CN114195341B - Reinforced pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of excess sludge - Google Patents
Reinforced pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of excess sludge Download PDFInfo
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- 239000010802 sludge Substances 0.000 title claims abstract description 174
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 52
- 239000011574 phosphorus Substances 0.000 title claims abstract description 52
- 238000002203 pretreatment Methods 0.000 title claims abstract description 24
- 230000029087 digestion Effects 0.000 claims abstract description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 35
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 35
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 22
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- 239000002245 particle Substances 0.000 claims description 18
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 17
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 9
- 239000001508 potassium citrate Substances 0.000 claims description 7
- 229960002635 potassium citrate Drugs 0.000 claims description 7
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 7
- 235000011082 potassium citrates Nutrition 0.000 claims description 7
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- 239000005416 organic matter Substances 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 abstract description 11
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 5
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 abstract description 4
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- 238000010668 complexation reaction Methods 0.000 abstract 1
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- 238000005189 flocculation Methods 0.000 abstract 1
- 230000007928 solubilization Effects 0.000 abstract 1
- 238000005063 solubilization Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
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- 238000007664 blowing Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
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- 229910021645 metal ion Inorganic materials 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 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
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910052567 struvite Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000002411 adverse Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 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
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 150000004666 short chain fatty acids Chemical class 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a strengthening pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of excess sludge, belonging to the field of solid waste excess sludge recycling treatment and disposal. According to the invention, citric acid or citrate and calcium hydroxide are combined to pretreat the surplus sludge, and the complexation of the citric acid or citrate and calcium ions is adopted to relieve the heavy flocculation effect of the calcium ions on macromolecular organic matters, enhance the solubilization of the calcium hydroxide on the sludge, promote the anaerobic digestion of the surplus sludge to produce methane, and effectively increase the content of available phosphorus easily absorbed by plants in the digested sludge.
Description
Technical Field
The invention belongs to the field of solid waste excess sludge recycling treatment and disposal, and particularly relates to a strengthening pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of excess sludge.
Background
The activated sludge process is used as a main process for municipal sewage treatment, and a large amount of surplus sludge is produced as a by-product in the treatment process. The excess sludge has a complex composition and contains harmful substances such as heavy metals and pathogens, and if the treatment is improper, the ecological environment is adversely affected. On the other hand, the residual sludge contains rich organic matters such as protein and polysaccharide, and also contains inorganic resources such as nitrogen, phosphorus and the like. Therefore, the treatment of the excess sludge to realize stabilization, innocuity and recycling has great value and significance.
The current sludge treatment methods 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 output. Under the anaerobic condition, the facultative anaerobic and anaerobic microorganism groups convert organic matters in the residual sludge into clean energy sources such as short-chain fatty acid, methane and the like, and meanwhile, pathogenic bacteria and parasites (eggs) can be killed, so that the reduction, stabilization and recycling of the residual sludge are realized. The process of anaerobic digestion of sludge can be broadly divided into: a hydrolysis stage, a hydrogen-producing and acid-producing stage and a methane-producing stage. The hydrolysis stage becomes the rate limiting step in the anaerobic digestion process of sludge due to the poor biodegradability caused by the protection of the Extracellular Polymer (EPS) and the semi-rigid structured cell wall/membrane of the excess sludge. Thus, researchers have developed a series of excess sludge pretreatment techniques.
By searching, related applications are disclosed in the prior art, for example, publication No. CN107055986A, chinese patent application of 8 months and 18 days of publication No. 2017 discloses a high-pressure microwave sludge pretreatment method which comprises a pressurizing microwave technology, a heat alkali treatment technology and H 2 O 2 The pretreatment technology and the high-pressure flash evaporation technology are combined, so that the synergistic effect on the cell wall breaking of the sludge is achieved. However, the method is complex to operate, has strict requirements on microwave frequency, pressure, temperature and other conditions, and has high energy consumption.
For another example, chinese patent application publication No. CN109354349a, publication No. 2019, 2, 19 discloses a sludge pretreatment method and a sludge anaerobic fermentation acid production method. According to the method, the sludge is pretreated by adopting ultrasonic coupling persulfate, so that the EPS structure and microbial cells of the sludge are damaged, the cracking effect of the sludge is enhanced, and nutrients are provided for the subsequent fermentation stage. However, this method has a problem of high energy output requirement.
Chinese patent application publication No. CN112661376a, publication No. 2021, 4 and 16 discloses a method for pretreating municipal sludge and application thereof, wherein the method comprises mixing biochar solid acid with municipal sludge, performing hydrothermal pretreatment, filtering to obtain hydrolysate, and performing anaerobic digestion reaction on the hydrolysate to obtain biogas. The pretreatment method can promote the rapid degradation of extracellular polymers in sludge and lignocellulose in cell walls, and shortens the reaction time of the hydrolysis and acid production stage of municipal sludge. However, the system still has high energy requirements and ignores the treatment problem of municipal sludge.
In biochemical units of urban sewage treatment plants in China, more than 90% of phosphorus in the influent water is transferred to sludge, so that the residual sludge becomes a potential secondary phosphorus source. At present, a chemical precipitation method is mostly adopted for phosphorus recovery, including a magnesium ammonium phosphate method and a calcium phosphate salt method. For example, chinese patent application publication No. CN103641283a, publication No. 2014, 3 and 19 discloses an economical method for recovering phosphorus from surplus sludge, which promotes the release of phosphorus in surplus sludge by single-stage alkaline hydrolysis or secondary 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 pH. However, the method has high cost due to the addition of an expensive magnesium source, only the recovery of phosphorus in the pretreatment stage is considered, and the residual sludge after the release of the phosphorus still exists in the form of waste, so that the carbon resource in the recovered sludge is ignored. In the study of Siqi Tang et al (Siqi Tang, and Xunchangg Fei.Refraction Calcium Phosphate-Derived Phosphorus Fertilizer Based on Hydroxyapatite Nanoparticles for Nutrient delivery ACS Applied Nano Materials 4 (2), 1364-1376)), apatite phosphorus has higher phosphorus availability for plants, so that the recovery of phosphorus 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 and high energy requirement of the residual sludge and how to recycle carbon and phosphorus resources contained in the residual sludge in the prior art, the invention provides a strengthening pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of the residual sludge. According to the invention, citric acid or citrate and calcium hydroxide are combined to pretreat the surplus sludge, firstly, the citrate is used for chelating multivalent metal ions, so that the metal ions playing a bridging role in the extracellular polymer of the sludge are removed, thereby destroying sludge flocs, and on the basis, the hydroxide is used for further promoting the disintegration of the sludge flocs and the rupture of sludge cells, so that more organic matters are released from a solid phase to a liquid phase, and a rich matrix is provided for the 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 combine with phosphorus in the sludge to form calcium phosphate precipitates, so that phosphorus resources in the sludge are recovered.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a strengthening pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of excess sludge, which comprises the following steps:
s10, removing large-particle impurities in the residual sludge to be treated, and then adding water for dilution to obtain diluted residual sludge;
s20, adding citric acid or citrate into the diluted surplus sludge, stirring, then adding calcium hydroxide, stirring, and carrying out joint pretreatment on the diluted surplus 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 step S10, the total solid content of the diluted surplus 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 surplus sludge to control the concentration of sodium citrate to 10-40 mM, and then calcium hydroxide is added to control the concentration of calcium hydroxide to 20mM.
Preferably, in step S20, the total reaction time of the combined pretreatment is 20 to 24 hours.
Preferably, in step S30, the ratio of the Volume (VS) 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 surplus sludge, stirred at a stirring rate of 150 to 180rpm for 1 hour, and then calcium hydroxide is added.
Preferably, the surplus sludge is dehydrated 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 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 matter 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 strengthening pretreatment method for improving the anaerobic methanogenesis efficiency and the phosphorus availability of the residual sludge, citric acid or citrate and calcium hydroxide are used for pretreating the residual sludge for the first time, the citric acid or citrate is complexed with calcium ions, so that the reflocculation of the calcium ions is relieved/inhibited, the cracking of the calcium hydroxide as an alkali additive to sludge flocs and cells is effectively enhanced, and more granular organic matters are dissolved out; the method provides rich nutrient medium for subsequent anaerobic digestion methanogenesis, can effectively shorten the anaerobic digestion methanogenesis period and improve the methanogenesis efficiency;
(2) According to the strengthening pretreatment method for improving the anaerobic methanogenesis efficiency and the phosphorus availability of the excess sludge, citric acid or citrate is firstly acted on the extracellular polymer of the sludge, and metal ions which play a role in coordination and bridging in the extracellular polymer structure are removed through chelation, so that the effective release of extracellular enzymes is realized, and more available functional enzymes are provided for the subsequent anaerobic digestion process;
(3) According to the reinforced pretreatment method for improving the anaerobic methanogenesis efficiency and the phosphorus availability of the excess sludge, calcium hydroxide is added, so that on one hand, hydroxide can continuously act on sludge cells to crack the sludge cells; on one hand, the introduced calcium ions can also recycle the phosphorus resource sediment in the surplus sludge, so that the content of available phosphorus 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 sodium citrate and calcium hydroxide;
FIG. 2 is a graph of cumulative methane production after pretreatment with 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 a combination of potassium citrate and calcium hydroxide;
FIG. 5 is a graph of cumulative methane production after pretreatment of sludge with a combination of potassium citrate and calcium hydroxide;
FIG. 6 is a graph showing the content of available phosphorus (Olsen-P) in a pretreated digested sludge of a combination of potassium citrate and calcium hydroxide.
Detailed Description
The invention is further described below in connection with specific embodiments.
Example 1
The strengthening pretreatment method for improving the anaerobic methanogenesis efficiency and the phosphorus availability of the excess sludge comprises the following specific operations:
step (1), manually selecting large-particle impurities such as plastics, tissues and the like from the collected excess sludge (dehydrated sludge), and then adding water to dilute the large-particle impurities to the total solid content of 54.4+/-0.7 g/L;
step (2), transferring the sludge in the step (1) into a pretreatment reaction bottle, adding 10mM sodium citrate, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM calcium hydroxide, and oscillating at 150rpm for 24 hours;
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 inoculating proportion is 1.87 (residual sludge VS/anaerobic sludge VS); then blowing off for 10min by using nitrogen, exhausting air to maintain anaerobic conditions, and immediately sealing the anaerobic digestion reactor; the temperature was controlled at 35.+ -. 1 ℃, the shaking intensity was 120rpm, and the digestion time was 12 days.
After pretreatment with sodium citrate and calcium hydroxide, the dissolved chemical oxygen demand in the excess sludge extracellular polymer was increased to 1925mg/L (as shown in FIG. 1). After 12 days of anaerobic digestion, the accumulated methane yield can reach 22.3mLCH 4 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 content of available phosphorus in digested sludge was 721.5mg/kg, which was 20.4% higher than that in comparative example 1 (as shown in FIG. 3).
Example 2
The strengthening pretreatment method for improving the anaerobic methanogenesis efficiency and the phosphorus availability of the excess sludge comprises the following specific operations:
step (1), manually selecting large-particle impurities such as plastics, tissues and the like from the collected excess sludge, and then adding water to dilute the large-particle impurities to a total solid content of 54.4+/-0.7 g/L;
step (2), transferring the sludge in the step (1) into a pretreatment reaction bottle, adding 20mM sodium citrate, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM calcium hydroxide, and oscillating at 150rpm for 24 hours;
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 inoculating proportion is 1.87 (residual sludge VS/anaerobic sludge VS); then blowing off for 10min by using nitrogen, exhausting air to maintain anaerobic conditions, and immediately sealing the anaerobic digestion reactor; the temperature was controlled at 35.+ -. 1 ℃, the shaking intensity was 120rpm, and the digestion time was 12 days.
After pretreatment of sodium citrate and calcium hydroxide, the excess sludge is polymerized outside cellsThe dissolved 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 34.9mLCH 4 The gVSS was increased by 317% compared to comparative example 1 and by 150.8% compared to comparative example 2 (as shown in FIG. 2). The content of available phosphorus in digested sludge was 720.2mg/kg, which was 20.2% higher than that in comparative example 1 (as shown in FIG. 3).
Example 3
The strengthening pretreatment method for improving the anaerobic methanogenesis efficiency and the phosphorus availability of the excess sludge comprises the following specific operations:
step (1), manually selecting large-particle impurities such as plastics, tissues and the like from the collected excess sludge, and then adding water to dilute the large-particle impurities to a total solid content of 54.4+/-0.7 g/L;
step (2), transferring the sludge in the step (1) into a pretreatment reaction bottle, adding 40mM sodium citrate, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM calcium hydroxide, and oscillating at 150rpm for 24 hours;
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 inoculating proportion is 1.87 (residual sludge VS/anaerobic sludge VS); then blowing off for 10min by using nitrogen, exhausting air to maintain anaerobic conditions, and immediately sealing the anaerobic digestion reactor; the temperature was controlled at 35.+ -. 1 ℃, the shaking intensity was 120rpm, and the digestion time was 12 days.
After pretreatment with sodium citrate and calcium hydroxide, the dissolved chemical oxygen demand in the extracellular polymer of the excess sludge was increased to 6690mg/L (as shown in FIG. 1). After 12 days of anaerobic digestion, the accumulated methane yield can reach 41.4mLCH 4 Per gVSS, 395.6% higher than comparative example 1 and 198.1% higher than comparative example 2 (as shown in FIG. 2). The content of available phosphorus in digested sludge was 950.2mg/kg, which was increased by 58.6% as compared with comparative example 1 (as shown in FIG. 3).
Example 4
The strengthening pretreatment method for improving the anaerobic methanogenesis efficiency and the phosphorus availability of the excess sludge comprises the following specific operations:
step (1), manually selecting large-particle impurities such as plastics, tissues and the like from the collected excess sludge, and then adding water to dilute the large-particle impurities to a total solid content of 51.6+/-1.3 g/L;
step (2), transferring the sludge obtained in the step (1) into a pretreatment reaction bottle, adding 20mM potassium citrate, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM calcium hydroxide, and oscillating at 150rpm for 24 hours;
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 inoculating proportion is 1.83 (excess sludge VS/anaerobic sludge VS); then blowing off for 10min by using nitrogen, exhausting air to maintain anaerobic conditions, and immediately sealing the anaerobic digestion reactor; the temperature was controlled at 35.+ -. 1 ℃, the shaking intensity was 120rpm, and the digestion time was 12 days.
After pretreatment with potassium citrate and calcium hydroxide, the dissolved chemical oxygen demand in the extracellular polymer of the excess sludge increased to 3125mg/L (as shown in FIG. 4). After 12 days of anaerobic digestion, the accumulated methane yield can reach 38.8mLCH 4 Per gVSS, 428.9% higher than comparative example 3 (as shown in FIG. 5). The content of available phosphorus in digested sludge was 699.5mg/kg, which was effectively improved by 25.6% as compared with comparative example 3 (as shown in FIG. 6).
Example 5
The strengthening pretreatment method for improving the anaerobic methanogenesis efficiency and the phosphorus availability of the excess sludge comprises the following specific operations:
step (1), manually selecting large-particle impurities such as plastics, tissues and the like from the collected excess sludge, and then adding water to dilute the large-particle impurities to a total solid content of 51.6+/-1.3 g/L;
step (2), transferring the sludge in the step (1) into a pretreatment reaction bottle, adding 20mM citric acid, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM calcium hydroxide, and oscillating at 150rpm for 24 hours;
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 inoculating proportion is 1.83 (excess sludge VS/anaerobic sludge VS); then blowing off for 10min by using nitrogen, exhausting air to maintain anaerobic conditions, and immediately sealing the anaerobic digestion reactor; the temperature was controlled at 35.+ -. 1 ℃, the shaking intensity was 120rpm, and the digestion time was 12 days.
After pretreatment with citric acid and calcium hydroxide, the dissolved chemical oxygen demand in the excess sludge extracellular polymer was increased to 2895mg/L (as shown in FIG. 4). After 12 days of anaerobic digestion, the accumulated methane yield can reach 35.0mLCH 4 Per gVSS, 376.6% higher than comparative example 3 (as shown in FIG. 5). The content of available phosphorus in digested sludge was 683.3mg/kg, which was 22.7% higher than that in comparative example 3 (as shown in FIG. 6).
Comparative example 1
The basic content of this comparative example is the same as in example 1, except that: the comparative example is that the residual sludge which is not pretreated in any way is subjected to anaerobic digestion, and the specific operation is as follows:
and (1) manually selecting large-particle impurities such as plastics, tissues and the like from the collected excess sludge, and then adding water to dilute the large-particle impurities to the total solid content of 54.4+/-0.7 g/L.
Transferring the sludge obtained in the step (1) into a pretreatment reaction bottle, and carrying out oscillating reaction for 24 hours at 150rpm without adding sodium citrate or calcium hydroxide;
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 inoculating proportion is 1.87 (residual sludge VS/anaerobic sludge VS); then blowing off for 10min by using nitrogen, exhausting air to maintain anaerobic conditions, and immediately sealing the anaerobic digestion reactor; the temperature was controlled at 35.+ -. 1 ℃, the shaking intensity was 120rpm, and the digestion time was 12 days.
The extracellular polymer of the excess sludge, which was not subjected to any pretreatment, had a dissolved chemical oxygen demand of 620mg/L (as shown in FIG. 1). After 12 days anaerobic digestion, the cumulative methane yield was 8.4mLCH 4 gVSS (as shown in FIG. 2). The content of available phosphorus in the digested sludge was 599.0mg/kg (as shown in FIG. 3).
Comparative example 2
The basic content of this comparative example is the same as in example 1, except that: in the comparative example, sodium citrate is not added, and only calcium hydroxide is added to pretreat the residual sludge for anaerobic digestion, and the specific operation is as follows:
step (1), manually selecting large-particle impurities such as plastics, tissues and the like from the collected excess sludge, and then adding water to dilute the large-particle impurities to a total solid content of 54.4+/-0.7 g/L g/L;
step (2), transferring the sludge in the step (1) into a pretreatment reaction bottle, adding sodium citrate 0mM, and carrying out oscillation reaction for 1h at 150 rpm; then adding 20mM calcium hydroxide, and oscillating at 150rpm for 24 hours;
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 inoculating proportion is 1.87 (residual sludge VS/anaerobic sludge VS); then blowing off for 10min by using nitrogen, exhausting air to maintain anaerobic conditions, and immediately sealing the anaerobic digestion reactor; the temperature was controlled at 35.+ -. 1 ℃, the shaking intensity was 120rpm, and the digestion time was 12 days.
After pretreatment with calcium hydroxide, the dissolved chemical oxygen demand in the extracellular polymer of the excess sludge was increased to 854.7mg/L (as shown in FIG. 1). After 12 days of anaerobic digestion, the cumulative methane yield was 13.9mLCH 4 The gVSS was increased by 66.3% as compared to comparative example 1 (as shown in FIG. 2). The content of available phosphorus in digested sludge was 661.8mg/kg, which was increased by only 10.5% as compared with comparative example 1 (as shown in FIG. 3).
Comparative example 3
The basic content of this comparative example is the same as in example 1, except that: the comparative example is that the residual sludge which is not pretreated in any way is subjected to anaerobic digestion, and the specific operation is as follows:
step (1), manually selecting large-particle impurities such as plastics, tissues and the like from the collected excess sludge, and then adding water to dilute the large-particle impurities to a total solid content of 51.6+/-1.3 g/L;
transferring the sludge obtained in the step (1) into a pretreatment reaction bottle, and carrying out oscillating reaction for 24 hours at 150rpm without adding sodium citrate or calcium hydroxide;
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 inoculating proportion is 1.83 (excess sludge VS/anaerobic sludge VS); then blowing off for 10min by using nitrogen, exhausting air to maintain anaerobic conditions, and immediately sealing the anaerobic digestion reactor; the temperature was controlled at 35.+ -. 1 ℃, the shaking intensity was 120rpm, and the digestion time was 12 days.
The extracellular polymer of the excess sludge, which was not subjected to any pretreatment, had a dissolved chemical oxygen demand of 590mg/L (as shown in FIG. 4). After 12 days of anaerobic digestion, the cumulative methane yield was 7.3mLCH 4 gVSS (as shown in FIG. 5). The content of available phosphorus in the digested sludge was 557mg/kg (as shown in FIG. 6).
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (7)
1. An enhanced pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of excess sludge comprises the following steps:
s10, removing large-particle impurities in the residual sludge to be treated, and then adding water for dilution to obtain diluted residual sludge with the total solid content of 50-60 g/L;
s20, adding citric acid or citrate into the diluted surplus sludge, stirring, then adding calcium hydroxide, stirring, and carrying out joint pretreatment on the diluted surplus sludge, wherein the molar ratio of the added citric acid or citrate to the added calcium hydroxide is 1: (0.5-2), and the total reaction time of the combined pretreatment is 20-24 h;
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 anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 1, wherein the method comprises the following steps: in step S20, the citrate is sodium citrate or potassium citrate.
3. The enhanced pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 1, wherein the method comprises the following steps: in step S30, the mass ratio of volatile suspended matter between the added anaerobic granular sludge and the residual sludge is 1: (1-2).
4. The enhanced pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 1, wherein the method comprises the following steps: in the step S30, the reaction time of the anaerobic digestion reaction is 7-15 days, and the reaction temperature is 33-37 ℃.
5. The enhanced pretreatment method for improving anaerobic methanogenesis efficiency and phosphorus availability of excess sludge according to claim 1, wherein the method comprises the following steps: in step S20, sodium citrate is added to the diluted surplus sludge, stirred for 1 hour at a stirring rate of 150 to 180rpm, and then calcium hydroxide is added.
6. An enhanced pretreatment method for improving anaerobic methanogenesis efficiency and availability of phosphorus of excess sludge according to any one of claims 1 to 5, wherein: the residual sludge is dehydrated 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.
7. An enhanced pretreatment method for improving anaerobic methanogenesis efficiency and availability of phosphorus of excess sludge according to any one of claims 1 to 5, wherein: 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 matter is 12.7+/-0.4 g/L, and the pH value is 6.5-7.8.
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| CN115043563A (en) * | 2022-06-28 | 2022-09-13 | 广州市市政工程设计研究总院有限公司 | Device and method for strengthening anaerobic fermentation of excess sludge and strengthening nitrogen and phosphorus removal of sewage by fermentation liquor backflow |
| CN115432897A (en) * | 2022-10-25 | 2022-12-06 | 西安建筑科技大学 | Method for promoting excess sludge to produce methane based on citric acid reinforced zero-valent iron |
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