CN114195341A - Enhanced pretreatment method for improving anaerobic methanogenesis efficiency of excess sludge and phosphorus availability - Google Patents
Enhanced pretreatment method for improving anaerobic methanogenesis efficiency of excess sludge and phosphorus availability Download PDFInfo
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 53
- 239000011574 phosphorus Substances 0.000 title claims abstract description 53
- 238000002203 pretreatment Methods 0.000 title claims abstract description 34
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- 239000003513 alkali Substances 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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Images
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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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a strengthening pretreatment method for improving the anaerobic methanogenesis efficiency of excess sludge and the availability of phosphorus, belonging to the field of resource treatment and disposal of excess sludge of solid wastes. The invention adopts citric acid or citrate and calcium hydroxide to pretreat the excess sludge jointly, relieves the heavy flocculation of calcium ions on macromolecular organic matters through the complexing action of the citric acid or citrate and calcium ions, enhances the solubilization of calcium hydroxide on sludge, promotes the anaerobic digestion of the excess sludge to produce methane, and effectively increases the content of available phosphorus easily absorbed by plants in the digested sludge.
Description
Technical Field
The invention belongs to the field of resource treatment and disposal of solid waste excess sludge, and particularly relates to an enhanced pretreatment method for improving anaerobic methanogenesis efficiency of excess sludge and phosphorus availability.
Background
The activated sludge process is a main process for municipal sewage treatment, and a large amount of excess sludge is generated as a byproduct in the treatment process. The residual sludge has complex components and contains harmful substances such as heavy metals and pathogens, and if the residual sludge is not treated properly, the residual sludge can have adverse effects on the ecological environment. On the other hand, the excess sludge contains abundant organic matters such as protein and polysaccharide, and also contains inorganic resources such as nitrogen, phosphorus and the like. Therefore, the method has great value and significance for treating and disposing the excess sludge to realize stabilization, harmlessness and resource utilization.
At present, the treatment methods of sludge mainly comprise anaerobic digestion, incineration, pyrolysis and the like, wherein the anaerobic digestion is the most used technology at present due to low cost and high energy yield. Under the anaerobic condition, the facultative anaerobic and anaerobic microbial communities convert organic matters in the excess sludge into clean energy such as short-chain fatty acid, methane and the like, and can kill pathogenic bacteria and parasites (eggs) so as to realize reduction, stabilization and resource utilization of the excess sludge. The process of anaerobic digestion of sludge can be broadly divided into: the hydrolysis stage, the hydrogen-producing acid-producing stage and the methane-producing stage. The hydrolysis stage becomes the rate limiting step of the anaerobic digestion process of the sludge due to poor biodegradability caused by the protection of Extracellular Polymers (EPS) of the excess sludge and semi-rigid structured cell walls/membranes. Therefore, researchers have developed a series of excess sludge pretreatment technologies.
Through retrieval, related applications are disclosed in the prior art, for example, the publication No. CN107055986A, Chinese patent application of 8 months and 18 days in 2017 discloses a high-pressure microwave sludge pretreatment method, and the method comprises a pressurized microwave technology, a hot alkali treatment technology and H2O2The pretreatment technology is combined with the high-pressure flash evaporation technology, and has synergistic effect on sludge cell lysis and wall breaking. However, the method is complex to operate, has strict requirements on conditions such as microwave frequency, pressure, temperature and the like, and has large energy consumption.
For another example, chinese patent application publication No. CN109354349A, published 2019, 2-19, discloses a sludge pretreatment method and a sludge anaerobic fermentation acid production method. The method adopts ultrasonic wave coupling persulfate to pretreat the sludge, destroys EPS structures and microbial cells of the sludge, increases the cracking effect of the sludge, and provides nutrient substances for the subsequent fermentation stage. However, this method has a problem that the requirement for energy output is high.
The invention discloses a method for pretreating municipal sludge and application thereof, which is published in China patent application No. CN112661376A, No. 2021, 4, month and 16, and the method comprises the steps of mixing biochar solid acid with municipal sludge, carrying out high-temperature hydrothermal pretreatment, then filtering to obtain hydrolysate, and carrying out anaerobic digestion reaction on the hydrolysate to obtain methane. The pretreatment method can promote the quick degradation of extracellular polymeric substances in the sludge and lignocellulose in cell walls, and shorten the reaction time of the acid production phase of the hydrolysis of the municipal sludge. But the system still has high energy demand and neglects the problem of municipal sludge treatment and disposal.
In biochemical units of municipal sewage treatment plants in China, more than 90% of phosphorus in inlet water can be transferred to sludge, so that the residual sludge becomes a potential secondary phosphorus source. At present, chemical precipitation methods are mostly adopted for phosphorus recovery, including magnesium ammonium phosphate method and calcium phosphate method. For example, chinese patent application publication No. CN103641283A, published 3/19/2014 discloses an economical method for recovering phosphorus from excess sludge, which promotes the release of phosphorus in excess sludge through single-stage alkaline hydrolysis or two-stage alkaline hydrolysis, and then adds magnesium salt solution with Mg/P molar ratio of 0.8-2 to the obtained phosphorus-rich supernatant to recover phosphorus in sludge in the form of magnesium ammonium phosphate precipitate. The method has simple process, can recover part of ammonia nitrogen while recovering phosphorus, and does not need to adjust the pH. However, the method has higher cost due to the addition of an expensive magnesium source, and only considers the recovery of phosphorus in the pretreatment stage, the residual sludge after the phosphorus release still exists in the nature of waste, and the carbon resource in the sludge is neglected to be recycled. In the study by Siqi Tang et al (Siqi Tang, and Xunfixing Fei. Refractory Calcium Phosphate-Derived Phosphorus Fertilizer Based on Hydroxyapatite Nanoparticles for Nutrient delivery. ACS Applied Nano Materials 4(2), 1364. sup. laid-in 1376)), apatite Phosphorus has a higher availability to plants, and thus the manner in which Phosphorus is recovered by Calcium Phosphate precipitation is of great significance for soil remediation.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of poor pretreatment effect of the excess sludge, high energy requirement and how to recycle carbon and phosphorus resources contained in the excess sludge in the prior art, the invention provides an enhanced pretreatment method for improving the anaerobic methanogenesis efficiency of the excess sludge and the availability of phosphorus. The method adopts citric acid or citrate and calcium hydroxide to pretreat the excess sludge, firstly utilizes the chelation of citrate and polyvalent metal ions to remove metal ions which play a bridging role in sludge extracellular polymeric substances, thereby destroying sludge flocs, and further promotes the sludge floc structure disintegration and the sludge cell disintegration by utilizing hydroxide on the basis, thereby releasing more organic matters from a solid phase to a liquid phase and providing rich substrates for subsequent acidification and methane production stages; on the other hand, calcium ions introduced by the calcium hydroxide can be used as a calcium source to be combined with phosphorus in the sludge to form calcium phosphate precipitate, so that the phosphorus resource in the sludge is recovered.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to an enhanced pretreatment method for improving the anaerobic methanogenesis efficiency of excess sludge and the availability of phosphorus, which comprises the following steps:
s10, removing large-particle impurities in the excess sludge to be treated, and then adding water for dilution to obtain diluted excess sludge;
s20, adding citric acid or citrate into the diluted excess sludge, stirring, then adding calcium hydroxide, stirring, and carrying out combined pretreatment on the diluted excess sludge;
s30, adding anaerobic granular sludge into the residual sludge after the combined pretreatment, and carrying out anaerobic digestion reaction to produce methane.
Preferably, in the step S10, the total solid content of the diluted excess sludge is 50-60 g/L.
Preferably, in step S20, the molar ratio between the added citric acid or citrate and the added calcium hydroxide is 1: (0.5-2), and the citrate is sodium citrate or potassium citrate.
More preferably, in step S20, sodium citrate is added to the diluted excess sludge to control the concentration of sodium citrate to 10 to 40mM, and then calcium hydroxide is added to control the concentration of calcium hydroxide to 20 mM.
Preferably, in the step S20, the total reaction time of the combined pretreatment is 20-24 h.
Preferably, in step S30, the Volume (VS) ratio between the added anaerobic granular sludge and the excess sludge is 1: (1-2).
Preferably, in step S30, the reaction time of the anaerobic digestion reaction is 7 to 15 days, and the reaction temperature is 33 to 37 ℃.
Preferably, in step S20, sodium citrate is added to the diluted excess sludge, the mixture is stirred for 1 hour at a stirring speed of 150-180 rpm, and then calcium hydroxide is added.
Preferably, the excess sludge is dewatered sludge, the total solid content after dilution is 54.4 +/-0.7 g/L, the volatile organic compounds are 23.8 +/-0.9 g/L, and the pH value is 6.93 +/-0.03.
Preferably, the anaerobic granular sludge is obtained from an anaerobic fermentation tank of a sewage treatment plant, the total solid content of the anaerobic granular sludge is 16.7 +/-0.5 g/L, the volatile organic compound is 12.7 +/-0.4 g/L, and the pH value is 6.5-7.8.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the intensified pretreatment method for improving the anaerobic methanogenesis efficiency of the excess sludge and the availability of phosphorus, citric acid or citrate and calcium hydroxide are used together to act on the pretreated excess sludge for the first time, the citric acid or citrate is complexed with calcium ions, the re-flocculation effect of the calcium ions is relieved/inhibited, the cracking of sludge flocs and cells by using the calcium hydroxide as an alkali additive is effectively enhanced, and more granular organic matters are dissolved out; and provides rich nutrient medium for the subsequent anaerobic digestion and methane production, thereby effectively shortening the anaerobic digestion and methane production period and improving the methane production efficiency;
(2) the invention relates to a strengthening pretreatment method for improving the anaerobic methanogenesis efficiency of excess sludge and the availability of phosphorus, which comprises the steps of firstly, acting citric acid or citrate on extracellular polymers of the sludge, removing metal ions which play a role in coordination and bridging in the extracellular polymer structure through a chelating effect, realizing the effective release of extracellular enzyme, and providing more available functional enzymes for the subsequent anaerobic digestion process;
(3) according to the reinforced pretreatment method for improving the anaerobic methane production efficiency and phosphorus availability of the excess sludge, calcium hydroxide is added, on one hand, hydroxide radicals can continuously act on sludge cells, so that the sludge cells are cracked; on one hand, the introduced calcium ions can also recover phosphorus resource sediment in the residual sludge, and the content of available phosphorus which is easily absorbed by plants in the digested sludge is effectively increased.
Drawings
FIG. 1 is a graph showing the change in SCOD in EPS after pretreatment with a combination of sodium citrate and calcium hydroxide;
FIG. 2 is a graph of cumulative methane yield after pretreatment with a combination of citric acid and calcium hydroxide;
FIG. 3 is a graph showing the content of available phosphorus (Olsen-P) in digested sludge;
FIG. 4 is a graph showing the change of SCOD in EPS after pretreatment of sludge by combination of potassium citrate and calcium hydroxide and combination of citric acid and calcium hydroxide;
FIG. 5 is a graph of the cumulative methane yield after pretreatment of sludge with a combination of potassium citrate and calcium hydroxide and a combination of citric acid and calcium hydroxide;
FIG. 6 is a graph showing the available phosphorus (Olsen-P) content in digested sludge pretreated with a combination of potassium citrate and calcium hydroxide and a combination of citric acid and calcium hydroxide.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
An enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge comprises the following specific operations:
manually selecting large-particle impurities such as plastics, paper towels and the like from the collected excess sludge (dewatered sludge), and then adding water to dilute the impurities until the total solid content is 54.4 +/-0.7 g/L;
transferring the sludge obtained in the step (1) to a pretreatment reaction bottle, adding 10mM sodium citrate, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM of calcium hydroxide, and oscillating at 150rpm for reaction for 24 h;
transferring the sludge obtained in the step (2) into an anaerobic digestion reaction bottle, and inoculating anaerobic granular sludge with the solid content of 16.7 +/-0.5 g/L, wherein the inoculation ratio is 1.87 (excess sludge VS/anaerobic sludge VS); then stripping for 10min by nitrogen, discharging air to keep anaerobic condition, and immediately sealing the anaerobic digestion reactor; the temperature is controlled at 35 + -1 deg.C, the shaking intensity is 120rpm, and the digestion time is 12 days.
After pretreatment with sodium citrate and calcium hydroxide, the soluble chemical oxygen demand in the extracellular polymeric substance of the excess sludge is increased to 1925mg/L (as shown in FIG. 1). After 12 days of anaerobic digestion, the accumulated methane yield can reach 22.3mLCH4the/gVSS was increased by 166.4% compared to comparative example 1 and 60.3% compared to comparative example 2 (as shown in FIG. 2). The available phosphorus content in the digested sludge was 721.5mg/kg, which was 20.4% higher than that in comparative example 1 (as shown in FIG. 3).
Example 2
An enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge comprises the following specific operations:
manually selecting large-particle impurities such as plastics, paper towels and the like from the collected excess sludge, and then adding water to dilute the impurities until the total solid content is 54.4 +/-0.7 g/L;
transferring the sludge obtained in the step (1) to a pretreatment reaction bottle, adding 20mM sodium citrate, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM of calcium hydroxide, and oscillating at 150rpm for reaction for 24 h;
transferring the sludge obtained in the step (2) into an anaerobic digestion reaction bottle, and inoculating anaerobic granular sludge with the solid content of 16.7 +/-0.5 g/L, wherein the inoculation ratio is 1.87 (excess sludge VS/anaerobic sludge VS); then stripping for 10min by nitrogen, discharging air to keep anaerobic condition, and immediately sealing the anaerobic digestion reactor; the temperature is controlled at 35 + -1 deg.C, the shaking intensity is 120rpm, and the digestion time is 12 days.
After the pretreatment of sodium citrate and calcium hydroxide, the residual sludge is polymerized outside cellsThe soluble chemical oxygen demand in the composition increased to 3975mg/L (as shown in FIG. 1). After 12 days of anaerobic digestion, the accumulated methane yield can reach 34.9mLCH4the/gVSS was increased by 317% compared to comparative example 1 and 150.8% compared to comparative example 2 (as shown in FIG. 2). The content of available phosphorus in the digested sludge was 720.2mg/kg, which was 20.2% higher than that in comparative example 1 (as shown in FIG. 3).
Example 3
An enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge comprises the following specific operations:
manually selecting large-particle impurities such as plastics, paper towels and the like from the collected excess sludge, and then adding water to dilute the impurities until the total solid content is 54.4 +/-0.7 g/L;
transferring the sludge obtained in the step (1) to a pretreatment reaction bottle, adding 40mM sodium citrate, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM of calcium hydroxide, and oscillating at 150rpm for reaction for 24 h;
transferring the sludge obtained in the step (2) into an anaerobic digestion reaction bottle, and inoculating anaerobic granular sludge with the solid content of 16.7 +/-0.5 g/L, wherein the inoculation ratio is 1.87 (excess sludge VS/anaerobic sludge VS); then stripping for 10min by nitrogen, discharging air to keep anaerobic condition, and immediately sealing the anaerobic digestion reactor; the temperature is controlled at 35 + -1 deg.C, the shaking intensity is 120rpm, and the digestion time is 12 days.
After pretreatment with sodium citrate and calcium hydroxide, the soluble chemical oxygen demand in the extracellular polymeric substance of the excess sludge is increased to 6690mg/L (as shown in FIG. 1). After 12 days of anaerobic digestion, the accumulated methane yield can reach 41.4mLCH4the/gVSS was increased by 395.6% compared to comparative example 1 and 198.1% compared to comparative example 2 (as shown in FIG. 2). The content of available phosphorus in the digested sludge is 950.2mg/kg, which is effectively increased by 58.6% compared with that of comparative example 1 (as shown in figure 3).
Example 4
An enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge comprises the following specific operations:
manually selecting large-particle impurities such as plastics, paper towels and the like from the collected excess sludge, and then adding water to dilute the impurities until the total solid content is 51.6 +/-1.3 g/L;
transferring the sludge obtained in the step (1) to a pretreatment reaction bottle, adding 20mM potassium citrate, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM of calcium hydroxide, and oscillating at 150rpm for reaction for 24 h;
transferring the sludge obtained in the step (2) into an anaerobic digestion reaction bottle, and inoculating anaerobic granular sludge with the solid content of 12.7 +/-0.9 g/L, wherein the inoculation ratio is 1.83 (excess sludge VS/anaerobic sludge VS); then stripping for 10min by nitrogen, discharging air to keep anaerobic condition, and immediately sealing the anaerobic digestion reactor; the temperature is controlled at 35 + -1 deg.C, the shaking intensity is 120rpm, and the digestion time is 12 days.
After the pretreatment of potassium citrate and calcium hydroxide, the soluble chemical oxygen demand in the extracellular polymeric substance of the residual sludge is increased to 3125mg/L (as shown in FIG. 4). After 12 days of anaerobic digestion, the accumulated methane yield can reach 38.8mLCH4the/gVSS was increased by 428.9% (as shown in FIG. 5) compared to comparative example 3. The available phosphorus content in the digested sludge was 699.5mg/kg, which is an effective 25.6% increase over comparative example 3 (as shown in FIG. 6).
Example 5
An enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge comprises the following specific operations:
manually selecting large-particle impurities such as plastics, paper towels and the like from the collected excess sludge, and then adding water to dilute the impurities until the total solid content is 51.6 +/-1.3 g/L;
transferring the sludge obtained in the step (1) to a pretreatment reaction bottle, adding 20mM citric acid, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM of calcium hydroxide, and oscillating at 150rpm for reaction for 24 h;
transferring the sludge obtained in the step (2) into an anaerobic digestion reaction bottle, and inoculating anaerobic granular sludge with the solid content of 12.7 +/-0.9 g/L, wherein the inoculation ratio is 1.83 (excess sludge VS/anaerobic sludge VS); then stripping for 10min by nitrogen, discharging air to keep anaerobic condition, and immediately sealing the anaerobic digestion reactor; the temperature is controlled at 35 + -1 deg.C, the shaking intensity is 120rpm, and the digestion time is 12 days.
After pretreatment with citric acid and calcium hydroxide, the soluble chemical oxygen demand in the extracellular polymeric substance of the excess sludge is increased to 2895mg/L (as shown in FIG. 4). After 12 days of anaerobic digestion, the accumulated methane yield can reach 35.0mLCH4the/gVSS was increased by 376.6% compared to comparative example 3 (as shown in FIG. 5). The available phosphorus content in the digested sludge was 683.3mg/kg, which is an effective 22.7% increase over comparative example 3 (as shown in FIG. 6).
Comparative example 1
The basic contents of this comparative example are the same as example 1, except that: the comparative example is an anaerobic digestion of excess sludge without any pretreatment, and the specific operation is as follows:
manually selecting large-particle impurities such as plastics, paper towels and the like from the collected excess sludge, and then adding water to dilute the impurities until the total solid content is 54.4 +/-0.7 g/L.
Step (2), transferring the sludge obtained in the step (1) into a pretreatment reaction bottle, adding neither sodium citrate nor calcium hydroxide, and oscillating and reacting for 24 hours at 150 rpm;
transferring the sludge obtained in the step (2) into an anaerobic digestion reaction bottle, and inoculating anaerobic granular sludge with the solid content of 16.7 +/-0.5 g/L, wherein the inoculation ratio is 1.87 (excess sludge VS/anaerobic sludge VS); then stripping for 10min by nitrogen, discharging air to keep anaerobic condition, and immediately sealing the anaerobic digestion reactor; the temperature is controlled at 35 + -1 deg.C, the shaking intensity is 120rpm, and the digestion time is 12 days.
The soluble chemical oxygen demand in the extracellular polymeric substance of the excess sludge without any pretreatment was 620mg/L (as shown in FIG. 1). After 12 days of anaerobic digestion, the cumulative methane production was 8.4mLCH4/gVSS (as shown in FIG. 2). The available phosphorus content of the digested sludge was 599.0mg/kg (as shown in FIG. 3).
Comparative example 2
The basic contents of this comparative example are the same as example 1, except that: in the comparative example, sodium citrate is not added, and only calcium hydroxide is added to pretreat excess sludge for anaerobic digestion, and the specific operation is as follows:
manually selecting large-particle impurities such as plastics, paper towels and the like from the collected excess sludge, and then adding water to dilute the impurities until the total solid content is 54.4 +/-0.7 g/L g/L;
transferring the sludge obtained in the step (1) to a pretreatment reaction bottle, adding 0mM of sodium citrate, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM of calcium hydroxide, and oscillating at 150rpm for reaction for 24 h;
transferring the sludge obtained in the step (2) into an anaerobic digestion reaction bottle, and inoculating anaerobic granular sludge with the solid content of 16.7 +/-0.5 g/L, wherein the inoculation ratio is 1.87 (excess sludge VS/anaerobic sludge VS); then stripping for 10min by nitrogen, discharging air to keep anaerobic condition, and immediately sealing the anaerobic digestion reactor; the temperature is controlled at 35 + -1 deg.C, the shaking intensity is 120rpm, and the digestion time is 12 days.
After the calcium hydroxide pretreatment, the soluble chemical oxygen demand in the extracellular polymeric substances of the excess sludge is increased to 854.7mg/L (shown in figure 1). After 12 days of anaerobic digestion, the cumulative methane production was 13.9mLCH4the/gVSS was increased by 66.3% compared to comparative example 1 (as shown in FIG. 2). The available phosphorus content in the digested sludge was 661.8mg/kg, which was only 10.5% higher than that in comparative example 1 (as shown in FIG. 3).
Comparative example 3
The basic contents of this comparative example are the same as example 1, except that: the comparative example is an anaerobic digestion of excess sludge without any pretreatment, and the specific operation is as follows:
manually selecting large-particle impurities such as plastics, paper towels and the like from the collected excess sludge, and then adding water to dilute the impurities until the total solid content is 51.6 +/-1.3 g/L;
step (2), transferring the sludge obtained in the step (1) into a pretreatment reaction bottle, adding neither sodium citrate nor calcium hydroxide, and oscillating and reacting for 24 hours at 150 rpm;
transferring the sludge obtained in the step (2) into an anaerobic digestion reaction bottle, and inoculating anaerobic granular sludge with the solid content of 12.7 +/-0.9 g/L, wherein the inoculation ratio is 1.83 (excess sludge VS/anaerobic sludge VS); then stripping for 10min by nitrogen, discharging air to keep anaerobic condition, and immediately sealing the anaerobic digestion reactor; the temperature is controlled at 35 + -1 deg.C, the shaking intensity is 120rpm, and the digestion time is 12 days.
The soluble chemical oxygen demand in the extracellular polymeric substance of the excess sludge without any pretreatment was 590mg/L (as shown in FIG. 4). After 12 days of anaerobic digestion, the cumulative methane production was 7.3mLCH4/gVSS (as shown in FIG. 5). The content of available phosphorus in the digested sludge was 557mg/kg (as shown in FIG. 6).
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. An enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge comprises the following steps:
s10, removing large-particle impurities in the excess sludge to be treated, and then adding water for dilution to obtain diluted excess sludge;
s20, adding citric acid or citrate into the diluted excess sludge, stirring, then adding calcium hydroxide, stirring, and carrying out combined pretreatment on the diluted excess sludge;
s30, adding anaerobic granular sludge into the residual sludge after the combined pretreatment, and carrying out anaerobic digestion reaction to produce methane.
2. The enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 1, wherein the enhanced pretreatment method comprises the following steps: in the step S10, the total solid content of the diluted excess sludge is 50-60 g/L.
3. The enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 1, wherein the enhanced pretreatment method comprises the following steps: in step S20, the molar ratio between the added citric acid or citrate and the added calcium hydroxide is 1: (0.5-2), and the citrate is sodium citrate or potassium citrate.
4. The enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 1, wherein the enhanced pretreatment method comprises the following steps: in step S20, the total reaction time of the combined pretreatment is 20-24 h.
5. The enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 1, wherein the enhanced pretreatment method comprises the following steps: in step S30, the mass ratio of the volatile suspension between the added anaerobic granular sludge and the excess sludge is 1: (1-2).
6. The enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 1, wherein the enhanced pretreatment method comprises the following steps: in step S30, the reaction time of the anaerobic digestion reaction is 7-15 days, and the reaction temperature is 33-37 ℃.
7. The enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 4, wherein the enhanced pretreatment method comprises the following steps: in step S20, sodium citrate is added into the diluted excess sludge, the mixture is stirred for 1 hour at a stirring speed of 150-180 rpm, and then calcium hydroxide is added.
8. The enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to any one of claims 1-7, wherein the enhanced pretreatment method comprises the following steps: the residual sludge is dewatered sludge, the total solid content after dilution is 54.4 +/-0.7 g/L, the volatile organic compound is 23.8 +/-0.9 g/L, and the pH value is 6.93 +/-0.03.
9. The enhanced pretreatment method for improving the anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to any one of claims 1-7, wherein the enhanced pretreatment method comprises the following steps: the anaerobic granular sludge is taken from an anaerobic fermentation tank of a sewage treatment plant, the total solid content of the anaerobic granular sludge is 16.7 +/-0.5 g/L, the volatile organic compound is 12.7 +/-0.4 g/L, and the pH value is 6.5-7.8.
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