CN108949835B - Method for improving high-solid anaerobic digestion methane production of straws - Google Patents
Method for improving high-solid anaerobic digestion methane production of straws Download PDFInfo
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Abstract
The invention provides a method for improving high-solid anaerobic digestion methane production of straws, which comprises the following steps: (1) soaking the ensiled straws in an inoculation liquid to pre-mix the ensiled straws; wherein, the solid content of the ensiled straws is 20 to 30 percent; (2) adding the mixture obtained in the step (1) into a garage type anaerobic reactor so as to enable the mixture to carry out anaerobic digestion to generate methane; (3) in the anaerobic digestion process, the biogas slurry flows back to the top of the garage-type anaerobic reactor and is sprayed into the reactor to realize mass transfer. The method provided by the invention optimizes a proper spraying mode for the reflux system of the high-solid anaerobic digestion system, can effectively improve the mass transfer efficiency, enhances the contact between the substrate and the microorganism, promotes the growth and enrichment of the microorganism in the anaerobic digestion system, and improves the efficiency of producing methane by anaerobic digestion. And the method saves energy consumption to a great extent, greatly reduces the water content in the biogas residue, and is convenient for subsequent composting and the like.
Description
Technical Field
The invention relates to a method for improving high-solid anaerobic digestion of straws to produce methane, and belongs to the technical field of solid waste treatment control and environment-friendly purification treatment.
Background
Anaerobic digestion refers to the stabilization of organic matter by the metabolic activity of microorganisms under anaerobic conditions, accompanied by methane and CO2The biochemical process that is generated. Byrant divides the process into a hydrolytic fermentation stage, an acidification stage and a methanogenesis stage. The hydrolysis fermentation stage mainly comprises hydrolysis zymocyte, and complex organic substances in the hydrolysis zymocyte and protein waterHydrolyzing and fermenting under the action of hydrolytic zymocyte such as zymocyte to convert into micromolecular organic matter; the acidification stage is to convert the intermediate products generated in the first stage except formic acid, acetic acid, methylamine and methanol, such as water-soluble small molecules of fatty acid (propionic acid, butyric acid) and alcohol (ethanol), into acetic acid and H under the action of hydrogen-producing acetogenic bacteria2And CO2(ii) a Methanogens in the methanogenic stage react formic acid, acetic acid, methylamine, methanol and (H)2+CO2) The substrates are converted to methane by different pathways, with the most predominant substrates being acetic acid and (H)2+CO2)。
The anaerobic digestion treatment technology of the garbage has high investment cost, but has high environmental benefit and can generate good economic benefit (the marsh gas can be used for generating electricity and supplying heat, and the marsh slag can be used for producing high-quality and sanitary fertilizers). At present, the anaerobic digestion technology is widely applied all over the world, more than eighty percent of civil natural gas in Germany comes from biogas generated by anaerobic digestion, and large-scale biogas engineering is available in Italy, Switzerland, Austria, England and other countries. The anaerobic digestion technology of China starts in 1973, goes through the unstable development stage of 10 years, the adjustment stage of 10 years and the stable development stage of 5 years, and starts to develop continuously and rapidly since the 21 st century. The anaerobic digestion technology in China is still in the initial stage and has great development potential.
The solid content of the general anaerobic digestion technology is required to be between 3 and 5 percent, and the fermentation mode is liquid, so the requirement on the volume of anaerobic digestion equipment is large, the manufacturing cost and the operating cost are high, and simultaneously, the biogas slurry in anaerobic digestion residues is more, and the subsequent treatment cost is high; in such anaerobic digestion systems the unit volume organic matter content is low, the reaction intensity is relatively small and the methane production is low.
The solid content of high-solid anaerobic digestion can reach 10-20%, the biogas slurry amount is small, the reactor volume is small, and the investment cost is low; the reaction system has high volume load and high microorganism concentration, and can effectively improve the reaction strength and the volume gas production rate; because the liquid phase content is less, the system is more stable, and the treatment effect is relatively better.
Chinese patent CN106434763A discloses a vertical continuous anaerobic dry fermentation method, which is to uniformly mix waste with high solid content and inoculum and then ferment the mixture in a fermentation tank to produce methane. And performing solid-liquid separation on the residues after fermentation in a spiral discharging device to obtain biogas slurry and biogas residues. Refluxing part of biogas slurry, and spraying into the fermentation tank at a spraying amount of 0.5L/kg material 6 times per day; part of the biogas residues are used as inoculum, and the solid content of the inoculum is required to be more than 35%. The fermentation period of the invention needs to be ensured to be more than 25 days, the fermentation time is long, and the backflow of the percolate causes the increase of the operation cost in the long-term fermentation process; solid-liquid separation equipment is required to be arranged by using the biogas residues as the inoculum, so that the cost is increased. Moreover, the gas production performance of the method is not described in the patent, and the method cannot be well applied to actual production.
Chinese patent CN102925494A discloses a method for producing biogas and organic fertilizer by using livestock and poultry waste and crop straws, which comprises the steps of enabling solid livestock and poultry manure with dry matter concentration of more than 15 percent and pretreated crop straws to enter an anaerobic dry fermentation device together with domesticated activated sludge according to a certain proportion, recycling a small amount of biogas slurry generated in the fermentation process as an inoculum again, and producing the organic fertilizer by fermenting residues through secondary composting. The method does not solve the problem of slow mass transfer rate of an anaerobic digestion system under high solid content rate, and can not effectively improve the efficiency of gas production by solid anaerobic digestion. Moreover, the patent only describes that the methane content of the produced gas is stabilized at 50-65%, and does not describe the gas production rate, delay time, fermentation period and the like, which are not beneficial to subsequent application.
Chinese patent CN107723332A provides a method for producing biogas by compressed straw anaerobic dry fermentation, which realizes the purpose of producing biogas by compressed straw anaerobic dry fermentation by selecting proper microbial inoculum, additive and process steps. Although the method has high gas production efficiency, the anaerobic digestion reaction period needs to reach 63 days, the time is too long, the spraying is started after the system biological community is stable after 28 days, the effect of well improving the contact between the biological phase and the substrate cannot be achieved, and the spraying efficiency is relatively low.
Therefore, providing a method capable of significantly improving the methane production through high-solid anaerobic digestion of straws has become an urgent technical problem to be solved in the field.
Disclosure of Invention
In order to solve the defects and shortcomings, the invention aims to provide a method for improving high-solid anaerobic digestion of straws to produce methane. The method comprises the steps of soaking and treating silage straws by using an inoculation liquid, putting the silage straws into a garage type anaerobic reactor for anaerobic digestion, keeping part of the inoculation liquid sprayed from the top of the reactor on materials after the inoculation liquid is in short contact with the materials, enabling part of the inoculation liquid to penetrate into leachate at the bottom, reflowing to the top under the action of a reflux pump, and spraying the leachate again into the reactor.
In order to achieve the above object, the present invention provides a method for improving methane production by high-solid anaerobic digestion of straws, wherein the method comprises:
(1) soaking the ensiled straws in an inoculation liquid to pre-mix the ensiled straws; wherein, the solid content of the ensiled straws is 20 to 30 percent;
(2) adding the mixture obtained in the step (1) into a garage type anaerobic reactor so as to enable the mixture to carry out anaerobic digestion to generate methane;
(3) in the anaerobic digestion process, the biogas slurry flows back to the top of the garage-type anaerobic reactor and is sprayed into the reactor to realize mass transfer.
According to the specific embodiment of the invention, in the method for improving high-solid anaerobic digestion methane production of straws, the garage type anaerobic reactor is conventional equipment used in the field and comprises a dry fermentation chamber, a percolate storage tank, a percolate circulating pump, a temperature detection device and the like, wherein percolate is sucked into the fermentation tank through the circulating pump to be sprayed and refluxed, and a timing system is adopted to receive liquid and spray.
According to the specific embodiment of the invention, in the method for improving the high-solid anaerobic digestion of straws to produce methane, the solid content of the ensiled straws is 30%.
According to the specific embodiment of the invention, in the method for improving high-solid anaerobic digestion methane production of straws, the grain size of the ensiled straws is 2-5 cm; preferably 2-3 cm.
According to the specific embodiment of the invention, in the method for improving the high-solid anaerobic digestion of straws to produce methane, the soaking time is 1-4 hours, and preferably 2 hours.
According to the specific embodiment of the invention, in the method for improving the high-solid anaerobic digestion methane production of the straws, the inoculation liquid is an inoculation liquid which is pre-domesticated under the constant temperature condition of 37 ℃;
preferably, the inoculation liquid comprises activated sludge of a refuse landfill or biogas slurry of an operating biogas plant.
The activated sludge of the refuse landfill or the biogas slurry of the running biogas plant are conventional substances in the field, and can be obtained conventionally by a person skilled in the art, for example, in the specific embodiment of the invention, the activated sludge of the refuse landfill can be activated sludge from an Ashbya refuse landfill in Beijing.
According to the specific embodiment of the invention, in the method for improving the high-solid anaerobic digestion methane production of the straws, the anaerobic digestion period is 28 days, the reaction temperature is 37 +/-1 ℃, and the pH is not adjusted.
According to a specific embodiment of the invention, in the method for improving the high-solid anaerobic digestion of straws to produce methane, the period of the anaerobic digestion is 14 days.
According to the specific embodiment of the invention, in the method for improving the high-solid anaerobic digestion methane production of the straws, the spraying time interval is 3-10 hours, and each spraying time is 1-30 minutes.
According to the specific embodiment of the invention, in the method for improving the high-solid anaerobic digestion methane production of the straws, the spraying time interval is 6-8 hours, and each spraying time is 2-6 minutes.
According to the specific embodiment of the invention, in the method for improving the high-solid anaerobic digestion methane production of the straws, the spraying mode adopts the following steps: the first two weeks are 4-6 minutes each time, the third week is 2-3 minutes each time, the fourth week is not sprayed, and the spraying time interval is 6-8 hours.
According to the specific embodiment of the invention, in the method for improving the high-solid anaerobic digestion methane production of the straws, the spraying mode adopts the following steps: every time for 4 minutes in the first two weeks, every time for 2 minutes in the third week, and no spraying in the fourth week, wherein the spraying time interval is 6 hours.
At present, the existing high-solid anaerobic digestion technology in the field still has a plurality of defects, and the reasons mainly include that the moisture content in the high-solid anaerobic digestion system is low, the mass transfer rate is influenced, the degradation of a substrate and the reaction are further influenced, the activity of anaerobic microorganisms in the system is influenced, and the gas production rate and the efficiency of the reaction system are finally influenced; meanwhile, substrates and microorganisms cannot be fully mixed, local organic load of a reaction system is too high, acidification is easy to occur, and absorption of methanogen cells to fatty acid is influenced; in addition, the acidification phenomenon causes the generation of a large amount of water-soluble organic acids and hydrogen sulfide, thereby inhibiting the growth of methanogens.
The method provided by the invention optimizes a proper spraying mode for the reflux system of the high-solid anaerobic digestion system, can effectively improve the mass transfer efficiency, enhances the contact between the substrate and the microorganism, promotes the growth and enrichment of the microorganism in the anaerobic digestion system, and improves the efficiency of producing methane by anaerobic digestion; when digestion enters a stable stage, namely after the enrichment of methanogens is improved to a certain stage, reflux is not recommended, because the continuous reflux energy consumption is higher, the methane yield is also limited, and in a mode of more spraying in the early stage (such as the first two weeks), less spraying in the middle stage (such as the third week) and no spraying in the later stage (such as the fourth week), 80% of the total gas yield is generated in 14 days, and the gas yield can reach 188mL/g (by CH)4VS meter), the energy consumption is saved to a great extent, and simultaneously, the water content in the biogas residues is greatly reduced, thereby facilitating the treatment of subsequent compost and the like.
According to the invention, the mass transfer process is improved by utilizing the spray-percolation cycle, the process parameters of the high-solid anaerobic digestion system are optimized, and the optimal solid content, spraying duration and spraying interval are selected, so that the straw is effectively treated, the harmlessness, reduction and recycling of solid wastes are realized, and the methane production efficiency of the high-solid anaerobic digestion of the straw is improved; meanwhile, the treatment cost is reduced to the maximum extent while the gas production efficiency is ensured. The anaerobic digestion system runs stably, the straw treatment effect is better, and the energy recovery rate is higher. The invention has good research and application prospect for the project of volume reduction of the high-solid anaerobic fermentation system.
Drawings
FIG. 1A is a graph of methane production over time at different solids loading in example 1 of the present invention: (a) cumulative yield of methane;
FIG. 1B is a graph of methane production over time at different solids loading in example 1 of the present invention: (b) the weekly methane yield;
FIG. 2A is a graph of methane production over time for different spray durations in accordance with example 2 of the present invention: (a) cumulative yield of methane;
FIG. 2B is a graph of the variation of methane production over time for different spray durations in example 2 of the present invention: (b) the weekly methane yield;
FIG. 3A is a graph of methane production over time for different spray intervals in example 3 of the present invention: (a) cumulative yield of methane;
FIG. 3B is a graph of methane production over time for different spray intervals in example 3 of the present invention: (b) the weekly methane yield;
FIG. 4A is a graph showing the variation of methane production with time at a spray interval of 6 hours in example 3 of the present invention: (a) cumulative yield of methane;
FIG. 4B is a graph showing the relationship between the methane production and the time when the spraying interval is 6 hours in example 3 of the present invention: (b) the weekly methane yield;
FIG. 5 is a graph showing the relationship between the Volatile Fatty Acid (VFA) of the system and time during fermentation at a spraying interval of 6 hours in example 3 of the present invention;
FIG. 6 is a graph showing the relationship between the pH value of the system and the ammonia nitrogen concentration with time during the fermentation process when the spraying interval is 6 hours in example 3 of the present invention.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description of the technical solutions of the present invention will be made with reference to the following specific examples, which should not be construed as limiting the implementable scope of the present invention.
Example 1
The embodiment provides a method for improving methane production through high-solid anaerobic digestion of straws, wherein the method comprises the following steps:
raw materials: corn stalks;
the production steps are as follows:
(1) the method comprises the steps of adjusting the solid content of silage corn straws with the particle size of 2-3cm to be 15%, 20% and 30% respectively by using mixed distilled water, taking out acclimatization biogas slurry in a constant-temperature incubator at 37 ℃ in advance as inoculation liquid, and soaking raw materials for 2 hours by using the inoculation liquid respectively before the experiment begins.
(2) And (2) adding the mixture obtained in the step (1) into a dry fermentation chamber of a garage type anaerobic reactor, and spraying back from the top, wherein the spraying mode adopts 6 minutes for each time in the first two weeks, 3 minutes for each time in the third week and no spraying in the fourth week, and the spraying time interval is 3 hours. The reaction time for anaerobic digestion of the mixed feed in the reactor to produce methane was 28 days. The reaction temperature is 37 +/-1 ℃, and the pH is not adjusted.
The gas production volume was measured at regular intervals during 28 days of the reaction and plotted as a function of time for methane production at different solid contents, wherein the cumulative methane production is shown in FIG. 1A, and the cumulative methane production is shown in FIG. 1B, and it can be seen from FIGS. 1A and 1B that the cumulative methane production is highest at 30% solid content and reaches 79.66L (193.6mL/g (in terms of CH/g)4a/VS meter)); while the cumulative yield of methane was 61.25L (148.9mL/g (in terms of CH) at 15% and 20% solids respectively4VS) and 54.81L (133.2mL/g (in CH))4VS meter)). The methane production of all three groups rapidly increased around day 7, and the total methane production was substantially stabilized around day 20.
Example 2
The embodiment provides a method for improving methane production through high-solid anaerobic digestion of straws, wherein the method comprises the following steps:
raw materials: corn stalks;
the production steps are as follows:
(1) the solid content of the silage corn stalks with the grain diameter of 2-3cm is adjusted to 30% by using mixed distilled water, the inoculation liquid is domesticated biogas liquid taken out from a constant-temperature incubator at 37 ℃, and the raw materials are respectively soaked in the inoculation liquid for 2 hours before the experiment begins.
(2) And (2) adding the mixture obtained in the step (1) into a dry fermentation chamber of a garage type anaerobic reactor, and spraying from the top, wherein the spraying modes respectively adopt a first mode: 6 minutes each for the first two weeks, 3 minutes each for the third week, no spray for the fourth week (denoted (6,3, 0));
the second method comprises the following steps: 4 minutes each for the first two weeks, 2 minutes each for the third week, no spray for the fourth week (denoted (4,2, 0));
the third method comprises the following steps: 2 minutes for the first two weeks, 1 minute for the third week, and no spray (indicated as (2,1, 0)) for the fourth week. The spraying time intervals were all 3 hours. The reaction time for anaerobic digestion of the mixed feed in the reactor to produce methane was 28 days. The reaction temperature is 37 +/-1 ℃, and the pH is not adjusted.
The gas production volume was measured at regular intervals during 28 days of the reaction and a graph of the methane production over time was plotted for different spray periods, wherein the cumulative methane production is shown in FIG. 2A, the weekly methane production is shown in FIG. 2B, and it can be seen from FIGS. 2A and 2B that the methane production of a group of (6,3,0) spray periods reached 80.85L (196.5mL/g (in terms of CH)4VS gauge)), slightly improved compared to the results of example 1 under the same experimental conditions, partly due to the improved properties of the percolate; while the methane yields of the two groups with spraying time lengths of (4,2,0) and (2,1,0) were respectively 76.42L (186.5mL/g (in terms of CH)4VS) and 53.04L (128.9mL/g (in CH)4VS meter)). It can be seen that the methane production performance of the (4,2,0) group is comparable to that of (6,3,0), and that the methane production in mode two is only 5.1% less than that in equation one, while the longer the spraying time, the greater the energy consumption, specifically the lower the energy consumption of (4,2,0) by 1/3 compared to (6,3, 0).
Example 3
The embodiment provides a method for improving methane production through high-solid anaerobic digestion of straws, wherein the method comprises the following steps:
raw materials: corn stalks;
the production steps are as follows:
(1) the solid content of the silage corn stalks with the grain diameter of 2-3cm is adjusted to 30% by using mixed distilled water, the inoculation liquid is domesticated biogas liquid taken out from a constant-temperature incubator at 37 ℃, and the raw materials are respectively soaked in the inoculation liquid for 2 hours before the experiment begins.
(2) And (2) adding the mixture obtained in the step (1) into a dry fermentation chamber of a garage type anaerobic reactor, and spraying from the top, wherein the spraying mode adopts the way that the mixture is sprayed for 4 minutes every time in the first two weeks, is sprayed for 2 minutes every time in the third week and is not sprayed all around. The spraying time intervals are 3 hours, 6 hours and 8 hours respectively. The reaction time for anaerobic digestion of the mixed feed in the reactor to produce methane was 28 days. The reaction temperature is 37 +/-1 ℃, and the pH is not adjusted.
The gas production volume was measured at regular intervals during 28 days of the reaction and a graph of the methane production at different spraying intervals as a function of time was plotted, wherein the cumulative methane production is shown in FIG. 3A, the weekly methane production is shown in FIG. 3B, and it can be seen from FIGS. 3A and 3B that the methane production reached 78.23L (190.1mL/g (in terms of CH/g) when the spraying interval was 3 hours4VS) spray interval of 6h (methane cumulative and weekly methane production are also shown in fig. 4A and 4B), and a comparable methane production of 77.43L (188.2mL/g (in terms of CH)) was obtained4VS) and when the spray interval is 8h, the methanogenic performance is very different and the methane yield is only 53.56L (130.2mL/g (in CH)4a/VS meter));
in addition, in this example, when the spraying interval is 6 hours, the graph of the time-dependent change of the Volatile Fatty Acid (VFA) of the system during the fermentation process is shown in fig. 5; the graph of the relationship between the pH value of the system and the ammonia nitrogen concentration along with time in the fermentation process is shown in FIG. 6;
according to the embodiment, the mixed liquor with the solid content of 30% is selected as the fermentation substrate, and the fermentation result is better when the fermentation is carried out in a spraying mode that the mixed liquor is 4 minutes every two weeks, 2 minutes every three weeks, no spraying is carried out on the periphery, and the spraying time interval is 6 hours; the fermentation under the process parameters can not only ensure that the high-solid anaerobic digestion system can efficiently produce gas in a short time, but also reduce the energy consumption brought by spraying to the maximum extent and reduce the process cost.
Claims (2)
1. A method for improving methane production through high-solid anaerobic digestion of straws, which is characterized by comprising the following steps:
(1) soaking the ensiled straws in an inoculation liquid to pre-mix the ensiled straws; wherein the solid content of the ensiled straws is 30 percent; the grain size of the ensiled straws is 2-3 cm; the soaking time is 2 hours; the inoculation liquid is an inoculation liquid which is pre-domesticated under the constant temperature condition of 37 ℃;
(2) adding the mixture obtained in the step (1) into a garage type anaerobic reactor so as to enable the mixture to carry out anaerobic digestion to generate methane; the anaerobic digestion cycle is 28 days, the reaction temperature is 37 +/-1 ℃, and the pH is not adjusted;
(3) in the anaerobic digestion process, the biogas slurry flows back to the top of the garage type anaerobic reactor and is sprayed into the reactor to realize mass transfer;
the spraying mode adopts: every time for 4 minutes in the first two weeks, every time for 2 minutes in the third week, and no spraying in the fourth week, wherein the spraying time interval is 6 hours.
2. The method of claim 1, wherein the inoculation liquid comprises landfill activated sludge or operating biogas plant biogas slurry.
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