NL2026413A - Method for anaerobic digestion of organic wastes - Google Patents
Method for anaerobic digestion of organic wastes Download PDFInfo
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- NL2026413A NL2026413A NL2026413A NL2026413A NL2026413A NL 2026413 A NL2026413 A NL 2026413A NL 2026413 A NL2026413 A NL 2026413A NL 2026413 A NL2026413 A NL 2026413A NL 2026413 A NL2026413 A NL 2026413A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such processes
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/15—Treatment of sludge; Devices therefor by de-watering, drying or thickening by treatment with electric, magnetic or electromagnetic fields; by treatment with ultrasonic waves
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/341—Consortia of bacteria
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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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Abstract
The present invention relates to a method for anaerobic digestion of organic wastes. The method includes: adding organic wastes, inoculum, and a catalyst enriched with highly-effective functional microorganisms to a reactor; and conducting stirring and reaction to produce methane. The catalyst, which adopts a magnet as a matrix and ferroferric oxide as a surface adsorbate, is used to enrich electrochemically active microorganisms that can efficiently achieve the anaerobic conversion of organic wastes. Microorganisms are rapidly combined with ferroferric oxide to form a biofilm on the surface of the magnet, which can accelerate the methane production by anaerobic digestion, increase the organic loading rate and methane yield of an anaerobic digestion system, and reduce the reaction period. Compared with the prior art, the catalyst of the present invention is used to enrich electrochemically active microorganisms that can efficiently achieve the anaerobic conversion of organic wastes. Microorganisms are rapidly combined with ferroferric oxide to form a biofilm on the surface of the magnet, which can accelerate the methane production by anaerobic digestion, increase the organic loading rate and methane yield of an anaerobic digestion system, and reduce the reaction period.
Description
TECHNICAL FIELD The present invention relates to the field of treatment and utilization of organic wastes, and in particular to a method for anaerobic digestion of organic wastes.
BACKGROUND As resources are consumed at an increasingly rate, there are also much more environmental problems. The organic waste has an organic carbon content equivalent to 1 billion tons of standard coal. Anaerobic digestion technology realizes the resource recovery while promoting the reduction, stabilization, and harmlessness of organic solid wastes, which is an important technical guarantee for improving the resource utilization and supporting the construction of ecological civilization. During the process of anaerobic digestion of organic wastes, complex organic matters need to be decomposed into small-molecule organic matters such as acetic acid by a series of biochemical steps, such as hydrolysis, acidification and acetification, which will then be used for methane production. During the traditional process of anaerobic digestion of organic wastes, such as municipal sludge, food or kitchen wastes, and crop straws, there are a series of problems, such as poor mass transfer performance, low methane-production efficiency, and long reaction period, which limit the application of anaerobic digestion technology in the field of organic wastes. It is a major concern for researchers to strengthen the anaerobic digestion of organic wastes and improve the methane-production efficiency by anaerobic digestion.
SUMMARY The present invention is intended to overcome the above defects in the prior art, and to provide a method for anaerobic digestion of organic wastes, which can increase the species abundance of highly-effective functional microorganisms, strengthen the anaerobic digestion of organic wastes, and promote the production of methane.
The objective of the present invention can be achieved by the following technical solutions. The process of syntrophic methane production involves the mass transfer and the interspecific electron transfer between acid-producing microorganisms and methane-producing
-2- microorganisms. The indirect interspecific electron transfer process, with hydrogen or formate as an electron carrier, is influenced by the concentration gradient and mass transfer rate of the electron carrier, so the process of syntrophic methane production cannot be carried out efficiently, and once the acid production increases in the system, it is easy to cause the case where the accumulation of hydrogen prevents the hydrogen-producing acetogenesis process from proceeding spontaneously, and thus the anaerobic digestion efficiency suffers a serious deterioration. Studies have shown that microorganisms such as Geobacter have the ability to carry out direct interspecific electron transfer via conductive pili or cytochrome ¢, and this phenomenon has also been observed in the methanogenic process by anaerobic digestion. Through the cultivation of microorganisms or the addition of exogenous substances, "channels" for electron transfer can be formed between some acid-producing microorganisms and methane-producing microorganisms, to increase the rate of interspecific electron transfer, thereby accelerating the methane production. Ferroferric oxide, which is a magnetic material with stable crystal structure, excellent electrical conductivity, and biocompatibility, can be added to the anaerobic digestion system to help establish and strengthen the direct interspecific electron transfer among syntrophic methaogenic microorganisms.
Moreover, the ferroferric oxide can also be added to help enrich the dissimilatory iron reducing bacteria (DIRB}, promote the hydrolysis and acidification of organic matters, and improve the efficiency of anaerobic digestion. However, organic wastes such as municipal sludge have a complex composition, the highly-effective syntrophic microorganisms that can achieve anaerobic conversion and direct interspecific electron transfer have low abundance in the system, and the system has poor flow and mass transfer effects. Therefore, simply adding ferroferric oxide is difficult to enrich highly-effective functional microorganisms in a complex organic waste system, the added ferroferric oxide is difficult to tightly combine highly-effective functional microorganisms to exert a stable effect, and a large amount of loss will occur.
Through improvement on the above theoretical basis, the present invention provides an economical and feasible method that can enrich and combine highly-effective functional microorganisms, and stably improve the methanogenic efficiency by anaerobic digestion of organic wastes. The specific solution is as follows:
-3- A method for anaerobic digestion of organic wastes is provided, including: adding organic wastes, inoculum, and a catalyst enriched with highly-effective functional microorganisms to a reactor; and conducting stirring and reaction to produce methane. Compared with the traditional anaerobic digestion of organic solid wastes, under the same organic loading rate, the method has higher degradation rate of organic matters, methane-producing rate, methane proportion in biogas, and methane yield.
Further, the catalyst adopts a magnet as a matrix and ferroferric oxide as a surface adsorbate.
The catalyst is used to enrich electrochemically active microorganisms that can efficiently achieve the anaerobic conversion of organic wastes. Microorganisms are rapidly combined with ferroferric oxide to form a biofilm on the surface of the magnet, which can accelerate the methane production by anaerobic digestion, increase the organic loading rate and methane yield of an anaerobic digestion system, and reduce the reaction period. The so-called enrichment of highly-effective functional microorganisms refers to the enrichment of bacteria or archaea that can decompose or convert organic matters and participate in the anaerobic digestion process, and especially of electrochemically active bacteria and methanogens that can allow the efficient direct interspecific electron transfer. The relative abundance of highly-effective functional microorganism species is increased compared with that before or without the use of the catalyst.
Further, the ferroferric oxide and the magnet have a mass ratio of 1:{1-10).
Further, the magnet includes ferrite magnet or neodymium magnet.
Further, the magnet has a shape including sphere, ellipsoid, cylinder or cuboid; the magnet has a structure including solid structure, hollow structure, porous structure or platy structure; and the ferroferric oxide has a particle diameter of 10 nm to 0.5 mm, namely, in micronscale or nanoscale, and a purity of over 85%.
Further, the source of organic wastes includes one or more of municipal sludge, food wastes, kitchen wastes and crop straws. The organic wastes have VS {Volatile Solid}/TS (Total Solid) =
45.1% to 80.9%, and TS = 1.5% to 23.3%.
-A- Further, the production method includes batch, semi-continuous or continuous production method. The method is suitable for low-temperature, medium-temperature and high-temperature anaerobic digestion systems. The operating mode, such as continuous stirring and shaking or intermittent stirring and shaking, can be adopted to form a biofilm on the surface of the catalyst. Solid Retention Time (SRT) = 10 d to 20 d in semi-continuous or continuous production. Further, the inoculum is taken from the effluent sludge of a sludge anaerobic digestion reactor, namely, anaerobically-digested sludge. The anaerobically-digested sludge includes various microorganisms, such as bacteria and methanogens that can efficiently carry out interspecific electron transfer. The anaerobically-digested sludge has VS/TS = 31.6% to 48.9%, and TS = 2.0% to 6.3%. The volatile solid {VS} in the inoculum and the VS in the organic wastes have a mass ratio of 1:{0.5-2}. Further, the ferroferric oxide and the total solid (TS} in the organic wastes have a mass ratio of 1:(1-6). Further, the reaction is conducted at 35°C to 55°C, and the stirring is conducted at 75 r/min to 120 r/min.
Compared with the prior art, the present invention has the following advantages: (1) The present invention adopts a catalyst with a magnet as a matrix and ferroferric oxide as a surface adsorbate for the first time, and the catalyst is used to enrich electrochemically active microorganisms that can efficiently achieve the anaerobic conversion of organic wastes. Microorganisms are rapidly combined with ferroferric oxide to form a biofilm on the surface of the magnet, which can accelerate the methane production by anaerobic digestion, increase the organic loading rate and methane yield of an anaerobic digestion system, and reduce the reaction period.
(2) Since the electrochemically active bacteria and methanogens in the anaerobically-digested sludge are tightly combined with ferroferric oxide particles on the surface of the magnet, the mass transfer and interspecific electron transfer are
-5- accelerated, the conversion of organic matters is promoted, and the methane-producing efficiency is improved. (3) Ferroferric oxide, tightly adsorbed on the surface of the magnet, exerts stable effect and is not easy to lose during the anaerobic digestion of organic wastes. After the reaction, ferroferric oxide can be separated by magnetic separation or other methods and reused, leading to both improved anaerobic digestion efficiency and reduced cost, which has prominent economic benefits and application prospects.
(4) The catalyst of the present invention is suitable for low-temperature, medium-temperature and high-temperature anaerobic digestion systems. The operating mode, such as continuous stirring and shaking or intermittent stirring and shaking, can be adopted to form a biofilm on the surface of the catalyst.
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic diagram for enriching highly-effective functional microorganisms by the catalyst of the present invention; FIG. 2 shows the cumulative methane production curves during the anaerobic digestion experiments in Example 1, Comparative Example 1 and Comparative Example 2; FIG. 3 shows twenty bacteria with the top relative abundance in the anaerobic digestion systems in Example 2 and Comparative Examples 3 to 5; FIG. 4 shows twenty archaea with the top relative abundance in the anaerobic digestion systems in Example 2 and Comparative Examples 3 to 5; and FIG.5 shows the methane-producing rate curves during the anaerobic digestion experiments in Example 3 and Comparative Example 6.
DETAILED DESCRIPTION The present invention is described in detail below with reference to the accompanying drawings and specific examples.
Example 1
-6- This example is intended to implement a method for enriching highly-effective functional microorganisms to enhance anaerobic digestion of organic wastes in a batch methane-producing experiment with municipal sludge as a substrate.
The excess activated sludge (VS/TS = 45.1% to 70.8%, TS = 1.5% to 5.1%) in the secondary sedimentation tank of a sewage treatment plant was adopted as the substrate, and the anaerobically-digested sludge in a stably-running reactor (VS/TS = 33.2% to 48.9%, TS= 2.1% to
6.3%) was adopted as the inoculum, to conduct a batch anaerobic methane-production experiment in a 500 mL serum bottle.
Then a magnet-ferroferric oxide catalyst was added, where the magnet was a spherical ferrite magnet with a diameter of 3 cm; the ferroferric oxide had a particle diameter of 200 nm; and the ferroferric oxide and the magnet had a mass ratio of 1:2. The VS in the excess activated sludge and the VS in the inoculum had a mass ratio of 2:1. The ferroferric oxide and the TS in the excess activated sludge had a mass ratio of 1:1. In addition, a blank group with only the inoculum was set to eliminate the influence of the inoculum. The experiment was conducted in a shaker at 100 r/min under a 37°C air bath. During the experiment, the volatile fatty acids (VFAs) content was monitored, the biogas production and gas composition were determined, and the TS and VS before and after anaerobic digestion were determined. Comparative Example 1 This example was different from Example 1 in that the same mass of ferroferric oxide was used instead of the magnet-ferroferric oxide catalyst. Comparative Example 2 This example was different from Example 1 in that the magnet-ferroferric oxide catalyst was not added.
As shown in FIG. 2, there is no significant difference between Comparative Example 1 and Comparative Example 2 in terms of the methane-producing rate and the methane yield, indicating that the direct addition of ferroferric oxide fails to enhance the anaerobic digestion
-7- of municipal sludge for methane production; and compared with Comparative Example 1 or Comparative Example 2, in Example 1, after the magnet-ferroferric oxide catalyst is added, the methane-producing rate of the system is significantly improved, and the maximum gas production is reached on day 13, where the proportion of methane in the biogas produced increases from 65% to more than 75%, and the amount of methane produced by degradation of one gram of VS increases significantly. Two batches of experiments were successively conducted to analyze the iron content in the effluent sludge. The results are shown in Table 1. Table 1 Iron content (%TS) in effluent sludge after anaerobic digestion® Batch 1 Batch 2 Example 1 7.8+0.5 5.8+0.5 Comparative Example 1 29.019.0 18.9+7.7 Comparative Example 2 4.0+0.4 3.8+0.5 a. The data shown are the averages and their standard deviations for three duplicate tests.
According to the data in Table 1, in Comparative Example 1, only ferroferric oxide is added, and a large amount of iron is lost, where, after batches 1 and 2 of anaerobic digestion experiments, the iron lost accounts for 29% and 18.9% of TS in sludge; and in Example 1 where a magnet and ferroferric oxide are added, the iron lost is greatly reduced, leading to both improved anaerobic digestion efficiency and reduced cost, which has prominent economic benefits and application prospects. Example 2 This example is intended to implement a method for enriching highly-effective functional microorganisms to enhance anaerobic digestion of organic wastes in a semi-continuous methane-producing experiment with food wastes as a substrate. The crushed food wastes (VS/TS = 58.7% to 80.9%, TS = 10.6% to 23.3%) were adopted as the substrate, and the anaerobically-digested sludge in a stably-running anaerobic digestion reactor (VS/TS = 31.6% to 48.9%, TS = 2.3% to 5.7%) was adopted as the inoculum, to conduct a semi-continuous anaerobic methane-production experiment in a reactor with a working volume of 2 L.
Then a magnet-ferroferric oxide catalyst was added, where the magnet was a cylindrical neodymium magnet with a diameter of 4 cm and a height of 1 cm; the ferroferric oxide had a particle diameter of 100 nm; and the ferroferric oxide and the magnet had a mass ratio of 1:10. The ferroferric oxide and the TS in the food wastes had a mass ratio of 1:3. The VS in the food wastes and the VS in the inoculum had a mass ratio of 2:1. In addition, a blank group with only the inoculum was set to eliminate the influence of the inoculum. The semi-continuous reactor had a daily discharge of 200 mL, a daily charge of 200 mL, and a sludge retention time (SRT) = 10 d. The reactor was heated under a 35°C to 45°C air bath, and the stirring was conducted at 80 r/min to 100 r/min for 1 min at an interval of 0.5 min. During the experiment, the VFAs, TS and VS contents were monitored for the charge and discharge, and the biogas production and gas composition were determined.
Comparative Example 3 This example was different from Example 2 in that the same mass of ferroferric oxide was used instead of the magnet-ferroferric oxide catalyst.
Comparative Example 4 This example was different from Example 2 in that the same mass of magnet was used instead of the magnet-ferroferric oxide catalyst.
Comparative Example 5 This example was different from Example 2 in that the magnet-ferroferric oxide catalyst was not added.
As shown in FIG. 3 to 4, in Comparative Examples 3 to 5, the microorganisms {bacteria and archaea) in the discharges have extremely-similar compositions, and highly-effective electrochemically active bacteria are not enriched, indicating that the addition of ferroferric oxide or magnet alone cannot achieve the enrichment of highly-effective microorganisms.
Compared with Comparative Examples 3 to 5, in Example 2, after the magnet-ferroferric oxide catalyst is added, the microorganisms in the discharge have significantly-different composition and abundance; bacteria 1 and 2 that can efficiently carry out interspecific electron transfer are enriched; methanogens 3, 4 and 5 in the archaea have significantly-increased abundance; and q- effective enrichment is achieved. In Example 2, the VFAs do not accumulate; the daily methane yield increases by more than 20%; the proportion of methane in biogas increases by 11%; and a stable operation is maintained.
Example 3 This example is intended to implement a method for enriching highly-effective functional microorganisms to enhance anaerobic digestion of organic wastes in a continuous methane-producing experiment.
The excess activated sludge (VS/TS = 50.9% to 68.8%, TS = 1.7% to 4.8%) in a secondary sedimentation tank was adopted as the substrate, and the anaerobically-digested sludge in a stably-running anaerobic digestion reactor {VS/TS = 33.1% to 45.8%, TS = 2.0% to 5.5%) was adopted as the inoculum, to conduct a continuous methane-production experiment in a reactor with a working volume of 4 L.
Then a magnet-ferroferric oxide catalyst was added, where the magnet was a ferrite magnet ring with an inner diameter of 2 cm, an outer diameter of 4 cm and a height of 1 cm; the ferroferric oxide had a particle diameter of 150 nm; and the ferroferric oxide and the magnet had a mass ratio of 1:1. The VS in the excess activated sludge and the VS in the inoculum had a mass ratio of 2:1. In addition, a blank group with only the inoculum was set to eliminate the influence of the inoculum.
The continuous charging and discharging mode was adopted, with SRT = 20 d. The reactor was heated under a 42°C air bath, and the stirring was conducted at 75 r/min for 1 min at an interval of 1 min. During the experiment, the VFAs, TS and VS contents were monitored for the charge and discharge, and the biogas production and gas composition were determined. Comparative Example 6 This example was different from Example 3 in that the same mass of ferroferric oxide was used instead of the magnet-ferroferric oxide catalyst.
As shown in FIG. 5, comparing Example 3 with Comparative Example 6, it is found that the gas-producing rate increases rapidly both in Example 3 and Comparative Example 6 during the
-10- initial period after start-up, and 14 days later, the gas-producing rate in Example 3 is higher than that in Comparative Example 6, and the rate gap gradually increases over time.
When both Example 3 and Comparative Example 6 operate stably, the gas-producing rate in Example 3 increases by about 50% compared with Comparative Example 6, and there is no accumulation of VFAs, indicating that the reactor added with a magnet-ferroferric oxide catalyst can operate stably.
The examples are described above to facilitate the comprehension and use of the present invention by those of ordinary skill in the art.
It is obvious that those skilled in the art can easily make various modifications to these examples, and apply the general principles described here to other examples without creative effort.
Therefore, the present invention is not limited to the above examples, and all improvements and modifications, made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention, should fall within the protection scope of the present invention.
-11- Embodiments:
1. A method for anaerobic digestion of organic wastes, comprising: adding organic wastes, inoculum, and a catalyst enriched with highly-effective functional microorganisms to a reactor; and conducting stirring and reaction to produce methane.
2. The method for anaerobic digestion of organic wastes according to embodiment 1, wherein the catalyst adopts a magnet as a matrix and ferroferric oxide as a surface adsorbate.
3. The method for anaerobic digestion of organic wastes according to embodiment 2, wherein, the ferroferric oxide and the magnet have a mass ratio of 1:{1-10).
4, The method for anaerobic digestion of organic wastes according to embodiment 2, wherein, the magnet comprises ferrite magnet or neodymium magnet.
5. The method for anaerobic digestion of organic wastes according to embodiment 2, wherein, the magnet has a shape comprising sphere, ellipsoid, cylinder or cuboid; the magnet has a structure comprising solid structure, hollow structure, porous structure or platy structure; and the ferroferric oxide has a particle diameter of 10 nm to 0.5 mm.
6. The method for anaerobic digestion of organic wastes according to embodiment 1, wherein the source of organic wastes comprises one or more of municipal sludge, food wastes, kitchen wastes and crop straws.
7. The method for anaerobic digestion of organic wastes according to embodiment 1, wherein the production method comprises batch, semi-continuous or continuous production method.
8. The method for anaerobic digestion of organic wastes according to embodiment 1, wherein the inoculum is taken from the effluent sludge of a sludge anaerobic digestion reactor; and the volatile solid {VS} in the inoculum and the VS in the organic wastes have a mass ratio of 1:{0.5-2}.
-12- 9, The method for anaerobic digestion of organic wastes according to embodiment 1 or 2, wherein the ferroferric oxide and the total solid {TS) in the organic wastes have a mass ratio of 1:{1-6).
10. The method for anaerobic digestion of organic wastes according to embodiment 1, wherein the reaction is conducted at 35°C to 55°C, and the stirring is conducted at 75 r/min to 120 r/min.
Claims (10)
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| CN112680480B (en) | 2021-01-04 | 2021-10-15 | 同济大学 | Anaerobic fermentation method for organic solid waste |
| CN113526818A (en) * | 2021-08-02 | 2021-10-22 | 江苏理工学院 | Process for accelerating methane generation from organic solid waste by using loaded ferromagnetic catalyst |
| CN115124140A (en) * | 2022-05-11 | 2022-09-30 | 郑州大学 | Method for enhancing anaerobic digestion of organic wastewater by using iron-modified volcanic rock |
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| JP4375832B2 (en) * | 1999-02-19 | 2009-12-02 | 独立行政法人科学技術振興機構 | Waste water treatment apparatus and waste water treatment method using magnetic sludge |
| EP3138892A1 (en) * | 2015-09-03 | 2017-03-08 | Synthopetrol | Use of multifunctional magnetic catalysts for the transformation of biomass |
| CN105771918A (en) * | 2016-05-04 | 2016-07-20 | 济南大学 | Preparation method and application of magnetic anaerobic granular sludge-chitosan adsorbent |
| CN106517503B (en) * | 2016-10-18 | 2019-06-04 | 兴业环保股份有限公司 | A kind of active sludge carbon anaerobic grain sludge and preparation method thereof |
| CN108479429A (en) * | 2018-05-31 | 2018-09-04 | 中国科学院城市环境研究所 | It is a kind of to utilize nanometer Fe3O4The preparation method of modified PVDF microfiltration membranes and its utilization |
| CN110551765B (en) * | 2019-09-02 | 2023-02-28 | 安徽舜禹水务股份有限公司 | Method for anaerobic preparation of methane from landfill leachate |
| CN110776228B (en) * | 2019-10-31 | 2020-10-02 | 同济大学 | Method for strengthening anaerobic digestion of municipal sludge to produce methane by applying filter screen structure |
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