CN101250554B - Method for improving hydrogen gas yield of kitchen waste anaerobic digestion - Google Patents
Method for improving hydrogen gas yield of kitchen waste anaerobic digestion Download PDFInfo
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- CN101250554B CN101250554B CN2008100354458A CN200810035445A CN101250554B CN 101250554 B CN101250554 B CN 101250554B CN 2008100354458 A CN2008100354458 A CN 2008100354458A CN 200810035445 A CN200810035445 A CN 200810035445A CN 101250554 B CN101250554 B CN 101250554B
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Abstract
The invention relates to a method for increasing the hydrogen output through anaerobically digesting restaurant garbage and relates to a method for producing the hydrogen output through anaerobically digesting the restaurant garbage, which comprises following steps: firstly, weighing according to granular sludge: the restaurant garbage=1:0.2-0.4 part dry weight, adding the granular sludge and therestaurant garbage into a bottle, filling nitrogen or argon, sealing, statically culturing under the temperature of 4-20DEG C, finishing domestication when the pH value is lowered to 4.5-5.5, preserving, then, weighing according to the restaurant garbage: the granular sludge which is domesticated well=1 part dry weight:0.59-0.294part dry weight, then, arranging the restaurant garbage and the granular sludge into a container, evenly mixing, filling the nitrogen or the argon, then, sealing, concussing and stirring under the temperature of 40-50DEG C and the speed of 100-130r/min, starting anaerobic digestion, wherein the hydrogen yield is 65.63mL/g VS-94.04mL/g VS, fermenting firedamp with residual material after the hydrogen stops producing, and transforming the residual material into the firedamp. The method of the invention has the characteristics of low energy consumption, low cost and high heat value net output rate, and the hydrogen yield can reach 93mL/g restaurant garbage (dry weight) through using the method of the invention, which is increased by 20-30% compared with existing hydrogen yield.
Description
Technical field
The present invention relates to a kind of method that can improve hydrogen gas yield of kitchen waste anaerobic digestion, specifically be to utilize the granule sludge of domestication to be inoculum, changing food waste is a fermentation substrate, do not need granule sludge is heat-treated the hydrogen yield that (90～100 ℃, 20～30 minutes) just can improve changing food waste.Belong to the reclamation of solid wastes field.
Background technology
Changing food waste is the main source of organic phase in the domestic waste, generally results from enterprises and institutions, school, the market of farm produce, supermarket and food service industry.With big cities such as Beijing, Shanghai, Guangzhou is example, and its changing food waste day output has all surpassed 1000 tons.Changing food waste is a main component with organic substances such as starch based, foodstuff fibre class, animal tallow classes, has characteristics such as high-moisture, high grease, high salinity and perishable smelly, readily biodegradable.The changing food waste of China is raised the live pig except being used as, and the overwhelming majority all is to handle with the form of landfill, has not only taken the land resources of a large amount of preciousnesses, and pollutes surrounding enviroment.At present, changing food waste be treated to anaerobic ferment process, this technology comes from the anaerobic treatment of industrial sewage, mud, is a kind of more sophisticated utilisation technology, also appears in the newspapers repeatly about the anaerobic treatment of changing food waste both at home and abroad and leads.The advantage of changing food waste anaerobic biological treatment is the high organic loading ability to bear of anaerobion, totally enclosed bio-reactor has reduced treating processes to second environmental pollution, and what is more important reclaims biomass energy (hydrogen, methane) when handling waste.This society now for energy growing tension has even more important realistic meaning.In addition, along with the increase of society to this clean energy demand of hydrogen, and Hydrogen Energy utilizes the exploitation of technology, utilizes changing food waste to obtain increasing concern for the bio-hydrogen production technology of raw material.The biological hydrogen production of changing food waste is based on carbohydrate and follows hydrogen to produce that this principle carries out in the acidication process.Owing to be rich in carbohydrate in the changing food waste, therefore say changing food waste anaerobic digestion hydrogen manufacturing feasibility height technically.But the hydrogen that carbohydrate produces in the acidication process is very easily utilized by methanogen and other consumption hydrogen microorganisms, and then be converted into methane gas or other materials with Greenhouse effect, therefore, hydrogen net yield for the acidication process that improves changing food waste, often the biological hydrogen process of producing of changing food waste is carried out certain pre-treatment measure, its purpose is to go out to remove and consumes the hydrogen microorganism.
Pre-treatment measure commonly used mainly is thermal treatment, the interpolation chemical agent of inoculum.The heat treatment operation method of inoculum is generally inoculum was heated 20～60 minutes under 90～100 ℃ of conditions, removes consumption hydrogen microorganism to go out, obtaining can spore-bearing shaft-like hydrogenogens.Consumption hydrogen microorganism can be comparatively effectively removed in thermal treatment, improve the productive rate of hydrogen to a certain extent, but aforesaid operations is comparatively complicated, need increase specific equipment when especially under fairly large, moving, and the energy consumption height of himself, thereby caused the increase (interpolation can suppress the active specific chemical agent of part hydrogen-consuming bacteria, and these chemical agents comprise metronidazole class microbiotic, tensio-active agent or the like) of processing cost.In addition, the use of chemical agent can be to a certain degree the productive rate of raising hydrogen the time, their degradation efficiency is low, often residual a large amount of undegradable chemical additives in the fermentation materials, influenced the subsequent disposal effect of fermentation materials, for example follow-up methane fermentation process usually is subjected to bigger influence because of the existence of tensio-active agent, metronidazole.Do not adopting the mud heat treating method and do not adopting the changing food waste of any additives to produce in the hydrogen report, the productive rate of hydrogen is generally 60～70mL H
2/ g changing food waste (dry weight).
In the at present domestic scientific and technical literature report, the mud that the changing food waste biological hydrogen production is adopted not is to be anaerobic grain sludge, and what the overwhelming majority all adopted is the waste sludge of municipal sewage plant.Chinese invention patent application " collaborative hogwash refuse of a kind of mineralized waste and mud are united the method for producing hydrogen ", application number is 200610027750.3 to be exactly to adopt Sewage Plant concentration basin mud, and mineralized waste, the hogwash refuse is broken to be mixed, and take (100 ℃～200 ℃ of dry sterilization or moist heat sterilizations, 0.5～2h) method is carried out pre-treatment, ferments under 25 ℃～55 ℃ constant temperatures, produces hydrogen.The problem that this method exists is that cost is higher.
Summary of the invention
The objective of the invention is to disclose the method for the changing food waste anaerobic digestion production hydrogen that a kind of technology is simple, with low cost, factor of created gase is high.Characteristics are to utilize anaerobic grain sludge to be inoculum, need not the method that mud is heated, need not to add any chemical agent.
In order to achieve the above object, the present invention discovers anaerobic grain sludge, contains a large amount of hydrolysis, acidifying bacterium, methanogen in this granule sludge, and the coexistence of these microorganisms has formed the complicated ecosystem.Changing food waste is under the effect of anaerobic grain sludge, its anaerobic degradation process can be divided into four-stage: hydrolysis stage, souring stage, product acetate stage and product methane phase, the task in each stage is all finished by specific microorganism species (hydrolysed ferment bacterium, hydrogen-producing acetogenic bacteria, homoacetogenic bacteria and methanogen floras).Therefore, the present invention adopts anaerobic grain sludge to produce the inoculum of hydrogen for the changing food waste anaerobic digestion, crossing the Cheng Qian at product hydrogen need not heat-treat anaerobic grain sludge, need in anaerobic digestion process, not add any additive yet, amount ratio by control changing food waste and granule sludge, and the time of control anaerobic digestion process, make the methanobacteria in the fermenting process generation organic acid inhibition granule sludge, anaerobic digestion process is ended at produce before the methane phase, thereby improved the net yield of by product hydrogen in the anaerobic digestion process, made and adopt the inventive method hydrogen yield can reach 93mL H
2/ g changing food waste (dry weight).
The present invention realizes by following steps:
The first step is tamed granule sludge
Earlier according to granule sludge: changing food waste=1 part dry weight: 0.2～0.4 part of dry weight is measured, and granule sludge is placed in the vial, adds changing food waste and charge into nitrogen or argon gas in bottle, the sealing bottleneck leaves standstill cultivation, when pH reduces to 4.5～5.5 under 4～20 ℃, finish domestication, stand-by;
In second step, hydrogen is produced in the changing food waste anaerobic digestion
Earlier according to changing food waste: the granule sludge that the first step is tamed=1 part dry weight: 0.059～0.294 part of dry weight is measured, then they are placed in the container, mix, seal after charging into nitrogen or argon gas, under 40～50 ℃, adopting speed is that concussion or alr mode begin anaerobic digestion under 100～130 rev/mins of conditions, and hydrogen yield is 65.63mL H
2/ g VS～94.04mL H
2/ g VS; After hydrogen stopped to produce, remaining tailing carried out follow-up methane fermentation, changes it into methane.
The present invention has following advantage:
1. because the present invention has carried out of short duration domestication to anaerobic grain sludge, the activity that suppresses most methanobacterias, and by changing changing food waste in the usage ratio of granule sludge, the further more efficiently inhibition methanobacteria activity of the organic acid that utilizes changing food waste in the acidication process, to produce, thereby improved the hydrogen yield in the changing food waste anaerobic digestion process, reached 94.04mL H
2/ g VS.
2. the present invention is by 4～20 ℃ of normal temperature short period of time domestications, just can make changing food waste under the effect of acidication bacterium, be converted into organic acid and be attended by a large amount of hydrogen and produce, make methanobacteria be subjected to remarkable inhibition because a large amount of organic acid exists this moment, no methane produces in the system, adopt the conventional thermal treatment of the mud that carries out 20～30 minutes under 90～100 ℃ of conditions relatively with prior art, the present invention has significantly reduced production cost.
3. for the technology that adopts tensio-active agent, Antibiotic Additive promotion product hydrogen, the present invention does not add any chemical substance, therefore after hydrogen in the anaerobic digestion system stopped to produce, remaining tailing can carry out follow-up methane fermentation, changes it into methane.
4. do not adopting the mud heat treating method and do not adopting the changing food waste of any additives to produce in the hydrogen report, the productive rate of hydrogen is generally 60～70mL H
2/ g changing food waste (dry weight), and adopt present method hydrogen yield can reach 93mL H
2/ g changing food waste (dry weight), gas production rate significantly rises.
5. technology of the present invention is simple, when the changing food waste solid content is non-constant value, only need adjusts granule sludge concentration and can guarantee to reach best hydrogen output, therefore for the biological hydrogen that produces of the mass-producing of changing food waste tangible convenient part is arranged.
6. the present invention is simple to operate, and the technology cost is obviously low, is convenient to use in the changing food waste biological hydrogen production engineering of industrially scalable.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Fig. 2 is the productive rate figure of hydrogen in five kinds of reaction systems of A1-E1 of the present invention
Fig. 3 is the productive rate figure of hydrogen in five kinds of reaction systems of A2-E2 of the present invention
Embodiment
Embodiment 1.
See also accompanying drawing 1.
Earlier granule sludge is tamed before the experiment beginning.The domestication step is according to granule sludge: changing food waste=1 part dry weight: 0.2～0.4 part of dry weight is measured, granule sludge is placed in the vial, add changing food waste and in bottle, charge into nitrogen or argon gas, the sealing bottleneck, under 4～20 ℃, leave standstill cultivation, when pH reduces to 4.5～5.5, finish domestication, stand-by.In order better to understand under these processing condition thermal treatment and non-heat treating method to producing the influence of hydrogen, this experiment is provided with control group and experimental group.
Experimental group is got 5 300ml serum bottles, take by weighing changing food waste 7.8 g (dry weight) after the fragmentation in each bottle, in each bottle, pack into respectively then and tame 0.46,0.92,1.38,1.84,2.30 good g mud (dry weight), in each bottle, add distilled water then 5 serum bottle endoparticle sludge concentrations are adjusted to 4.6 respectively; 9.2; 13.8; 18.4; 23g (dry weight)/L.Charge into rare gas element, envelope bottle subsequently.Place in 40～50 ℃ of constant temperature vibration casees 100～130 rev/mins of oscillation rate.
An ad hoc control group, control group have adopted the conventional heat treating method of the mud that carries out 20～30 minutes under 90～100 ℃ of conditions that granule sludge is carried out pre-treatment, but all the other experiment conditions are all identical with experimental group.
Experiment is regularly gathered gas with sampling needle in bottle, use each component and content thereof in the gas Chromatographic Determination gas simultaneously.Concrete experimental result is shown in Table 1.
Table 1 changing food waste and granule sludge amount ratio produce the influence of hydrogen rate to the biological hydrogen production process
By above-mentioned chart as can be known, (dry weight when the changing food waste constant concentration is at 77.85g/L in the reaction system, in the contained solid substance VS of changing food waste, g/L, hereinafter all represent dry weight), along with granule sludge concentration rises to 23g/L (dry weight in the contained solid substance VS of mud, g/L, is hereinafter all represented dry weight) from 4.6, obvious increase has appearred in final hydrogen output, hydrogen yield increases significantly, and the product hydrogen of anaerobic digestion process also shortens retardation time greatly.Compare with having carried out the heat treated control experiment group of granule sludge, the control experiment group with anaerobic grain sludge under 90 ℃ of conditions, heat 30 minutes with results can spore-bearing shaft-like hydrogen-producing bacteria.Under identical test conditions, control experiment group hydrogen yield is only at 5-10mL H
2/ g VS.The reason that the control experiment group is produced the hydrogen weak effect is that the microorganism species in the granule sludge is single relatively, and a large amount of microorganisms that comprise hydrogenogens have been killed in thermal treatment, so caused the failure of producing hydrogen.Proved also simultaneously that the mud heat treating method that usually adopts is not only applicable to municipal wastewater treatment plant excess sludge (non-particulate mud) in anaerobe hydrogen manufacturing, and be not suitable for the granule sludge that Sewage Plant anaerobic treatment facility is produced.In embodiment 1, it is 94.04 mL/g VS that the best of experimental group is produced the hydrogen rate, corresponding changing food waste concentration, granule sludge concentration and amount ratio be respectively 77.85g/L, 18.4g/L, 4.23: 1.
Earlier granule sludge is tamed before the experiment beginning.The domestication step is according to granule sludge: changing food waste=1 part dry weight: 0.2～0.4 part of dry weight is measured, granule sludge is placed in the vial, add changing food waste and in bottle, charge into nitrogen or argon gas, the sealing bottleneck, under 4～20 ℃, leave standstill cultivation, when pH reduces to 4.5～5.5, finish domestication, stand-by.In order better to understand under these processing condition thermal treatment and non-heat treating method to producing the influence of hydrogen, this experiment also is provided with control group and experimental group.
Experimental group is got 5 300ml serum bottles, take by weighing the changing food waste 7.8g (dry weight) after the fragmentation in each bottle, the domestication of in each bottle, packing into respectively then good 0.46,0.92,1.38,1.84,2.30g granule sludge (dry weight), charge into rare gas element, envelope bottle subsequently.Place in 40～50 ℃ of constant temperature vibration casees 100～130 rev/mins of oscillation rate.Different with experimental group is, control group has adopted heat treating method that granule sludge is carried out pre-treatment, but all the other experiment conditions are all identical with experimental group.Experiment is regularly gathered gas with sampling needle in bottle, use each component and content thereof in the gas Chromatographic Determination gas simultaneously.Concrete experimental result is shown in Table 2.
Table 2 changing food waste and mud amount ratio produce the influence of hydrogen rate to the biological hydrogen production process
5 interior changing food waste concentration of reaction system among changing food waste concentration in 5 reaction systems among the embodiment 2, granule sludge concentration and the embodiment 1, granule sludge concentration are all different, but among the embodiment 1 usage ratio of the changing food waste consumption of A1, B1, C1, D1, these 5 reaction systems of E1 and granule sludge respectively with embodiment 2 in A2, B2, C2, D2, the E2 reaction system usage ratio of changing food waste consumption and mud identical.In embodiment 2, changing food waste concentration is 129.75g/L in reaction system A2, and changing food waste and granule sludge amount ratio are 16.9: 1 o'clock, and hydrogen yield only is 1.16mL H
2/ g VS.And the hydrogen yield of reaction system B2, C2, D2, E2 is respectively 70.71,68.02,79.55,67.71 mL H
2/ g VS.The product hydrogen rate of reaction system A2 is starkly lower than other reaction systems among the embodiment 2 among the embodiment 2 as can be seen, and its reason mainly is that acidization is aggravated because the usage ratio of changing food waste consumption and granule sludge is too high, thereby causes the decline that has of hydrogen yield.In order better to understand under these processing condition thermal treatment and non-heat treating method to producing the influence of hydrogen, also be provided with among the embodiment 2 and adopt the heat treated control group of mud, under identical test conditions, control experiment group hydrogen yield is at 0.3-2.4mL H
2/ g VS.This result proves that once more the method that mud thermal treatment promotes hydrogen to produce is not suitable for granule sludge.
We find that the hydrogen output of anaerobic digestion process is significantly improved along with the decline of changing food waste concentration and the rising of changing food waste and granule sludge amount ratio in the experimental group in embodiment 2.Changing food waste concentration is 86.50g/L in reaction system, when granule sludge concentration is 20.44g/L, produces the hydrogen rate and reaches maximum 79.55mL H
2/ g VS, and this moment changing food waste and granule sludge amount ratio for being 4.23: 1 equally, the amount ratio of changing food waste and mud was identical when product hydrogen rate reached maximum among this value and the embodiment 1.Can find that by embodiment 1,2 even fluctuation appears in changing food waste concentration, granule sludge concentration, as long as changing food waste and granule sludge amount ratio be at 4.23: 1 o'clock, the hydrogen generation efficiency of anaerobic digester system is the highest.
In sum, use anaerobic grain sludge to be inoculum, can when not adopting granule sludge heat treatment, make the anaerobic digestion of kitchen wastes biological hydrogen production become possibility. And conventional changing food waste bio-hydrogen production method often to adopt municipal sewage sludge be inoculum, and must heat-treat mud. That this method is compared with conventional method is simple to operate, energy consumption is low, effective.
Claims (1)
1. method that improves hydrogen gas yield of kitchen waste anaerobic digestion is characterized in that:
The first step is tamed granule sludge
Earlier according to granule sludge: changing food waste=1 part dry weight: 0.2-0.4 part dry weight is measured, and granule sludge is placed in the vial, adds changing food waste and charge into nitrogen or argon gas in bottle, the sealing bottleneck leaves standstill cultivation, when pH reduces to 4.5～5.5 under 4～20 ℃, finish domestication, stand-by;
In second step, hydrogen is produced in the changing food waste anaerobic digestion
Earlier according to changing food waste: the granule sludge that the first step is tamed=4.23 part dry weight: 1 part of dry weight is measured, then they are placed in the container, add distilled water the granule sludge concentration adjustment is arrived 18.4g/L, mix, seal after charging into nitrogen or argon gas, under 40～50 ℃, adopting speed is that 100～130 rev/mins of concussions or alr mode begin anaerobic digestion, and hydrogen yield is 94.04mL H
2/ g VS; After hydrogen stopped to produce, remaining tailing carried out follow-up methane fermentation, changes it into methane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102284465B (en) * | 2011-04-25 | 2013-02-13 | 华南师范大学 | Biological treatment method for efficiently degrading kitchen garbage grease |
| CN102363794B (en) * | 2011-10-28 | 2013-06-26 | 山东轻工业学院 | Method for producing hydrogen through kitchen waste enzymolysis and reinforced dark fermentation |
| CN102382858B (en) * | 2011-10-28 | 2013-06-05 | 山东轻工业学院 | Application of papermaking white clay in biological fermentative hydrogen production |
| CN103172243A (en) * | 2013-03-14 | 2013-06-26 | 杨顺生 | Method for realizing zero discharge of anaerobic sludge digestion wastewater |
| CN103451236B (en) * | 2013-09-04 | 2015-07-22 | 中国环境科学研究院 | Method for jointly producing hydrogen and methane by carrying out coupling anaerobic fermentation on preprandial garbage and kitchen garbage |
| CN106734053A (en) * | 2016-11-18 | 2017-05-31 | 浙江工商大学 | A kind of method for accelerating anaerobic fermentation of kitchen waste aerogenesis |
| CN107227318A (en) * | 2017-07-27 | 2017-10-03 | 江南大学 | It is a kind of to strengthen the method that kitchen garbage anaerobic dry fermentation produces hydrogen |
| CN108689564A (en) * | 2018-06-25 | 2018-10-23 | 同济大学 | A method of anaerobic sludge digestion methane phase gas is promoted using graphene |
| CN111424056B (en) * | 2020-02-28 | 2022-03-08 | 长沙工研院环保有限公司 | Method for improving efficiency of anaerobic digestion biogas production of kitchen waste |
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