CN105578875A - 用于高效减少氮和磷酸盐的新的杂混物可生物降解的聚合物 - Google Patents
用于高效减少氮和磷酸盐的新的杂混物可生物降解的聚合物 Download PDFInfo
- Publication number
- CN105578875A CN105578875A CN201480042032.6A CN201480042032A CN105578875A CN 105578875 A CN105578875 A CN 105578875A CN 201480042032 A CN201480042032 A CN 201480042032A CN 105578875 A CN105578875 A CN 105578875A
- Authority
- CN
- China
- Prior art keywords
- metal
- aqueous solution
- pol
- polymer
- hybridization thing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004621 biodegradable polymer Substances 0.000 title claims abstract description 14
- 229920002988 biodegradable polymer Polymers 0.000 title abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title description 29
- 229910019142 PO4 Inorganic materials 0.000 title description 28
- 239000010452 phosphate Substances 0.000 title description 28
- 229910052757 nitrogen Inorganic materials 0.000 title description 19
- 238000001914 filtration Methods 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000009396 hybridization Methods 0.000 claims description 68
- 239000008187 granular material Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- -1 3-hydroxybutyrate ester Chemical class 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 26
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 20
- 239000002351 wastewater Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000013535 sea water Substances 0.000 claims description 12
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 11
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000013505 freshwater Substances 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 239000004626 polylactic acid Substances 0.000 claims description 4
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- 229940006015 4-hydroxybutyric acid Drugs 0.000 claims description 2
- 229920005615 natural polymer Polymers 0.000 claims description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 239000011324 bead Substances 0.000 abstract description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 abstract description 2
- 150000002830 nitrogen compounds Chemical class 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 31
- 229910002651 NO3 Inorganic materials 0.000 description 27
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 27
- 241000894006 Bacteria Species 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 12
- 239000011572 manganese Substances 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 230000001580 bacterial effect Effects 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 235000014413 iron hydroxide Nutrition 0.000 description 8
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 7
- 102000004169 proteins and genes Human genes 0.000 description 7
- 108090000623 proteins and genes Proteins 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003203 everyday effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 241000251468 Actinopterygii Species 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 235000013980 iron oxide Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- AHEWZZJEDQVLOP-UHFFFAOYSA-N monobromobimane Chemical compound BrCC1=C(C)C(=O)N2N1C(C)=C(C)C2=O AHEWZZJEDQVLOP-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000012851 eutrophication Methods 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical group O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010841 municipal wastewater Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- 241000589876 Campylobacter Species 0.000 description 2
- 235000014653 Carica parviflora Nutrition 0.000 description 2
- 241000243321 Cnidaria Species 0.000 description 2
- 241000605122 Nitrosomonas Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000605008 Spirillum Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 102000010638 Kinesin Human genes 0.000 description 1
- 108010063296 Kinesin Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000192121 Nitrospira <genus> Species 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 241001148470 aerobic bacillus Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 235000013613 poultry product Nutrition 0.000 description 1
- 238000009021 pre-vaccination Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K63/00—Receptacles for live fish, e.g. aquaria; Terraria
- A01K63/04—Arrangements for treating water specially adapted to receptacles for live fish
- A01K63/045—Filters for aquaria
-
- 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
- C02F3/08—Aerobic processes using moving contact bodies
- C02F3/085—Fluidized beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3028—Granulating, agglomerating or aggregating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2307/00—Location of water treatment or water treatment device
- C02F2307/08—Treatment of wastewater in the sewer, e.g. to reduce grease, odour
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Environmental Sciences (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Biodiversity & Conservation Biology (AREA)
- Animal Husbandry (AREA)
- Marine Sciences & Fisheries (AREA)
- Hydrology & Water Resources (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Biological Treatment Of Waste Water (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
本发明涉及一种偶联到金属-(OH/CO3)n小珠的可生物降解的聚合物(杂混物POL/金属-(OH/CO3)n)。本发明还涉及包含杂混物POL/金属-(OH/CO3)n的容器和过滤剂,涉及将杂混物POL/金属-(OH/CO3)n用于从水性溶液减少氮化合物的方法。
Description
领域:本发明涉及用于从水性溶液去除或减少无机化合物、优选氮和磷酸盐化合物的试剂,该试剂包含杂混物可生物地降解的聚合物-金属复合物,称为杂混物POL/金属-(OH/CO3)n。
背景
动物例如鱼、虾、珊瑚和其它无脊椎动物需要较低水平的禽产品(fowlingproducts)例如硝酸盐和磷酸盐。在水性溶液例如养鱼池中保持较低水平的磷酸盐的方法包括以下的一种或多种:养殖和收割宏观藻类或其它快速生长的生物体,使用不含过量磷酸盐的食物,使用石灰水除沫,使用其它结合磷酸盐的介质,以及引入大片的微生物例如细菌。目前,磷酸盐通过使用颗粒状氢氧化铁或氧化铁(GFH)颗粒或粉末来去除。这高效地除去磷酸盐。然而,GFH迅速饱和,然后用新的GFH进行更换,或用NaOH进行再生。这两种方法都成本高、耗时长,并得到不可回收利用的废弃产物。
氮可通过添加以下氢碳源诱导细菌生长来去除:例如糖、乙酸或在养鱼池中更流行的可生物降解的聚合物例如聚羟基烷酸酯(PHA),其包括聚羟基丁酸酯(PHB)和3-羟基丁酸酯/3-羟基戊酸酯共聚物(PHBV)。所用的其它聚合物是聚己内酯,如US7244358所述。特别是在缺氧条件下,细菌快速消耗NO3,并将其降解成N2和CO2。然而,该过程的副产物是有毒化合物H2S。
PHA小珠甚至可在封闭系统中于高氧条件下除去硝酸盐。然而,对于流通式系统例如废水处理厂,它们的效率不够好,因为当接触时间较短时(例如在废水处理厂中通常如此),其只除去小百分比的硝酸盐。
发明人观察到,当大量的团粒用于具有较低水平(约0.01-0.03ppm)的磷酸盐的系统中时,可生物降解的聚合物基团粒只能有效地进行脱氮。据推测,磷酸盐可能为可生物降解的聚合物基团粒上的细菌生长的速率限制步骤。
因此,本发明提供用于水过滤器的过滤剂,其包含与金属-(OH/CO3)n小珠混合的可生物降解的聚合物(杂混物POL/金属-(OH/CO3)n)。已经发现,根据本发明的碳能源例如PHA与能结合磷酸盐的化合物的组合可促进聚合物上的细菌生长。虽然无意受限于理论,但聚合物之上或附近的局部磷酸盐水平的增加导致细菌的生长增加。细菌生长的增加导致更高效地从水性溶液去除氮和磷酸盐化合物。此外,杂混物小珠中能结合磷酸盐的金属-(OH/CO3)n通过由细菌去除结合的磷酸盐而进行恒定的再生。换句话说,偶联到聚合物上的金属-(OH/CO3)n小珠结合磷酸盐,由此使细菌更容易地接触这些磷酸盐,这带来更好的细菌生长并带来恒定地回收利用能结合磷酸盐的金属-(OH/CO3)n小珠。这导致恒定地减少磷酸盐化合物和氮化合物,却无需再生金属-(OH/CO3)n小珠。
如本文所使用,术语可生物降解的聚合物指无毒且能用微生物降解的聚合物。优选的可生物降解的聚合物不仅提供刚性和合适的机械性质,还用作微生物生长的氢碳源。优选的聚合物包含或选自下组:聚己内酯、聚乳酸、乳酸-乙醇酸共聚物、聚羟基烷酸酯类聚合物、包含多糖例如淀粉或纤维素的天然聚合物,和/或聚(3-羟基丙酸)(P(3-HP),或所述聚合物中至少两种的混合物。所述可生物降解的聚合物更优选地选自下组:聚己内酯、聚乳酸、聚羟基烷酸酯类聚合物,和所述聚合物中至少两种的混合物。
如本文所使用,术语氮化合物指有机含氮化合物,优选地指无机含氮化合物。优选的无机氮化合物包含铵、亚硝酸盐和硝酸盐。
如本文所使用,术语磷酸盐化合物指有机含磷化合物,优选地指无机含磷化合物。优选的无机磷酸盐化合物包含H3PO4,H2PO4 -,HPO4 2-,和PO4。
如本文所使用,术语聚羟基烷酸酯类聚合物指在自然中通过细菌发酵生成的线性聚合物。它们是均聚物或各种羟基烷酸的共聚物。根据本发明的优选的聚羟基烷酸酯类聚合物是聚羟基丁酸酯、3-羟基丁酸酯/3-羟基戊酸酯共聚物(PHBV)、3-羟基丁酸酯/3-羟基己酸酯共聚物(PHBHHX)、3-羟基丁酸酯/4-羟基丁酸酯共聚物(P3HB4HB),或所述聚合物中至少两种的混合物。
根据本发明的优选的金属-(OH/CO3)n是或包含Fe(OH)3,Fe(OH)2,Fe2(CO3)3,Fe2O3,Mg(OH)3,MgO,Mg2(CO3)3,Ca(OH)2,CaCO3,La(OH)3,La2(CO3)3,MnO,MnO2,Mn(CO)n,Mn(OH)n例如Mn(OH)2,Mn(OH)3,Mn(OH)4,Mn(OH)6,和Mn(OH)7,Al(OH)3和/或Al2(CO3)3。所述金属-(OH/CO3)n优选地是或包含Fe(OH)3,Fe2O3,La(OH)3,Al(OH)3,和Al2(CO3)3。所述金属-(OH/CO3)n优选地选自下组:Fe(OH)3,Fe2O3,Al(OH)3,和Al2(CO3)3,或其混合物。根据本发明的最优选的金属-(OH/CO3)n包含Fe(OH)3,Fe2O3,或其混合物,或者是Fe(OH)3,Fe2O3,或其混合物。
一般来说,在水性溶液中,金属氢氧化物是与金属氧化物形成平衡。例如,已知氢氧化铁(Fe(OH)3)与氧化铁Fe2O3形成平衡。固体Fe(OH)3自发地失去水,以形成在氢氧化铁(Fe(OH)3)和氧化铁Fe2O3之间的材料,将该材料称为氢氧化氧化铁。水合氢氧化氧化铁主要由氢氧化铁组成。氢氧化氧化铁可为完全无定形的、完全结晶的或两种形式的混合物。出现不同的晶体形式,包括例如针铁矿、纤铁矿和褐铁矿。因此,如本文所使用,术语金属-(OH)n指金属的氢氧化物形式、金属的氧化物形式以及混合的氧化物-氢氧化物形式。
此外,术语金属-(OH/CO3)n还指与水性溶液接触或溶解于水性溶液之后的金属盐。例如,取决于水性溶液的pH等,当溶解于水性溶液中时,FeCl3可形成Fe(OH)3或Fe2(CO3)3。因此,如果与水性溶液接触或溶解于水性溶液之后,金属盐转化成金属氢氧化物或金属碳酸盐,则术语金属(OH/CO3)n涵盖使用金属离子例如FeCl3。
以杂混物POL/金属-(OH/CO3)n)的总重量为基准计,所述金属-(OH/CO3)n的含量优选地是约0.1%-80%(重量/重量),优选地0.5%-50%(重量/重量),优选地1%-25%(重量/重量),更优选地约10%(重量/重量)。
根据本发明的杂混物POL/金属-(OH/CO3)n优选地是粉末,更优选地是聚集体(agglomerate),更优选地是细粒(granulate),更优选地是团粒(pellet),或其混合物。聚集体由较大的颗粒形成,该较大的颗粒通过将初级颗粒连接或结合在一起来形成,在最终聚集体形式中,该初级颗粒的原始界限仍然是可见的。细粒由通过初级颗粒逐渐增大直到它们的原始的界限不再可见而形成的颗粒组成。团粒由在成型和机械加工操作中产生的微粒组成。
如本技术领域所公知,聚集、细粒化和切粒方法可涉及微粒的湿加工和机械加工。通过改变润湿和混合的程度,可将开放的多孔聚集体结构转变成更封闭的和更像颗粒的细粒结构。微粒的产生涉及控制输入的水分和能量,从而获得所需的结构和其它性质的变化。
所述聚集体、细粒或优选的团粒的平均尺寸优选地是0.1mm-10mm,更优选0.5mm-5mm,更优选1mm-3mm,例如1mm、1.5mm、2mm、2.5mm或3mm。所述聚集体、细粒或优选的团粒的绝对尺寸优选地是0.01-25mm,优选0.05-20mm。
所述团粒优选地借助团粒磨机或挤出和/或滚圆(也称为一步造粒法)设备来生产。产生根据本发明的杂混物POL/金属-(OH/CO3)n的优选的方法包含以所示比例共混(优选干燥共混)金属-(OH/CO3)n和聚合物粉末,然后进行挤出来获得杂混物团粒。所述团粒可为小球(marble)、杆、纤维、网,中空型材例如中空管,优选地是小球。
共混时间优选地是10分钟-24小时,更优选20分钟-10小时,更优选30分钟-5小时,更优选的是约1小时。所述共混优选地在以下温度实施:0℃-160℃,更优选20℃-100℃,更优选30℃-90℃。挤出步骤优选地通过热挤出或冷挤出来实施。热挤出在室温以上但在材料重结晶温度以下的温度下实施,通常是60℃-400℃。冷挤出在室温或接近室温下实施,通常是0℃-60℃。例如,室温下将100克Fe(OH)3与900克PHBV粉末干燥共混1小时,然后使其移动通过标准挤出机来获得杂混物团粒。优选地,将挤出机的模腔加热到至少60℃,从而确保各部分在模具中结晶到其最大的量。如通过卡尔·费舍尔(KarlFischer)方法所测量,还优选地将树脂或混合的树脂干燥到水分最大为500ppm,更优选地水分最大为250ppm。
因此,本发明还提供生产杂混物团粒的方法,该杂混物团粒包含用于水过滤器的过滤剂,所述过滤剂包含根据本发明的与金属-(OH/CO3)n小珠混合的可生物降解的聚合物(杂混物POL/金属-(OH/CO3)n),该方法包含共混金属-(OH/CO3)n与聚合物粉末,然后进行挤出来获得杂混物团粒,其中所述金属-(OH/CO3)n的含量是0.1%-80%(重量/重量,以杂混物POL/金属-(OH/CO3)n的总重量为基准计)。
本发明还提供容器,该容器包含过滤剂,该过滤剂包含根据本发明的杂混物POL/金属-(OH/CO3)n。所述容器优选地是过滤器腔室、羊毛袋(fleecebag)、纱袋(gauzebag)或其它可渗透水的容器。除了杂混物POL/金属-(OH/CO3)n以外,所述容器还可包含其它材料例如砂和/或砂砾。所述容器优选地是需氧地或厌氧地操作的过滤系统或是其的一部分,例如滴流(Trickle)过滤器和流化床过滤器。所述容器优选地包含包封杂混物POL/金属-(OH/CO3)n的壳体,该壳体还包含a)液体进口,液体样品可通过该液体进口进入壳体,且其适于与所述液体样品啮合,和b)液体出口,所述液体样品可通过该液体出口离开过滤器壳体,且其适于与所述液体样品啮合。
滴流过滤器也称为湿/干过滤器,它是用于海水和淡水养鱼池的水过滤系统。该过滤器放置在养鱼池顶部或养鱼池下方。如果湿/干过滤器放置在养鱼池顶部,通过多个穿孔的托盘泵吸水,该托盘包含过滤羊毛或其它过滤材料。水滴流穿过托盘,使过滤材料保持润湿但不完全浸没,这允许好氧细菌生长,并帮助生物地过滤例如氮化合物。过滤之后,将水返回到养鱼池。
如果湿/干过滤器放置在槽下方,通过重力将水加入过滤器。将预过滤的水递送到穿孔的板(滴漏板)。可通过溢流中的泡沫板或套筒或者堰虹吸在养鱼池中进行预过滤,或者可通过设置在穿孔的板上的过滤羊毛来进行预过滤。来自养鱼池的含废弃物的水在滴漏板上铺展,并通过介质大量降下。这可为卷成圆形形状的过滤羊毛/塑料栅格(DLS或“双层螺旋”)或本技术领域所公知的任意数目的塑料介质。当水在介质上如瀑布般落下时,放出CO2并吸收氧气,且细菌将来自槽的包含氮化合物的废弃物转换成害处更小的材料例如硝酸盐。水进入污水坑,其可包含多个隔室,每个隔室具有其自己的过滤材料。通常,在污水坑中设置加热器和恒温控制器。
流化床过滤器的原理是从下方引导水通过包含杂混物POL/金属-(OH/CO3)n的床,从而该床被流化。这种机械装置可用于液化和工业过程,包括工业和/或市政污水处理。过滤器中包含杂混物POL/金属-(OH/CO3)n的床的表面非常大,因此存在用于好氧脱氮细菌的较大的表面。因此,过滤器的尺寸可为中等。流化床过滤器可为内部的或外部的。
作为替代,可将移动床生物膜反应器用于氮的去除,其中杂混物POL/金属-(OH/CO3)n优选地是细粒或团粒并在曝气沉淀池中以混合运动进行操作。各细粒或团粒提供表面积来支持异养和自养细菌的生长。正是这些高密度的细菌群落在系统之内实现高速生物降解,这还提供了工艺可靠性和操作方便性。移动床生物膜反应器特别适用于废水处理。
包含根据本发明的容器的需氧操作过滤系统优选地还包含蛋白质分离器,也称为泡沫分离器。蛋白质分离器主要用于海水系统且不用于淡水系统,因为淡水的密度没有高到使蛋白质分离器适当地工作。存在4种设计类型:文丘里(Venturi)、共流(空气和水单向流动)、对流(相反的流动)和下冲气流(DownDraft)。用于海水养鱼池的优选的蛋白质分离器是文丘里驱动蛋白质分离器,其为除去溶解的和小颗粒有机化合物提供高效的方式。下冲气流蛋白质分离器对于较大的海水系统,例如大于1000升的养鱼池是优选的,因为可对更大体积的水进行过滤。
本发明还提供从水性溶液减少氮化合物例如铵、亚硝酸盐和硝酸盐的方法,该方法包含提供包含根据本发明的杂混物POL/金属-(OH/CO3)n的过滤剂,使水性溶液的至少一部分接触杂混物POL/金属-(OH/CO3)n(输入水性溶液),和从杂混物POL/金属-(OH/CO3)n去除经过过滤的水性溶液,该经过过滤的水性溶液已经接触杂混物POL/金属-(OH/CO3)n并相比于输入水性溶液具有减少的氮化合物水平。如果所述水性溶液存在于接收器例如养鱼池中,优选地将经过过滤的水性溶液循环回到接收器中,该经过过滤的水性溶液已经接触杂混物POL/金属-(OH/CO3)n并相比于输入水性溶液具有减少的氮化合物水平。
每天喂养鱼和其它水生物导致常规地将有机氮化合物引入养鱼池系统。适当地管理氮循环是成功的养鱼池的关键元素。排泄物和其它分解有机物质产生氨,这对鱼的毒性非常高。细菌过程将这种氨氧化成毒性稍微更小的亚硝酸盐,这些亚硝酸盐进而被氧化成毒性小得多的硝酸盐。这些硝酸盐后续地作为氮源被相同的或其它微生物吸收,或通过厌氧细菌转化成氮气。根据本发明的包含杂混物POL/金属-(OH/CO3)n的过滤剂非常适用于除去或消除有机氮化合物,优选氨、亚硝酸盐和硝酸盐。
此外,氮和磷酸盐化合物是水生系统的主要污染物,这可来自不同的污染源,并产生严重的环境问题和生态问题。富营养化(Eutrophication)是河流湖泊的天然营养物的缓慢富集,并造成池塘、湖泊和水库的“老化”。过量的营养物特别是氮和磷,加速该富营养化过程。随着藻类生长和随后分解,它们消耗了水中溶解的氧。这种情况通常导致鱼死亡、恶臭、不美观,以及更不利于将水用于娱乐和其它公共应用。本发明的方法能在将处理过的水排放到地表水之前,在水处理厂中有效地从例如地下水、工业和/或市政污水除去氮和磷酸盐化合物。
使用根据本发明的包含杂混物POL/金属-(OH/CO3)n的过滤剂令人惊讶地导致在需氧操作条件下快速、非常有效地将氨减少到低于1ppm,或甚至接近0ppm的水平。此外,使用根据本发明的包含杂混物POL/金属-(OH/CO3)n的过滤剂令人惊讶地导致在需氧操作条件下快速、非常有效地将磷酸盐减少到低于0.02-0.03ppm的水平。令人惊讶的是,本发明无需更换金属-(OH/CO3)n或用例如氢氧化钠对金属-(OH/CO3)n进行再生。显然,杂混物POL/金属-(OH/CO3)n上的细菌能够用于恒定地回收利用结合磷酸盐的金属-(OH/CO3)n小珠。
本发明的方法中所用的水性溶液优选地包含淡水、海水或废水,或者是淡水、海水或废水。
在一种实施方式中,根据本发明的方法能从接收器例如包含淡水或海水的养鱼池中的水性溶液高效地减少氨。所述方法有助于保持循环系统或闭环系统中的水质。
在其它实施方式中,根据本发明的方法能从废水例如从市政污水或工业污水高效地减少氨。优选的用于从废水减少氨的过滤系统包含滴流过滤器系统,包含例如石头、岩浆、焦炭、砂砾、渣、聚氨酯泡沫、水藓泥炭苔藓、陶瓷或塑料介质的固定床,污水或其它废水在该固定床上向下流动,并导致生长一层微生物粘泥(生物膜),覆盖介质的床。通过下述方法来保持需氧条件:泼洒、扩散,以及当过滤介质是多孔的时候流动通过该床的强制空气,或者空气的自然对流。从废水减少氨的其它优选的过滤系统是流化床过滤器和移动床生物膜反应器。
优选地用细菌接种根据本发明的包含杂混物POL/金属-(OH/CO3)n过滤剂,例如根据本发明的容器。一般来说,存在为水产养殖移生于生物过滤器的3种好氧微生物:异养细菌,亚硝化单胞菌(Nitrosomonos)属细菌和硝化螺旋菌(Nitrospira)属细菌。
异养细菌利用溶解的来自聚合物的含碳材料作为它们的碳源。亚硝化单胞菌属细菌利用氨,并产生亚硝酸盐作为废弃产物。硝化螺旋菌属细菌利用亚硝酸盐,并产生硝酸盐作为废弃产物。只要存在可用的碳源和氮源,亚硝化单胞菌和硝化螺旋菌都将生长和移生于生物过滤器。硝酸盐被包含异养细菌的生物利用,将其作为氮源来生物转化成生物分子例如蛋白质,或可被异养细菌还原成N2。来自废水处理厂的废水提供异养细菌、亚硝化单胞菌属细菌和硝化螺旋菌属细菌的优选的来源。
除了减少铵、硝酸盐和亚硝酸盐的水平以外,根据本发明的方法还导致从水性溶液减少磷酸盐化合物。无机正磷酸盐,包含H3PO4,H2PO4 -,HPO4 2-,和PO4 3-,是易于通过氢氧化氧化铁材料结合的磷的形式。尽管存在其它形式,正磷酸盐还存在于天然海水中。它在海水中的浓度随位置显著变化,且还随深度和随每天的时间变化。相对于更深的水,地表水的磷酸盐大大减少,因为地表水中的生物活性将磷酸盐隔绝在生物中。典型的海洋表面磷酸盐浓度非常低,有时低至0.005ppm。
如果不为最小化磷酸盐水平付出具体努力,养鱼池中磷酸盐通常累积并升高。磷酸盐常常是藻类生长的限制性营养物。磷酸盐化合物增多将使不想要的藻类过量生长。此外,磷酸盐化合物的增多将直接抑制珊瑚和珊瑚藻的钙化活动。因此,特别是在海水养鱼池中,包括在礁石养鱼池中,将磷酸盐水平保持较低,优选地低于约0.03ppm,更优选地低于0.01ppm。如果将铁和/或氮源例如硝酸盐保持在正常水平,当磷酸盐水平大于0.03ppm时,特别是藻类的生长速率变得与磷酸盐浓度无关。
本发明还提供将根据本发明的包含杂混物POL/金属-(OH/CO3)n的过滤剂(例如根据本发明的容器)用于从水性溶液(优选地从接收器中的水性溶液)减少氮化合物和磷酸盐化合物。
本发明还提供用于水过滤器的过滤剂,其包含根据本发明的杂混物POL/金属-(OH/CO3)n,例如包含根据本发明的容器。所述过滤剂优选地是滴流过滤器、流化床过滤器或移动床生物膜反应器。
附图说明
图1.流通式系统中硝酸盐随时间减少,其使用根据本发明的杂混物POL/金属-(OH/CO3)n。
图2.循环系统中硝酸盐随时间减少,其使用根据本发明的杂混物POL/金属-(OH/CO3)n。
图3.循环系统中磷酸盐随时间减少,其使用根据本发明的杂混物POL/金属-(OH/CO3)n。
实施例
实施例1.淡水流通式系统中单独的PHBV小珠与杂混物POL/金属-(OH/CO3)n的比较。
材料和方法
室温下,将50克或100克Fe(OH)3(默克(Merck))分别与950克或900克的PHBV粉末(天安生物聚合物公司(TianAnBiopolymer),中国宁波市)干燥共混1小时,然后使用注塑使其经过标准挤出机来获得杂混物团粒。优选地,将模腔加热到至少60℃,从而确保各部分在模具中结晶到其最大的量。如通过卡尔·费舍尔(KarlFischer)方法所测量,还优选地将树脂或混合的树脂干燥到水分最大为250ppm。典型的加工温度设定参见下表1:
表1.典型的加工温度设定
作为对照,在不使用氢氧化铁的情况下,挤出950克或900克PHBV粉末。将50克和100克的GFO(颗粒氧化铁/氢氧化铁)(Fe(OH)3)用作第二对照。
将所有的小珠设置在具有圆筒柱的流通式系统中,硝酸盐的起始浓度是15ppm,磷酸盐的起始浓度是5ppm。在计量添加硝酸盐之前,用来自当地废水处理厂的废水,对小珠接种细菌。流动速度是100毫升/30分钟。
每天获取样品,并使用赛莫菲科技奥朗(ThermoScientificOrion)硝酸盐测试试剂盒(产品号700005)测试硝酸盐(表达为百万分之份数(ppm))。
结果
如图1所示,在10天时间之后,正常PHBV团粒的流出物的平均氮含量是12ppm。因此,正常PHBV团粒将硝酸盐减少(15-12)×100/15=20%。在10天的时间之后,杂混物POL/金属-(OH/CO3)n团粒的流出物的氮含量是1ppm。杂混物POL/金属-(OH/CO3)n团粒上的微生物特别是细菌的生长,导致硝酸盐的去除随时间增加。存在FeOH3时硝酸盐减少0%(数据未显示)。
该结果清楚地表明相比于单一组分,杂混物POL/金属-(OH/CO3)n中50Fe(OH)3和PHBV的组合获得令人惊讶的效果。
虽然尚不知氢氧化铁是否参与氮固定,但正常PHBV团粒和氢氧化铁的组合导致的预期减少幅度可按E=X+Y-[(X·Y)/100]计算。X是存在正常PHBV团粒时的氮去除百分比,而Y是存在氢氧化铁时的氮去除百分比。在本发明的情况下,X=20,且Y=0。这意味着PHBV-FeOH3杂混物(E)的预期硝酸盐去除率是20%。
杂混物POL/金属-(OH/CO3)n团粒的流出物的氮含量是1ppm。流入物是15ppm。因此,观察到的减少幅度是(15-1)×100/15=93%。因此,观察结果/预期结果的比值=4.7,高于1。因此,对于实验1,杂混物对硝酸盐减少存在明确的协同效应。
实施例2.在封闭的海水系统中,POL/金属-(OH/CO3)n与平行使用的PHBV小珠和颗粒氧化铁(GFO)的比较。
材料和方法
为了进行该实验,我们使用了全功能和生物活性的650升海洋槽,其包含无脊椎动物和鱼(约60个物种)。该系统包含蛋白质分离器(BBK超级马林(supermarine)250),即2000升/小时的循环泵(Sicce)。海盐(红海优(RedSeaPro))浓度是35ppm,温度保持在26℃,且pH在7.9-8.2之间变化。
在第一个装置(装置1)中,将2kg的GFO和5kg的PHBV团粒置于连续的圆筒流化过滤器中。当观察到磷酸盐水平增加时,每两周更换GFO小珠。
装置2):将5kg(总计)的PHBV-FeOH3杂混物置于连续的圆筒流化过滤器。
每天给两个装置中的养鱼池添加5克的礁石珍珠(reefpearl)(力夫因特力特(ReefInterets),荷兰乌特勒支(Utrecht))。使用购自索里法特(Salifert)(荷兰)的标准NO3和PO4试剂盒,每2天在早上8点测量硝酸盐和磷酸盐水平。
结果
不存在PHBV团粒时,每天添加5克的礁石珍珠将硝酸盐水平增加约20ppm/天,而当不存在GFO(颗粒氧化铁/氢氧化铁)时磷酸盐水平增加约0.1ppm/天。如图2所示,装置1中的硝酸盐水平或多或少仍然保持在约20ppm。这意味着当使用独立的GFO和PHBV团粒时,氮的减少是约20ppm/天,因此是约50%。
当使用杂混物时,观察到硝酸盐额外地降低到约1ppm。这表明杂混物POL/金属-(OH/CO3)n)的形式的GFO和可生物降解的聚合物的组合比单独组分之和大得多。当使用根据本发明的杂混物POL/金属-(OH/CO3)n)时,对硝酸盐去除而言存在协同效应。
我们还测试了在两个实验装置中去除磷酸盐的效率。我们假设细菌的存在将使杂混物中的FeOH3进行恒定的生物再生,因为细菌从铁化合物去除磷酸盐。这使新的磷酸盐化合物恒定地结合到杂混物中存在的Fe3+离子上。
由图3可知,在2-3周之后,GFO小珠被磷酸盐饱和。槽中的磷酸盐水平持续增加,直到用2kg新鲜的GFO配料更换原来的GFO。
相比之下,当使用根据本发明的只包含10%FeOH3(约500克)的杂混物POL/金属-(OH/CO3)n)时,我们观察到磷酸盐下降,其从来没有超过0.01ppm。
甚至在60天之后,磷酸盐水平低至0.01ppm,无需更换杂混物POL/金属-(OH/CO3)n)。这清楚地表明,根据本发明的杂混物POL/金属-(OH/CO3)n)还具有去除磷酸盐的显著优势。
实施例3具有不同金属-(OH/CO3)n的PHBV小珠的对比。
材料和方法
使初始氮含量为15ppm的废水连续地流动通过圆筒流化过滤器,其包含200克不同的PHBV-金属杂混物。废水中已经存在在生物团粒上的细菌生长,且无需预接种。在12天的时间段中,每天使用标准NO2-检测试剂盒来测定氮(硝酸盐)含量,所述试剂盒购自默克(Merck)(默克米里博(MerckMillipore),荷兰阿姆斯特丹)。
结果
如表2所示,单独的PHBV或PHBV-Ca(OH)2不能有效地对废水进行脱氮。PHBV与锰的组合导致稍微更有效地对废水进行脱氮,该锰为氧化锰(MnO)的形式或氢氧化锰(Mn(OH)2)的形式。从该表还可知,PHBV与铝如Al(OH)3的组合或与铁如Fe(OH)3的组合导致非常有效地从废水去除氮化合物。
表2.具有不同PHBV-金属杂混物的废水中的氮
Claims (15)
1.一种用于水过滤器的过滤剂,该过滤剂包含与金属-(OH/CO3)n小珠混合的可生物降解的聚合物(杂混物POL/金属-(OH/CO3)n),其中该聚合物选自下组:聚己内酯、聚乳酸,乳酸-乙醇酸共聚物、聚羟基烷酸酯类聚合物、天然聚合物和聚(3-羟基丙酸)(P(3-HP),或所述聚合物中至少两种的混合物,且其中该金属-(OH/CO3)n选自下组:Fe(OH)3,Fe2O3,Al(OH)3,Al2(CO3)3,和La(OH)3。
2.如权利要求1所述的过滤剂,其特征在于,该聚合物是聚己内酯、聚乳酸、聚羟基烷酸酯类聚合物,或所述聚合物中至少两种的混合物。
3.如权利要求1或2所述的过滤剂,其特征在于,该聚羟基烷酸酯类聚合物是聚羟基丁酸酯、3-羟基丁酸酯/3-羟基戊酸酯共聚物(PHBV)、3-羟基丁酸酯/3-羟基己酸酯共聚物(PHBHHX)、3-羟基丁酸酯/4-羟基丁酸酯共聚物(P3HB4HB),或所述聚合物中至少两种的混合物。
4.如权利要求1-3中任一项所述的过滤剂,其特征在于,该金属-(OH/CO3)n是Fe(OH)3或Fe2O3。
5.如前述权利要求中任一项所述的过滤剂,其特征在于,该杂混物POL/金属-(OH/CO3)n是颗粒化的。
6.如权利要求1-4中任一项所述的过滤剂,其特征在于,该杂混物POL/金属-(OH/CO3)n作为团粒来提供。
7.一种容器,其包含如前述权利要求中任一项所述的过滤剂。
8.如权利要求7所述的容器,其特征在于,该容器是流化床反应器。
9.一种从水性溶液减少氮化合物的方法,该方法包含:
提供如权利要求1-6中任一项所述的过滤剂,或如权利要求7或8所述的容器;
使水性溶液的至少一部分接触杂混物POL/金属-(OH/CO3)n(输入水性溶液);和
从杂混物POL/金属-(OH/CO3)n去除水性溶液,该水性溶液已经接触杂混物POL/金属-(OH/CO3)n并相比于输入水性溶液具有减少的氮化合物水平。
10.如权利要求9所述的方法,其特征在于,所述水性溶液存在于接收器中,并将已经接触杂混物POL/金属-(OH/CO3)n并相比于输入水性溶液具有减少的氮化合物水平的水性溶液循环回到接收器中。
11.如权利要求9或10所述的方法,其特征在于,该水性溶液包括淡水、海水或废水。
12.如权利要求9-11中任一项所述的方法,其特征在于,用细菌接种如权利要求1-6中任一项所述的杂混物过滤剂,或如权利要求7或8所述的容器。
13.如权利要求9-12中任一项所述的方法,其特征在于,还导致从水性溶液减少磷酸盐化合物。
14.如权利要求1-6中任一项所述的过滤剂,或如权利要求7或8所述的容器用于从水性溶液减少氮化合物的用途。
15.一种生产杂混物团粒的方法,该杂混物团粒包含用于水过滤器的过滤剂,所述过滤剂包含与金属-(OH/CO3)n小珠混合的可生物降解的聚合物(杂混物POL/金属-(OH/CO3)n),该方法包含共混金属-(OH/CO3)n与聚合物粉末,然后进行挤出来获得杂混物团粒,其中所述金属-(OH/CO3)n的含量是0.1%-80%(重量/重量,以杂混物POL/金属-(OH/CO3)n的总重量为基准计)。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13178223 | 2013-07-26 | ||
EP13178223.7 | 2013-07-26 | ||
PCT/NL2014/050525 WO2015012700A1 (en) | 2013-07-26 | 2014-07-28 | New hybrid biodegradable polymer for efficient nitrogen and phosphate reduction |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105578875A true CN105578875A (zh) | 2016-05-11 |
Family
ID=48874208
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201480042032.6A Pending CN105578875A (zh) | 2013-07-26 | 2014-07-28 | 用于高效减少氮和磷酸盐的新的杂混物可生物降解的聚合物 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20160152498A1 (zh) |
EP (1) | EP3024319B1 (zh) |
CN (1) | CN105578875A (zh) |
WO (1) | WO2015012700A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106345397A (zh) * | 2016-11-14 | 2017-01-25 | 中国科学院生态环境研究中心 | 一种高效去除水体中磷的新型吸附材料 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113003720A (zh) * | 2021-04-09 | 2021-06-22 | 湖南三友环保科技有限公司 | 一种有机复合滤料的制备及其在污水处理脱氮中的应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984313A (en) * | 1973-09-18 | 1976-10-05 | Chemical Separations Corporation | Preferential removal of ammonia and phosphates |
JP2004175848A (ja) * | 2002-11-25 | 2004-06-24 | Taiho Ind Co Ltd | 脱窒作用を有する生分解性樹脂成形体 |
CN1520255A (zh) * | 2001-04-26 | 2004-08-11 | ���˻�˹�����̩�˹ɷ�����˾ | 水族箱水的脱硝 |
US20050143502A1 (en) * | 2002-04-24 | 2005-06-30 | Shinichiro Yamada | Biodegradable flame retardant composite composition and process for producing the same |
JP2008150560A (ja) * | 2006-12-20 | 2008-07-03 | Unitika Ltd | ポリ乳酸系樹脂組成物、およびそれを成形してなる成形体 |
EP2264103A1 (en) * | 2008-04-08 | 2010-12-22 | Kao Corporation | Polylactic acid resin composite |
-
2014
- 2014-07-28 US US14/906,406 patent/US20160152498A1/en not_active Abandoned
- 2014-07-28 EP EP14753341.8A patent/EP3024319B1/en not_active Not-in-force
- 2014-07-28 WO PCT/NL2014/050525 patent/WO2015012700A1/en active Application Filing
- 2014-07-28 CN CN201480042032.6A patent/CN105578875A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984313A (en) * | 1973-09-18 | 1976-10-05 | Chemical Separations Corporation | Preferential removal of ammonia and phosphates |
CN1520255A (zh) * | 2001-04-26 | 2004-08-11 | ���˻�˹�����̩�˹ɷ�����˾ | 水族箱水的脱硝 |
US20050143502A1 (en) * | 2002-04-24 | 2005-06-30 | Shinichiro Yamada | Biodegradable flame retardant composite composition and process for producing the same |
JP2004175848A (ja) * | 2002-11-25 | 2004-06-24 | Taiho Ind Co Ltd | 脱窒作用を有する生分解性樹脂成形体 |
JP2008150560A (ja) * | 2006-12-20 | 2008-07-03 | Unitika Ltd | ポリ乳酸系樹脂組成物、およびそれを成形してなる成形体 |
EP2264103A1 (en) * | 2008-04-08 | 2010-12-22 | Kao Corporation | Polylactic acid resin composite |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106345397A (zh) * | 2016-11-14 | 2017-01-25 | 中国科学院生态环境研究中心 | 一种高效去除水体中磷的新型吸附材料 |
Also Published As
Publication number | Publication date |
---|---|
EP3024319A1 (en) | 2016-06-01 |
WO2015012700A1 (en) | 2015-01-29 |
US20160152498A1 (en) | 2016-06-02 |
EP3024319B1 (en) | 2018-01-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhu et al. | Biological denitrification using poly (butylene succinate) as carbon source and biofilm carrier for recirculating aquaculture system effluent treatment | |
EP2139313B1 (en) | Method for the conversion of fish waste from aquaculture systems to methane via a modified uasb reactor | |
Li et al. | Hazardous substances and their removal in recirculating aquaculture systems: A review | |
JP5847376B2 (ja) | 魚介類の閉鎖循環式養殖方法 | |
KR102051259B1 (ko) | 내염성 호기성 그래뉼 슬러지 기반 친환경 탈질조 | |
KR102103668B1 (ko) | 내염성 호기성 그래뉼 슬러지 기반 친환경 순환여과 양식시스템 | |
JP2017209647A (ja) | 水処理用微生物の包括担体、水処理方法、包括担体の製造方法 | |
CN109293138A (zh) | 一种养殖污水净化处理方法 | |
CN102295394B (zh) | 沙蚕生物滤池内微生物膜的培养方法 | |
He et al. | A sulfur-based cyclic denitrification filter for marine recirculating aquaculture systems | |
Ngo et al. | Aerobic treatment of effluents from the aquaculture industry | |
WO2020004635A1 (ja) | 水浄化装置、養殖水浄化システム、水の浄化方法及び水生生物の生産方法 | |
CN105578875A (zh) | 用于高效减少氮和磷酸盐的新的杂混物可生物降解的聚合物 | |
JP2008200637A (ja) | 水処理施設、水処理設備、並びに水処理方法 | |
Sarosh et al. | Packed bed biofilm reactor for high-rate, robust and efficient nitrification in recirculating aquaculture system: a preliminary investigation | |
Ling et al. | Wastewater management in freshwater pond aquaculture in China | |
US7244358B2 (en) | Denitrification of aquarium water | |
Sánchez-O et al. | Performance of different biofilters in a recirculating system for rainbow trout farming | |
KR20160114506A (ko) | 부상여재 여과를 이용한 중소규모 고도하수처리 방법 | |
Yamamoto | Characteristics of closed recirculating systems | |
Abdelfatah et al. | Recent Used Techniques and Promised Solutions for Biofiltration Treatment of Fish Wastewater | |
Wang et al. | Performance of a combined eco-system of ponds and constructed wetlands for wastewater reclamation and reuse | |
JP2005081230A (ja) | 水質浄化資材の製造方法、および水質浄化システム | |
Abdelbary | Bioremediation of fish wastewater using a modified aerated beads biological filter | |
Abdelbary | Comparative study of nitrogen bioremoval from aquaculture wastewater using bioflocs technique (bft) versus biofiltration system |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160511 |