WO2023118145A1 - Procédé d'élimination de nitrate à partir de concentrés de filtration sur membrane - Google Patents
Procédé d'élimination de nitrate à partir de concentrés de filtration sur membrane Download PDFInfo
- Publication number
- WO2023118145A1 WO2023118145A1 PCT/EP2022/086995 EP2022086995W WO2023118145A1 WO 2023118145 A1 WO2023118145 A1 WO 2023118145A1 EP 2022086995 W EP2022086995 W EP 2022086995W WO 2023118145 A1 WO2023118145 A1 WO 2023118145A1
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- WO
- WIPO (PCT)
- Prior art keywords
- concentrate
- filter
- filter bed
- fluid
- filter material
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 200
- 239000012141 concentrate Substances 0.000 title claims abstract description 194
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims description 61
- 229910002651 NO3 Inorganic materials 0.000 title claims description 60
- 238000005374 membrane filtration Methods 0.000 title description 9
- 239000000463 material Substances 0.000 claims abstract description 108
- 230000008569 process Effects 0.000 claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 71
- 238000001728 nano-filtration Methods 0.000 claims abstract description 38
- 230000000813 microbial effect Effects 0.000 claims abstract description 19
- 230000035622 drinking Effects 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 123
- 239000012530 fluid Substances 0.000 claims description 85
- 229910052757 nitrogen Inorganic materials 0.000 claims description 58
- 244000005700 microbiome Species 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- 239000003651 drinking water Substances 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 25
- 235000020188 drinking water Nutrition 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000004576 sand Substances 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 230000033228 biological regulation Effects 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 239000011573 trace mineral Substances 0.000 claims description 10
- 235000013619 trace mineral Nutrition 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000011236 particulate material Substances 0.000 claims description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 239000008235 industrial water Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 239000002352 surface water Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 239000013535 sea water Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 230000001143 conditioned effect Effects 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 description 34
- 238000006731 degradation reaction Methods 0.000 description 33
- 238000005243 fluidization Methods 0.000 description 18
- 239000002351 wastewater Substances 0.000 description 18
- 239000002028 Biomass Substances 0.000 description 17
- 230000009467 reduction Effects 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 12
- 241001503485 Mammuthus Species 0.000 description 11
- 239000008237 rinsing water Substances 0.000 description 10
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 239000004848 polyfunctional curative Substances 0.000 description 9
- 239000003673 groundwater Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 230000006978 adaptation Effects 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 230000004060 metabolic process Effects 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 241000726119 Acidovorax Species 0.000 description 3
- 241001135163 Arcobacter Species 0.000 description 3
- 241000589565 Flavobacterium Species 0.000 description 3
- 241000216643 Hydrogenophaga Species 0.000 description 3
- 241001053668 Simplicispira Species 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000012465 retentate Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 241000589597 Paracoccus denitrificans Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000032770 biofilm formation Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 229960001730 nitrous oxide Drugs 0.000 description 2
- 235000013842 nitrous oxide Nutrition 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- -1 spring Substances 0.000 description 2
- 235000020681 well water Nutrition 0.000 description 2
- 239000002349 well water Substances 0.000 description 2
- 241000589158 Agrobacterium Species 0.000 description 1
- 241000588986 Alcaligenes Species 0.000 description 1
- 241000589941 Azospirillum Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000604933 Bdellovibrio Species 0.000 description 1
- 241000852385 Chitinophagaceae Species 0.000 description 1
- 241000862974 Hyphomicrobium Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 108090000913 Nitrate Reductases Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 108010025915 Nitrite Reductases Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241001057811 Paracoccus <mealybug> Species 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 241000187747 Streptomyces Species 0.000 description 1
- 241000605118 Thiobacillus Species 0.000 description 1
- 241000605261 Thiomicrospira Species 0.000 description 1
- POQKXAGEBNZGTF-UHFFFAOYSA-N [C].CC(O)=O Chemical compound [C].CC(O)=O POQKXAGEBNZGTF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000037358 bacterial metabolism Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000109 continuous material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 108010028128 nitric-oxide reductase Proteins 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 108010076678 nitrous oxide reductase Proteins 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/06—Aerobic processes using submerged filters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/104—Granular carriers
Definitions
- the present invention relates to the technical field of water technology, in particular to the treatment of membrane filtration concentrates from drinking and process water treatment.
- the present invention relates to a method for treating reverse osmosis and nanofiltration concentrates, in particular reverse osmosis concentrates, and also to a reactor which is set up for carrying out the method according to the invention for treating reverse osmosis and nanofiltration concentrates, in particular reverse osmosis concentrates.
- nitrates can be removed from reverse osmosis or nanofiltration concentration with the aid of the method according to the invention or with the reactor according to the invention.
- Nitrates are water-soluble salts of nitric acid, which are formed as part of the nitrogen cycle through a metabolic conversion of nitrogen-containing compounds by nitrifying bacteria in the soil.
- the nitrates are taken up by plants and used as a source of nitrogen by plant metabolism or converted into atmospheric nitrogen by so-called denitrifying (soil) bacteria.
- denitrifying (soil) bacteria Under natural conditions, only small amounts of nitrogen are applied overall, so that its availability is the limiting growth factor in almost all terrestrial and some aquatic ecosystems.
- Drinking or process water is usually obtained from so-called raw water, such as spring, surface and ground water or even seawater. Since spring, surface and groundwater that is heavily polluted with nitrate is associated with the health hazards described above, many waterworks have to give up existing groundwater reservoirs and create new, deeper-lying groundwater. develop reserves or alternatively use more complex treatment techniques for water treatment.
- nitrate low-molecular substances, such as nitrate
- membrane filtration processes in particular reverse osmosis or nanofiltration.
- the treatment of industrial or drinking water by means of membrane filtration, in particular reverse osmosis and, in some cases, nanofiltration leads to a considerable accumulation of nitrate in the waste water stream or in the concentrate or retentate of the filtration process.
- the nitrate concentration in reverse osmosis concentrates from industrial or drinking water treatment regularly exceeds the statutory limit values for total nitrogen for direct discharge into running water or a public sewage system (for Germany: Ordinance of the Federal Minister for Agriculture and Forestry on the limitation of waste water emissions from water treatment ( AEV water treatment), Federal Law Gazette II No.
- the yield of drinking or process water in membrane filtration processes is limited by the high nitrate load in the concentrate or retentate.
- An increase in yield is usually also associated with an increase in the amount of nitrate remaining in the concentrate. The result is improved productivity of the processing ren, especially membrane filtration processes, desirable for drinking and service water.
- the present invention is therefore based on the object of providing a method or a device which overcomes or at least alleviates the aforementioned disadvantages.
- a method is to be provided which improves the production of service or drinking water with regard to sustainability, environmental compatibility and productivity.
- Another aspect of the present invention is - according to a second aspect of the invention - a reactor with a filter bed for use in the treatment of reverse osmosis and / or nanofiltration concentrate ("concentrate").
- the present invention is thus - according to a first aspect - a method for treating reverse osmosis and / or nanofiltration concentrate ("concentrate”), the concentrate from the treatment of raw water by means of reverse osmosis and / or nanofiltration, in particular reverse osmosis, for drinking - and/or process water treatment, comprising:
- a method using a particulate or granular filter material is therefore provided for the first time, which is also suitable for the treatment of water with a high content of salt, particularly in the form of nitrates, and hardeners and is used to remove nitrate.
- the method according to the invention can be used to achieve a significant increase in the drinking water yield in membrane filtration methods, in particular nanofiltration and reverse osmosis methods, for treating raw water to drinking water or process water quality.
- the yield of reverse osmosis or sodium nofiltration process is limited by the nitrate or total nitrogen enrichment in the resulting concentrates or waste water, ie the treatment processes are currently not running at full capacity in order to avoid excessive nitrate or nitrogen concentrations in the resulting waste water or concentrate.
- High nitrate or total nitrogen concentrations especially above the legally specified limit values, generally prevent the concentrates from being discharged directly into running water or other bodies of water for the purpose of disposal or recycling into the water cycle.
- the method according to the invention which follows the reverse osmosis or nanofiltration, in particular reverse osmosis, makes it possible for the treatment to be carried out under increased utilization up to pre-utilization, since efficient nitrate removal from the concentrates produced is possible.
- the method according to the invention therefore provides an economical and environmentally friendly and resource-saving separate cleaning stage for waste water from drinking and/or process water treatment, which also enables the removal of large amounts of nitrate from the waste water and thus their direct introduction into the water cycle.
- a nitrate degradation rate or denitrification rate of more than 2.0 kgNO3-N/(m 3 d) can sometimes be achieved with the method according to the invention.
- the total nitrogen concentration in nitrogen- or nitrate-loaded waste water from the treatment of drinking water or process water can also be brought to values below the legal limit values for direct discharge.
- the method according to the invention sometimes achieves a degree of degradation of the total nitrogen of more than 90%, even in water or concentrates which are heavily contaminated with nitrate.
- the process according to the invention in continuous operation, as a result of which the process efficiency can be further increased.
- continuous operation in particular only a one-time start-up phase or one-time adaptation of the microorganisms to the process conditions for denitrification is required.
- the method according to the invention is environmentally friendly and resource-friendly, since it does not require the addition of chemicals that are harmful to the environment or difficult to dispose of.
- the method can also be carried out without temperature regulation, ie no energy is required for cooling or heating.
- the term “reverse osmosis or nanofiltration concentrates” is understood to mean concentrates or waste water which occurs during the treatment of raw water by means of membrane filtration processes, in particular reverse osmosis or nanofiltration.
- the term “retentate” can also be used synonymously for the concentrates.
- the concentrates that are treated with the method according to the invention come from the treatment of raw water into drinking or process water.
- the concentrate or waste water contains the low-molecular substances retained during treatment by filtration, such as salts, which also include nitrates.
- the concentrate to be treated comes from the treatment of raw water by means of reverse osmosis for drinking water treatment.
- raw water means any untreated water which comes from surface sources such as ponds, dams, lakes or rivers, or from subsurface water sources such as wells or groundwater.
- seawater is also understood to be raw water within the meaning of the invention.
- denitrification refers to the microbial conversion of the nitrogen bound in the form of nitrate to molecular nitrogen or nitrogen gas and nitrogen oxides by denitrifiers or denitr rificante understood. Denitrification includes - without wanting to be limited to this theory - as the first part, the reduction of nitrate to nitrite, which is catalyzed by the enzyme nitrate reductase. Denitrification also includes the reduction of nitrite to nitrogen monoxide, which is catalyzed by the enzyme nitrite reductase.
- denitrification includes the reduction of nitrogen monoxide to dinitrogen monoxide as a further sub-step, with the reaction being implemented by the enzyme nitric oxide reductase.
- the reduction of dinitrogen monoxide to molecular nitrogen or nitrogen gas is catalyzed by the enzyme nitrous oxide reductase.
- the biofilm with microorganisms which are able to catalyze a microbial denitrification, is settled or grows on the filter material, in particular its particles or grains.
- the microorganisms that carry out or bring about the denitrification can also be referred to as denitrifiers or denitrifiers.
- denitrifying bacteria or denitrifiers can be facultatively anaerobic bacteria of different genera, which preferably gain energy through denitrification under essentially anaerobic conditions.
- Bacteria which are capable of denitrification belong, for example, to the genera Agrobacterium, Alcaligenes, Azospirillum, Acidovorax, Arcobacter Bacillus, Flavobacterium, Hydrogenophaga, Hyphomicrobium, Paracoccus, Pseudomonas, Rhodopseudonomas, Thiobacillus, Thiomicrospira, Simplicispira, Streptomyces or Actonomyces, in particular Acidovorax, Arcobacter, Flavobacterium, Hydrogenophaga and/or Simplicispira, although the present list is not to be understood as conclusive.
- the biocenosis of the biofilm on the filter material depends in particular on the concentrates treated with the process, i.e. the microorganisms contained therein.
- a mixed population of a wide variety of microorganisms preferably occurs in the biofilm, which ultimately bring about the elimination of nitrogen, in particular nitrate, in the concentrates to be treated.
- the biocenosis in the biofilm required for carrying out the denitrification or nitrate elimination occurs in particular as a result of the conditioning of the reverse osmosis or nanofiltration concentrate used, as described below.
- the settlement and setting of the biocenosis takes place in As part of the method according to the invention, preferably in a start-up phase of the filter bed over the period of time required in this regard.
- the filter bed Before loading the filter bed with the concentrates or before starting up with concentrates, the filter bed can be inoculated with a starter culture, eg based on Paracoccus denitrificans.
- the biocenosis in the biofilm usually occurs depending on the microorganisms already contained in the reverse osmosis or nanofiltration concentrate used, or varies depending on the reverse osmosis or nanofiltration concentrate used.
- Reverse osmosis and/or nanofiltration concentrate in particular from drinking and/or process water treatment, as such is usually at least essentially free of or at least low in carbon compounds or has no appreciable chemical oxygen demand.
- the chemical oxygen demand is a measure of the sum of all organic compounds in the water.
- the COD characterizes the amount of oxygen that is used to oxidize all the organic substances contained in the water.
- the COD can be determined in particular using a photometric measuring method in accordance with DIN 15705 or using a dimensional analytical measuring method in accordance with DIN 38409-H41.
- the materials and substances forming the COD can serve as a source of energy, especially carbon, for the microorganisms in the biofilm.
- the concentrate before and/or during the process preferably in process step (a) or in the feed, to a COD (chemical oxygen demand) in the range from 5 to 200 mg/l, in particular 20 to 160 mg/l, preferably 30 to 150 mg/l, preferably 40 to 130 mg/l.
- COD chemical oxygen demand
- the COD can also be provided to adapt the COD to the nitrogen or nitrate content in the concentrate, in particular with the COD being adjusted in such a way that the nitrate degradation is not limited by a lack of organic energy sources, but the denitrified concentrate is released when it is discharged or .in the effluent only shows a COD below the limit values for the COD specified in the Direct Discharge Ordinance.
- the Direct Discharge Ordinance currently sets a maximum limit of 90 mg/l for the COD.
- the COD is preferably adjusted by adding a carbon source for the microorganisms contained in the biofilm, in particular by adding easily biodegradable organic acids, in particular acetic acid.
- Acetic acid is an easily degradable, inexpensive and therefore overall process-economical source of carbon.
- the method according to the invention can also be carried out with all other carbon sources for microorganisms with a preferably heterotrophic metabolism that are known in principle to the person skilled in the art, such as citric acid, succinate or various saccharides.
- the selection of a suitable carbon source is known in principle to a person skilled in the art and does not require any further explanation.
- a phosphorus source for the microorganisms contained in the biofilm is metered, in particular phosphoric acid is used as the source of phosphorus.
- phosphoric acid is used as the source of phosphorus.
- 0.3% phosphoric acid is used as the phosphorus source.
- the source of phosphorus is also preferably metered in such a way that nitrate degradation is not limited by a phosphorus deficiency, but the phosphate concentration in the denitrified concentrate does not exceed the statutory limit values for phosphorus - currently 2 mg/l in Germany - for direct discharge.
- Iron(II) sulfate in particular in the form of FeSO4 ⁇ 7H2O, is preferably used as the iron(II) source.
- a concentration of iron in the feed is in the range from 0.0001 mg/l to 10 mg/l, in particular 0.001 to 5 mg/l, preferably 0.01 to 2 mg/l, particularly preferably 0 1 to 1 mg/l, based on the feed, is used.
- a concentration of 0.2 mg/l iron, in particular iron(II) sulfate, based on the feed is used in the feed.
- trace elements for the microorganisms contained in the biofilm are metered into the concentrate before and/or during the process, preferably in process step (a) or in the feed become.
- the trace elements are preferably selected from the group consisting of zinc, manganese, boron, cobalt, copper, nickel and/or molybdenum and/or their salts.
- the trace elements are added to the concentrate in the form of zinc sulfate (ZnSO4), manganese chloride (MgCh), boric acid (H3B03), cobalt chloride (C0Cl2), copper chloride (CuCh), nickel chloride (NiCh) and /or sodium molybdate (Na2MoO4), preferably in dissolved form, are supplied or metered in.
- ZnSO4 zinc sulfate
- MgCh manganese chloride
- boric acid H3B03
- cobalt chloride C0Cl2
- CuCh copper chloride
- NiCh nickel chloride
- Na2MoO4 sodium molybdate
- the environmental conditions for the microbial denitrification or the microorganisms contained in the biofilm can be set in a targeted manner, which ultimately leads to an improved or high nitrate degradation rate, as the microorganisms have optimal denitrification metabolism conditions are created.
- the formation of the biofilm on the granular and/or particulate filter material is regulated and/or controlled.
- the regulation or control ensures, on the one hand, that excessive growth of the microorganisms or excessive formation of the biofilm, which would lead to blockage of the filter bed, is prevented.
- the biofilm on the particulate or granular filter material is nevertheless sufficiently developed to allow efficient denitrification.
- the formation of the biofilm on the filter material is regulated or controlled by reducing the biofilm on the granular and/or particulate filter material.
- Biofilm reduction can be continuous or intermittent.
- the formation of the biofilm is regulated and/or controlled by introducing at least one fluid into the filter bed.
- the filter bed and/or the filter material is completely or partially fluidized.
- turbulent flows are generated by the fluid entry in the filter bed, which on the one hand leads to a boundary layer around the particles and on the other hand to a shearing off of part of the biomass on the particles.
- the difficulty of fluidization consists in particular in the fact that on the one hand the flow through the filter bed with its specialized microorganisms should be so slow and uniform that the longest possible contact time with the surrounding medium is ensured. At the same time, however, it must also be ensured that the growing biomass does not block the filter bed and thus prevent the exchange of substances with the surrounding medium. If the fluid input or the currents generated by fluid input are too strong, the biofilm on the carrier is sheared off too much and the biomass is reduced too much and at the same time the time for a mass exchange with the surrounding fluid is reduced. If the fluid entry is too weak or too low, the constant growing biomass block the filter bed, so that a media exchange is disadvantageously prevented. In addition, with particulate or granular filter materials there is a risk of precipitation of hardeners and salts, since the reverse osmosis or nanofiltration concentrates have a high salt and nitrate content.
- the fluid is selected from air, technical gases and/or water, particularly preferably air and/or technical gases.
- the problems described above with regard to under certain circumstances too much or too little detachment of the biomass from the particles or granules of the filter material can be overcome if the fluid entry is controlled as a function of the filter resistance becomes.
- the introduction of fluid is controlled by means of time-pause control as a function of the filter resistance.
- the filter resistance has proven to be a suitable, indirect measure for the formation of the biofilm on the filter material.
- the filter resistance is understood to mean the pressure drop occurring when the concentrate to be treated flows through the filter bed, measured or stated in cm water column [cm Ws].
- cm Ws cm water column
- the measurement or monitoring of the filter resistance takes place within the scope of the method according to the invention using means or measuring devices or pressure sensors which are fundamentally known to the person skilled in the art.
- Suitable values for the filter resistance or a time-pause control can vary widely and depend in particular on the particulate or granular filter material, but also on the dimensioning of the filter bed and must be selected or determined accordingly by the person skilled in the art.
- the nitrate degradation rate is preferably used to determine a suitable filter resistance. Both a filter resistance that is too low and one that is too high would negatively affect the nitrate degradation rate.
- the fluid entry is used to achieve a filter resistance in the range of 20 cmWs and 60 cmH2O. If the particles or granules of the filter material have a larger or coarser grain size, higher values are conceivable. If the filter material has a finer grain, lower values should be advantageous.
- the filter resistance has proven to be a suitable reference value for setting or controlling the fluid input.
- the entry of the fluid into the filter bed or filter material preferably takes place via fluid inlets, in particular air or gas inlets, which are basically known or customary to those skilled in the art.
- fluid inlets in particular air or gas inlets, which are basically known or customary to those skilled in the art.
- the at least one fluid is introduced into the filter bed and/or filter material via at least one, preferably several, fluid inlets.
- the arrangement or positioning of the fluid input into the filter bed depends primarily on the areas of the filter bed that are to be fluidized, in particular on whether complete or only partial fluidization is provided.
- the fluid inlets or their number and arrangement must be adapted to the shape and dimensions of the filter bed.
- the treated or denitrified concentrate when it is discharged from the filter bed, preferably in the outlet, undergoes further filtration, in particular via a particle and/or sterile filter.
- the fluid is introduced via at least one fluid inlet in the area of the longitudinal axis of the filter bed.
- a fluidization or a fluid entry via at least one fluid inlet in the area of the longitudinal axis of the filter bed has proven to be particularly advantageous with regard to a continuous, but only partial fluidization of the filter bed.
- Introducing fluid via inlets in the wall or in the base of a filter module or reactor enclosing the filter bed has proven particularly useful for intermittent, preferably essentially complete, fluidization of the filter material or filter bed.
- the two embodiments described above with regard to the selection of the fluid inlets in the area of the longitudinal axis or in the wall or in the bottom of the filter module or reactor enclosing the filter bed can also be used in combination or the fluid entry can be carried out both by means of fluid inlets in the Area of the longitudinal axis as well as in the wall or in the bottom of the reactor.
- continuous fluidization of the filter bed takes place via the fluid inlet in the area of the longitudinal axis, whereas via the inlets in the wall or in the bottom of the filter module or reactor only intermittently, in particular by means of time-pause control, at least one fluid is introduced, for example when the filter resistance increases excessively or a limit value for the filter resistance is exceeded.
- the fluid input takes place via lances for fluid input that protrude and/or are immersed into the filter bed.
- a particularly targeted control of the fluid input into the filter material is possible via lances projecting and/or immersed into the filter bed.
- the complete fluidization of the filter bed is particularly advantageous in this embodiment.
- the number and arrangement of the lances depends on the size and shape of the filter and the areas of the filter bed to be fluidized.
- fluid can be introduced into the lower, central area of the filter bed via a line arranged axially along the longitudinal axis.
- continuous fluidization has proven particularly advantageous.
- the fluid it is possible for the fluid to be introduced via lances that protrude and/or are immersed into the filter bed and, moreover, a line arranged axially along the longitudinal axis for the introduction of the fluid.
- a particularly targeted control or regulation of the formation of the biofilm and removal of other particulate residues of the process is possible in the process of the invention if the filter material is a is subjected to cleaning outside the filter bed, particularly when the biomass reduction is predominantly outside the filter bed:
- the particulate and/or granular filter material is conveyed to a rinsing unit arranged outside of the filter bed.
- the filter material is conveyed to the rinsing unit by introducing at least one fluid, preferably air or a technical gas, into the filter bed, in particular as a function of the filter resistance.
- the filter material can be cleaned in the rinsing unit.
- the introduction of the at least one fluid and/or the cleaning in the rinsing unit reduces the biofilm by at least 10%, in particular at least 20%, preferably by at least 30% and/or by at most 80%, in particular by at most 70%. preferably by at most 60%.
- the rinsing unit is arranged above the filter bed in the area of the outlet for the cleaned concentrate.
- the filter material is cleaned and/or rinsed with filtrate flowing in the opposite direction or in the direction of the outlet and sinks back onto the filter bed with reduced biofilm.
- the waste water from the rinsing unit containing the biomass removed from the filter material and other particulate residues is preferably discharged via a rinsing water outlet.
- the waste water occurring during the rinsing and/or cleaning of the filter material is cleaned by means of particle retention and is preferably fed back into the filter bed via the inlet.
- the filter material is conveyed from the lower region of the filter bed to a rinsing unit arranged above the filter bed by means of a compressed air lifter (also known as a mammoth pump) that is preferably arranged axially along the longitudinal axis of the filter bed.
- a compressed air lifter also known as a mammoth pump
- the intake of air is preferably adjusted as a function of the dimensioning of the filter bed, the filter material, in particular its grain size, and/or the filter resistance.
- the rinsing unit is preferably a sand washer, with the particulate or granular filter material being washed in a counterflowing, already denitrified or treated concentrate and sinking back onto the filter bed after cleaning.
- FIG. 2 An example of a reactor for carrying out the process according to the invention is shown in FIG. 2, which is described in detail below.
- particulate or granular filter material As far as the particulate or granular filter material is concerned, it must on the one hand provide a sufficiently large surface area for the biomass to grow and on the other hand ensure that the concentrate to be treated can flow through it and also be able to form a filter bed. In this context, it has proven to be advantageous to use particulate or granular material with defined particle or grain diameters for the method according to the invention.
- the filter material used is a particulate and/or granular material with particle or grain sizes, in particular average particle or grain diameters, preferably determined according to DIN EN 120904, in the range from 0.1 to 15 mm, in particular 0.2 to 10 mm, preferably 0.5 to 5 mm, preferably 0.7 to 3 mm, particularly preferably 1 to 2 mm.
- a particulate and/or granular material is used as the filter material with a specific density in the range from 0.7 to 6 g/cm 3 , in particular 1 to 5 g/cm 3 , preferably 1.5 to 4 g/cm 3 , preferably 2 to 3.5 g/cm 3 , particularly preferred 2.5 to 3.2 g/cm 3 , based on a single grain or particle, is used.
- the use of particles or granules with the previously defined specific density has proven to be advantageous with regard to the formation of the filter bed. By using a filter material with the previously defined specific density, an undesired buoyancy of the particles or grains in the concentrate to be treated can be counteracted.
- sand, bentonite and/or crushed lava stones are preferably used according to the invention as the particulate and/or granular material. Due to their surface properties, the aforementioned filter materials allow the biofilm to grow, since they have a certain surface roughness.
- the method according to the invention is operated in a sand filter or sand, in particular quartz sand, is used as the particulate or granular filter material.
- the situation in the method according to the invention is preferably such that the microorganisms for the microbial denitrification grow sessile on the grains and/or particles of the filter material.
- the process according to the invention can be carried out continuously or intermittently, preferably continuously.
- a continuous procedure has proven to be particularly advantageous with regard to the process efficiency, especially against the background that a start-up phase or adaptation of the biocenosis to the denitrification conditions is only necessary once.
- the concentrate has a bed load (amount of total nitrogen per cubic meter of filter material per day) in the range from 100 to 2500 g/m 3 /d, in particular 300 to 2200 g/m 3 /d, preferably 500 to 2000 g/m 3 /d, preferably 800 to 1800 g/m 3 /d, into the filter bed.
- a bed load amount of total nitrogen per cubic meter of filter material per day
- the concentrate with a bed load (amount of nitrate nitrogen per cubic meter of filter material per day) in the range of 80 to 2,500 g / m 3 / d, in particular 100 to 2,100 g / m 3 / d, preferably 200 to 1,900 g/m 3 /d, preferably 400 to 1,700 g/m 3 /d, is passed into the filter bed.
- the concentrate has a bed load (amount of nitrate nitrogen per cubic meter of filter material per day) of at least 80 g/m 3 /d, in particular at least 100 g/m 3 /d, preferably at least 200 g/m m 3 /d, preferably at least 400 g/m 3 /d, particularly preferably at least 600 g/m 3 /d, into the filter bed.
- a bed load amount of nitrate nitrogen per cubic meter of filter material per day
- the bed loading is understood to be the total amount of nitrogen (unit: g) with which a defined volume of the filter mass (unit: m 3 ) in the filter, ie the “filter bed” in the filter, per unit of time (unit: d or day) will be charged.
- the method according to the invention can be transferred to all types of filters or filter beds, since the amount of nitrogen introduced into the filter bed or filter per unit of time is independent of the type, size or volume of the reaction space on the volume of the Filter mass relates.
- the volume flow of the concentrate to be treated can vary within a wide range and depends primarily on the dimensioning of the plant or the filter bed for carrying out the process according to the invention.
- a volume flow Q volume of concentrate per hour
- the concentrate with a volume flow Q volume of concentrate per hour in the range of 0.3 to 4 m 3 / h, in particular 0.5 to 3.5 m 3 /h, preferably 6.0 to 3.0 m 3 /h, preferably 0.9 to 2.5 m 3 /h, into the filter bed.
- the concentrates from reverse osmosis or nanofiltration processes to be treated with the process according to the invention can be traced back to all types of raw water.
- the concentrate comes from reverse osmosis and/or nanofiltration processes, in particular reverse osmosis processes, for the treatment of groundwater, spring water, seawater and/or surface water to process and/or drinking water, preferably drinking water.
- the concentrate in the feed has a total nitrogen concentration TNb of at least 30 mg/l, in particular at least 40 mg/l, preferably at least 50 mg/l, preferably at least 60 mg/l.
- the concentrate in the feed has a nitrate nitrogen concentration of at least 20 mg/l, in particular at least 30 mg/l, preferably at least 40 mg/l, preferably at least 50 mg/l.
- this can usually have a water hardness [total hardness] in the inflow in the range from 10 to 150 °dH, in particular 20 to 120 °dH, preferably 30 to 100 “dH, preferably 40 to 80 °dH, preferably determined according to DIN 38409-6.
- total hardness total hardness
- the concentrate in the feed has a temperature in the range from 2 to 40 °C, in particular 3 to 30 °C, preferably 4 to 25 °C, preferably 5 to 20 °C.
- the concentrate has a pH value in the range from 6 to 8.5, preferably 7 to 8, in the feed. It is equally preferred according to the invention if the concentrate in the feed has a pH of at least 6, in particular at least 6.5, preferably at least 7.
- the filter is operated as a downstream or upstream filter, preferably as an upstream filter.
- the concentrate is fed into the lower area of the filter bed or the concentrate is distributed in the filter bed, preferably in the lower area of the filter bed, and the filter bed, in particular the filter material, is flows from bottom to top.
- “Lower part” in this case means the lower half, preferably the lower third, of the filter bed.
- the process is not temperature-controlled and/or carried out at ambient temperature.
- the pH value, the temperature, the electrical conductivity, the nitrite concentration, the turbidity and/or the concentration of substances that can be filtered off in the concentrate to be treated and/or in the denitrified concentrate are measured, in particular in the Feed and/or in process step (a) and/or in the course and/or in process step (c).
- the measurements are carried out using measuring devices which are fundamentally known to those skilled in the art.
- the method according to the invention provides a high-performance, separate cleaning stage for concentrates or waste water from the treatment of industrial or drinking water from raw water, which is suitable for removing large amounts of nitrate from the concentrate or waste water.
- the statutory limit value for nitrogen or nitrate for direct discharge is generally achieved or can be complied with.
- the yield of drinking water treatment can be significantly increased, since large amounts of nitrate in the resulting waste water or concentrate are no longer a limiting factor.
- the present invention is also - according to the second aspect of the present invention - a reactor 1 for use in the treatment of reverse osmosis and / or nanofiltration concentrate ("concentrate”), the concentrate from the treatment of raw water by means of reverse osmosis and / or Nanofiltration for drinking and/or process water treatment originates, in particular the reactor being set up and designed to carry out a method according to one of the preceding claims, comprising an inlet 2 for the concentrate to be treated, an outlet 3 for the denitrified concentrate, a fluidized filter bed 4, wherein the filter bed 2 has a granular and/or particulate and biologically activated filter material 32 with a biofilm for microbial denitrification, and at least one device for fluidizing the filter bed 5, in particular wherein the device for fluidizing controls the fluid input depending on the filter resistance, in particular such that the formation of the biofilm on the particulate and/or granular filter material is regulated and/or controlled.
- concentration reverse osmosis and / or nanofiltration concentrate
- the reactor according to the invention is preferably set up and designed for carrying out the method described above.
- the reactor is equipped with a device for fluidization, which allows targeted regulation or control of the formation of the biofilm on the granular or particulate filter material, in particular as a function of the filter resistance measured in the operating state.
- a device for fluidization which allows targeted regulation or control of the formation of the biofilm on the granular or particulate filter material, in particular as a function of the filter resistance measured in the operating state.
- a plant and a reactor which are set up for carrying out the method according to the invention are described below by way of example with reference to FIGS. 1 and 2 .
- FIG. 2A a schematic representation of a reactor suitable for the method according to the invention, which has a filter bed based on a particulate or granular filter material with a biofilm growing thereon for microbial denitrification;
- FIG. 2B a schematic representation of a further reactor suitable for the process according to the invention, the embodiment shown in FIG. 2B having additional lances arranged in the region of the reactor wall for introducing fluid in comparison to the reactor shown in FIG. 2A.
- FIG. 1 shows a flow chart of a plant for the treatment of reverse osmosis and/or nanofiltration concentrate, which originates from the treatment of raw water by means of reverse osmosis and/or nanofiltration for drinking and/or process water treatment:
- the concentrate to be treated in the feed 6 is first fed into a feed receiver 8 and fed into the reactor 1 via a feed line 18 and an inlet 2 .
- the inflow is adjusted via valves 16 and pumping devices 14 .
- Provision can preferably also be made to monitor and further regulate the inflow of the concentrate to be treated by means of a flow meter 22 .
- the concentrations of relevant water constituents such as total nitrogen TNb, nitrate concentration, COD, water hardness, pH value, phosphorus content, etc., can be measured via measuring devices 17 .
- chemicals such as a carbon source, preferably in the form of acetic acid, and/or a phosphorus source, preferably in the form of 0.3% phosphoric acid, can be added to the concentrate via dosing devices 10, 11.
- Iron(II) sulfate preferably at a rate of 0.2 mg/l based on iron(II) sulfate in the feed, and various trace elements are metered in.
- the metering can be adjusted or controlled via pump devices 14 .
- the substances for conditioning are fed to the concentrate to be treated, preferably in dissolved form, via a mixer 21 in the inlet 6 or in the inlet line 18 .
- the concentrate is treated by filtration through the filter material with microbial denitrification to remove the nitrate.
- the filter bed is preferably fluidized via a fluidization system 13 .
- the fluid input is preferably controlled via a control cabinet 23 .
- the fluid is air, in particular compressed air, and/or at least one industrial gas, it being possible for the fluid to be introduced from the fluidization system 13 via a fluid line 24 into the reactor 1 or the filter bed.
- the reactor 1 is also equipped with sensor devices for measuring or monitoring the filter resistance.
- Gases arising in the process according to the invention can escape from the reactor 1 via an exhaust air system 12 which preferably has a fan 15 .
- the rinsing water produced by the cleaning of the filter material can be discharged from the reactor 1 via a rinsing water line 20 .
- the waste water discharged via the flushing water line 20 is preferably recycled via the inflow receiver 8 in order to further reduce the amounts of waste water occurring in the context of the method according to the invention.
- the denitrified or treated concentrate is routed via the outlet 3 and a discharge line 19 into a discharge receiver 9 for the denitrified concentrate or treated concentrate.
- a discharge receiver 9 for the denitrified concentrate or treated concentrate.
- it can be provided in the outlet 7 by means of measuring devices 17 the concentration of relevant water constituents to determine fe or properties in the treated concentrate, in particular the total nitrogen content, the pH value, the nitrate concentration and/or the total hardness.
- FIG. 2A shows a reactor 1 which is set up and designed for carrying out the method according to the invention.
- the reactor 1 has an inlet 2 for the concentrate to be treated, an outlet 3 for the denitrified or treated concentrate and a filter bed 4 based on a granular or particulate filter material 32, in particular based on sand, with a biofilm for microbial denitrification on.
- the reactor 1 shown in FIG. 2 is set up for operation as an upflow filter.
- the reactor 1 has an internal feed line 31 for the concentrate to be treated, which opens into a preferably star-shaped distribution device 26 reaching into the filter bed for the even distribution of the concentrate to be treated in the filter bed 4 .
- the concentrate to be treated flows through the filter bed 4 from bottom to top, as indicated schematically by the flow direction 27 for the concentrate to be treated.
- the method according to the invention provides for the formation of the biofilm on the granular or particulate filter material 32 to be regulated or controlled, preferably by continuously or intermittently reducing the biofilm on the granular or particulate filter material 32. This is preferably done by fluidizing the filter bed 4 or filter material 32. In this context, it is particularly preferred to measure or monitor the filter resistance of the filter bed and to control the fluid entry as a function of the filter resistance.
- the fluidization of the filter bed 4 takes place via a mammoth pump 25 arranged axially along the longitudinal axis of the filter bed 4 or of the reactor, with the introduction of compressed air as the fluid.
- the fluid preferably in the form of compressed air
- the mammoth pump (compressed air lifter) 25 is introduced into the mammoth pump (compressed air lifter) 25 via a fluidization system 13 (not shown in FIG. 2) and a fluid line 24 .
- the compressed air introduced into the mammoth pump 25 causes particulate or granular total filter material 32 sucked from the lower area of the filter bed 4 by the mammoth pump and promoted in the fluid flow from bottom to top.
- the entry of the fluid is preferably controlled via a control cabinet 23 depending on the filter resistance.
- the filter material 32 is conveyed with the aid of the mammoth pump 25 to a rinsing unit 28 arranged above the filter bed, here in the form of a sand washer, and washed in the rinsing unit 28 with counterflowing, denitrified concentrate 30.
- the cleaned filter material 32 sinks back onto the filter bed 4, while the waste water flow arising in the rinsing unit 28, which in particular contains removed biomass and possibly other particulate residues, such as fine abrasion of the filter material or precipitated hardeners, is removed from the reactor 1 via a rinsing water outlet 29 becomes.
- the denitrified concentrate 30 is routed out of the plant via an outlet 3 and the outlet 7 .
- FIG. 2B shows a reactor 1 which is also suitable for carrying out the process according to the invention.
- the reactor 1 corresponds to the reactor shown in FIG. 2A, the reactor 1 according to FIG. 2B additionally having at least two lances 33 for introducing at least one fluid into the filter bed 4.
- the lances may have fluid outlets 34 along their longitudinal axis. Equally, it can also be provided that the lances 33 only have a fluid outlet 34 at the lower end that dips into the filter bed.
- the fluid line 24 can have valves that allow the fluid to be fed in independently via the lances 33 .
- the additional lances 33 in the area of the reactor wall can further improve the fluidization of the filter bed 4 with regard to the regulation or control of the formation of the biofilm.
- lances in the area of the reactor wall an even more uniform fluidization of the filter terbetts 4, which in turn improves the regulation of the biofilm and thus also the nitrate degradation rate.
- the starting point for the exemplary embodiments described below is a natural filter system in which raw water, such as well water, is treated to drinking water quality by means of reverse osmosis (synonymous with reverse osmosis, abbreviated to RO).
- the concentrate obtained during treatment using reverse osmosis is discharged into a watercourse for disposal or recycling in the water cycle.
- the large-scale natural filter system has so far been operated in such a way that the nitrogen or nitrate concentration in the reverse osmosis concentrate maintains this value.
- the method according to the invention makes it possible to reduce the total nitrogen load in reverse osmosis concentrates from drinking water treatment and thus allows an increase in the yield in drinking water treatment.
- Fig. 1 which has a reactor as shown in Fig. 2, carried out. Commissioning of the reactor
- the reactor was first filled with quartz sand according to DIN EN 120904 as filter material, the grains of sand having a particle diameter or a particle size in the range from 1 to 2 mm. The plant and the reactor were then put into operation.
- the inflow reservoir of the plant was fed with a selected bacterial or microorganism culture. In the present case it was a pure culture of Paracoccus dentrificans.
- the adaptation was initially carried out using only service water with the addition of acetic and phosphoric acid. Further microorganisms were introduced into the filter bed with the service water. After a stable biofilm had formed on the filter material, the process water was replaced by reverse osmosis concentrate, with acetic and phosphoric acid being added to the concentrate for conditioning.
- RNA analyzes showed that bacteria of the genera Arcobacter, Hydrogenophaga, Bdellovibrio, Flavobacterium, Simplicispira, Acidovorax and Chitinophagaceae had settled in the biofilm.
- the reactor was charged with a pump device from the feed reservoir, which was supplied with reverse osmosis concentrate from an upstream reverse osmosis system.
- the inflow volume flow of the concentrate to the inflow template was greater than that to the reactor.
- the concentrate to be treated was fed by means of a feed line via the inlet into the reactor to the star-shaped distributor and distributed evenly over the filter bed.
- the loading of the filter bed with reverse osmosis concentrate was slowly increased.
- the reverse osmosis concentrate was first fed into the filter bed with a bed loading (amount of total nitrogen per cubic meter of filter material per day) of up to 500 g/m 3 /d.
- the bed load was increased to up to 2,100 g/m 3 /d.
- a filter resistance in the range of 20 cmWS to 60 cmWS has proven to be suitable.
- the filter was operated as an upflow filter, ie the concentrate flowed through the filter bed from bottom to top for denitrification purposes.
- nitrite (NO 2 ) as an intermediate product and nitrate (NO 3 ) were reduced to molecular nitrogen (N 2 ) by the sessile microorganisms growing on the particulate filter material.
- N 2 molecular nitrogen
- the molecular nitrogen formed during the denitrification was removed from the reactor via an exhaust air system.
- the treated or denitrified concentrate was discharged from the reactor via the outlet and a drain line or via the drain.
- the filter material was continuously fluidized and cleaned in the rinsing unit located above the filter bed.
- the filter resistance was monitored and adjusted to suitable values with the help of the fluid input.
- the fluidization of the filter bed and the conveyance of the filter material to the rinsing unit took place by means of a mammoth pump arranged axially along the longitudinal axis of the reactor or filter.
- the filter material was transported or conveyed from the cone at the bottom of the reactor into the rinsing unit in the form of a sand washer in the upper area of the reactor and cleaned using a small part of the outflow or the counterflowing, already treated concentrate .
- part of the biofilm was removed from the filter material in order to prevent the filter bed from becoming overgrown with biomass.
- the rate at which the biofilm was removed was controlled by the compressed air input into the mammoth pump.
- the rinsing water occurring in the rinsing unit and containing biomass and possibly other particulate residues of the process was conducted out of the reactor via a rinsing water outlet and recycled via the feed receiver.
- the cleaned filter material in the form of sand was also recycled by sinking back from the rinsing unit onto the filter bed.
- a carbon source and, if required, a phosphorus source and possibly trace elements, each in dissolved form were metered into the concentrate in the feed using metering devices within the scope of the process according to the invention.
- the trace element solution contained zinc sulfate (ZnSC), manganese chloride (MgCh), boric acid (H3B03), cobalt chloride (C0Cl2), copper chloride (CuCk), nickel chloride (NiCh) and/or sodium molybdate (NazMoO ⁇ ), each in dissolved form.
- the filter resistance and the inflow volume flow were also monitored with the aid of means that are fundamentally known to those skilled in the art, e.g. pressure measuring probes and/or flow meters.
- the process was operated continuously and without interruption.
- the control of the process in particular the entry of compressed air to fluidize the filter bed, was carried out via a control cabinet.
- the nitrate and nitrogen degradation performance of the process according to the invention was examined with different loading and dwell times of the reverse osmosis concentrate to be cleaned in the filter bed in the start-up and operating phase.
- the following table shows the volume flow and the total nitrogen concentration in the inlet for the start-up and first operating phases:
- the reactor or filter bed was fed continuously with reverse osmosis concentrate, as described above.
- acetic acid as a carbon source and phosphoric acid as a phosphorus source were added to the concentrate in the feed.
- the inflow volume flow and the total nitrogen concentration in the inflow were further varied.
- the total nitrogen concentration in the inflow was increased from 1.2 m 3 /h or 1.5 m 3 /h to around 49 mg/l to 59 mg/l at a reduced volume flow.
- phase I of the start-up phase an average degree of degradation of 88% of the total nitrogen was achieved.
- the minimum and maximum degrees of degradation were 84% and 93%, respectively.
- an average degree of degradation of 86% of the total nitrogen was achieved.
- a maximum reduction of 97% an almost complete reduction of nitrogen in the reverse osmosis concentrate has already been achieved.
- the minimum degree of degradation in phase II was 77%.
- the average total nitrogen concentration in the outflow was around 3.25 mg/l and thus well below the legal limit of 20 mg/l for discharge into running water.
- the inflow volume flow was increased further to 1.8 m 3 /h, with the total nitrogen being almost completely reduced (on average by 95%).
- the values were subject to a small range of fluctuation with a minimum of 90% and a maximum of 100% degree of degradation.
- phase IV with an inflow volume flow of 2.0 m 3 /h, a very significant reduction in total nitrogen with an average degree of degradation of 94% was recorded. the.
- the values for the degree of degradation were in a very small range of variation between a minimum of 90% and a maximum of 97%.
- the total nitrogen concentration in the effluent was on average 1.38 mg/l in this operating phase and thus also well below the legal limit of 20 mg/l.
- the total nitrogen concentration in the inflow was increased later on.
- the data from test days 193 to 204 are used here as an example, when the total nitrogen concentration in the inflow was increased to approx. 49 mg/l to 58 mg/l.
- a minimum degree of degradation of about 80% and a maximum degree of degradation of more than 99% were achieved even with a significantly increased total nitrogen concentration or nitrogen load. Even with an increased total nitrogen concentration, the legal limit of 20 mg/l for direct discharge was easily complied with.
- FIG. 4A the specific degradation rate versus bed load, based on the total nitrogen concentration, is shown for phases I to IV. Appendix of Fig. 4A it can be seen that with the method according to the invention, after an adjustment phase, the entire nitrogen load that is fed to the plant is degraded in the reactor, so a degree of degradation of almost 100% can be achieved. Against the background of the results, it can even be assumed that the limit for a complete reduction of the nitrogen load has not yet been reached and that the potential for the largest possible loading of the filter bed and the increase in the nitrate concentration has not yet been exhausted.
- FIG. 4B shows the specific decomposition rate in relation to the bed load, based on the specific decomposition rate for nitrate nitrogen, as an example for the later test days 193 to 204. It can be seen from FIG. 4B that even after increasing the total or nitrate nitrogen load that is fed to the plant, a degree of nitrate degradation of 85 to almost 100% can still be achieved. The method according to the invention is therefore distinguished by an excellent nitrate degradation rate.
- FIG. 5 graphically shows the nitrate nitrogen concentration in the inflow and outflow for test days 193 to 204.
- the nitrate nitrogen concentration in the inlet was in the range from 41 to 51 mg/l.
- the effluent on the other hand, only nitrate nitrogen concentrations in the range of approximately 0 mg/l to max. measured at a maximum of 12 mg/l.
- large amounts or concentrations of nitrate can be almost completely removed from reverse osmosis filtrates with the method according to the invention and the denitrification carried out therein.
- nitrate degradation levels of around 85% to 99% were achieved. - Control of the fluid entry depending on the filter resistance
- the filter resistance serves in particular as an indirect measure of the formation of the biofilm on the filter resistance.
- a filter resistance in the range from 20 to a maximum of 60 cm water column based on the nitrate degradation rate, especially in the Range of 25 to 40 cmWS proven to be suitable.
- FIG. 7 shows the filter resistance, given in cm of water column [cmWS], and the fluid input, given in volume of standard air per minute [Nl/min], as an example for test days 193 to 204. If the filter resistance increased excessively, as on test days 201 and 202 to 46 to 47 cm water column, the fluid input was increased in order to reduce the biomass on the filter material and thus reduce the filter resistance again. When a filter resistance in the particularly preferred range was reached, in this case in the range from approx. 30 to 35, the fluid input was reduced again in order to avoid further shearing off of the biomass. . Measurement of the COD
- the Direct Discharge Ordinance currently sets a limit value of 90 mg/l, which must not be exceeded in water when it is discharged directly into running water and municipal waste water.
- phase I of the start-up phase the average COD concentration in the outflow was around 7.4 mg/l, so that with a degree of degradation of around 93%, the carbon supplied was optimally used to reduce the total nitrogen.
- the dosage of acetic acid was increased twice by 4.5% and 13.6%.
- the carbon supplied was used up by approximately 91% in each case and was at an average value of 7.8 mg/l in the outflow (cf. FIG. 6A). As a result, the breakdown of the total nitrogen could be increased to up to 97% (cf. FIG. 3A).
- the concentration of cloudy matter and hardeners is regulated by law for direct discharge into running water.
- a limit value of 30 mg/l is currently being set in Germany for substances that can be filtered off.
- the concentrations of the filterable substances in the effluent with an average of 12.3 mg/l were below the legal limit of 30 mg/l.
- FIG. 8 the outflow, rinsing water and inflow (from left to right) from the previously described process are shown set up next to one another. It is readily apparent that both the influent and the effluent are clear with no turbidity. In contrast, the rinsing water shows a clear turbidity. The mean of the substances in the effluent that could be filtered off was 10.1 mg/l. The filterable substances in the rinsing water were 202 mg/l.
- the method according to the invention in particular the filtration through a particulate filter material with a biofilm, does not result in any accumulation of turbid matter in the effluent. Abrasion of the particulate filter material, which can occur in particular when using sand as the filter material, potentially precipitated hardeners and detached biomass are retained by the filter bed and discharged with the rinsing water.
- Substances that can be filtered off are also reliably retained with the method according to the invention at a value in the effluent that is below the legal limit value. A failure of hardness components in the process is also not observed.
- the method according to the invention is therefore a promising starting point for increasing the yield of drinking water in the treatment of raw water to increase this by means of reverse osmosis or nanofiltration. Otherwise, the method according to the invention is environmentally friendly and resource-friendly.
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Abstract
La présente invention concerne un procédé de traitement de concentré d'osmose inverse et/ou de nanofiltration ("concentré"), le concentré provenant du traitement d'eaux brutes par osmose inverse et/ou nanofiltration pour la production d'eau potable et/ou d'eau de service. Le procédé comprend le guidage du concentré sur un lit filtrant contenant un matériau filtrant granulaire et/ou particulaire biologiquement activé pour réaliser une dénitrification microbienne. L'invention concerne également un réacteur conçu et agencé pour la mise en oeuvre du procédé selon l'invention.
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DE102022102019.3A DE102022102019A1 (de) | 2021-12-21 | 2022-01-28 | Verfahren zur Entfernung von Nitrat aus Membranfiltrationskonzentraten |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP3368150B2 (ja) * | 1996-06-25 | 2003-01-20 | 株式会社荏原製作所 | 流動床式生物処理装置及び方法 |
DE20121793U1 (de) * | 2001-10-27 | 2003-07-31 | Hermsdorfer Institut für Technische Keramik e.V., 07629 Hermsdorf | Aufwuchsträger für Mikroorganismen und Vorrichtung zur Manipulation solcher Aufwuchsträger |
WO2010076794A1 (fr) * | 2008-12-31 | 2010-07-08 | Technion Research & Development Foundation Ltd. | Procédé pour dénitrifier une saumure et systèmes aptes à une telle dénitrification |
US20110168615A1 (en) * | 2010-01-08 | 2011-07-14 | Parkson Corporation | Apparatus for treating liquid containing impurities |
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2022
- 2022-12-20 WO PCT/EP2022/086995 patent/WO2023118145A1/fr active Application Filing
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JP3368150B2 (ja) * | 1996-06-25 | 2003-01-20 | 株式会社荏原製作所 | 流動床式生物処理装置及び方法 |
DE20121793U1 (de) * | 2001-10-27 | 2003-07-31 | Hermsdorfer Institut für Technische Keramik e.V., 07629 Hermsdorf | Aufwuchsträger für Mikroorganismen und Vorrichtung zur Manipulation solcher Aufwuchsträger |
WO2010076794A1 (fr) * | 2008-12-31 | 2010-07-08 | Technion Research & Development Foundation Ltd. | Procédé pour dénitrifier une saumure et systèmes aptes à une telle dénitrification |
US20110168615A1 (en) * | 2010-01-08 | 2011-07-14 | Parkson Corporation | Apparatus for treating liquid containing impurities |
Non-Patent Citations (1)
Title |
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ERSEVER ILKNUR ET AL: "Modeling and design of anaerobic fluidized bed reactor with recycling for denitrification of reverse osmosis concentrates", CHEMICAL ENGINEERING SCIENCE, OXFORD, GB, vol. 108, 31 December 2013 (2013-12-31), pages 111 - 122, XP028667850, ISSN: 0009-2509, DOI: 10.1016/J.CES.2013.12.036 * |
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