CN106115932B - The method that sponge iron cooperates with removing sulfate and Cr (VI) waste water with microorganism - Google Patents
The method that sponge iron cooperates with removing sulfate and Cr (VI) waste water with microorganism Download PDFInfo
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- CN106115932B CN106115932B CN201610508413.XA CN201610508413A CN106115932B CN 106115932 B CN106115932 B CN 106115932B CN 201610508413 A CN201610508413 A CN 201610508413A CN 106115932 B CN106115932 B CN 106115932B
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- Prior art keywords
- iron
- sulfate
- waste water
- sponge iron
- reducing
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Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 256
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 126
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 97
- 239000002351 wastewater Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 51
- 244000005700 microbiome Species 0.000 title claims abstract description 26
- 241000894006 Bacteria Species 0.000 claims abstract description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 230000001603 reducing effect Effects 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 239000004005 microsphere Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 38
- 241000605716 Desulfovibrio Species 0.000 claims description 30
- 235000015097 nutrients Nutrition 0.000 claims description 28
- 244000061456 Solanum tuberosum Species 0.000 claims description 24
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 24
- 239000001963 growth medium Substances 0.000 claims description 24
- 239000002609 medium Substances 0.000 claims description 22
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 230000002829 reductive effect Effects 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 16
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 239000007836 KH2PO4 Substances 0.000 claims description 12
- 239000007832 Na2SO4 Substances 0.000 claims description 12
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000004568 cement Substances 0.000 claims description 12
- 239000006071 cream Substances 0.000 claims description 12
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 239000002054 inoculum Substances 0.000 claims description 12
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 239000001540 sodium lactate Substances 0.000 claims description 12
- 229940005581 sodium lactate Drugs 0.000 claims description 12
- 235000011088 sodium lactate Nutrition 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052603 melanterite Inorganic materials 0.000 claims description 11
- 241000589519 Comamonas Species 0.000 claims description 10
- 229910052564 epsomite Inorganic materials 0.000 claims description 10
- 230000003698 anagen phase Effects 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052925 anhydrite Inorganic materials 0.000 claims description 6
- 235000015278 beef Nutrition 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 3
- 239000001888 Peptone Substances 0.000 claims description 2
- 108010080698 Peptones Proteins 0.000 claims description 2
- 241000607598 Vibrio Species 0.000 claims description 2
- 206010047400 Vibrio infections Diseases 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 210000000496 pancreas Anatomy 0.000 claims description 2
- 235000019319 peptone Nutrition 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims 2
- 101100150274 Caenorhabditis elegans srb-2 gene Proteins 0.000 claims 1
- 230000032683 aging Effects 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 claims 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000012263 liquid product Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 78
- 229910001385 heavy metal Inorganic materials 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 8
- 238000009629 microbiological culture Methods 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical group [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000011953 bioanalysis Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000012137 tryptone Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035755 proliferation Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- 241000605739 Desulfovibrio desulfuricans Species 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000010786 composite waste Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940077449 dichromate ion Drugs 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010336 energy treatment Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 244000039328 opportunistic pathogen Species 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/346—Iron bacteria
-
- 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
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The method that the invention discloses sponge iron to cooperate with removing sulfate and Cr (VI) waste water with microorganism；This method is under anaerobic, by sponge iron solution A) the bacteria suspension C of the bacteria suspension B of sulfate reducing bacteria and iron-reducing bacterium with volume ratio is that 1:1:1~1:3:4 is mixed, it is aged 30~60min, after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, impregnated in sterile saline；Obtain sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixture；Gained sponge iron is mixed with sulfate reducing bacteria/iron-reducing bacterium mixture with sulfate and Cr (VI) waste water, is reacted 24 hours or more under room temperature, while purifying sulfate and Cr (VI) in waste water.The method of the present invention reaches 89% or more to the removal rate of Cr (VI) metal, and required equipment is simple, reaction is completed at normal temperatures and pressures, and product is solid phase, and reaction system is liquid phase, and product can be easily separated, and is used for large-scale industrial production.
Description
Technical field
The present invention relates to the methods of advanced treatment of wastewater, specifically processing containing sulfate and heavy metal Cr (VI) concentration
The deep treatment method of exceeded sewage.
Background technique
Chromate waste water is acknowledged as one of environmentally hazardous public hazards of current most serious.Pollution of chromium in water body mainly from
The waste water of the discharges such as process hides, plating and chromium salt production, chromium is in water mainly in the form of trivalent [Cr (III)] and sexavalence [Cr (VI)]
In the presence of, wherein the toxicity of Cr (VI) is very big, and 100 times of about Cr (III), if the content of Cr (VI) is greater than 0.1mgL in water-1, toxic action will be generated to human body.The exceeded chromate waste water of content is mixed into agricultural irrigation or aquifer cultivation, is taken the photograph through food
Enter human body, it will cause cancer.And it is irritant to human skin, mucous membrane, seriously threaten the health of the mankind.Therefore, how
Rationally and effectively processing waste water containing chrome is that the improvement of the important subject industrial wastewater of current environmental protection and comprehensive utilization is
One of main task of water pollution control.The concentration of Cr (VI) should be lower than 0.05mgL in China's regulation Drinking Water-1；Ground
The maximum permissible concentration of Cr (III) is 0.5mgL in the water of face-1, Cr (VI) is 0.05mgL-1；In industrial wastewater Cr (VI) and
Its compound highest permissible discharge standard is 0.5mgL-1；Chromium maximum permissible concentration is 0.5mgL in fishery water-1[Cr
And 0.05mgL (III)]-1[Cr(Ⅵ)].Compared with the Conventional pollutions such as COD, nitrogen, phosphorus, heavy metal Cr low, toxicity with concentration
Greatly, it is not easy to be metabolized in the environment, is easily bioaccumulation and has the features such as biological amplification, be difficult to go by natural degradation
It removes, it is therefore necessary to develop the minimizing technology for chromate waste water.
In recent years, domestic and foreign scholars and research institution do a lot of work for the removal of chromate waste water, and a variety of sides
Practical application has been put into method.There are many method of processing waste water containing chrome at present, have the electronation precipitation method, absorption method, ion to hand over
Change method, electrolysis method, membrane separation process, bioanalysis etc..Wherein, the electronation precipitation method have small investment, and processing cost is low, operation letter
The advantages that single, is widely used in multiclass route for treatment of chromium containing waste water, but its effluent quality is poor, is unable to reuse, when handling composite waste, easily
Cause secondary pollution, and general oxidant there are also the problem of supply of material and toxicity have it is to be solved.Such as to reach higher reuse standard,
It should be in subsequent increase advanced treating facility.Biological adsorption agent is with source is wide, price is low, adsorption capacity is strong, is easily isolated and recycled
The features such as heavy metal, and use dead microorganism as biological source have easily fixing, and can be made as needed it is special
Biological adsorption agent and Reusability, absorption method has absorption and reduction to Cr VI, is generally chiefly used in chromate waste water
Pretreatment.Using anion exchange resin, the Cr in waste water in chromate or dichromate ion state can be effectively removed
(VI), Cr in waste water (III) and other metal ions, ion exchange resin can be then removed using cation exchange resin is had
Good physicochemical property and ion-exchange group abundant have biggish exchange adsorption capacity containing chromium ion in aqueous solution,
The disadvantage is that resin is easily oxidized and pollutes, it is higher to pre-processing requirements.Electrolytic Theatment of Chrome Containing Wastewater is easy to operate, processing effect
Fruit is stablized, and Cr (VI) can be down to 0.1mg/L hereinafter, the disadvantage is that power consumption is more, need to consume a large amount of iron plate, effluent quality is poor, and generates
A large amount of reluctant sludge.Membrane separation process includes electrodialysis, reverse osmosis, ultrafiltration, liquid film etc., is widely used in heavy metal at present
In wastewater treatment process, but its energy consumption is high, low concentration wastewater can only be handled, cocnentration factor is limited, and film quality need
It improves.Bioanalysis handles heavy metal wastewater thereby as a kind of method that low energy consumption, since the 1980s both at home and abroad just energetically
It conducts a research and cooperates.Bioanalysis administers chromate waste water, relies primarily on the function bacterium manually cultivated, it makees with Electrostatic Absorption
With, the catalyzed conversion effect of enzyme, complexing, flocculation, co-precipitation and to the buffer function of pH value.Bioanalysis is main
It is that bio-flocculation process, biology can be divided into according to the mechanism difference of biological removal heavy metal ion by the function bacterium manually cultivated
Chemical method, biosorption process and phytoremediation remove the Cr in waste water (VI).Biochemical method chromate waste water has peace
Facilitate that nontoxic, not generate secondary pollution, treatment effeciency high entirely, and grow fast, the features such as being easily industrialized, has wide
Application prospect.
As a kind of novel zeroth order iron material, sponge iron shows stronger place during handling water pollutant
Reason ability.Relative to other zeroth order iron materials, iron filings and iron powder need secondary rust removal, and specific surface area is small, and there are secondary dirts
The defect low with removal efficiency is contaminated, nanometer iron powder preparation cost is higher, is easy to secondary oxidation, has potential environment and biology poison
Property.Sponge iron has large specific surface area, specific surface energy height, stronger electrochemistry enrichment, strong reducing property, physical absorption and flocculation heavy
The superior physical and chemical performances such as shallow lake.Since sponge iron main component is iron, loose porous internal structure, the ratio table provided
Area is 5-10 times of common iron filings, can make oxygen and iron in water that thorough oxidation reaction rapidly occur, lead to filtering type and remove shallow lake side
Formula is excluded, to pipeline, boiler recirculated water dissolved oxygen corrosion, after processing water dissolved oxygen content can reach 0.005mg/L with
Under, it can effectively reinforced anaerobic process.Sponge iron all has very well the pollutants such as organic matter, heavy metal and inorganic salts in water body
Removal capacity, be the zeroth order iron material of a kind of great potential.It is reported that sponge iron and microorganism form a kind of immobilization biological
System, synergistic effect, at optimum conditions, water outlet TP can be down to 0.5mg/L or less, and (Zhang Lidong, sponge iron are cooperateed with microorganism
Mutually promote dephosphorization research [J]).When pH value is 5, reaction 1h, sponge iron can reach 0.30mg/g (Gu Yingying, sea to nitrate reduction
The Primary Study [J] of nitrate in continuous iron reductive water).And for heavy metal, in certain initial concentration, optimal pH, temperature and
Under partial size, sponge iron can reach 0.18mg/g to the removal of Cr (VI) (Sun Yingxue, sponge iron handle Cr dynamics [J]).
Sulfate reducing bacteria (SRB) handles heavy metal wastewater thereby, is the S generated under anaerobic using SRB2-In waste water
Heavy metal ion reaction, generate metal sulfide precipitating with heavy-metal ion removal, SRB pure culture processing method has separation
Purification is many and diverse, operating condition is harsh, strain is lost the problems such as big.And anaerobic sludge method can provide sludge load for SRB strain
Body forms a metastable environment.But common anaerobic sludge flocculation structure is loose, and settling property is poor, unit microorganism
The problem of content is few, and activity is not high, and there is also strain losses.Therefore, it is necessary to which SRB strain sludge immobilization to be handled to a huge sum of money
Belong to waste water.
Summary of the invention
It is an object of that present invention to provide the effect of a kind of performance sponge iron, sulfate reducing bacteria and iron-reducing bacterium coordinated,
89% or more is reached to the removal rate of Cr (VI) metal, is significantly higher than removal when sponge iron and sulfate reducing bacteria independent role
Efficiency, and make the sponge iron of the synchronous removal of heavy metal in waste water Cr (VI) and sulfate cooperateed with microorganism removing sulfate and
The method of Cr (VI) waste water.
Iron also pathogenic microorganism is often referred to the microorganism with dissimilatory reduction Fe (III) function.Alienation Fe (III) reduction is anaerobism
It is that electronics supplies that important one of Biochemical processes in deposit and rice soil, which are some special microorganisms, using organic matter
Body, using Fe (III) as only electron acceptor, makes Fe (III) be reduced to Fe (II), and by generation while oxidation of organic compounds
Energy is obtained during thanking supports growth.(VI) indicates the chemical valence price of Cr ion in Cr (VI).
A kind of sponge iron/sulfate reducing bacteria/iron-reducing bacterium microballoon of the present invention, under anaerobic state, sulfate reducing bacteria
SRB and iron-reducing bacterium (Comamonas) are attached on the sponge iron for possessing huge specific surface area, and sulfate reducing bacteria will be in waste liquid
SO4 2-It is reduced to divalent, generates S2-.Sponge iron keeps reduction activation under the effect of iron-reducing bacterium supplied for electronic, while strong
Change heavy metal reduction process, effectively Cr (VI) can be reduced into Cr (III), then with S2-It reacts and is combined into sulfide
Precipitating.Sponge iron with high reproducibility not only owned certain reducing heavy metal ability, but also the dissolution that system will be made
Oxygen is maintained under 0.005mg/L, guarantees that system is under anaerobic state, to guarantee the suboxides of sulfate reducing bacteria SRB also
Former current potential constitutes a stably and controllable anaerobic reaction system.
The object of the invention is achieved through the following technical solutions:
The method that sponge iron cooperates with removing sulfate and Cr (VI) waste water with microorganism, comprising the following steps:
(1) preparation of sponge ferrous solution
Sponge iron solid is activated with dilute hydrochloric acid, the sponge ferrous solution that preparation concentration is 0.1-0.6g/L is denoted as reaction solution
A；
(2) preparation of sulfate reducing bacteria SRB
2 rings are selected from desulfovibrio (Desulfovibrio), are transferred in desulfovibrio nutrient medium, in 35-37
DEG C it is protected from light 3~5d of culture, 2-3d is expanded culture using desulfovibrio proliferated culture medium with the inoculum concentration of 5-10wt%, is centrifuged
Processing obtains the logarithmic growth phase cell of desulfovibrio, abandons supernatant, bacteria suspension B is made；
(3) preparation of iron-reducing bacterium
2 rings are selected from iron-reduced tuftedmonas (Comamonas), are transferred in iron-reducing bacterium nutrient medium,
28-30 DEG C is protected from light 3~5d of culture, expands culture 2- using iron-reducing bacterium proliferated culture medium with the inoculum concentration of 5-10wt%
3d, centrifugal treating obtain the logarithmic growth phase cell of iron-reducing bacterium, abandon supernatant, bacteria suspension C is made；
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixture
Under anaerobic, reaction solution A, bacteria suspension B and bacteria suspension C are mixed with volume ratio for 1:1:1~1:3:4, it is old
Change 30~60min, after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, in sterile saline
Middle immersion；Obtain sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixture；
(5) sulfate and Cr (VI) purification of waste water
Sponge iron obtained by step (4) and sulfate reducing bacteria/iron-reducing bacterium mixture and sulfate and Cr (VI) is useless
Water mixes, and reacts 20 hours or more under room temperature, while purifying sulfate and Cr (VI) in waste water.
To further realize the object of the invention, it is preferable that the sponge iron solid is prepared via a method which: with iron cement and
Simple substance carbon dust is raw material, and the mass ratio for controlling simple substance carbon dust and iron cement is 1:1-1:4, under the conditions of temperature is 1100-1200 DEG C
15-20min is calcined to be made.
Preferably, the centrifugal treating is that 3000r/min is centrifuged 10~20min；Bacteria suspension B is saved in 4 DEG C；The desulfurization
2 ring of vibrios (Desulfovibrio) is transferred in 30-40ml desulfovibrio nutrient medium.
Preferably, the formula composition of the desulfovibrio nutrient medium are as follows: KH2PO40.6g/L, NH4Cl 1.2g/L,
MgSO4·7H2O 0.2g/L, sodium lactate 3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O
0.3g/L, Na2SO45.5g/L, CaCl2·6H2O 0.2g/L, citric acid 0.3g/L adjust pH 7.0-7.5, remaining is water.
Preferably, the formula composition of the desulfovibrio proliferated culture medium are as follows: KH2PO40.8g/L, NH4Cl 1.5g/L,
CaCl2·2H2O 0.3g/L, Na2SO46g/L, MgSO4·7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L,
FeSO4·7H2O 3.0g/L, sodium citrate 0.5g/L adjust pH 7.0-7.5, remaining is water.
Preferably, the iron-reducing bacterium nutrient medium: if taking fresh potato juice dry volume, addition glucose 20~
24g/L, remaining is water；The preparation method of potato juice: removing 160~220 grams of skin fresh potato, be cut into small pieces, add from
Sub- 800~1000mL of water boils 30-35 minutes, filters off potato ball, filtrate is complemented to 1000mL with deionized water.
Preferably, the iron-reducing bacterium proliferated culture medium main component be 2.0~2.5g/L of beef extract, glucose 1.5~
2.5g/L, 5.5~6.0g/L of tryptone, yeast powder 3.0~4.5g/L, pH 6.5~7.5, remaining is water.
Preferably, in step (3), the centrifugal treating is that 3000r/min is centrifuged 10~15min, and bacteria suspension C is protected in 4 DEG C
It deposits；2 ring of iron-reduced tuftedmonas (Comamonas) is transferred in 30-40ml iron-reducing bacterium nutrient medium.
Preferably, the sponge iron impregnated in sterile saline and the mixing of sulfate reducing bacteria/iron-reducing bacterium
Object is placed in refrigerator and is saved at 4 DEG C.
Preferably, control sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixture 70-150mg/L in step 5)；Institute
State the Na that sulfate and Cr (VI) waste water contain 0.5g/L2SO4；The K of 141mg/L2Cr2O7, wherein Cr content is 50mg/L, remaining
For water.
The present invention is directed to the waste water containing high concentration sulfate and heavy metal Cr (VI), and screening is obtained with sulfate Gao Xuan
Selecting property reducing bacteria SRB flora realizes sulfuric acid using synergistic effect between the Anaerobic Corrosion of spongy iron and the sulfate metabolism of SRB
Salt removal synchronous with heavy metal Cr (VI).In the present invention, under anaerobic state, sulfate reducing bacteria SRB and iron-reducing bacterium are attached
In on the sponge iron for possessing huge specific surface area, sulfate reducing bacteria is by the SO in waste liquid4 2-It is reduced to divalent, is produced
Raw S2-.Sponge iron not only keeps reduction activation by the effect of iron-reducing bacterium supplied for electronic, while strengthening the reduction process of heavy metal, energy
It is enough to be effectively reduced into Cr (VI) Cr (III), then with S2-It reacts and is combined into sulfide precipitation.Sea with high reproducibility
Continuous iron not only owned certain reducing heavy metal ability, but also it is maintained at the dissolved oxygen of system under 0.005mg/L, it protects
Card system is under anaerobic state, to guarantee the lower oxidation reduction potential of sulfate reducing bacteria SRB, composition one is stably and controllable
Anaerobic reaction system.
Compared with the existing technology, the advantages of invention and the utility model has the advantages that
1. sponge ferrous-fortifier selected by the present invention is a kind of with large specific surface area, specific surface energy height, stronger electricity
The zeroth order iron material of the superior functions such as chemical enrichment, strong reducing property, physical absorption and flocculation sedimentation, to organic matter in water body, again
The pollutants such as metal and inorganic salts all have good removal capacity, sewage treatment field with development potential.
2. the sulfate reducing bacteria that the present invention selects, can be in an anaerobic environment by sulfate reduction at S2-, with heavy metal Cr
It generates and precipitates and then achieve the purpose that remove Cr.Sponge iron has certain adsorption capacity to heavy metal, and capture can be facilitated to restore
Cr.And Fe (III) can be reduced to Fe (II) by iron-reducing bacterium, Fe's is constant in holding system.
3. equipment needed for the present invention is simple and convenient to operate, reaction is completed at normal temperatures and pressures, and product is solid phase, reactant
System is liquid phase, and product can be easily separated, and therefore, is suitable for large-scale industrial production.
Detailed description of the invention
Fig. 1 is the removal effect figure of metal Cr (VI) in embodiment 1-4.
Specific embodiment
The present invention is described in further detail by following embodiment, but the technology contents that are described of the present embodiment be it is illustrative,
Without being restrictive, protection scope of the present invention should not be limited to according to this.
Embodiment 1
A kind of method that sponge iron cooperates with removing sulfate and Cr (VI) waste water with microorganism, comprising the following steps:
(1) preparation of sponge iron
Mixed carbon comtent (mass ratio of simple substance carbon dust and iron cement) 1:1,1160 DEG C of reaction temperature, reaction time 20min item
Under part, is calcined by raw material of iron cement, prepare conventional sponge iron solid.It is activated with dilute hydrochloric acid, the sea that preparation concentration is 0.2g/L
Continuous ferrous solution is denoted as reaction solution A.
(2) preparation of sulfate reducing bacteria SRB
From China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.3469) a kind of sulfate reducing bacteria-desulfovibrio (Desulfovibrio bought；Desulfovibrio desulfuricans subspecies) in
2 rings are selected, are transferred into 30ml desulfovibrio nutrient medium, culture 3d is protected from light at 35 DEG C, is adopted with the inoculum concentration of 5wt%
2d is expanded culture with desulfovibrio proliferated culture medium, 10min is centrifuged with 3000r/min, the logarithm for obtaining desulfovibrio is raw
Long-term cell abandons supernatant, bacteria suspension B is made, and saves in 4 DEG C.
Wherein, desulfovibrio nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L,
Sodium lactate 3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O 0.3g/L, Na2SO45.5g/L
CaCl2·6H2O 0.2g/L, citric acid 0.3g/L adjust pH 7.0, remaining is water.
Desulfovibrio proliferated culture medium: KH2PO40.8g/L, NH4Cl 1.5g/L, CaCl2·2H2O 0.3g/L,
Na2SO46g/L, MgSO4·7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L, FeSO4·7H2O 3.0g/L,
Sodium citrate 0.5g/L adjusts pH7.2, remaining is water.
(3) preparation of iron-reducing bacterium
It selects from China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.8048) 2 ring of iron-reduced tuftedmonas (Comamonas) bought, is transferred into 40ml iron-reducing bacterium comamonas
In nutrient medium, it is protected from light culture 5d at 28 DEG C, is carried out with 5% inoculum concentration using iron-reduced tuftedmonas proliferated culture medium
Expand culture 2d, 10min is centrifuged with 3000r/min, obtains the logarithmic growth phase cell of iron-reducing bacterium, supernatant is abandoned, bacterium is made
Suspension C is saved in 4 DEG C.
Wherein, iron-reducing bacterium comamonas nutrient medium is fresh potato juice 800mL, and glucose 20g, remaining is
Water；The preparation method of potato juice: 200 grams of skin fresh potato are removed, is cut into small pieces, deionized water 800mL is added to boil 30 points
Clock filters off potato ball, filtrate is complemented to 800mL with deionized water；
The iron-reduced tuftedmonas proliferated culture medium main component is beef extract 2.2g/L, glucose 1.5g/L, pancreas
Peptone 5.5g/L, yeast powder 3.5g/L, pH 6.5, remaining is water.
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixture
It is under anaerobic that 4:7:9 is mixed with volume ratio with suspension bacteria liquid B and C by reaction solution A, after being thoroughly mixed,
Continue to be aged 50min, obtains sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixture, whole process is passed through nitrogen protection
Anaerobic environment.
(5) after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, in sterile saline
Middle immersion is placed in refrigerator and is saved at 4 DEG C.
Using the waste water of the present embodiment method processing containing sulfate and heavy metal Cr (VI), waste water is formulated as that Na is added2SO4
Concentration is 0.5g/L, K2Cr2O7Concentration is 141mg/L (wherein Cr content is 50mg/L), sponge iron/sulfate reduction of addition
Bacterium/iron-reducing bacterium mixture concentration is 1g/L, remaining is water.Room temperature (at 25 DEG C) react, the reaction time be for 24 hours, at interval of
4h sampling, Cr use Flame Atomic Absorption Spectrometry Determination concentration, as a result as shown in Figure 1.It can be seen from the figure that with reaction
Time continues, and Cr remaining concentration gradually decreases, its residual concentration only has 3.6mg/L when for 24 hours, that is, can reach 92.8% and go
Except rate.
Embodiment 2
A kind of method that sponge iron cooperates with removing sulfate and Cr (VI) waste water with microorganism, comprising the following steps:
(1) preparation of sponge iron
Mixed carbon comtent (mass ratio of simple substance carbon dust and iron cement) 1:1,1160 DEG C of reaction temperature, reaction time 20min item
Under part, is calcined by raw material of iron cement, prepare conventional sponge iron solid.It is activated with dilute hydrochloric acid, the sea that preparation concentration is 0.1g/L
Continuous ferrous solution is denoted as reaction solution A.
(2) preparation of sulfate reducing bacteria SRB
A kind of sulfate reducing bacteria-the desulfovibrio bought from China General Microbiological culture presevation administrative center is (the same as real
Apply example 1) in select 2 rings, be transferred into 30ml nutrient solution, be protected from light at 35 DEG C culture 3d, with 5% inoculum concentration using proliferation
Culture medium expands culture 2d, is centrifuged 15min with 3000r/min, obtains the logarithmic growth phase cell of desulfovibrio, abandons supernatant
Bacteria suspension B is made in liquid, saves in 4 DEG C.
Wherein, nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L, sodium lactate
3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O 0.3g/L, Na2SO45.5g/L, CaCl2·
6H2O 0.2g/L, citric acid 0.3g/L adjust pH 7.0, remaining is water.
Proliferated culture medium: KH2PO40.8g/L, NH4Cl 1.5g/L, CaCl2·2H2O 0.3g/L, Na2SO46g/L,
MgSO4·7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L, FeSO4·7H2O 3.0g/L, sodium citrate
0.5g/L adjusts pH 7.4, remaining is water.
(3) preparation of iron-reducing bacterium
It selects from China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.8048) 2 ring of iron-reduced tuftedmonas bought, is transferred into 40ml nutrient solution, and culture 5d is protected from light at 28 DEG C, with
5% inoculum concentration expands culture 2d using proliferated culture medium, is centrifuged 15min with 3000r/min, obtains pair of iron-reducing bacterium
Number growth period cell, abandons supernatant, bacteria suspension C is made, and saves in 4 DEG C.
Wherein, the nutrient medium of iron-reducing bacterium is fresh potato juice 900mL, glucose 20g, remaining is water；Ma Ling
The preparation method of potato juice: removing 160 grams of skin fresh potato, be cut into small pieces, and deionized water 900mL is added to boil 35 minutes, filters off
Filtrate is complemented to 900mL with deionized water by potato ball；
The proliferated culture medium main component is beef extract 2.4g/L, glucose 2.3g/L, tryptone 6.0g/L, yeast
Powder 3.5g/L, pH 6.5, remaining is water.
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixed system
It is under anaerobic that 5:7:8 is mixed with volume ratio with suspension bacteria liquid B and C by reaction solution A, after being thoroughly mixed,
Continue to be aged 50min, obtain sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixed system, whole process is passed through nitrogen guarantor
Protect anaerobic environment.
(5) after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, in sterile saline
Middle immersion is placed in refrigerator and is saved at 4 DEG C.
Using the waste water of the present embodiment method processing containing sulfate and heavy metal Cr (VI), waste water is formulated as that Na is added2SO4
Concentration is 0.5g/L, K2Cr2O7Concentration is 141mg/L (wherein Cr content is 50mg/L), sponge iron/sulfate reduction of addition
Bacterium/iron-reducing bacterium mixture concentration is 1g/L, remaining is water.Reacted under room temperature (25 DEG C), the reaction time be for 24 hours, at interval of
4h sampling, Cr use Flame Atomic Absorption Spectrometry Determination concentration.As a result as shown in Figure 1.It can be seen from the figure that with reaction
Time continues, and Cr remaining concentration gradually decreases, its residual concentration only has 5.1mg/L when for 24 hours, that is, can reach 89.8% and go
Except rate.
Embodiment 3
A kind of method that sponge iron cooperates with removing sulfate and Cr (VI) waste water with microorganism, comprising the following steps:
(1) preparation of sponge iron
Mixed carbon comtent (mass ratio of simple substance carbon dust and iron cement) 1:1,1160 DEG C of reaction temperature, reaction time 20min item
Under part, is calcined by raw material of iron cement, prepare conventional sponge iron solid.It is activated with dilute hydrochloric acid, the sea that preparation concentration is 0.5g/L
Continuous ferrous solution is denoted as reaction solution A.
(2) preparation of sulfate reducing bacteria SRB
A kind of sulfate reducing bacteria-the desulfovibrio bought from China General Microbiological culture presevation administrative center is (the same as real
Apply example 1) in select 2 rings, be transferred into 30ml nutrient solution, be protected from light at 35 DEG C culture 3d, with 5% inoculum concentration using proliferation
Culture medium expands culture 2d, is centrifuged 10min with 3000r/min, obtains the logarithmic growth phase cell of desulfovibrio, abandons supernatant
Bacteria suspension B is made in liquid, saves in 4 DEG C.
Wherein, nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L, sodium lactate
3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O 0.3g/L, Na2SO45.5g/L, CaCl2·
6H2O 0.2g/L, citric acid 0.3g/L adjust pH 7.1, remaining is water.
Proliferated culture medium: KH2PO40.8g/L, NH4Cl 1.5g/L, CaCl2·2H2O 0.3g/L, Na2SO46g/L,
MgSO4·7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L, FeSO4·7H2O 3.0g/L, sodium citrate
0.5g/L adjusts pH 7.5, remaining is water.
(3) preparation of iron-reducing bacterium
It selects from China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.8048) 2 ring of iron-reduced tuftedmonas bought, is transferred into 30ml nutrient solution, and culture 3d is protected from light at 28 DEG C, with
5% inoculum concentration expands culture 2d using proliferated culture medium, is centrifuged 12min with 3000r/min, obtains pair of iron-reducing bacterium
Number growth period cell, abandons supernatant, bacteria suspension C is made, and saves in 4 DEG C.
Wherein, the nutrient medium of iron-reducing bacterium is fresh potato juice 1000mL, glucose 20g, remaining is water；Ma Ling
The preparation method of potato juice: removing 220 grams of skin fresh potato, be cut into small pieces, and deionized water 1000mL is added to boil 30 minutes, filters off
Filtrate is complemented to 1000mL with deionized water by potato ball；
The proliferated culture medium main component is beef extract 2.2g/L, glucose 2.5g/L, tryptone 6.0g/L, yeast
Powder 3.8g/L, pH 7.5, remaining is water.
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixed system
It is under anaerobic that 3:7:10 is mixed with volume ratio with suspension bacteria liquid B and C by reaction solution A, after being thoroughly mixed,
Continue to be aged 50min, obtain sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixed system, whole process is passed through nitrogen guarantor
Protect anaerobic environment.
(5) after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, in sterile saline
Middle immersion is placed in refrigerator and is saved at 4 DEG C.
Using the waste water of the present embodiment method processing containing sulfate and heavy metal Cr (VI), waste water is formulated as that Na is added2SO4
Concentration is 0.5g/L, K2Cr2O7Concentration is 141mg/L (wherein Cr content is 50mg/L), sponge iron/sulfate reduction of addition
Bacterium/iron-reducing bacterium mixture concentration is 1g/L, remaining is water.Reacted under room temperature (25 DEG C), the reaction time be for 24 hours, at interval of
4h sampling, Cr use Flame Atomic Absorption Spectrometry Determination concentration.As a result as shown in Figure 1.It can be seen from the figure that with reaction
Time continues, and Cr remaining concentration gradually decreases, its residual concentration only has 4.1mg/L when for 24 hours, that is, can reach 91.8% and go
Except rate.
Embodiment 4
A kind of method that sponge iron cooperates with removing sulfate and Cr (VI) waste water with microorganism, comprising the following steps: a kind of
The method that sponge iron cooperates with removing sulfate and Cr (VI) waste water with microorganism, comprising the following steps:
(1) preparation of sponge iron
Mixed carbon comtent (mass ratio of simple substance carbon dust and iron cement) 1:1,1160 DEG C of reaction temperature, reaction time 20min item
Under part, is calcined by raw material of iron cement, prepare conventional sponge iron solid.It is activated with dilute hydrochloric acid, the sea that preparation concentration is 0.3g/L
Continuous ferrous solution is denoted as reaction solution A.
(2) preparation of sulfate reducing bacteria SRB
A kind of sulfate reducing bacteria-the desulfovibrio bought from China General Microbiological culture presevation administrative center is (the same as real
Apply example 1) in select 2 rings, be transferred into 30ml nutrient solution, be protected from light at 35 DEG C culture 3d, with 5% inoculum concentration using proliferation
Culture medium expands culture 2d, is centrifuged 10min with 3000r/min, obtains the logarithmic growth phase cell of desulfovibrio, abandons supernatant
Bacteria suspension B is made in liquid, saves in 4 DEG C.
Wherein, nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L, sodium lactate
3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O 0.3g/L, Na2SO45.5g/L, CaCl2·
6H2O 0.2g/L, citric acid 0.3g/L adjust pH 7.0, remaining is water.
Proliferated culture medium: KH2PO40.8g/L, NH4Cl1.5g/L, CaCl2·2H2O0.3g/L, Na2SO46g/L, MgSO4·
7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L, FeSO4·7H2O 3.0g/L, sodium citrate 0.5g/L are adjusted
PH 7.1, remaining is water.
(3) preparation of iron-reducing bacterium
It selects from China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.8048) 2 ring of iron-reduced tuftedmonas (Comamonas), is transferred into 30ml nutrient solution, is protected from light culture at 28 DEG C
5d, expands culture 3d using proliferated culture medium with 5% inoculum concentration, is centrifuged 10min with 3000r/min, obtains iron reduction
The logarithmic growth phase cell of bacterium abandons supernatant, bacteria suspension C is made, and saves in 4 DEG C.
Wherein, the nutrient medium of iron-reducing bacterium is fresh potato juice 1000mL, glucose 24g, remaining is water；Ma Ling
The preparation method of potato juice: removing 160 grams of skin fresh potato, be cut into small pieces, and deionized water 1000mL is added to boil 30 minutes, filters off
Filtrate is complemented to 1000mL with deionized water by potato ball；
The proliferated culture medium main component is beef extract 2.5g/L, glucose 2.0g/L, tryptone 5.5g/L, yeast
Powder 3.5g/L, pH 6.5, remaining is water.
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixed system
It is under anaerobic that 6:7:7 is mixed with volume ratio with suspension bacteria liquid B and C by reaction solution A, after being thoroughly mixed,
Continue to be aged 50min, obtain sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixed system, whole process is passed through nitrogen guarantor
Protect anaerobic environment.
(5) after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, in sterile saline
Middle immersion is placed in refrigerator and is saved at 4 DEG C.
Using the waste water of the present embodiment method processing containing sulfate and heavy metal Cr (VI), waste water is formulated as that Na is added2SO4
Concentration is 0.5g/L, K2Cr2O7Concentration is 141mg/L (wherein Cr content is 50mg/L), sponge iron/sulfate reduction of addition
Bacterium/iron-reducing bacterium mixture concentration is 1g/L, remaining is water.Reacted under room temperature (25 DEG C), the reaction time be for 24 hours, at interval of
4h sampling, Cr use Flame Atomic Absorption Spectrometry Determination concentration.As a result as shown in Figure 1.It can be seen from the figure that with reaction
Time continues, and Cr remaining concentration gradually decreases, its residual concentration only has 3.7mg/L when for 24 hours, that is, can reach 92.6% and go
Except rate.
In the present invention, SRB Biology-iron Anaerobic Biotechnology combines in such a way that sponge iron electronation is strengthened, and makes sulphur
Hydrochlorate reducing bacteria (SRB) is in a kind of active state, and organic matter, which is digested to decompose by anaerobe, generates electronics, also for sulfate
Opportunistic pathogen provides electronics, so that sulfate reduction is sulfide by sulfate reducing bacteria.While the generation of sulfide, also and in water
Micro heavy Cr react and generate sulfide precipitation, do not remove only Cr remaining in water, and consume H2S prevents
Only it overflows from water and is got into the air, and generates threat to the life of staff.The sponge that this project uses simultaneously is iron-based
The addition at bottom increases the activity of sulfate reducing bacteria SRB, can facilitate out the maximum sulphur removal potential of SRB.
The advanced research of common SRB depollution object technology be based primarily upon electrochemistry in terms of research, such as Harbin industry
Anaerobism suspension growth reactor is studied to the removal effect of sulfate and ammonia nitrogen, within the residence time of 3d, sulphur in the sea university Zheng Huan
Acid group, ammonia nitrogen removal frank have only reached 69%, 58%, by 31 bacterial strains isolated, discovery removing sulfate radical and except deammoniation
Nitrogen is in the coefficient result of various bacteria.Under the invigoration effect of electric field, expand cathodic process, so that the effect that desulfurization is denitrogenated
Fruit is promoted.The Li Guanghe seminar of Tsinghua University studies electric field-enhanced research sulfate reducing bacteria and goes to create sulfate process, hair
Now as I≤1.50mA, with the increase of electric current, the sulfate reduction rate increases, and optimum current intensity is 1.50mA, average to go back
Former rate is 28.3~35.3mg/d.Compared to these electrochemical research, not only reduced using sponge iron SRB anaerobic reduction system
Energy consumption, and treatment effeciency, engineering practical operation be simple.
According to the report that heavy metals are handled, under conditions of initial concentration is 50mg/L, sponge iron is to Cr's (VI)
Removal rate can reach 70.0% (Bi Na, the preparation of sphere sponge iron and its removes cadmium performance study [J], HBLG08-015).First
Under conditions of beginning concentration is 100mg/L, after acting on 2h, sulfate reducing bacteria is to the removal rate of Cr (VI) up to 26.43% (Chai Li
Member, Treatment of chromium wastewater by immobilized sulfate-reducing bacteria-containing activated sludge [J], Central South University's journal 2005.12 36 (6) 965-
970) attached drawing, is compared, it can be seen that by sponge iron/sulfate reducing bacteria/iron-reducing bacterium microballoon invigoration effect, initial dense
Degree is 50mg/L, after action time is 1d, 92.8% has been respectively reached to the removal rate of Cr (VI) metal in embodiment 1-4,
89.8%, 91.8%, 92.6%, it is much higher than removal efficiency when sponge iron and sulfate reducing bacteria independent role, shows this
Invention be for the removal of the formation of microballoon and heavy metal Cr (VI) it is effectively, in heavy metal containing wastewater treatment have it is good
Application prospect.
Embodiment of the present invention are not limited by the above embodiments, other any real without departing from spirit of the invention
Made changes, modifications, substitutions, combinations, simplifications under matter and principle, should be equivalent substitute mode, are included in the present invention
Protection scope within.
Claims (10)
1. sponge iron cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, it is characterised in that the following steps are included:
(1) preparation of sponge ferrous solution
Sponge iron solid is activated with dilute hydrochloric acid, the sponge ferrous solution that preparation concentration is 0.1-0.6g/L is denoted as reaction solution A；
(2) preparation of sulfate reducing bacteria SRB
2 rings are selected from desulfovibrio (Desulfovibrio), is transferred in desulfovibrio nutrient medium, is kept away at 35-37 DEG C
3~5d of optical culture expands culture 2-3d using desulfovibrio proliferated culture medium with the inoculum concentration of 5-10wt%, centrifugal treating,
The logarithmic growth phase cell of desulfovibrio is obtained, supernatant is abandoned, bacteria suspension B is made；
(3) preparation of iron-reducing bacterium
2 rings are selected from iron-reduced tuftedmonas (Comamonas), are transferred in iron-reducing bacterium nutrient medium, in 28-30
DEG C it is protected from light 3~5d of culture, 2-3d is expanded culture using iron-reducing bacterium proliferated culture medium with the inoculum concentration of 5-10wt%, is centrifuged
Processing obtains the logarithmic growth phase cell of iron-reducing bacterium, abandons supernatant, bacteria suspension C is made；
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixture
Under anaerobic, reaction solution A, bacteria suspension B and bacteria suspension C are mixed with volume ratio for 1:1:1~1:3:4, ageing 30
~60min with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, soaks in sterile saline after reaction
Bubble；Obtain sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixture；
(5) sulfate and Cr 6+Purification of waste water
Sponge iron obtained by step (4) and sulfate reducing bacteria/iron-reducing bacterium mixture and sulfate and Cr (VI) waste water is mixed
It closes, is reacted 20 hours or more under room temperature, while purifying sulfate and Cr in waste water 6+。
2. sponge iron according to claim 1 cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, feature
It is, the sponge iron solid is prepared via a method which: using iron cement and simple substance carbon dust as raw material, controls simple substance carbon dust and iron cement
Mass ratio be 1:1-1:4, temperature be 1100-1200 DEG C under the conditions of calcining 15-20min be made.
3. sponge iron according to claim 1 cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, feature
It is, in step (2), the centrifugal treating is that 3000 r/min are centrifuged 10~20 min；Bacteria suspension B is saved in 4 DEG C；It is described de-
2 ring of sulphur vibrios (Desulfovibrio) is transferred in 30-40ml desulfovibrio nutrient medium.
4. sponge iron according to claim 1 cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, feature
It is, the formula composition of the desulfovibrio nutrient medium are as follows: KH2PO4 0.6 g/L, NH4Cl 1.2g/L, MgSO4·
7H20.2 g of O/L, sodium lactate 3.22g/L, yeast leach 1.2 g of cream/L, CaSO4 1. 6 g/L, FeSO4·7H2O 0.
3 g/L, Na2SO4 5. 5 g/L, CaCl2·6H20.2 g of O/L, 0. 3 g of citric acid/L adjust pH 7.0-7.5,
Yu Weishui.
5. sponge iron according to claim 1 cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, feature
It is, the formula composition of the desulfovibrio proliferated culture medium are as follows: KH2PO4 0.8 g/L, NH4Cl 1.5g/L, CaCl2·
2H20.3 g of O/L, Na2SO4 6g/L, MgSO4·7H2O 0. 6g/L, sodium lactate 4.8g/L, yeast leaching cream 3.5g/L,
FeSO4·7H23.0 g of O/L, sodium citrate 0.5g/L adjust pH 7.0-7.5, remaining is water.
6. sponge iron according to claim 1 cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, feature
It is, the iron-reducing bacterium nutrient medium: if taking fresh potato juice dry volume, 20~24g/L of glucose is added, remaining is
Water；The preparation method of potato juice: 160~220 grams of skin fresh potato are removed, is cut into small pieces, deionized water 800~1000 is added
ML boils 30-35 minutes, filters off potato ball, filtrate is complemented to 1000 mL with deionized water.
7. sponge iron according to claim 1 cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, feature
It is, the iron-reducing bacterium proliferated culture medium main component is 2.0~2.5 g/L of beef extract, 1.5~2.5 g/L of glucose, pancreas
5.5~6.0 g/L of peptone, yeast powder 3.0~4.5 g/L, pH 6.5~7.5, remaining is water.
8. sponge iron according to claim 1 cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, feature
It is, in step (3), the centrifugal treating is that 3000 r/min are centrifuged 10~15 min, and bacteria suspension C is saved in 4 DEG C；Iron reduction
2 ring of comamonas (Comamonas) is transferred in 30-40ml iron-reducing bacterium nutrient medium.
9. sponge iron according to claim 1 cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, feature
It is, the sponge iron impregnated in sterile saline and sulfate reducing bacteria/iron-reducing bacterium mixture place refrigerator
In save at 4 DEG C.
10. sponge iron according to claim 1 cooperates with removing sulfate and Cr with microorganism 6+The method of waste water, feature
It is, sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixture 70-150mg/L is controlled in step 5)；The sulfate and
Cr 6+Waste water contains the Na of 0.5g/L2SO4, 141mg/L K2Cr2O7, wherein Cr content is 50mg/L, remaining is water.
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