CN117164108A - Wastewater treatment functional material prepared based on natural wurtzite and natural limonite and application thereof in synchronous denitrification and phosphorus recovery - Google Patents
Wastewater treatment functional material prepared based on natural wurtzite and natural limonite and application thereof in synchronous denitrification and phosphorus recovery Download PDFInfo
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 186
- 239000011574 phosphorus Substances 0.000 title claims abstract description 186
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 239000000463 material Substances 0.000 title claims abstract description 131
- 238000011084 recovery Methods 0.000 title claims abstract description 75
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 65
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 27
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000002131 composite material Substances 0.000 claims abstract description 95
- 229910052595 hematite Inorganic materials 0.000 claims abstract description 66
- 239000011019 hematite Substances 0.000 claims abstract description 66
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 66
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000013265 porous functional material Substances 0.000 claims abstract description 63
- YBCFASPYBHNQOC-UHFFFAOYSA-N [P].[S].[Fe] Chemical compound [P].[S].[Fe] YBCFASPYBHNQOC-UHFFFAOYSA-N 0.000 claims abstract description 61
- 244000005700 microbiome Species 0.000 claims abstract description 57
- 239000011593 sulfur Substances 0.000 claims abstract description 56
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 56
- 229910052742 iron Inorganic materials 0.000 claims abstract description 39
- 230000001651 autotrophic effect Effects 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005516 engineering process Methods 0.000 claims abstract description 20
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000010146 3D printing Methods 0.000 claims abstract description 16
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 100
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 53
- 239000000843 powder Substances 0.000 claims description 49
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 239000002351 wastewater Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- 239000011165 3D composite Substances 0.000 claims description 16
- 229960000892 attapulgite Drugs 0.000 claims description 16
- 229910052625 palygorskite Inorganic materials 0.000 claims description 16
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 15
- 239000004927 clay Substances 0.000 claims description 13
- 238000007639 printing Methods 0.000 claims description 13
- 241000894006 Bacteria Species 0.000 claims description 12
- 239000004113 Sepiolite Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052624 sepiolite Inorganic materials 0.000 claims description 12
- 235000019355 sepiolite Nutrition 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
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- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
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- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 230000033116 oxidation-reduction process Effects 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 20
- 241001509286 Thiobacillus denitrificans Species 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 18
- 241001453382 Nitrosomonadales Species 0.000 abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 14
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- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 229910002651 NO3 Inorganic materials 0.000 abstract description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010865 sewage Substances 0.000 abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 abstract description 7
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 4
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- 108091005804 Peptidases Proteins 0.000 abstract description 3
- 239000004365 Protease Substances 0.000 abstract description 3
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 abstract description 3
- 102000004190 Enzymes Human genes 0.000 abstract description 2
- 108090000790 Enzymes Proteins 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 description 15
- 239000011707 mineral Substances 0.000 description 15
- 238000004064 recycling Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
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- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000945 filler Substances 0.000 description 12
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- QYTBWVFCSVDTEC-UHFFFAOYSA-N azane;iron Chemical compound N.[Fe] QYTBWVFCSVDTEC-UHFFFAOYSA-N 0.000 description 9
- 238000011049 filling Methods 0.000 description 9
- 230000003321 amplification Effects 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
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- 238000012258 culturing Methods 0.000 description 7
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- 239000000047 product Substances 0.000 description 7
- 229910052952 pyrrhotite Inorganic materials 0.000 description 7
- 239000002352 surface water Substances 0.000 description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 239000008204 material by function Substances 0.000 description 6
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 6
- 235000019796 monopotassium phosphate Nutrition 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003203 everyday effect Effects 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 5
- 229910021646 siderite Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
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- 238000001514 detection method Methods 0.000 description 4
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- 239000003337 fertilizer Substances 0.000 description 4
- 229910052598 goethite Inorganic materials 0.000 description 4
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 4
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 4
- 229910052683 pyrite Inorganic materials 0.000 description 4
- 239000011028 pyrite Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 239000010802 sludge Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 235000014653 Carica parviflora Nutrition 0.000 description 2
- 241000243321 Cnidaria Species 0.000 description 2
- 241000605118 Thiobacillus Species 0.000 description 2
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- 238000012544 monitoring process Methods 0.000 description 2
- 229910052585 phosphate mineral Inorganic materials 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 239000002686 phosphate fertilizer Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
A wastewater treatment functional material prepared based on natural wurtzite and natural limonite, a preparation method and application thereof in synchronous denitrification and phosphorus recovery relate to the technical field of advanced denitrification and phosphorus recovery in wastewater treatment, and a 3D iron-sulfur-phosphorus porous functional material or a 3D hematite composite phosphorus functional material is prepared by adopting natural wurtzite, natural limonite, a binder, a pore-forming agent or sulfur through a 3D printing technology. The nanometer zero-valent iron phosphorus, sulfur and other components in the 3D iron-sulfur-phosphorus porous functional material can be used as electron donors and electron transfer media of the thiobacillus denitrificans in the autotrophic denitrification process to reduce nitrate and nitrite or used as protease synthesis of an electron shuttle to improve the denitrification biological activity of the thiobacillus denitrificans; or the 3D hematite composite phosphorus functional material is used as an electron acceptor of the iron anaerobic ammonia oxidizing bacteria in the iron anaerobic ammonia oxidizing process, so that the electron transfer of microorganisms and the synthesis of enzymes are promoted, the denitrification performance of the sewage is improved, and the oxidation of ammonia nitrogen and the recovery of phosphorus are realized.
Description
Technical Field
The invention relates to the technical field of deep denitrification and phosphorus recovery in sewage treatment, in particular to a wastewater treatment functional material prepared based on natural wustite and natural limonite, a preparation method and application thereof in synchronous denitrification and phosphorus recovery.
Background
Phosphorus and nitrogen are the main factors causing eutrophication of lakes and oceans, and in recent years, the main treatment in the surface water environment and water treatment is the control of ammonia nitrogen and phosphorus. With the increasing severity of eutrophication of lakes and oceans, particularly urban black and odorous rivers, total phosphorus, total nitrogen and nitrate nitrogen are discharged out of standard, so that the main indexes of water pollution control and pollution discharge are classified, and strict discharge standards of total nitrogen and total phosphorus are formulated all over the country in recent years.
Heterotrophic denitrification-nitrification is always a main process route technology for denitrification of wastewater, ammonia nitrogen and organic nitrogen in water are converted into nitrate nitrogen through biochemical reaction in an aerobic process, water containing nitrate nitrogen is put into an anoxic tank, and organic matters or a reducing agent is utilized for denitrification reduction of the nitrate nitrogen into nitrogen. At present, the heterotrophic denitrification technology also has some problems: firstly, the high reflux ratio enables the total nitrogen to reach the discharge standard, so that the water treatment of a sewage treatment plant is uneconomical and the energy consumption is overlarge; secondly, as the residence time of the wastewater in a drainage pipeline and a septic tank is too long, the carbon source is insufficient, the carbon-nitrogen ratio is too low, and the requirement of heterotrophic denitrification on organic carbon cannot be met; thirdly, under the condition of insufficient carbon source, adding sodium acetate to supplement the carbon source can cause the problems of high denitrification cost, secondary pollution and the like caused by high COD of the effluent.
In order to make up for the deficiency of heterotrophic denitrification, the method is suitable for the requirement of advanced denitrification of water treatment, and is rapidly developed as a representative autotrophic denitrification technology in recent years. Sulfur autotrophic denitrification is a process of reducing nitrate to nitrogen by utilizing facultative anaerobic microorganisms such as thiobacillus denitrificans to finish anabolism by taking inorganic carbon as a carbon source and simultaneously taking sulfur and reducing sulfur compounds (sulfide, sulfite and thiosulfate) as electron donors, wherein the denitrification by taking sulfur as the electron donors is the main direction of development.
The existing solid sulfur autotrophic nitrogen removal material also has the problem of low nitrogen removal speed. Sulfur autotrophic nitrogen removal materials are insoluble solid substances which interact with microorganisms, and complex electron shuttling bodies are required to be added in the microbial metabolism process, so that the sulfur autotrophic nitrogen removal materials are key factors for limiting the nitrogen removal reaction speed and are root causes of low sulfur autotrophic nitrogen removal speed. The heterotrophic denitrification anaerobic biological deep filter added with sodium acetate generally has the problem of overlong water conservancy residence time, and most of natural iron sulfide autotrophic denitrification hydraulic residence time is required to be more than 4 hours, so that the construction investment of the sulfur autotrophic denitrification treatment pool is too high, and the economical efficiency is poor. How to improve the biological reaction speed of the sulfur autotrophic nitrogen removal and phosphorus recovery material by improving the material preparation method is a key technical problem which needs to be solved urgently at present. In addition, the existing sulfur autotrophic nitrogen removal and phosphorus recovery materials have the problems of low biological load of autotrophic microorganisms, low open porosity, low phosphorus recovery efficiency and the like.
In recent years, iron ammoxidation has received extensive attention from students as a novel biological denitrification technique. Iron ammoxidation (Feamox) is a novel environment-friendly autotrophic nitrogen removal technology mediated by iron. The iron ammoxidation reaction is NH under anaerobic environment and under the driving action of microorganism 4 + And Fe (III) as electron donor and electron acceptor, respectively, fe (III) being reduced to Fe (II) and NH 4 + Then the nitrogen is converted into nitrite, nitrate and nitrogen in several different forms. In the wastewater treatment process, the reaction is carried out in the anoxic and autotrophic processes, so that the costs related to aeration, external carbon source addition and sludge treatment can be reduced, and the wastewater treatment process is environment-friendly. Iron ammoxidation has a broader pH application range and, compared with anaerobic ammoxidation, iron alsoThe original bacteria also have stronger viability than anammox bacteria. However, the existing ferric iron-containing filler has the problems of low porosity, low biological activity, low biological load, low phosphorus recovery efficiency and the like, so that the removal effect is influenced.
Natural limonite is a widely distributed iron oxide mineral that is formed in a wetlands environment by anaerobic reduction by microorganisms. Limonite ores are often associated with other iron-bearing minerals, clay minerals, and organic matter in addition to goethite. The iron oxide obtained by roasting natural limonite is used for iron making, low-grade limonite is not utilized under the common condition, and is often discarded as waste rock in ore exploitation, so that the environment is damaged, and the land is occupied. Natural wurtzite is a hydrated iron-containing phosphate mineral found in geological environments and contains small amounts of Mg 2+ 、Mn 2+ And Ca 2+ Can replace Fe in the structure 2+ . Meanwhile, natural wurtzite is a secondary mineral that can be found in many geological environments: the oxidation zone of metal deposits replaces organic materials such as lignite, peat, forest soil and swamp iron ore in phosphate mineral-containing granite peganite, in glauconite deposits and clays, and in the recent alluvial layers.
In order to realize the resource utilization of the natural wurtzite and the natural limonite, the invention utilizes the 3D iron-sulfur-phosphorus porous functional material and the 3D hematite composite phosphorus functional material, and applies the materials to the wastewater treatment and the synchronous denitrification and phosphorus recovery, thereby greatly reducing the wastewater treatment cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a wastewater treatment functional material prepared based on natural wurtzite and natural limonite, a preparation method and application thereof in synchronous denitrification and phosphorus recovery. The 3D iron-sulfur-phosphorus porous functional material or the 3D hematite composite phosphorus functional material is prepared by adopting natural wurtzite, natural limonite, a binder, a pore-forming agent or sulfur through a 3D printing technology. The components such as nano zero-valent iron phosphorus, nano zero-valent iron and sulfur in the 3D iron-sulfur-phosphorus porous functional material can be used as electron donors and electron transfer media of the thiobacillus denitrificans in the autotrophic denitrification process to reduce nitrate and nitrite or used as protease synthesis of an electron shuttle to improve the denitrification biological activity of the thiobacillus denitrificans. The 3D hematite composite phosphorus functional material can be used as an electron acceptor of the iron anaerobic ammonia oxidation bacteria, promote electron transfer of microorganisms and synthesis of enzymes, improve the denitrification performance of sewage and realize synchronous recovery of ammonia nitrogen and phosphorus.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
firstly, the invention provides a wastewater treatment functional material prepared based on natural wurtzite and natural limonite, which is prepared from 80-95% of natural wurtzite and natural limonite, 4-14% of binder, 0.1-10% of pore-forming agent and 0-10% of sulfur, wherein the mass ratio of the natural wurtzite to the natural limonite is 1-5:1.
as a preferable technical scheme of the invention, the pore-forming agent adopted for preparing the wastewater treatment functional material is selected from straw scraps, leaf scraps, paper pulp fibers or sawdust, and the adopted binder is selected from water glass, attapulgite clay, sepiolite clay, bentonite, montmorillonite or kaolin.
Secondly, the invention provides a preparation method of a wastewater treatment functional material, namely a 3D iron-sulfur-phosphorus porous functional material, which is prepared from 80-95% of natural wurtzite, 4-14% of binder, 0.1-10% of pore-forming agent and 0.1-10% of sulfur, wherein the natural wurtzite, the natural limonite, the pore-forming agent, the binder and the sulfur are crushed to obtain powder with the particle size of 0.0075mm, and then the natural wurtzite powder and the natural limonite powder are respectively baked for 1-4 hours at 400-1000 ℃ in hydrogen atmosphere to respectively obtain a nano zero-valent iron-phosphorus composite material and a nano zero-valent iron composite material; and uniformly mixing the nano zero-valent iron-phosphorus composite material, the nano zero-valent iron composite material, the binder powder, the pore-forming agent powder and the sulfur powder according to the mass percent, finally weighing the mixed material, and printing by adopting a 3D printing technology to prepare the 3D iron-sulfur-phosphorus porous functional material with the particle size of 1-20 mm.
The 3D iron-sulfur-phosphorus porous functional material is added into wastewater which needs deep denitrification and phosphorus recovery, and is used as an electron donor in autotrophic denitrification, nitrate nitrogen is reduced into nitrogen to realize denitrification, meanwhile ferrous ions are combined with phosphorus in a water body under the induction of a phosphorus-containing seed crystal to realize phosphorus mineralization, and the nitrogen is recovered in a form of wurtzite. In the treatment method, the 3D iron-sulfur-phosphorus porous functional material is used as a microorganism carrier, a microorganism electron donor, a microorganism electron shuttle and a seed crystal for recycling phosphorus, and can be applied to deep denitrification of polluted water and recycling of phosphorus. The specific treatment scheme can be as follows:
building a biological filter for denitrification and phosphorus recovery in a process section of an urban sewage treatment plant, and adding a 3D iron-sulfur-phosphorus porous functional material into the biological filter to serve as an electron donor and a carrier of denitrification microorganisms; before the biological filter is started; filling the 3D Fe-S-P porous functional material into a biological filter tank for denitrification thiobacillus film formation by using wastewater to be denitrified and recovered with phosphorus (such as wastewater containing nitrate and phosphorus or secondary sedimentation tank effluent of municipal domestic sewage treatment plant).
Before starting operation, the main steps of the denitrification thiobacillus hanging membrane culture of the autotrophic denitrification biological filter of the 3D iron-sulfur-phosphorus porous functional material are as follows:
(A) Filling 3D Fe-S-P porous functional material into the biological filter tank in need of denitrification and phosphorus recovery, so that the content of sulfur in the 3D Fe-S-P porous functional material in the biological filter tank is 50-1000mg/L.
(B) Adding sludge containing thiobacillus denitrificans or thiobacillus denitrificans culture solution accounting for 0.1-10% of the volume of the biological filter into the biological filter. The water (containing a large amount of thiobacillus denitrificans) flowing out of the water outlet of the denitrification and phosphorus recovery filter tank is conveyed to the water inlet by a high-power peristaltic pump, water inlet and water outlet circulation is carried out according to the hydraulic retention time of 1-10h, and after a period of time of microbial domestication, the thiobacillus denitrificans grows and is attached to the surface and the inner pores of the 3D iron-sulfur-phosphorus porous functional material to be attached to a film, so that the 3D iron-sulfur-phosphorus porous functional material is loaded with a large amount of thiobacillus denitrificans.
(C) Monitoring Total Nitrogen (TN), total Phosphorus (TP) and COD concentration in water in the process of starting the film formation of the thiobacillus denitrificans, preparing TN concentration in water to be 5-50mg/L, phosphorus concentration to be 5-50mg/L and COD concentration to be 1-10mg/L by adding sodium nitrate, potassium dihydrogen phosphate and glucose, circulating water in and out, and maturing the film formation of the thiobacillus denitrificans after culturing for 5-10 days, or maturing the film formation of the thiobacillus denitrificans when TN concentration in water is less than 1mg/L, phosphorus concentration is less than 1mg/L and COD concentration is less than 1 mg/L. The hydraulic retention time is regulated to be between 0.5 and 2 hours, so that the concentration of TN, TP and COD gradually reach the quality standard class II of the surface water environment, and synchronous denitrification and phosphorus recovery are realized.
The preparation and application of the 3D iron-sulfur-phosphorus porous functional material provided by the invention have the beneficial effects that:
(1) The 3D iron-sulfur-phosphorus porous functional material prepared by the invention has the main chemical components as follows in the process of anaerobic denitrification and phosphorus recovery: the nano zero-valent iron phosphorus, sulfur and nano zero-valent iron are metabolized by microorganisms firstly to become carbon sources for heterotrophic denitrification, so that the microbial denitrification is promoted, and the main advantage is that the denitrification function of autotrophic microorganisms is enhanced under the synergistic effect of the nano zero-valent iron and sulfur. The nano zero-valent iron and sulfur can be used as electron donors and electron transfer media in the process of reducing nitrate and nitrite by the thiobacillus denitrificans, or enhance the synthesis of protease serving as an electronic shuttle, improve the denitrification biological activity of the thiobacillus denitrificans, shorten the hydraulic retention time of a denitrification recovery phosphorus filter tank, and enable the hydraulic retention time to be equal to or smaller than the hydraulic retention time of heterotrophic microorganism denitrification.
(2) The 3D iron-sulfur-phosphorus porous functional material prepared by the invention has light weight and is porous. Can be directly used as a carrier of autotrophic microorganisms, and solves the problem that the reactor is easy to be blocked due to the adoption of powdery sulfur, sulfur paste, natural pyrite, natural pyrrhotite, nano-structured pyrrhotite and other sulfur-containing nano mineral materials. The method can also overcome the defects of smooth surface, low microorganism load and the like of sulfur-containing nano mineral materials such as natural pyrite, natural pyrrhotite, sulfur paste, nano structured pyrrhotite, sulfur particles and the like. The 3D iron-sulfur-phosphorus porous functional material has a large specific surface area and an open porous structure, can accelerate the dissolution rate of sulfur, improves the activity of the thiobacillus denitrificans, and overcomes the problems of low mass transfer rate, slow dissolution rate of sulfur and the like of other sulfur-containing nano minerals. In addition, the raw material adopted by the invention is natural nano mineral material, and has the advantages of low cost, environmental protection, low cost and low energy consumption. Meanwhile, compared with heterotrophic denitrification taking sodium acetate as a carbon source, the cost of the 3D iron-sulfur-phosphorus porous functional material is greatly reduced.
(3) The 3D iron-sulfur-phosphorus porous functional material is of a porous structure, has a shape similar to coral shape, has affinity to microorganisms, is easy for growth, propagation and metabolism of autotrophic microorganisms, is easy for microorganisms to form flocculent extracellular organic matters, is easy to adsorb and fix by extracellular membranes of the microorganisms, and can effectively improve the denitrification and phosphorus recovery rate compared with the use of sulfur, sulfur paste, natural pyrrhotite, nano-structured pyrrhotite and natural pyrite.
(4) The 3D iron-sulfur-phosphorus porous functional material is used as a filler for deep denitrification and phosphorus recovery, is not only an autotrophic microorganism and nano zero-valent sulfur attached carrier, but also a neutralization material (containing a calcium-containing clay mineral material) for nano zero-valent sulfur acid production and autotrophic microorganism oxidation acid production. Not only provides the alkalinity and inorganic carbon source required by the sulfur autotrophic metabolism, but also stabilizes the pH value to create a micro-environment which is beneficial to self-propagation for the metabolism of microorganisms. The biochemical reaction equation is as follows:
the chemical equation of the acid production process of the 3D iron-sulfur-phosphorus porous functional material through autotrophic denitrification reaction is as follows:
6NO 3 - +5S+2H 2 O＝3N 2 +5SO 4 2- +4H +
the acid is neutralized by the 3D iron-sulfur-phosphorus porous functional material, and the chemical reaction equation is as follows:
CaCO 3 +2H + ＝Ca 2+ +CO 2 +H 2 O
CaMg(CO 3 ) 2 +4H + ＝2CO 2 +2H 2 O+Ca 2+ +Mg 2+
(5) The 3D iron-sulfur-phosphorus porous functional material prepared by the invention is applied to the conditions of insufficient carbon source and low phosphorus recovery efficiency of urban sewage treatment plants, and can not complete the heterotrophic denitrification and phosphorus recovery process, is a supplement to the existing water treatment functional material, and can realize the autotrophic denitrification and the synergistic organic heterotrophic denitrification of the 3D iron-sulfur-phosphorus porous functional material by taking the 3D iron-sulfur-phosphorus porous functional material as a carrier of microorganisms and a seed crystal of phosphorus crystallization, and can strengthen the phosphorus recovery effect. The 3D iron-sulfur-phosphorus porous functional material prepared by the invention has large adsorption capacity (100 mg/g) to phosphorus. The present invention avoids the introduction of unwanted or even harmful anions compared to the use of flocculants.
(6) The process of wurtzite formation can be generalized into 4 elements: (1) the water body needs to have iron and phosphorus elements with higher concentration; (2) the presence of reducing aqueous environmental conditions (redox potential<-300 mV); (3) the organic matters are rich (carbon sources are provided for heterotrophic microorganisms such as metal reducing bacteria); (4) the pH condition is 6-9. The 3D iron-sulfur-phosphorus porous functional material prepared by the invention does not need to realize the function of the iron-reducing bacteria of the iron-dissimilatory sp ＝10 -36 ) Is recovered, and the standard electrode potential E of the 3D Fe-S-P porous functional material 0 (Fe (II)/Fe (0)) is less than the oxidation-reduction potential<440mV forms wurtzite with phosphate in water. In the invention, a process of forming the wurtzite by using the 3D iron-sulfur-phosphorus porous functional material exists in the sewage or sewage treatment process, and the reaction equation is as follows:
Fe 0 +2H + ＝Fe 2+ +H 2 ↑
Fe(OH) 3 +3H + +e - ＝3H 2 O+Fe 2+
3Fe 2+ +2PO 4 3- +8H 2 O＝Fe 3 (PO 4 ) 2 ·8H 2 O
3Fe 2+ +2HPO 4 2- +8H 2 O＝Fe 3 (PO 4 ) 2 ·8H 2 O+2H +
finally, the invention also provides a preparation method of the wastewater treatment functional material, namely the 3D hematite composite phosphorus functional material, which is prepared from 80-94% of natural wurtzite and natural limonite, 4-14% of binder and 0.1-6% of pore-forming agent, wherein the natural wurtzite and the natural limonite are crushed to obtain powder with the particle size of 0.0075mm, the materials are weighed according to the mass percentage and uniformly mixed, water accounting for 20-40% of the total mass of the mixed materials is added, the water is uniformly stirred, the water is dried, 3D composite particles with the particle size of 1-20mm are prepared by printing the 3D composite particles by adopting a 3D printing technology, and finally the 3D composite particles are calcined in a muffle furnace at 400-1000 ℃ for 1-4h to obtain the 3D hematite composite phosphorus functional material.
Filling the 3D hematite composite phosphorus functional material into an anaerobic biological filter reactor, inoculating an anaerobic bacterial seed solution mainly containing Feamox microorganisms and iron dissimilators, and under the anaerobic condition, using trivalent iron in the 3D hematite composite phosphorus functional material as an electron acceptor, reducing the trivalent iron into divalent iron, combining with phosphate in water, directly oxidizing ammonia nitrogen into nitrogen, and simultaneously under the action of taking the 3D hematite composite phosphorus functional material as seed crystals, strengthening the synchronous removal and recovery action of phosphorus, finally forming the synchronous oxidation ammonia nitrogen of the wurtzite, and realizing the recovery of phosphorus and the removal of ammonia nitrogen in wastewater. The technical scheme for applying the 3D hematite composite phosphorus functional material to the water treatment of the iron anaerobic ammonia oxidation biological filter is as follows:
Building a biological filter for denitrification and phosphorus recovery in a process section of an urban sewage treatment plant, and adding a 3D hematite composite phosphorus functional material into the biological filter to serve as an electron acceptor for iron anaerobic ammonia oxidation, a carrier and a crystal seed for phosphorus recovery crystallization; before the biological filter is started, a film is formed on the 3D hematite composite phosphorus functional material; and filling the 3D hematite composite phosphorus functional material into a biological filter by using wastewater (such as wastewater containing high-concentration nitrogen and phosphorus) to be denitrified and recovered. Before starting operation, the main steps of the film-forming culture of the 3D hematite composite phosphorus functional material-iron anaerobic ammonia oxidation biological filter are as follows:
(A) And filling the biological filter tank with the nitrogen and phosphorus recovery requirement with the 3D hematite composite phosphorus functional material. Adding sludge containing iron anaerobic ammonia oxidation microorganisms or iron anaerobic ammonia oxidation culture solution accounting for 0.1-30% of the volume of the biological filter into the biological filter. The water flowing out from the water outlet of the denitrification and phosphorus recovery filter tank is conveyed to the water inlet again by a high-power peristaltic pump because the water contains a large amount of iron anaerobic ammonia oxidizing bacteria, the water is circulated in and out according to the hydraulic retention time of 1-10h, after a period of time of domestication of microorganisms, the iron anaerobic ammonia oxidizing bacteria grow and propagate, and are attached to the surface and the inner pores of the 3D hematite composite phosphorus functional material to attach a hanging film, so that the 3D hematite composite phosphorus functional material loads a large amount of iron anaerobic ammonia oxidizing bacteria.
(B) In the process of starting the iron anaerobic ammonia oxidizing bacteria film hanging, monitoring TN, TP and COD concentrations in water inlet and outlet, preparing TN concentration in water inlet by adding ammonium chloride, monopotassium phosphate and glucose to be 5-500mg/L, phosphorus concentration to be 5-50mg/L, COD concentration to be 1-10mg/L, circulating water inlet and outlet, and maturing when the iron anaerobic ammonia oxidizing bacteria film hanging is cultured for 2-20 days, or maturing when TN concentration of water outlet is less than 2mg/L, TP concentration is less than 2mg/L and COD concentration is less than 2 mg/L. The hydraulic retention time is regulated to be 1-4h, so that TN, TP and COD of the effluent gradually reach the quality standard class II of the surface water environment, and denitrification and phosphorus recovery are realized.
The preparation and application of the 3D hematite composite phosphorus functional material provided by the invention have the beneficial effects that:
(1) The 3D hematite composite phosphorus functional material prepared by the invention takes porous hematite and phosphorus as main components, and has the characteristics of large specific surface area, high porosity, large microorganism load capacity and the like. The 3D hematite composite phosphorus functional material is not only a carrier of Feamox microorganisms, a shuttle body of microorganism electrons, but also an electron acceptor of anaerobic microorganisms and a seed crystal for recovering phosphate, and can promote the activities of the Feamox microorganisms and the iron dissimilators, and can realize synchronous recovery of phosphorus and removal of nitrogen in wastewater.
(2) The 3D hematite composite phosphorus functional material prepared by the invention is filled into a fixed bed reactor in a natural stacking way, different microorganism zoning is formed at different parts of the fixed bed reactor after microorganism film formation, the upper part of the reactor has high dissolved oxygen concentration, the organic pollutant and ammonia nitrogen nitrification of aerobic microorganisms are mainly metabolized, the microorganisms gradually go from facultative bacteria to anaerobic bacteria from the middle part to the lower part are excessive, feamox microorganisms and iron dissimilatory reducing bacteria can realize the reduction of ferric iron to generate bivalent and synchronous ammonia nitrogen oxidation, and the bivalent iron is rapidly enriched with phosphorus and phosphorus in wastewater under the induction of seed crystals at the momentAcid radical (PO) 4 3- ) Fe formed by biological reduction 2+ The combination can produce the wurtzite crystal, and the wurtzite which can be recovered as phosphate fertilizer is produced. The 3D hematite composite phosphorus functional material can solve the problem of low efficiency of synchronous denitrification and phosphorus recovery in the traditional Feamox oxidation process.
Drawings
Fig. 1 is a pictorial view of different materials.
Figure 2 is an XRD pattern of the nano-minerals and the preparation of functional materials.
Fig. 3 is an SEM image of sulfur.
Fig. 4 is an SEM image of natural wurtzite.
Fig. 5 is an SEM image of calcined natural wurtzite in a hydrogen atmosphere at 700 ℃.
Fig. 6 is an SEM image of natural limonite.
Fig. 7 is an SEM image of calcined natural limonite through a hydrogen atmosphere at 700 ℃.
Fig. 8 is an SEM image of attapulgite clay.
Fig. 9 is an SEM image of the 3D iron-sulfur-phosphorus porous functional material.
Fig. 10 is an SEM image of the 3D hematite composite phosphorus functional material.
FIG. 11 is an SEM image of a 3D iron-sulfur-phosphorus porous functional material-supported thiobacillus denitrificans.
Detailed Description
The invention provides a preparation method of a wastewater treatment functional material, namely a 3D iron-sulfur-phosphorus porous functional material, which is prepared from 80-95% of natural wurtzite, 4-14% of binder, 0.1-10% of pore-forming agent and 0.1-10% of sulfur, wherein the natural wurtzite, the natural limonite, the pore-forming agent, the binder and the sulfur are crushed to obtain powder with the particle size of 0.0075mm, and then the natural wurtzite powder and the natural limonite powder are respectively baked for 1-4 hours at 400-1000 ℃ in hydrogen atmosphere to respectively obtain a nano zero-valent iron-phosphorus composite material and a nano zero-valent iron composite material; and uniformly mixing the nano zero-valent iron-phosphorus composite material, the nano zero-valent iron composite material, the binder powder, the pore-forming agent powder and the sulfur powder according to the mass percent, finally weighing the mixed material, and printing by adopting a 3D printing technology to prepare the 3D iron-sulfur-phosphorus porous functional material with the particle size of 1-20 mm.
The invention provides a preparation method of a wastewater treatment functional material, namely a 3D hematite composite phosphorus functional material, which is prepared from 80-94% of natural wurtzite and natural limonite, 4-14% of a binder and 0.1-6% of a pore-forming agent, wherein the natural wurtzite and the natural limonite are crushed to obtain powder with the particle size of 0.0075mm, the materials are weighed according to the mass percentage and uniformly mixed, water accounting for 20-40% of the total mass of the mixed materials is added, the water is uniformly stirred, then the water is dried, 3D composite particles with the particle size of 1-20mm are prepared by printing the 3D composite particles by adopting a 3D printing technology, and finally the 3D composite particles are calcined in a muffle furnace at 400-1000 ℃ for 1-4h to obtain the 3D hematite composite phosphorus functional material.
The natural minerals adopted by the invention and the functional material objects prepared by the invention are shown in figure 1, wherein A is natural limonite, B is natural wurtzite, C is 3D hematite composite phosphorus functional material, and D is 3D iron-sulfur-phosphorus porous functional material.
The invention adopts natural minerals, the prepared 3D iron-sulfur-phosphorus porous functional material and the 3D hematite composite phosphorus functional material, and the phase and structure morphology characterization of the material is as follows:
figure 2 is an XRD pattern of the nano-minerals and the preparation of functional materials. Wherein FIG. 2 (A) is an XRD pattern of natural wurtzite, as can be seen from the figure, at 5 0 -70 0 In the range, the characteristic diffraction peak of the wurtzite is strong, which indicates that the natural wurtzite has high crystallinity. FIG. 2 (B) is an XRD pattern of sepiolite and kaolin, as can be seen at 3 0 -70 0 Within this range, characteristic diffraction peaks for sepiolite and kaolin appear, indicating high crystallinity for sepiolite and kaolin. Fig. 2 (C) is an XRD pattern of the 3D iron-sulfur-phosphorus porous functional material and the 3D hematite composite phosphorus functional material, and the functional materials prepared in example 1 and example 2 are 3D iron-sulfur-phosphorus porous functional materials, and it can be seen from the figure that characteristic diffraction peaks of nano zero-valent iron exist. The functional materials prepared in example 5 and example 6 are 3D hematite composite phosphorus functional materials, and it can be seen from the figure that there are characteristic diffraction peaks of hematite.
Fig. 3 is an SEM image of sulfur. A-D shows different amplification factors, and the graph shows that the sulfur has compact particles and low porosity, so that the dissolution rate of the sulfur is low, and the sulfur has the appearance of large particle blocks.
Fig. 4 is an SEM image of natural wurtzite. A-D shows different amplification factors, and the graph shows that the wurtzite has a nano particle morphology, a platy and flocculent nano structure morphology, a dense natural wurtzite structure and low activity.
Fig. 5 is an SEM image of calcined natural wurtzite in a hydrogen atmosphere at 700 ℃. A-D represents different amplification factors, and the figure shows that the removal of structural water, crystal water, zeolite water and adsorbed water in the natural wurtzite forms nanostructured Fe 0 The P composite porous material has high porosity and large specific surface area, and the material with higher activity can be used as seed crystal for recovering phosphorus and electron donor of sulfur autotrophic denitrifying bacteria to realize synchronous denitrification and phosphorus recovery.
Fig. 6 is an SEM image of natural limonite. a-D represent different magnifications, and it can be seen from the figure that natural limonite is an addictive crystalline mineral, and is composed of an aggregate of various minerals, including goethite, hematite and siderite, which have a nanoneedle-like structural morphology.
Fig. 7 is an SEM image of calcined natural limonite through a hydrogen atmosphere at 700 ℃. A-D shows different amplification factors, and the graph shows that the natural limonite has a nanostructured porous structure and has larger specific surface area, high porosity and high activity.
Fig. 8 is an SEM image of attapulgite clay. A-D represents different amplification factors, and the graph shows that the attapulgite clay has a nanorod shape, is arranged in disorder, and has higher activity and large specific surface area.
Fig. 9 is an SEM image of the 3D iron-sulfur-phosphorus porous functional material. A-D shows different amplification factors, and the graph shows that the 3D iron-sulfur-phosphorus porous functional material prepared by adopting the 3D printing technology has the advantages of an open pore structure, coral structure morphology, capability of attaching and growing anaerobic microorganisms on the inner surface and the outer surface, affinity for the microorganisms, large specific surface area and the like.
Fig. 10 is an SEM image of the 3D hematite composite phosphorus functional material. The A-D shows different amplification factors, and the figure shows that the 3D hematite composite phosphorus functional material has an open pore structure, large specific surface area and high activity, and iron ammonia oxidizing bacteria can enter the interior of the material for propagation and growth through the open pore structure.
FIG. 11 is an SEM image of a 3D iron-sulfur-phosphorus porous functional material-supported thiobacillus denitrificans. A-E shows different amplification factors, and when the 3D iron-sulfur-phosphorus porous functional material is operated for about 6 months, a large amount of thiobacillus denitrificans, filamentous bacteria, aerobic microorganisms and the like can be observed on the inner and outer surfaces of the material, so that the 3D iron-sulfur-phosphorus porous functional material has hydrophilicity and is suitable for propagation and growth of microorganisms.
The following describes in detail a wastewater treatment functional material prepared based on natural wurtzite and natural limonite, a preparation method and application thereof in simultaneous denitrification and phosphorus recovery.
1. Preparation and application of 3D iron-sulfur-phosphorus porous functional material
Example 1
(1) Firstly, crushing natural wurtzite, natural limonite, attapulgite clay, sawdust and sulfur to obtain powder with the particle size of 0.0075mm, and then roasting the natural wurtzite powder and the natural limonite powder at 800 ℃ for 2 hours in a hydrogen atmosphere respectively to obtain a nano zero-valent iron-phosphorus composite material and a nano zero-valent iron composite material respectively.
(2) Then according to the mass percentages of the nano zero-valent iron-phosphorus functional material, the nano zero-valent iron composite material, the attapulgite clay powder, the saw dust powder and the sulfur powder, the method comprises the following steps: 63% of nano zero-valent iron-phosphorus functional material, 25% of nano zero-valent iron composite material, 5% of attapulgite powder, 2% of saw dust and 5% of sulfur powder, uniformly mixing the materials, finally weighing the mixed materials, printing by adopting a 3D printing technology to prepare the 3D iron-sulfur-phosphorus porous functional material with the particle size of 4-8mm, wherein the specific surface area is 175m 2 Per g, porosity 87% and oxidation-reduction potential-500 MV.
(3) An inverted cone-shaped container is made of acrylic organic glass and is used as an anoxic denitrification recycling phosphorus biological filter, an acrylic organic glass tube is arranged at the bottom and is used as a water inlet, and an acrylic organic glass tube is arranged at the top and is used as a water outlet. The inverted cone-shaped structural design ensures that the 3D iron-sulfur-phosphorus porous functional material and the microorganism composite floccule are reserved in the denitrification recycling phosphorus pond, thereby reducing the loss of the 3D iron-sulfur-phosphorus porous functional material and the microorganism and reducing the turbidity of effluent.
(4) The simulated wastewater for experiments is prepared by adding nitrate, monopotassium phosphate and glucose into tap water, wherein the concentration of nitrate nitrogen is 50mg/L, the concentration of phosphorus is 20mg/L, COD and the concentration of phosphorus is 6mg/L.
(5) And (3) injecting simulated wastewater into the anoxic denitrification and phosphorus recovery filter tank by using a peristaltic pump, and adding the 3D iron-sulfur-phosphorus porous functional material prepared in the step (2) and the enriched and cultured sulfur autotrophic denitrification bacterial liquid accounting for 20% of the volume of the denitrification and phosphorus recovery tank.
(6) The water discharged from the upper part of the denitrification and phosphorus recovery tank is conveyed into the denitrification and phosphorus recovery tank from a water inlet at the lower part to form water circulation, heterotrophic microorganisms are domesticated and cultured, and composite flocs are formed with the 3D iron-sulfur-phosphorus porous functional material until TN concentration is less than 5mg/L, TP water outlet concentration is less than 1mg/L, and COD water outlet concentration is less than 1mg/L to be considered to be domesticated and mature.
(7) The flow is regulated to gradually reduce the water power residence time in the anoxic denitrification and phosphorus recovery reactor to be within 1h, the ion concentration of effluent TN, TP, COD is monitored every day, when the TN concentration of the effluent is lower than 0.01mg/L, the concentration of phosphorus is lower than 0.02mg/L, the concentration of COD is lower than 0.01mg/L, the denitrification and phosphorus recovery filter tank reaches a stable state, a final wustite recovery product is obtained, and the effluent reaches the surface water environment quality standard II.
Example 2
(1) Firstly, crushing natural wurtzite, natural limonite, sepiolite clay, straw scraps and sulfur to obtain powder with the particle size of 0.0075mm, and then roasting the natural wurtzite powder and the natural limonite powder at 700 ℃ for 3 hours in a hydrogen atmosphere respectively to obtain a nano zero-valent iron-phosphorus composite material and a nano zero-valent iron composite material respectively.
(2) Then according to the mass percentages of the nano zero-valent iron-phosphorus composite material, the nano zero-valent iron composite material, sepiolite clay powder, straw powder and sulfur powder as follows: nano zero-valent iron-phosphorus function60% of material, 32% of nano zero-valent iron composite material, 4% of sepiolite powder, 1% of straw powder and 3% of sulfur powder, uniformly mixing the materials, finally weighing the mixed materials, printing by adopting a 3D printing technology to prepare the 3D iron-sulfur-phosphorus porous functional material with the particle size of 3-10mm, wherein the specific surface area is 183m 2 Per g, porosity 76% and oxidation-reduction potential 550MV.
(3) An inverted cone-shaped container is made of acrylic organic glass and is used as an anoxic denitrification recycling phosphorus biological filter, an acrylic organic glass tube is arranged at the bottom and is used as a water inlet, and an acrylic organic glass tube is arranged at the top and is used as a water outlet. The inverted cone-shaped structural design ensures that the 3D iron-sulfur-phosphorus porous functional material and the microorganism composite floccule are reserved in the denitrification recycling phosphorus pond, thereby reducing the loss of the 3D iron-sulfur-phosphorus porous functional material and the microorganism and reducing the turbidity of effluent.
(4) The simulated wastewater for experiments is prepared by adding nitrate, monopotassium phosphate and glucose into tap water, wherein the concentration of nitrate nitrogen is 30mg/L, the concentration of phosphorus is 30mg/L, COD and the concentration of phosphorus is 5mg/L.
(5) And (3) injecting simulated wastewater into the anoxic denitrification and phosphorus recovery filter tank by using a peristaltic pump, and adding the 3D iron-sulfur-phosphorus porous functional material prepared in the step (2) and the enriched and cultured sulfur autotrophic denitrification bacterial liquid accounting for 10% of the volume of the denitrification and phosphorus recovery tank.
(6) The water discharged from the upper part of the denitrification and phosphorus recovery tank is conveyed into the denitrification and phosphorus recovery tank from a water inlet at the lower part to form water circulation, heterotrophic microorganisms are domesticated and cultured, and composite flocs are formed with the 3D iron-sulfur-phosphorus porous functional material until TN concentration is less than 5mg/L, TP water outlet concentration is less than 2mg/L, and COD water outlet concentration is less than 2mg/L to be considered to be domesticated and mature.
(7) The flow is regulated to gradually reduce the water force residence time in the anoxic denitrification and phosphorus recovery reactor to be within 0.5h, the ion concentration of effluent TN, TP, COD is monitored every day, when the TN concentration of the effluent is lower than 0.01mg/L, the concentration of phosphorus is lower than 0.02mg/L, the concentration of COD is lower than 0.01mg/L, the denitrification and phosphorus recovery filter tank reaches a stable state, a final wustite recovery product is obtained, and the effluent reaches the surface water environment quality standard II.
Example 3
(1) Firstly, crushing natural wurtzite, natural limonite, kaolin, pulp fiber and sulfur to obtain powder with the particle size of 0.0075mm, and then roasting the natural wurtzite powder and the natural limonite powder at 600 ℃ for 2 hours in a hydrogen atmosphere to obtain a nano zero-valent iron-phosphorus composite material and a nano zero-valent iron composite material respectively.
(2) Then according to the mass percentages of the nano zero-valent iron-phosphorus composite material, the nano zero-valent iron composite material, the kaolin powder, the pulp fiber powder and the sulfur powder as follows: 75% of nano zero-valent iron-phosphorus functional material, 17% of nano zero-valent iron composite material, 2% of kaolin powder, 3% of pulp fiber powder and 3% of sulfur powder, uniformly mixing the materials, finally weighing the mixed materials, printing by adopting a 3D printing technology to prepare the 3D iron-sulfur-phosphorus porous functional material with the particle size of 10-15mm, wherein the specific surface area is 215m 2 Per g, porosity 83% and oxidation-reduction potential-650 MV.
(3) An inverted cone-shaped container is made of acrylic organic glass and is used as an anoxic denitrification recycling phosphorus biological filter, an acrylic organic glass tube is arranged at the bottom and is used as a water inlet, and an acrylic organic glass tube is arranged at the top and is used as a water outlet. The inverted cone-shaped structural design ensures that the 3D iron-sulfur-phosphorus porous functional material and the microorganism composite floccule are reserved in the denitrification recycling phosphorus pond, thereby reducing the loss of the 3D iron-sulfur-phosphorus porous functional material and the microorganism and reducing the turbidity of effluent.
(4) The simulated wastewater for experiments is prepared by adding nitrate, monopotassium phosphate and glucose into tap water, wherein the concentration of nitrate nitrogen is 20mg/L, the concentration of phosphorus is 10mg/L, COD and the concentration of phosphorus is 7mg/L.
(5) And (3) injecting simulated wastewater into the anoxic denitrification and phosphorus recovery filter tank by using a peristaltic pump, and adding the 3D iron-sulfur-phosphorus porous functional material prepared in the step (2) and the enriched and cultured sulfur autotrophic denitrification bacterial liquid accounting for 10% of the volume of the denitrification and phosphorus recovery tank.
(6) The water discharged from the upper part of the denitrification and phosphorus recovery tank is conveyed into the denitrification and phosphorus recovery tank from a water inlet at the lower part to form water circulation, heterotrophic microorganisms are domesticated and cultured, and composite flocs are formed with the 3D iron-sulfur-phosphorus porous functional material until TN concentration is less than 3mg/L, phosphorus water outlet concentration is less than 2mg/L, and COD water outlet concentration is less than 0.1mg/L to be considered to be domesticated and mature.
(7) The flow is regulated to gradually reduce the water force residence time in the anoxic denitrification and phosphorus recovery reactor to be within 2 hours, the ion concentration of effluent TN, TP, COD is monitored every day, when the TN concentration of the effluent is lower than 0.01mg/L, the concentration of phosphorus is lower than 0.02mg/L, the concentration of COD is lower than 0.01mg/L, the denitrification and phosphorus recovery filter tank reaches a stable state, a final wustite recovery product is obtained, and the effluent reaches the surface water environment quality standard II.
Comparative example 4
(1) Crushing natural limonite and natural wurtzite to obtain 1-10mm granule, wherein the specific surface area of natural limonite is 12m 2 Specific surface area of natural wurtzite (14 m)/g 2 /g。
(2) Crushing natural limonite to obtain 1-10mm grains, and calcining the grains at 700 deg.c in hydrogen atmosphere for 2 hr to obtain nanometer zero valent iron composite stuffing and nanometer zero valent Fe 0 The specific surface area of the nano zero-valent iron composite filler is 23m 2 /g, nano zero-valent Fe 0 The specific surface area of the composite filler/P is 25m 2 /g。
(3) Mixing sulfur tablet particles with calcium-containing attapulgite particles (mass ratio of 1:1), sulfur paste particles with calcium-containing attapulgite particles (mass ratio of 1:1), pyrite particles with calcium-containing attapulgite particles (mass ratio of 1:1), pyrrhotite particles with calcium-containing attapulgite particles (mass ratio of 1:1) to obtain 4 mixed mineral materials.
(4) Commercial porous autotrophic denitrification fillers were purchased.
(5) 9 inverted cone-shaped containers are respectively manufactured by using acrylic organic glass as an anoxic denitrification recycling phosphorus biological filter, an acrylic organic glass tube is arranged at the bottom and is used as a water inlet, and an acrylic organic glass tube is arranged at the top and is used as a water outlet. The inverted cone-shaped structural design ensures that the iron-containing nano mineral materials prepared in the steps (1), (2) and (3) and the purchased porous autotrophic denitrification filler and microorganism composite flocs are reserved in the denitrification recycling phosphorus pool, so that the material and microorganism loss is reduced, and the turbidity of effluent is reduced.
(6) The simulated wastewater for experiments is prepared by adding nitrate, monopotassium phosphate and glucose into tap water, wherein the concentration of nitrate nitrogen is 30mg/L, the concentration of phosphorus is 30mg/L, COD and the concentration of phosphorus is 5mg/L.
(7) Parallel comparison experiments were set up separately: and (3) injecting simulated wastewater into the anoxic denitrification and phosphorus recovery filter tank by using a peristaltic pump, and enriching and culturing sulfur autotrophic nitrogen removal bacteria liquid accounting for 20% of the volume of the denitrification and phosphorus recovery tank.
(8) And (3) conveying water discharged from the upper part of the denitrification and phosphorus recovery tank into the denitrification and phosphorus recovery tank from a water inlet at the lower part to form water circulation, domesticating and culturing heterotrophic microorganisms, and forming composite flocs with the functional materials (1), (2) and (3) and the commercially available porous autotrophic denitrification filler (4).
(9) The flow rate is regulated to gradually reduce the water force residence time in the anoxic denitrification and phosphorus recovery reactor to be within 1h, the concentration of effluent TN, TP, COD is monitored every day, table 1 shows the effluent concentration data after 6 months of operation, and the following table shows that the nitrogen and phosphorus concentrations of all the effluent of the comparison materials are far higher than the discharge standard of the surface water environment quality.
TABLE 1 comparative example 4 TN, TP, COD Water concentration detection data after 6 months of operation
2. Preparation and application of 3D hematite composite phosphorus functional material
Example 5
(1) Crushing natural limonite and natural wurtzite to obtain powder with the particle size of 0.0075mm, wherein the mass percentages of the natural limonite, the natural wurtzite, the attapulgite clay and the pulp fiber are as follows: 66% of natural hematite powder, 25% of natural limonite powder, 8% of attapulgite clay and 1% of paper pulp fiber, weighing materials, uniformly mixing, adding water with the mass ratio of 25% of the mixed materials, uniformly stirring, drying the water, printing by adopting a 3D printing technology to prepare 3D composite particles with the particle size of 1-20mm, and finally placing the 3D composite particles in a muffle furnace for calcination at 600 ℃ for 4 hours. The 3D hematite composite phosphorus functional material is prepared, and the specific surface area thereof170m of 2 Per g, porosity 65%.
(2) The control group experiment adopts natural limonite, natural hematite, natural magnetite and natural siderite as the filler, and the preparation method comprises the following steps: crushing natural limonite, natural hematite, natural magnetite and natural siderite respectively to obtain 3-10mm of each particle material, wherein the specific surface areas of the prepared 4 materials are as follows: 10m 2 /g、12m 2 /g、19m 2 /g and 13m 2 /g。
(3) And (3) respectively filling the prepared 3D hematite composite phosphorus functional material and the material for the control group experiment in the step (2) into experimental water treatment columns with the same size, inoculating and enriching and culturing iron ammonia oxidizing bacteria, wherein the ODP value of bacterial liquid is more than 0.5. The volume of the bacterial liquid is 2% of the volume of the experimental column, the culture liquid in the experimental column circulates for 2-3 days by a peristaltic pump, so that the iron ammonia oxidizing bacteria are promoted to form films on the surface and the inside of the 3D hematite composite phosphorus functional material, and then water inflow treatment is started according to normal conditions. The initial water inlet is controlled to have ammonia nitrogen concentration of 300mg/L, phosphorus concentration of 30mg/L, COD concentration of 3mg/L and hydraulic retention time of 1d.
(4) The concentration of TN, TP, COD was monitored daily for about 6 months of operation. When the running effluent can not meet the discharge or water recycling requirements, the 3D hematite composite phosphorus functional material is proved to have electronic failure or saturated adsorption phosphorus removal capacity, and a wustite ore recovery product can be obtained and is applied to the production of agricultural phosphorus fertilizers.
Table 2 example 5 and control test TN and TP effluent concentration test data after 6 months of operation
Example 6
(1) Crushing natural limonite and natural wurtzite to obtain powder with the particle size of 0.0075mm, wherein the powder comprises the following natural limonite, natural wurtzite, sepiolite and leaf debris in percentage by mass: 57% of natural wuyite, 30% of natural limonite, 10% of sepiolite and 3% of leaf scraps, weighing materials, uniformly mixing, adding water with the mass ratio of 25% of the mixed materials, uniformly stirring, drying, and making the mixture into a powder3D composite particles with the particle size of 1-20mm are prepared by printing through a 3D printing technology, and the 3D composite particles are calcined in a muffle furnace at 800 ℃ for 3 hours. The specific surface area of the prepared 3D hematite composite phosphorus functional material is 180m 2 Per g, the porosity is 73%.
(2) Control group experiments: the preparation method adopts brown-porous hematite, red-porous hematite, magnetic-porous hematite and rhombohedral-porous hematite as fillers and comprises the following steps: crushing natural limonite, natural hematite, natural magnetite and natural siderite respectively to obtain 4-10mm particle materials, and calcining in a muffle furnace at 300 ℃ for 2h respectively. The specific surface areas of the prepared 4 materials are respectively as follows: brown-porous hematite 25m 2 /g, red-porous hematite 22m 2 Per g, magnetic-porous hematite 29m 2 /g, rhombohedral-porous hematite 23m 2 /g。
(3) Filling the prepared 3D hematite composite phosphorus functional material and the material prepared by the control group experiment in the step (2) into an experimental water treatment column with the same size, inoculating and enriching and culturing iron ammonia oxidizing bacteria, wherein the ODP value of bacterial liquid is more than 0.3. The volume of the bacterial liquid is 2% of that of the experimental column, the culture liquid in the experimental column circulates for 5-7 days by a peristaltic pump, so that the iron ammonia oxidizing bacteria are promoted to form films on the surface and the inside of the 3D hematite composite phosphorus functional material, and then water inflow treatment is started according to normal conditions. The initial water inlet is controlled to have ammonia nitrogen concentration of 400mg/L, phosphorus concentration of 50mg/L, COD concentration of 4mg/L and hydraulic retention time of 2d.
(4) The concentration of TN, TN, COD was monitored daily for about 6 months of operation. When the running effluent can not meet the discharge or water recycling requirements, the 3D hematite composite phosphorus functional material is proved to have electronic failure or saturated adsorption phosphorus removal capacity, and a wustite ore recovery product can be obtained and is applied to the production of agricultural phosphorus fertilizers.
TABLE 3 TN and TP Water concentration detection data after 6 months of operation of example 6 and control experiments
Example 7
(1) Crushing natural limonite and natural wurtzite to obtain powder with the particle size of 0.0075mm, wherein the powder comprises the following natural limonite, natural wurtzite, bentonite and straw scraps in percentage by mass: 68% of natural blue iron ore powder, 25% of natural limonite, 6% of bentonite and 1% of straw scraps, weighing materials, uniformly mixing, adding water with the mass ratio of 25% of the mixed materials, uniformly stirring, drying the water, printing the mixture by a 3D printing technology to prepare 3D composite particles with the particle size of 1-20mm, and finally calcining the 3D composite particles in a muffle furnace at 900 ℃ for 2 hours. The specific surface area of the prepared 3D hematite composite phosphorus functional material is 186m 2 And/g, porosity 92%.
(2) Control group experiments: the preparation method respectively adopts concave-iron oxide porous ceramsite, sea-iron oxide porous ceramsite, expanded-iron oxide porous ceramsite and high-iron oxide porous ceramsite as filler, and comprises the following steps: attapulgite, straw and goethite (mass ratio: 10:1:5); sepiolite, sawdust, hematite (mass ratio: 10:1:5); bentonite, leaves and magnetite (mass ratio: 10:1:5); mixing the four components in total (mass ratio: 10:1:5) to obtain attapulgite composite goethite, sepiolite composite hematite and bentonite composite magnetite, and calcining the kaolin composite siderite at 900 ℃ for 2 hours in an air atmosphere to obtain concave-iron oxide porous ceramsite, sea-iron oxide porous ceramsite, expanded-iron oxide porous ceramsite and high-iron oxide porous ceramsite.
(3) Filling the prepared 3D hematite composite phosphorus functional material and the material prepared by the control group experiment in the step (2) into an experiment water treatment column with the same size, inoculating and enriching and culturing iron ammonia oxidizing bacteria, wherein the ODP value of bacterial liquid is more than 0.5. The volume of the bacterial liquid is 2% of the volume of the experimental column, the culture liquid in the experimental column circulates for 2-3 days by a peristaltic pump, so that the iron ammonia oxidizing bacteria are promoted to form films on the surfaces and the interiors of the 3D hematite composite phosphorus functional material and the material in the step (2), and then water inflow treatment is started according to normal conditions. The initial water inlet is controlled to have ammonia nitrogen concentration of 500mg/L, phosphorus concentration of 5mg/L, COD concentration of 4mg/L and hydraulic retention time of 3d.
(4) The operation is carried out for about 6 months, and the effluent concentration of TN, TP and COD is monitored every day. When the running effluent can not meet the discharge or water recycling requirements, the 3D hematite composite phosphorus functional material is proved to have electronic failure or saturated adsorption phosphorus removal capacity, and a wustite ore recovery product can be obtained and is applied to the production of agricultural phosphorus fertilizers.
Table 4 example 7 and control experiment total nitrogen and phosphorus effluent concentration detection data after 6 months of operation
Example 8
(1) Crushing natural limonite and natural wurtzite to obtain powder with the particle size of 0.0075mm, wherein the powder comprises the following components in percentage by mass: 60% of natural blue iron ore powder, 26% of natural limonite, 12% of water glass and 2% of paper pulp fiber, weighing materials, uniformly mixing, adding water with the mass ratio of 25% of the mixed materials, uniformly stirring, drying the water, printing the mixture by adopting a 3D printing technology to prepare 3D composite particles with the particle size of 1-20mm, and calcining the 3D composite particles in a muffle furnace at 650 ℃ for 4 hours. The specific surface area of the prepared 3D hematite composite phosphorus functional material is 198m 2 And/g, the porosity is 95%.
(2) The control group experiment uses commercial iron-containing porous ceramsite as a filler.
(3) Filling the prepared 3D hematite composite phosphorus functional material and the commercial iron-containing porous ceramsite in the step (2) serving as a filler into an experimental water treatment column with the same size, inoculating and enriching and culturing iron ammonia oxidizing bacteria, wherein the ODP value of bacterial liquid is more than 0.5. The volume of the bacterial liquid is 2% of the volume of the experimental column, the culture liquid in the experimental column circulates for 2-3 days by a peristaltic pump, so that the iron ammonia oxidizing bacteria are promoted to form films on the surface and the inside of the 3D hematite composite phosphorus functional material, and then water inflow treatment is started according to normal conditions. The initial water inlet is controlled to have ammonia nitrogen concentration of 450mg/L, phosphorus concentration of 10mg/L, COD concentration of 5mg/L and hydraulic retention time of 0.5d.
(4) The concentration of TN, TP, COD was monitored daily for about 6 months of operation. When the running effluent can not meet the discharge or water recycling requirements, the 3D hematite composite phosphorus functional material is proved to have electronic failure or saturated adsorption phosphorus removal capacity, and a wustite ore recovery product can be obtained and is applied to the production of agricultural phosphorus fertilizers.
Table 5 example 8 and control experiment detection data of ammonia nitrogen and phosphorus effluent concentration after 6 months of operation
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (8)
1. The wastewater treatment functional material prepared based on the natural wurtzite and the natural limonite is characterized by being prepared from 80-95% of the natural wurtzite and the natural limonite, 4-14% of a binder, 0.1-10% of a pore-forming agent and 0-10% of sulfur, wherein the mass ratio of the natural wurtzite to the natural limonite is 1-5:1.
2. the wastewater treatment functional material according to claim 1, wherein the pore-forming agent is selected from straw chips, leaf chips, pulp fibers or sawdust, and the binder is selected from water glass, attapulgite clay, sepiolite clay, bentonite, montmorillonite or kaolin.
3. The wastewater treatment functional material according to claim 1 or 2, wherein the wastewater treatment functional material made of 80-95% of natural wurtzite and natural limonite, 4-14% of binder, 0.1-10% of pore-forming agent and 0.1-10% of sulfur is a 3D iron-sulfur-phosphorus porous functional material.
4. A method for preparing the wastewater treatment functional material according to claim 3, which is characterized in that firstly, natural wurtzite, natural limonite, pore-forming agent, binder and sulfur are crushed and sieved to obtain powder; then roasting the natural wurtzite powder and the natural limonite powder at 400-1000 ℃ for 1-4 hours in hydrogen atmosphere respectively to obtain a nano zero-valent iron-phosphorus composite material and a nano zero-valent iron composite material respectively; and uniformly mixing the nano zero-valent iron-phosphorus composite material, the nano zero-valent iron composite material, the binder powder, the pore-forming agent powder and the sulfur powder according to the mass percent, finally weighing the mixed material, and printing by adopting a 3D printing technology to prepare the 3D iron-sulfur-phosphorus porous functional material with the particle size of 1-20 mm.
5. The wastewater treatment functional material according to claim 1 or 2, wherein the wastewater treatment functional material made of 80-94% of natural wurtzite and natural limonite, 4-14% of binder and 0.1-6% of pore-forming agent is a 3D hematite composite phosphorus functional material.
6. A method for preparing the wastewater treatment functional material according to claim 5, which is characterized in that firstly, natural wurtzite and natural limonite are crushed and sieved to obtain powder, then, each material is weighed and mixed uniformly according to mass percent, water accounting for 20-40% of the total mass of the mixed material is added, the water is dried and stirred uniformly, 3D composite particles with particle size of 1-20mm are prepared by printing the 3D composite particles by adopting a 3D printing technology, and finally, the 3D composite particles are calcined in a muffle furnace at 400-1000 ℃ for 1-4 hours to obtain the 3D hematite composite phosphorus functional material.
7. The use of the wastewater treatment functional material in synchronous denitrification and phosphorus recovery according to claim 3, wherein the 3D iron-sulfur-phosphorus porous functional material is added into wastewater requiring deep denitrification and phosphorus recovery, nitrate nitrogen is reduced to nitrogen as an electron donor in a sulfur autotrophic denitrification and phosphorus recovery filter tank, simultaneously ferrous ions are combined with phosphorus in a water body, and the synchronous denitrification and phosphorus recovery is realized by rapidly forming wurtzite under the conditions of phosphorus enrichment, reduction condition oxidation-reduction potential < -300MV and pH value of 6-9 under the induction of phosphorus-containing seed crystal and the drive of the 3D iron-sulfur-phosphorus porous functional material.
8. The application of the wastewater treatment functional material in synchronous denitrification and phosphorus recovery according to claim 5, wherein the 3D hematite composite phosphorus functional material is filled into an anaerobic iron ammoxidation reactor, feamox microorganisms and anaerobe seed liquid mainly containing the anaerobe reducing bacteria are inoculated, under the anaerobic condition, the Feamox microorganisms and the anaerobe reducing bacteria take the 3D hematite composite phosphorus functional material as a carrier, ammonia nitrogen is directly oxidized under the action of the Feamox microorganisms as nitrogen, ferric iron is taken as an electron acceptor, trivalent iron reduction is realized, phosphate in water is combined, the recovery effect on phosphorus is enhanced under the action of phosphorus as a seed crystal, denitrification and phosphorus recovery in wastewater are realized, and finally the blue iron ore is used for phosphorus recovery.
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| CN117862195B (en) * | 2024-03-12 | 2024-05-14 | 山西青联农业科技有限公司 | Method for carrying out iron tailing soil formation by utilizing ectopic ore-decomposing biological fermentation bed |
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