CN103740764B - A kind of biogas fermentation functional biological catalyst and the method that utilizes catalyzer to ferment - Google Patents

A kind of biogas fermentation functional biological catalyst and the method that utilizes catalyzer to ferment Download PDF

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CN103740764B
CN103740764B CN201310744961.9A CN201310744961A CN103740764B CN 103740764 B CN103740764 B CN 103740764B CN 201310744961 A CN201310744961 A CN 201310744961A CN 103740764 B CN103740764 B CN 103740764B
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biogas fermentation
micritization
poultry
livestock
feces
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CN201310744961.9A
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Chinese (zh)
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CN103740764A (en
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云斯宁
张仙梅
杨玉芬
何振全
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西安建筑科技大学
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

The method that the invention discloses the functional biological catalyst of a kind of biogas fermentation and utilize catalyzer to ferment, catalyzer comprises complex microbial inoculum 1-3 part; Lytic enzyme promotor 100 parts; Mineral nutrient promotor 61-329 part.Mineral nutrient promotor is one or more in micritization ground phosphate rock, micritization zeolite powder, micritization Paris white, urea, phosphoric acid salt, wilkinite or gac.Biogas fermentation method is: feces of livestock and poultry 350-650 part, inoculum 100-300 part and functional living being catalyzer 163-430 part carry out biogas fermentation, and the water ratio controlling feces of livestock and poultry is 75-85%; Whole original liquid concentration is 7-12%, is uniformly mixed and ferments.The present invention supplements outside the nutritive element needed for biogas fermentation, by the effect of having complementary functions of the absorption of sorbent material, ion-exchange, biological degradation and membrane filtration, reaches deodorizing and suppresses pathogenic micro-organism, making it innoxious; And its preparation technology's flow process is simple, processing ease, effective, less investment, pollution-free, be with a wide range of applications.

Description

A kind of biogas fermentation functional biological catalyst and the method that utilizes catalyzer to ferment
Technical field
The invention belongs to technical field of methane fermentation, relate to a kind of containing the multi-functional biological catalyst of micritization ground phosphate rock and utilize catalyzer to carry out the method for biogas fermentation.
Background technology
The province 23, whole nation livestock and poultry farms in scale concentrated according to State Environmental Protection Administration 2000, city's investigation display; nineteen ninety-five; the COD total emission volumn of national trade effluent is then 768.37 ten thousand tons; and the waste discharge amount of livestock and poultry breeding industry is converted to COD is 728.6 ten thousand tons, close to the COD total emission volumn of national trade effluent.1999, the generation of China's animal waste was about 1,900,000,000 tons, was 2.4 times of industrial solid wastes.2000, national feces of livestock and poultry year generation reached about 17.3 hundred million tons, be 2.7 times of trade waste.The organic pollutant contained in animal waste, only COD mono-just reaches 7,118 ten thousand tons, considerably beyond COD summation that is industrial and Sewage Pollution thing.But these feces of livestock and poultry and sewage are good biogas fermentation materials, fully utilize these wastes, realize the recycling of waste, turn waste into wealth, turn harm into good, have important practical significance.
Anaerobic methane fermenting process is that a methanogen and non-methanogen interact, the homeostasis process of restriction mutually.Multiple organic matter, under certain temperature, humidity, potential of hydrogen and anaerobic condition, by microbial decomposition and hydrolysis, resolves into small molecules insoluble organic macromolecule, utilizes, a kind of inflammable gas of final generation for producing hydrogen, acetogen and methanogen.Its main component is CH 4, be secondly CO 2, H 2s, nitrogen and other compositions.
Marsh gas fermentation processes is in fact microorganism, metabolism and energy conversion process, and in catabolic process, biogas microorganism obtains energy and material, and to meet own growth and breeding, most of Substance Transformation is CH simultaneously 4and CO 2.Anaerobically fermenting microbial growth needs certain nutritive substance, and C, N, P are methane fermentating microorganisms grows the three kinds of nutritive elements needed most.Carbohydrate in organism is the C element nutrition of bacterium, and the organonitrogen in organism is then the N element nutrition of bacterium, and the nutrition of P element is then added by external source.Except ensureing necessary anaerobically fermenting nutritive element, in marsh gas fermentation processes, need comparatively suitable C/N ratio, its scope is generally 10:1 ~ 30:1.In practical engineering application, generally take to add the method for crop material to regulate C/N value to reaching better aerogenesis effect in fowl and animal excrement (pig manure, cow dung, chicken manure etc.).Such as, cornstalk, rice straw, Cotton Stalk, straw and Herba Eichhorniae are mixed with cow dung, improve anaerobically fermenting environment, the biogas output of 10% ~ 80% can be improved.But because a large amount of Mierocrystalline celluloses, hemicellulose and xylogen are present in plant stem-leaf or poultry manure, xylogen and hemicellulose are with covalent bonds, cellulosic molecule is embedded in wherein, form a kind of natural cover for defense, enzyme is not easily contacted with cellulosic molecule, be difficult to, by acid or enzymic hydrolysis, cause stalk to decompose when anaerobically fermenting slowly.C/N value is general at about 25:1-30:1, does not need to add other carbon source or nitrogenous source and just can meet C/N ratio needed for anaerobically fermenting.
In addition, in biogas fermentation engineering practice, also there is the problem of some ubiquities.Such as, (1) biogas output cold season obviously reduces, and the marsh gas raw materials gas production rate of same quantity is usually not as good as 1/3rd of summer; (2) biogas fermentation material can not get decomposing fully and utilizing in pond, and actual biogas turnover ratio (raw material factor of created gase) is lower.In order to improve decomposition utilization ratio and the gas production rate of biogas fermentation material, all very focus on the quality and quantity of methanogen floras (anaerobic sludge) in biogas both at home and abroad.Research shows: methanogen can only utilize ammonium nitrogen as nitrogenous source, and can not utilize complicated nitride.Urea facile hydrolysis is ammonium nitrogen, therefore can provide sufficient nitrogenous source for methanogen and methane-oxidizing bacteria.Add urea and Secondary ammonium phosphate etc. and can provide required nutritive element for anaerobically fermenting, improve the gas production rate of biogas fermentation.Add Rock Phosphate (72Min BPL) than elemental phosphorous better effects if.While effectively utilizing Mineral resources, be conducive to the raising of the propagation of microorganism and the surge capability of reactor.Further research shows: add sorbent material and also can improve aerogenesis effect.Major cause be sorbent material by germs collect, increase microbe density, simultaneously can keep the environment favourable to microorganism growth, thus allow the consumption of microorganism degradation of organic substances matter better, quickening volatile acid, raising gas production rate.In addition, sorbent material also can reduce heavy metal content in methane fermentation system.
We think, except increasing the quality and quantity of methanogen floras, should add a kind of multifunctional bio catalyzer, improve environment and the metabolic function of bacterial classification, organism is more thoroughly decomposed for biogas fermentation, improve the gas production rate of biogas fermentation.Practice shows: for process solid content higher, containing the biogas fermentation material of more more difficult decomposing organic matter, take this measure to seem particularly important.
Summary of the invention
The object of the invention is to overcome above-mentioned shortcoming and defect, the method functional biological catalyst of a kind of biogas fermentation being provided and utilizing this catalyzer to ferment.This catalyzer can significantly improve biogas anaerobic fermentation environment, biogas output is obviously increased, fermentation efficiency improves, mid low grade phosphate rock is utilized effectively, environmental pollution reduces, phosphor resource dependency is reduced, achieve the recycling of agricultural wastes, for the modern agriculture of China's development cost-saving synergistic, green, environmental protection plays great pushing effect.
The object of the invention is to be realized by following technical proposals:
The functional biological catalyst of a kind of biogas fermentation, comprises the raw material of following mass fraction:
Complex microbial inoculum 1-3 part;
Lytic enzyme promotor 100 parts;
Mineral nutrient promotor 61-329 part.
Further, described complex microbial inoculum is methanogen, cellulose-decomposing bacterium, yeast, phosphate solubilizing bacteria, milk-acid bacteria or photosynthetic bacteria.
Further, described lytic enzyme promotor comprises the raw material of following mass fraction:
Saccharifying enzyme 54-70 part;
Amylase 2 0-31.5 part;
Cellulase 5-13 part;
Proteolytic enzyme 1-5 part.
Further, described mineral nutrient promotor comprises the raw material of following mass fraction:
Micritization ground phosphate rock 5-100 part;
Micritization zeolite powder 0-3 part;
Micritization Paris white 0-70 part;
Urea 0-9 part;
Phosphoric acid salt 0-15 part;
Wilkinite 0-300 part;
Gac 0-5.5 part.
Further, described micritization ground phosphate rock, micritization zeolite powder and micritization Paris white are prepared from according to the raw material of following mass percent:
Phosphorus ore containing or zeolite or calcium carbonate 96%-98%;
Activator 2%-4%;
Described activator is trolamine, poly amic acid or ethylene glycol.
Further, described phosphoric acid salt is the one in Secondary ammonium phosphate or potassium primary phosphate.
Correspondingly, the present invention gives the preparation method of a kind of biogas fermentation with functional biological catalyst, and the method comprises the steps:
Be that the mineral nutrient promotor of 61-329 part, 100 parts of lytic enzyme promotor and 1-3 part complex microbial inoculum mix at normal temperatures by mass fraction, obtain the functional biological catalyst of biogas fermentation.
Further, described micritization ground phosphate rock, micritization zeolite powder or micritization Paris white are prepared by following method:
Different disintegrating apparatus is placed in respectively by containing the Phosphate minerals of 96%-98% mass percent, zeolite or calcium carbonate, each powder after pulverizing is placed in three grinding plant respectively, and in each grinding plant, add the activator of 2%-4% mass percent respectively, carry out super-fine processing, utilize the mechanical shock effect of mechanical force and chemical and high-shear natural mineral to be prepared into the product that mean particle size reaches more than 400 orders, obtain P respectively 2o 5the biogas fermentation micritization ground phosphate rock of content between 15%-25% or biogas fermentation micritization zeolite powder, or biogas fermentation micritization Paris white, and package spare.
Correspondingly, the present invention and then give and a kind ofly utilize the biogas fermentation fermentation process of functional biological catalyst, the method comprises the steps:
Take feces of livestock and poultry as raw material, add fresh feces of livestock and poultry 350-650 part according to mass fraction, inoculum 100-300 part and functional living being catalyzer 163-430 part carry out biogas fermentation, and the water ratio controlling feces of livestock and poultry is 75-85%; Add the dechlorination tap water of placement, controlling whole original liquid concentration is 7-12%, is fully uniformly mixed, and ferments at 20 ~ 40 DEG C.
Further, described feces of livestock and poultry is the one in cow dung, chicken manure, pig manure, sheep excrement;
Described inoculum is the mixture of natural pond liquid and feces of livestock and poultry or the mud of sewage work;
The mixture ratio of described natural pond liquid and feces of livestock and poultry is 10:1, and obtain 26 ~ 28 DEG C of condition domestications after being sealed by barrelling, the domestication time is 8d.
The present invention take natural mineral as raw material, compare with other inorganics etc. with traditional enzyme, inorganic salts, organism, innovative point of the present invention is exactly add the mechanical shock effect utilizing mechanical force and chemical and high-shear, natural mineral is prepared into micritization breeze in biogas fermentation material formula.The present invention, under the prerequisite of adding activator, after mineral are ground to certain fineness, activates nutritive element wherein.When biogas fermentation starts, add the propagation that micritization breeze is conducive to microorganism, improve system biological amount, be conducive to the surge capability improving reactor, the metabolism of methane fermentation system microorganism can be promoted, improve the functioning efficiency in anaerobically fermenting each stage, thus more effectively utilize substrate, finally improve biogas output.In addition, a kind of polyfunctional catalyst micritization zeolite powder that can be used for simultaneously removing organic pollutants and heavy-metal pollution thing is added in methane fermentation system.This methane fermentation system energy consumption is little, unit consumption of energy treatment capacity is large, work flow is short, cost is low, high, easy and simple to handle, the whole technique environmental protection of ozone decomposed efficiency, economy, achieve sustainable development, have broad application prospects.
Feature of the present invention is:
1, the present invention adopts mechanical activation method by the phosphoric activation in phosphorus ore containing, and this processing method makes the utilization ratio of phosphorus ore containing reach 100%, discharges without mine tailing.
2, the effect of having complementary functions of the absorption of micritization zeolite powder, ion-exchange, biological degradation and membrane filtration is taken full advantage of, while except the pollution substance such as arsenic, ammonia nitrogen, heavy metal in anhydrating, methane phase effect stability, reach deodorizing and suppress pathogenic micro-organism, make it innoxious, be easy to control.
3, whole fermentation system obtains good gas production rate, biogas output and raw material availability, and preparation technology's flow process is simple, processing ease, effective, less investment, pollution-free etc.
4, adopt and add multifunctional bio catalyzer anaerobically fermenting mode, for biogas fermentation industrial production opens a new technological approaches, be with a wide range of applications, the practical application for mass-producing biogas production provides powerful technical support.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
The present invention utilizes the fermentation process of the functional biological catalyst of biogas fermentation to carry out by the following method:
The first step, preparation micritization ground phosphate rock:
Phosphate minerals containing 96%-98% mass percent is placed in disintegrating apparatus, powder after pulverizing is placed in grinding plant, and in grinding plant, add the activator of 2%-4% mass percent, carry out super-fine processing, utilize the mechanical shock effect of mechanical force and chemical and high-shear natural mineral to be prepared into the product that mean particle size reaches more than 400 orders, obtain P 2o 5the biogas fermentation micritization ground phosphate rock of content between 15%-25%, and package spare.
Micritization zeolite powder is prepared by following method: the zeolite containing 96%-98% mass percent is placed in disintegrating apparatus, powder after pulverizing is placed in grinding plant, and in grinding plant, add the activator of 2%-4% mass percent, carry out super-fine processing, the mechanical shock effect of mechanical force and chemical and high-shear is utilized natural mineral to be prepared into the product that mean particle size reaches more than 400 orders, obtain biogas fermentation micritization zeolite powder, and package spare.
Micritization Paris white is prepared by following method: the calcium carbonate containing 96%-98% mass percent is placed in disintegrating apparatus, powder after pulverizing is placed in grinding plant, and in grinding plant, add the activator of 2%-4% mass percent, carry out super-fine processing, the mechanical shock effect of mechanical force and chemical and high-shear is utilized natural mineral to be prepared into the product that mean particle size reaches more than 400 orders, obtain biogas fermentation micritization Paris white, and package spare.
Wherein, above-mentioned activator adopts trolamine, poly amic acid or ethylene glycol.
Second step, prepare functional living being catalyzer:
According to the formula of every cubic metre of fermented feed liquid one kilogram be:
Complex microbial inoculum 1-3 part;
Lytic enzyme promotor 100 parts;
Mineral nutrient promotor 61-329 part.
The mineral nutrient promotor of aforementioned proportion, lytic enzyme promotor and complex microbial inoculum are mixed at normal temperatures, obtains the functional biological catalyst of biogas fermentation.
In above-mentioned functions biological catalyst:
Complex microbial inoculum is methanogen, cellulose-decomposing bacterium, yeast, phosphate solubilizing bacteria, milk-acid bacteria or photosynthetic bacteria.
Lytic enzyme promotor total addition level is according to 100 parts of calculating: wherein saccharifying enzyme 54-70 part; Amylase 2 0-31.5 part; Cellulase 5-13 part; Proteolytic enzyme 1-5 part.
Mineral nutrient promotor is added according to following material rate, get wherein two or more:
5-100 part micritization ground phosphate rock, 0-3 part micritization zeolite powder, 0-70 part micritization Paris white, 0-9 part urea, 0-15 part phosphoric acid salt, 0-300 part wilkinite, 0-5.5 part gac.
Above-mentioned phosphoric acid salt takes from the one in Secondary ammonium phosphate or potassium primary phosphate.
3rd step, utilizes functional living being catalyzer to carry out biogas fermentation:
With feces of livestock and poultry (one in cow dung, chicken manure, pig manure, sheep excrement) for raw material, fresh feces of livestock and poultry (one in cow dung, chicken manure, pig manure, sheep excrement) 350-650 part is added according to mass fraction, inoculum is (with fresh weight than being the natural pond liquid of 10:1 and the mud of feces of livestock and poultry mixture or Sewage Plant, natural pond liquid and feces of livestock and poultry mixture seal 26 ~ 28 DEG C of domestications by barrelling and obtain, and the domestication time is 8d; ) 100-300 part, add functional living being catalyzer 163-430 part and carry out biogas fermentation; The water ratio controlling feces of livestock and poultry is 75-85%, and add the dechlorination tap water of a certain proportion of placement, controlling whole original liquid concentration is 7-12%, is fully uniformly mixed, and ferments at 20 ~ 40 DEG C.
According to above-mentioned steps, further illustrate the different material constituents of catalyzer fermentation methane of the present invention below by embodiment 1-9.
Table 1 biogas fermentation one kg feed material composition parts by weight (unit: gram)
According to the embodiment 1-9 of above-mentioned different material constituents catalyzer fermentation methane, provide following table 2 catalytic effect comparative illustration.
Table 2 adopts the technology of the present invention application biogas fermentation biocatalysis implementation result to contrast
As can be seen from above-described embodiment, under identical experiment condition, known by contrasting different biogas fermentation polyfunctional catalysts, raw material sources of the present invention extensively, aboundresources, make the utilization ratio of phosphorus ore containing high, and moderate, be practical as biogas fermentation polyfunctional catalyst.Micritization powder prepared by the present invention shows the various advantages less than common powder:
1) anaerobically fermenting microbial growth needs certain nutritive substance, and C, N, P are that methane fermentating microorganism grows the three kinds of nutritive elements needed most, and mainly controls the ratio entering the carbon of anaerobic reactor raw material, nitrogen, phosphorus in engineering.
2) mechanical activation can realize the transformation of phosphorus ore crystalline network, and mechanical activation mid low grade phosphate rock can improve the leaching yield of phosphoric.When fermenting, add micritization ground phosphate rock, its grain diameter is little, and specific surface area is large, crystalline network height disordering, promotes dissolving and the release of mineral element.Than the elemental phosphorous propagation and the procreation that are more conducive to microorganism, be conducive to the surge capability improving reactor, and then improve gas production rate.With the addition of micritization zeolite powder in the present invention, reduce that biogas is agricultural has heavy metal contamination risk.Add micritization Paris white, the pH value stable maintenance of fermented liquid can not only be made in neutrality to weakly alkaline, and the pH value of producing process of methane fermented liquid can be maintained, reach stable yeasting.
3) add appropriate urea and can provide nitrogenous source, the utilization ratio of fermented substrate can be improved, start marsh gas fermentation processes fast, improve the methane content in biogas.Phosphoric acid salt can provide stable phosphorus source, promotes the breeding of methanobacteria, keeps fixing heavy metal muchly, reduces the effective concentration of heavy metal in fermentation system.Add gac, obviously can improve the performance of active sludge, absorption and biochemical decomposition synergy can be realized.Powdered Activated Carbon is due to its high-specific surface area, significantly reduce the concentration of dissolved matter in mud mixed liquid, the absorption and the Pore Blocking that alleviate dissolved matter pollute, and improve mud flocculation structure, increase mud flco size, hence improve mixed solution membrane filterability.Wilkinites etc. can promote that feces of livestock and poultry is the biogas fermentation of matrix.
4) if when being used alone proteolytic enzyme, not only can not promote biogas fermentation, also can reduce the output of biogas on the contrary.The present invention adopts the mixed hydrolysis enzyme of applicable zymin formula, improves the speed of reaction of hydrolysis stage, can provide more substrate, can improve utilization ratio and the gas producing efficiency of the raw material of biogas fermentation significantly, finally improve biogas output for follow-up each stage.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.

Claims (5)

1. the functional biological catalyst of biogas fermentation, is characterized in that, comprises the raw material of following mass fraction:
Complex microbial inoculum 1-3 part;
Lytic enzyme promotor 100 parts;
Mineral nutrient promotor 61-329 part;
Described mineral nutrient promotor comprises the raw material of following mass fraction:
Described complex microbial inoculum is methanogen, cellulose-decomposing bacterium, yeast, phosphate solubilizing bacteria, milk-acid bacteria or photosynthetic bacteria;
Described lytic enzyme promotor comprises the raw material of following mass fraction:
2. the functional biological catalyst of a kind of biogas fermentation according to claim 1, is characterized in that, described micritization ground phosphate rock, micritization zeolite powder and micritization Paris white are prepared from according to the raw material of following mass percent:
Phosphorus ore containing, zeolite or calcium carbonate 96%-98%;
Activator 2%-4%;
Described activator is trolamine, poly amic acid or ethylene glycol.
3. the functional biological catalyst of a kind of biogas fermentation according to claim 1, is characterized in that, described phosphoric acid salt is the one in Secondary ammonium phosphate or potassium primary phosphate.
4. a biogas fermentation according to claim 1 preparation method for functional biological catalyst, it is characterized in that, the method comprises the steps:
Be that the mineral nutrient promotor of 61-329 part, 100 parts of lytic enzyme promotor and 1-3 part complex microbial inoculum mix at normal temperatures by mass fraction, obtain the functional biological catalyst of biogas fermentation;
Described micritization ground phosphate rock, micritization zeolite powder or micritization Paris white are prepared by following method:
Different disintegrating apparatus is placed in respectively by containing the Phosphate minerals of 96%-98% mass percent, zeolite or calcium carbonate, each powder after pulverizing is placed in three grinding plant respectively, and in each grinding plant, add the activator of 2%-4% mass percent respectively, carry out super-fine processing, utilize the mechanical shock effect of mechanical force and chemical and high-shear natural mineral to be prepared into the product that mean particle size reaches more than 400 orders, obtain P respectively 2o 5the biogas fermentation micritization ground phosphate rock of content between 15%-25% or biogas fermentation micritization zeolite powder, or biogas fermentation micritization Paris white, and package spare.
5. utilize the fermentation process for functional biological catalyst of the biogas fermentation described in claim 1, it is characterized in that, the method comprises the steps:
Take feces of livestock and poultry as raw material, add fresh feces of livestock and poultry 350-650 part according to mass fraction, inoculum 100-300 part and functional living being catalyzer 163-430 part carry out biogas fermentation, and the water ratio controlling feces of livestock and poultry is 75-85%; Add the dechlorination tap water of placement, controlling whole original liquid concentration is 7-12%, is fully uniformly mixed, and ferments at 20 ~ 40 DEG C;
Described feces of livestock and poultry is the one in cow dung, chicken manure, pig manure, sheep excrement;
Described inoculum is the mixture of natural pond liquid and feces of livestock and poultry or the mud of sewage work;
The mixture ratio of described natural pond liquid and feces of livestock and poultry is 10:1, and obtain 26 ~ 28 DEG C of condition domestications after being sealed by barrelling, the domestication time is 8d.
CN201310744961.9A 2013-12-27 2013-12-27 A kind of biogas fermentation functional biological catalyst and the method that utilizes catalyzer to ferment CN103740764B (en)

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CN105063095A (en) * 2015-09-08 2015-11-18 长岭县一鑫农业开发有限公司 Fermentation method of biomass biogas
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