CN116692954B - Fe-Fe 2 O 3 Preparation method of core-shell material and anaerobic sludge fermentation method - Google Patents
Fe-Fe 2 O 3 Preparation method of core-shell material and anaerobic sludge fermentation method Download PDFInfo
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- CN116692954B CN116692954B CN202310864153.XA CN202310864153A CN116692954B CN 116692954 B CN116692954 B CN 116692954B CN 202310864153 A CN202310864153 A CN 202310864153A CN 116692954 B CN116692954 B CN 116692954B
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- 239000010802 sludge Substances 0.000 title claims abstract description 219
- 238000000855 fermentation Methods 0.000 title claims abstract description 169
- 229910017108 Fe—Fe Inorganic materials 0.000 title claims abstract description 138
- 239000011258 core-shell material Substances 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000004151 fermentation Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000006228 supernatant Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 19
- 230000002378 acidificating effect Effects 0.000 claims abstract description 17
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000003638 chemical reducing agent Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 16
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 15
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- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 150000004666 short chain fatty acids Chemical class 0.000 abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 22
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- 239000011574 phosphorus Substances 0.000 abstract description 22
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 6
- 239000010452 phosphate Substances 0.000 abstract description 6
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
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- 241001142109 Chloroflexi Species 0.000 description 2
- 241000192125 Firmicutes Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000192142 Proteobacteria Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- GEHSZWRGPHDXJO-ALELSXGZSA-N coenzyme f420 Chemical compound OC(=O)CC[C@@H](C(O)=O)NC(=O)CC[C@H](C(O)=O)NC(=O)[C@@H](C)O[P@@](O)(=O)OC[C@H](O)[C@@H](O)[C@H](O)CN1C2=CC(O)=CC=C2C=C2C1=NC(=O)NC2=O GEHSZWRGPHDXJO-ALELSXGZSA-N 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
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- QAQREVBBADEHPA-IEXPHMLFSA-N propionyl-CoA Chemical group O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCSC(=O)CC)O[C@H]1N1C2=NC=NC(N)=C2N=C1 QAQREVBBADEHPA-IEXPHMLFSA-N 0.000 description 2
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- 210000002966 serum Anatomy 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention provides Fe-Fe 2 O 3 A preparation method of a core-shell material and a sludge anaerobic fermentation method. The anaerobic fermentation method of sludge of the invention adds Fe-Fe into the sludge 2 O 3 Anaerobic fermentation of core-shell material, destruction of microbial extracellular polymeric substance structure, promotion of protein and polysaccharide elution, and destruction of cell wall structure under acidic, alkaline or neutral conditions, release of intracellular substances, and the use of Fe-Fe 2 O 3 The electron transfer in the anaerobic fermentation process is enhanced, acid-producing functional bacteria are enriched, the yield of short chain fatty acid is effectively improved, and in addition, fe-Fe in the sludge fermentation process is improved 2 O 3 Releasing ferrous ions, combining with phosphate to form precipitate in anaerobic environment, and Fe-Fe 2 O 3 Or the generated precipitate can adsorb part of phosphate to reduce the content of phosphorus element; the anaerobic fermentation supernatant obtained by the method has extremely low phosphorus content, and the anaerobic fermentation supernatant used as a carbon source has little influence on the subsequent biological treatment section of the sewage plant.
Description
Technical Field
The invention relates to the technical field of sludge recycling, in particular to Fe-Fe 2 O 3 A preparation method of a core-shell material and a sludge anaerobic fermentation method.
Background
Along with fourteen-five planning and the proposal of a double-carbon target, the industrial revolution in the transformation of economic high-quality development of China is continuously deepened, and the environmental pollution, resource and energy crisis become the urgent need of the China. By the end of 2021, the national urban sewage treatment capacity reaches 2.1 hundred million cubic meters per day, the national urban and county sludge treatment capacity reaches 10.0 ten thousand tons per day, and the per ton sludge treatment cost reaches 400 yuan, so that in the sewage treatment process, a large amount of surplus sludge discharged by the urban sewage treatment plant every day occupies a large area, and high treatment and disposal cost is required, and the sewage treatment plant becomes another form of pollution if improperly treated. Meanwhile, the residual sludge contains a large amount of organic matters in the forms of soluble polysaccharide, soluble protein and the like, and can be converted into fatty acid through the action of microorganisms in the anaerobic fermentation process, so that the recycling of the sludge is realized. Short Chain Fatty Acids (SCFAs) generated by anaerobic fermentation of sludge are a carbon source which is easy to use in the biological denitrification and dephosphorization process, so that the anaerobic fermentation treatment of the residual sludge can realize the reduction of the sludge and simultaneously generate the SCFAs.
The traditional anaerobic fermentation mode has the problems of low acid yield, high cost, insufficient utilization of sludge organic matters and over-high phosphorus concentration in supernatant. Therefore, there is a need for improvements to existing anaerobic sludge fermentation modes.
Disclosure of Invention
In view of this, the present invention provides a Fe-Fe 2 O 3 The preparation method of the core-shell material and the anaerobic sludge fermentation method are used for solving the defects in the prior art.
In a first aspect, the present invention provides a Fe-Fe 2 O 3 The preparation method of the core-shell material comprises the following steps:
adding ferric salt into water to obtain ferric iron solution;
adding a reducing agent into water to obtain a reducing agent solution;
adding a reducing agent solution into a ferric iron solution, reacting, filtering and drying to obtain Fe-Fe 2 O 3 A core-shell material;
and/or, the ferric salt comprises FeCl 3 At least one of ferric sulfate and ferric nitrate;
and/or, the reductionThe agent comprises NaBH 4 、Al(BH 4 ) 3 、KBH 4 At least one of hydrazine hydrate.
And/or adding a reducing agent solution to the ferric iron solution at a flow rate of 0.1 to 0.3 mL/s;
and/or adding ferric salt into water, wherein the mass ratio of the ferric salt to the water is (1-5) (800-1200);
and/or, in the step of adding the reducing agent into the water, the mass ratio of the reducing agent to the water is (3-9) (300-500).
In a second aspect, the invention also provides a sludge anaerobic fermentation method, which comprises the following steps:
providing the Fe-Fe prepared by the preparation method 2 O 3 A core-shell material;
adding sludge to be treated into a sludge anaerobic fermentation tank, and adding Fe-Fe 2 O 3 And (3) the core-shell material is used for adjusting the sludge to be treated to be acidic, alkaline or neutral, and carrying out anaerobic fermentation at the temperature of 33-37 ℃.
Preferably, in the sludge anaerobic fermentation method, the concentration of the sludge to be treated is 15-100 g/L, and the MLVSS/MLSS value in the sludge to be treated is more than 0.5.
Preferably, in the anaerobic sludge fermentation method, the Fe-Fe 2 O 3 The addition amount of the core-shell material is as follows: 0.1-0.5 g Fe-Fe is added into each g VSS 2 O 3 Core shell material.
Preferably, in the anaerobic sludge fermentation method, in the step of adjusting the sludge to be treated to be acidic or alkaline or neutral, the acidic pH is 5-6, and the alkaline pH is 8-12.
Preferably, in the anaerobic fermentation method of the sludge, the oxidation-reduction potential is controlled to be-300 mV to-200 mV in the anaerobic fermentation process.
Preferably, in the sludge anaerobic fermentation method, sludge to be treated is added into a sludge anaerobic fermentation tank, and Fe-Fe is added 2 O 3 The core-shell material is used for adjusting the sludge to be treated to be acidic, alkaline or neutral, stirring the sludge at the temperature of 33-37 ℃ for anaerobic fermentation, and standing the sludgeSeparating water and treated sludge;
and then Fe-Fe is separated from the treated sludge 2 O 3 Core-shell material to obtain separated Fe-Fe 2 O 3 A core-shell material;
separating Fe-Fe 2 O 3 And (3) re-adding the core-shell material into a sludge anaerobic fermentation tank to perform anaerobic fermentation on sludge to be treated.
Preferably, the anaerobic sludge fermentation method comprises the following steps:
storing sludge to be treated into a sludge storage tank, and pumping the sludge to be treated in the sludge storage tank into a pretreatment tank by using a first sludge pump;
Fe-Fe 2 O 3 Adding core-shell material into a pretreatment tank, and using a second sludge pump to treat sludge and Fe-Fe in the pretreatment tank 2 O 3 Pumping the core-shell material into an anaerobic fermentation tank for anaerobic fermentation;
separating the fermented sludge into a sedimentation tank;
pumping the bottom sludge precipitated in the sedimentation tank into a magnetic drum, and recovering the separated Fe-Fe through the magnetic drum 2 O 3 A core-shell material;
separated Fe-Fe 2 O 3 The core-shell material is added into a pretreatment tank, and anaerobic fermentation of the sludge to be treated is carried out for the next period.
Preferably, the sludge anaerobic fermentation method is to separate Fe-Fe 2 O 3 Adding core-shell material into pretreatment tank, and adding new Fe-Fe 2 O 3 Core-shell materials in which Fe-Fe is newly produced 2 O 3 Core-shell material and separated Fe-Fe 2 O 3 The mass ratio of the core-shell materials is 1 (1-4).
Preferably, in the anaerobic sludge fermentation method, after the fermented sludge is separated into a sedimentation tank, supernatant fluid is pumped into an acid liquid storage tank, and is pumped into an AAO biological tank through a dosing pump to serve as a carbon source of the AAO biological tank.
Compared with the prior art, the invention has the following beneficial effects:
1. Fe-Fe prepared by the method 2 O 3 Preparation method of core-shell material, reducing trivalent iron by using reducing agent to obtain Fe-Fe 2 O 3 Core-shell material using Fe as core layer and Fe 2 O 3 Is a shell layer; fe-Fe prepared by the method 2 O 3 The core-shell structure material can remarkably improve the yield of SCFAs in anaerobic sludge fermentation, greatly improve the value of fermentation supernatant as a carbon source, and show potential of practical application and popularization;
2. the anaerobic fermentation method of sludge of the invention adds Fe-Fe into the sludge 2 O 3 Anaerobic fermentation of core-shell material, destruction of microbial extracellular polymeric substance structure, promotion of protein and polysaccharide elution, and destruction of cell wall structure under acidic, alkaline or neutral conditions, release of intracellular substances, and the use of Fe-Fe 2 O 3 The electron transfer in the anaerobic fermentation process is enhanced, acid-producing functional bacteria are enriched, the yield of short chain fatty acid is effectively improved, and in addition, fe-Fe in the sludge fermentation process is improved 2 O 3 Releasing ferrous ions, combining with phosphate to form precipitate in anaerobic environment, and Fe-Fe 2 O 3 Or the generated precipitate can adsorb part of phosphate to reduce the content of phosphorus element; according to the sludge anaerobic fermentation method, the phosphorus content in the obtained anaerobic fermentation supernatant is extremely low, and the anaerobic fermentation supernatant is used as a carbon source and has little influence on the subsequent biological treatment section of a sewage plant.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 shows an anaerobic fermentation apparatus according to the present invention;
FIG. 2 shows the Fe-Fe prepared in example 1 of the present invention 2 O 3 Particle size distribution diagram of core-shell material;
FIGS. 3 to 5 show the Fe-Fe prepared in example 1 of the present invention 2 O 3 SEM images of core-shell material at different fold;
FIGS. 6 to 8 show the Fe-Fe prepared in example 1 of the present invention 2 O 3 Mapping graph of core-shell material;
FIG. 9 shows the Fe-Fe prepared in example 1 of the present invention 2 O 3 A total iron oxygen element distribution diagram of the core-shell material;
FIG. 10 shows the Fe-Fe prepared in example 1 of the present invention 2 O 3 XRD pattern of core-shell material;
FIG. 11 shows the Fe-Fe prepared in example 1 of the present invention 2 O 3 XPS diagram of core-shell material;
FIG. 12 is a graph showing the Fe@Fe prepared in comparative example 1 3 O 4 Particle size distribution of the material;
FIGS. 13 to 15 show Fe@Fe prepared in comparative example 1 3 O 4 SEM images of the material at different fold;
FIGS. 16 to 18 show Fe@Fe prepared in comparative example 1 3 O 4 Mapping graph of material;
FIG. 19 is a graph showing the Fe@Fe prepared in comparative example 1 3 O 4 XRD pattern of the material;
FIG. 20 is a graph showing the Fe@Fe prepared in comparative example 1 3 O 4 XPS diagram of material;
FIG. 21 is a graph showing the changes over time in the yields of short chain fatty acids in supernatants after anaerobic fermentation according to the method of example 2, comparative examples 2 to 4;
FIG. 22 is a graph showing the change with time of the content of the soluble organic matters in the supernatant after anaerobic fermentation according to the method of example 2 and comparative examples 2 to 4;
FIG. 23 is a graph showing the total phosphorus content of the supernatant after anaerobic fermentation as in example 2 and comparative examples 2 to 4, over time;
FIGS. 24 to 25 are graphs showing the short chain fatty acid yield of anaerobic fermentation supernatants and the total phosphorus content of anaerobic fermentation supernatants over time according to example 3 at different pH values;
FIG. 26 is a graph showing the dissolution of organic matter from sludge after pretreatment at different pH values according to example 3;
FIGS. 27 to 28 show different Fe-Fe according to example 4 2 O 3 A change chart of the yield of short chain fatty acid of the anaerobic fermentation supernatant and the total phosphorus content of the anaerobic fermentation supernatant with time under the addition amount of the core-shell material;
FIG. 29 shows the different Fe-Fe values according to example 4 2 O 3 A diagram of the dissolution situation of the pretreated sludge organic matters under the adding amount of the core-shell material;
FIG. 30 shows the difference of Fe-Fe according to example 5 2 O 3 A graph of the yield of short chain fatty acids of the supernatant of anaerobic fermentation under the core-shell material over time;
FIG. 31 is an XRD pattern of sludge obtained after anaerobic fermentation at pH 6 in example 3.
FIG. 32 is a graph showing the change in the activity of key enzymes at different pretreatment pH according to example 3;
FIG. 33 shows the different Fe-Fe values according to example 4 2 O 3 An activity change diagram of key enzyme under the addition amount of core-shell materials;
FIG. 34 is a gate level distribution (ten times before relative abundance in%) of bacterial populations in sludge at different pretreatment pH according to example 3;
FIG. 35 is a distribution of genus levels (relative abundance in%) of bacterial and archaea populations in sludge at different pretreatment pH's according to example 3;
FIG. 36 shows the different Fe-Fe values according to example 4 2 O 3 The gate level distribution (ten positions in front of relative abundance, unit is%) of bacterial population in the sludge under the addition amount of the core-shell material;
FIG. 37 shows the difference of Fe-Fe according to example 4 2 O 3 The bacterial population in the sludge is horizontally distributed (ten positions in front of the relative abundance, the unit is%) under the dosage of the core-shell material.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the embodiments of the present invention, but it should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The following description of the embodiments is not intended to limit the preferred embodiments. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the invention may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the ranges, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The embodiment of the application provides Fe-Fe 2 O 3 The preparation method of the core-shell material comprises the following steps:
s1, adding ferric salt into water to obtain a ferric iron solution;
s2, adding a reducing agent into water to obtain a reducing agent solution;
s3, adding the reducer solution into the ferric iron solution, reacting, filtering and drying to obtain Fe-Fe 2 O 3 Core shell material.
Fe-Fe of the present invention 2 O 3 Preparation method of core-shell material, reducing trivalent iron by using reducing agent to obtain Fe-Fe 2 O 3 Core-shell material using Fe as core layer and Fe 2 O 3 Is a shell layer; fe-Fe prepared by the method 2 O 3 The core-shell structure material can obviously improve the yield of SCFAs in anaerobic sludge fermentation, and greatly improve the fermentation supernatantThe value of the liquid as a carbon source shows potential of practical application and popularization.
In some embodiments, the ferric salt comprises FeCl 3 At least one of ferric sulfate and ferric nitrate.
In some embodiments, the reducing agent comprises NaBH 4 、Al(BH 4 ) 3 、KBH 4 At least one of hydrazine hydrate.
In some embodiments, the reducing agent solution is added to the ferric iron solution at a flow rate of 0.1 to 0.3 mL/s. Specifically, a reducing agent solution is injected into the ferric iron solution using a peristaltic pump.
In some embodiments, in the step of adding the ferric salt to the water, the mass ratio of the ferric salt to the water is (1-5): 800-1200;
in some embodiments, the reducing agent is added to the water in a mass ratio of reducing agent to water of (3-9) (300-500).
Specifically, the Fe-Fe of the present invention 2 O 3 The preparation method of the core-shell material is carried out under normal pressure in the whole synthesis process without inert gas or vacuum protection; the ferric iron solution is added to the flask and then the reducing agent solution is added dropwise, during which the flask is shaken with a water bath shaker (magnetic stirring cannot be used, otherwise magnetic induction aggregation of the iron particles would result therefrom), followed by the reducing agent solution (e.g., naBH 4 Solution) which emits a large amount of gas, a fluffy black precipitate appears on the surface of the solution, and a reducing agent solution (such as NaBH) 4 Solution), collecting black precipitate, washing with deionized water, and drying under nitrogen flow or vacuum to obtain Fe-Fe 2 O 3 Core shell material.
Based on the same inventive concept, the invention also provides a sludge anaerobic fermentation method, which comprises the following steps:
s1, providing Fe-Fe prepared by the preparation method 2 O 3 A core-shell material;
s2, adding sludge to be treated into a sludge anaerobic fermentation tank, and adding Fe-Fe 2 O 3 Core-shell material, conditioning to beThe treated sludge is acidic or alkaline or neutral, and anaerobic fermentation is carried out at the temperature of 33-37 ℃.
The anaerobic fermentation method of sludge of the invention adds Fe-Fe into the sludge 2 O 3 Anaerobic fermentation of core-shell material, destruction of microbial extracellular polymer structure, promotion of protein and polysaccharide elution, and destruction of cell wall structure under acidic, alkaline or neutral (i.e. pH 7) conditions, release of intracellular substances, by use of Fe-Fe 2 O 3 The electron transfer in the anaerobic fermentation process is enhanced, acid-producing functional bacteria are enriched, the yield of short chain fatty acid is effectively improved, in addition, the sludge fermentation process promotes the reduction of ferric iron into ferrous ions, and the ferric iron is combined with phosphate to generate precipitate in an anaerobic environment, and meanwhile, fe-Fe is produced 2 O 3 Or the generated precipitate substance can adsorb partial phosphate to reduce the content of phosphorus element.
The anaerobic fermentation method of the sludge aims at the problems of high cost, insufficient utilization of sludge organic matters and overhigh concentration of phosphorus in supernatant in the traditional anaerobic fermentation mode; in order to realize anaerobic fermentation of sludge to produce acid and use the acid as a carbon source, the invention adopts Fe-Fe 2 O 3 The anaerobic fermentation mode of the core-shell material can improve the yield of SCFAs, reduce the content of phosphorus in supernatant and reduce the influence on the subsequent biological treatment section.
In some embodiments, the sludge to be treated has a concentration of 15-100 g/L and a MLVSS/MLSS value in the sludge to be treated of greater than 0.5.
Specifically, MLVSS in the sludge is the volatile solid suspension concentration, and MLSS is the total solid suspension concentration; MLVSS/MLSS represents the content of volatile substances in sludge, and is related to the activity of the sludge.
In some embodiments, fe-Fe 2 O 3 The addition amount of the core-shell material is as follows: 0.1 to 0.5g of Fe-Fe is added per g of VSS (representing the mass of volatile solid suspended matters in the sludge) 2 O 3 Core shell material. Namely Fe-Fe 2 O 3 The adding amount of the core-shell material is determined according to the mass of VSS volatile solid suspension in the sludge, and Fe-Fe 2 O 3 The adding amount of the core-shell material is 0.1-0.5 g/g VSS sludge volatilizing amountMass of the primary suspended solids.
In some embodiments, in the step of adjusting the sludge to be treated to be acidic or alkaline or neutral, the acidic pH is 5 to 6 and the alkaline pH is 8 to 12.
Specifically, hydrochloric acid or sulfuric acid is used for adjusting the treated sludge to be acidic, and sodium hydroxide or ammonia water is used for adjusting the sludge to be alkaline.
In some embodiments, the oxidation-reduction potential is controlled to be-300 mV to-200 mV during anaerobic fermentation. Specifically, anaerobic fermentation is controlled by controlling oxidation-reduction potential in the anaerobic fermentation process, and specific oxidation-reduction potential can be controlled by aeration and stirring.
In some embodiments, the sludge to be treated is added to a sludge anaerobic fermentation tank, and Fe-Fe is added 2 O 3 The core-shell material is used for adjusting the sludge to be treated to be acidic or alkaline or neutral, stirring the sludge at the temperature of 33-37 ℃ for anaerobic fermentation, standing the sludge, and separating water and treated sludge;
and then Fe-Fe is separated from the treated sludge 2 O 3 Core-shell material to obtain separated Fe-Fe 2 O 3 Core-shell material and separated sludge;
separating Fe-Fe 2 O 3 And (3) re-adding the core-shell material into a sludge anaerobic fermentation tank to perform anaerobic fermentation on sludge to be treated.
In some embodiments, the separated Fe-Fe is added 2 O 3 The core-shell material is anaerobic fermented and simultaneously added with new Fe-Fe 2 O 3 Core-shell materials in which Fe-Fe is newly produced 2 O 3 Core-shell material and separated Fe-Fe 2 O 3 The mass ratio of the core-shell materials is 1 (1-4).
In some embodiments, a method of anaerobic fermentation of sludge comprises the steps of:
s1, storing sludge to be treated in a sludge storage tank, and pumping the sludge to be treated in the sludge storage tank into a pretreatment tank by using a first sludge pump;
s2, fe-Fe 2 O 3 The core-shell material is added into a pretreatment tank for benefitingSludge to be treated and Fe-Fe in the pretreatment tank are pumped by a second sludge pump 2 O 3 Pumping the core-shell material into an anaerobic fermentation tank for anaerobic fermentation;
s3, separating the fermented sludge into a sedimentation tank;
s4, pumping the bottom sludge precipitated in the sedimentation tank into a magnetic drum, and recovering the separated Fe-Fe through the magnetic drum 2 O 3 A core-shell material;
s5, separated Fe-Fe 2 O 3 The core-shell material is added into a pretreatment tank, and anaerobic fermentation of the sludge to be treated is carried out for the next period.
Specifically, the anaerobic fermentation device shown in fig. 1 is used for anaerobic fermentation, and comprises the following steps: a sludge storage tank 1, a pretreatment tank 2, an anaerobic fermentation tank 3, a sedimentation tank 4, an acid liquid storage tank 5, an AAO biological tank 6, a magnetic drum 7, a first sludge pump 8, a second sludge pump 9, a third sludge pump 10 and a dosing pump 11;
wherein the sludge a to be treated is added into the sludge storage tank 1, the sludge a to be treated in the sludge storage tank 1 is pumped into the pretreatment tank 2 under the action of the first sludge pump 8, and Fe-Fe is added into the pretreatment tank 2 2 O 3 The core-shell material b is used for preprocessing the sludge to be processed and Fe-Fe in the tank 2 under the action of the second sludge pump 9 2 O 3 Pumping the core-shell material into an anaerobic fermentation tank 3 (provided with a stirring device therein) for stirring anaerobic fermentation; the fermented sludge is separated into a sedimentation tank 4, and the supernatant is pumped into an acid liquid storage tank 5 and pumped into an AAO biological tank 6 through a dosing pump 11 to be used as a biological tank carbon source.
Further, sludge to be treated and Fe-Fe 2 O 3 After the core-shell material is fermented in the anaerobic fermentation tank 3, separating out water, storing the fermented sludge into a sedimentation tank 4, pumping the bottom sludge precipitated in the sedimentation tank 4 into a magnetic drum 7 through a third sludge pump 10, and recovering the separated Fe-Fe through the magnetic drum 7 2 O 3 Core-shell material c, separated Fe-Fe 2 O 3 The core-shell material c is added into the pretreatment tank 2, namely, the separated Fe-Fe 2 O 3 The core-shell material c is reused after the next round of anaerobic fermentation.
Anaerobic fermentation is carried out by adopting the device shown in fig. 1, a semi-continuous flow process is adopted, and four processes of stirring, standing, water yielding and mud feeding are circularly carried out; the effluent of the anaerobic fermentation tank can be used as a carbon source of a biological tank after passing through a sedimentation tank, and Fe-Fe is recovered from sludge after fermentation by using a magnetic drum 2 O 3 Core-shell materials for recycling; recovered Fe-Fe 2 O 3 Core-shell materials (i.e. old Fe-Fe 2 O 3 Core-shell material) can be used with freshly prepared Fe-Fe 2 O 3 The core-shell material is used together, and new and old Fe-Fe 2 O 3 The mass ratio of the core-shell materials is 1 (1-4), and depends on the actual recovery rate.
In some embodiments, the fermented sludge (i.e., sludge to be treated) is sludge produced by sewage treatment plants such as biological pond sludge discharge, secondary sedimentation pond sludge discharge, and dewatered sludge.
In some embodiments, the sludge solids loading of the storage pond should be 10-30 kg/(m) 2 M), the concentration time is 36h, and the interval time for entering and exiting mud is 12h.
In some embodiments, the anaerobic fermentation device should have a sludge retention time of 5 to 8 days.
In some embodiments, the total duration of a single period of the anaerobic fermentation device should be 12-24 hours, the standing time should be 1-2 hours, the water outlet time should be 0.5-1 hour, and the mud inlet time should be 0.5-1 hour.
In some embodiments, the anaerobic fermentation device should have a water drainage ratio of 20 to 40%.
The Fe-Fe of the present application is further described in the following specific examples 2 O 3 A preparation method of a core-shell material and a sludge anaerobic fermentation method. This section further illustrates the summary of the invention in connection with specific embodiments, but should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless specifically stated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
The embodiment of the application provides Fe-Fe 2 O 3 The preparation method of the core-shell material comprises the following steps ofThe method comprises the following steps:
s1, 3g FeCl 3 ·6H 2 Adding O into 1000mL of deionized water to obtain ferric iron solution;
s2, 6g NaBH 4 Adding the mixture into 400mL of deionized water to obtain NaBH 4 A solution;
s3, naBH is added 4 The solution was dropped into the ferric iron solution at a flow rate of 0.2mL/s (using peristaltic pump), naBH 4 After all the solution is added, collecting black precipitate, washing with deionized water, and finally drying under nitrogen flow or vacuum environment to obtain Fe-Fe 2 O 3 Core shell material.
FIG. 2 shows the Fe-Fe prepared in example 1 2 O 3 Particle size distribution of core shell material.
As can be seen from FIG. 2, fe-Fe 2 O 3 The particle size of the core-shell material is concentrated in the range of 250-400 nm, wherein the particle size of the core-shell material is more in the range of 300-350 nm, and the average particle size is 329.67nm, which is consistent with the SEM display result.
FIGS. 3 to 5 show the Fe-Fe prepared in example 1 2 O 3 SEM images of core shell material at different fold ratios.
As can be seen from FIGS. 3 to 5, fe-Fe 2 O 3 The core-shell material is in a nano necklace shape, a plurality of pellets with the diameter of 250-500 nm are connected one by one to form a linear structure, and the surfaces of the pellets are relatively smooth. The linear structure is easy to agglomerate into pellets with the diameter of about 1-10 nm.
FIGS. 6 to 8 show the Fe-Fe prepared in example 1 2 O 3 Mapping diagram of core-shell material.
FIG. 9 is a diagram of Fe-Fe prepared in example 1 2 O 3 And a total iron oxygen element distribution diagram of the core-shell material.
As can be seen from FIGS. 6 to 9, fe-Fe 2 O 3 The surface of the core-shell material is uniformly distributed with ferrite, so that the oxidation degree of each pellet is similar, and the content of Fe element is far higher than that of O element, which indicates that Fe is only partially oxidized. In the preparation process of the bonding material, in FeCl 3 With NaBH 4 Reaction to produce Fe 0 At the time, due to BH 4 - Is protected by the reducing atmosphere of Fe to be produced 0 The inside of the pellets is difficult to oxidize, and only the subsequent steps of drying, preservation and the like can cause oxidation reaction, so that the Fe-Fe can be presumed 2 O 3 The surface layer part or the whole surface layer of the pellet is oxidized, and the inner core still keeps Fe 0 Status of the device.
FIG. 10 shows the Fe-Fe prepared in example 1 2 O 3 XRD patterns of core-shell materials, FIG. 11 shows Fe-Fe prepared in example 1 2 O 3 XPS map of core-shell material.
Comparative example 1
This comparative example provides a Fe@Fe 3 O 4 The preparation method of the material comprises the following steps:
s1, first preparing a solution containing 2.86mM NaNO 3 And 3mM FeCl 2 Introducing nitrogen gas into the mixed solution for 30min to remove dissolved oxygen;
s2, adding 1L of the solution obtained in the step S1 into a 2L serum bottle with 1g of iron powder weighed in advance, covering a butyl rubber plug, pressing with an aluminum cap, and winding with black rubber cloth to form a dark environment in the bottle; placing the serum bottle into a rotary oscillator, reacting for more than 16 hours at a rotating speed of 30rpm, collecting precipitate after the reaction is finished, washing with deionized water, and finally drying in a vacuum environment to obtain Fe@Fe 3 O 4 A material.
FIG. 12 is a graph showing the Fe@Fe prepared in comparative example 1 3 O 4 Particle size distribution of the material.
As can be seen from FIG. 12, fe@Fe 3 O 4 The average particle size is 5.85 mu m, and the particle size distribution of the material is more dispersed.
FIGS. 13 to 15 show Fe@Fe prepared in comparative example 1 3 O 4 SEM images of the material at different fold.
As can be seen from FIGS. 13 to 15, fe@Fe 3 O 4 In a smooth state, there are partially oxidized particles, and a large number of oxidized particles having a diameter of about 100nm appear on the surface.
FIGS. 16 to 18 show Fe@Fe prepared in comparative example 1 3 O 4 Mapping diagram of material.
As can be seen from FIGS. 16 to 18, the smooth portion has a high iron content and a low oxygen content, while the granular portion has a high oxygen content and a low iron content.
FIG. 19 is a graph showing the Fe@Fe prepared in comparative example 1 3 O 4 XRD patterns of the material, FIG. 20 shows Fe@Fe prepared in comparative example 1 3 O 4 XPS map of material.
Example 2
The embodiment of the application provides a sludge anaerobic fermentation method, which comprises the following steps:
s1, adding 700mL of sludge to be treated (MLSS (mixed liquor suspended solid concentration, namely sludge concentration) in the sludge is 17.43g/L, MLVSS (volatile solid suspended solids) is 9.26g/L, MLVSS/MLSS is 0.53) into a sludge anaerobic fermentation tank, and adding 2.1g of Fe-Fe prepared in the embodiment 1 2 O 3 And (3) the core-shell material is stirred for 24 hours after the pH of the sludge to be treated is regulated to 9 (regulated by sodium hydroxide), nitrogen is filled for 5 minutes after stirring, and anaerobic fermentation experiment is started under the water bath oscillation environment at 35 ℃ and is carried out for 14 days.
Example 3
The embodiment of the application provides a sludge anaerobic fermentation method, which comprises the following steps:
s1, 700mL of sludge to be treated (MLSS 15.36g/L, MLVSS 9.59g/L, MLVSS/MLSS 0.62) was added to a sludge anaerobic fermentation tank, and the Fe-Fe prepared in example 1 was added according to 0.3g/g VSS 2 O 3 The pH of the core-shell material is respectively regulated to 5, 6, 7, 8 and 9 (the acidity is regulated by HCl and the alkalinity is regulated by NaOH), stirring is carried out for 24 hours, nitrogen is filled for 5 minutes after stirring, 70mL of inoculation sludge (the inoculation sludge is anaerobic fermentation acid-producing sludge which is operated for a long time (the specific operation time is 1-2 months) under the conditions of pH=5.5, ORP= -300mv and 35 ℃ C.) is added, the MLSS in the inoculation sludge is 34g/L, MLVSS and 22.4g/L, MLVSS/MLSS is 0.66), and the anaerobic fermentation experiment is started under the water bath oscillation environment at 35 ℃ C. And is carried out for 12 days.
Example 4
The embodiment of the application provides a sludge anaerobic fermentation method, which comprises the following steps:
s1, 700mL is to be at the positionAdding treated sludge (MLSS is 17.49g/L, MLVSS is 9.23g/L, MLVSS/MLSS is 0.53) into sludge anaerobic fermentation tank, adding 0g, 0.1g, 0.2g, 0.3g, 0.5g/g VSS into Fe-Fe prepared in example 1 2 O 3 The core-shell material is stirred for 24 hours by adjusting the pH to 6 (by adopting HCl), nitrogen is filled for 5 minutes after stirring, 70mL of inoculation sludge (the inoculation sludge is the same as in example 3) is added, and the anaerobic fermentation experiment is started under the water bath oscillation environment at 35 ℃ and is carried out for 12 days.
Example 5
The embodiment of the application provides a sludge anaerobic fermentation method, which comprises the following steps:
s1, adding 700mL of sludge to be treated (MLSS is 17.49g/L, MLVSS is 9.23g/L, MLVSS/MLSS is 0.53) into a sludge anaerobic fermentation tank, and adding 0.3g/g of the Fe-Fe prepared in example 1 2 O 3 Core-shell materials (i.e. new Fe-Fe 2 O 3 ) Recovered Fe-Fe 2 O 3 Core-shell material (old Fe-Fe) 2 O 3 ) Fe-Fe mixed between old and new 2 O 3 Core-shell material (New and old Fe-Fe) 2 O 3 The mass ratio of (1:1), adjusting the pH to 6 (by adopting HCl to adjust), stirring for 24 hours, filling nitrogen for 5 minutes after stirring, adding 70mL of inoculation sludge (the inoculation sludge is the same as that of example 3), and starting anaerobic fermentation experiment in a water bath oscillation environment at 35 ℃ for 12 days.
Comparative example 2
The comparative example tests the effect of producing SCFAs by anaerobic fermentation of sludge under a simple alkaline condition, and the anaerobic fermentation method of sludge comprises the following steps:
s1, 700mL of sludge to be treated (MLSS in the sludge is 17.43g/L, MLVSS is 9.26g/L, MLVSS/MLSS is 0.53) is added into a sludge anaerobic fermentation tank, the sludge to be treated is regulated to be pH 9 and then stirred for 24 hours, nitrogen is filled for 5 minutes after stirring, anaerobic fermentation experiment is started under the water bath oscillation environment at 35 ℃, and the experiment is carried out for 14 days.
Comparative example 3
Comparative example study of Fe@Fe 3 O 4 The method for testing the effect of producing SCFAs by anaerobic fermentation of sludge comprises the following steps of：
S1, adding 700mL of sludge to be treated (MLSS in the sludge is 17.43g/L, MLVSS is 9.26g/L, and MLVSS/MLSS is 0.53) into a sludge anaerobic fermentation tank, and adding 2.1g of Fe@Fe prepared in comparative example 1 3 O 4 The material is stirred for 24 hours after the pH value of the sludge to be treated is adjusted to 9, nitrogen is filled for 5 minutes after stirring, anaerobic fermentation experiment is started under the water bath oscillation environment of 35 ℃, and the experiment is carried out for 14 days.
Comparative example 4
The comparative example researches the effect of micron-sized reduced iron powder on SCFAs production by anaerobic fermentation of sludge, and the anaerobic fermentation method of sludge comprises the following steps:
s1, 700mL of sludge to be treated (MLSS in the sludge is 17.43g/L, MLVSS is 9.26g/L, MLVSS/MLSS is 0.53) is added into a sludge anaerobic fermentation tank, 2.1g of micron-sized reduced iron powder is added, the sludge to be treated is stirred for 24 hours after the pH value is regulated to be 9, nitrogen is filled for 5 minutes after stirring, anaerobic fermentation experiment is started under the water bath oscillation environment at 35 ℃, and the experiment is carried out for 14 days.
Performance testing
The anaerobic fermentation methods of example 2 and comparative examples 2 to 4 were used to test the change with time of the yield of short chain fatty acids in the supernatant after anaerobic fermentation, and the results are shown in FIG. 21.
FIG. 21 (a) shows a blank of comparative example 2 in which no core-shell material was added, and (b) shows an example 2 in which Fe-Fe was added 2 O 3 Anaerobic fermentation was carried out, (c) Fe@Fe was added to comparative example 3 3 O 4 Anaerobic fermentation was performed, and (d) anaerobic fermentation was performed by adding micro-sized reduced iron powder ZVI (zero-valent iron) to comparative example 4.
The anaerobic fermentation methods of example 2 and comparative examples 2 to 4 were used to test the change with time of the content of the soluble organic matters in the supernatant after anaerobic fermentation, and the results are shown in FIG. 22. FIG. 22 (a) SCOD (soluble chemical oxygen demand); (b) a polysaccharide; (c) protein.
The total phosphorus content of the supernatant after anaerobic fermentation was measured as time-dependent according to the anaerobic fermentation methods in example 2 and comparative examples 2 to 4, respectively, and the results are shown in FIG. 23.
In FIGS. 22 to 23, blank is a Blank without core-shell material added in comparative example 2, fe@Fe 2 O 3 To add Fe-Fe in example 2 2 O 3 Anaerobic fermentation is carried out, fe@Fe 3 O 4 To comparative example 3, fe@Fe was added 3 O 4 Anaerobic fermentation was carried out with ZVI being comparative example 4 in which micron-sized reduced iron powder ZVI (zero valent iron) was added for anaerobic fermentation.
As can be seen from FIGS. 21 to 23, in example 2, fe-Fe is added 2 O 3 Anaerobic fermentation is carried out, the yield of short chain fatty acid in the supernatant of anaerobic fermentation is rapidly increased in 1-7 days, peak value 2167mg COD/L is reached in 7 days, the soluble polysaccharide is reached to 115mg/L, and the soluble protein is reached to 330mg/L, as shown in figure 22, fe-Fe 2 O 3 The pretreatment is optimal for promoting the elution of proteins and polysaccharides. Total phosphorus reached a minimum of 3mg/L on day five and was consistently below 10mg/L after day six, as shown in figure 23.
The control without core-shell material in comparative example 2 was anaerobic fermented, and the short chain fatty acid yield reached a peak of 281mg COD/L the next day, both soluble polysaccharide and soluble protein were lower than in example 1 as shown in FIG. 22, and total phosphorus reached 60mg/L on day 14 as shown in FIG. 23.
Comparative example 3 in which Fe@Fe was added 3 O 4 Anaerobic fermentation was carried out, and the short chain fatty acid yield reached a peak of 224mg COD/L on the next day, and both the soluble polysaccharide and soluble protein were lower than in example 2 as shown in FIG. 22, slightly higher than in comparative example 2, and total phosphorus reached a peak of 68mg/L on day 7 as shown in FIG. 23.
In comparative example 4, micro-scale reduced iron powder ZVI (zero valent iron) was fed for anaerobic fermentation, and short chain fatty acid yield reached a peak of 272mg COD/L at the third day, as shown in fig. 22, the soluble polysaccharide was slightly lower than comparative example 2, the soluble protein was slightly higher than comparative example 2, both were lower than example 2, and total phosphorus reached a peak of 57mg/L at the 7 th day, as shown in fig. 23.
The short chain fatty acid yields of the anaerobic fermentation supernatants at different pH's, and the total phosphorus content of the anaerobic fermentation supernatants over time as described in example 3 are shown in FIGS. 24 to 25.
The organic matter elution of the sludge after pretreatment at different pH values according to example 3 is shown in FIG. 26, and the sludge to be treated without any treatment is shown in FIG. 26 before pretreatment.
As shown in fig. 26, after pretreatment at different pH, the sludge soluble polysaccharide, protein and SCOD of each group were greatly improved, wherein at ph=6, the soluble polysaccharide content was 60.3mg/L, and the soluble protein content was 67.0mg/L, SCOD was 1802mg/L. As in figure 24, where at ph=5, 7, 8, 9, SCFAs yields peaked at day 6, and at ph=6, SCFAs yields peaked at day 5. The peaks of SCFAs production were ranked 6502 (ph=5) >6311 (ph=6) >5900 (ph=9) >5684 (ph=8) >2286 (ph=7) in mg COD/L, in order of magnitude from high to low. As shown in FIG. 25, the total phosphorus concentration of each experimental group was greatly reduced after pretreatment, and was lower than 10mg/L after day 6.
As shown in FIG. 31, the XRD pattern of the sludge subjected to anaerobic fermentation at pH 6 in example 3 was shown, and the formation of wurtzite was detected in the sludge after fermentation.
The fermentation was performed at different pH (pH 5, 6, 7, 8, 9) according to the method of example 3, and the activity of the key enzyme was measured on the next day of fermentation by taking a part of the sludge, and the results are shown in FIG. 32. Wherein, alpha-glucosidase is alpha-glucosidase, protease is proteinase (the two above are key enzymes in the hydrolysis process), AK is acetate kinase, PCAT is propionyl coenzyme A transferase, BK is butyrate kinase (the three above are key enzymes in the acidogenesis process), CODH is carbon monoxide dehydrogenase, and F420 is coenzyme F420 (the two above are key enzymes in the methanogenesis process).
As can be seen from fig. 32, the hydrolase activity is higher at acidic or alkaline than at ph=7, where the activity is highest at ph=9, consistent with the dissolution of the organics before and after pretreatment; the acidogenic enzyme is higher at ph=5, 6, 9, lower at ph=7, 8; at ph=7 to 8, the methanogenic enzyme activity increases with pH, and at ph=9, the methanogenic enzyme activity is slightly lower than at ph=8, but higher than at ph=7. Taken together, ph=5, 6 is beneficial to increase the activity of hydrolytic acidogenic enzymes and inhibit methanogenic enzymes, is Fe-Fe 2 O 3 The core-shell material is pretreated to a suitable pH.
Fermentation was performed at different pretreatment pH (pH 6, 7, 9) in example 3, and after completion of fermentation, the microbial population structure distribution was measured by taking part of the sludge, and the results are shown in FIGS. 34 and 35.
Fig. 34 shows the portal level distribution of bacterial populations, wherein the main bacterial portal is Proteobacteria, chloroflexi, patescibacteria, firmicutes, bacteroidota, actinobacteriota, which are common strains in anaerobic fermentation systems, and the total abundance at different pH is 86% (ph=6), 82% (ph=7), 88% (ph=9), respectively.
Fig. 35 is a distribution of genus levels of bacterial, archaea populations, from which it can be seen that the hydrolytic bacteria Dojkabacteria are greatly enriched at ph=9, which explains the excellent organic leaching effect at ph=9; at ph=6, the abundance of acid-forming bacteria such as christensenenlalaae_r-7_group and Romboutsia, petrimonas, macellibacteroides is increased to a greater level, so that the SCFAs yield is also highest among the three groups; at the same time, at ph=6, the abundance of both methanogens, methanosaeta and methanospiralum, was greatly inhibited. In summary, when the pretreatment ph=6, fe—fe 2 O 3 The core-shell material can play a role in enriching acid-producing bacteria and inhibiting methanogens, thereby promoting the process of producing short-chain fatty acid by anaerobic fermentation.
According to the different Fe-Fe in example 4 2 O 3 The yield of short chain fatty acid in the anaerobic fermentation supernatant with the addition amount of the core-shell material and the change of the total phosphorus content of the anaerobic fermentation supernatant with time are shown in figures 27-28. In FIG. 27, (a) 0g/g VSS, (b) 0.1g/g VSS, (c) 0.2g/g VSS, (d) 0.3g/g VSS, and (e) 0.5g/g VSS.
According to the different Fe-Fe in example 4 2 O 3 The leaching condition of the organic matters of the sludge after pretreatment under the adding amount of the core-shell material is shown in fig. 29, and the sludge to be treated which is not subjected to any treatment is shown before pretreatment in fig. 29.
As shown in FIG. 29, in the case of different Fe-Fe 2 O 3 After pretreatment of the core-shell material in the addition amount, sludge soluble polysaccharide, protein and SCOD of each group are greatly improved, wherein Fe-Fe 2 O 3 When the addition amount is 0.1g/g VSS, the content of the soluble polysaccharide is 31.1mg/L,The content of soluble protein is 51.1mg/L, SCOD to 862mg/L, and SCOD is higher than that of blank group (namely Fe-Fe 2 O 3 The addition amount is 0), and the improvement is 71 percent. As shown in FIG. 27, in the case of different Fe-Fe 2 O 3 Anaerobic fermentation is carried out under the condition of adding the core-shell material, the yield of each group of SCFAs reaches a peak value on the 6 th day, and the SCFAs yield peak values are sequentially sorted into 5229 (0.5 g/g VSS) from large to small>5047(0.3g/gVSS)>5041(0.2g/g VSS)>5037(0.1g/g VSS)>2870 (0 g/g VSS) (unit: mg COD/L). As shown in FIG. 28, the blank (i.e., fe-Fe 2 O 3 The addition amount is 0), the total phosphorus concentration is continuously increased, the total phosphorus concentration reaches 175mg/L on the 12 th day, the total phosphorus concentration of each experimental group is greatly reduced after pretreatment, the 0.1g/g VSS group is stabilized at about 30mg/L, the 0.2g/g VSS group is stabilized at about 6mg/L, and the 0.3g/g VSS and 0.5g/g VSS groups are stabilized at about 3 mg/L.
According to the different Fe-Fe in example 5 2 O 3 The change in yield of short chain fatty acids in the supernatant of anaerobic fermentation under the core-shell material over time is shown in FIG. 30. FIG. 30 shows a new material, namely Fe-Fe prepared in example 1 2 O 3 Core-shell materials (i.e. new Fe-Fe 2 O 3 ) Recovering material, namely recovered Fe-Fe 2 O 3 Core-shell material (old Fe-Fe) 2 O 3 ) Fe-Fe mixed in 1:1, namely new and old 2 O 3 Core shell material.
As can be seen from FIG. 30, the recovered material has an effect of promoting acid production comparable to that of the freshly prepared material, and is novel Fe-Fe 2 O 3 Recovered Fe-Fe 2 O 3 After anaerobic fermentation of the core-shell material, the acid production reaches a peak value at 6 days, the peak values are 5041 mg COD/L and 4874mg COD/L respectively, and the peak value of the new and old mixed group reaches 5030mg COD/L at 5 days.
FIG. 33 shows anaerobic sludge fermentation with different Fe-Fe according to the method of example 4 2 O 3 An activity change diagram of key enzyme under the addition amount of core-shell materials; wherein Blank is Fe-Fe prepared in example 1 with 0g/g VSS 2 O 3 Core shell material. On the next day of fermentation, a portion of the sludge was taken to determine the activity of the key enzyme, and the results are shown in FIG. 33, which is the same in symbol as FIG. 32. As can be seen from FIG. 33, alpha-glucosidase and propionyl-CoA transferThe activity of the enzyme is correspondingly improved along with the increase of the adding amount; the activities of the protease and the acetate kinase are also improved correspondingly along with the increase of the addition amount, but the activities of the protease and the acetate kinase are basically the same as those of the addition amount of 0.3g/g VSS except for the addition amount of 0.1g/g VSS, so that theoretical support is provided for the fact that the organic matter dissolving effect after pretreatment is better than that of the addition amount of 0.2 and 0.3g/g VSS when the addition amount of 0.1g/g VSS in the graph 29; in addition, fe-Fe 2 O 3 The addition of the core-shell material inhibits the activities of carbon monoxide dehydrogenase and coenzyme F420, but the inhibition effect is impaired with the increase of the addition amount.
FIG. 33 shows the process according to example 4 (different Fe-Fe 2 O 3 The addition amount of the core-shell material) is subjected to anaerobic fermentation, and after the fermentation is finished, partial sludge is taken to determine the microbial population structure distribution, and the results are shown in figures 36 and 37.
FIG. 36 shows the phylum horizontal distribution of bacterial populations, wherein the main phylum Firmicutes, proteobacteria, actinobacteriota, bacteroidota, chloroflexi is the common species in anaerobic fermentation systems, different Fe-Fe 2 O 3 The total abundance of the core-shell materials under the addition amount is 82.0 percent (0 g/g VSS), 83.7 percent (0.1 g/g VSS), 86.2 percent (0.2 g/g VSS), 86.7 percent (0.3 g/g VSS) and 90.7 percent (0.5 g/g VSS) respectively.
FIG. 37 shows the genus level distribution of bacterial populations wherein Petrimonas is a hydrolytic species and the remaining 9 species are acidogenic (some bacteria also possess the ability to break down macromolecular organics). As can be seen from the figure, fe-Fe 2 O 3 The addition of the core-shell material can increase the concentration of the hydrolytic bacteria Petrimonas. The abundance of the acid-producing bacteria Christensenelaceae_R-7_group follows the Fe-Fe 2 O 3 The addition amount of the core-shell material rises and rises, and the positive correlation relation is obvious. In addition, when the addition amount is 0.1g/g VSS, the acid-producing bacteria UCG-009 and Parabacteroides, rikenellaceae _Rc9_gun_group are better enriched, when the addition amount is 0.2g/g VSS, romboutsia is better enriched, when the addition amount is 0.3g/g VSS, the acid-producing bacteria Christensenelaceae_R-7_group and Romboutsia, NK A214_ group, aminicenantales are higher in abundance, and when the addition amount is 0.5g/g VSS, the acid-producing bacteria are used for culturingChristensenelaceae_R-7_group is the main, and Romboutsia, NK A214-group, aminicenantales, OPB41 is also high in abundance. To sum up, fe-Fe 2 O 3 The core-shell material can play a role of enriching acid-producing bacteria, thereby promoting the process of producing short-chain fatty acid by anaerobic fermentation.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. The anaerobic sludge fermentation method is characterized by comprising the following steps of:
providing Fe-Fe 2 O 3 A core-shell material;
adding sludge to be treated into a sludge anaerobic fermentation tank, and adding Fe-Fe 2 O 3 The core-shell material is used for adjusting sludge to be treated to be acidic, alkaline or neutral, and carrying out anaerobic fermentation at the temperature of 33-37 ℃;
the Fe-Fe 2 O 3 The addition amount of the core-shell material is as follows: 0.1 to 0.5g of Fe-Fe is added per g of VSS 2 O 3 A core-shell material;
in the step of adjusting the sludge to be treated to be acidic, alkaline or neutral, the acidic pH value is 5-6, and the alkaline pH value is 8-9;
the Fe-Fe 2 O 3 The preparation method of the core-shell material comprises the following steps:
adding ferric salt into water to obtain ferric iron solution;
adding a reducing agent into water to obtain a reducing agent solution;
adding a reducing agent solution into a ferric iron solution, reacting, filtering and drying to obtain Fe-Fe 2 O 3 A core-shell material;
the ferric salt comprises FeCl 3 At least one of ferric sulfate and ferric nitrate;
the reducing agent comprises NaBH 4 、Al(BH 4 ) 3 、KBH 4 At least one of hydrazine hydrateOne of the two;
adding a reducing agent solution into the ferric iron solution at a flow rate of 0.1-0.3 mL/s;
in the step of adding ferric salt into water, the mass ratio of the ferric salt to the water is (1-5) (800-1200);
in the step of adding the reducing agent into water, the mass ratio of the reducing agent to the water is (3-9) (300-500);
the concentration of the sludge to be treated is 15-100 g/L, and the MLVSS/MLSS value in the sludge to be treated is greater than 0.5.
2. The anaerobic sludge fermentation method according to claim 1, wherein the oxidation-reduction potential is controlled to be-300 to-200 mV in the anaerobic fermentation process.
3. The anaerobic sludge fermentation method according to claim 1, wherein the sludge to be treated is added into a sludge anaerobic fermentation tank, and Fe-Fe is added 2 O 3 The core-shell material is used for adjusting the sludge to be treated to be acidic or alkaline or neutral, stirring the sludge at the temperature of 33-37 ℃ for anaerobic fermentation, standing the sludge, and separating water and treated sludge;
and then Fe-Fe is separated from the treated sludge 2 O 3 Core-shell material to obtain separated Fe-Fe 2 O 3 A core-shell material;
separating Fe-Fe 2 O 3 And (3) re-adding the core-shell material into a sludge anaerobic fermentation tank to perform anaerobic fermentation on sludge to be treated.
4. The anaerobic sludge fermentation process of claim 1, comprising the steps of:
storing sludge to be treated into a sludge storage tank, and pumping the sludge to be treated in the sludge storage tank into a pretreatment tank by using a first sludge pump;
Fe-Fe 2 O 3 Adding core-shell material into a pretreatment tank, and using a second sludge pump to treat sludge and Fe-Fe in the pretreatment tank 2 O 3 Pumping the core-shell material into a sludge anaerobic fermentation tank for anaerobic fermentation；
Separating the fermented sludge into a sedimentation tank;
pumping the bottom sludge precipitated in the sedimentation tank into a magnetic drum, and recovering the separated Fe-Fe through the magnetic drum 2 O 3 A core-shell material;
separated Fe-Fe 2 O 3 The core-shell material is added into a pretreatment tank, and anaerobic fermentation of the sludge to be treated is carried out for the next period.
5. The anaerobic sludge fermentation process as claimed in claim 4, wherein the separated Fe-Fe 2 O 3 Adding core-shell material into pretreatment tank, and adding new Fe-Fe 2 O 3 Core-shell materials in which Fe-Fe is newly produced 2 O 3 Core-shell material and separated Fe-Fe 2 O 3 The mass ratio of the core-shell material is 1 (1-4).
6. The anaerobic fermentation method of sludge, as claimed in claim 4, wherein after the fermented sludge is separated into a sedimentation tank, the supernatant is pumped into an acid liquid storage tank, and the supernatant is pumped into an AAO biological tank through a dosing pump to serve as a carbon source of the AAO biological tank.
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