CN103451236A - Method for jointly producing hydrogen and methane by carrying out coupling anaerobic fermentation on preprandial garbage and kitchen garbage - Google Patents
Method for jointly producing hydrogen and methane by carrying out coupling anaerobic fermentation on preprandial garbage and kitchen garbage Download PDFInfo
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- CN103451236A CN103451236A CN2013103971192A CN201310397119A CN103451236A CN 103451236 A CN103451236 A CN 103451236A CN 2013103971192 A CN2013103971192 A CN 2013103971192A CN 201310397119 A CN201310397119 A CN 201310397119A CN 103451236 A CN103451236 A CN 103451236A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses an environment-friendly method for jointly producing hydrogen and methane by carrying out coupling anaerobic fermentation on preprandial garbage and kitchen garbage, and belongs to the technical field of solid waste treatment and biological energy. The method comprises the following steps: firstly carrying out soaking pretreatment on the preprandial garbage by utilizing biogas slurry generated through the anaerobic fermentation, and carrying out damp heat flash evaporation pretreatment on the kitchen garbage; then mixing the pretreated preprandial garbage and kitchen garbage to prepare the hydrogen and the methane through an anaerobic fermentation process by taking biogas residues discharged by a system after a methane production stage as inocula. The method disclosed by the invention is suitable for recovering the biomass energy contained in solid organic matters with multiple high-organic matters, high-water ratio and high-cellulose organic solid wastes in hydrogen and methane forms, integrates energy conservation, emission reduction, renewable resource utilization and pollution control into a whole, is a pollution-free, low-energy consumption and high-productive capacity kitchen garbage anaerobic fermentation treatment process and has the advantages of important environmental benefit and wide application prospect.
Description
Technical field
The invention belongs to solid waste and process and the bioenergy technical field, relate to the technology of a kind of anaerobically fermenting co-producing hydrogen and methane, be specifically related to a kind of employing be coupled green method of anaerobically fermenting co-producing hydrogen and methane of rubbish and changing food waste before the meal.
Background technology
Along with the ambient atmosphere pollution problem that the exhaustion day by day of global Nonrenewable energy resources and fossil fuel energy burning produce, serious threat the mankind's Sustainable development and living environment.Hydrogen is considered to one of important clean energy of 21 century, and methane is also the renewable energy source of most possible instead of natural gas, enjoys people's concern.In many kinds of biological flue gas preparation methods, anaerobically fermenting is because the characteristics such as its environment friendly, less energy-consumption, high energy gamma source output have attracted a large amount of Chinese scholars to be studied it.In recent years, raising along with people's living standard, the changing food waste generation improves constantly, be sharp increase trend, 2008 to be only Beijing's changing food waste day generation be 1600 tons, and at present China's some areas changing food waste in unordered supervisor status, common simple and easy stacking, grow mosquitos and flies, produce stench, environmental pollution and HUMAN HEALTH produce very big risk.Utilize traditional landfill method to be processed the loss that not only can cause nutritive value in changing food waste, and easily produce the secondary pollutions such as foul gas, percolate; Burning method is processed changing food waste because the changing food waste water ratio is higher, and its calorific value is lower, and produces a large amount of obnoxious flavoures, has a strong impact on peripheral ecotope and human residential environment's quality.
Anaerobic biological treatment is to utilize the under anaerobic process of degradation of organic substances of microbial process.Existing changing food waste anaerobic fermentation processing method mainly be take two-stage method anaerobic digestion process and whole one-stage process as main.Two-stage method is separated the acidication stage in digestive process and methane fermentation stage, and one-stage process has been integrated this two stages.In Chinese meal kitchen refuse treatment industry, whole one-stage process occupies superiority at present, its major advantage is less investment, process operation is simple, the aerogenesis cycle is short, but its shortcoming is also comparatively obvious, in treating processes, whole one-stage process is larger compared to the fluctuation of two-stage method aerogenesis, accurate control in being difficult to realize processing, thereby affect the stability of system long-time running, and be applied to mixture when fermentation, the fermentation period of different material differs greatly, be difficult to realize high-level efficiency utilization organic in material, it is comparatively obvious that material is processed incomplete phenomenon, and a large amount of biogas residue and biogas liquids that produce can't reach emission standard, usually need to again process, strengthened the anaerobically fermenting cost.Usually be mixed with rubbish before the meal in changing food waste; rubbish is mainly the higher plant residues of content of cellulose such as dish leaf, half rotten fruits and vegetables before the meal; take it when substrate carries out anaerobically fermenting; usually the system toggle speed is slow, and changing food waste is mainly that leftovers are mixed in together, and its fat content, water ratio, organic content are higher; while carrying out anaerobically fermenting; usually acidifying speed is fast, causes system generally to be moved under underload, and is difficult to the stability of keeping system operation.These two kinds of rubbish required top condition difference when carrying out the coproduction of hydrogen methane, overall treatment technology is perfect not enough, and the energy recovery efficiency that further improves changing food waste how also needs further systematic study.
Therefore, researching and developing a kind of different pretreatments of utilizing processes respectively before the meal, changing food waste, and rubbish and changing food waste coupling before the meal carried out to the anaerobically fermenting co-producing hydrogen, methane, make the two mutual supplement with each other's advantages, effectively improve changing food waste energy recovery efficiency, and the long-term stability that can guarantee anaerobically fermenting coproduction reactor is moved, not only having solved changing food waste is difficult to dispose by traditional method, be easy to produce the problem of secondary pollution, and more common anaerobic fermentation technology is processed the ability that changing food waste has improved the production green bio energy, reduced the dependency to the traditional energy material, energy structure optimizing for China, the improvement that improves the capability of sustainable development and ecotope has certain contribution.
Summary of the invention
The object of the present invention is to provide a kind of before the meal with the method for changing food waste coupling anaerobically fermenting co-producing hydrogen and methane.The present invention is applicable to the organic solid castoff of multiple high organic, high-moisture percentage, high-cellulose, as the rubbish such as domestic refuse, fowl and animal excrement, fruits and vegetables rubbish, agricultural residues body, animal deformed limb, aquatic products refuse reclaim contained biomass energy in SOLID ORGANIC matter with the form of hydrogen and methane.The present invention integrates energy-saving and emission-reduction, renewable resources utilization and Pollution abatement, is a set of pollution-free, less energy-consumption, changing food waste anaerobically fermenting treatment process that production capacity is high, has important environmental benefit and wide application prospect.
Of the present inventionly with changing food waste coupling anaerobically fermenting co-producing hydrogen and the method for methane, be before the meal: at first utilize and produce system is discharged after methane phase natural pond liquid, as soak solution, rubbish is before the meal carried out to dipping pretreatment, the while changing food waste adopts damp and hot flash distillation pre-treatment; Then pretreated rubbish before the meal and changing food waste are mixed, using and produce system is discharged after methane phase natural pond slag as inoculum, by anaerobic ferment process, prepare hydrogen and methane.
The step that system is discharged after methane phase natural pond liquid carries out dipping pretreatment as soak solution to rubbish is before the meal produced in described utilization: at first refuse breaking to particle diameter is 2-20mm before the meal, then rubbish mixes for (1:1)-(1:10) in mass ratio with soak solution before the meal, and the rubbish quality is in the butt quality before the meal; Pass into nitrogen 5-20min in the pre-treatment steeping tank, excluding air keeps anaerobic environment, and temperature remains on 30-40 ℃, and stir speed (S.S.) is 60-100r/min, per hour stirs 5-15min, and soak time is 1-5 days; Described soak solution is for producing system is discharged after methane phase natural pond liquid and through the screen filtration of aperture 1-10mm.
Keep anaerobism in above-mentioned screen filtration process, maintain the anaerobion activity.
Described changing food waste adopts the pretreated step of damp and hot flash distillation to be: by kitchen garbage breaking to particle diameter, be at first 2-40mm, adding the water rate is 50-100wt%, control pressure is 2-4Pa, stir speed (S.S.) is at 80-150r/min, temperature is to be cooled to room temperature after 90-150 ℃ of heating 30-60min, then centrifugal with 4000-8000r/min or use the pressure filter press filtration, but remove oil slick, standby.
The high-temperature steam formed after above-mentioned flash distillation reclaims heat by waste heat recovery unit, utilizes the heat reclaimed to be heated to anaerobic fermentation tank.
Described by pretreated rubbish before the meal and changing food waste mixing, using and produce system is discharged after methane phase natural pond slag as inoculum, preparing hydrogen by anaerobic ferment process with the reaction conditions of methane is: the rubbish before the meal after dipping pretreatment with through damp and hot flash distillation pretreated changing food waste with VS than (1:1)-(1:5) mix, after vibration mixes by mixture and inoculum with VS than (1:1)-(1:4) mix, the initial organic load of Controlling System is at 1-4.5kgL
-1d
-1, guarantee that system C/N is at (10-15): in 1 scope, utilize centrifugal after the damp and hot flash distillation pre-treatment of changing food waste or water that be press-filtered out to regulate material water ratio to tinning after 90-95wt%;
Produce hydroformylation stage: with 0.5-2mol/LHCl and 0.5-2mol/LNaOH, regulate the pH value to 4.5-6.5, pass into high pure nitrogen 2-15min with the 1-5mL/s flow, air in removal system, guarantee intrasystem anaerobic environment, control temperature range at 30-40 ℃, control stir speed (S.S.) in the 100-300r/min scope, the system operation entered the product methane phase after 2-7 days;
Produce methane phase: adopt 0.5-2mol/LHCl and 0.5-2mol/LNaOH to regulate the pH value to 7-8, temperature is controlled at 30-40 ℃, and stir speed (S.S.) is controlled at 100-300r/min, keeps anaerobic condition, stops two days later anaerobically fermenting stopping aerogenesis.
Produce after methane phase completes the natural pond liquid that obtains as soak solution, the natural pond slag, as inoculum, continues cyclical operation by above-mentioned steps, to before the meal with changing food waste be coupled anaerobically fermenting co-producing hydrogen and methane.
By the butt quality, by (1:1)-(1:10) mixing anaerobic domestication 1-2 month in mass ratio of changing food waste and anaerobically digested sludge, until it not after aerogenesis, utilize the 1-10mm screen filtration to obtain anaerobic fermented liquid, as rubbish soak solution before the meal in the first batch, the rubbish soak solution is and produces the natural pond liquid that system is discharged after methane phase before the meal thereafter; Active sludge through taming is as first batch of inoculum, and inoculum is and produces the natural pond slag that system is discharged after methane phase thereafter.
Principle of the present invention is to utilize microorganism abundant in anaerobic fermented liquid to carry out pre-treatment to the rubbish before the meal of high cellulose content, increased the microorganism active in reactor start-up stage, reduced matrix viscosity in reactor, and the basicity of utilizing anaerobic fermented liquid slows down after mixing with changing food waste produces that acid is too fast and Accumulation of Organic Acids that produce suppresses the phenomenon of aerogenesis, also can improve the water content in reactor simultaneously, promote being uniformly distributed of organic constituent and enzyme, improve the efficiency of anaerobically fermenting.For fat content in changing food waste, too high phenomenon adopts damp and hot flash distillation treatment technology to carry out pre-treatment to changing food waste, but the grease that the dispersed oil that exists in changing food waste, oil in water emulsion, dissolving oil, oil-containing solids etc. are difficult to deviate from changes oil slick into, utilize filtering equipment to deviate from, prevent the restraining effect of high grease to anaerobic fermentation gas production, utilize High Temperature High Pressure that the structure of matter in changing food waste is changed simultaneously, it is more easily utilized by Institute of Micro-biology.
The invention has the advantages that:
(1) the present invention utilizes anaerobic fermentation system, from row's natural pond liquid, rubbish is before the meal carried out to immersion treatment, has solved to a certain extent the secondary treatment problem that anaerobic fermentation system produces natural pond liquid.
(2) the present invention utilizes anaerobic fermentation system, from row's anaerobic fermented liquid, rubbish is before the meal carried out to immersion treatment, owing to containing abundant microorganism in anaerobic fermented liquid, especially hydrogenogens, methanogen and cellulose-decomposing bacterium, can effectively shorten start time of anaerobic fermentation system.
(3) the present invention carries out damp and hot flash distillation pre-treatment to changing food waste, effectively reduce fat content in changing food waste, and changed to a certain extent the immanent structure of organic matter in the changing food waste, make more easily by Institute of Micro-biology, being decomposed and utilize of its change, thereby reach the purpose of reduction treatment cycle.
(4) the invention solves in souring stage rubbish acidifying after the meal too fastly, organic acid accumulates the problem that suppresses aerogenesis in a large number, has improved the organic loading of reactor, has guaranteed the high-level efficiency of aerogenesis and the stability of reactor in the reaction process.
(5) the High Temperature High Pressure hot steam that the present invention produces a large amount of damp and hot flash distillations is carried out waste heat recovery, and utilizes it to anaerobic fermentation tank, to carry out heat tracing, improves efficiency of energy utilization.
(6) rubbish before the meal that the present invention processed different pretreatments mixes with changing food waste and carries out anaerobically fermenting, two kinds of different substrates are by after pre-treatment separately, all be more suitable for carrying out anaerobically fermenting co-producing hydrogen methane, carry out separately the anaerobic fermentation gas production amount than two kinds of substrates and be greatly improved.
(7) easy handling regulation and control of the present invention, less investment, saved the fund input of processing for biogas residue and biogas liquid, the reaction conditions gentleness, stability is higher, is applicable to the through engineering approaches application.
The accompanying drawing explanation
Fig. 1 for the present invention design before the meal with the process flow sheet of changing food waste coupling anaerobically fermenting co-producing hydrogen and methane.
The color atlas that Fig. 2 is the 4th anaerobic fermentation to produce hydrogen stage gas-phase product of embodiment 1 midloop operation.
Fig. 3 is the color atlas that the 4th anaerobically fermenting of embodiment 1 midloop operation produces the methane phase gas-phase product.
Embodiment
Embodiment 1
Employing is from rubbish before the meal and the changing food waste in dining room.
Refuse breaking to particle diameter is 2-20mm before the meal, and anaerobic fermented liquid is got filtrate with the screen filtration of aperture 1mm, keeps anaerobism in the screen filtration process; Rubbish mixes with mass ratio 1:2 ratio with anaerobic fermented liquid before the meal, and the rubbish quality is in the butt quality before the meal; Pass into high pure nitrogen nitrogen and blow 5min, and keep anaerobic environment, temperature remains on 35 ℃ of left and right, and stir speed (S.S.) is 80r/min, per hour stirs 10min, soaks 2 days, stand-by;
Be 2-40mm by kitchen garbage breaking to particle diameter, add water rate 50%, pressure remains on 2Pa, and stir speed (S.S.) is at 100r/min, 90 ℃ of heating of damp and hot pre-treatment 30 minutes, but be cooled to the centrifugal removal oil slick of 8000r/min after room temperature, standby;
Changing food waste and the anaerobically digested sludge that picks up from sewage work are tamed 2 months with mass ratio 1:10 mixing anaerobic, until it not after aerogenesis, utilize the 1mm screen filtration to obtain anaerobic fermented liquid, as rubbish soak solution before the meal in the first batch, all originate from thereafter the natural pond liquid of system discharge after methane phase as the anaerobic fermented liquid of rubbish soak solution before the meal; Active sludge through taming is as first batch of inoculum, and inoculum is and produces the natural pond slag that system is discharged after methane phase thereafter;
Rubbish before the meal after immersion treatment is mixed than 1:4 with VS with the changing food waste pretreated through damp and hot flash distillation, after vibration mixes, mixture is mixed than 1:4 with VS with inoculum, the Controlling System organic load is at 1kgL
-1d
-1, guarantee that system C/N is in the 13:1 scope, utilize the centrifugal water gone out after the damp and hot flash distillation pre-treatment of changing food waste to regulate water ratio to 90%, tinning;
Produce hydroformylation stage: with 0.5mol/LHCl and 2mol/LNaOH, regulate pH value to 5.5, flow 5mL/s passes into high pure nitrogen 5min to carry out nitrogen and blows, air in removal system, guarantee intrasystem anaerobic environment, control temperature range at 35 ℃, control stir speed (S.S.) in the 150r/min scope, start hydrogen production through anaerobic fermentation, the system operation entered the product methane phase after 4 days;
Produce methane phase: regulate pH value to 7.5 with 0.5mol/LHCl and 2mol/LNaOH, temperature is controlled at 35 ℃, and stir speed (S.S.) is controlled at 150r/min, and the maintenance anaerobic condition, enter the product methane phase, stops anaerobically fermenting after 2 days stopping aerogenesis.
Produce after methane phase completes the natural pond liquid that obtains as soak solution, the natural pond slag, as inoculum, continues cyclical operation by above-mentioned steps, to before the meal with changing food waste be coupled anaerobically fermenting co-producing hydrogen and methane.
After employing gas chromatograph and hplc determination anaerobically fermenting, gas phase and liquid product form, and wet test meter is measured gas production rate.Adopt SP-6890 type gas chromatograph for determination anaerobically fermenting gas-phase product moiety and concentration, GC conditions is: the TCD thermal conductivity cell detector, high-purity argon gas is as carrier gas, intake pressure is 1.6p, 120 ℃ of column temperatures, detector and injector temperature are 150 ℃, sample size is 1mL, with peak area quantification, proofread and correct normalization method and calculate each component concentration of gas.Cyclical operation produces the color atlas of each composition measurement of biogas for the 4th time referring to Fig. 2 and 3.
Claims (7)
- One kind before the meal with the method for changing food waste coupling anaerobically fermenting co-producing hydrogen and methane, it is characterized in that, its operation steps is: at first utilize to produce system is discharged after methane phase natural pond liquid, as soak solution, rubbish is before the meal carried out to dipping pretreatment, changing food waste adopts damp and hot flash distillation pre-treatment simultaneously; Then pretreated rubbish before the meal and changing food waste are mixed, using and produce system is discharged after methane phase natural pond slag as inoculum, by anaerobic ferment process, prepare hydrogen and methane.
- 2. method according to claim 1, it is characterized in that, the concrete steps that system is discharged after methane phase natural pond liquid carries out dipping pretreatment as soak solution to rubbish are before the meal produced in described utilization: at first refuse breaking to particle diameter is 2-20mm before the meal, then rubbish mixes for (1:1)-(1:10) in mass ratio with soak solution before the meal, and the rubbish quality is in the butt quality before the meal; Pass into nitrogen 5-20min in the pre-treatment steeping tank, excluding air keeps anaerobic environment, and temperature remains on 30-40 ℃, and stir speed (S.S.) is 60-100r/min, per hour stirs 5-15min, and soak time is 1-5 days; Described soak solution is for producing system is discharged after methane phase natural pond liquid and through the screen filtration of aperture 1-10mm.
- 3. method according to claim 2, is characterized in that, in described screen filtration process, keeps anaerobism, maintains the anaerobion activity.
- 4. method according to claim 1, it is characterized in that, described changing food waste adopts the pretreated concrete steps of damp and hot flash distillation to be: by kitchen garbage breaking to particle diameter, be at first 2-40mm, adding the water rate is 50-100wt%, and control pressure is 2-4Pa, and stir speed (S.S.) is at 80-150r/min, temperature is to be cooled to room temperature after 90-150 ℃ of heating 30-60min, then centrifugal with 4000-8000r/min or use the pressure filter press filtration, but remove oil slick, standby.
- 5. method according to claim 4, is characterized in that, the high-temperature steam formed after described flash distillation reclaims heat by waste heat recovery unit, utilizes the heat reclaimed to be heated to anaerobic fermentation tank.
- 6. method according to claim 1, it is characterized in that, described by pretreated rubbish before the meal and changing food waste mixing, using and produce system is discharged after methane phase natural pond slag as inoculum, preparing hydrogen by anaerobic ferment process with the reaction conditions of methane is: the rubbish before the meal after dipping pretreatment with through damp and hot flash distillation pretreated changing food waste with VS than (1:1)-(1:5) mix, after vibration mixes by mixture and inoculum with VS than (1:1)-(1:4) mix, the initial organic load of Controlling System is at 1-4.5kgL -1d -1, guarantee that system C/N is at (10-15): in 1 scope, utilize centrifugal after the damp and hot flash distillation pre-treatment of changing food waste or water that be press-filtered out to regulate material water ratio to tinning after 90-95wt%;Produce hydroformylation stage: with 0.5-2mol/LHCl and 0.5-2mol/LNaOH, regulate the pH value to 4.5-6.5, pass into high pure nitrogen 2-15min with the 1-5mL/s flow, air in removal system, guarantee intrasystem anaerobic environment, control temperature range at 30-40 ℃, control stir speed (S.S.) in the 100-300r/min scope, the system operation entered the product methane phase after 2-7 days;Produce methane phase: adopt 0.5-2mol/LHCl and 0.5-2mol/LNaOH to regulate the pH value to 7-8, temperature is controlled at 30-40 ℃, and stir speed (S.S.) is controlled at 100-300r/min, keeps anaerobic condition, stops two days later anaerobically fermenting stopping aerogenesis.
- 7. method according to claim 1, it is characterized in that, the preparation of described soak solution and inoculum: by the butt quality, by (1:1)-(1:10) mixing anaerobic domestication 1-2 month in mass ratio of changing food waste and anaerobically digested sludge, until it not after aerogenesis, utilize the 1-10mm screen filtration to obtain anaerobic fermented liquid, as rubbish soak solution before the meal in the first batch, the rubbish soak solution is and produces the natural pond liquid that system is discharged after methane phase before the meal thereafter; Active sludge through taming is as first batch of inoculum, and inoculum is and produces the natural pond slag that system is discharged after methane phase thereafter.
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| CN106497983A (en) * | 2016-10-10 | 2017-03-15 | 清华大学 | A kind of product hydrogen sludge refolding method |
| CN112375676A (en) * | 2020-11-19 | 2021-02-19 | 哈尔滨工业大学 | Horizontal flow anaerobic digestion reaction device and method for treating high-solid-content kitchen garbage |
| CN113801898A (en) * | 2021-09-15 | 2021-12-17 | 上海交通大学 | Method for producing hydrogen and methane by adopting multi-component material mixing two-stage anaerobic fermentation |
| CN114378105A (en) * | 2022-01-19 | 2022-04-22 | 重庆大学 | Kitchen waste and cellulose biomass synergistic multi-stage treatment system and method |
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| CN114378105A (en) * | 2022-01-19 | 2022-04-22 | 重庆大学 | Kitchen waste and cellulose biomass synergistic multi-stage treatment system and method |
| CN114378105B (en) * | 2022-01-19 | 2024-04-12 | 重庆大学 | Multistage treatment system and method for kitchen waste and cellulosic biomass in cooperation |
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