CN115583773A - Method for improving methane yield in anaerobic digestion process of sludge by using nano zero-valent iron - Google Patents

Method for improving methane yield in anaerobic digestion process of sludge by using nano zero-valent iron Download PDF

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CN115583773A
CN115583773A CN202211049262.8A CN202211049262A CN115583773A CN 115583773 A CN115583773 A CN 115583773A CN 202211049262 A CN202211049262 A CN 202211049262A CN 115583773 A CN115583773 A CN 115583773A
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sludge
valent iron
nano zero
anaerobic digestion
anaerobic
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刘洁
李清
邓婕
邹翠华
彭小梅
陈亮
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Hunan Pingan Environmental Protection Co ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/02Biological treatment
    • C02F11/04Anaerobic treatment; Production of methane by such processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

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  • Treatment Of Sludge (AREA)

Abstract

The invention relates to a method for increasing methane yield in a sludge anaerobic digestion process by using nano zero-valent iron. Fully mixing municipal sludge and anaerobic sludge to obtain a sludge mixture which is uniformly mixed; and then adding nano zero-valent iron into the mixed sludge, continuously filling inert gas, and after oxygen is removed, hermetically culturing the reaction vessel for at least 30 days. The invention utilizes the nano zero-valent iron which can be flocculated and adsorbed on extracellular polymers around anaerobic microorganisms, thereby protecting cell membranes of most active microorganisms from contact damage, maintaining the stability of an anaerobic digestion system, improving the anaerobic digestion efficiency, promoting the dissolution and release of organic matters in the anaerobic digestion process, and achieving the purpose of improving the methanogenesis; the method has high efficiency of treating the anaerobic digestion sludge, is simple to operate, and realizes the high efficiency and the application prospect of treating the excess sludge.

Description

Method for improving methane yield in anaerobic digestion process of sludge by using nano zero-valent iron
Technical Field
The invention relates to resource utilization of solid wastes, in particular to a method for improving methane yield in a sludge anaerobic digestion process by using nano zero-valent iron.
Background
At present, the number of urban sewage treatment plants and the sewage treatment capacity in China are greatly increased. The sewage treatment process is accompanied by a large amount of excess sludge. According to statistics, the yield of the excess sludge in China in 2013 reaches 3500 million tons (the water content is 80%), and the increase rate is increased by 20% every year. On the one hand, global resource and energy crisis is are increasing. On the other hand, the sludge contains rich bioavailable organic matters, so the resource treatment of the sludge is a widely concerned issue at present, and in the process, the sludge can be effectively reduced and harmlessly treated, and the effective recovery of energy and resources can be realized.
Anaerobic sludge digestion is a common sludge resource utilization means, and methane which is a high-quality energy substance can be produced in the process. However, most of organic matters contained in the sludge are mainly distributed in extracellular polymeric substances and intracellular organic matters wrapped by cell walls, and are difficult to be directly utilized by anaerobic microorganisms, so the sludge lysis process is considered as a rate-limiting step of anaerobic fermentation of the sludge. In addition, the anaerobic digestion process of sludge is a biological process in which various microorganisms participate together. Some sludge pretreatment methods such as acid-base method, heat treatment method, advanced oxidation method and combined treatment method are applied to promote the sludge cracking process, so that the organic matters in the sludge are released in a large amount, a large amount of available matrix is provided for methanogenic microorganisms, and the methane yield is remarkably promoted. However, the method has a complex operation flow, and additional chemical substances or energy are required, so that long-term large-scale application is difficult to realize.
The nanometer zero-valent iron is used as a cheap and easily-obtained environment-friendly material, has strong reducibility, can reduce partial oxidizing ions or organic matters, and is increasingly paid attention to in environmental management. Research reports that zero-valent iron is applied to groundwater remediation and can provide electrons required for reductive dechlorination of organic chloride. Based on that the zero-valent iron can improve the removal of harmful substances such as heavy metals and the biodegradability of organic pollutants, domestic and foreign researches begin to focus on the exploration of nano zero-valent iron on the aspects of sludge anaerobic digestion process and gas production performance improvement.
Disclosure of Invention
The invention aims to provide a method for improving the methane yield in the anaerobic digestion process of sludge by using nano zero-valent iron, and overcomes the defects of high cost, low treatment efficiency and the like in the prior art.
In order to achieve the purpose, the scheme of the invention is as follows:
a method for improving methane yield in a sludge anaerobic digestion process by using nano zero-valent iron comprises the following steps:
(1) Taking sludge in a secondary sedimentation tank of a municipal sewage treatment plant as municipal sludge, firstly carrying out sedimentation and then sieving;
(2) Anaerobic digestion is carried out on the screened municipal sludge at the temperature of 30-35 ℃, and glucose, ammonium sulfate and potassium dihydrogen phosphate are respectively adopted as a carbon source, a nitrogen source and a phosphorus source (the molar ratio is 180-220, 3-7);
(3) Dispersing nano zero-valent iron into the residual sludge obtained in the step (2), adding the sieved municipal sludge obtained in the step (1), and performing anaerobic digestion for 28-31 days under the conditions that the temperature is 25-35 ℃ and the stirring speed is 120-180 rpm.
Furthermore, in the step (1), the sedimentation is gravity sedimentation, the sedimentation temperature is 2-6 ℃, and the sedimentation time is 20-30 h, so that good solid-liquid separation of the sludge can be realized.
Furthermore, in the step (1), a sieve with the size of 1-5 mm is adopted for sieving.
Further, in the step (3), before the nano zero-valent iron is added, the nano zero-valent iron is ultrasonically dispersed in a 0.1-0.3 mmol/L sodium dodecyl benzene sulfonate solution for 10-30 minutes.
Further, in the step (3), the adding dosage of the nano zero-valent iron is 10-30 mmol/L; the adding amount within the range can realize better effect of promoting the production of methane, the activity of various active bacteria including hydrogen-producing bacteria can be gradually inhibited when the adding amount is too high, and the promoting effect is not obvious when the adding amount is too low.
Further, in the step (3), anaerobic digestion is carried out in the fermentation reactor, and an anaerobic environment is maintained in the form of nitrogen gas injection.
Furthermore, the stirring speed is 120-180 rpm, the stirring effect is the best, the stirring speed of more than 120rpm/min can realize repeated uniform stirring effect, and when the stirring speed exceeds 180rpm/min, the methane production process of active bacteria is influenced, so that the promotion effect on methane production is reduced.
The process for producing methane by anaerobic fermentation of sludge mainly comprises four processes, namely dissolution, hydrolysis, acidification and methanation. The dissolution process is the rate-limiting step in anaerobic digestion of sludge. In the technical scheme, the target product methane is the final product in the anaerobic digestion process of the sludge. Therefore, the key to promoting the anaerobic digestion of the sludge to produce the methane is to strengthen the dissolution of the sludge, promote the release of organic matters and provide more substrates for producing the methane.
In the technical scheme, the used nano zero-valent iron is a cheap and easily-obtained environment-friendly material, the nano zero-valent iron can be flocculated and adsorbed on extracellular polymers around anaerobic microorganisms, so that the decaying microorganisms with less extracellular polymers are damaged and intracellular substances are released, and the cell membranes of the microorganisms with stronger activity are protected from being damaged by the nano zero-valent iron due to more extracellular polymers. Some decayed microbial cells may be directly adsorbed and damaged due to degradation of extracellular polymers around the nano zero-valent iron particles, and the damaged cell membranes can promote release of substances in the cells, so that most of active microbial cell membranes are protected from contact damage, stability of an anaerobic digestion system is maintained, anaerobic digestion efficiency is improved, organic matter dissolution and release in the anaerobic digestion process are promoted, and the purpose of improving methane production is achieved.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention greatly improves the yield of methane in the anaerobic digestion process of excess sludge by utilizing the nano zero-valent iron;
2) In the prior art, such as an acid-base method, a heat treatment method, an advanced oxidation method and a combined treatment method, the pretreatment time is long, the operation flow is complex, and more importantly, a large amount of exogenous chemical substances are required to be added or a large amount of energy is consumed, so that the treatment cost of sludge is greatly increased. The method has high efficiency of treating the anaerobic digestion sludge, is simple to operate, and realizes high efficiency of treating the excess sludge and application prospect.
Drawings
FIG. 1 is a graph of cumulative methane production over time for examples 1-4 and comparative example 1.
Detailed Description
The present invention is further described with reference to specific embodiments, but the scope of the present invention is not limited thereto.
The sludge used in the following examples was obtained from a sewage treatment plant having a daily average flow rate of 150,000m 3 And d. The obtained municipal sludge is sludge (solid content is 0.8%) in the secondary sedimentation tank after dehydration. In order to keep the components of the sludge unchanged, the withdrawn sludge is stored at 4 ℃ for later use. The excess sludge is anaerobic digested by the same municipal sludge at 35 plus or minus 1 ℃ and acclimatized for 1 month to obtain anaerobic sludge. In the excess sludge acclimatization stage, glucose, ammonium sulfate and potassium dihydrogen phosphate are respectively adopted as a carbon source, a nitrogen source and a phosphorus source, and the molar ratio of carbon to nitrogen to phosphorus is 200. And (4) continuously stirring the domesticated excess sludge for 2 hours, and then, passing through a 1mm screen to remove impurities with larger particles for use.
In the following examples, the nanoscale zero-valent iron used was ultrasonically dispersed in a 0.1mmol/L sodium dodecylbenzenesulfonate solution for 10 minutes before being added.
Example 1
(1) In a plexiglass reactor with a working volume of 500mL, 300mL of substrate and 200mL of inoculum are added through the sieve.
(2) Adding 10mmol/L nano zero-valent iron into the reactor, stirring uniformly, filling nitrogen into the reactor for 10min to completely discharge oxygen in the reactor, sealing the reactor and placing the reactor in an oscillator for anaerobic digestion. Under the action of various anaerobic and facultative microorganisms, organic matters in the sludge are converted into methane. During the anaerobic digestion process, the stirring speed of the oscillator is controlled to be 120rpm, the fermentation temperature of the reactor is controlled to be 35 ℃, the digestion reaction time is controlled to be 31d, and the yield of the produced methane is 58.0mL/g VS.
Example 2
(1) In a plexiglass reactor with a working volume of 500mL, 300mL of substrate and 200mL of inoculum are added through the sieve.
(2) Adding 20mmol/L nano zero-valent iron into the reactor, stirring uniformly, filling nitrogen into the reactor for 10min to completely discharge oxygen in the reactor, sealing the reactor and placing the reactor in an oscillator for anaerobic digestion. Under the action of various anaerobic and facultative microorganisms, organic matters in the sludge are converted into methane. During anaerobic digestion, the stirring speed of the oscillator is controlled to be 120rpm, the fermentation temperature of the reactor is controlled to be 35 ℃, the digestion reaction time is controlled to be 31d, and the yield of produced methane is 67.1mL/g VS.
Example 3
(1) In a plexiglass reactor with a working volume of 500mL, 300mL of substrate and 200mL of inoculum are added through the sieve.
(2) Adding 30mmol/L nano zero-valent iron into the reactor, stirring uniformly, filling nitrogen into the reactor for 10min to completely discharge oxygen in the reactor, sealing the reactor and placing the reactor in an oscillator for anaerobic digestion. Under the action of various anaerobic and facultative microorganisms, organic matters in the sludge are converted into methane. During anaerobic digestion, the stirring speed of the oscillator is controlled to be 120rpm, the fermentation temperature of the reactor is controlled to be 35 ℃, the digestion reaction time is controlled to be 31d, and the yield of produced methane is 71.5mL/g VS.
Example 4
(1) In a plexiglass reactor with a working volume of 500mL, 300mL of substrate and 200mL of inoculum, which have passed through the sieve, are added.
(2) Adding 30mmol/L nano zero-valent iron into the reactor, stirring uniformly, filling nitrogen into the reactor for 10min to completely discharge oxygen in the reactor, sealing the reactor and placing the reactor in an oscillator for anaerobic digestion. Under the action of various anaerobic and facultative microorganisms, organic matters in the sludge are converted into methane. During the anaerobic digestion process, the stirring speed of the oscillator is controlled to be 120rpm, the fermentation temperature of the reactor is controlled to be 35 ℃, the digestion reaction time is controlled to be 31d, and the yield of the produced methane is 71.5mL/g VS.
Comparative example
(1) In a plexiglass reactor with a working volume of 500mL, 300mL of substrate and 200mL of inoculum, which have passed through the sieve, are added.
(2) Subsequently, the reactor was purged with nitrogen for 10min to completely discharge oxygen in the reactor, sealed and placed in a shaker for anaerobic digestion. Under the action of various anaerobic and facultative microorganisms, organic matters in the sludge are converted into methane. During anaerobic digestion, the stirring speed of the oscillator is controlled to be 120rpm, the fermentation temperature of the reactor is controlled to be 35 ℃, the digestion reaction time is controlled to be 31d, and the yield of produced methane is 52.0mL/g VS.
The methane production of examples 1-4 and comparative examples are shown in table 1.
TABLE 1 methane production for examples 1-4 and comparative examples
Figure BDA0003823082540000051
As can be seen from Table 1, the methane yield of examples 1-4 is significantly improved compared with that of the comparative example, wherein the improvement amount of example 3 is the largest compared with that of the comparative example, the improvement rate is 37.5%, that is, the concentration of the nano zero-valent iron for promoting anaerobic digestion of sludge to produce methane is preferably 30mmol/L.

Claims (7)

1. A method for improving methane yield in a sludge anaerobic digestion process by using nano zero-valent iron is characterized by comprising the following steps:
(1) Taking sludge in a secondary sedimentation tank of a municipal sewage treatment plant as municipal sludge, firstly carrying out sedimentation and then sieving;
(2) Anaerobic digestion is carried out on the screened municipal sludge at the temperature of 30-35 ℃, and glucose, ammonium sulfate and potassium dihydrogen phosphate are respectively adopted as a carbon source, a nitrogen source and a phosphorus source to carry out acclimation for 25-35 days, and the sludge obtained by screening after acclimation is anaerobic sludge and is used as excess sludge;
(3) Dispersing nano zero-valent iron into the residual sludge obtained in the step (2), adding the sieved municipal sludge obtained in the step (1), and performing anaerobic digestion for 28-31 days under the conditions that the temperature is 25-35 ℃ and the stirring speed is 120-180 rpm.
2. The method for improving the yield of methane in the anaerobic digestion process of sludge by using the nano zero-valent iron as claimed in claim 1, wherein in the step (1), the sedimentation is gravity sedimentation, the sedimentation temperature is 2-6 ℃, and the sedimentation time is 20-30 h.
3. The method for improving the methane yield in the anaerobic digestion process of the sludge by using the nano zero-valent iron as claimed in claim 1, wherein a sieve with the size of 1-5 mm is adopted in the step (1).
4. The method for improving the methane yield in the anaerobic digestion process of the sludge by using the nano zero-valent iron as claimed in claim 1, wherein in the step (1), the molar ratio of the carbon source to the nitrogen source to the phosphorus source is 180-220.
5. The method for improving the methane yield in the anaerobic digestion process of sludge according to claim 1, wherein in the step (3), before the nano zero-valent iron is added, the nano zero-valent iron is ultrasonically dispersed in a 0.1-0.3 mmol/L sodium dodecyl benzene sulfonate solution for 10-30 minutes.
6. The method for improving the methane yield in the anaerobic sludge digestion process by using the nano zero-valent iron as claimed in claim 1, wherein in the step (3), the adding amount of the nano zero-valent iron is 10-30 mmol/L.
7. The method for improving the methane yield in the anaerobic sludge digestion process by using the nano zero-valent iron as claimed in claim 1, wherein in the step (3), the anaerobic digestion is carried out in a fermentation reactor, and an anaerobic environment is maintained in the form of nitrogen gas filling.
CN202211049262.8A 2022-08-30 2022-08-30 Method for improving methane yield in anaerobic digestion process of sludge by using nano zero-valent iron Pending CN115583773A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117486363A (en) * 2024-01-02 2024-02-02 南京大学 Method for strengthening anaerobic digestion of sulfanilamide wastewater by nano iron

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Publication number Priority date Publication date Assignee Title
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CN107522375A (en) * 2017-08-22 2017-12-29 华南理工大学 A kind of method that Zero-valent Iron and activated carbon strengthen excess sludge anaerobic digestion methane phase
CN111099802A (en) * 2020-01-02 2020-05-05 广州大学 Method for producing methane by promoting anaerobic digestion of high-solid-content municipal sludge through zero-valent iron

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Publication number Priority date Publication date Assignee Title
CN103288319A (en) * 2013-06-19 2013-09-11 大连理工大学 Method for accelerating anaerobic fermentation of residual sludge by utilizing zero-valent iron technology
CN107522375A (en) * 2017-08-22 2017-12-29 华南理工大学 A kind of method that Zero-valent Iron and activated carbon strengthen excess sludge anaerobic digestion methane phase
CN111099802A (en) * 2020-01-02 2020-05-05 广州大学 Method for producing methane by promoting anaerobic digestion of high-solid-content municipal sludge through zero-valent iron

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由晓刚: "纳米零价铁(NZVI)对污泥厌氧消化过程的影响研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, vol. 2021, no. 01, 15 January 2021 (2021-01-15), pages 17 - 19 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117486363A (en) * 2024-01-02 2024-02-02 南京大学 Method for strengthening anaerobic digestion of sulfanilamide wastewater by nano iron
CN117486363B (en) * 2024-01-02 2024-04-09 南京大学 Method for strengthening anaerobic digestion of sulfanilamide wastewater by nano iron

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