises the following steps:
(1) it takes the seed sludge that pig manure is raw material in anaerobic fermentation tank, adds methanogen culture medium, trained in advance It supports, at 37 DEG C of preferable temperature, mainly with methane content for main monitor control index during preculture, when methane phase content is 60% More than, and stablize and maintain a period of time, wait for that its organic matter is depleted.
(2) preferred volume ratio is (1~3) to the pig manure seed sludge Yu culture medium of step (1) under anaerobic:(1~3) Mixing, adds above-mentioned trace element, vitamin, and the content for increasing sodium acetate, sodium propionate and sodium butyrate step by step is cultivated, often 37 DEG C of the preferred cultivation temperature of level-one, cultivation cycle period are 14~20 days.
(3) step (2) culture reaches certain limit, anaerobic digestion to inoculum to the tolerance level of acetic acid, propionic acid and butyric acid System still stable operation.
(4) microbial inoculum obtained by step (3) is concentrated.
Trace element described in step (2) is iron content (Fe), cobalt (Co), nickel (Ni), molybdenum (Mo), tungsten (W) and selenium (Se) Compound, including but not limited to ferrous sulfate, cobalt chloride, nickel chloride, sodium molybdate, sodium tungstate and sodium selenate.Trace element addition Amount is the iron (Fe) of 0.5~5mg, the cobalt (Co) of 0.1~1mg, 0.2 in the mixed liquor of every 1L pig manures seed sludge and culture medium The selenium (Se) of the nickel (Ni) of~2mg, the molybdenum (Mo) of 0.1~1mg, the tungsten (W) of 0.01~0.1mg, 0.01~0.1mg.
Vitamin described in step (2) is (to tremble including but not limited to pyrrole containing niacin, p-aminobenzoic acid, vitamin B6 Element), vitamin B7 (including but not limited to biotin), folic acid, vitamin B2 (including but not limited to riboflavin), thiamine.
Vitamin additive amount be the niacin of 0.01~0.05mg in mixed liquor per 1L pig manures seed sludge and culture medium, The p-aminobenzoic acid of 0.01~0.03mg, the vitamin B6 of 0.05~0.1mg, 0.001~0.005mg vitamin B7s, The thiamine of the folic acid of 0.001~0.005mg, the vitamin B2 of 0.005~0.01mg, 0.005~0.01mg.
Culture medium described in step (2) is ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, potassium dihydrogen phosphate, phosphoric acid hydrogen two Potassium, sodium bicarbonate, yeast powder, above-mentioned trace element and vitamin.
Ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, phosphorus are added per 1L pig manures seed sludge and in the mixed liquor of culture medium Acid dihydride potassium, dipotassium hydrogen phosphate, sodium bicarbonate, yeast powder, it is above-mentioned trace element and vitamin, they preferred content difference For 0.5~1.0g, 0.5~1.0g, 0.5~1.0g, 0.15~0.3g, 0.2~0.5g, 0.5~1.0g, 2~5g, 5~10g, 2~5mL, 0.5~1mL.
It, can be with for ease of long-term preservation, in the liquid composite biological agent in addition, as an improvement of the present invention Add ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, yeast powder, sodium acetate, sodium propionate and sodium butyrate, their preferred content point It Wei not 0.5~1.0g/L, 0.5~1.0g/L, 0.8~1.0g/L, 0.2~0.5g/L, 2~5g/L, 10~15g/L, 8~10g/ L, 7~10g/L.And it is stored in 2~8 DEG C.
It is multiple to provide a kind of above-mentioned solid-state for restoring aerogenesis for the acidification marsh gas fermenting system that pig manure is raw material by the present invention four The preparation method of biological agent is closed, this method comprises the following steps:
(1) rice bran or wheat bran or pig manure or pig manure sludge or two or more arbitrary mixing are dried, as Auxiliary material.
(2) auxiliary material for the liquid composite biological agent and step (1) for obtaining the present invention three is under anaerobic by quality Than being 1:1 mixing, stirs evenly, and it is 5~25% that water content is dried under 37 DEG C of constant temperatures of anaerobism, is as directed to pig manure Restore the solid union biological agent of aerogenesis for the acidification marsh gas fermenting system of raw material, encapsulation is stored in 2~8 DEG C.
It, can be with for ease of long-term preservation, in the solid union biological agent in addition, as an improvement of the present invention Add ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, yeast powder, sodium acetate, sodium propionate and sodium butyrate, their preferred content point It Wei not 0.5~1.0g/kg, 0.5~1.0g/kg, 0.8~1.0g/kg, 0.2~0.5g/kg, 2~5g/kg, 10~15g/kg, 8 ~10g/kg, 7~10g/kg.
The present invention design and action principle be:The Biological Principles that the present invention is acidified according to marsh gas fermenting system, and Methanogen, syntrophism acetic acid oxidation bacteria, syntrophism propionic acid oxidation bacteria and syntrophism butyric acid oxidized bacterium growth and metabolic characteristic, pass through by Methanogen, syntrophism acetic acid oxidation bacteria, syntrophism propionic acid oxidation bacteria and the growth of syntrophism butyric acid oxidized bacterium and metabolic characteristic combination, together Shi Tianjia trace elements are finally prepared into liquid or solid-state as methane metabolic improver, addition vitamin as nutritional supplementation Composite biological agent.In addition, carrying out enrichment methanogen, syntrophism acetic acid oxidation bacteria, syntrophism with the inoculum that pig manure is raw material Propionic acid oxidation bacteria and syntrophism butyric acid oxidized bacterium, microbiologic population is similar with microbiologic population in pig manure anaerobic digester system, because And it is more adaptable for the anaerobic digester system that pig manure is raw material.The composite biological agent is added to the natural pond that pig manure is raw material In gas fermentation system, propionic acid can be oxidized to acetic acid and CO by syntrophism propionic acid oxidation bacteria by methylmalonyl-CoA approach2, syntrophism Acetic acid oxidation bacteria can with methanogen cooperation by acetic acid oxidation be CO2And H2, then pass through original hydrogen nutrition in marsh gas fermenting system Type methane phase Gu bacterium is converted into CH4, syntrophism butyric acid oxidized bacterium by beta-oxidation approach aoxidize butyric acid, oxidation product be mainly acetic acid, Propionic acid and H2, product is converted by syntrophism acetic acid and propionic acid oxidation bacteria and methanogen again, to may make biogas fermentation The acetic acid of system, propionic acid, butyric acid content reduce and increase pH value, original in marsh gas fermenting system when pH value rises to neutral range Methanogen start activity recovery, normally growth and methane phase metabolism are carried out, to restore pig manure acidification biogas fermentation system System normal gas producing.Trace element and vitamin have activation facilitation to methanogen, can improve the speed of methane phase metabolism Rate, to promote marsh gas fermenting system to restore normal gas producing.
Specific implementation mode
Embodiment of the present invention described further below.
It is prepared by 1 liquid composite biological agent of embodiment
It selects to be mainly the seed sludge 56L of raw material in 70L anaerobic fermentation tanks using pig manure, to improve the activity of sludge, Early period is tamed, methane phase culture medium is added, and add a small amount of pig manure, at 37 DEG C of medium temperature condition, during domestication, mainly with methane Content is as main monitor control index, when system methane phase content is up to 60% or more, and stablizes and maintains a period of time, and waits for that biogas is sent out Organic matter in ferment system is depleted.
The pig manure inoculum that 1L is above-mentioned is taken, 1L culture mediums are prepared, which includes the anhydrous sulphur of ammonium chloride, 1.0g of 1.6g The carbonic acid of sour magnesium, the potassium chloride of 1.6g, 0.5g anhydrous calcium chlorides, the potassium dihydrogen phosphate of 0.8g, the dipotassium hydrogen phosphate of 1.6g, 10g The above-mentioned trace element of hydrogen sodium, 8g yeast powders, 10mL and 2mL said vitamins, inoculum is mixed with culture medium, adjusts pH 7.3, it is blown with High Purity Nitrogen and blows out oxygen so that keep anaerobic environment, sodium acetate, sodium propionate and sodium butyrate in fermentation tank Addition content is respectively 600mg/L, 300mg/L, 150mg/L, and cultivation temperature is 37 DEG C, and cultivation cycle is 14 days, then with 1:1 Volume ratio be forwarded to second level culture, keep and the same terms of first order culture, sodium acetate, sodium propionate, sodium butyrate point 1000mg/L, 500mg/L, 250mg/L, incubation time 14 days are not increased to.Increase sodium acetate, sodium propionate and butyric acid step by step backward Sodium content increases to anaerobic digester system and reaches maximum to the tolerance level of acetic acid, propionic acid, butyric acid, while incubation time suitably prolongs It is long, the stabilization of anaerobic digester system is kept, the liquid compound bio system for the marsh gas fermenting system that pig manure is raw material is obtained The chlorination of the ammonium chloride, 0.5g/L anhydrous magnesium sulfates, the potassium chloride of 0.8g/L, 0.3g/L of 0.8g/L is added in agent for long-term preservation Calcium, the yeast powder of 4g/L, the sodium acetate of 10g/L, the sodium propionate of 8g/L and 7.5g/L sodium butyrate anaerobic condition under be stored in 4 ℃。
It is prepared by 2 solid union biological agent of embodiment
Liquid biological preparation is obtained under High Purity Nitrogen atmosphere with mass ratio 1 by pig manure sterilizing-drying, and with embodiment 1:1 is mixed It closes, stirs evenly, and water content is dried to 8% under 37 DEG C of constant temperatures under above-mentioned anaerobic condition, added for long-term preservation The ammonium chloride of 0.8g/kg, the ferment of 0.5g/kg anhydrous magnesium sulfates, the potassium chloride of 0.8g/kg, the calcium chloride of 0.3g/kg, 4g/kg The sodium butyrate of female powder, the sodium acetate of 10g/kg, the sodium propionate of 8g/kg and 7.5g/kg is as directed to the biogas that pig manure is raw material The solid-state Biological compound preparation of fermentation system is stored in 4 DEG C under anaerobic condition.
3 liquid composite biological agent effect test of embodiment
Select pig manure for the marsh gas fermenting system of raw material being acidified, pH value 5.8, CH4Content 35%, acetic acid content: 15000mg/L, propionic acid content:8000mg/L, butyric acid content:7000mg/L.Seven groups of control batch of a, b, c, d, f, g, h are set Fermentation, takes the biogas fermentative liquid of above-mentioned acidification in a, b, c, d, f;The g groups biogas that vegetable castoff is that raw material has been acidified Zymotic fluid, pH value 6.0, CH4Content 34%, acetic acid content:15000mg/L, propionic acid content:8000mg/L, butyric acid content: 700mg/L;The h groups biogas fermentative liquid that cow dung is that raw material has been acidified, pH value 5.9, CH4Content 35%, acetic acid content: 15000, propionic acid:8000mg/L, butyric acid content:7000mg/L.Biogas fermentative liquid volume is 2L, and equal anaerobic condition simultaneously controls hair 37 DEG C of ferment temperature.
It is to add embodiment 1 in b fermentation tanks to add liquid composite biological agent 200mL made from embodiment 1 at the beginning Liquid composite biological agent 300mL obtained adds liquid composite biological agent 300mL made from embodiment 1 in c fermentation tanks In g fermentation tanks, liquid composite biological agent 300mL is in h fermentation tanks made from addition embodiment 1, and a, d, e, f are as a contrast Group does not add liquid composite biological agent.
It is observed within the 2nd~5 day in fermentation:Add b, c group of liquid composite biological agent, pH from 5.8 through 6.2,6.8, 6.9 rise to 7.3, and gas production gradually increases, and c group gas production is more than b groups, and methane content increases to 65%, 35% increasing from 35% respectively To 68%;G and h groups, gas production increase is less apparent, and methane content increases to 39%, 35% from 34% respectively and increases to 40%;Not A, d, e, f group of liquid composite biological agent are added, aerogenesis state, methane content are not even as low as 28% substantially.At this point, addition Liquid composite biological agent 200mL made from embodiment 1 is to add the compound life of liquid made from embodiment 1 in d fermentation tanks In e fermentation tanks, addition ammonium bicarbonate soln to f groups, adjusting pH to 7.2, a groups continues as a control group both object preparation 300mL Liquid composite biological agent is not added, does not add ammonium bicarbonate soln yet.
In fermentation the 6th~10 day, observed:B, c group of liquid composite biological agent are added, pH value continues to increase and tend to Stablize, stablize from 7.3 to 7.6, gas production, which continues to increase, to tend towards stability, and methane content all continues to increase, and stablizes respectively 70% With 72%;G and h groups, pH rise to 6.3 and 6.2 respectively, and gas production also has continuation increase tendency, methane content to increase respectively from 39% 42% is increased to 41%, 40%;D, e group of liquid composite biological agent are added, pH rises to 7.2 from 5.5 through 5.9,6.7,6.9, Gas production gradually increases, and e group gas production is more than d groups, and methane content increases to 59%, 29% from 28% respectively and increases to 59%;Addition The f groups of ammonium hydrogen carbonate, though pH still keeps neutral range, but still not aerogenesis, methane content are still very low.It is compound to be not added with liquid Biological agent is also not added with a groups of ammonium hydrogen carbonate alkaline matter, does not observe that aerogenesis, pH maintain 5.5.
Fermenting experiment proceeds to the 20th day, is not added with liquid composite biological agent and is also not added with ammonium hydrogen carbonate alkaline matter A groups, substantially not aerogenesis, for methane content down to stablizing 26%, acetic acid, propionic acid and butyric acid content also have increase;Add liquid life B, c, d, e group of object compound formulation, pH are basically stable at 7.5 or so, and methane content is basically stable at 70%, wherein b, c group second Acid, propionic acid, butyric acid content are down to 1600mg/L, 900mg/L, 300mg/L and 1300mg/L, 750mg/L, 200mg/L respectively;d、 E groups acetic acid, propionic acid, butyric acid content be down to respectively 2500mg/L, 1400mg/L, 600mg/L and 2000mg/L, 900mg/L, 450mg/L;It is not added with liquid biological compound formulation but adds the f groups of ammonium hydrogen carbonate alkaline matter, do not observe that aerogenesis, pH maintain 7.1, methane content 25%, acetic acid, propionic acid, butyric acid content be not also because addition ammonium hydrogen carbonate decreases;Add liquid life G, h group of object compound formulation restore slower, and methane content is respectively maintained at 52% and 54%, acetic acid, propionic acid and butyric acid content drop Low amplitude is all smaller.
The above description of test, the acidification even marsh gas fermenting system of severe acidification for pig manure as raw material, addition is originally The liquid composite biological agent of invention can make its fast quick-recovery aerogenesis, effectively reduce the content of acetic acid, propionic acid, butyric acid, from And stable operation;For the marsh gas fermenting system of severe acidification, though pH can be adjusted to neutral model by addition ammonium hydrogen carbonate alkaline matter It encloses, but gas generation property is still very low;Acidification marsh gas fermenting system for vegetable castoff and cow dung as raw material, adds this hair Bright composite biological agent restores slower.It is raw material that this liquid composite biological agent for being primarily due to the present invention, which is by pig manure, Pig manure inoculum Anaerobic culturel, for pig manure be raw material marsh gas fermenting system it is adaptable, then by methanogen, mutually The common cooperation for seeking acetic acid oxidation bacteria, syntrophism propionic acid oxidation bacteria, syntrophism butyric acid oxidized bacterium efficiently uses conversion acetic acid, propionic acid, fourth Acid, so that marsh gas fermenting system pH is adjusted to neutrality range.And although the addition of ammonium hydrogen carbonate has adjusted pH, but biogas is sent out Volatile organic aliphatic acid in ferment system is not degraded, and the activity of methanogen is still inhibited.
4 solid union biological agent effect test of embodiment
The experiment is continuously fermented using the marsh-gas fermentation tank of 70L, initial inoculum 60%, controls biogas fermentation temperature 37 DEG C of degree.Pig manure is respectively adopted, vegetable castoff, cow dung are that raw material carries out biogas fermentation, total solid (TS) content of pig manure is 58%, total solid (TS) content of vegetable castoff is 10%, and total solid (TS) content of cow dung is 15%.A, B, C, D are set Four groups of controls are continuously fermented, and A, B, C, D anaerobic fermentation tank group are using pig manure as raw material.
During operation in 1st month, daily according to 1.0kgTS/ (m3Day organic loading rate charging), four groups of fermentations Tank aerogenesis is stablized, and pH value is held in the range of 7.3~7.6.
During operation in 2nd month, daily according to 2.0kgTS/ (m3Day organic loading rate charging), four groups of fermentations Tank aerogenesis tends towards stability after increasing, and pH value is held in the range of 7.3~7.6.
During operation in 3rd month, daily according to 3.0kgTS/ (m3Day organic loading rate charging), four groups of fermentations Tank aerogenesis tends towards stability after increasing, and pH value is held in the range of 7.3~7.6, but the content of acetic acid, propionic acid, butyric acid is all It increased.
During operation in 4th month, daily according to 4.0kgTS/ (m3Day organic loading rate charging), runs to the After 15 days, four groups of fermentation tank pH value are reduced to 5.5~5.8 ranges, aerogenesis to continuously decrease, acetic acid, the propionic acid of four groups of experiments There are a large amount of accumulations with butyric acid, four groups of fermentation tanks all stop feeding at this time, while adding solid-state biological agent made from embodiment 2 500g adds solid-state biological agent 300g made from embodiment 2 to C group marsh-gas fermentation tanks, addition is implemented to B group marsh-gas fermentation tanks Solid-state biological agent 100g made from example 2 does not add solid-state made from embodiment 2 to D group marsh-gas fermentation tanks, A groups marsh-gas fermentation tank Biological agent.By observation in 7 days, the fast quick-recovery aerogenesis of B, C group marsh-gas fermentation tank, pH value can rise to 7.3;D group fermentation tanks It is slow compared to B, C group marsh-gas fermentation tank regeneration rate, but can also restore aerogenesis, pH value can rise to 7.1;A groups are fermented Tank aerogenesis continues to reduce, and pH value is down to 5.1.
The above description of test, since organic loading is excessively high, marsh gas fermenting system acidification is serious, stops charging to severe acidification System and for generate it is effective restore, after the solid union biological agent for adding the present invention, bionethanation system is enabled to restore Aerogenesis, especially using pig manure as the marsh gas fermenting system of raw material.It is because while to stop charging, but in marsh gas fermenting system still There is the organic matter of accumulation to continue production acid, and the organic acid of high-content inhibits the activity of methanogen, this results in rate of producing acid big In methane phase rate, cause marsh gas fermenting system unbalance, pH continues to reduce, and organic acid continues to build up, and methanogen is more pressed down System.And add the present invention solid union biological agent, by methanogen, syntrophism acetic acid oxidation bacteria, syntrophism propionic acid oxidation bacteria, The common cooperation of syntrophism butyric acid oxidized bacterium, efficiently uses conversion organic acid, releases the inhibition of methanogen, so that biogas is sent out Ferment system effectively restores aerogenesis.
Finally, it should also be noted that it is listed above be only specific embodiments of the present invention son.Obviously, the present invention is not It is limited to above embodiment, acceptable there are many deformations.Those skilled in the art can be straight from present disclosure All deformations for connecing export or associating, are considered as protection scope of the present invention.

Claims (9)

1. restoring the liquid composite biological agent of aerogenesis for the acidification marsh gas fermenting system that pig manure is raw material, which is characterized in that The reagent contains methanogen, and syntrophism methanogen, medium temperature syntrophism acetic acid oxidation bacteria, medium temperature syntrophism propionic acid oxidation bacteria, medium temperature are mutual Seek butyric acid oxidized bacterium, trace element and vitamin;
The methanogen include but not limited to methanimicrococcus, methanococcoides, methanohalobium、halomethanococcus、methanocella、methanolinea、methanocalculus、 Methanospirillum, methanocorpusculum etc..
The medium temperature syntrophism acetic acid oxidation bacteria including but not limited to SAOB Clostridium ultunense, Thermacetogenium phaeum、Tepidanaerobacter acetatoxydans Re1、 Thermoanaerobacteraceae and Thermotoga lettingae etc..
The medium temperature syntrophism propionic acid oxidation bacteria is including but not limited to Smithella propionica, Syntrophobacter Fumaroxidans and Pelotomaculum thermopropionicum etc..
The medium temperature syntrophism butyric acid oxidized bacterium is including but not limited to Syntrophomonas wolfei subsp.Methylbutyratica subsp、Syntrophomonas cellicola、Syntrophomonas erecta、 Syntrophomonas erecta subsp.sporosyntropha subsp, Syntrophomonas sapovorans and Syntrophomonas palpitatica etc..
The trace element is iron content (Fe), the compound of cobalt (Co), nickel (Ni), molybdenum (Mo), tungsten (W) and selenium (Se).
The vitamin is containing niacin, p-aminobenzoic acid, vitamin B6, vitamin B7, folic acid, vitamin B2, thiamine.
2. liquid composite biological agent according to claim 1 or claim 2, which is characterized in that it is described trace element be ferrous sulfate, Cobalt chloride, nickel chloride, sodium molybdate, sodium tungstate and sodium selenate;A concentration of 0.5~5mg/L of iron, a concentration of 0.1~1mg/ of cobalt L, the concentration of a concentration of 0.2~2mg/L of nickel, a concentration of 0.1~1mg/L of molybdenum, a concentration of 0.01~0.1mg/L of tungsten, selenium For 0.01~0.1mg/L;In the vitamin Nicotinic be 0.01~0.05mg/L, p-aminobenzoic acid a concentration of 0.01~ A concentration of 0.05~0.1mg/L of 0.03mg/L, vitamin B6, a concentration of 0.001~0.005mg/L of vitamin B7, folic acid concentration For 0.001~0.005mg/L, a concentration of 0.005~0.01mg/L of vitamin B2, a concentration of 0.005~0.01mg/L of thiamine; Ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, yeast powder, sodium acetate, sodium propionate and sodium butyrate content be respectively 0.5~ 1.0g/L, 0.5~1.0g/L, 0.8~1.0g/L, 0.2~0.5g/L, 2~5g/L, 10~15g/L, 8~10g/L, 7~10g/ L。
3. a kind of solid union biological agent restoring aerogenesis for the acidification marsh gas fermenting system that pig manure is raw material, feature exist In the reagent contains methanogen, syntrophism methanogen, medium temperature syntrophism acetic acid oxidation bacteria, medium temperature syntrophism propionic acid oxidation bacteria, medium temperature Syntrophism butyric acid oxidized bacterium, trace element and vitamin;
The methanogen include but not limited to methanimicrococcus, methanococcoides, methanohalobium、halomethanococcus、methanocella、methanolinea、methanocalculus、 Methanospirillum, methanocorpusculum etc..
The medium temperature syntrophism acetic acid oxidation bacteria including but not limited to SAOB Clostridium ultunense, Thermacetogenium phaeum、Tepidanaerobacter acetatoxydans Re1、 Thermoanaerobacteraceae and Thermotoga lettingae etc..
The medium temperature syntrophism propionic acid oxidation bacteria is including but not limited to Smithella propionica, Syntrophobacter Fumaroxidans and Pelotomaculum thermopropionicum etc..
The medium temperature syntrophism butyric acid oxidized bacterium is including but not limited to Syntrophomonas wolfei subsp.Methylbutyratica subsp、Syntrophomonas cellicola、Syntrophomonas erecta、 Syntrophomonas erecta subsp.sporosyntropha subsp, Syntrophomonas sapovorans and Syntrophomonas palpitatica etc..
The trace element is iron content (Fe), the compound of cobalt (Co), nickel (Ni), molybdenum (Mo), tungsten (W) and selenium (Se).
The vitamin is containing niacin, p-aminobenzoic acid, vitamin B6, vitamin B7, folic acid, vitamin B2, thiamine.
4. solid union biological agent according to claim 3, which is characterized in that the trace element is ferrous sulfate, chlorine Change cobalt, nickel chloride, sodium molybdate, sodium tungstate and sodium selenate;A concentration of 0.5~5g/kg of iron, a concentration of 0.1~1g/kg of cobalt, A concentration of 0.2~2g/kg of nickel, a concentration of 0.1~1g/kg of molybdenum, a concentration of 0.01~0.1g/kg of tungsten, selenium it is a concentration of 0.01~0.1g/kg;In the vitamin Nicotinic be 0.01~0.05mg/kg, p-aminobenzoic acid a concentration of 0.01~ A concentration of 0.05~0.1mg/kg of 0.03mg/kg, vitamin B6, a concentration of 0.001~0.005mg/kg of vitamin B7, folic acid are dense Degree be 0.001~0.005mg/kg, a concentration of 0.005~0.01mg/kg of vitamin B2, thiamine a concentration of 0.005~ 0.01mg/kg;The content difference of ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, yeast powder, sodium acetate, sodium propionate and sodium butyrate For 0.5~1.0g/kg, 0.5~1.0g/kg, 0.8~1.0g/kg, 0.2~0.5g/kg, 2~5g/kg, 10~15g/kg, 8~ 10g/kg, 7~10g/kg.
5. restoring aerogenesis for the acidification marsh gas fermenting system that pig manure is raw material according to claim 1-2 any one of them is a kind of Liquid composite biological agent preparation method, which is characterized in that this method comprises the following steps:
(1) it is that the seed sludge of raw material carries out preculture under 37 DEG C of anaerobic conditions to take pig manure
(2) step (1) pig manure seed sludge and culture medium anaerobic condition volume ratio are (1~3):It is mixed under (1~3), addition is micro- Secondary element, vitamin, sodium acetate, sodium propionate, sodium butyrate optimize enrichment culture
(3) step (2) composite bacteria liquid is concentrated
(4) step (2) addition ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, yeast powder, sodium acetate, sodium propionate and sodium butyrate, envelope It is stored in 2~8 DEG C.
Wherein, the trace element is iron content (Fe), the compound of cobalt (Co), nickel (Ni), molybdenum (Mo), tungsten (W) and selenium (Se).
The vitamin is containing niacin, p-aminobenzoic acid, vitamin B6 (including but not limited to pyridoxine), vitamin B7 (packet Contain but be not limited to biotin), folic acid, vitamin B2 (including but not limited to riboflavin), thiamine.
The culture medium is ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, ferment Female powder, above-mentioned trace element and vitamin.
6. the preparation method of liquid composite biological agent according to claim 5, which is characterized in that the trace element is Ferrous sulfate, cobalt chloride, nickel chloride, sodium molybdate, sodium tungstate and sodium selenate;A concentration of 0.5~5mg/L of iron, cobalt it is a concentration of 0.1~1mg/L, a concentration of 0.2~2mg/L of nickel, a concentration of 0.1~1mg/L of molybdenum, tungsten a concentration of 0.01~0.1mg/L, A concentration of 0.01~0.1mg/L of selenium;Vitamin described in step (2) is containing niacin, p-aminobenzoic acid, vitamin B6 (packet Contain but be not limited to pyridoxine), vitamin B7 (including but not limited to biotin), folic acid, vitamin B2 is (including but not limited to core yellow Element), thiamine, their contents be respectively 0.01~0.05mg/L, 0.01~0.03mg/L, 0.05~0.1mg/L, 0.001~ 0.005mg/L, 0.001~0.005mg/L, 0.005~0.01mg/L, 0.005~0.01mg/L;Step (2) described culture medium Including ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, it is yeast powder, above-mentioned micro- Secondary element and vitamin, their contents be respectively 0.5~1.0g, 0.5~1.0g, 0.5~1.0g, 0.15~0.3g, 0.2~ 0.5g, 0.5~1.0g, 2~5g, 5~10g, 2~5mL, 0.5~1mL.
7. according to any one of the claim 5-6 liquid composite biological agent preparation methods, which is characterized in that the liquid is made Ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, yeast powder, sodium acetate, sodium propionate and butyric acid are also added in state composite biological agent Sodium, their content are respectively 0.5~1.0g/L, 0.5~1.0g/L, 0.8~1.0g/L, 0.2~0.5g/L, 2~5g/L, 10 ~15g/L, 8~10g/L, 7~10g/L.
8. restoring consolidating for aerogenesis for the acidification marsh gas fermenting system that pig manure is raw material according to claim 3-4 any one of them State composite biological agent preparation method, which is characterized in that this method comprises the following steps:
(1) rice bran or wheat bran or pig manure sludge or two or more arbitrary mixing are dried, as auxiliary material.
(2) by any one of the claim 5-7 liquid composite biological agents obtained and the auxiliary material of step (1) in anaerobism item It is 1 in mass ratio under part:1 mixing, stirs evenly, and it is 5~25% that water content is dried under 37 DEG C of constant temperatures of anaerobism, as Restore the solid union biological agent of aerogenesis for the acidification marsh gas fermenting system that pig manure is raw material, encapsulation is stored in 2~8 DEG C.
9. solid union biological agent preparation method according to claim 8, which is characterized in that the solid-state obtained is multiple It closes in biological agent and also adds ammonium chloride, magnesium sulfate, potassium chloride, calcium chloride, yeast powder, sodium acetate, sodium propionate and sodium butyrate, it Content be respectively 0.5~1.0g/kg, 0.5~1.0g/kg, 0.8~1.0g/kg, 0.2~0.5g/kg, 2~5g/kg, 10 ~15g/kg, 8~10g/kg, 7~10g/kg.
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Application publication date: 20180727