CN116332344B - Micro-electrolysis-sulfur autotrophic denitrification sintering-free filler and preparation method and application thereof - Google Patents
Micro-electrolysis-sulfur autotrophic denitrification sintering-free filler and preparation method and application thereof Download PDFInfo
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- 239000000945 filler Substances 0.000 title claims abstract description 58
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 35
- 239000011593 sulfur Substances 0.000 title claims abstract description 35
- 230000001651 autotrophic effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004814 polyurethane Substances 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000010881 fly ash Substances 0.000 claims abstract description 16
- 239000012751 acid resistant agent Substances 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical group [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000010440 gypsum Substances 0.000 claims description 7
- 229910052602 gypsum Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004568 cement Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- 239000011574 phosphorus Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 4
- 230000001360 synchronised effect Effects 0.000 abstract description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000011398 Portland cement Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000000813 microbial effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- VNWKTOKETHGBQD-AKLPVKDBSA-N carbane Chemical group [15CH4] VNWKTOKETHGBQD-AKLPVKDBSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000003469 silicate cement Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F3/005—Combined electrochemical biological processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
- C02F2001/4619—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only cathodic or alkaline water, e.g. for reducing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention belongs to the technical field of water pollution control, and particularly relates to a micro-electrolysis-sulfur autotrophic denitrification sintering-free filler, and a preparation method and application thereof. The micro-electrolysis-sulfur autotrophic denitrification sintering-free filler comprises polyurethane sponge and slurry filled in polyurethane sponge cells; the slurry comprises the following raw material components in parts by weight: 15-40 parts of fly ash, 10-50 parts of exciting agent, 1-5 parts of acid-resistant agent, 1-5 parts of water reducer, 10-40 parts of iron powder, 3-15 parts of activated carbon powder and 10-40 parts of sulfur powder. The filler is a water quality purifying material which is resistant to hardening, high in porosity, capable of maintaining the pH stability of effluent water, high in denitrification efficiency and synchronous in dephosphorization, and capable of realizing synchronous removal of nitrogen and phosphorus of a water body with a low carbon nitrogen ratio. And the preparation process of the filler is simple, high-temperature sintering is not needed, and the preparation condition is more environment-friendly and economical.
Description
Technical Field
The invention belongs to the technical field of water pollution control, and particularly relates to a micro-electrolysis-sulfur autotrophic denitrification sintering-free filler, and a preparation method and application thereof.
Background
The excessive nutrient elements such as nitrogen, phosphorus and the like in the water body can cause eutrophication and the like, and seriously threaten the ecological safety of the water body and the safety of drinking water. At present, biological denitrification is a widely applied technology, but a certain amount of organic carbon is required to provide electrons to realize complete denitrification. For the water body with insufficient organic carbon source, the carbon source needs to be added, or an inorganic electron donor is adopted. More inorganic electron donors are currently used including low valence sulfur compounds, elemental iron, and ferrous iron, hydrogen, and the like. The elemental sulfur is a commonly used inorganic electron donor due to the characteristics of no toxicity, easy transportation, high denitrification efficiency and the like. However, autotrophic denitrification with sulfur as electron donorThe process generates a large amount of H + The pH of the reaction system is lowered, resulting in a decrease in microbial activity, and therefore it is necessary to add an alkalinity to maintain the pH balance. The iron source is wide, the cost is low, and the iron source is also a more common inorganic electron donor. By utilizing the potential difference between iron and carbon, an iron and carbon micro-electrolysis system can be constructed, and Fe is generated by an anode 2+ And electrons, the cathode generates H 2 For nitrate reduction. The micro-electrolysis reaction of iron and carbon can generate OH - Leading to an increase in pH while the iron oxide adheres to the filler surface, which passivates the filler surface and is detrimental to microbial growth and reaction.
In order to adjust the acidity produced by the sulfur autotrophic denitrification process, it is often necessary to add lye to the solution for neutralization, or by adding a solid alkaline material such as lime. Lime increases the hardness of the body of water. In the prior art CN105923757A, CN111137973A is added with iron or iron-carbon materials in a elemental sulfur bed body, and the pH of the water body is maintained to be stable through the coupling effect of sulfur and iron, but the method has the defects that: the iron and carbon may be hardened due to uneven mixing, so that the efficiency is reduced; as sulfur particles are continuously utilized by microorganisms, the variation of the particle size of the sulfur particles can also lead to the enhancement of the non-uniformity of the water flow of the sulfur packed bed, and even cause the short circuit of the water flow, thereby affecting the pollutant removal efficiency.
The porous biomembrane carrier rich in sulfur and other functional components is prepared, and the design of the internal microenvironment is expected to realize various functions such as microbial load, sulfur autotrophic denitrification and dephosphorization, and the like, and the acid-base balance of the effluent is maintained. Inorganic biomembrane carriers such as biological ceramsite, iron carbon and the like are usually prepared by a high-temperature sintering method under the protection of a gas atmosphere, and have high requirements on conditions, complex method and high energy consumption.
Therefore, in the current water quality purification technology, sulfur-iron coupling integrated denitrification filler which has the advantages of hardening resistance, stable pH of effluent water maintenance, high-efficiency denitrification and dephosphorization and environment-friendly and economic preparation method is not available.
Disclosure of Invention
The invention aims to provide a micro-electrolysis-sulfur autotrophic denitrification sintering-free filler and a preparation method thereof, aiming at the problems existing in the prior art. The filler is a water quality purifying material which is resistant to hardening, high in porosity, capable of maintaining the pH stability of effluent water, high in denitrification efficiency and synchronous in dephosphorization, and capable of realizing synchronous removal of nitrogen and phosphorus of a water body with a low carbon nitrogen ratio. And the preparation process of the filler is simple, high-temperature sintering is not needed, and the preparation condition is more environment-friendly and economical.
In order to achieve the above object, the present invention adopts the following technical scheme:
in a first aspect of the invention, a micro-electrolysis-sulfur autotrophic denitrification sintering-free filler is provided, comprising polyurethane sponge and slurry filled in polyurethane sponge cells; the slurry comprises the following raw material components in parts by weight: 15-40 parts of fly ash, 10-50 parts of exciting agent, 1-5 parts of acid-resistant agent, 1-5 parts of water reducer, 10-40 parts of iron powder, 3-15 parts of activated carbon powder and 10-40 parts of sulfur powder.
Further, the particle size of the fly ash is 200-400 meshes; and/or the particle sizes of the iron powder, the activated carbon powder and the sulfur powder are all 100-150 meshes.
Further, the exciting agent comprises the following raw materials in parts by weight: 5-30 parts of cement, 5-15 parts of calcium hydroxide and 0.5-3 parts of gypsum; still further, the cement was 42.5 portland cement.
Portland cement is also called silicate cement, and any hydraulic cementing material prepared by grinding Portland cement clinker, 0-5% limestone or granulated blast furnace slag and a proper amount of gypsum is called silicate cement.
Further, the acid-resistant agent is water glass with the modulus of 3.
Further, the water reducing agent is at least one of lignosulfonate and naphthalene sulfonate.
Cement, calcium hydroxide and the like are alkaline materials, water glass is acid-resistant, and meanwhile, the strength of the filler can be improved.
Further, the specification of the polyurethane sponge is 5-20PPI (pores per inch length), and the polyurethane sponge is in the shape of a sphere or cube with the diameter of 2-6 cm.
The polyurethane sponge has a foam density of less than 18kg/m 3 The low density PU has the advantages of no toxicity and no harm, and is harder than other bullets under the same hardnessThe bearing capacity of the body is high, and the wear resistance and the impact resistance are relatively high.
In a second aspect, the invention provides a preparation method of a micro-electrolysis-sulfur autotrophic denitrification sintering-free filler, wherein the filler is prepared by taking polyurethane sponge as a framework material, preparing and molding the polyurethane sponge by an organic foam impregnation method and combining a fly ash sintering-free ceramsite preparation principle. The fly ash contains a large amount of SiO 2 、Al 2 O 3 An inorganic gel is generated by the alkali-activator, and thus a certain strength can be generated. Specifically, the preparation method comprises the following steps:
(1) Mixing each component of the slurry raw material with water and stirring uniformly to obtain slurry;
(2) And (3) immersing the polyurethane sponge into the slurry obtained in the step (1), fully extruding and immersing, taking out the polyurethane sponge immersed with the slurry, placing the polyurethane sponge at room temperature for molding, drying in a drying oven, and performing autoclaved curing to obtain the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler.
Further, in the step (1), the mass of water accounts for 20% -40% of the total mass of the slurry.
Further, in the step (2), the room temperature standing time is 1-2h; drying at 90-120deg.C for 1-3h; the autoclaved curing temperature is 90-105 ℃, and the autoclaved curing time is 6-16h.
In a third aspect of the invention, a water purification system is provided, which contains the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler.
In a fourth aspect, the invention provides the application of the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler in water quality purification. The filler prepared by the invention can be used as a biomembrane carrier, and deep denitrification and dephosphorization of the water body with low carbon nitrogen ratio can be realized through processes of heterotrophic and sulfur autotrophic biodegradation, micro-electrolysis and the like.
The beneficial effects of the invention are as follows:
(1) The filler is prepared by adopting an organic foam impregnation method, has a porous structure, is beneficial to microorganism adhesion and mass transfer, does not need sintering in the preparation process, is beneficial to energy conservation, and is green and efficient in the preparation process.
(2) The filler is sulfur-iron coupled integrated baking-free ceramic particles, wherein iron and carbon are uniformly distributed, and hardening can be effectively prevented; iron as an inorganic electron donor can reduce sulfur consumption, thereby reducing SO in effluent 4 2- Concentration; the alkalinity generated by the micro-electrolysis of alkaline materials (cement) and Fe-C in the material can effectively neutralize the acidity generated in the microbial sulfur oxide process, and is favorable for stabilizing the pH value of treated water within the range of 6-9.
(3) The autotrophic denitrification microorganism can utilize elemental sulfur, zero-valent iron, ferrous iron and hydrogen generated by micro-electrolysis in the filler as electron donors to carry out denitrification.
(4) The filler can remove phosphorus in various ways, has good denitrification and dephosphorization performance, and mainly comprises the following components: microelectrolytically produced Fe 2+ 、Fe 3+ Hydrolysis product Fe (OH) 2 、Fe(OH) 3 Can remove phosphate, and the glass body in the fly ash has good dephosphorization capability on metal components after curing to form hydraulic gel.
Drawings
FIG. 1 is a physical view of the filler prepared in example 1 of the present invention;
FIG. 2 is a graph showing the effect of removing phosphorus of the filler prepared in example 1 of the present invention;
FIG. 3 is a graph showing denitrification effect of the packing prepared in example 1 of the present invention when continuously operated in a reactor;
FIG. 4 is a graph showing the effect of removing phosphorus when the filler prepared in example 1 of the present invention is continuously operated in a reactor.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims. In the examples below, 1 serving represents 1g.
Example 1
The micro-electrolysis-sulfur autotrophic denitrification sintering-free filler comprises polyurethane sponge and slurry raw materials, wherein the slurry raw materials comprise: 30 parts of fly ash, 20 parts of cement and Ca (OH) 2 8 parts of gypsum, 1 part of sodium silicate with the modulus of 3, 2 parts of naphthalene sulfonate, 20 parts of iron powder, 7 parts of activated carbon powder and 15 parts of sulfur powder.
The preparation method comprises the following steps: taking the components of the slurry raw materials, and uniformly mixing. Wherein, the particle size of the fly ash is 300 meshes, the particle size of the iron powder is 100 meshes, the particle size of the activated carbon powder is 100 meshes, and the particle size of the sulfur powder is 100 meshes. Water accounting for 25 percent of the total mass of the solids is added and stirred into uniform thick slurry. Polyurethane sponge balls with the diameter of 2cm and the specification of 5 PPI are immersed into the slurry, and the slurry is continuously extruded to fill the sponge balls with the slurry. Taking out, placing at room temperature for 1 h, then placing in a drying oven for drying at 100 ℃ for 2h, and finally autoclaved curing at 105 ℃ for 8 h to obtain the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler with the particle size of 2cm, wherein fig. 1 is a real image of the sintering-free filler.
The application conditions are as follows: firstly, a certain amount of sintering-free filler is weighed and placed in a conical bottle for isothermal adsorption dephosphorization experiment, and fig. 2 is a dephosphorization effect diagram, and the maximum adsorption capacity is calculated to be 5.08 mg/g according to a Langmuir isothermal adsorption equation. When the prepared sintering-free filler is used for a denitrification and dephosphorization experiment, the sintering-free filler is filled in a reactor and inoculated with activated sludge. The nitrate nitrogen concentration of the prepared feed water is 20mg/L, the ammonia nitrogen concentration is 5mg/L, the phosphorus concentration is 2mg/L, the COD is 40mg/L, the hydraulic retention time is 4h, and FIG. 3 is a graph showing the denitrification effect when the feed water runs continuously in the reactor, and the nitrate nitrogen removal rate reaches 99.91%. FIG. 4 is a graph showing denitrification effect during continuous flow operation in a reactor, and the phosphate removal rate can reach 56.90% after stabilization.
Example 2
The micro-electrolysis-sulfur autotrophic denitrification sintering-free filler comprises polyurethane sponge and slurry raw materials, wherein the slurry raw materials comprise: 35 parts of fly ash, 20 parts of 42.5 portland cement and Ca (OH) 2 10 parts of gypsum, 2 parts of sodium silicate with the modulus of 3, 2 parts of sodium lignin sulfonate, 25 parts of iron powder, 8 parts of activated carbon powder and 15 parts of sulfur powder.
The preparation method comprises the following steps: taking the components of the slurry raw materials, and uniformly mixing. Wherein, the particle size of the fly ash is 200 meshes, the particle size of the iron powder is 100 meshes, the particle size of the activated carbon powder is 100 meshes, and the particle size of the sulfur powder is 100 meshes. Adding water accounting for 30% of the total mass of the solid, and stirring to obtain uniform thick slurry. Polyurethane sponge balls with the diameter of 2cm and the specification of 10 PPI are immersed into the slurry, and the slurry is continuously extruded to fill the sponge balls with the slurry. Taking out, placing at room temperature for 1 h, then placing in a drying oven for drying at 95 ℃ for 2h, and finally autoclaved curing at 100 ℃ for 10 h to obtain the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler.
The application conditions are as follows: firstly, weighing a certain amount of sintering-free filler, placing the sintering-free filler into a conical flask, performing isothermal adsorption dephosphorization experiment, and calculating according to a Langmuir isothermal adsorption equation to obtain the maximum adsorption capacity of 8.87 mg/g. When the prepared sintering-free filler is used for a denitrification and dephosphorization experiment, the sintering-free filler is filled in a reactor and inoculated with activated sludge. The nitrate nitrogen concentration of the prepared feed water is 20mg/L, the ammonia nitrogen concentration is 5mg/L, the phosphorus concentration is 2mg/L, the COD is 40mg/L, the hydraulic retention time is 3.5h, the nitrate nitrogen removal rate reaches 95.12%, and the phosphate removal rate can reach 51.36% after stability.
Example 3
The micro-electrolysis-sulfur autotrophic denitrification sintering-free filler comprises polyurethane sponge and slurry raw materials, wherein the slurry raw materials comprise: 15 parts of fly ash, 5 parts of 42.5 portland cement and Ca (OH) 2 5 parts of gypsum, 0.5 part of sodium silicate with the modulus of 3, 1 part of sodium lignin sulfonate, 10 parts of iron powder, 3 parts of activated carbon powder and 10 parts of sulfur powder.
The preparation method comprises the following steps: taking the components of the slurry raw materials, and uniformly mixing. Wherein, the particle size of the fly ash is 400 meshes, the particle size of the iron powder is 100 meshes, the particle size of the activated carbon powder is 100 meshes, and the particle size of the sulfur powder is 100 meshes. Adding water accounting for 30% of the total mass of the solid, and stirring to obtain uniform thick slurry. Polyurethane sponge balls with the diameter of 2cm and the specification of 10 PPI are immersed into the slurry, and the slurry is continuously extruded to fill the sponge balls with the slurry. Taking out, placing at room temperature for 1 h, then placing in a drying oven for drying at 95 ℃ for 2h, and finally autoclaved curing at 100 ℃ for 10 h to obtain the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler.
The application conditions are as follows: firstly, weighing a certain amount of sintering-free filler, placing the sintering-free filler into a conical flask, performing isothermal adsorption dephosphorization experiment, and calculating according to a Langmuir isothermal adsorption equation to obtain the maximum adsorption capacity of 5.65 mg/g. When the prepared sintering-free filler is used for a denitrification and dephosphorization experiment, the sintering-free filler is filled in a reactor and inoculated with activated sludge. The nitrate nitrogen concentration of the prepared feed water is 20mg/L, the ammonia nitrogen concentration is 5mg/L, the phosphorus concentration is 2mg/L, the COD is 40mg/L, the hydraulic retention time is 4 hours, the nitrate nitrogen removal rate reaches 91.24%, and the phosphate removal rate can reach 50.35% after stability.
Example 4
The micro-electrolysis-sulfur autotrophic denitrification sintering-free filler comprises polyurethane sponge and slurry raw materials, wherein the slurry raw materials comprise: 40 parts of fly ash, 30 parts of 42.5 portland cement and Ca (OH) 2 15 parts of gypsum, 5 parts of sodium silicate with the modulus of 3, 5 parts of sodium lignin sulfonate, 40 parts of iron powder, 15 parts of activated carbon powder and 40 parts of sulfur powder.
The preparation method comprises the following steps: taking the components of the slurry raw materials, and uniformly mixing. Wherein, the particle size of the fly ash is 200 meshes, the particle size of the iron powder is 100 meshes, the particle size of the activated carbon powder is 100 meshes, and the particle size of the sulfur powder is 100 meshes. Adding water accounting for 30% of the total mass of the solid, and stirring to obtain uniform thick slurry. Polyurethane sponge balls with the diameter of 2cm and the specification of 10 PPI are immersed into the slurry, and the slurry is continuously extruded to fill the sponge balls with the slurry. Taking out, placing at room temperature for 1 h, then placing in a drying oven for drying at 95 ℃ for 2h, and finally autoclaved curing at 100 ℃ for 10 h to obtain the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler.
The application conditions are as follows: firstly, weighing a certain amount of sintering-free filler, placing the sintering-free filler into a conical flask, performing isothermal adsorption dephosphorization experiment, and calculating according to a Langmuir isothermal adsorption equation to obtain the maximum adsorption capacity of 4.52 mg/g. When the prepared sintering-free filler is used for a denitrification and dephosphorization experiment, the sintering-free filler is filled in a reactor and inoculated with activated sludge. The nitrate nitrogen concentration of the prepared feed water is 20mg/L, the ammonia nitrogen concentration is 5mg/L, the phosphorus concentration is 2mg/L, the COD is 40mg/L, the hydraulic retention time is 4 hours, the nitrate nitrogen removal rate reaches 93.16%, and the phosphate removal rate can reach 49.39% after stability.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. The micro-electrolysis-sulfur autotrophic denitrification sintering-free filler is characterized by comprising polyurethane sponge and slurry filled in polyurethane sponge pores;
the slurry comprises the following raw material components in parts by weight: 15-40 parts of fly ash, 10-50 parts of exciting agent, 1-5 parts of acid-resistant agent, 1-5 parts of water reducer, 10-40 parts of iron powder, 3-15 parts of activated carbon powder and 10-40 parts of sulfur powder;
the particle size of the fly ash is 200-400 meshes; the particle sizes of the iron powder, the activated carbon powder and the sulfur powder are all 100-150 meshes;
the exciting agent comprises the following raw materials in parts by weight: 5-30 parts of cement, 5-15 parts of calcium hydroxide and 0.5-3 parts of gypsum;
the acid-resistant agent is water glass with the modulus of 3;
the water reducer is at least one of lignosulfonate and naphthalene sulfonate;
the specification of the polyurethane sponge is 5-20PPI, and the polyurethane sponge is in the shape of a sphere with the diameter of 2-6 cm.
2. The method for preparing the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler according to claim 1, which is characterized by comprising the following steps:
(1) Mixing each component of the slurry raw material with water and stirring uniformly to obtain slurry;
(2) And (3) immersing the polyurethane sponge into the slurry obtained in the step (1), fully extruding and immersing, taking out the polyurethane sponge immersed with the slurry, placing the polyurethane sponge at room temperature for molding, drying in a drying oven, and performing autoclaved curing to obtain the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler.
3. The method for preparing the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler according to claim 2, wherein in the step (1), the mass of water accounts for 20% -40% of the total mass of the slurry;
in the step (2), the room temperature standing time is 1-2h; the drying temperature is 90-120 ℃, and the drying time is 1-3h; the autoclaved curing temperature is 90-105 ℃, and the autoclaved curing time is 6-16h.
4. A water purification system comprising the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler of claim 1.
5. The use of the micro-electrolysis-sulfur autotrophic denitrification sintering-free filler according to claim 1 in water purification.
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| CN108793390A (en) * | 2018-05-25 | 2018-11-13 | 广东博宇集团有限公司 | A kind of catalyst filling and its preparation method and application for purifying aquarium water quality |
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