CN116332343B - Sulfur autotrophic denitrification sulfur-based magnetic filler and preparation method and application thereof - Google Patents
Sulfur autotrophic denitrification sulfur-based magnetic filler and preparation method and application thereof Download PDFInfo
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- CN116332343B CN116332343B CN202310572802.9A CN202310572802A CN116332343B CN 116332343 B CN116332343 B CN 116332343B CN 202310572802 A CN202310572802 A CN 202310572802A CN 116332343 B CN116332343 B CN 116332343B
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 171
- 239000011593 sulfur Substances 0.000 title claims abstract description 170
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 230000001651 autotrophic effect Effects 0.000 title claims abstract description 69
- 239000012762 magnetic filler Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010802 sludge Substances 0.000 claims abstract description 61
- 239000000945 filler Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 239000000696 magnetic material Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 241000894006 Bacteria Species 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- -1 aluminum nickel cobalt Chemical compound 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 238000004065 wastewater treatment Methods 0.000 claims description 5
- 241000609240 Ambelania acida Species 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 239000010905 bagasse Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 244000005700 microbiome Species 0.000 abstract description 16
- 239000010865 sewage Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000005842 biochemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 238000012163 sequencing technique Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 241000605118 Thiobacillus Species 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 229910000828 alnico Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000012543 microbiological analysis Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000003911 water pollution 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
Abstract
The invention relates to the technical field of sewage treatment, and provides a sulfur autotrophic denitrification sulfur-based magnetic filler, and a preparation method and application thereof. The sulfur-based magnetic filler comprises sulfur-containing sludge, biomass, a slow-release inorganic carbon source, an alkaline substance, a metal load, a magnetic material and an adhesive, wherein the sulfur-containing sludge can be obtained from a high-sulfate wastewater anaerobic reactor. The sulfur-based magnetic filler prepared by the method can greatly promote the sulfur autotrophic denitrification process of microorganisms, and the biological filter is filled with the sulfur-based magnetic filler for sewage denitrification, so that a better denitrification treatment effect can be achieved. The invention couples the treatment of high sulfate wastewater, the treatment of sludge and the autotrophic denitrification of sewage sulfur. The sulfur-containing sludge is prepared into a filler through recycling, and the filler is added into the denitrification filter, so that waste is turned into wealth, and the disposal cost of the sludge is reduced.
Description
Technical Field
The invention belongs to the technical field of sewage denitrification treatment, and particularly relates to a sulfur autotrophic denitrification sulfur-based magnetic filler, and a preparation method and application thereof.
Background
Sulfur autotrophic denitrification is one of many sewage biological denitrification treatment methods, which uses sulfur autotrophic microorganisms, takes reduced sulfur source as electron donor, and uses CO 3 2- 、HCO 3 - 、CO 2 And the like are inorganic carbon sources, and nitrate nitrogen is reduced into nitrogen in an anoxic environment, so that the denitrification of sewage is realized. The chemical reaction of sulfur autotrophic denitrification is as follows: NO (NO) 3 - +1.10S +0.40CO 2 +0.76H 2 O+0.08NH 4 + →0.5N 2 ↑+1.10SO 4 2- +1.28H + +0.08C 5 H 7 O 2 N. The sulfur autotrophic denitrification reactor needs to be added with a filler or form a fixed bed reactor, so as to provide an electron donor and an inorganic carbon source for sulfur autotrophic denitrification bacteria in sewage. During operation, the filler is consumed by itself for the growth of sulfur autotrophic denitrifying bacteria and the progress of biochemical reactions.
In a conventional sulfur autotrophic denitrification reactor, sulfur and the like are often directly used as fillers to provide a sulfur source required by the reaction. However, these fillers have a single action effect and do not significantly promote the growth and biochemical reaction of sulfur autotrophic denitrifying bacteria in the reactor. In addition, the sulfur simple substance is used as a sulfur source, has higher cost, and is used as dangerous chemicals, and the safety risk is hidden in the production, transportation or use process. In the improvement research of the sulfur autotrophic denitrification process, the function and the action effect of the filler are required to be improved, and the sulfur source is also required to be replaced by the replacement with higher cost performance and better safety.
On the other hand, when the high-sulfate wastewater is treated by a biological method, sulfate in the wastewater is reduced into hydrogen sulfide gas by utilizing sulfate reducing bacteria mainly through an anaerobic reactor and discharged, so that sulfate in the wastewater is removed, and sludge is discharged periodically. The method is used for treating the high-sulfate wastewater, wherein sulfur element is discharged in the form of hydrogen sulfide gas, equipment, pipelines and the like are corroded, the sludge is also treated in a simple stacking or landfill mode, the high-sulfate wastewater occupies land space as solid waste, and the open-air stacking also has negative influence on the surrounding ecological environment.
Disclosure of Invention
The invention provides a sulfur autotrophic denitrification sulfur-based magnetic filler and a preparation method thereof, and application of the sulfur autotrophic denitrification sulfur-based magnetic filler in sewage treatment, so as to solve the problems that in the prior art, the promotion effect of the sulfur autotrophic denitrification filler on denitrification and other biochemical reactions of sulfur autotrophic denitrification microorganisms is not strong, and denitrification of a sulfur autotrophic denitrification process is not efficient enough.
In a first aspect of the invention, a sulfur autotrophic denitrification sulfur-based magnetic filler is provided, comprising sulfur-containing sludge, biomass, a slow-release inorganic carbon source, an alkaline substance, a metal load, a magnetic material and a binder.
Optionally, the sulfur autotrophic denitrification sulfur-based magnetic filler comprises the following components in parts by weight: 50-200 parts of sulfur-containing sludge, 1-20 parts of biomass, 5-30 parts of slow-release inorganic carbon source, 5-20 parts of alkaline substance, 1-10 parts of metal load, 1-10 parts of magnetic material and 5-20 parts of adhesive; the sulfur element content in the sulfur-containing sludge is more than or equal to 50wt%.
Optionally, the metal load comprises one or more of a metal compound of magnesium, iron or copper.
Optionally, the magnetic material comprises one or more of neodymium iron boron, samarium cobalt and alnico.
Optionally, the biomass is one or more of straw, sawdust, bagasse and rice chaff; the slow-release inorganic carbon source comprises one or the combination of two of calcium carbonate and magnesium carbonate; the alkaline substance comprises one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; the adhesive comprises one or more of starch, sodium alginate, dextrin and carboxymethyl cellulose.
Optionally, the sulfur-containing sludge is obtained from a high sulfate wastewater anaerobic reactor, and the obtaining method comprises the following steps: introducing the high-sulfate wastewater to be treated into an anaerobic reactor enriched with sulfate reducing bacteria, so that sulfate in the high-sulfate wastewater is converted into sulfide in the anaerobic reactor; adjusting the pH of wastewater in an anaerobic reactor to be slightly alkaline, wherein the slightly alkaline is more particularly pH 7-8; adding ferric salt into the anaerobic reactor to obtain sulfur-containing sludge.
Optionally, uniformly mixing sulfur-containing sludge, biomass and metal load, drying, and then sending into a muffle furnace for anaerobic calcination to obtain a calcined filler matrix; uniformly mixing a slow-release inorganic carbon source, an alkaline substance, a magnetic material and an adhesive, and grinding to obtain grinding powder; and (3) mixing the calcined filler matrix and the grinding powder with water to form paste, aging and granulating to obtain filler particles.
Optionally, when the calcined filler matrix and the grinding powder are prepared into paste by using water, the mass ratio of the grinding powder to the water is 1 (0.2-5); the aging time is 8-24 hours, and the particle size of filler particles is 3-8 mm; the calcination temperature is 300-800 ℃, and the calcination time is 2-12 hours.
In a second aspect of the invention, a sulfur autotrophic denitrification biological filter is provided, and the biological filter is filled with the sulfur autotrophic denitrification sulfur-based magnetic filler according to the scheme.
In a third aspect, the invention provides the application of the sulfur autotrophic denitrification sulfur-based magnetic filler in sewage treatment.
The fourth aspect of the invention provides an application of the sulfur autotrophic denitrification sulfur-based magnetic filler in sludge treatment, namely a method for treating and utilizing sludge produced by a high-sulfate wastewater treatment facility, and the produced sludge is used as a sulfur-containing sludge raw material to prepare the sulfur autotrophic denitrification sulfur-based magnetic filler.
The sulfur-based magnetic filler with good promotion effect on the denitrification process of the sulfur-containing autotrophic microorganisms is prepared by using sulfur-containing sludge as a sulfur source, adding magnetic materials, metal loads, biomass and other components into the sulfur-containing sludge and reasonably proportioning the components.
Specifically, the invention adds the magnetic material and the metal load in the process of preparing the sulfur-based magnetic filler, so that the denitrification efficiency can be enhanced. Further, the filler of the present invention uses sulfur-containing sludge as a sulfur source and preferably obtains sludge from a high sulfate wastewater treatment process. The three processes of high-sulfate wastewater treatment, sludge treatment and sewage sulfur autotrophic denitrification are coupled through the cooperation of the two processes of anaerobic digestion of high-sulfate wastewater and sulfur autotrophic denitrification of sewage which are common in water pollution treatment engineering. The sulfur-containing sludge is prepared into a filler through recycling, and the filler is added into the denitrification filter, so that waste is turned into wealth, and the disposal cost of the sludge is reduced. In addition, ferric salt is added into the anaerobic digestion reaction tank of the high-sulfate wastewater, and the precipitation capture is carried out on the hydrogen sulfide generated by anaerobic digestion, so that the sludge enriched with sulfur can be obtained, and the corrosion of the hydrogen sulfide on water treatment related equipment and pipelines can be slowed down. The filler provided by the invention is applied to a sulfur autotrophic denitrification process for sewage denitrification treatment, and can obtain a good sewage denitrification water outlet effect. Compared with the traditional heterotrophic denitrification, the sulfur autotrophic denitrification process can save the addition cost of carbon sources such as sodium acetate, methanol and the like, and reduce the carbon emission of greenhouse gases.
Drawings
FIG. 1 is a graph of total nitrogen output from a denitrification biological filter filled with sulfur-based magnetic filler according to the present invention;
FIG. 2 is a scanning electron microscope SEM image of the sulfur autotrophic denitrification bio-filler of the present invention;
FIG. 3 is a graph of microbiological analysis data for sulfur autotrophic denitrification fillers of example 1 and comparative example 1 of the present invention.
Description of the embodiments
The technical scheme of the invention is described in detail below with reference to the accompanying drawings and the specific embodiments.
The invention relates to a sulfur autotrophic denitrification biological filler, which is a sulfur-based magnetic filler, and the raw material components of the sulfur-based magnetic filler comprise sulfur-containing sludge, biomass, a slow-release inorganic carbon source, an alkaline substance, a metal load, a magnetic material and an adhesive.
Wherein the sulfur-containing sludge is used as a sulfur source to provide electrons for sulfur autotrophic denitrifying bacteria. Biomass is derived from agricultural and forestry solid wastes such as straw, sawdust, bagasse and rice chaff, and the biomass materials can be emptied in the calcining process of filler preparation, so that the specific surface area of the filler is increased. The slow-release inorganic carbon source provides an inorganic carbon source for the growth of the sulfur autotrophic denitrifying bacteria, and the alkaline substance supplements a certain alkalinity for the sulfur autotrophic denitrifying process. The binder serves to promote adhesion between the filler components.
Preferably, the biomass is one or more of straw, sawdust, bagasse and rice chaff; the slow-release inorganic carbon source comprises one or the combination of two of calcium carbonate and magnesium carbonate; the alkaline substance comprises one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; the adhesive comprises one or more of starch, sodium alginate, dextrin and carboxymethyl cellulose.
In particular, the filler of the present invention is also added with a metal support and a magnetic material. Specifically, through metal load modification, the specific surface area of the filler can be increased, the adhesion capability of microorganisms to the filler can be improved, and the filler can be used as trace elements necessary for the microorganisms for the growth and metabolism consumption of the microorganisms. The metal support may preferably be a compound containing magnesium, iron or copper metal elements, and when iron is selected for the metal support, iron ions also assist in phosphorus removal. More specifically, the metal-supported specific compound may use any one or a combination of plural kinds of magnesium chloride, ferric chloride, copper chloride.
The added magnetic material of the invention can promote the activity and proliferation rate of sulfur autotrophic denitrifying bacteria through the endogenous magnetic strengthening effect. Preferably, the magnetic material specifically comprises one or more of neodymium iron boron, samarium cobalt and alnico.
The filler comprises the following specific components in parts by weight: 50-200 parts of sulfur-containing sludge, and 50-150 parts and 100-200 parts; 1-20 parts of biomass, and 1-10 parts and 10-20 parts of biomass; 5-30 parts of slow-release inorganic carbon source, and 10-20 parts and 15-30 parts; 5-20 parts of alkaline substances, and 5-10 parts and 10-20 parts of alkaline substances; 1-10 parts of metal load, 1-3 parts and 3-5 parts; 1-10 parts of magnetic material, and 1-2 parts, 2-5 parts or 5-10 parts of magnetic material; 5-20 parts of adhesive, and 5-10 parts, 10-15 parts or 10-20 parts of adhesive.
The weight parts of the sulfur-containing sludge are dry weight, and the sulfur-containing sludge is subjected to pretreatment, such as primary screening, drying, crushing and other procedures, so as to form sludge powder. The content of sulfur element in the sulfur-containing sludge, namely the mass fraction in the sulfur-containing sludge, should be not less than 50%.
As a preferred embodiment, the sulfur-containing sludge may be obtained from a high sulfate wastewater anaerobic reactor by the following method: introducing the high-sulfate wastewater to be treated into an anaerobic reactor enriched with sulfate reducing bacteria, so that sulfate in the high-sulfate wastewater is converted into sulfide in the anaerobic reactor; adjusting the pH of the wastewater in the anaerobic reactor to be slightly alkaline; adding ferric salt into the anaerobic reactor to obtain sulfur-containing sludge. More specifically, the alkalescence refers to a pH of 7-8; by maintaining the pH of the wastewater to be slightly alkaline, the overflow proportion of sulfides in the anaerobic reactor in the form of hydrogen sulfide gas can be reduced, and sulfur loss can be avoided. The ferric salt is one or more of ferric ion salts including ferric chloride and poly ferric chloride, and the adding concentration can be preferably 5-10 mgFe/L. The sulfur in the hydrogen sulfide gas is captured by adding ferric salt, and the hydrogen sulfide is treated by S or FeS 2 The form of the catalyst is fixed in anaerobic sludge, so that high-content sulfur-containing sludge can be obtained, and the discharge of hydrogen sulfide gas can be effectively avoided. In addition, the obtained sulfur-containing sludge can be used for preparing sulfur autotrophic denitrification sulfur-based magnetic fillers, and the treatment and the recycling of sludge solid waste are realized.
The invention also discloses a method for treating and utilizing the sludge produced in the high-sulfate wastewater treatment facility, namely, the sludge is used as a raw material to prepare the sulfur autotrophic denitrification filler, so that the sludge is harmless and recycled.
The invention also provides a specific preparation method of the sulfur autotrophic denitrification sulfur-based magnetic filler, which comprises the following steps: uniformly mixing sulfur-containing sludge, biomass and metal load, drying, and then sending into a muffle furnace for anaerobic calcination to obtain a calcined filler matrix; uniformly mixing a slow-release inorganic carbon source, an alkaline substance, a magnetic material and an adhesive, and grinding to obtain grinding powder; and (3) mixing the calcined filler matrix and the grinding powder with water to form paste, aging and granulating to obtain filler particles.
More specifically, the calcination temperature is 300-800 ℃, the calcination time is 2-12 h, and nitrogen atmosphere can be used for anaerobic calcination. When the calcined filler matrix and the grinding powder are prepared into paste by using water, the mass ratio of the grinding powder to the water is 1 (0.2-5). The aging time is 8-24 hours, and the particle size of the filler particles is 3-8 mm.
Based on the scheme, the invention also discloses a sulfur autotrophic denitrification filter, and the sulfur autotrophic denitrification filter is filled with the sulfur autotrophic denitrification sulfur-based magnetic filler. The invention also discloses application of the sulfur autotrophic denitrification sulfur-based magnetic filler in sewage treatment, and the application comprises a sewage sulfur autotrophic denitrification treatment method. The method is to put the sulfur-based magnetic filler in a sulfur autotrophic denitrification biological filter or a reactor, remove total nitrogen in wastewater through the sulfur autotrophic denitrification of microorganisms, and realize standard discharge of effluent of the denitrification filter or access to other advanced treatment units. More specifically, the pH in the denitrification biological filter can be controlled to be 7-8, and the hydraulic retention time is controlled to be 30-120 min.
Example 1
Obtaining sulfur-containing sludge: the inlet water of the anaerobic reactor is the outlet water of a biochemical reaction tank of a sewage treatment plant in a printing and dyeing park, and the sulfate concentration is 3000-6000 mg/L. The internal temperature of the anaerobic reactor is controlled at 35 ℃, the pH is regulated to about 7.5, and the hydraulic retention time is controlled at 12h. Adding poly ferric chloride with the concentration of 5mgFe/L into an anaerobic reactor, enabling sulfur ions and iron ions to react to generate ferric sulfide, and enriching the ferric sulfide in sulfur-containing sludge. Sulfur-containing sludge is obtained from the sludge discharge of the reactor. Drying, sieving and crushing the sulfur-containing sludge to obtain pretreated sulfur-containing sludge, wherein the sulfur content of the pretreated sulfur-containing sludge is 60wt%.
Preparation of sulfur-based magnetic filler: 200 parts of sulfur-containing sludge, 1 part of straw and 1 part of magnesium chloride are uniformly mixed, dried for 8 hours at 105 ℃, and sent into a muffle furnace to be subjected to anaerobic calcination at 600 ℃. Uniformly mixing 5 parts of calcium carbonate, 5 parts of sodium bicarbonate, 1 part of neodymium iron boron and 5 parts of starch, and grinding to obtain grinding powder. And (3) preparing the calcined filler matrix and the grinding powder into paste by using water, aging for 12 hours, and granulating to obtain filler particles with the particle size of 3-8 mm. And (3) drying the filler particles at 105 ℃ for 8 hours, and cooling to obtain the sulfur-based magnetic filler.
The prepared filler was subjected to elemental analysis, and the results of ICP-OES elemental analysis of the filler are shown in Table 1.
TABLE 1
The content of S element is about 54% and the content of Fe element is about 26%, so that the prepared filler has a large amount of S and Fe according to the method and the component proportion of the invention, and meets the expectations of filler preparation. In addition, the element analysis result shows that a certain amount of magnesium element is successfully loaded on the filler, and the addition of magnesium chloride metal loading is beneficial to increasing the specific surface area of the filler, improving the film forming capability of microorganisms and promoting the biochemical reaction of the microorganisms.
And stacking and filling the obtained sulfur-based magnetic filler into a denitrification filter, wherein the filling height is about 2/3 of the total height, the pH value in the denitrification filter is regulated to about 7.5, and the hydraulic retention time is regulated to 60min. As shown in the results of the reactor effluent shown in FIG. 1, the total nitrogen of the effluent can be stabilized below 8mg/L and the total nitrogen removal rate can be stabilized above 80% in 40 days of stable operation of the reactor.
FIG. 2 is a Scanning Electron Microscope (SEM) analysis of the surface of a sulfur-based magnetic filler after microorganism adhesion, the scale of the graph being 5. Mu.m. As can be seen in fig. 2, the surface of the filler is rugged, providing a good attachment point for microorganisms; the filler surface has a large number of microorganism species, indicating a high diversity of microorganisms.
The following table shows the results of microbiological sequencing analysis of sulfur-based magnetic fillers in a sulfur autotrophic denitrification reactor after 30 days of operation.
TABLE 2
The results of the sequencing analysis of microorganisms in the table show that the relative abundance of the typical sulfur autotrophic denitrifying bacteria Thiobacillus is about 18 percent. It can be seen that by using the packing of the present invention, a large amount of sulfur autotrophic denitrifying bacteria are enriched in the reactor in a short period of time.
Example 2
100 parts of sulfur-containing sludge, 10 parts of straw, 1 part of cupric chloride and 1 part of magnesium chloride are uniformly mixed, dried for 8 hours at 105 ℃, and sent into a muffle furnace to be subjected to anaerobic calcination at 600 ℃. Uniformly mixing 20 parts of calcium carbonate, 10 parts of sodium bicarbonate, 1 part of neodymium iron boron and 10 parts of starch, and grinding to obtain grinding powder. And (3) preparing the calcined filler matrix and the grinding powder into paste by using water, wherein the mass ratio of the grinding powder to the water is 1:1, aging for 12 hours, and granulating to obtain filler particles with the particle size of 3-8 mm. And (3) drying the filler particles at 105 ℃ for 8 hours, and cooling to obtain the sulfur-based magnetic filler. The sulfur-based magnetic filler is also placed in a sulfur autotrophic denitrification biological filter, and after the sulfur-based magnetic filler is operated for a period of time, the total nitrogen of effluent is below 8mg/L, and the total nitrogen removal rate is above 80%.
Comparative example 1
In this example, no magnetic material neodymium iron boron is added, and the rest components, preparation method, application method and the like are substantially the same as those of example 1. And after the obtained filler is piled and filled into the denitrification biological filter, and stably runs, the total nitrogen in the effluent of the sulfur autotrophic denitrification biological filter is below 12mg/L, the total nitrogen removal rate is finally above 60%, the effect of the filler on denitrification cannot continuously reach the requirement of effluent standard, and certain fluctuation exists.
Sequencing analysis of the filler microorganisms revealed that the relative abundance of sulfur autotrophic denitrifying bacteria Thiobacillus is about 15% in table 3. FIG. 3 is a bar graph showing the results of the microbial sequencing analyses of example 1 and comparative example 1. In combination with tables 2, 3 and 3, it can be seen that the relative abundance of the sulfur autotrophic denitrifying bacteria Thiobacillus of comparative example 1 is lower than that of example 1. Comparing the microbial analysis and the effluent data results of the fillers in the comparative example 1 and the example 1, it can be seen that the addition of the magnetic material in the fillers is helpful to increase the relative abundance of the sulfur autotrophic denitrifying bacteria in the denitrification biological filter, promote the sulfur autotrophic denitrification biochemical reaction and increase the treatment effect of the sulfur autotrophic denitrification.
TABLE 3 Table 3
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention.
Claims (8)
1. The sulfur autotrophic denitrification sulfur-based magnetic filler is characterized by comprising sulfur-containing sludge, biomass, a slow-release inorganic carbon source, an alkaline substance, a metal load, a magnetic material and an adhesive; the magnetic material comprises one or more of neodymium iron boron, samarium cobalt and aluminum nickel cobalt;
the preparation method of the sulfur autotrophic denitrification sulfur-based magnetic filler comprises the following steps: uniformly mixing sulfur-containing sludge, biomass and metal load, drying, and then sending into a muffle furnace for anaerobic calcination to obtain a calcined filler matrix; uniformly mixing a slow-release inorganic carbon source, an alkaline substance, a magnetic material and an adhesive, and grinding to obtain grinding powder; and (3) mixing the calcined filler matrix and the grinding powder with water to form paste, aging and granulating to obtain filler particles.
2. The sulfur autotrophic denitrification sulfur-based magnetic filler according to claim 1, wherein the contents of the components in parts by weight are: 50-200 parts of sulfur-containing sludge, 1-20 parts of biomass, 5-30 parts of slow-release inorganic carbon source, 5-20 parts of alkaline substance, 1-10 parts of metal load, 1-10 parts of magnetic material and 5-20 parts of adhesive; the sulfur element content in the sulfur-containing sludge is more than or equal to 50wt%.
3. The sulfur autotrophic denitrification sulfur-based magnetic filler of claim 1, wherein the metal support comprises one or more of a metal compound of magnesium, iron, or copper.
4. The sulfur autotrophic denitrification sulfur-based magnetic filler of claim 1, wherein the biomass is one or more of straw, sawdust, bagasse, rice chaff; the slow-release inorganic carbon source comprises one or the combination of two of calcium carbonate and magnesium carbonate; the alkaline substance comprises one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; the adhesive comprises one or more of starch, sodium alginate, dextrin and carboxymethyl cellulose.
5. The sulfur autotrophic denitrification sulfur-based magnetic filler according to claim 1, wherein the sulfur-containing sludge is obtained from a high sulfate wastewater anaerobic reactor by the following steps: introducing the high-sulfate wastewater to be treated into an anaerobic reactor enriched with sulfate reducing bacteria, so that sulfate in the high-sulfate wastewater is converted into sulfide in the anaerobic reactor; adjusting the pH value of wastewater in the anaerobic reactor to 7-8; adding ferric salt into the anaerobic reactor to obtain sulfur-containing sludge.
6. The sulfur autotrophic denitrification sulfur-based magnetic filler according to claim 1, wherein when the calcined filler matrix and the abrasive powder are mixed into paste with water, the mass ratio of the abrasive powder to the water is 1 (0.2-5); the aging time is 8-24 hours, and the particle size of the filler particles is 3-8 mm; the calcination temperature is 300-800 ℃, and the calcination time is 2-12 h.
7. A sulfur autotrophic denitrification biological filter, wherein the biological filter is filled with the sulfur autotrophic denitrification sulfur-based magnetic filler according to any one of claims 1-6.
8. A method for treating and utilizing sludge produced by a high sulfate wastewater treatment facility, characterized in that the produced sludge is used as a sulfur-containing sludge raw material to prepare the sulfur autotrophic denitrification sulfur-based magnetic filler according to any one of claims 1 to 6.
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