CN103146760A - High-efficiency, energy-saving and environment-friendly technology for fermentation and purification of biogas - Google Patents

High-efficiency, energy-saving and environment-friendly technology for fermentation and purification of biogas Download PDF

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CN103146760A
CN103146760A CN2013100859025A CN201310085902A CN103146760A CN 103146760 A CN103146760 A CN 103146760A CN 2013100859025 A CN2013100859025 A CN 2013100859025A CN 201310085902 A CN201310085902 A CN 201310085902A CN 103146760 A CN103146760 A CN 103146760A
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张其标
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Abstract

The invention discloses a high-efficiency, energy-saving and environment-friendly technology for fermentation and purification of biogas, comprising the following steps of: inoculating the micro-organisms of anaerobic cellulose enzyme producing bacteria in the reaction tank of a biogas fermentation system, so as to realize fermentation for the organic matters of straw and livestock excrements, and controlling the temperature of biogas fermentation to be at a constant-temperature level of 37+/-0.2 DEG C; and performing purification and separation on methane and carbon dioxide in biogas, comprising desulfuration treatment and drying treatment for biogas, and separation for methane and carbon dioxide. With the adoption of the high-efficiency, energy-saving and environment-friendly technology for fermentation and purification of the biogas the fermentation efficiency of the biogas is effectively increased, the purification effect of the biogas is enhanced, and the fermentation cost of the biogas is reduced.

Description

A kind of high-efficient energy-saving environment friendly biogas fermentation and purification technology
Technical field
The present invention relates to the biogas production technology, specifically a kind of high-efficient energy-saving environment friendly biogas fermentation and purification technology.
Background technology
Biogas is a kind of higher thermal value that has, and can be generally, the inflammable gas of the biomass energy that easily obtains, its calorific value is about 20～25MJ/m 3, namely the calorific value of every cubic metre of biogas is equivalent to the 0.8kg standard coal, and compares with other combustion gas, and its capability of antidetonance is good, is a kind of generally acknowledged clean recyclable fuel.The biogas development utilization has the history of decades, utilizes biogas as a kind of approach of curbing environmental pollution, and has both reduced environmental pollution, has obtained again the energy and efficient organic fertilizer.
Biogas is mainly produced acquisition biogas by utilizing organic waste to carry out anaerobically fermenting, then biogas is carried out purifying, isolates methane wherein.The fuel (methane) that can obtain to clean in processing environment pollutent such as domestic refuse, feces of livestock and poultry, crop material etc., not only can reduce people to the dependence of fossil energy such as coal, oil, Sweet natural gas, can also tackle people's demand growing to the energy, be one of effective way that solves energy problem.
Biogas fermentation mainly is divided into three phases: hydrolysis stage, product acetic acid stage, product methane phase.Hydrolysis stage is mainly to promote the hydrolysis of stalk by the microorganism that utilization produces cellulase, for the anaerobically fermenting in latter two stage provides substrate, if this stage stalk hydrolysis is insufficient, easily cause the available micromolecular carbohydrate of microorganism less, affect microbial growth in biogas fermentation, can not provide sufficient substrate for acetic acid bacteria and methanobacteria, thereby cause gas production rate low.
In prior art, biogas fermentation and purification poor effect.
Summary of the invention
Technical problem to be solved: the purpose of this invention is to provide a kind of high-efficient energy-saving environment friendly biogas fermentation and purification technology, further improve biogas fermentation efficient, reduce the biogas fermentation cost.
Technical scheme: a kind of high-efficient energy-saving environment friendly biogas fermentation and purification technology, comprise: the microorganism that produces bacterium in the retort of methane fermentation system by inoculation anaerobic cellulose enzyme, realization is to stalk, the organic fermentation of feces of livestock and poultry, and the biogas fermentation temperature is controlled at the constant temperature level of 37 ± 0.2 ℃;
Methane in sewage gas and purifying carbon dioxide are purified and are separated, and comprise desulfurization processing to biogas, drying treatment and to the separation of methane and carbon dioxide.
Described " anaerobic cellulose enzyme produce bacterium " is to isolate respectively the bacterial strain that many strains can produce transparent circle mud at the bottom of bovine rumen content, sewage disposal thing and the pond,---single-cell suspension liquid---mutagenic treatment---dull and stereotyped primary dcreening operation------multiple sieve---variant genetic stability---culture presevation that single bacterium colony separates that measure enzymic activity by anaerobically fermenting and sift out again the higher amphimicrobian cellulase producing bacteria of a strain enzymic activity, its strain improvement route is: starting strain.
Described " the biogas fermentation temperature is controlled at the constant temperature level of 37 ± 0.2 ℃ ", adopt solar heating constant temperature, utilize solar water heater that water is heated, utilize temperature in sensor sensing biogas retort, control by temperature intelligent the circulation that transmission device is realized hot water, thereby guarantee to keep constant temperature in the biogas retort.
Described " to the desulfurization processing of biogas, drying treatment and to the separation of methane and carbon dioxide ", adopting modified activated carbon is that sweetening agent carries out the desulfurization processing to biogas, adopt the solid absorption method to carry out drying treatment to biogas, adopt the pressure swing adsorption process realization to the separation of methane and carbon dioxide.
Described modified activated carbon is that just massfraction is that 7% NaOH solution impregnation is carried on gac, and with 1% MCM-41 molecular sieve as additive, gac is carried out modification, can make the activated carbon fiber surface have a large amount of active function groups, enlarge the charcoal pore structure, increase the loading capacity of gac.
Described " adopt solid absorption method biogas is carried out drying treatment " is to be used as dry sorbent material with silica gel to realize drying to biogas.
Described " adopting the pressure swing adsorption process realization to the separation of methane and carbon dioxide " adopts the 4A molecular sieve as sorbent material; Workflow is: dried biogas is boosted to by the adsorption bed compressor under the pressure of 0.5MPa and adsorb, adsorb step-down desorption after 2 hours, first carry out the release of 5 minutes, then vacuumize 1.5 hours, keep when being depressurized to 1kPa all pressing 10 minutes, can complete the desorption process of sorbent material 4A molecular sieve.
Beneficial effect:
1, adopt induced-mutation technique to cultivate novel anaerobism high active cellulase bacterium.
By utilizing Congo red double-layer plate method, nitrous acid-ultraviolet separately and the technology such as multiple mutated, the present invention has cultivated a kind of novel anaerobism high active cellulase bacterium, its enzymic activity is more than 180% of bacterial classification enzymic activity before mutagenic treatment, well promoted the efficient and the hydrolysis degree that are hydrolyzed in the marsh gas fermentation processes further to have promoted biogas fermentation efficient.
2, realize the perfect adaptation of heliotechnics and biogas fermentation technology.
The present invention is by the solar heating technology, utilize hot water circulation to come the heating biogas retort, heliotechnics and biogas fermentation are united use, the problems such as biogas retort internal temperature is unstable, factor of created gase is low have been solved, sun power is as a kind of high-quality, clean energy in addition, further reduce the biogas fermentation cost, and realized green production.
3, gac is carried out metal ion loaded modified, strengthen its desulfuration efficiency.
The present invention selects gac as sweetening agent, and gac is carried out the loaded modified processing of metal ion, can form metal oxide on gac, in the new active sites of the inner formation of gac, and metal ion and SO 2Between have good binding ability, and further enlarge active carbon pore structure, can effectively promote desulfuration efficiency.
The loaded modified method of metal ion can realize SO more targetedly with respect to other method of modifying 2Absorption.
4, realize producing of methane in sewage gas with the 4A molecular sieve as the pressure swing adsorption process of sorbent material.
All with carbonaceous molecular sieve, silica gel or some metal oxides sorbent material as pressure swing adsorption process, adsorb the carbonic acid gas in biogas, thereby realize producing of methane in sewage gas at present existing technique.
The present invention adopts the 4A molecular sieve as sorbent material, with respect to molecular sieve mentioned above, 4A molecular sieve main advantage is embodied in: the 4A molecular sieve is polar adsorbent, strong and undersaturated molecule has stronger adsorptive power to polarity, even non-polar molecule, easily the large molecule of polarizability of polarization also easily is adsorbed.CO 2Though the molecule moment of dipole is zero, the existence due to the lone-pair electron of the polarity of carbon-oxygen bond and Sauerstoffatom makes CO 2With 4A molecular sieve positively charged ion, strong effect is arranged, cause adsorptive capacity to increase.
Description of drawings
Fig. 1 is the purification of methane in sewage gas of the present invention and carbonic acid gas and recycles production technological process.
Fig. 2 is solar heating constant temperature biogas fermentation unit schematic diagram of the present invention.
Fig. 3 is solar heating constant temperature biogas fermentation system cardinal principle figure of the present invention.
Fig. 4 is CO2 of the present invention and the sorption isotherm schematic diagram of CH4 on molecular sieve.
Embodiment
A kind of high-efficient energy-saving environment friendly biogas fermentation and purification technology, comprise: the microorganism that produces bacterium in the retort of methane fermentation system by inoculation anaerobic cellulose enzyme, realization is to stalk, the organic fermentation of feces of livestock and poultry, and the biogas fermentation temperature is controlled at the constant temperature level of 37 ± 0.2 ℃;
Methane in sewage gas and purifying carbon dioxide are purified and are separated, and comprise desulfurization processing to biogas, drying treatment and to the separation of methane and carbon dioxide.
Described " anaerobic cellulose enzyme produce bacterium " is to isolate respectively the bacterial strain that many strains can produce transparent circle mud at the bottom of bovine rumen content, sewage disposal thing and the pond,---single-cell suspension liquid---mutagenic treatment---dull and stereotyped primary dcreening operation------multiple sieve---variant genetic stability---culture presevation that single bacterium colony separates that measure enzymic activity by anaerobically fermenting and sift out again the higher amphimicrobian cellulase producing bacteria of a strain enzymic activity, its strain improvement route is: starting strain.
Described " the biogas fermentation temperature is controlled at the constant temperature level of 37 ± 0.2 ℃ ", adopt solar heating constant temperature, utilize solar water heater that water is heated, utilize temperature in sensor sensing biogas retort, control by temperature intelligent the circulation that transmission device is realized hot water, thereby guarantee to keep constant temperature in the biogas retort.
Described " to the desulfurization processing of biogas, drying treatment and to the separation of methane and carbon dioxide ", adopting modified activated carbon is that sweetening agent carries out the desulfurization processing to biogas, adopt the solid absorption method to carry out drying treatment to biogas, adopt the pressure swing adsorption process realization to the separation of methane and carbon dioxide.
Described modified activated carbon is that just massfraction is that 7% NaOH solution impregnation is carried on gac, and with 1% MCM-41 molecular sieve as additive, gac is carried out modification, can make the activated carbon fiber surface have a large amount of active function groups, enlarge the charcoal pore structure, increase the loading capacity of gac.
Described " adopt solid absorption method biogas is carried out drying treatment " is to be used as dry sorbent material with silica gel to realize drying to biogas.
Described " adopting the pressure swing adsorption process realization to the separation of methane and carbon dioxide " adopts the 4A molecular sieve as sorbent material; Workflow is: dried biogas is boosted to by the adsorption bed compressor under the pressure of 0.5MPa and adsorb, adsorb step-down desorption after 2 hours, first carry out the release of 5 minutes, then vacuumize 1.5 hours, keep when being depressurized to 1kPa all pressing 10 minutes, can complete the desorption process of sorbent material 4A molecular sieve.
Particular content of the present invention is described as follows.
1, cultivate a kind of anaerobism high active cellulase and produce bacterium, promote fermentation efficiency.
Biogas fermentation mainly is divided into three phases: hydrolysis stage, product acetic acid stage, product methane phase.Hydrolysis stage is mainly to promote the hydrolysis of stalk by the microorganism that utilization produces cellulase, for the anaerobically fermenting in latter two stage provides substrate, if this stage stalk hydrolysis is insufficient, easily cause the available micromolecular carbohydrate of microorganism less, affect microbial growth in biogas fermentation, can not provide sufficient substrate for acetic acid bacteria and methanobacteria, thereby cause gas production rate low.General generally lower from the microbial strains cellulase-producing activity of occurring in nature separation and purification, be not suitable for direct operation, must carry out strain improvement, this be improve the cellulase producing strain enzymatic productivity effective means.
The anaerobism high active cellulase produces the breeding technique of bacterium, and strain improvement route of the present invention is:
Starting strain---single-cell suspension liquid---mutagenic treatment---dull and stereotyped primary dcreening operation------multiple sieve---variant genetic stability---culture presevation that single bacterium colony separates.
(1) starting strain: respectively isolate bacterial strain that many strains can produce transparent circle mud by the Congo red flat band method of bilayer at the bottom of bovine rumen content, sewage disposal thing and the pond, measure enzymic activity by anaerobically fermenting and sift out again the higher amphimicrobian cellulase producing bacteria of a strain enzymic activity.By this strain morphology feature, physiological and biochemical property and 16SrDNA homology and systematize are set Analysis and Identification, this bacterial strain belongs to Celloulonmonas sp., with its called after CR-14.
(2) single-cell suspension liquid: to logarithmic phase, then the centrifugation thalline, prepare bacteria suspension with physiological saline with strain culturing, regulates bacteria suspension concentration and be about 1 * 10 7Individual/mL.
(3) mutagenic treatment: this project take nitrous acid mutagenesis, ultraviolet mutagenesis and both the complex mutation method bacterial strain is carried out mutagenic treatment.Bacteria suspension after mutagenesis is poured into carried out mixing on the primary dcreening operation substratum, pour again the water cooling of one deck agar into after band primary dcreening operation nutrient solution is cooling, place 30 ℃ of incubators and cultivate.
(4) triage techniques: carry out primary dcreening operation according to each bacterial strain transparent circle on Congo red flat board and the size of colony diameter ratio, the bacterial strain that the odds ratio starting strain is large is chosen, be inoculated in semi-solid stab culture base, cultivate 36h under 30 ℃, cultivate 60h in being inoculated into fermention medium after, with the centrifugal 10min of fermented liquid, get supernatant liquor at 4 ℃, 8000r/min, the tstr enzymic activity is chosen wherein the relatively large bacterial strain of transparent circle and is cultivated.
(5) the variant genetic stability is processed: the bacterial strain of mutagenic and breeding, sudden change in the present age often, the poor stability of heredity.In order to check the genetic stability of mutant strain, propagated continuously for 8 generations, each inclined-plane in 8 generations is activated secondary fermentation simultaneously, measure the enzyme of fermented liquid and live, choose wherein the heritability blast resistance and further cultivate.
2, novel pressure swing adsorption process realize to the purification of methane in sewage gas with separate.
In biogas, main component comprises methane (CH 4) 50% ~ 75%, carbonic acid gas (CO 2) 25% ~ 45%, water (H 2O) 2% ~ 7%, nitrogen (N 2) 0 ~ 2%, a small amount of oxygen (O 2) and the hydrogen (H that is less than l% 2) and hydrogen sulfide (H 2The material such as S).In biogas, main material as biomass energy is methane, must separating-purifying is out from biogas with methane.The purification of biogas and isolation technique mainly include desulfurization processing to biogas, drying treatment and to three parts of separation of methane and carbon dioxide.
(1) adopting modified activated carbon is that sweetening agent carries out the desulfurization processing to biogas.
The modification of gac: all inevitably exist hydrogen sulfide (H in biogas 2S) sulfides, its content is because the difference of fermentation raw material changes to some extent.Hydrogen sulfide (H 2S) sulfides contacts with water, be dissolved in wherein to form acid very strong vaporific hydrogen sulfide solution, can with most of metal reaction.As hydrogen sulfide in methane (H 2S) content surpasses 0.01%, and when directly entering engine, easily corrodes compressor, gas storage tank and engine, and its intensity and life-span are caused very large harm.Therefore, in the purification of biogas, sulfur removal technology is an indispensable technique wherein.
The present invention is mainly to be that sweetening agent absorbs the biogas medium sulphide content by adopting gac.Gac has physical adsorption, and has katalysis, and adsorption process is generally carried out at 5 ~ 60 ℃, and have that surface-area is large, microvoid structure is flourishing, Heat stability is good and the advantage such as with low cost, well suited in H 2S content is lower than 0.3% biogas.
The present invention is adopting on the basis of gac as sweetening agent, gac is carried out study on the modification research, be that 7% NaOH solution impregnation is carried on gac with massfraction, and with 1% MCM-41 molecular sieve as additive, gac is carried out modification, can make the activated carbon fiber surface have a large amount of active function groups, enlarge the charcoal pore structure, increase the loading capacity of gac, promote adsorption effect of activated carbon in water, the current capacity of gac is increased more than 200% at least, and make it have lasting sweetening power.
The absorption principle of gac: the process for adsorption desulfuration of gac is mainly completed the katalysis of sulfide and oxygen by the active group of activated carbon surface.Its absorption and regeneration flow process and principle are mainly:
1. adsorption process: 2H 2S+O 2→ 2S+2H 2O。Its main process is: after charcoal absorption hydrogen sulfide, be converted into sulphur and water by oxygen, and gac itself has the katalysis that the accelerated cure hydrogen-oxygen turns to sulphur.
2. regenerative process: (NH 4) 2+ nS → (NH 4) 2S n+1Its main process is: will be adsorbed on the sulphur on gac, be 12%～14% ammonium sulfide ((NH with massfraction 4) 2) on the solution extraction gac free sulphur and be recycled.
(2) adopt the solid absorption method to carry out drying treatment to biogas.
In the separating-purifying process of biogas, dewatering process is a wherein very important link.It is not carried out drying treatment if contain moisture in biogas, can easily make sour gas such as H in biogas 2S, CO 2Deng, these gases can ionize in water, ionize the existence meeting corroding metal equipment of proton, affect performance and the work-ing life of equipment; And affect the use of methane.Therefore, technique must must be dehydrated in the process for separating and purifying of biogas.
The present invention adopts the solid absorption method to carry out drying treatment to biogas, and by the comparative analysis to all kinds of dry sorbent materials, choice for use silica gel of the present invention is used as dry sorbent material and realizes drying to biogas.
The main component of silica gel is silicon-dioxide (SiO 2), be a kind of high reactivity sorbing material, belong to amorphous substance, chemical molecular formula is mSiO 2NH 2O, cavernous body of its physical structure extraordinary image consists of a pore adsorption system that huge surface-area is arranged by the aperture that interconnects, and can adsorb and preserve aqueous vapor; And silica gel is water insoluble and any solvent, and is nonpoisonous and tasteless, and stable chemical nature does not react with any material except highly basic, hydrofluoric acid.
The chemical composition of silica gel and physical structure have determined that it has the not available characteristics that are difficult to replace of many same type of material: adsorptive power is high, Heat stability is good, stable chemical nature, have higher physical strength, therefore can be well suited in the drying treatment of this project biogas.
(3) adopt the pressure swing adsorption process realization to the good separation of methane and carbon dioxide.
Carbon dioxide in methane content is generally 25% ~ 50%(according to different biogas fermentation materials and zymotechnique and difference).When biogas uses as automotive fuel, if wherein carbon dioxide content is too high, can have influence on the combustion heat value of biogas, thereby affect the performances such as output rating of engine.Therefore, must carry out the separating treatment of methane and carbon dioxide to biogas, make carbon dioxide in methane content lower than 3%.
Because carbonic acid gas is a kind of strong adsorbent, easily be adsorbed agent and adsorb and reclaim, therefore, for this characteristic, the present invention takes pressure swing adsorption process, realizes separating methane in sewage gas and carbonic acid gas.The pressure swing adsorption process that the present invention takes has specific requirement to sorbent material, and needing can be to CO 2Good adsorption is arranged, simultaneously to CH 4Adsorption is not obvious.For this requirement, the present invention has chosen the 4A molecular sieve as sorbent material, CO 2And CH 4Sorption isotherm on molecular sieve as shown in Figure 4, as seen from the figure, CO 2And CH 4Adsorption on the 4A molecular sieve is very large, and carbonic acid gas is had good adsorption, and is less to the methane adsorption, well satisfied the requirement of pressure swing adsorption process sorbent material.
Invention adopts pressure swing adsorption process to CO in biogas 2And CH 4The groundwork flow process of separating is divided into 3 stages and carries out:
1. boost phase: dried biogas is boosted by the adsorption bed compressor, during to top pressure till.Gas density is increased, and gas molecule collision increases to the chance of adsorbent surface, and the residue gravitation that more easily is adsorbed the agent surface is caught.According to the difference of upper Fig. 4 A molecular sieve to the adsorptive power of methane and carbon dioxide, the present invention selects to boost under the pressure of 0.5MPa adsorbs, and can reach satisfied effect.
2. absorption phase: keep pressure constant, by sorbent material 4A molecular sieve, the component carbonic acid gas of strong absorption is adsorbed with certain speed, weak absorbed component methane is discharged from.This Project design is to adsorb 2 hours under 0.5MPa.
3. step-down desorption stage: reduce pressure, obtain rich extremely strong absorbed component carbonic acid gas from sorbent material, reach the separating effect of carbonic acid gas and methane, make sorbent material obtain regeneration, for next circulation is prepared.The groundwork flow process that the present invention designs the desorption stage is: first carry out the release of 5min, then vacuumize 1.5 hours, keep when being depressurized to 1kPa all pressing 10min, can complete the desorption process of sorbent material 4A molecular sieve.
The present invention be mainly research and development be carbonic acid gas and the methane that utilizes in absorption method separating-purifying biogas.Wherein master operation includes biogas desulfurization processing, biogas drying treatment, CH 4And CO 2Separation, CH 4And CO 2Condensation storage etc.
Due to H in biogas 2S is sour gas, and generation acidic solution corrosion device soluble in water is processed so should first carry out desulfurization to biogas; Contain part water vapour in biogas after desulfurization, can other performances such as absorption property of molecular sieve in follow-up separation process be impacted, so should carry out drying treatment to biogas; Next need biogas is carried out the CH of separating treatment and storage separation 4And CO 2
3, the design of solar heating constant temperature biogas fermentation system.
Active in whole fermenting process is all kinds of anaerobic bacteriums, mainly comprises all kinds of decomposers and methane-producing bacteria.During the fermentation, temperature is the important factor that affects the anaerobion vital movement.It is by to the activity of enzyme, and microbial metabolism mode, material aspects such as solubleness in water affect the physico-chemical property of biogas fermentation final product.For methane-producing reactor, temperature fluctuation range should not surpass 2 ℃ of scholars among general one day, when 3 ℃ of scholars' variation is arranged, will suppress the generation speed of methane, when 5 ℃ of scholars' sharply variation is arranged, will suppress the generation of methane fully.Therefore, the present invention need to design and develop a kind of constant temperature biogas pond, guarantees carrying out smoothly of fermenting process.
In the fermenting process of biogas, what wherein play a major role is each quasi-microorganism, analysis according to metabolic rule and the optimum activity of anaerobion, the biogas fermentation temperature need to be controlled at a constant temperature level of 37 ± 0.2 ℃, can guarantee that like this enzyme that in fermenting process, microorganism produces is during the fermentation keeping high reactivity.
Referring to Fig. 3, solar heating constant temperature biogas fermentation system cardinal principle.The present invention is by being applied to the solar heating technology in biogas fermentation, its main implementation technique is: design a kind of solar constant temperature heating system, utilize solar water heater that water is heated, utilize temperature in sensor sensing biogas retort, control by temperature intelligent the circulation that transmission device is realized hot water, thereby guarantee to keep constant temperature in the biogas retort.
Referring to Fig. 2, solar heating constant temperature biogas fermentation unit includes biogas fermentation retort 5, solar water heater 1, hot water snubber 12, votator 4, automatic control system (temperature sensor 3,10, interchange electric shock device, temperature controller 2 and magnetic valve 6,7,8,11,13,15,16,19), recycle pump 9 and hot-water circulation pipe 18, indoor tap water interface 17, indoor pond interface 14.And other accessories etc.Whole device mainly comprises methane fermentation system, Temperature Intelligent Control System and hot water cyclesystem etc.
(1) methane fermentation system: methane fermentation system carries out in retort, produces the multiple-microorganisms such as bacterium, methanogen by inoculation anaerobic cellulose enzyme, controls wherein temperature, pressure etc., realizes all kinds of organic fermentations such as stalk, feces of livestock and poultry.
(2) Temperature Intelligent Control System: formed by temperature sensor and temperature intelligent control instrument.First send temperature signal to temperature control box by temperature sensor, whether temperature control box determines switch water pump and corresponding magnetic valve according to the temperature that sets, thereby determines that the heating cycle route reaches the purpose of controlling the inner leavening temperature of reaction unit.
(3) hot water cyclesystem: hot water cyclesystem mainly comprises circulation and two parts of the circulation between hot water snubber and solar water heater between hot water snubber and retort.
Circulation between hot water snubber and retort: when temperature in retort during less than design temperature (37 ℃), thereby feed back to temperature control box ON cycle pump by temperature sensor 2, impel the water in hot well tank to circulate between hot water snubber and retort, thereby the temperature in the lifting retort, when in retort, temperature reaches design temperature, thereby feed back to temperature control box by temperature sensor again and close recycle pump, loop termination.
Circulation between hot water snubber and solar water heater: when the water temperature in the hot water snubber during lower than design temperature, thereby feed back to temperature control box by temperature sensor 1 and open pump 2, impel the water in hot well tank and solar water heater to circulate, thereby the temperature of water in the lifting hot well tank, water temperature reaches design temperature constantly in hot well tank, thereby feed back to temperature control box by temperature sensor l again and close pump 2, loop termination.Circulating line is provided with check valve, thereby can guarantee the one-way circulation of water, the refluence of anti-sealing.
4, the purification of methane in sewage gas and carbonic acid gas and the recycling technological process of production are referring to Fig. 1.
Mainly send system, automatic control system and Safety monitoring system etc. partly to form by biogas compression system, biogas desulfurization system, biogas dehumidification system, pressure swing adsorption system, product collection.
(1) biogas compression system: the biogas compression system is mainly the described compressor section of Fig. 1, and its major function is that the pressure in the biogas storage tank is increased to 5.0MPa, to satisfy the required pressure of biogas separating-purifying flow process.
(2) marsh gas preprocessing system: marsh gas preprocessing system mainly includes desulphurization system and dehumidification system, is respectively arranged with desulfurizer and drying installation biogas is carried out desulfurization processing and drying treatment.ρ (H in biogas after general requirement is processed 2S)＜15mg/m 3, φ (H 2O)＜1 * 10 -6
(3) biogas separation system: due to CH in biogas 4And CO 2Content all very large, carry out the larger of separating-purifying timer, so the separating-purifying flow process adopts 4 molecular sieve vacuum desorption flow processs.The biogas separation system mainly is comprised of 4 adsorption towers, duct-type pneumatic valve, exhaust silencer, vacuum pump etc., and major function is to realize the sorption and desorption of molecular sieve in adsorber, by vacuum pump the CO that is adsorbed in the molecular sieve hole 2Molecule is released, thereby obtains products C H 4And CO 2
(4) the product collection send system: the product collection send system mainly by oil free screw compressor, CH 4Hold-up vessel, CO 2Hold-up vessel, flow sensor, pressure transmitter, CH 4Concentration sensor, CO 2The compositions such as concentration sensor.It act as: the one, provide gas product to adsorber, cleaning the impure gas in the space between molecular sieve, for the absorption of adnexa provides condition; The 2nd, carry the CH after concentrated in the storage tank 4And CO 2The 3rd, testing product CH 4And CO 2Flow, purity and pressure.
(5) automatic control system: because by-pass valve control quantity in pressure-variable adsorption vacuum flow process is many, the flow process reference mark is also many, therefore, in order to simplify production operation, improve automatization level, all controls are focused on the watch-keeping cubicle, operating process realizes real-time demonstration, automatic alarm and Long-distance Control.
(6) Safety monitoring system: whole plant is placed in factory building or outdoor, has to leak just might produce CH 4Gather, cause personnel poisoning, just might cause CH in case there is burning things which may cause a fire disaster to exist 4Blast.For this reason, must be at each reference mark particularly setting pressure sensor and safety valve on adsorption tower and gas product storage tank, and oxygen concentration sensor and CH are installed in factory building 4In case concentration sensor is Working environment or facility environment CH 4Volume fraction surpasses 3%, carries out auto-breaking and shuts down.In addition, at concentrated CH 4In the support equipment of device, all electromechanical equipments, instrument must be selected the product with explosion-proof test conformity certification.Unit to concentrating unit before entering compressor should arrange spark arrester, prevents the diffusion of flame.Due to the CH in biogas 4Concentration is unstable, for simplifying the operation, improves level of automation, and current stabilization, voltage stabilizing should be set on flow process, and analog quantity is regulated and measured, analyzes, and realizes automatically regulating and controlling.The equipment fabricating yard should meet associated safety regulation, and the fire-extinguishing system such as fine spray extinguisher is installed.

Claims (7)

1. a high-efficient energy-saving environment friendly biogas fermentation and purification technology is characterized in that comprising:
Produce the microorganism of bacterium by inoculation anaerobic cellulose enzyme in the retort of methane fermentation system, realize stalk, the organic fermentation of feces of livestock and poultry, the biogas fermentation temperature is controlled at the constant temperature level of 37 ± 0.2 ℃;
Methane in sewage gas and purifying carbon dioxide are purified and are separated, and comprise desulfurization processing to biogas, drying treatment and to the separation of methane and carbon dioxide.
2. high-efficient energy-saving environment friendly biogas fermentation according to claim 1 and purification technology, it is characterized in that: described " the anaerobic cellulose enzyme produces bacterium " is from the bovine rumen content, isolate respectively the bacterial strain that many strains can produce transparent circle at the bottom of sewage disposal thing and pond in mud, measure enzymic activity by anaerobically fermenting and sift out again the higher amphimicrobian cellulase producing bacteria of a strain enzymic activity,---single-cell suspension liquid---mutagenic treatment---dull and stereotyped primary dcreening operation------multiple sieve---variant genetic stability---culture presevation that single bacterium colony separates that its strain improvement route is: starting strain.
3. high-efficient energy-saving environment friendly biogas fermentation according to claim 1 and purification technology, it is characterized in that: described " the biogas fermentation temperature is controlled at the constant temperature level of 37 ± 0.2 ℃ ", adopt solar heating constant temperature, utilize solar water heater that water is heated, utilize temperature in sensor sensing biogas retort, control by temperature intelligent the circulation that transmission device is realized hot water, thereby guarantee to keep constant temperature in the biogas retort.
4. high-efficient energy-saving environment friendly biogas fermentation according to claim 1 and purification technology, it is characterized in that: described " to the desulfurization processing of biogas, drying treatment and to the separation of methane and carbon dioxide ", adopting modified activated carbon is that sweetening agent carries out the desulfurization processing to biogas, adopt the solid absorption method to carry out drying treatment to biogas, adopt the pressure swing adsorption process realization to the separation of methane and carbon dioxide.
5. high-efficient energy-saving environment friendly biogas fermentation according to claim 4 and purification technology, it is characterized in that: described modified activated carbon is that just massfraction is that 7% NaOH solution impregnation is carried on gac, and with 1% MCM-41 molecular sieve as additive, gac is carried out modification, can make the activated carbon fiber surface have a large amount of active function groups, enlarge the charcoal pore structure, increase the loading capacity of gac.
6. high-efficient energy-saving environment friendly biogas fermentation according to claim 4 and purification technology is characterized in that: described " adopting the solid absorption method to carry out drying treatment to biogas " is to be used as dry sorbent material with silica gel to realize drying to biogas.
7. high-efficient energy-saving environment friendly biogas fermentation according to claim 4 and purification technology is characterized in that: described " adopting pressure swing adsorption process to realize separation to methane and carbon dioxide ", and adopt the 4A molecular sieve as sorbent material; Workflow is: dried biogas is boosted to by the adsorption bed compressor under the pressure of 0.5MPa and adsorb, adsorb step-down desorption after 2 hours, first carry out the release of 5 minutes, then vacuumize 1.5 hours, keep when being depressurized to 1kPa all pressing 10 minutes, can complete the desorption process of sorbent material 4A molecular sieve.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103484502A (en) * 2013-09-22 2014-01-01 大连理工大学 Method for producing methane by using anerobic fermentation of rumen microorganism
CN104531249A (en) * 2014-12-31 2015-04-22 山东圣琪生物有限公司 Methane desulfurizer
US9371545B2 (en) 2014-07-11 2016-06-21 Uniwersytet Warszawski Consortium and preparation of microorganisms for catalyzing cellulose hydrolysis, preparation for methane fermentation supplementation, combination preparation, use thereof and method using the same
CN105861088A (en) * 2016-05-24 2016-08-17 安徽瑞丝环保能源有限公司 Biogas purifying tank
CN106118777A (en) * 2016-08-24 2016-11-16 深圳前海中盛环保科技有限公司 A kind of marsh gas purifying purifies the method for methane
CN109563421A (en) * 2016-06-09 2019-04-02 积水化学工业株式会社 The manufacture system of organic substance and the manufacturing method of organic substance
CN111690693A (en) * 2020-08-07 2020-09-22 东营市延旭环保科技有限公司 Environment-friendly biogas power generation biogas production process
CN114107404A (en) * 2020-09-01 2022-03-01 中国科学院青岛生物能源与过程研究所 Integrated separation type microorganism fixed bed in-situ hydrogen alkane conversion method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003340408A (en) * 2002-05-24 2003-12-02 Takuma Co Ltd Treatment system and treatment method for methane fermentation
DE10361196A1 (en) * 2003-12-24 2005-07-28 Sten Flehmig Anaerobic waste water treatment plant with low-pressure distillation discharges gas to external gas cooler
CN1796220A (en) * 2004-12-27 2006-07-05 本田技研工业株式会社 Body foreside structure for two-wheeled automobile
CN1884509A (en) * 2006-07-11 2006-12-27 云南师范大学 Preparation method of hybrid hydrolase formulation for promoting methane yield from fermentation
JP2008045060A (en) * 2006-08-18 2008-02-28 Kyuchaku Gijutsu Kogyo Kk Method for recovering and purifying methane from biofermented gas by using adsorbent
CN101886306A (en) * 2010-07-07 2010-11-17 厦门东纶股份有限公司 Warping machine blowing device
CN102321676A (en) * 2011-09-07 2012-01-18 乌鲁木齐市隆盛达环保科技有限公司 Biogas engineering two gas one fertile complex method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003340408A (en) * 2002-05-24 2003-12-02 Takuma Co Ltd Treatment system and treatment method for methane fermentation
DE10361196A1 (en) * 2003-12-24 2005-07-28 Sten Flehmig Anaerobic waste water treatment plant with low-pressure distillation discharges gas to external gas cooler
CN1796220A (en) * 2004-12-27 2006-07-05 本田技研工业株式会社 Body foreside structure for two-wheeled automobile
CN1884509A (en) * 2006-07-11 2006-12-27 云南师范大学 Preparation method of hybrid hydrolase formulation for promoting methane yield from fermentation
JP2008045060A (en) * 2006-08-18 2008-02-28 Kyuchaku Gijutsu Kogyo Kk Method for recovering and purifying methane from biofermented gas by using adsorbent
CN101886306A (en) * 2010-07-07 2010-11-17 厦门东纶股份有限公司 Warping machine blowing device
CN102321676A (en) * 2011-09-07 2012-01-18 乌鲁木齐市隆盛达环保科技有限公司 Biogas engineering two gas one fertile complex method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
丁羽等: "太阳能加热沼气反应装置的设计及参数选择", 《农机化研究》, no. 8, 31 August 2008 (2008-08-31) *
冯琛然等: "变压吸附法分离沼气装置研究", 《宁波化工》, no. 2, 31 December 2010 (2010-12-31) *
秦悦等: "浸渍改性活性炭脱除低浓度H2S的研究", 《低温与特气》, vol. 27, no. 4, 31 August 2009 (2009-08-31) *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103484502A (en) * 2013-09-22 2014-01-01 大连理工大学 Method for producing methane by using anerobic fermentation of rumen microorganism
CN103484502B (en) * 2013-09-22 2015-04-08 大连理工大学 Method for producing methane by using anerobic fermentation of rumen microorganism
US9371545B2 (en) 2014-07-11 2016-06-21 Uniwersytet Warszawski Consortium and preparation of microorganisms for catalyzing cellulose hydrolysis, preparation for methane fermentation supplementation, combination preparation, use thereof and method using the same
CN104531249A (en) * 2014-12-31 2015-04-22 山东圣琪生物有限公司 Methane desulfurizer
CN105861088A (en) * 2016-05-24 2016-08-17 安徽瑞丝环保能源有限公司 Biogas purifying tank
CN109563421A (en) * 2016-06-09 2019-04-02 积水化学工业株式会社 The manufacture system of organic substance and the manufacturing method of organic substance
US10865425B2 (en) 2016-06-09 2020-12-15 Sekisui Chemical Co., Ltd. System for producing organic substance and method for producing organic substance
US11525147B2 (en) 2016-06-09 2022-12-13 Sekisui Chemical Co., Ltd. System for producing organic substance and method for producing organic substance
CN106118777A (en) * 2016-08-24 2016-11-16 深圳前海中盛环保科技有限公司 A kind of marsh gas purifying purifies the method for methane
CN111690693A (en) * 2020-08-07 2020-09-22 东营市延旭环保科技有限公司 Environment-friendly biogas power generation biogas production process
CN114107404A (en) * 2020-09-01 2022-03-01 中国科学院青岛生物能源与过程研究所 Integrated separation type microorganism fixed bed in-situ hydrogen alkane conversion method

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Application publication date: 20130612