WO2022056954A1 - Enhanced anaerobic remediation reagent for chromium-contaminated site, preparation method, and usage method - Google Patents
Enhanced anaerobic remediation reagent for chromium-contaminated site, preparation method, and usage method Download PDFInfo
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- WO2022056954A1 WO2022056954A1 PCT/CN2020/118073 CN2020118073W WO2022056954A1 WO 2022056954 A1 WO2022056954 A1 WO 2022056954A1 CN 2020118073 W CN2020118073 W CN 2020118073W WO 2022056954 A1 WO2022056954 A1 WO 2022056954A1
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- WO
- WIPO (PCT)
- Prior art keywords
- lactate
- oil
- emulsifier
- water
- vegetable oil
- Prior art date
Links
- 238000005067 remediation Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 title abstract 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 42
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 39
- 239000008158 vegetable oil Substances 0.000 claims abstract description 39
- -1 lactate ester Chemical class 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 28
- 229930003779 Vitamin B12 Natural products 0.000 claims abstract description 23
- 235000019163 vitamin B12 Nutrition 0.000 claims abstract description 23
- 239000011715 vitamin B12 Substances 0.000 claims abstract description 23
- 235000011187 glycerol Nutrition 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002689 soil Substances 0.000 claims abstract description 13
- 239000003673 groundwater Substances 0.000 claims abstract description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004945 emulsification Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 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 abstract 6
- 229940001447 lactate Drugs 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical group CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 18
- 230000008439 repair process Effects 0.000 claims description 14
- 229940116333 ethyl lactate Drugs 0.000 claims description 9
- 238000005728 strengthening Methods 0.000 claims description 9
- 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 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 239000001540 sodium lactate Substances 0.000 claims description 7
- 235000011088 sodium lactate Nutrition 0.000 claims description 7
- 229940005581 sodium lactate Drugs 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 5
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 claims description 5
- 239000001521 potassium lactate Substances 0.000 claims description 5
- 235000011085 potassium lactate Nutrition 0.000 claims description 5
- 229960001304 potassium lactate Drugs 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 235000019483 Peanut oil Nutrition 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 235000005687 corn oil Nutrition 0.000 claims description 4
- 239000002285 corn oil Substances 0.000 claims description 4
- 239000000312 peanut oil Substances 0.000 claims description 4
- 229940066675 ricinoleate Drugs 0.000 claims description 4
- ODFAPIRLUPAQCQ-UHFFFAOYSA-M sodium stearoyl lactylate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC(=O)OC(C)C(=O)OC(C)C([O-])=O ODFAPIRLUPAQCQ-UHFFFAOYSA-M 0.000 claims description 4
- 229940080352 sodium stearoyl lactylate Drugs 0.000 claims description 4
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 3
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 3
- 235000019486 Sunflower oil Nutrition 0.000 claims description 3
- 235000012343 cottonseed oil Nutrition 0.000 claims description 3
- 239000002385 cottonseed oil Substances 0.000 claims description 3
- 239000002540 palm oil Substances 0.000 claims description 3
- 229940083466 soybean lecithin Drugs 0.000 claims description 3
- 239000002600 sunflower oil Substances 0.000 claims description 3
- 229960005150 glycerol Drugs 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 claims description 2
- 229920000223 polyglycerol Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000005696 Diammonium phosphate Substances 0.000 abstract 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 abstract 2
- 235000019838 diammonium phosphate Nutrition 0.000 abstract 2
- 238000013268 sustained release Methods 0.000 abstract 1
- 239000012730 sustained-release form Substances 0.000 abstract 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 24
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(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+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 238000000855 fermentation Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003814 drug Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 244000005700 microbiome Species 0.000 description 7
- 230000004151 fermentation Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000813 microbial effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- ARIWANIATODDMH-AWEZNQCLSA-N 1-lauroyl-sn-glycerol Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)CO ARIWANIATODDMH-AWEZNQCLSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 235000019960 monoglycerides of fatty acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003445 sucroses Chemical class 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Definitions
- the invention relates to the technical field of chromium pollution control, in particular to an enhanced anaerobic repair agent, a preparation method and a use method for chromium-contaminated soil or groundwater and other sites.
- Hexavalent chromium is one of the most serious pollutants that endangers the health of residents.
- the main sources of pollution include: chrome salt chemical industry, tanning, and electroplating enterprises. Unreasonable stacking, etc.
- Cr(VI) has the strongest toxicity, which is about 100 times that of Cr(III), the toxicity of Cr(III) is relatively low; Cr(VI) has strong migration ability, while Cr(III) has weak migration ability.
- removal techniques include soil leaching, phytoremediation, electric restoration, and extraction-treatment.
- Commonly used treatment techniques are: chemical reduction (adding reducing substances, such as zero-valent iron, Ferrous salt, sulfite, calcium polysulfide, humus, organic carbon, etc.); microbial reduction (such as using indigenous hexavalent chromium-reducing bacteria, sulfate-reducing bacteria, iron-reducing bacteria); electrochemically enhanced hexavalent chromium reduction.
- Typical commercial biostimulant products include: Regenesis's biostimulant Hydrogen Release Compound Emulsified Vegetable Oil by EOS Series of products, products based on unsaturated vegetable oils from CARUS and ABC-Olé mixed with glycerol, fatty acid and phosphate buffer, ABC+ (Anaerobic Bio Chem+) mixed with zero-valent iron and ABC, Terra's Emulsified vegetable oil.
- One of the main components of the above-mentioned medicament is emulsified vegetable oil.
- emulsified vegetable oil can act as an electron donor for a long time to promote the dissimilatory iron reduction of microorganisms.
- the time of emulsified vegetable oil to maintain the normal growth of microorganisms is more than five times that of glucose.
- there are few domestic studies on the enhancement of hexavalent chromium microbial reduction by emulsified vegetable oil Only Zhao Yongsheng et al.
- the present invention provides an enhanced anaerobic remediation agent for chromium-contaminated sites, a preparation method and a use method.
- the invention discloses an enhanced anaerobic repair agent for chromium-polluted sites, comprising:
- Vegetable oil Vegetable oil, emulsifier, glycerin, lactate, lactate, vitamin B12, diamine phosphate and water.
- weight percentage including:
- the weight ratio of the vegetable oil to the emulsifier is (5-6):1.
- weight percentage including:
- the vegetable oil includes one or more of soybean oil, peanut oil, palm oil, corn oil, rapeseed oil, cottonseed oil and sunflower oil.
- the emulsifier includes food-grade emulsifiers, including sucrose esters, monoglycerides of fatty acids, polyoxyethylene ether-20 oleoyl ricinoleate, sodium stearoyl lactylate, soybean lecithin, polyoxyethylene ether One or more of glycerol monolaurate.
- the lactate includes one or more of sodium lactate and potassium lactate, and the lactate is ethyl lactate.
- the invention also discloses a preparation method for strengthening the anaerobic repairing agent, comprising:
- the invention also discloses a method for using the strengthening anaerobic repairing agent, comprising:
- the hydrogen content in the hydrogen-containing water is 0.0001%-0.0002%.
- the enhanced anaerobic repairing agent of the present invention uses vegetable oil, emulsifier, lactate, ethyl lactate, vitamin B12, diamine phosphate, etc. as the main components, and has the characteristics of easy availability of raw materials, degradability, and environmental protection;
- the enhanced anaerobic remediation agent of the present invention can produce hydrogen by fast, medium and slow fermentation underground, and realize the purpose of long-acting slow-release hydrogen, thereby realizing long-term remediation of hexavalent chromium polluted sites;
- the present invention uses hydrogen-containing water as the diluent for strengthening the anaerobic remediation agent, which accelerates the formation of the anaerobic reaction zone, thereby further strengthening the anaerobic bioremediation.
- the invention provides an enhanced anaerobic repairing agent for chromium-contaminated sites.
- the chromium-contaminated sites include hexavalent chromium-contaminated soil and groundwater; the repairing agent is composed of vegetable oil, emulsifier, glycerin, lactate, and lactic acid. Esters, Vitamin B12, Diamine Phosphate, and Water.
- the addition amount of each component is: vegetable oil 50-70%, emulsifier 8-12%, glycerin 0.5-2%, lactate 0.5-2%, lactate 0.5-2%, vitamin B12 0.1-0.5%, phosphoric acid diamine 0.5-1% and the balance of water; preferably, the weight ratio of vegetable oil to emulsifier is (5-6):1.
- each component is: vegetable oil 55-65%, emulsifier 10%, glycerin 1.8-2.2%, lactate 0.8-1.2%, lactate 0.8-1.2%, vitamin B12 0.4-0.5%, phosphoric acid diamine 0.5-1% and water 26%.
- each component is: vegetable oil 60%, emulsifier 10%, glycerol 1%, lactate 1%, lactate 1%, vitamin B12 0.5%, phosphate diamine 0.5% % and water 26%.
- the vegetable oil of the invention is slowly fermented to generate hydrogen under the action of microorganisms, maintains an underground anaerobic environment for a long time, and provides electron donors for the reduction of hexavalent chromium; it includes soybean oil, peanut oil, palm oil, corn oil, rapeseed oil, and cottonseed oil. A blend of one or more of oil and sunflower oil.
- the emulsifier of the present invention is used for emulsification of vegetable oil, which includes food-grade emulsifiers, including sucrose ester, monoglyceride, polyoxyethylene ether-20 oleoyl ricinoleate, sodium stearoyl lactylate, soybean lecithin, One or more of polyglycerol monolaurate is mixed.
- the glycerol of the present invention is used to ensure sufficient dissolution of the emulsifier in water.
- the lactate of the present invention can quickly provide a carbon source for anaerobic microorganisms, produce hydrogen by anaerobic fermentation, and promote the formation of an underground anaerobic environment; it includes one or more of sodium lactate and potassium lactate. If the addition amount of lactate is too low, the hydrogen production of rapid fermentation will be insufficient; if the addition amount is too high, the rapid anaerobic fermentation will easily lead to groundwater odor.
- the lactate of the present invention can ferment hydrogen at a medium speed and maintain an underground anaerobic environment, and ethyl lactate is selected. If the addition amount of lactate is less than 1%, the hydrogen production of medium-speed fermentation is insufficient; if the addition amount of lactate is too high, the cost will increase; the principle of selecting ethyl lactate as the material for medium-speed fermentation hydrogen production in the present invention is as follows: : Methyl lactate is irritating, and the hydrolysis rate is fast (twice that of ethyl lactate); propyl lactate, melting point is 1°C, which affects product storage when the temperature is low; butyl lactate and other lactic acid esters with longer chains are Low solubility in water makes it unsuitable; therefore, ethyl lactate is used as the lactate ester.
- the vitamin B12 of the present invention has an electron transfer function (equivalent to a catalyst), which is beneficial to the dissimilation reduction of iron in soil and aquifer media, and the divalent iron produced by iron reduction can react with hexavalent chromium, thereby indirectly promoting the reduction of hexavalent chromium ;
- the main function of adding diamine phosphate in the present invention is to provide nitrogen and phosphorus for anaerobic microorganisms to promote the growth of the community, thereby promoting the anaerobic fermentation of lactate, lactate and vegetable oil to produce hydrogen.
- the initial content of nitrogen and phosphorus is 10 -20 mg/L is beneficial to the growth of related microorganisms (after a large number of microorganisms are formed, they can be added later according to the reaction conditions), then the content of nitrogen and phosphorus in groundwater should be 0.01-0.02 g/L, and the dosage of chemicals is generally 1% -3%, the concentration of nitrogen and phosphorus in the agent is 0.033%-0.2%, converted into phosphoric acid diamine (molecular weight 132) is 0.075%-0.45%, and the conservative value is calculated at 0.5% of phosphoric acid diamine.
- the release mechanism of the enhanced anaerobic repair agent of the present invention is as follows:
- the first step the lactate in the agent can be rapidly fermented to generate hydrogen, thereby promoting the formation of an underground anaerobic environment;
- the second step the medium-speed fermentation of ethyl lactate produces hydrogen
- the third step the slow fermentation of vegetable oil is converted into hydrogen, which provides electron donors for a long time.
- adding agents to enhance bioremediation can achieve rapid, medium-speed, and long-term reduction of Cr(VI) through hydrogen production through anaerobic fermentation.
- the present invention also provides a preparation method for strengthening anaerobic repairing agent, comprising:
- Step 1 Add the emulsifier and glycerin to part of the water, dissolve by heating at 40-50°C, stir and mix to form solution A;
- Step 2 Add lactate, lactate, vitamin B12, and phosphoric acid diamine into the remaining part of the water, and at room temperature, stir and mix to form solution B;
- Step 3 Mix the vegetable oil, solution A and solution B into the vacuum-sealed high-shear emulsification tank, start the equipment and stir and mix for 40-60 minutes, the stirring speed is 2000-3000 rpm, and let stand for 20-40 minutes after stirring Discharging; among them, it is preferable to stand for 30 minutes to discharge.
- the present invention provides a method for strengthening anaerobic repairing agent, comprising:
- the effect of adding hydrogen-containing water in the present invention is as follows: the hydrogen-containing water is mixed with the medicament and then injected into the soil or groundwater, which can reduce the consumption of carbon sources (lactate, lactate, vegetable oil, etc.)
- the layer forms an anaerobic reaction zone, which plays a role in rapidly strengthening anaerobic bioremediation.
- the reasons are as follows:
- Electron acceptors in soil and groundwater exist in dissolved or solid form, and 1 gram of molecular hydrogen is sufficient to consume 7 grams of oxygen, or 10.6 grams of sulfate ions, or 5.5 grams of carbon dioxide, or 10.2 grams of nitrate, or 55.9 grams of trivalent Iron ions are reduced to divalent iron ions, or 27.5 grams of hexavalent manganese is reduced to trivalent manganese.
- hydrogen-rich water enters the ground, it can rapidly diffuse in the aquifer and form a reaction zone, thereby enhancing anaerobic bioremediation.
- solution A 10 grams of sucrose ester, 1 gram of glycerol, and 15 grams of water at a temperature of 50°C to form solution A.
- solution B 10 grams of sucrose ester, 1 gram of glycerol, and 15 grams of water at a temperature of 50°C.
- solution B 10 grams of sucrose ester, 1 gram of glycerol, and 15 grams of water at a temperature of 50°C.
- solution A 1 gram of sodium lactate, 1 gram of ethyl lactate, 0.5 grams of vitamin B12, 0.5 grams of phosphate diamine, and 11 grams of room temperature water.
- solution B mix solution A, solution B, and 60 grams of soybean oil into a vacuum-sealed high-shear emulsification tank, start the equipment, stir and mix for 60 minutes, and stir at a speed of 2,000 rpm. After stirring, let stand for 30 minutes before discharging. , stored in an airtight, oil-free, water-free, clean poly
- Group A 100ml of hexavalent chromium wastewater with a concentration of 20mg/L was placed in a 150ml transparent plastic bottle, the transparent plastic bottle was sealed with an infusion bottle with a butyl rubber stopper, and 3ml of enhanced biological
- syringe B to extract 27 ml of distilled water containing hydrogen 0.0001%
- tilt the plastic bottle to ensure that the needles of syringes A and B are below the liquid surface, and push the syringe to inject the medicine and water into the transparent plastic bottle, and shake the bottle quickly
- the chemical, hydrogen-containing distilled water, and chromium-contaminated wastewater were rapidly mixed.
- a total of 5 parallel samples were set up and placed in an incubator with a constant temperature of 35°C.
- Group B The method of group A was adopted, but the distilled water containing 0.0001% hydrogen in group A was replaced with ordinary distilled water, and 5 parallel samples were set up and placed in an incubator with a constant temperature of 35°C.
- Blank 100ml of 20mg/L hexavalent chromium wastewater, 30ml of distilled water, placed in a 150ml transparent plastic bottle, sealed with a butyl rubber stopper for the infusion bottle, and placed at a constant temperature of 35°C for incubation in the box.
- sucrose ester of Example 1 was replaced with monoglyceride, sodium lactate was replaced with potassium lactate, and soybean oil was replaced with peanut oil; all the other were consistent with Example 1;
- sucrose ester of Example 1 was replaced with polyoxyethylene ether-20 oleoyl ricinoleate and sodium stearoyl lactylate, sodium lactate was replaced with sodium lactate and potassium lactate, and soybean oil was replaced with corn oil and rapeseed oil;
- Example 1 is consistent;
- the present invention replaces vegetable oil with one or more of the above-mentioned optional vegetable oils, and replaces the food-grade emulsifier with one or more of the above-mentioned optional emulsifiers, all of which can reach Table 2-4. obtained approximation.
- the present invention can also appropriately adjust the addition amount of each component according to the above-mentioned component distribution ratio, and can achieve the approximate effects obtained in Tables 2-4, so it is not listed here.
- the enhanced biological remediation agent of the present invention is also suitable for enhanced anaerobic remediation of contaminated soil and groundwater such as hexavalent uranium, pentavalent vanadium, and chlorine-containing organic compounds.
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Abstract
An enhanced anaerobic remediation reagent for a chromium-contaminated site, a preparation method, and a usage method. The enhanced anaerobic remediation reagent comprises: vegetable oil, an emulsifier, glycerin, lactate, lactate ester, vitamin B12, diammonium phosphate, and water. The preparation method comprises: adding an emulsifier and glycerin to part of water, and heating to dissolve same to form a solution A; adding lactate, lactate ester, vitamin B12, and diammonium phosphate to the remaining part of water, and mixing same to form a solution B; stirring vegetable oil, the solution A, and the solution B for emulsification, and standing for discharging. The usage method comprises: mixing 6%-10% by volume of an enhanced anaerobic remediation reagent with 90%-94% by volume of hydrogen-containing water, and then injecting same into the soil or groundwater. The remediation reagent is efficient, long in sustained release time, environmentally friendly, and easy in material acquisition.
Description
本发明涉及铬污染治理技术领域，具体涉及用于铬污染土壤或地下水等场地的强化厌氧修复药剂、制备方法及使用方法。The invention relates to the technical field of chromium pollution control, in particular to an enhanced anaerobic repair agent, a preparation method and a use method for chromium-contaminated soil or groundwater and other sites.
六价铬是危害居民健康最严重的污染物之一，其污染来源主要包括：铬盐化工、制革、电镀企业生产过程的跑冒滴漏、超标废水排放、含铬废渣及含铬污泥的不合理堆放等。Hexavalent chromium is one of the most serious pollutants that endangers the health of residents. The main sources of pollution include: chrome salt chemical industry, tanning, and electroplating enterprises. Unreasonable stacking, etc.
由于Cr(Ⅵ)的毒性最强，大约是Cr(Ⅲ)的100倍，Cr(Ⅲ)的毒性相对较低；Cr(Ⅵ)的迁移能力强，而Cr(Ⅲ)迁移能力弱。目前处理Cr(Ⅵ)污染的方式主要有2种：(1)、将Cr(Ⅵ)从污染介质中去除，常用的去除技术有土壤淋洗、植物修复、电动修复、抽出-处理等。(2)、将Cr(Ⅵ)还原为Cr(Ⅲ)，降低铬在土壤中的移动性和生物可利用性，常采用的处理技术有：化学还原(添加还原性物质，如零价铁、亚铁盐、亚硫酸盐、多硫化钙、腐殖质、有机碳等)；微生物还原(比如利用土著六价铬还原菌、硫酸盐还原菌、铁还原菌)；电化学强化六价铬还原。Since Cr(VI) has the strongest toxicity, which is about 100 times that of Cr(III), the toxicity of Cr(III) is relatively low; Cr(VI) has strong migration ability, while Cr(III) has weak migration ability. At present, there are two main ways to deal with Cr(VI) pollution: (1) Removal of Cr(VI) from the polluted medium. Commonly used removal techniques include soil leaching, phytoremediation, electric restoration, and extraction-treatment. (2) Reduce Cr(VI) to Cr(III) to reduce the mobility and bioavailability of chromium in the soil. Commonly used treatment techniques are: chemical reduction (adding reducing substances, such as zero-valent iron, Ferrous salt, sulfite, calcium polysulfide, humus, organic carbon, etc.); microbial reduction (such as using indigenous hexavalent chromium-reducing bacteria, sulfate-reducing bacteria, iron-reducing bacteria); electrochemically enhanced hexavalent chromium reduction.
在化学还原Cr(Ⅵ)技术研发方面，大量的研究集中在绿色高效还原材料的开发上，尤其以纳米零价铁、微米零价铁、缓释还原材料的研究较多，典型的化学还原材料有：Regenesis公司的硫化微米零价铁S-MicroZVI
TM、缓释金属修复药剂
In the research and development of chemical reduction Cr(Ⅵ) technology, a lot of research focuses on the development of green and efficient reduction materials, especially the research on nano-zero-valent iron, micro-zero-valent iron, and slow-release reducing materials. Typical chemical reduction materials There are: S-MicroZVI TM of S-MicroZVI TM of Regenesis Company, slow-release metal repair agent
在微生物还原Cr(Ⅵ)技术研发方面，集中在强化土著微生物还原六价铬材料的研究，典型的生物刺激剂商业化产品有：Regenesis公司的生物刺激剂
Hydrogen Release Compound
EOS公司的Emulsified Vegetable Oil
系列产品，CARUS公司的以不饱和植物油为基础的产品
和
以甘油、脂肪酸和磷酸盐缓冲液等混合而成的ABC-Olé、由零价铁与ABC混合而成的ABC+(Anaerobic Bio Chem+)，Terra公司的
乳化植物油。上述药剂的主要成分之一是乳化植物油，研究表明，乳化植物油可长期作为电子供体促进微生物的异化铁还 原作用，乳化植物油维持微生物正常生长的时间是葡萄糖的五倍以上。但国内在乳化植物油强化六价铬微生物还原方面的研究较少，只有赵勇胜等发明了一种以乳化植物油为缓释性碳源的原位修复剂(申请号CN201910681691.9)；但，该专利乳化植物油制备环节用表面活性剂(吐温80)多、用植物油少，导致药剂成本增高，长期缓释效果受限；同时，大量使用的吐温80表面活性剂，有潜在的毒性；该专利药剂同时使用了抗坏血酸和碳酸氢钠，二者会发生反应产生二氧化碳导致药剂中抗坏血酸、部分碳酸氢钠失效。
In the research and development of microbial reduction Cr(VI) technology, the focus is on strengthening the research of indigenous microbial reduction of hexavalent chromium materials. Typical commercial biostimulant products include: Regenesis's biostimulant Hydrogen Release Compound Emulsified Vegetable Oil by EOS Series of products, products based on unsaturated vegetable oils from CARUS and ABC-Olé mixed with glycerol, fatty acid and phosphate buffer, ABC+ (Anaerobic Bio Chem+) mixed with zero-valent iron and ABC, Terra's Emulsified vegetable oil. One of the main components of the above-mentioned medicament is emulsified vegetable oil. Studies have shown that emulsified vegetable oil can act as an electron donor for a long time to promote the dissimilatory iron reduction of microorganisms. The time of emulsified vegetable oil to maintain the normal growth of microorganisms is more than five times that of glucose. However, there are few domestic studies on the enhancement of hexavalent chromium microbial reduction by emulsified vegetable oil. Only Zhao Yongsheng et al. invented an in-situ repair agent using emulsified vegetable oil as a slow-release carbon source (application number CN201910681691.9); In the preparation of patented emulsified vegetable oil, more surfactants (Tween 80) and less vegetable oil are used, which leads to higher pharmaceutical costs and limited long-term slow-release effect; at the same time, the widely used Tween 80 surfactant has potential toxicity; The patented medicine uses ascorbic acid and sodium bicarbonate at the same time, and the two will react to produce carbon dioxide, causing the ascorbic acid and part of the sodium bicarbonate in the medicine to fail.
为了更加绿色、环保、经济有效地实现对铬污染土壤和下水进行修复，研发以乳化植物油为主要基质的生物强化药剂十分必要。In order to realize the remediation of chromium-contaminated soil and sewage in a greener, more environmentally friendly, and more cost-effective way, it is necessary to develop biofortified agents with emulsified vegetable oil as the main matrix.
发明内容SUMMARY OF THE INVENTION
针对现有技术中存在的上述问题，本发明提供一种用于铬污染场地的强化厌氧修复药剂、制备方法及使用方法。In view of the above problems existing in the prior art, the present invention provides an enhanced anaerobic remediation agent for chromium-contaminated sites, a preparation method and a use method.
本发明公开了一种用于铬污染场地的强化厌氧修复药剂，包括：The invention discloses an enhanced anaerobic repair agent for chromium-polluted sites, comprising:
植物油、乳化剂、甘油、乳酸盐、乳酸酯、维生素B12、磷酸二胺和水。Vegetable oil, emulsifier, glycerin, lactate, lactate, vitamin B12, diamine phosphate and water.
作为本发明的进一步改进，按重量百分比计，包括：As a further improvement of the present invention, by weight percentage, including:
植物油50～70％、乳化剂8～12％、甘油0.5～2％、乳酸盐0.5～2％、乳酸酯0.5～2％、维生素B12 0.1～0.5％、磷酸二胺0.5～1％和余量水。Vegetable oil 50-70%, emulsifier 8-12%, glycerin 0.5-2%, lactate 0.5-2%, lactate 0.5-2%, vitamin B12 0.1-0.5%, phosphate diamine 0.5-1% and residual water.
作为本发明的进一步改进，所述植物油与乳化剂的重量比为(5～6)：1。As a further improvement of the present invention, the weight ratio of the vegetable oil to the emulsifier is (5-6):1.
作为本发明的进一步改进，按重量百分比计，包括：As a further improvement of the present invention, by weight percentage, including:
植物油60％、乳化剂10％、甘油1％、乳酸盐1％、乳酸酯1％、维生素B12 0.5％、磷酸二胺0.5％和水26％。Vegetable oil 60%, emulsifier 10%, glycerin 1%, lactate 1%, lactate 1%, vitamin B12 0.5%, phosphate diamine 0.5% and water 26%.
作为本发明的进一步改进，所述植物油包括豆油、花生油、棕榈油、玉米油、菜籽油、棉籽油和葵花籽油中的一种或多种。As a further improvement of the present invention, the vegetable oil includes one or more of soybean oil, peanut oil, palm oil, corn oil, rapeseed oil, cottonseed oil and sunflower oil.
作为本发明的进一步改进，所述乳化剂包括食品级乳化剂，包括蔗糖酸酯、单脂肪酸甘油酯、聚氧乙烯醚-20油酰蓖麻醇酸酯、硬脂酰乳酸钠、大豆磷脂、聚甘油单月桂酸脂中的一种或多种。As a further improvement of the present invention, the emulsifier includes food-grade emulsifiers, including sucrose esters, monoglycerides of fatty acids, polyoxyethylene ether-20 oleoyl ricinoleate, sodium stearoyl lactylate, soybean lecithin, polyoxyethylene ether One or more of glycerol monolaurate.
作为本发明的进一步改进，所述乳酸盐包括乳酸钠、乳酸钾中的一种或多种，所述乳酸酯为乳酸乙酯。As a further improvement of the present invention, the lactate includes one or more of sodium lactate and potassium lactate, and the lactate is ethyl lactate.
本发明还公开了一种强化厌氧修复药剂的制备方法，包括：The invention also discloses a preparation method for strengthening the anaerobic repairing agent, comprising:
将乳化剂、甘油加入部分水中，受热溶解形成溶液A；Add the emulsifier and glycerin to part of the water, and dissolve by heating to form solution A;
将乳酸盐、乳酸酯、维生素B12、磷酸二胺加入剩余部分水中，混合形成溶液B；Add lactate, lactate, vitamin B12, and phosphoric acid diamine into the remaining part of the water, and mix to form solution B;
将植物油、溶液A和溶液B混合加入真空密封型高剪切乳化罐中，启动设备搅拌混合40-60分钟，搅拌速度2000-3000转/分钟，搅拌结束后静置20-40分钟出料。Mix vegetable oil, solution A and solution B into a vacuum-sealed high-shear emulsification tank, start the equipment and stir and mix for 40-60 minutes at a stirring speed of 2000-3000 r/min. After stirring, let stand for 20-40 minutes to discharge.
本发明还公开了一种强化厌氧修复药剂的使用方法，包括：The invention also discloses a method for using the strengthening anaerobic repairing agent, comprising:
将6％-10％体积的强化厌氧修复药剂与90％-94％体积的含氢水混合后注入土壤或地下水。Mix 6%-10% volume of enhanced anaerobic remediation agent with 90%-94% volume of hydrogen-containing water and inject into soil or groundwater.
作为本发明的进一步改进，所述含氢水中氢气含量为0.0001％-0.0002％。As a further improvement of the present invention, the hydrogen content in the hydrogen-containing water is 0.0001%-0.0002%.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
1、本发明的强化厌氧修复药剂以植物油、乳化剂、乳酸盐、乳酸乙酯、维生素B12、磷酸二胺等作为主要成分，具有原料易得、可降解、绿色环保等特点；1. The enhanced anaerobic repairing agent of the present invention uses vegetable oil, emulsifier, lactate, ethyl lactate, vitamin B12, diamine phosphate, etc. as the main components, and has the characteristics of easy availability of raw materials, degradability, and environmental protection;
2、本发明的强化厌氧修复药剂在地下可以快速、中速、慢速发酵产氢，实现了长效缓释氢气的目的，从而可以实现对六价铬污染场地的长效修复；2. The enhanced anaerobic remediation agent of the present invention can produce hydrogen by fast, medium and slow fermentation underground, and realize the purpose of long-acting slow-release hydrogen, thereby realizing long-term remediation of hexavalent chromium polluted sites;
3、本发明采用含氢水作为强化厌氧修复药剂的稀释剂，加速了厌氧反应区的形成，从而进一步强化了厌氧生物修复。3. The present invention uses hydrogen-containing water as the diluent for strengthening the anaerobic remediation agent, which accelerates the formation of the anaerobic reaction zone, thereby further strengthening the anaerobic bioremediation.
为使本发明实施例的目的、技术方案和优点更加清楚，下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purposes, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. example. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.
下面对本发明做进一步的详细描述：The present invention is described in further detail below:
本发明提供一种用于铬污染场地的强化厌氧修复药剂，铬污染场地包括六价铬污染土壤和地下水；该修复药剂的组分包括：植物油、乳化剂、甘油、乳酸盐、乳酸酯、维生素B12、磷酸二胺和水。The invention provides an enhanced anaerobic repairing agent for chromium-contaminated sites. The chromium-contaminated sites include hexavalent chromium-contaminated soil and groundwater; the repairing agent is composed of vegetable oil, emulsifier, glycerin, lactate, and lactic acid. Esters, Vitamin B12, Diamine Phosphate, and Water.
按重量百分比计，各组分的添加量为：植物油50～70％、乳化剂8～12％、 甘油0.5～2％、乳酸盐0.5～2％、乳酸酯0.5～2％、维生素B12 0.1～0.5％、磷酸二胺0.5～1％和余量水；优选植物油与乳化剂的重量比为(5～6)：1。By weight percentage, the addition amount of each component is: vegetable oil 50-70%, emulsifier 8-12%, glycerin 0.5-2%, lactate 0.5-2%, lactate 0.5-2%, vitamin B12 0.1-0.5%, phosphoric acid diamine 0.5-1% and the balance of water; preferably, the weight ratio of vegetable oil to emulsifier is (5-6):1.
进一步，按重量百分比计，各组分的添加量为：植物油55～65％、乳化剂10％、甘油1.8～2.2％、乳酸盐0.8～1.2％、乳酸酯0.8～1.2％、维生素B12 0.4～0.5％、磷酸二胺0.5～1％和水26％。Further, by weight percentage, the addition amount of each component is: vegetable oil 55-65%, emulsifier 10%, glycerin 1.8-2.2%, lactate 0.8-1.2%, lactate 0.8-1.2%, vitamin B12 0.4-0.5%, phosphoric acid diamine 0.5-1% and water 26%.
更进一步，按重量百分比计，各组分的添加量为：植物油60％、乳化剂10％、甘油1％、乳酸盐1％、乳酸酯1％、维生素B12 0.5％、磷酸二胺0.5％和水26％。Further, by weight percentage, the addition amount of each component is: vegetable oil 60%, emulsifier 10%, glycerol 1%, lactate 1%, lactate 1%, vitamin B12 0.5%, phosphate diamine 0.5% % and water 26%.
其中，in,
本发明的植物油在微生物作用下慢速发酵产生氢气，长期维持地下的厌氧环境，为六价铬的还原提供电子供体；其包括豆油、花生油、棕榈油、玉米油、菜籽油、棉籽油和葵花籽油中的一种或多种混合。The vegetable oil of the invention is slowly fermented to generate hydrogen under the action of microorganisms, maintains an underground anaerobic environment for a long time, and provides electron donors for the reduction of hexavalent chromium; it includes soybean oil, peanut oil, palm oil, corn oil, rapeseed oil, and cottonseed oil. A blend of one or more of oil and sunflower oil.
本发明的乳化剂用于植物油的乳化，其包括食品级乳化剂，包括蔗糖酸酯、单脂肪酸甘油酯、聚氧乙烯醚-20油酰蓖麻醇酸酯、硬脂酰乳酸钠、大豆磷脂、聚甘油单月桂酸脂中的一种或多种混合。The emulsifier of the present invention is used for emulsification of vegetable oil, which includes food-grade emulsifiers, including sucrose ester, monoglyceride, polyoxyethylene ether-20 oleoyl ricinoleate, sodium stearoyl lactylate, soybean lecithin, One or more of polyglycerol monolaurate is mixed.
本发明的甘油用于保证乳化剂在水中的充分溶解。The glycerol of the present invention is used to ensure sufficient dissolution of the emulsifier in water.
本发明的乳酸盐可以快速为厌氧微生物提供碳源，厌氧发酵产氢，促进地下厌氧环境的形成；其包括乳酸钠、乳酸钾中的一种或多种。若乳酸盐添加量过低，则快速发酵产氢不足；若添加量过高，则快速厌氧发酵容易导致地下水发臭。The lactate of the present invention can quickly provide a carbon source for anaerobic microorganisms, produce hydrogen by anaerobic fermentation, and promote the formation of an underground anaerobic environment; it includes one or more of sodium lactate and potassium lactate. If the addition amount of lactate is too low, the hydrogen production of rapid fermentation will be insufficient; if the addition amount is too high, the rapid anaerobic fermentation will easily lead to groundwater odor.
本发明的乳酸酯可中速发酵产氢，维持地下的厌氧环境，其选用乳酸乙酯。若乳酸酯添加量少于1％，则中速发酵产氢不足；若乳酸酯添加量过高，则成本会增加；本发明选用乳酸乙酯作为中速发酵产氢的材料的原理为：乳酸甲酯具有刺激性，水解速度快(是乳酸乙酯的2倍)；乳酸丙酯，熔点1℃，温度低时影响产品存放；乳酸丁酯以及其他链更长的乳酸酯，在水中的溶解性低，不适合；因此，乳酸酯选用乳酸乙酯。The lactate of the present invention can ferment hydrogen at a medium speed and maintain an underground anaerobic environment, and ethyl lactate is selected. If the addition amount of lactate is less than 1%, the hydrogen production of medium-speed fermentation is insufficient; if the addition amount of lactate is too high, the cost will increase; the principle of selecting ethyl lactate as the material for medium-speed fermentation hydrogen production in the present invention is as follows: : Methyl lactate is irritating, and the hydrolysis rate is fast (twice that of ethyl lactate); propyl lactate, melting point is 1°C, which affects product storage when the temperature is low; butyl lactate and other lactic acid esters with longer chains are Low solubility in water makes it unsuitable; therefore, ethyl lactate is used as the lactate ester.
本发明的维生素B12具有电子传递功能(相当于一个催化剂)，其利于土壤和含水层介质中铁的异化还原，铁还原产生的二价铁可与六价铬反应，从而间接促进六价铬的还原；维生素B12的添加量：试验表明1微摩尔/升浓度的维生素B12即可以起到良好的催化作用，即地下水中维生素B12的浓度为 0.001355克/升，添加到地下后地下水不断流动换新再次稀释(反应2-3年按稀释20-40倍计)，则需要B12的最大浓度为0.001355克/升*40＝0.0542克/升，按药剂添加量一般为1％-3％来计，则药剂中维生素B12的浓度为0.18％-0.542％，为确保效果，取维生素B12的浓度为0.5％；The vitamin B12 of the present invention has an electron transfer function (equivalent to a catalyst), which is beneficial to the dissimilation reduction of iron in soil and aquifer media, and the divalent iron produced by iron reduction can react with hexavalent chromium, thereby indirectly promoting the reduction of hexavalent chromium ; Adding amount of vitamin B12: The test shows that vitamin B12 at a concentration of 1 micromol/L can play a good catalytic role, that is, the concentration of vitamin B12 in groundwater is 0.001355 g/L. Dilution (20-40 times dilution for 2-3 years of reaction), the maximum concentration of B12 is 0.001355 g/L*40=0.0542 g/L. According to the dosage of 1%-3% of the drug, then The concentration of vitamin B12 in the medicine is 0.18%-0.542%, in order to ensure the effect, the concentration of vitamin B12 is 0.5%;
本发明加入磷酸二胺的主要作用是为厌氧微生物提供氮和磷，促进群落的增长，从而促进对乳酸盐、乳酸酯、植物油的厌氧发酵产氢，氮磷的初始含量在10-20毫克/升左右利于相关微生物的生长(大量微生物形成后，后续可以再根据反应情况添加)，则地下水中氮磷的含量应为0.01-0.02克/升，按药剂添加量一般为1％-3％来计，则药剂中氮磷浓度为0.033％-0.2％，换算成磷酸二胺(分子量132)为0.075％-0.45％，保守取值按磷酸二胺0.5％计。The main function of adding diamine phosphate in the present invention is to provide nitrogen and phosphorus for anaerobic microorganisms to promote the growth of the community, thereby promoting the anaerobic fermentation of lactate, lactate and vegetable oil to produce hydrogen. The initial content of nitrogen and phosphorus is 10 -20 mg/L is beneficial to the growth of related microorganisms (after a large number of microorganisms are formed, they can be added later according to the reaction conditions), then the content of nitrogen and phosphorus in groundwater should be 0.01-0.02 g/L, and the dosage of chemicals is generally 1% -3%, the concentration of nitrogen and phosphorus in the agent is 0.033%-0.2%, converted into phosphoric acid diamine (molecular weight 132) is 0.075%-0.45%, and the conservative value is calculated at 0.5% of phosphoric acid diamine.
本发明强化厌氧修复药剂的释放机理如下：The release mechanism of the enhanced anaerobic repair agent of the present invention is as follows:
第一步：药剂中的乳酸盐可以快速进行发酵产生氢气，从而促进地下厌氧环境的形成；The first step: the lactate in the agent can be rapidly fermented to generate hydrogen, thereby promoting the formation of an underground anaerobic environment;
Na(K)C
3H
5O
3+6H
2O→6H
2+3HCO
3
-+2H
++Na(K)
+
Na(K)C 3 H 5 O 3 +6H 2 O→6H 2 +3HCO 3 - +2H + +Na(K) +
第二步：乳酸乙酯中速发酵产生氢气；The second step: the medium-speed fermentation of ethyl lactate produces hydrogen;
C
5H
10O
3+H
2O→12H
2+5HCO
3
-+5H
+
C 5 H 10 O 3 +H 2 O→12H 2 +5HCO 3 - +5H +
第三步：植物油慢速发酵转换成氢气，长期提供电子供体。The third step: the slow fermentation of vegetable oil is converted into hydrogen, which provides electron donors for a long time.
C
18H
32O
2+52H
2O→50H
2+18HCO
3
-+18H
+
C 18 H 32 O 2 +52H 2 O→50H 2 +18HCO 3 - +18H +
总之，添加强化生物修复的药剂，通过厌氧发酵产氢实现对Cr(Ⅵ)的快速、中速、长期还原。In a word, adding agents to enhance bioremediation can achieve rapid, medium-speed, and long-term reduction of Cr(VI) through hydrogen production through anaerobic fermentation.
本发明还提供一种强化厌氧修复药剂的制备方法，包括：The present invention also provides a preparation method for strengthening anaerobic repairing agent, comprising:
步骤1、将乳化剂、甘油加入部分水中，40-50℃下受热溶解，搅拌混合形成溶液A；Step 1. Add the emulsifier and glycerin to part of the water, dissolve by heating at 40-50°C, stir and mix to form solution A;
步骤2、将乳酸盐、乳酸酯、维生素B12、磷酸二胺加入剩余部分水中，常温下，搅拌混合形成溶液B；Step 2. Add lactate, lactate, vitamin B12, and phosphoric acid diamine into the remaining part of the water, and at room temperature, stir and mix to form solution B;
步骤3、将植物油、溶液A和溶液B混合加入真空密封型高剪切乳化罐中，启动设备搅拌混合40-60分钟，搅拌速度2000-3000转/分钟，搅拌结束后静置20-40分钟出料；其中，优选静置30分钟出料。Step 3. Mix the vegetable oil, solution A and solution B into the vacuum-sealed high-shear emulsification tank, start the equipment and stir and mix for 40-60 minutes, the stirring speed is 2000-3000 rpm, and let stand for 20-40 minutes after stirring Discharging; among them, it is preferable to stand for 30 minutes to discharge.
本发明提供一种强化厌氧修复药剂的使用方法，包括：The present invention provides a method for strengthening anaerobic repairing agent, comprising:
将6％-10％体积的强化厌氧修复药剂与90％-94％体积的含氢水混合后注 入土壤或地下水；其中，含氢水中氢气含量为0.0001％-0.0002％。Mix 6%-10% volume of enhanced anaerobic remediation agent with 90%-94% volume of hydrogen-containing water and then inject into soil or groundwater; wherein, the hydrogen content in hydrogen-containing water is 0.0001%-0.0002%.
本发明加入含氢水的作用如下：采用含氢水与药剂混合后注入土壤或地下水中，可以减少场地对碳源(乳酸盐、乳酸酯、植物油等)的消耗，并可迅速在含水层形成厌氧反应区，起到快速强化厌氧生物修复的作用。原因如下：The effect of adding hydrogen-containing water in the present invention is as follows: the hydrogen-containing water is mixed with the medicament and then injected into the soil or groundwater, which can reduce the consumption of carbon sources (lactate, lactate, vegetable oil, etc.) The layer forms an anaerobic reaction zone, which plays a role in rapidly strengthening anaerobic bioremediation. The reasons are as follows:
土壤和地下水中的电子受体以溶解态或固态形式存在，1克分子氢足够消耗7克氧气、或10.6克硫酸根离子、或5.5克二氧化碳、或10.2克硝酸根，或将55.9克三价铁离子还原为二价铁离子，或将27.5克六价锰还原为三价锰。当富含氢气的水进入地下，可以迅速在含水层扩散并形成反应区，从而强化厌氧生物修复。Electron acceptors in soil and groundwater exist in dissolved or solid form, and 1 gram of molecular hydrogen is sufficient to consume 7 grams of oxygen, or 10.6 grams of sulfate ions, or 5.5 grams of carbon dioxide, or 10.2 grams of nitrate, or 55.9 grams of trivalent Iron ions are reduced to divalent iron ions, or 27.5 grams of hexavalent manganese is reduced to trivalent manganese. When hydrogen-rich water enters the ground, it can rapidly diffuse in the aquifer and form a reaction zone, thereby enhancing anaerobic bioremediation.
实施例1：Example 1:
将10克蔗糖酸酯、1克甘油、15克温度为50℃的水混合形成溶液A，将1克乳酸钠、1克乳酸乙酯、0.5克维生素B12、0.5克磷酸二胺、11克常温水混合形成溶液B；将溶液A、溶液B、60克豆油混合加入真空密封型高剪切乳化罐中，启动设备搅拌混合60分钟，搅拌速度2000转/分钟，搅拌结束后静置30分钟出料，密闭保存于无油、无水的干净聚丙烯塑料瓶中待用。Mix 10 grams of sucrose ester, 1 gram of glycerol, and 15 grams of water at a temperature of 50°C to form solution A. Mix 1 gram of sodium lactate, 1 gram of ethyl lactate, 0.5 grams of vitamin B12, 0.5 grams of phosphate diamine, and 11 grams of room temperature water. Mix to form solution B; mix solution A, solution B, and 60 grams of soybean oil into a vacuum-sealed high-shear emulsification tank, start the equipment, stir and mix for 60 minutes, and stir at a speed of 2,000 rpm. After stirring, let stand for 30 minutes before discharging. , stored in an airtight, oil-free, water-free, clean polypropylene plastic bottle for later use.
开展以下2组实验：Carry out the following 2 sets of experiments:
表1实验设置Table 1 Experimental setup
A组：将100毫升浓度为20mg/L的六价铬废水置于150毫升透明塑料瓶中，采用输液瓶用翻口丁基胶塞对透明塑料瓶进行密封，采用注射器A抽取3毫升强化生物修复药剂、采用注射器B抽取含氢气0.0001％的蒸馏水27毫升，倾斜塑料瓶，确保注射器A、B的针头在液面下，同时推动注射器将药剂和水注入透明塑料瓶中，并迅速摇晃瓶体使药剂、含氢蒸馏水、铬污染废水快速混合，采用此方法，共设置5个平行样，置于恒温35℃的培养箱中。Group A: 100ml of hexavalent chromium wastewater with a concentration of 20mg/L was placed in a 150ml transparent plastic bottle, the transparent plastic bottle was sealed with an infusion bottle with a butyl rubber stopper, and 3ml of enhanced biological To repair the medicine, use syringe B to extract 27 ml of distilled water containing hydrogen 0.0001%, tilt the plastic bottle to ensure that the needles of syringes A and B are below the liquid surface, and push the syringe to inject the medicine and water into the transparent plastic bottle, and shake the bottle quickly The chemical, hydrogen-containing distilled water, and chromium-contaminated wastewater were rapidly mixed. Using this method, a total of 5 parallel samples were set up and placed in an incubator with a constant temperature of 35°C.
B组：采用A组方法，但将A组中含氢气0.0001％的蒸馏水换为普通蒸 馏水，共设置5个平行样，置于恒温35℃的培养箱中。Group B: The method of group A was adopted, but the distilled water containing 0.0001% hydrogen in group A was replaced with ordinary distilled water, and 5 parallel samples were set up and placed in an incubator with a constant temperature of 35°C.
空白：100毫升20mg/L的六价铬废水，30毫升蒸馏水，置于150毫升透明塑料瓶中，采用输液瓶用翻口丁基胶塞对透明塑料瓶进行密封，置于恒温35℃的培养箱中。Blank: 100ml of 20mg/L hexavalent chromium wastewater, 30ml of distilled water, placed in a 150ml transparent plastic bottle, sealed with a butyl rubber stopper for the infusion bottle, and placed at a constant temperature of 35°C for incubation in the box.
分别在反应1天、5天、10天、20天、30天进行取样检测，2组实验废水中六价铬含量见下表。Sampling and testing were carried out on 1 day, 5 days, 10 days, 20 days and 30 days of reaction respectively, and the content of hexavalent chromium in the two groups of experimental wastewater is shown in the following table.
表2不同反应时间六价铬含量Table 2 Hexavalent chromium content at different reaction times
实施例2：Example 2:
将实施例1的蔗糖酸酯更换为单脂肪酸甘油酯，乳酸钠更换为乳酸钾，豆油更换为花生油；其余与实施例1一致；The sucrose ester of Example 1 was replaced with monoglyceride, sodium lactate was replaced with potassium lactate, and soybean oil was replaced with peanut oil; all the other were consistent with Example 1;
分别在反应1天、5天、10天、20天、30天进行取样检测，2组实验废水中六价铬含量见下表。Sampling and testing were carried out on 1 day, 5 days, 10 days, 20 days and 30 days of reaction respectively, and the content of hexavalent chromium in the two groups of experimental wastewater is shown in the following table.
表3不同反应时间六价铬含量Table 3 Hexavalent chromium content at different reaction times
实施例3：Example 3:
将实施例1的蔗糖酸酯更换为聚氧乙烯醚-20油酰蓖麻醇酸酯和硬脂酰乳酸钠，乳酸钠更换为乳酸钠和乳酸钾，豆油更换为玉米油和菜籽油；其余与实施例1一致；The sucrose ester of Example 1 was replaced with polyoxyethylene ether-20 oleoyl ricinoleate and sodium stearoyl lactylate, sodium lactate was replaced with sodium lactate and potassium lactate, and soybean oil was replaced with corn oil and rapeseed oil; Example 1 is consistent;
分别在反应1天、5天、10天、20天、30天进行取样检测，2组实验废水中六价铬含量见下表。Sampling and testing were carried out on 1 day, 5 days, 10 days, 20 days and 30 days of reaction respectively, and the content of hexavalent chromium in the two groups of experimental wastewater is shown in the following table.
表4不同反应时间六价铬含量Table 4 Hexavalent chromium content at different reaction times
同理，本发明将植物油替换为上述可选的植物油中的一种或多种，将食品级乳化剂替换为上述可选的乳化剂中的一种或多种，均可达到表2-4所得到的近似效果。同时，本发明也可按照上述组分配比适当调整各组分的添加量，可达到表2-4所得到的近似效果，故在此不一一列举。Similarly, the present invention replaces vegetable oil with one or more of the above-mentioned optional vegetable oils, and replaces the food-grade emulsifier with one or more of the above-mentioned optional emulsifiers, all of which can reach Table 2-4. obtained approximation. At the same time, the present invention can also appropriately adjust the addition amount of each component according to the above-mentioned component distribution ratio, and can achieve the approximate effects obtained in Tables 2-4, so it is not listed here.
进一步，基于上述强化生物厌氧修复技术原理，本发明强化生物修复药剂也适用于修复六价铀、五价钒、含氯有机物等污染土壤和地下水的强化厌氧修复。Further, based on the above-mentioned principles of enhanced biological anaerobic remediation technology, the enhanced biological remediation agent of the present invention is also suitable for enhanced anaerobic remediation of contaminated soil and groundwater such as hexavalent uranium, pentavalent vanadium, and chlorine-containing organic compounds.
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims (10)
- 一种用于铬污染场地的强化厌氧修复药剂，其特征在于，包括：An enhanced anaerobic repair agent for chromium-contaminated sites, comprising:植物油、乳化剂、甘油、乳酸盐、乳酸酯、维生素B12、磷酸二胺和水。Vegetable oil, emulsifier, glycerin, lactate, lactate, vitamin B12, diamine phosphate and water.
- 如权利要求1所述的强化厌氧修复药剂，其特征在于，按重量百分比计，包括：The enhanced anaerobic repair agent according to claim 1, characterized in that, by weight percentage, comprising:植物油50～70％、乳化剂8～12％、甘油0.5～2％、乳酸盐0.5～2％、乳酸酯0.5～2％、维生素B12 0.1～0.5％、磷酸二胺0.5～1％和余量水。Vegetable oil 50-70%, emulsifier 8-12%, glycerin 0.5-2%, lactate 0.5-2%, lactate 0.5-2%, vitamin B12 0.1-0.5%, phosphate diamine 0.5-1% and residual water.
- 如权利要求2所述的强化厌氧修复药剂，其特征在于，所述植物油与乳化剂的重量比为(5～6)：1。The enhanced anaerobic repair agent according to claim 2, wherein the weight ratio of the vegetable oil to the emulsifier is (5-6):1.
- 如权利要求2所述的强化厌氧修复药剂，其特征在于，按重量百分比计，包括：The enhanced anaerobic repair agent according to claim 2, characterized in that, by weight percentage, comprising:植物油60％、乳化剂10％、甘油1％、乳酸盐1％、乳酸酯1％、维生素B12 0.5％、磷酸二胺0.5％和水26％。Vegetable oil 60%, emulsifier 10%, glycerin 1%, lactate 1%, lactate 1%, vitamin B12 0.5%, phosphate diamine 0.5% and water 26%.
- 如权利要求1-4中任一项所述的强化厌氧修复药剂，其特征在于，所述植物油包括豆油、花生油、棕榈油、玉米油、菜籽油、棉籽油和葵花籽油中的一种或多种。The enhanced anaerobic repair agent according to any one of claims 1-4, wherein the vegetable oil comprises one of soybean oil, peanut oil, palm oil, corn oil, rapeseed oil, cottonseed oil and sunflower oil one or more.
- 如权利要求1-4中任一项所述的强化厌氧修复药剂，其特征在于，所述乳化剂包括食品级乳化剂，包括蔗糖酸酯、单脂肪酸甘油酯、聚氧乙烯醚-20油酰蓖麻醇酸酯、硬脂酰乳酸钠、大豆磷脂、聚甘油单月桂酸脂中的一种或多种。The enhanced anaerobic repair agent according to any one of claims 1-4, wherein the emulsifier comprises a food-grade emulsifier, including sucrose ester, monoglyceride, polyoxyethylene ether-20 oil One or more of acyl ricinoleate, sodium stearoyl lactylate, soybean lecithin, and polyglycerol monolaurate.
- 如权利要求1-4中任一项所述的强化厌氧修复药剂，其特征在于，所述乳酸盐包括乳酸钠、乳酸钾中的一种或多种，所述乳酸酯为乳酸乙酯。The enhanced anaerobic repair agent according to any one of claims 1-4, wherein the lactate comprises one or more of sodium lactate and potassium lactate, and the lactate is ethyl lactate .
- 一种如权利要求1-7中任一项所述的强化厌氧修复药剂的制备方法，其特征在于，包括：A preparation method for strengthening anaerobic repairing agent according to any one of claims 1-7, characterized in that, comprising:将乳化剂、甘油加入部分水中，受热溶解形成溶液A；Add the emulsifier and glycerin to part of the water, and dissolve by heating to form solution A;将乳酸盐、乳酸酯、维生素B12、磷酸二胺加入剩余部分水中，混合形成溶液B；Add lactate, lactate, vitamin B12, and phosphoric acid diamine into the remaining part of the water, and mix to form solution B;将植物油、溶液A和溶液B混合加入真空密封型高剪切乳化罐中，启动设备搅拌混合40-60分钟，搅拌速度2000-3000转/分钟，搅拌结束后静置20-40分钟出料。Mix vegetable oil, solution A and solution B into a vacuum-sealed high-shear emulsification tank, start the equipment and stir and mix for 40-60 minutes at a stirring speed of 2000-3000 r/min. After stirring, let stand for 20-40 minutes to discharge.
- 一种如权利要求1-7中任一项所述的强化厌氧修复药剂的使用方法， 其特征在于，包括：A method of using an enhanced anaerobic repair agent according to any one of claims 1-7, characterized in that, comprising:将6％-10％体积的强化厌氧修复药剂与90％-94％体积的含氢水混合后注入土壤或地下水。Mix 6%-10% volume of enhanced anaerobic remediation agent with 90%-94% volume of hydrogen-containing water and inject into soil or groundwater.
- 如权利要求9所述的使用方法，其特征在于，所述含氢水中氢气含量为0.0001％-0.0002％。The using method according to claim 9, wherein the hydrogen content in the hydrogen-containing water is 0.0001%-0.0002%.
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| CN109534517A (en) * | 2018-12-19 | 2019-03-29 | 北京高能时代环境修复有限公司 | Prosparol and its preparation method and application |
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| TWI511935B (en) * | 2010-04-30 | 2015-12-11 | Nat Univ Chung Hsing | A novel emulsion as a remedy for soil, groundwater, sediments, and other environmental matrices |
| CH706161A1 (en) * | 2012-03-15 | 2013-10-15 | Oti Greentech Group Ag | Oil recovery. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015013231A (en) * | 2013-07-03 | 2015-01-22 | オルガノ株式会社 | Method of purifying contaminated soil and contaminated ground water, purification promotion material and production method thereof |
| CN103978028A (en) * | 2014-05-05 | 2014-08-13 | 苏州市环境科学研究所 | Microbe stabilization solidification restoration method of chromium-contaminated soil |
| CN109365522A (en) * | 2018-12-10 | 2019-02-22 | 北京博诚立新环境科技股份有限公司 | A method of the reparation of contaminated soil anaerobic organism is carried out using bioreactor |
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| CN110076188A (en) * | 2019-04-03 | 2019-08-02 | 北京高能时代环境技术股份有限公司 | A kind of long-acting reparation medicament and restorative procedure of severe chromium-polluted soil |
| CN110305673A (en) * | 2019-07-04 | 2019-10-08 | 上海吾励环境技术有限公司 | Soil remediation agent for anaerobic microorganisms and application thereof |
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| CN112139233A (en) | 2020-12-29 |
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