CN110498587A - A kind of method of electrochemical couple anaerobic fermentation processing milk cattle cultivating waste - Google Patents
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- CN110498587A CN110498587A CN201910781567.XA CN201910781567A CN110498587A CN 110498587 A CN110498587 A CN 110498587A CN 201910781567 A CN201910781567 A CN 201910781567A CN 110498587 A CN110498587 A CN 110498587A
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- 241000283690 Bos taurus Species 0.000 title claims abstract description 63
- 238000000855 fermentation Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000008267 milk Substances 0.000 title claims abstract description 22
- 210000004080 milk Anatomy 0.000 title claims abstract description 22
- 235000013336 milk Nutrition 0.000 title claims abstract description 22
- 239000002699 waste material Substances 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 210000003608 fece Anatomy 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 230000004151 fermentation Effects 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 28
- 239000002054 inoculum Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000428 dust Substances 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 32
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 239000010871 livestock manure Substances 0.000 abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 abstract description 10
- 229910017112 Fe—C Inorganic materials 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 8
- 244000144972 livestock Species 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 244000144977 poultry Species 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000028327 secretion Effects 0.000 description 2
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 241000736262 Microbiota Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 210000004681 ovum Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a kind of method of electrochemical couple anaerobic fermentation processing milk cattle cultivating waste, this method is to promote the method for milk cattle cultivating waste methane phase using electrochemistry and Fe-C light electrolysis, while can also efficiently utilize more metal iron tailings；The present invention, which not only solves existing cattle manure anaerobic fermentation production biogas, has that slow fermentation starting, low efficiency, the period is long, substrate cannot handle completely and methane production is low, and add the double action of Fe-C light electrolysis further to promote utilization for cellulosic substrate difficult to degrade by electrochemistry, there are apparent society, economy and ecological benefits.
Description
Technical field
The present invention relates to environment, biomass energy and electrochemical fields, and in particular to a kind of electrochemical couple anaerobic fermentation
The method of milk cattle cultivating waste methane phase is efficiently utilized under Fe-C light electrolysis booster action.
Background technique
Milk cattle cultivating development in rural area is increasingly flourishing, but also brings certain problem of environmental pollution while development.Now
Rural area individual raiser and the mixed residence of decentralized household mostly people ox, cow manure are arbitrarily stacked, and generate foul odour, and cause to breed disease
Bacterium and mosquitos and flies；And in rainy season set, untreated breeding wastewater flows into basin nearby, wherein a large amount of organic matters contained,
The nutriments such as nitrogen, phosphorus and pathogenic bacteria and disease worm's ovum, it is easy to enter neighbouring river and stream with heavy rain or rainwash
Milk cattle cultivating waste nitrogen and phosphorus loss is caused in domain, will cause water eutrophication pollution when serious, and in recent years, aquaculture it is rapid
A large amount of livestock wastes that development generates have become one of the main source of China's underground water and pollution of water.
The processing of livestock waste energy is an opportunity of world economy, environment and resource joint development now, and cultivation is useless
Object recycling not only can solve its bring pollution of area source problem, while can also generate biggish economic benefit and be the current energy
Anxiety provides a solution path.Livestock waste recovery energy has important in terms of solving rural energy shortage and environmental pollution
Value.In view of the feature that livestock waste moisture content is higher, develop a kind of method that anaerobic ferment for methane is most development prospect.
Livestock waste is subjected to anaerobic ferment process processing, clean energy resource can not only be provided --- biogas also can solve livestock waste pollution
Problem, while the biogas slurry generated can make Liquid Fertilizer, biogas residue makes organic fertilizer.
But there is the starting of (1) anaerobic fermentation system very currently for the problem of the energy process face pair of milk cattle cultivating waste
Slowly；(2) entire process cycle is too long；(3) methane phase efficiency is very low；(4) the very high lignocellulosic of content is difficult to drop in cow dung
Solution causes the waste of biomass energy, causes feed stock conversion low.The serious further development for limiting the technology of these problems.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of sides of electrochemical couple anaerobic fermentation processing milk cattle cultivating waste
Method, by the method for electrochemical couple anaerobic fermentation, the external electric field of invigoration effect using to(for) microorganism, by directly energizing thorn
Swash microbiota metabolic activity and promote methanogen floras growth, accelerates the starting of anaerobic fermentation system, while iron tailings or iron is added
The mixture of powder and C, the progress entirely reacted can not only be accelerated by forming micro-electrolysis reaction in systems, can also substantially be promoted
The degradation of lignocellulosic, other metallic elements contained in iron tailings can substantially promote the growth of related microorganisms, mention
It rises the utilization rate to substrate and accelerates methane production, specific embodiment is as follows:
(1) pulverization process is carried out to fresh cow dung or dry cow dung, is diluted with water to fermented feed liquid；
It is described in terms of the quality of over dry cow dung, in fermented feed liquid cow dung mass concentration be 8%-20%；
(2) biogas slurry from methane-generating pit being added in cow dung will ferment after carrying out anaerobic fermentation 3-5 days under the conditions of 30-40 DEG C
Liquid is added in new cow dung under the conditions of 30-40 DEG C anaerobic fermentation 3-5 days again, collects fermentation liquid and repeats the above process one
It is secondary, inoculum is obtained, wherein the additive amount of biogas slurry is the 10-20% of cow dung quality；
(3) fermented feed liquid, inoculum, 40-60 mesh iron tailings powder or iron powder, carbon dust are mixed after stirring, is placed in anti-
It answers in device and seals, be in reactant in the strictly anaerobic environment of medium temperature, reactant carries out anaerobic fermentation under low-voltage effect,
Collect tunning；
The fermented feed liquid, inoculum, 40-60 mesh iron tailings powder or iron powder, carbon dust mass ratio are (100-200): (10-20):
(3-15): (15-20)；
The iron tailings is iron ore remaining solid waste after selecting concentrate.
The medium temperature is 25-35 DEG C；
The low-voltage is 0.3-0.8V.
The principle of the invention lies in, add iron tailings powder and carbon dust or iron powder and carbon dust in anaerobic fermentation system, Fe with
Carbon dust occurs electrochemistry light electrolysis effect generation soluble iron ion and helps to detest so that methanogen can absorb Fe element
The breeding of oxygen flora growth, while the utilization to small organic molecules such as acetic acid is improved, feed stock conversion and Methane production are improved,
In addition Fe can also be reacted with sulfide, eliminate sulfide inhibiting effect movable for the methane phase of methanogen；And Fe-C group
Fe content is more in conjunction, and the electrochemistry light electrolysis effect in anaerobic system is stronger, so that in anaerobic fermentation methanogen early period etc.
Anaerobic bacteria flora breeding is accelerated, and rises rapidly so that producing methane content in gas, at the same time, the addition of Fe-C combination, and between the two
The light electrolysis galvanic effect of generation enables Fe element to be absorbed by anaerobic fermentation flora, so that microorganism tachyauxesis is bred,
The lignocellulosic microbial degradation enzyme amount of synthesis secretion increases, so that ligocellulose degradation leads rising；It is alive outside
Under the influence of, the anaerobe bacterial activity in anaerobic fermentation system improves, and metabolism accelerates, biological enzyme needed for anaerobic fermentation
Secretion increases, so that anaerobic fermentation normal gas producing arrives ahead of time, shortens the anaerobic fermentation period.Applied voltage accelerates and detests
Mass transfer rate in aerobe fermentation system, to may gradually solidify hardened Fe-C combination light electrolysis galvanic effect can also play it is sharp
Effect living has further promotion to make the growth of microorganism simultaneously because containing other metallic elements in more metal iron tailings
With this just more accelerates anaerobic bacteria flora and decomposes the efficiency for utilizing milk cattle cultivating excrement.
Compared with prior art the present invention has the advantages that
(1) Fe-C combination is introduced into anaerobic fermentation system, so that biological treatment is combined processing milk cow with light electrolysis effect and supports
Excrement is grown, gas production can not only be promoted, while promoting methane content in total yield gas, and it is useless to milk cattle cultivating to enhance anaerobic fermentation
The degradation of object lignocellulosic；
(2) applied voltage has milk cattle cultivating excrement anaerobic fermentation and significantly affects, and on-load voltage can promote milk cattle cultivating excrement
Just the gas production rate of anaerobic fermentation makes anaerobic fermentation rapidly enter the normal gas producing stage, mention the last week enter produce gas peak period, and
Shorten the entire anaerobic fermentation period；And in a certain range, as on-load voltage improves, the conversion of milk cattle cultivating waste excrement raw material
Rate rises, and the degradation rate of cellulose and lignin also rises with it, and daily methane phase content is obviously improved when production gas；
(3) electrochemical techniques and Fe-C light electrolysis effect are joined together, enhances the raw material of milk cattle cultivating excrement anaerobic fermentation
Conversion ratio, while improving and producing methane content in gas, greatly promote milk cattle cultivating dung recovery effect.
(4) it is reacted using discarded multi-metal tailings, can also accelerate entirely to react while waste reclamation
Progress, have significant economic and social benefit.
Specific embodiment
Below by embodiment, invention is further described in detail, but the scope of the present invention is not limited in described
Hold.
Embodiment 1:
(1) pulverization process is carried out to the fresh cow dung for being derived from Dali peasant household, it is directly diluted with water, with the matter of over dry cow dung
Meter, cow dung mass concentration is 10% in fermented feed liquid；
(2) acquire biogas slurry in certain peasant household's methane-generating pit (animal wastes fermentation), be added in cow manure, under the conditions of 35 DEG C into
After row anaerobic fermentation 4 days, fermentation liquid is added to in new cow manure under the conditions of 35 DEG C anaerobic fermentation 4 days again, collects hair
It is primary that zymotic fluid repeats the above process, obtains inoculum, and wherein the additive amount of biogas slurry is the 17% of cow manure quality；
(3) iron tailings for being derived from Guizhou iron ore mine is carried out crushing obtained 40-50 mesh powder；
(4) fermented feed liquid, inoculum, iron tailings powder, carbon dust mixing are sufficiently stirred the ratio of 100:10:9:15 in mass ratio
It after uniformly, is placed in reactor and seals, be in reactant in 30 DEG C of strictly anaerobic environment, provided using constant voltage dc source
The low-voltage of 0.6 V carries out anaerobic fermentation, initially enters the normal gas producing phase from 46h, can obtain unit gas production is
286.72mL/g, wherein methane accounts for the 78% of total gas production, and lignocellulosic conversion ratio is 37%.
Embodiment 2:
(1) pulverization process is carried out to the fresh cow dung for being derived from Dali gathering station, it is directly diluted with water, with over dry cow dung
Quality meter, cow dung mass concentration is 17% in fermented feed liquid；
(2) it is added in cow manure, is carried out under the conditions of 30 DEG C after acquisition biogas slurry in certain peasant household's methane-generating pit (feces of livestock and poultry)
After anaerobic fermentation 5 days, fermentation liquid is added to in new cow manure under the conditions of 30 DEG C anaerobic fermentation 5 days again, collects fermentation
It is primary that liquid repeats the above process, obtains inoculum, and wherein the additive amount of biogas slurry is the 12% of cow manure quality；
(3) iron tailings for being derived from Iron Ore in Yunnan Province mountain is carried out crushing obtained 50-60 mesh powder；
(4) ratio of 150:15:11:18 sufficiently stirs fermented feed liquid, inoculum, iron tailings powder, carbon dust mixing in mass ratio
It after mixing uniformly, is placed in reactor and seals, be in reactor in 35 DEG C of strictly anaerobic environment, use constant voltage dc source
The low-voltage of 0.5V is provided, anaerobic fermentation is carried out, initially enters the normal gas producing phase from the 44th h, can obtain unit gas production is
245.72mL/g, wherein methane accounts for the 73% of total gas production, and lignocellulosic conversion ratio is 35%.
Embodiment 3
(1) pulverization process is carried out to the dry cow dung for being derived from man, Dali peasant household, and it is directly diluted with water, with over dry cow dung
Quality meter, cow dung mass concentration is 20% in fermented feed liquid；
(2) it is added in cow manure after acquisition biogas slurry in certain peasant household's methane-generating pit (sheep dung), carries out anaerobism under the conditions of 40 DEG C
After fermentation 3 days, fermentation liquid is added to in new cow manure under the conditions of 40 DEG C anaerobic fermentation 3 days again, collects fermentation liquid again
It repeats the above process once, obtains inoculum, wherein the additive amount of biogas slurry is the 20% of cow manure quality；
(3) iron tailings for being derived from Iron Ore in Yunnan Province mountain is carried out crushing obtained 40-60 mesh powder；
(4) fermented feed liquid, inoculum, iron tailings powder, carbon dust conjunction are sufficiently stirred the ratio of 200:10:15:20 in mass ratio
It after even, be placed in reactor and seal, be in reactor in 28 DEG C of strictly anaerobic environment, provided using constant voltage dc source
The low-voltage of 0.8V carries out anaerobic fermentation, initially enters the normal gas producing phase from the 56th h, can obtain unit gas production is
198.72mL/g, wherein methane accounts for the 67% of total gas production, and lignocellulosic conversion ratio is 39%.
Embodiment 4
(1) pulverization process is carried out to the dry cow dung for being derived from man, Dali peasant household, and it is directly diluted with water, with over dry cow dung
Quality meter, cow dung mass concentration is 8% in fermented feed liquid；
(2) it is added in cow manure, is carried out under the conditions of 35 DEG C after acquisition biogas slurry in certain peasant household's methane-generating pit (feces of livestock and poultry)
After anaerobic fermentation 3 days, fermentation liquid is added to in new cow manure under the conditions of 35 DEG C anaerobic fermentation 3 days again, collects fermentation
It is primary that liquid repeats the above process, obtains inoculum, and wherein the additive amount of biogas slurry is the 15% of cow manure quality；
(3) fermented feed liquid, inoculum, 40 mesh iron powders, carbon dust conjunction are sufficiently stirred the ratio of 100:20:10:15 in mass ratio
It after even, be placed in reactor and seal, be in reactor in 35 DEG C of strictly anaerobic environment, provided using constant voltage dc source
The low-voltage of 0.3V carries out anaerobic fermentation, initially enters the normal gas producing phase from the 29th h, and can obtain unit gas production is 157 mL/
G, wherein methane accounts for 55 % of total gas production, and lignocellulosic conversion ratio is 32 %.
Claims (5)
1. a kind of method of electrochemical couple anaerobic fermentation processing milk cattle cultivating waste, which is characterized in that steps are as follows:
(1) pulverization process is carried out to fresh cow dung or dry cow dung, is diluted with water to fermented feed liquid；
(2) biogas slurry from methane-generating pit being added in cow dung will ferment after carrying out anaerobic fermentation 3-5 days under the conditions of 30-40 DEG C
Liquid is added in new cow dung under the conditions of 30-40 DEG C anaerobic fermentation 3-5 days again, collects fermentation liquid and repeats the above process one
It is secondary, inoculum is obtained, wherein the additive amount of biogas slurry is the 10-20% of cow dung quality；
(3) fermented feed liquid, inoculum, 40-60 mesh iron tailings powder or iron powder, carbon dust are mixed after stirring, is placed in anti-
It answers in device and seals, be in reactant in the strictly anaerobic environment of medium temperature, reactant carries out anaerobic fermentation under low-voltage effect,
Collect tunning.
2. the method for electrochemical couple anaerobic fermentation processing milk cattle cultivating waste according to claim 1, it is characterised in that:
In terms of the quality of over dry cow dung, cow dung mass concentration is 8%-20% in fermented feed liquid.
3. the method for electrochemical couple anaerobic fermentation processing milk cattle cultivating waste according to claim 1, it is characterised in that:
Fermented feed liquid, inoculum, 40-60 mesh iron tailings powder or iron powder, carbon dust mass ratio are (100-200): (10-20): (3-15):
(15-20).
4. the method for electrochemical couple anaerobic fermentation processing milk cattle cultivating waste according to claim 1, it is characterised in that:
Medium temperature in step (3) is 25-35 DEG C.
5. the method for electrochemical couple anaerobic fermentation processing milk cattle cultivating waste according to claim 1, it is characterised in that:
Low-voltage is 0.3-0.8V in step (4).
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