CN101270368B - Method for preparing hydrogen with biology and with utilization of organic waste water step - Google Patents
Method for preparing hydrogen with biology and with utilization of organic waste water step Download PDFInfo
- Publication number
- CN101270368B CN101270368B CN2008100645364A CN200810064536A CN101270368B CN 101270368 B CN101270368 B CN 101270368B CN 2008100645364 A CN2008100645364 A CN 2008100645364A CN 200810064536 A CN200810064536 A CN 200810064536A CN 101270368 B CN101270368 B CN 101270368B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- chloride
- chamber
- organic wastewater
- anode
- 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.)
- Active
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 88
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 88
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 49
- 239000010815 organic waste Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- 239000002351 wastewater Substances 0.000 claims abstract description 18
- 239000010802 sludge Substances 0.000 claims abstract description 17
- 238000005273 aeration Methods 0.000 claims abstract description 15
- 235000015097 nutrients Nutrition 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000008363 phosphate buffer Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229940088594 vitamin Drugs 0.000 claims description 11
- 235000013343 vitamin Nutrition 0.000 claims description 11
- 239000011782 vitamin Substances 0.000 claims description 11
- 229930003231 vitamin Natural products 0.000 claims description 11
- 150000003722 vitamin derivatives Chemical class 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 230000000813 microbial effect Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000003014 ion exchange membrane Substances 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 5
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 3
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 3
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000003011 anion exchange membrane Substances 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- FAPWYRCQGJNNSJ-UBKPKTQASA-L calcium D-pantothenic acid Chemical compound [Ca+2].OCC(C)(C)[C@@H](O)C(=O)NCCC([O-])=O.OCC(C)(C)[C@@H](O)C(=O)NCCC([O-])=O FAPWYRCQGJNNSJ-UBKPKTQASA-L 0.000 claims description 3
- 229960002079 calcium pantothenate Drugs 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 229960000304 folic acid Drugs 0.000 claims description 3
- 235000019152 folic acid Nutrition 0.000 claims description 3
- 239000011724 folic acid Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 235000019136 lipoic acid Nutrition 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229960003512 nicotinic acid Drugs 0.000 claims description 3
- 235000001968 nicotinic acid Nutrition 0.000 claims description 3
- 239000011664 nicotinic acid Substances 0.000 claims description 3
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011655 sodium selenate Substances 0.000 claims description 3
- 235000018716 sodium selenate Nutrition 0.000 claims description 3
- 229960001881 sodium selenate Drugs 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 229960002663 thioctic acid Drugs 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 241000589774 Pseudomonas sp. Species 0.000 claims description 2
- 241000490596 Shewanella sp. Species 0.000 claims description 2
- 239000011573 trace mineral Substances 0.000 claims 4
- 235000013619 trace mineral Nutrition 0.000 claims 4
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 claims 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 2
- 239000001103 potassium chloride Substances 0.000 claims 2
- 235000011164 potassium chloride Nutrition 0.000 claims 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 claims 2
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 claims 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- 229930003451 Vitamin B1 Natural products 0.000 claims 1
- 229930003779 Vitamin B12 Natural products 0.000 claims 1
- 229960004050 aminobenzoic acid Drugs 0.000 claims 1
- 229960002685 biotin Drugs 0.000 claims 1
- 235000020958 biotin Nutrition 0.000 claims 1
- 239000011616 biotin Substances 0.000 claims 1
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims 1
- KDQPSPMLNJTZAL-UHFFFAOYSA-L disodium hydrogenphosphate dihydrate Chemical compound O.O.[Na+].[Na+].OP([O-])([O-])=O KDQPSPMLNJTZAL-UHFFFAOYSA-L 0.000 claims 1
- 229960002089 ferrous chloride Drugs 0.000 claims 1
- -1 hydrogen ions Chemical class 0.000 claims 1
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 claims 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims 1
- 235000019341 magnesium sulphate Nutrition 0.000 claims 1
- 239000011565 manganese chloride Substances 0.000 claims 1
- 235000002867 manganese chloride Nutrition 0.000 claims 1
- 229940099607 manganese chloride Drugs 0.000 claims 1
- 229940099596 manganese sulfate Drugs 0.000 claims 1
- 239000011702 manganese sulphate Substances 0.000 claims 1
- 235000007079 manganese sulphate Nutrition 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims 1
- 235000019799 monosodium phosphate Nutrition 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000008055 phosphate buffer solution Substances 0.000 claims 1
- CKRORYDHXIRZCH-UHFFFAOYSA-N phosphoric acid;dihydrate Chemical compound O.O.OP(O)(O)=O CKRORYDHXIRZCH-UHFFFAOYSA-N 0.000 claims 1
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 239000011684 sodium molybdate Substances 0.000 claims 1
- 235000015393 sodium molybdate Nutrition 0.000 claims 1
- 229960003495 thiamine Drugs 0.000 claims 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 claims 1
- 235000010374 vitamin B1 Nutrition 0.000 claims 1
- 239000011691 vitamin B1 Substances 0.000 claims 1
- 235000019163 vitamin B12 Nutrition 0.000 claims 1
- 239000011715 vitamin B12 Substances 0.000 claims 1
- 235000019158 vitamin B6 Nutrition 0.000 claims 1
- 239000011726 vitamin B6 Substances 0.000 claims 1
- 229940011671 vitamin b6 Drugs 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 16
- 238000000855 fermentation Methods 0.000 abstract description 13
- 230000004151 fermentation Effects 0.000 abstract description 13
- 238000013459 approach Methods 0.000 abstract 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 11
- 230000002906 microbiologic effect Effects 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 8
- 244000005700 microbiome Species 0.000 description 8
- 230000000050 nutritive effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 7
- 239000008103 glucose Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000872 buffer Substances 0.000 description 6
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000002953 phosphate buffered saline Substances 0.000 description 6
- 230000004060 metabolic process Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PLZNPHDJGFDNRM-UHFFFAOYSA-M O.[Na+].[O-][PH2]=O Chemical compound O.[Na+].[O-][PH2]=O PLZNPHDJGFDNRM-UHFFFAOYSA-M 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- AGBQKNBQESQNJD-SSDOTTSWSA-N (R)-lipoic acid Chemical compound OC(=O)CCCC[C@@H]1CCSS1 AGBQKNBQESQNJD-SSDOTTSWSA-N 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- 229930003756 Vitamin B7 Natural products 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- AGBQKNBQESQNJD-UHFFFAOYSA-N alpha-Lipoic acid Natural products OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 description 2
- 229940103272 aluminum potassium sulfate Drugs 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007269 microbial metabolism Effects 0.000 description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229960002477 riboflavin Drugs 0.000 description 2
- 235000019192 riboflavin Nutrition 0.000 description 2
- 239000002151 riboflavin Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229960004249 sodium acetate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- 235000011912 vitamin B7 Nutrition 0.000 description 2
- 239000011735 vitamin B7 Substances 0.000 description 2
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 1
- 241000588807 Bordetella Species 0.000 description 1
- 241001350695 Ethanoligenens Species 0.000 description 1
- 206010029379 Neutrophilia Diseases 0.000 description 1
- 241000190932 Rhodopseudomonas Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 244000005706 microflora Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 201000007094 prostatitis Diseases 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method of hydrogen production of biological cascade utilization on organic wastewater and relates to a method of producing hydrogen. The invention solves the existing problem of low conversion on biological hydrogen production with organic wastewater fermentation by using anaerobic activated sludge. The hydrogen production method of the invention is carried out as follows: firstly an anode chamber is in the anaerobic condition during startup procedure, anaerobic activated sludge is put into the anode chamber, the nutrient solution with pH value of 6.8 to 7.0 is introduced into the anode chamber, phosphate buffer is added into a cathode chamber, aeration is carried out in the cathode chamber in the previous 28 to 35 days of the startup procedure, startup is successful till the output voltage is continuously and steadily over 400 mV; secondly the organic wastewater is filled into the anode chamber from an inlet of the anode chamber and the organic wastewater is processed in the anode chamber, consequently hydrogen is obtained in the cathode chamber. The coulombic efficiency of the organic substrate conversion of the method reaches as high as over 80 percent, the electron transfer efficiency of transferring the cathode electron into hydrogen approaches to 100 percent, the purity of the hydrogen obtained in the cathode chamber in the entire process reaches 99.5 percent, the energy conversion efficiency of the entire process reaches over 80 percent, and the hydrogen yield calculated based on the input voltage is 288 percent.
Description
Technical field
The present invention relates to a kind of method of producing hydrogen.
Background technology
At present, the energy more than 80% and organic raw material come from fossil energy.Along with the exhausted of fossil energy and use the serious day by day of the environmental problem brought, the mankind will face serious energy dilemma and environmental pollution.Hydrogen is a kind of ideal new forms of energy, has aboundresources, combustion heat value height, cleanliness without any pollution, advantage of wide range of application.Thereby hydrogen extremely concern of countries in the world in future source of energy.Utilize biomass (organic waste water, stalk class agroforestry waste, organic waste etc.) to carry out microbial fermentation hydrogen manufacturing and possess multiple superiority such as pollution treatment, environmental protection and production capacity, DEVELOPMENT PROSPECT is wide.The microorganism hydrogen producing technology also is subjected to people's attention.At present, the research that utilizes anaerobism to carry out microorganism hydrogen manufacturing can be divided into three types substantially: the one, and adopt pure strain and technique for fixing to carry out microorganism hydrogen manufacturing, but strict because of its fermentation condition, also be in the laboratory study stage at present.The 2nd, utilize anaerobic activated sludge to carry out organic waste water fermentation method biological hydrogen production; The 3rd, the material decomposition of utilizing continuous on-fixed highly effective hydrogen yield bacterium to make to contain carbohydrate, protein etc. is produced hydrogen, and the hydrogen conversion of back two kinds of methods low (generally about 30%) has limited the practical application and the popularization of hydrogen.
Summary of the invention
The objective of the invention is to carry out the low problem of transformation efficiency of organic waste water fermentation method biological hydrogen production, and provide a kind of organic waste water step to utilize biological method of producing hydrogen in order to solve existing anaerobic activated sludge.
The biological hydrogen producing of organic waste water step utilization of the present invention is to carry out in having the double-chamber microbiological fuel cell of ion-exchange membrane, realize by following step: one, start reactor: the anolyte compartment is in anaerobic state in start-up course, anaerobic activated sludge is put into the anolyte compartment, the anaerobic activated sludge dosage accounts for anolyte compartment's volume 50%～60%, be that 6.8～7.0 nutritive medium feeds the anolyte compartment then with the pH value, the volume ratio of nutritive medium and anaerobic activated sludge is 1: 1, in cathode compartment, add the phosphate buffered saline buffer that accounts for cathode compartment volume 90% simultaneously, preceding 28～35 days air aerations in cathode compartment that start, aeration rate is 0.3～0.6m
3/ min when cell voltage is lower than 50mV, changes or additional nutrient solution fully, treats output voltage continually and steadily more than 400mV, and double-chamber microbiological fuel cell starts successfully; Two, the water-in of organic waste water by the anolyte compartment injected in the anolyte compartment, organism in the anode microbial film function yeast metabolism organic waste water in the anolyte compartment, hydrogen ion combines with electronics and obtains hydrogen in the cathode compartment, when cell voltage is lower than 50mV, change or be supplemented with organic waste water fully, the condition of hydrogen manufacturing operation: 25～30 ℃ of temperature of reaction, pH=6.8～7.1, boosting voltage is 250～800mV.
Anaerobic activated sludge in the step 1 is from the aeration tank of municipal sewage treatment or concentration basin obtains.
The nutritive medium of step 1 is formulated by 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 2g sodium acetate trihydrate, 1L deionized water and 2ml liquid microelement; Wherein every liter of liquid microelement is made up of the water of 600mg calcium chloride, 400mg magnesium chloride, 80mg iron protochloride, 400mg cobalt chloride, cupric chloride, 100mg Manganous chloride tetrahydrate, 10mg zinc chloride, 10mg sodium selenate, 15mg sodium wolframate, 20mg nickelous chloride, 100mg disodium ethylene diamine tetraacetate, 10mg ammonium molybdate and surplus.
The another kind of prescription of nutritive medium is as follows in the step 1: every liter of nutritive medium is made up of 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 1L deionized water, 10mL Wolfe mcg vitamin mixed solution, 10mL Wolfe trace quantity mineral substance element mixed solution and 10mmol sodium-acetate (electron donor); Wherein Wolfe mcg vitamin liquid mixed solution is by 2.0mg vitamin H, 2.0mg folic acid, 10.0mg vitamin B6,5.0mg VITMAIN B1,5.0mg riboflavin; 5.0mg niacin, 5.0mg calcium pantothenate, 0.1mg vitamin B12,5.0mg benzaminic acid, 5.0mg Thioctic Acid and 1.0L distilled water are formulated; Wolfe trace quantity mineral mixed solution is formulated by 1.5g nitrilotriacetic acid(NTA), 3.0g sal epsom, 0.5g manganous sulfate, 1.0g sodium-chlor, 0.1g ferrous sulfate, 0.1g cobalt chloride, 0.1g calcium chloride, 0.1g zinc sulfate, 0.01g copper sulfate, 0.01g aluminum potassium sulfate, 0.01g boric acid, 0.01g Sodium orthomolybdate and 1.0L distilled water.
Phosphate buffered saline buffer is made up of 5.618g SODIUM PHOSPHATE, MONOBASIC, 6.155g Sodium phosphate dibasic and 1000mL water in the step 1; The perhaps Tris-HCl buffered soln of pH=7.0.
The anode material of described double-chamber microbiological battery is carbon cloth or Graphite Electrodes; Its negative electrode is made by non-immersion carbon paper, and cathode surface is loaded with 0.35mg/cm
2Pt; Ion-exchange membrane is Nafion 117 films or anion-exchange membrane AMI-7001.
The principle of method: functional flora is electron donor with the organism in the start-up course, anode electrode is arrived in the electron transport that metabolism produces, arrive negative electrode via external circuit, combine consumption with oxygen and proton and form current circuit, functional flora shows in anode electrode with this understanding and forms function yeast microbial film (as shown in Figure 1) gradually, produce the organism in the functional microorganism metabolism organic waste water on the anode in the hydrogen process, hydrogen ion combines with electronics and obtains hydrogen in the cathode compartment.
The present invention transforms the coulombic efficiency of organic substrates (small molecules such as acetate) up to more than 80%, cathode electronics is converted into the electronics transformation efficiency of hydrogen near 100%, whole technology cathode compartment acquisition purity is 99.5% hydrogen, the integrated artistic energy transformation ratio is up to more than 80%, is 288% based on the hydrogen earning rate of input voltage.Processing product hydrogen experiment acquisition reactor unit volume hydrogen production potential result by different substrates is as follows: acetate is that substrate product hydrogen top speed is 1.5m
3d
-1m
-3It is 0.11m that cellulosic substrate is produced the hydrogen top speed
3d
-1m
-3It is 1.23m that glucose sugar substrate produces the hydrogen top speed
3d
-1m
-3It is 1.04m that the lactic acid substrate produces the hydrogen top speed
3d
-1m
-3It is 0.14m that the valeric acid substrate produces the hydrogen top speed
3d
-1m
-3
The present invention all obtains considerable progress in macromolecular substance such as small organic molecule utilization and glucose, Mierocrystalline cellulose are handled.The present invention is combined with the present microorganism ferment for hydrogen production, utilize the organic waste water of the discharge of ferment for hydrogen production technology, it is carried out zymophyte collect in the double-chamber microbiological battery that separates after re-adjustment pH value back feeds startup, realize the utilization of organic waste water organic waste water step; Can effectively solve the problem that fermentation end products composition can't recovered energy, further obtain hydrogen in the auxiliary lower step utilization of electrochemistry, thereby provide new way for breaking through the hydrogen transformation efficiency that improves unit matrix.This method makes full use of the end products of many biological fermentations or complete processing more, can handle organic waste water completely and reclaim biomass energy with the form of hydrogen.Combining with fermentation process for making hydrogen of the present invention with unit matrix hydrogen transformation efficiency from 3molH
2/ mol glucose is brought up to 7～11molH
2/ mol glucose.
Description of drawings
Fig. 1 is the schematic diagram that the present invention produces hydrogen, 1 expression anode among Fig. 1, and 2 expression external circuit, 3 expression negative electrodes, 4 expression cathode compartments, 5 expression ion-exchange membranees, 6 expression anolyte compartments, 7 express water pipe, 8 expression water inlet pipes.Fig. 2 is microbiological fuel cell start-up course voltage and a potential ph diagram ph in the embodiment 12, among Fig. 2 ●-expression anolyte compartment redox potential, zero expression cathode compartment redox potential ,-▲-expression load voltage curve (being that the electrogenesis domestication produces voltage, load 1000 Ω).Fig. 3 is the auxiliary hydrogen production by biological technology running current periodogram (boosting voltage 0.6V) of bioelectrochemistry in the embodiment 12, among Fig. 3-▲-the indication circuit current curve ,-◇-expression boosting voltage curve.Fig. 4 is the auxiliary microorganism electrode potential ph diagram ph of bioelectrochemistry in the embodiment 12, among Fig. 4-●-expression anodic oxidation reduction potential curve ,-zero-expression cathode oxidation reduction potential curve.Fig. 5 is the auxiliary hydrogen production by biological figure (boosting voltage 0.6V) of bioelectrochemistry in the embodiment 12 ,-zero-expression gas volume among Fig. 5 ,-▲-metabolism of expression acetate.Fig. 6 is the scanning electron mirror figure of anode microbial film function yeast of the present invention.
Embodiment
Embodiment one: the biological hydrogen producing of organic waste water step utilization is to carry out in having the double-chamber microbiological battery of ion-exchange membrane, realize by following step: one, start reactor: the anolyte compartment is in anaerobic state in start-up course, anaerobic activated sludge is put into the anolyte compartment, the anaerobic activated sludge dosage accounts for anolyte compartment's volume 50%～60%, be that 6.8～7.0 nutrient solution feeds the anolyte compartment then with the pH value, the volume ratio of nutrient solution and anaerobic activated sludge is 1: 1, in cathode compartment, add the phosphate buffered saline buffer that accounts for cathode compartment volume 90% simultaneously, preceding 28～35 days air aerations in cathode compartment that start, aeration rate is 0.3～0.6m
3/ min when cell voltage is lower than 50mV, changes or additional nutrient solution fully, treats output voltage continually and steadily more than 400mV, and double-chamber microbiological fuel cell starts successfully (forming more stable functional biological film on anode, startup needs 1～2 month); Two, the water-in of organic waste water by the anolyte compartment injected in the anolyte compartment, organism in the anode microbial film function yeast metabolism organic waste water in the anolyte compartment, hydrogen ion combines with electronics and obtains hydrogen in the cathode compartment, when cell voltage is lower than 50mV, change or be supplemented with organic waste water fully, the condition of technological operation: 25～30 ℃ of temperature of reaction, pH=6.8～7.1, boosting voltage is 250～800mV.
The effect of phosphate buffered saline buffer is to make its pH to remaining on 7.0 in order to keep the cathode compartment environment in the step 1, keeps the proton concentration in the solution simultaneously, and the anaerobic activated sludge in the step 1 is from the aeration tank of municipal sewage treatment or concentration basin obtains.What present embodiment organic waste water adopted is city domestic sewage, especially is rich in the processing waste water of organic molecule composition, and water outlet waste water etc. for example ferments.Be main dominant microflora (see figure 6) with Shiva Bordetella (Shewanella sp.) and Rhodopseudomonas (Pseudomonas sp.) in the anode microbial film function yeast that forms of anode surface after testing.
Present embodiment transforms the coulombic efficiency of organic substrates up to more than 80%, cathode electronics is converted into the electronics transformation efficiency of hydrogen near 100%, whole technology cathode compartment acquisition purity is 99.5% hydrogen, the integrated artistic energy transformation ratio is up to more than 80%, is 288% based on the hydrogen earning rate of input voltage.Processing product hydrogen experiment acquisition reactor unit volume hydrogen production potential result by different substrates is as follows: acetate is that substrate product hydrogen top speed is 1.5m
3d
-1m
-3It is 0.11m that cellulosic substrate is produced the hydrogen top speed
3d
-1m
-3It is 1.23m that glucose sugar substrate produces the hydrogen top speed
3d
-1m
-3It is 1.04m that the lactic acid substrate produces the hydrogen top speed
3d
-1m
-3It is 0.14m that the valeric acid substrate produces the hydrogen top speed
3d
-1m
-3
Embodiment two: what present embodiment and embodiment one were different is: the nutritive medium of step 1 is formulated by 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 2g sodium acetate trihydrate, 1L deionized water and 2ml liquid microelement.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment two were different is: every liter of liquid microelement is made up of the water of 600mg calcium chloride, 400mg magnesium chloride, 80mg iron protochloride, 400mg cobalt chloride, cupric chloride, 100mg Manganous chloride tetrahydrate, 10mg zinc chloride, 10mg sodium selenate, 15mg sodium wolframate, 20mg nickelous chloride, 100mg disodium ethylene diamine tetraacetate (EDTA disodium), 10mg ammonium molybdate and surplus.Other is identical with embodiment two.
Embodiment four: what present embodiment and embodiment one were different is: every liter of nutritive medium is made up of 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 1L deionized water, 10mL Wolfe mcg vitamin mixed solution, 10mLWolfe trace quantity mineral substance element mixed solution and 10mmol sodium-acetate in the step 1.Other is identical with embodiment one.
The Wolfe mcg vitamin liquid mixed solution and the Wolfe trace quantity mineral mixed solution of present embodiment need keep in Dark Place.
Wolfe mcg vitamin liquid mixed solution is by 2.0mg vitamin H, 2.0mg folic acid, 10.0mg vitamin B6,5.0mg VITMAIN B1,5.0mg riboflavin; 5.0mg niacin, 5.0mg calcium pantothenate, 0.1mg vitamin B12,5.0mg benzaminic acid, 5.0mg Thioctic Acid and 1.0L distilled water are formulated.
Wolfe trace quantity mineral mixed solution is formulated by 1.5g nitrilotriacetic acid(NTA), 3.0g sal epsom, 0.5g manganous sulfate, 1.0g sodium-chlor, 0.1g ferrous sulfate, 0.1g cobalt chloride, 0.1g calcium chloride, 0.1g zinc sulfate, 0.01g copper sulfate, 0.01g aluminum potassium sulfate, 0.01g boric acid, 0.01g Sodium orthomolybdate and 1.0L distilled water; Wolfe trace quantity mineral mixed solution compound method is as follows: earlier nitrilotriacetic acid(NTA) is added in the 500ml distilled water, regulate pH to 7.5 with dissolving with NaOH then, then water is added to 1L, again other composition is added mixing successively and get final product.
Embodiment five: what present embodiment and embodiment one were different is: phosphate buffered saline buffer is made up of 5.618g SODIUM PHOSPHATE, MONOBASIC, 6.155g Sodium phosphate dibasic and 1000mL water in the step 1.Other is identical with embodiment one.
Embodiment six: what this enforcement and embodiment one were different is that phosphate buffered saline buffer is the Tris-HCl buffered soln of pH=7.0.Other is identical with embodiment one.
Embodiment seven: what present embodiment and embodiment one were different is: the anode material of double-chamber microbiological battery is carbon cloth or Graphite Electrodes.Other is identical with embodiment one.
Embodiment eight: what present embodiment and embodiment one were different is: the negative electrode of double-chamber microbiological battery is made by non-immersion carbon paper, and cathode surface is loaded with 0.35mg/cm
2Pt.Other is identical with embodiment one.
Embodiment nine: what present embodiment and embodiment one were different is: ion-exchange membrane is Nafion 117 films or anion-exchange membrane AMI-7001.Other is identical with embodiment one.
Present embodiment intermediate ion exchange membrane is the commercial goods.
Embodiment ten: what present embodiment and embodiment one were different is: aeration rate is 0.35～0.5m in the step 1
3/ min.
Embodiment 11: what present embodiment and embodiment one were different is: aeration rate is 0.4m in the step 1
3/ min.
Embodiment 12: present embodiment combines embodiment one with present microorganism ferment for hydrogen production technology, the discharge of ferment for hydrogen production technology organic useless carried out zymophyte collects in the double-chamber microbiological battery after re-adjustment pH value back feeds startup, boosting voltage 0.6V in the step 3 wherein, function yeast is to be obligate anaerobic flora of representative etc. with bacterial strain B49 (Ethanologenbacterium hit B49).B
49Be middle temperature neutrophilia fermenting bacteria, its fermented type is an ethanol-type, can be at 28～43 ℃, grow under pH3.3～8.5 conditions; Optimum growth temperature is 37 ℃, and optimum growh pH value is about 4.8; Dai Shiwei 7.2h.B
49Q
H2Be 25.0mmolH
2/ gdrycellh, Y
H2Be 1813.8ml/L-culture, hydrogen production potential occupy the world level prostatitis.Its fermentation end products composition such as subordinate list 1.
Present embodiment is to serve as inoculation bacterium source with Harbin urban sewage disposal plant aeration tank and concentration basin active sludge.
Table 1
Can find after deliberation: terminal small molecules organic composition acetate of ethanol-type fermentation and proportion of ethanol are up to (seeing Table 1) more than 90%.But these materials still can't utilize and handle as waste water, have not only wasted the energy but also have not met the aim of current cleaner production.Therefore, the auxiliary biological thorough utilization that the coupling of hydrogen novel method then can realize small organic molecules such as acetate, ethanol of producing of electrochemistry further obtains hydrogen simultaneously.Ethanol-type fermentation two other fermented types of one of carbon tip product constituent ratio have more advantage and potentiality.The combining with fermentation process for making hydrogen with unit matrix hydrogen transformation efficiency from 3molH
2/ mol glucose is brought up to 7～11molH
2/ mol glucose (as Fig. 4, shown in Figure 5).
Present embodiment in double-chamber microbiological start battery process, in the anolyte compartment redox potential basicly stable-500mV near; The redox potential of environment under the air aeration state in the cathode compartment can reach 200mV.Along with the advantage enrichment of function yeast, the voltage that can obtain progressively to raise at 1000 Ω load two ends output tames that output voltage can reach 450mV after one month, and output rating is 32mW/m
2When the acetate in the waste water is depleted to a certain degree, output voltage can quickly fall near the 50mV, mean this moment in the waste water organism base conditioning finish, replenish more than the new horizontal 400mV that is rich in before outward current can go back up to rapidly behind the organic waste water.(referring to Fig. 2)
Along with the metabolism of acetate in the water inlet, circuital current demonstrates periodic variation as seen from Figure 3, and bigger electronics circulation is promptly arranged in the circuit when the microbial metabolism organic substrates, and the generation of hydrogen can continue to take place; The electronics that function yeast produces after nutriment is depleted to certain level reduces rapidly, and circuital current decreases, and hydrogen produces speed to be reduced, and output descends; After replenishing new nutriment, microbial metabolism recovers rapidly, and the electron transport amount increases, and circuital current returns to higher level.
Present method will further be expanded fermentative hydrogen production technology, not only thoroughly handle organic waste water, also improve the conversion capability of hydrogen simultaneously, reduce the cost of fermentation method bio-hydrogen production technology, further improve the bio-hydrogen production technology industrialization technical support is provided.As can see from Figure 2, the electropotential of anode room environmental is progressively stable in start-up course, and the anolyte compartment is stable at-500mV, is stable at 200mV under the cathode compartment aeration condition, output voltage progressively improve and the peak value 300mV that tends towards stability near.Because nutriment consumption demonstrates the reduction of output voltage, add or change after the acetate nutritive medium output voltage returning to peak level rapidly and be increased near the 500mV in the time of the 28th day.This expression system starts successfully, as long as the sufficient technology of nutriment can continuous service.Fig. 3 has added the product hydroformylation stage behind the boosting voltage.Can see first day and add the stable impressed voltage of 0.58V at the electrode two ends, system current peak occurred about 3 days, along with the consumption system of nutriment presents periodic running status, and reflect that from levels of current the state of system is stable gradually, produce the hydrogen system structure and finish, can collect hydrogen at negative electrode.Fig. 4 is Fig. 3 electropotential monitoring curve of the same period.Can see that the electropotential behind the product stabilized hydrogen is very steady, cathode compartment is-600mV that the anolyte compartment is-450mV.Product hydrogen effect after system is stable as shown in Figure 5.Can see that acetate consumed in the cycle of 220mg, cathode compartment is collected 40ml gas, and by the gas chromatographic analysis gas purity, the hydrogen yield that can calculate this preliminary operation acquisition is 0.5mol hydrogen/mol acetate.When system is stablized by the functional microorganism that adheres on the sem observation anode carbon cloth electrode as shown in Figure 6.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100645364A CN101270368B (en) | 2008-05-19 | 2008-05-19 | Method for preparing hydrogen with biology and with utilization of organic waste water step |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100645364A CN101270368B (en) | 2008-05-19 | 2008-05-19 | Method for preparing hydrogen with biology and with utilization of organic waste water step |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101270368A CN101270368A (en) | 2008-09-24 |
| CN101270368B true CN101270368B (en) | 2010-12-29 |
Family
ID=40004595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100645364A Active CN101270368B (en) | 2008-05-19 | 2008-05-19 | Method for preparing hydrogen with biology and with utilization of organic waste water step |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101270368B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532286A (en) * | 2014-12-22 | 2015-04-22 | 中山大学 | Bioelectrochemical method for recovering gluconic acid in gluconate waste water |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101853955B (en) * | 2009-11-24 | 2012-08-22 | 哈尔滨工业大学 | Two-chambered alga microbial fuel cell and treatment wastewater method of low energy consumption thereof |
| CN101924228B (en) * | 2010-08-25 | 2012-11-21 | 天津理工大学 | Microbial fuel cell and method thereof for treating aniline wastewater |
| CN102034998B (en) * | 2010-11-22 | 2012-12-19 | 四川大学 | Enhancing method of oxygen mass transfer efficiency of microbial fuel cell cathode and corresponding cell |
| CN102642926B (en) * | 2012-04-28 | 2013-07-03 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Sewage treatment system and sewage treatment method of anaerobic fluidized bed-micro aerobic membrane bioreactor |
| CN103864201A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院生态环境研究中心 | Method for microbial electrolytic preparation of hydrogen by use of source separated urine |
| CN103146568B (en) * | 2013-03-19 | 2014-07-02 | 哈尔滨工业大学 | Dark-light fermentation integrated biohydrogen production device |
| US9340436B2 (en) * | 2013-04-16 | 2016-05-17 | Palo Alto Research Center Incorporated | Sea water desalination system |
| CN103319002B (en) * | 2013-06-27 | 2015-04-15 | 中国科学院过程工程研究所 | Method for biological treatment of sulfate wastewater employing synchronous electric catalysis of anode and cathode |
| CN104190443B (en) * | 2014-09-04 | 2016-11-02 | 上海交通大学 | A kind of preparation method of electrolyzing water to prepare hydrogen catalyst material |
| JP6288473B2 (en) * | 2015-10-20 | 2018-03-07 | 三菱重工環境・化学エンジニアリング株式会社 | Hydrogen generator |
| CN106754589B (en) * | 2015-11-20 | 2020-06-12 | 天津大学 | Mixed flora and application thereof, and microbial power generation system and microbial fuel cell containing mixed flora |
| CN106754457B (en) * | 2015-11-20 | 2020-06-12 | 天津大学 | Mixed flora and use thereof, microbial power generation system and microbial fuel cell containing the mixed flora |
| CN106754456B (en) * | 2015-11-20 | 2020-09-04 | 天津大学 | Microbial power generation system and microbial fuel cell containing mixed flora |
| CN105671584A (en) * | 2016-01-19 | 2016-06-15 | 辽宁大学 | Method for optimizing microbial electrolysis hydrogen production effect of sludge fermentation broth |
| CN105845959A (en) * | 2016-05-06 | 2016-08-10 | 深圳市宇驰检测技术有限公司 | Microbial fuel cell for sewage water degradation |
| CN108017241B (en) * | 2016-10-28 | 2021-02-09 | 中国石油化工股份有限公司 | Method for reducing and synchronously producing hydrogen by municipal sludge and municipal sludge treatment device |
| CN106430568B (en) * | 2016-11-10 | 2020-02-14 | 福建农林大学 | Electrochemical enrichment culture method of anaerobic ammonia oxidation biomembrane |
| CN106941179A (en) * | 2017-03-20 | 2017-07-11 | 哈尔滨工业大学 | A kind of preparation of graphene Polyaniline-modified carbon cloth electrode material and the method for accelerating biological anode domestication |
| CN106882996A (en) * | 2017-03-29 | 2017-06-23 | 上海净豚环保科技有限公司 | It is applied to micronutrient liquid of micro-organism treatment process and preparation method thereof |
| CN110482681A (en) * | 2019-08-23 | 2019-11-22 | 昆明理工大学 | A method of sour water containing heavy metal handles coproduction new energy |
| CN112062265A (en) * | 2020-09-08 | 2020-12-11 | 广西大学 | A method for simultaneous photocatalysis and microbial degradation of 2,4,6-trichlorophenol in adsorbable organic halides |
| CN112296080A (en) * | 2020-09-28 | 2021-02-02 | 东南大学 | Microbial fuel cell system for removing and recovering heavy metals in soil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506465A (en) * | 2002-12-11 | 2004-06-23 | 中国科学院化学研究所 | Method for Biological Hydrogen Production Using Industrial Organic Wastewater |
| CN101007682A (en) * | 2007-01-19 | 2007-08-01 | 哈尔滨工业大学 | Hydrogen making apparatus using high concentrated organic wastewater and its hydrogen making method |
| CN101041831A (en) * | 2007-02-25 | 2007-09-26 | 汕头大学 | Activated sludge hydrogen production and application for power generation |
-
2008
- 2008-05-19 CN CN2008100645364A patent/CN101270368B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506465A (en) * | 2002-12-11 | 2004-06-23 | 中国科学院化学研究所 | Method for Biological Hydrogen Production Using Industrial Organic Wastewater |
| CN101007682A (en) * | 2007-01-19 | 2007-08-01 | 哈尔滨工业大学 | Hydrogen making apparatus using high concentrated organic wastewater and its hydrogen making method |
| CN101041831A (en) * | 2007-02-25 | 2007-09-26 | 汕头大学 | Activated sludge hydrogen production and application for power generation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532286A (en) * | 2014-12-22 | 2015-04-22 | 中山大学 | Bioelectrochemical method for recovering gluconic acid in gluconate waste water |
| CN104532286B (en) * | 2014-12-22 | 2017-12-19 | 中山大学 | A kind of bio-electrochemical process for reclaiming gluconic acid in gluconate waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101270368A (en) | 2008-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101270368B (en) | Method for preparing hydrogen with biology and with utilization of organic waste water step | |
| Liu et al. | Organic matter and ammonia removal by a novel integrated process of constructed wetland and microbial fuel cells | |
| Wang et al. | Integrated hydrogen production process from cellulose by combining dark fermentation, microbial fuel cells, and a microbial electrolysis cell | |
| CN102400169B (en) | Method for producing hydrogen by alkalescent microbe electrolysis | |
| Fornero et al. | Electric power generation from municipal, food, and animal wastewaters using microbial fuel cells | |
| CN101409355B (en) | A photosynthetic microbial fuel cell | |
| CN101667649B (en) | Microbe fuel cell inoculation and acclimation starting method for energizing organic waste water | |
| CN102557272B (en) | Microbial fuel cell three-level continuous type waste water nitrogen-removing treatment method and device | |
| CN107180987A (en) | Couple the negative electrode efficient denitrification type microbiological fuel cell of Anammox technology | |
| CN108178328B (en) | A bio-cathode electrochemical system for treating sewage with low C/N ratio and method for treating wastewater | |
| CN113430234B (en) | Method for producing medium-chain fatty acid by using external potential to strengthen anaerobic microorganisms | |
| WO2022121550A1 (en) | Technological method for strengthening denitrification of low carbon-nitrogen ratio sewage by using electrode biological carrier | |
| CN112142199A (en) | Device and method for improving integrated partial denitrification-anaerobic ammonia oxidation coupling denitrification performance | |
| CN106630177A (en) | Method and device for treating coking wastewater and producing hydrogen gas by microbial electrolysis cell | |
| JP7359309B2 (en) | Encipher and its applications in biopower generation | |
| CN207925585U (en) | Couple the cathode efficient denitrification type microbiological fuel cell of Anammox technology | |
| CN203346383U (en) | Device for preparing hydrogen by utilizing organic waste | |
| CN103304037A (en) | Method for treating sewage, generating electric energy and assisting fermentation by virtue of bioelectrochemical system | |
| CN105489919B (en) | Air cathode microbial fuel cell and performance improvement method under no buffer solution operation | |
| CN113403234B (en) | A marine self-flocculating bacterium and its development-driven salt-adapted nitrogen assimilation microbiome and its construction method and application | |
| Ma et al. | Redox mediators stimulated chain elongation process in fluidized cathode electro-fermentation systems for caproate production | |
| CN101402926B (en) | Biological reinforcing method of hydrogenogen compensating material cultivation and biological hydrogen production system | |
| CN209912966U (en) | Dark fermentation hydrogen-iron production circulating fuel power generation device | |
| Li et al. | Simulation of cathode for synthesizing organic acids by MES reduction of CO2 | |
| Bélafi-Bako et al. | Study on operation of a microbial fuel cell using mesophilic anaerobic sludge |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |