CN117209054A - Sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, and preparation method and application thereof - Google Patents
Sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, and preparation method and application thereof Download PDFInfo
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- CN117209054A CN117209054A CN202311166826.0A CN202311166826A CN117209054A CN 117209054 A CN117209054 A CN 117209054A CN 202311166826 A CN202311166826 A CN 202311166826A CN 117209054 A CN117209054 A CN 117209054A
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- sulfur
- magnesium
- phosphorus removal
- nitrogen
- biological carrier
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 184
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000011593 sulfur Substances 0.000 title claims abstract description 108
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 108
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 103
- 239000011574 phosphorus Substances 0.000 title claims abstract description 103
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000011777 magnesium Substances 0.000 title claims abstract description 102
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 102
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 92
- 230000001651 autotrophic effect Effects 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 44
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011149 active material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 9
- 239000011707 mineral Substances 0.000 claims abstract description 9
- 239000010865 sewage Substances 0.000 claims description 30
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 26
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 25
- 239000001095 magnesium carbonate Substances 0.000 claims description 25
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 17
- 239000000969 carrier Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 235000010755 mineral Nutrition 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 3
- 229910052599 brucite Inorganic materials 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000001360 synchronised effect Effects 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 43
- 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 abstract description 25
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 7
- 239000013049 sediment Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011010 flushing procedure Methods 0.000 description 10
- 239000012798 spherical particle Substances 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 4
- 238000012851 eutrophication Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000002057 nanoflower Substances 0.000 description 3
- 239000008239 natural water Substances 0.000 description 3
- 230000001546 nitrifying effect Effects 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910021646 siderite Inorganic materials 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention relates to a sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, and a preparation method and application thereof, and belongs to the field of water advanced treatment. The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier comprises a matrix material and an active material distributed in the matrix material and/or at least on part of the surface; the matrix material comprises elemental sulfur and sulfur-containing compounds; the active material comprises an alkaline magnesium-containing compound and/or a mineral containing an alkaline magnesium-containing compound. The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier has sulfur morphology which is easy to be utilized in the denitrification process and the capability of automatically adjusting the pH value of a system, realizes deep denitrification and removal of nitrogen, and the dissolved magnesium ions endow the carrier with the function of efficiently removing ammonia nitrogen and phosphate by improving the transfer efficiency of ammonia nitrogen into cells and forming phosphate-containing sediment. The sulfur-based alkaline magnesium-containing functional material provided by the invention can realize synergistic deep removal of nitrate nitrogen, ammonia nitrogen and phosphate when applied to scenes such as deep treatment or ecological buffer areas, and has wide application prospect.
Description
Technical Field
The invention relates to the field of advanced water treatment, in particular to a sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier with the synergistic and efficient removal of nitrate nitrogen, ammonia nitrogen and phosphate, and a preparation method and application thereof.
Background
Nitrogen has been a major contributor to eutrophication of water and has received much attention. At present, the nitrogen capacity of most areas of ecological water bodies tends to be saturated, and the ecological water bodies are at the risk edge of eutrophication burst. The secondary treatment effluent of a sewage treatment plant has relatively low nutrient content (nitrate nitrogen, ammonia nitrogen and phosphate), but is also sufficient to cause eutrophication of natural water bodies, and in recent years, the secondary treatment effluent has increasingly obvious performance in some inland watercourses and lakes. Because of the limited self-cleaning capability of water bodies, the environment capacity of the areas is saturated gradually, and the total nitrogen emission limit of the pollution discharge units around the areas is gradually increased, so that powerful measures for preventing the further deterioration of water quality are taken. Thereby continuously improving the total nitrogen emission standard of the sewage treatment plant, for example, 15 mg.L of total nitrogen from national standard in 2012 -1 Lifting to 10 mg.L -1 In 2020, total nitrogen in effluent is required to reach 5 mg.L -1 Can be discharged. Although the sewage treatment plant continuously improves the standard, the water quality of the effluent is still greatly different from that of the natural water body, and particularly for an environment sensitive area, the advanced treatment is generally required or the difference between the water quality discharged by the sewage treatment plant and that of the natural water body is pulled by an ecological buffer zone.
Sulfur autotrophic denitrification is a denitrification technology which is very focused at present, and is mainly due to the prominent advantages of low cost of elemental sulfur and the functions of electron donors and biological carriers. However, a key problem with this technique is that denitrification acid production can adversely affect microbial activity, often requiring additional alkalinity to regulate the microbial growth environment.
The prior art discloses an autotrophic denitrification biological carrier (CN 208980406U) which is prepared from sulfur and limestone (CaCO) 3 ) StructureThe substrate is sulfur, limestone particles are blended on the surface and the inside of the substrate to adjust the pH value of the system and supplement carbon sources, but the carrier has limited nitrate nitrogen removal capability when applied to an advanced treatment system; the method has no obvious removal effect on the ammonia nitrogen and phosphate remained in the secondary effluent.
The prior art also discloses a slow-release electron donor, a method for deep denitrification of sewage by using the slow-release electron donor (CN 109879415B), a denitrification and dephosphorization active biological carrier, a preparation method and application thereof (CN 109019877B). The sulfur and siderite are fused together in a physical way, and the integrated composite biological carrier with a novel structure is manufactured under the condition of not changing the composition of the composite biological carrier. The sulfur in the novel structure can participate in the denitrification process to realize deep denitrification, siderite can assist in realizing automatic adjustment of pH, and the generated ferrous ions can be used for phosphorus removal and denitrification processes. But still cannot realize the removal of residual ammonia nitrogen in the secondary effluent.
Therefore, at present, no autotrophic denitrification and dephosphorization biological carrier with the synergistic effect of removing nitrate nitrogen, ammonia nitrogen and phosphate is available, and the autotrophic denitrification and dephosphorization biological carrier is used for advanced treatment or an ecological buffer zone so as to meet the requirement of a downstream environment sensitive water area as a receiving water body.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier which has the functions of removing nitrate nitrogen, ammonia nitrogen and phosphate together and is used for advanced treatment or ecological buffer areas and the like so as to protect a downstream environment-sensitive water area.
The second object of the invention is to provide a preparation method of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier.
The third object of the invention is to provide a sewage treatment device based on sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers.
The fourth object of the invention is to provide a sewage treatment method based on sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers.
In order to achieve the above purpose, the invention adopts the following technical scheme: a sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, comprising a matrix material and an active material distributed within and/or at least partially on the surface of the matrix material.
The matrix material comprises elemental sulfur and sulfur-containing compounds.
The active material comprises an alkaline magnesium-containing compound and/or a mineral containing an alkaline magnesium-containing compound.
Preferably, the basic magnesium-containing compound comprises magnesium carbonate and/or magnesium hydroxide.
Preferably, the mineral containing the basic magnesium-containing compound comprises magnesite, dolomite, brucite or serpentine.
Preferably, the mass ratio of the matrix material to the active material is 50:1-1:8.
More preferably, the mass ratio of the matrix material to the active material is 10:1-1:4.
Preferably, the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier is in a bulk, block, sphere-like or irregular shape, and the maximum directional size is 1.5-12 mm.
More preferably, the particle size of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier is 2-6 mm.
A preparation method of a sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier comprises the following steps:
1) Melting the matrix material into a liquid state at 120-180 ℃;
2) Mixing the molten matrix material and the active material at 160-180 ℃, and maintaining the stirring speed of 400-700 rpm for 30-300 s to obtain uniform mixed solution;
3) Controlling the dripping speed to be 0.5-5 L.min -1 Dropwise adding the obtained mixed solution into cooling water at the temperature of 4-60 ℃, and cooling and molding for 1-10 min;
4) Filtering, putting the obtained solid substance into a baking oven, and drying for 12-48 h at 40-60 ℃ to obtain the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier.
Preferably, before the molten matrix material is mixed with the active material, the molten matrix material is subjected to impurity removal treatment.
More preferably, the impurity removing treatment specifically includes: and (3) classifying and filtering the molten matrix material to remove impurities which are more than or equal to 0.8 mu m in the molten matrix material.
Preferably, before the molten matrix material is mixed with the active material, the active material is subjected to a pulverizing and sieving treatment.
More preferably, the crushing and sieving treatment specifically includes: crushing the active material, sieving with a 60-300 mesh sieve, and taking out the undersize.
A sewage treatment device based on sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers comprises: a packed bed or fixed bed filter packed with packing.
The filler comprises the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier.
Preferably, the filler accounts for 10-90% of the volume of the fixed bed filter tank.
A sewage treatment method based on sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers utilizes the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers to perform denitrification treatment and/or synchronous ammonia nitrogen and phosphate removal on sewage.
The beneficial effects of the invention are as follows:
1. the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention has the sulfur morphology which is easy to be utilized in the denitrification process and the capability of automatically adjusting the pH value of a system, realizes deep denitrification and simultaneously has the function of removing ammonia nitrogen and phosphate.
2. The preparation method of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention is simple, convenient to operate, does not need to use complex instruments or equipment, and does not depend on a special process.
3. The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier mainly comprises a matrix material and an active material, wherein simple substance sulfur in the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier prepared by the method is converted into polysulfide from zero-valent sulfur, and annular sulfur is converted into linear sulfur, so that enrichment of denitrifying bacteria taking reduced sulfur as an electron donor is facilitated, and nitrate removal is enhanced.
4、When the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention is taken as a filler to construct a packed bed, OH which is dissolved out along with the denitrification process - 、CO 3 2- The pH value of the system can be adjusted by the alkaline component, and sewage or wastewater can be well treated.
5. When the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention is used as a filler to construct a packed bed, the dissolved free magnesium ions can promote the absorption and utilization of nitrifying bacteria to ammonia nitrogen by improving the transfer efficiency of ammonia nitrogen into cells. Both aspects simultaneously promote the efficient removal of ammonia nitrogen in the system.
6. When the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention is used as a filler to construct a packed bed, dissolved magnesium ions can be combined with phosphate to form chemical sediment, so that the control of the phosphate in the effluent is realized.
7. According to the sewage treatment device provided by the invention, the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier is used as the filler to be filled in the packed bed or the fixed bed filter tank, so that the nitrate, ammonia nitrogen and phosphate can be removed cooperatively and efficiently, the filling can be conveniently and rapidly completed when the carrier is required to be supplemented, and the material has good uniformity.
8. The sewage treatment method provided by the invention can realize deep denitrification and has the synergistic deep removal effect of ammonia nitrogen and phosphate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural diagram of a sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier.
FIG. 2 shows the results of a surface Scanning Electron Microscope (SEM) (a) and an energy spectrum (EDS) (b) of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention.
FIG. 3 shows the photoelectron spectroscopy (XPS) characterization result of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier.
Fig. 4 is a schematic structural diagram of a sewage treatment apparatus according to the present invention.
Reference numerals:
1-water inlet device, 2-back flushing device, 3-back flushing air path and air inlet device, 4-bearing filter plate, 5-filler, 6-water outlet and 7-fixed bed filter tank.
Fig. 5 is an SEM result of the collected sediment after a period of operation of the sewage treatment apparatus provided by the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are examples of part of the present invention, not all of which are intended to be illustrative of the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions not specified in the examples were either conventional or manufacturer-recommended. The reagents or apparatus used were conventional products available commercially without the manufacturer's attention.
In a first aspect, the present invention relates to a sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, as shown in fig. 1, comprising a matrix material and an active material distributed within and/or at least partially on the surface of the matrix material.
The matrix material comprises elemental sulfur and sulfur-containing compounds.
The active material comprises an alkaline magnesium-containing compound and/or a mineral containing an alkaline magnesium-containing compound.
Preferably, the basic magnesium-containing compound comprises magnesium carbonate and/or magnesium hydroxide.
Preferably, the mineral containing the basic magnesium-containing compound comprises magnesite, dolomite, brucite or serpentine.
The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier has sulfur morphology which is easy to be utilized in the denitrification process and the capability of automatically adjusting the pH value of a system, realizes deep denitrification and has the function of removing ammonia nitrogen and phosphate.
In the denitrification process, elemental sulfur on the surface of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier is consumed, nitrate nitrogen is reduced into nitrogen, the denitrification target is realized, and hydrogen ions are released. The generated hydrogen ions can dissolve out carbonate/hydroxide and magnesium ions in the basic magnesium-containing compound and/or the mineral containing the basic magnesium-containing compound. Wherein, the former can realize automatic pH adjustment of the system and has the function of microorganism carbon source; the latter can enhance ammonia nitrogen removal by accelerating the ammonia nitrogen entering nitrifying bacteria process, and can also combine with phosphate in secondary effluent to form chemical sediment to realize phosphate removal.
Preferably, the mass ratio of the matrix material to the active material is 50:1-1:8.
More preferably, the mass ratio of the matrix material to the active material is from 10:1 to 1:4 (e.g., 10:1, 4:1, 2:1, 1:1, or 1:4).
It is further preferable that the mass ratio of the matrix material to the active material is such that the amounts of hydrogen ions, magnesium ions and carbonate radicals generated during the denitrification process are more reasonable, and the whole denitrification and dephosphorization process is promoted to be stably and permanently carried out.
Preferably, the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier is in a bulk, block, sphere-like or irregular shape, and the maximum directional size is 1.5-12 mm.
More preferably, the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier has a particle size of 2 to 6mm (e.g., 2mm, 3.5mm, 4.5mm, 5mm, or 6 mm).
The second aspect of the invention also relates to a preparation method of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, which comprises the following steps:
1) The matrix material is melted into a liquid state at 120-180 ℃ (e.g., 120 ℃, 130 ℃, 140 ℃, 160 ℃, or 180 ℃).
2) The matrix material in a molten state and the active material are mixed at 160 to 180 ℃ (e.g., 160 ℃, 165 ℃, 170 ℃, 175 ℃, or 180 ℃) and a stirring speed of 400 to 700rpm (e.g., 400rpm, 500rpm, 600rpm, or 700 rpm) is maintained for 30 to 300 seconds (e.g., 30 seconds, 50 seconds, 80 seconds, 100 seconds, 150 seconds, 180 seconds, 200 seconds, 230 seconds, 260 seconds, or 300 seconds), to obtain a uniform mixed solution.
3) Controlling the dripping speed to be 0.5-5 L.min -1 (e.g. 0.5 L.min -1 、0.8L·min -1 、1.5L·min -1 、2.5L·min -1 、4L·min -1 、5L·min -1 ) The mixed solution is dropwise added into cooling water of 4-60 ℃ (e.g. 4 ℃, 10 ℃,20 ℃, 40 ℃, 50 ℃ or 60 ℃) and is cooled and molded for 1-10 min (e.g. 1min, 2min, 5min, 6min, 8min or 10 min).
4) Filtering, placing the obtained solid matter into an oven, and drying at 40-60 ℃ (40 ℃ for example, 45 ℃, 50 ℃, 55 ℃ or 60 ℃) for 12-48 hours (12 hours, 15 hours, 18 hours, 24 hours, 36 hours, 42 hours or 48 hours for example) to obtain the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier.
Preferably, before the molten matrix material is mixed with the active material, the molten matrix material is subjected to impurity removal treatment.
More preferably, the impurity removing treatment specifically includes: melting and standing the molten matrix material at 120-180 ℃ (for example, 120 ℃, 130 ℃, 140 ℃, 160 ℃ or 180 ℃), or classifying and filtering the molten matrix material to remove impurities which are more than or equal to 0.8 mu m in the molten matrix material.
Impurities in the matrix material are removed, so that the content of effective components can be further improved, and the denitrification capability of the autotrophic denitrification and dephosphorization biological carrier is improved.
Preferably, before the molten matrix material is mixed with the active material, the active material is subjected to a pulverizing and sieving treatment.
More preferably, the crushing and sieving treatment specifically includes: the active material is crushed and sieved by a 60-300 mesh sieve (for example, 60 mesh, 80 mesh, 100 mesh, 120 mesh, 140 mesh, 150 mesh, 160 mesh, 190 mesh, 220 mesh, 250 mesh, 280 mesh or 300 mesh), and the sieved active material is taken as a raw material.
The particle size of the active material is selected within a reasonable range, so that the connection between the active material and the matrix material is more compact, and the layering phenomenon can not occur in the denitrification process.
In a third aspect, the invention also relates to a sewage treatment device based on the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, which comprises: a packed bed or fixed bed filter packed with packing.
The filler comprises the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier.
The sewage treatment device has a good denitrification function.
Preferably, as shown in fig. 4, the sewage treatment device comprises a water inlet device 1, a back flushing device 2, a back flushing air path and air inlet device 3, a bearing filter plate 4, a filler 5, a water outlet 6 and a fixed bed filter tank 7.
Preferably, an air inlet and a water inlet are arranged on the side wall of the bottom of the fixed bed filter tank.
Preferably, the air inlet device is connected with the air inlet of the fixed bed filter through the back flushing air circuit.
Preferably, the water inlet device is connected with the water inlet of the fixed bed filter tank.
Preferably, a back flush water inlet at the bottom of the fixed bed filter tank is connected with a water outlet of the back flush device through a back flush water pipe.
Preferably, the bearing filter plate is arranged in the fixed bed filter tank.
Preferably, the bearing filter plate is arranged above the air inlet and the water inlet which are arranged on the side wall of the bottom of the fixed bed filter tank.
Preferably, the packing is placed on the support filter plate.
Preferably, a back flushing water outlet and a flushing water outlet are arranged on the side wall of the top of the fixed bed filter.
Preferably, the filler accounts for 10-90% of the volume of the fixed bed filter.
The fourth aspect of the invention also relates to a sewage treatment method based on the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, and the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier is used for carrying out denitrification treatment on sewage.
The present invention will be further explained and illustrated with reference to specific examples and comparative examples.
Example 1
The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the embodiment adopts elemental sulfur and magnesium carbonate with the mass ratio of 10:1, and the preparation method comprises the following steps:
1) Adding solid elemental sulfur into a heating kettle, heating and melting the solid elemental sulfur into liquid elemental sulfur at 140 ℃, and carrying out fractional filtration on the liquid elemental sulfur to remove impurities with the particle size of more than 0.8 mu m.
2) The temperature of the heating kettle is increased and kept at 160 ℃, and the undersize magnesium carbonate screened by the 120-mesh sieve is added into the liquid elemental sulfur in the heating kettle; the temperature in the heating kettle is controlled at 160 ℃, and the mixture of magnesium carbonate and elemental sulfur is stirred and mixed for 50s at the frequency of 600rpm, so as to obtain uniform mixed solution.
3) Keeping the dripping speed at 1.5 L.min -1 And (3) dropwise adding the mixed solution into cooling water at the temperature of 10 ℃, and cooling and molding for 1min to form solid spherical particles.
4) Filtering, putting the solid spherical particles into a baking oven, and drying at 40 ℃ for 12 hours to obtain the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier with the particle size of 3-4 mm.
Example 2
The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the embodiment adopts elemental sulfur and magnesite (the content of magnesium carbonate is about 90%) with the mass ratio of 10:1, and the preparation method comprises the following steps:
1) Adding solid elemental sulfur into a heating kettle, heating and melting the solid elemental sulfur into liquid elemental sulfur at 160 ℃, and carrying out fractional filtration on the liquid elemental sulfur to remove impurities with the particle size of more than 0.8 mu m.
2) The temperature of the heating kettle is increased and kept at 180 ℃, and undersize magnesite screened by a 250-mesh sieve is added into liquid elemental sulfur in the heating kettle; the temperature in the heating kettle is controlled at 180 ℃, and the mixture of magnesite and elemental sulfur is stirred and mixed for 150s at the frequency of 700rpm, so as to obtain uniform mixed solution.
3) Keeping the dripping speed at 1.5 L.min -1 The mixed solution is dropwise added into cooling water at 20 ℃ to be cooled and molded for 6 minutes, so as to form solid spherical particles.
4) Filtering, putting the solid spherical particles into a baking oven, and drying at 55 ℃ for 24 hours to obtain the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier with the particle size of 3-4 mm.
Example 3
The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the embodiment adopts elemental sulfur and magnesite (the magnesium carbonate content is about 90%) with the mass ratio of 4:1, and the preparation method is the same as that of the embodiment 2, so that the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier with the particle size of 3-4 mm is obtained.
Example 4
The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the embodiment adopts elemental sulfur and magnesite (the content of magnesium carbonate is about 90%) in a mass ratio of 1:1, and the preparation method comprises the following steps:
1) Adding solid elemental sulfur into a heating kettle, heating and melting the solid elemental sulfur into liquid elemental sulfur at 120 ℃, and carrying out fractional filtration on the liquid elemental sulfur to remove impurities with the particle size of more than 0.8 mu m.
2) The temperature of the heating kettle is increased and kept at 175 ℃, and undersize magnesite screened by a 160-mesh sieve is added into liquid elemental sulfur in the heating kettle; the temperature in the heating kettle is controlled at 175 ℃, and the mixture of magnesite and elemental sulfur is stirred and mixed for 300s at the frequency of 400rpm, so that uniform mixed solution is obtained.
3) Keeping the dripping speed at 1.5 L.min -1 And (3) dropwise adding the mixed solution into cooling water at the temperature of 4 ℃, and cooling and molding for 10min to form solid spherical particles.
4) Filtering, putting the solid spherical particles into a baking oven, and drying at 60 ℃ for 18 hours to obtain the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier with the particle size of 3-4 mm.
Example 5
The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the embodiment adopts elemental sulfur and magnesite (the content of magnesium carbonate is about 90%) with the mass ratio of 1:4, and the preparation method comprises the following steps:
1) Adding solid elemental sulfur into a heating kettle, heating and melting the solid elemental sulfur into liquid elemental sulfur at 180 ℃, and carrying out fractional filtration on the liquid elemental sulfur to remove impurities with the particle size of more than 0.8 mu m.
2) The temperature of the heating kettle is kept at 180 ℃, and undersize magnesite screened by a 300-mesh sieve is added into liquid elemental sulfur in the heating kettle; the temperature in the heating kettle is controlled at 180 ℃, and the mixture of magnesite and sulfur is stirred and mixed for 200s at the frequency of 500rpm, so that uniform mixed solution is obtained.
3) Keeping the dripping speed at 1.5 L.min -1 The mixed solution is dropwise added into cooling water at 50 ℃ to be cooled and molded for 5 minutes, so as to form solid spherical particles.
4) Filtering, putting the solid spherical particles into an oven, and drying at 50 ℃ for 42 hours to obtain the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier with the particle size of 3-4 mm.
As shown in (a) of fig. 2, the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention has a nano flower structure on microcosmic scale, and the gaps formed by lamellar overlapping endow the material with larger specific surface area and more active sites; as shown in an EDS result of (b) in FIG. 2, the carrier takes elemental sulfur as a substrate, and the nanoflower inlaid on the carrier is mainly formed by doping a small amount of elemental sulfur with most active materials.
As shown in the results of FIG. 3, the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention has polysulfide and linear sulfur forms which are easy to be absorbed and utilized by microorganisms.
Example 6A method for treating wastewater based on a sulfur-based magnesium-containing autotrophic denitrification and dephosphorization biological carrier
A sewage treatment method based on sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers adopts a sewage treatment device shown in figure 4, and comprises a water inlet device 1, a back flushing device 2, a back flushing air path and air inlet device 3, a bearing filter plate 4, a filler 5, a water outlet 6 and a fixed bed filter 7.
An air inlet and a water inlet are formed in the bottom of the side wall of the fixed bed filter tank 7; the back flushing air circuit and the air inlet device 3 are connected with an air inlet of the fixed bed filter tank 7; the water inlet device 1 is connected with a water inlet of the fixed bed filter tank 7; the back flush water inlet at the bottom of the fixed bed filter tank 7 is connected with the water outlet of the back flush device 2; the bearing filter plate 4 is arranged in the fixed bed filter tank 7; the bearing filter plate 4 is arranged at the bottom of the side wall of the fixed bed filter 7 and above the air inlet and the water inlet; the filler 5 is arranged on the bearing filter plate 4; and a water outlet 6 is formed in the side wall of the top of the fixed bed filter tank 7.
The method comprises the following steps of (a) influence of sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers prepared at different dropping speeds on removal of nitrate nitrogen, ammonia nitrogen and total phosphorus
1. The preparation method of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier comprises the following steps:
the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the embodiment adopts elemental sulfur and magnesite (the magnesium carbonate content is about 90%) with the mass ratio of 1:1, and the preparation method is the same as that of the embodiment 4, except that the dripping speed is controlled as shown in the table 1, so that the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier prepared at different dripping speeds is obtained.
2. Method for removing nitrate nitrogen, ammonia nitrogen and total phosphorus
The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers prepared under different dropping speeds are respectively placed into a fixed bed filter 7 of a sewage treatment device as shown in fig. 4 as a filler 5, the filling ratio is 70%, anaerobic sludge of a sewage treatment plant is added into the fixed bed filter 7, and water is introduced into the fixed bed filter 7 for starting after soaking for 24 hours. In the starting process, the hydraulic retention time of the fixed bed filter reactor is set to be 1h, water distribution (containing nitrate nitrogen, ammonia nitrogen, phosphorus and the like) containing a culture medium is stably conveyed into the reactor by a peristaltic pump, dynamic culture and domestication are carried out, sampling and testing are carried out once every 24h until the concentration of the nitrate nitrogen, the ammonia nitrogen, the phosphorus and the like in the yielding water is stable. The nitrate nitrogen concentration in the simulated wastewater is 30mg L -1 Ammonia nitrogen concentration of 4mg L -1 The total phosphorus concentration was 3.5mg L -1 The pH of the inlet water is 7.52+/-0.10.The nitrate nitrogen, ammonia nitrogen and total phosphorus concentrations of the device effluent are respectively measured, and the results of the nitrate nitrogen, ammonia nitrogen and total phosphorus removal rates are shown in Table 1.
TABLE 1 nitrate nitrogen, ammonia nitrogen and Total phosphorus removal rates of Sulfur-based magnesium-containing autotrophic Denitrification and dephosphorization biological Carriers formed at different mixing droplet speeds
(II) influence of different sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers on removal of nitrate nitrogen, ammonia nitrogen and total phosphorus
1. Comparative example 1
The sulfur autotrophic nitrogen and phosphorus removal biological carrier provided in this comparative example is different from example 1 only in that it is composed of only elemental sulfur as a matrix material, and no active material (alkaline magnesium-containing compound and/or mineral containing alkaline magnesium-containing compound) is added.
2. Comparative example 2
This comparative example is example 1 of prior art CN 109019877B.
3. Method for removing nitrate nitrogen, ammonia nitrogen and total phosphorus
The autotrophic nitrogen and phosphorus removal biological carriers prepared in examples 1 to 5 and comparative examples 1 and 2 are respectively placed as a filler 5 in a fixed bed filter 7 of a sewage treatment device provided in fig. 4, the filling ratio is 70%, anaerobic sludge of a sewage treatment plant is added into the fixed bed filter 7, and water is introduced and started after soaking for 24 hours. In the starting process, the hydraulic retention time of the fixed bed filter reactor is set to be 1h, water distribution (containing nitrate nitrogen, ammonia nitrogen, phosphorus and the like) containing a culture medium is stably conveyed into the reactor by a peristaltic pump, dynamic culture and domestication are carried out, sampling and testing are carried out once every 24h until the concentration of the nitrate nitrogen, the ammonia nitrogen, the phosphorus and the like in the yielding water is stable. The nitrate nitrogen concentration in the simulated wastewater is 30mg L -1 Ammonia nitrogen concentration of 4mg L -1 The total phosphorus concentration was 3.5mg L -1 The pH of the inlet water is 7.52+/-0.10. The nitrate nitrogen, ammonia nitrogen and total phosphorus concentrations of the device effluent are respectively measured, and the results of the nitrate nitrogen, ammonia nitrogen and total phosphorus removal rate and the effluent pH are shown in Table 2.
TABLE 2 nitrate nitrogen, ammonia nitrogen and Total phosphorus removal and effluent pH
| Nitrate nitrogen removal rate | Ammonia nitrogen removal rate | Total phosphorus removal rate | pH of effluent | |
| Example 1 | 80.7±3.9％ | 52.1±3.1％ | 22.5±1.4％ | 7.31±0.11 |
| Example 2 | 72.2±1.9％ | 62.7±3.6％ | 39.6±2.1％ | 7.35±0.17 |
| Example 3 | 90.9±3.2％ | 85.6±4.2％ | 60.1±4.2％ | 7.35±0.12 |
| Example 4 | 87.3±2.4％ | 72.3±2.8％ | 57.2±3.4％ | 7.29±0.23 |
| Example 5 | 92.1±2.2％ | 98.1±1.5％ | 70.1±3.6％ | 7.31±0.14 |
| Comparative example 1 | 58.2±1.4％ | Not removed | 10.2±3.2％ | 6.98±0.13 |
| Comparative example 2 | 84.3±5.7％ | Not removed | 76.0±8.0％ | 7.01±0.11 |
In the continuous flow water inlet process, stable biological films are gradually grown on the surface of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, and the nitrate nitrogen and ammonia nitrogen removal capacity is gradually improved. Wherein, the nitrate removal rate of the effluent of the example 5 is 92.1+/-2.2%, which is improved by 33.9% compared with the nitrate removal rate of the comparative example 1, and is improved by 7.8% compared with the nitrate removal rate of the comparative example 2; the ammonia nitrogen removal rate of the effluent of example 5 is 98.1+/-1.5%, while the ammonia nitrogen is not obviously removed in both comparative example 1 and comparative example 2; the total phosphorus removal rate of the effluent of example 5 is 70.1+/-3.6%; the pH of the effluent of example 5 can be maintained at 7.31.+ -. 0.14, which is advantageous for denitrification and dephosphorization processes.
It can be seen that when the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier of the invention is filled in the fixed bed filter tank, the nano-flower structure of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier endows the biological carrier with large specific surface area and more active sites (figure 2), and the released OH - 、CO 3 2- The alkaline component can realize the automatic balance of pH, thereby being beneficial to the enrichment and growth of more microorganisms; the sulfur in the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier prepared by the method is converted into polysulfide from zero-valent sulfur, and annular sulfur is converted into linear sulfur (figure 3), so that enrichment of denitrifying bacteria taking reduced sulfur as an electron donor is facilitated, and stable high nitrogen removal efficiency is provided for the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier. When the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier is reduced in efficiency due to consumption, the prepared active biological carrier is supplemented to restore the bed to the original height, and additional operations such as uniform mixing and the like are not needed.
The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention has the high-efficiency removal capacity of ammonia nitrogen and total phosphorus: when the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier provided by the invention is used as a filler to construct a packed bed, the dissolved free magnesium ions can promote the absorption and utilization of nitrifying bacteria to ammonia nitrogen by improving the transfer efficiency of ammonia nitrogen into cells; as shown in fig. 5, the leached magnesium ions may combine with phosphate to form chemical sediment, enabling effluent phosphate control. Has wide application prospect.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier, characterized in that the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier comprises a matrix material and an active material distributed inside and/or at least on part of the surface of the matrix material;
the matrix material comprises elemental sulfur and sulfur-containing compounds;
the active material comprises an alkaline magnesium-containing compound and/or a mineral containing an alkaline magnesium-containing compound.
2. A sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier according to claim 1, wherein said basic magnesium-containing compound comprises magnesium carbonate and/or magnesium hydroxide; the minerals containing basic magnesium-containing compounds include magnesite, dolomite, brucite or serpentine.
3. The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier according to claim 1, wherein the mass ratio of the matrix material to the active material is 50:1-1:8;
preferably, the mass ratio of the matrix material to the active material is 10:1-1:4.
4. The sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier according to claim 1, wherein the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier is in a shape of a lump, a block, a sphere or an irregular shape, and the maximum directional size is 1.5-12 mm;
preferably, the particle size of the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier is 2-6 mm.
5. The method for preparing the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
1) Melting the matrix material into a liquid state at 120-180 ℃;
2) Mixing the molten matrix material and the active material at 160-180 ℃, and maintaining the stirring speed of 400-700 rpm for 30-300 s to obtain uniform mixed solution;
3) Controlling the dripping speed to be 0.5-5 L.min -1 Dropwise adding the obtained mixed solution into cooling water at the temperature of 4-60 ℃, and cooling and molding for 1-10 min;
4) Filtering, putting the obtained solid substance into a baking oven, and drying for 12-48 h at 40-60 ℃ to obtain the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier.
6. The method according to claim 5, wherein the molten matrix material is subjected to a impurity removal treatment before being mixed with the active material;
preferably, the impurity removing treatment specifically includes: and (3) classifying and filtering the molten matrix material to remove impurities which are more than or equal to 0.8 mu m in the molten matrix material.
7. The method according to claim 5, wherein the active material is subjected to a pulverizing and sieving treatment before the matrix material in the molten state is uniformly mixed with the active material;
preferably, the crushing and screening treatment specifically includes: crushing the active material, sieving with a 60-300 mesh sieve, and taking out the undersize.
8. A sewage treatment device based on sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers, which is characterized in that the sewage treatment device comprises: a packed bed or fixed bed filter filled with a filler;
the filler comprises the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carrier as claimed in any one of claims 1 to 4.
9. The wastewater treatment apparatus according to claim 8, wherein the packing occupies 10 to 90% of the volume of the fixed bed filter.
10. A sewage treatment method based on sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers, which is characterized in that the sulfur-based magnesium-containing autotrophic nitrogen and phosphorus removal biological carriers are utilized to perform denitrification treatment and/or synchronous ammonia nitrogen and phosphate removal on sewage.
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