CN110615540A - Degradation agent for removing phenol pollution of underground water, preparation method and application thereof - Google Patents
Degradation agent for removing phenol pollution of underground water, preparation method and application thereof Download PDFInfo
- Publication number
- CN110615540A CN110615540A CN201910781689.9A CN201910781689A CN110615540A CN 110615540 A CN110615540 A CN 110615540A CN 201910781689 A CN201910781689 A CN 201910781689A CN 110615540 A CN110615540 A CN 110615540A
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- CN
- China
- Prior art keywords
- phenol
- carbon quantum
- pillared montmorillonite
- degradation agent
- stirring
- 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.)
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 77
- 230000015556 catabolic process Effects 0.000 title claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000010936 titanium Substances 0.000 claims abstract description 54
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 54
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 241000191043 Rhodobacter sphaeroides Species 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 36
- 230000000593 degrading effect Effects 0.000 claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 33
- 238000000855 fermentation Methods 0.000 claims description 30
- 230000004151 fermentation Effects 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003673 groundwater Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000001963 growth medium Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 235000010413 sodium alginate Nutrition 0.000 claims description 7
- 239000000661 sodium alginate Substances 0.000 claims description 7
- 229940005550 sodium alginate Drugs 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000001954 sterilising effect Effects 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 241000191025 Rhodobacter Species 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 229940041514 candida albicans extract Drugs 0.000 claims description 3
- 238000012258 culturing Methods 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000012138 yeast extract Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000011081 inoculation Methods 0.000 claims description 2
- 229940116298 l- malic acid Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 244000177578 Bacterium linens Species 0.000 abstract description 12
- 235000012539 Bacterium linens Nutrition 0.000 abstract description 12
- 238000011068 loading method Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- -1 phenol compound Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- HVCOBJNICQPDBP-UHFFFAOYSA-N 3-[3-[3,5-dihydroxy-6-methyl-4-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid;hydrate Chemical class O.OC1C(OC(CC(=O)OC(CCCCCCC)CC(O)=O)CCCCCCC)OC(C)C(O)C1OC1C(O)C(O)C(O)C(C)O1 HVCOBJNICQPDBP-UHFFFAOYSA-N 0.000 description 5
- 239000003876 biosurfactant Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 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 description 4
- 229930186217 Glycolipid Natural products 0.000 description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005063 solubilization Methods 0.000 description 3
- 230000007928 solubilization Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007836 KH2PO4 Substances 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229960002685 biotin Drugs 0.000 description 2
- 235000020958 biotin Nutrition 0.000 description 2
- 239000011616 biotin Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000013923 monosodium glutamate Nutrition 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 229960003512 nicotinic acid Drugs 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229940073490 sodium glutamate Drugs 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 229960000344 thiamine hydrochloride Drugs 0.000 description 2
- 235000019190 thiamine hydrochloride Nutrition 0.000 description 2
- 239000011747 thiamine hydrochloride Substances 0.000 description 2
- 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 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000191023 Rhodobacter capsulatus Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008380 degradant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 229940099690 malic acid Drugs 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Biodiversity & Conservation Biology (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a phenol pollution degradation agent, in particular to a degradation agent for removing phenol pollution of underground water, a preparation method and application thereofA montmorillonite particle, wherein the rhodobacter sphaeroides strain is rhodopseudomonas sphaeroides; the adsorption capacity of the rhodobacter sphaeroides is 109～1010cells/100g carbon quantum dots are doped with titanium pillared montmorillonite particles. Phenol and monochromatic blue light irradiation are combined to domesticate spherical red bacteria to strengthen the phenol degrading effect of the spherical red bacteria, and the degrading agent formed by loading the spherical red bacteria into carbon quantum dot doped titanium pillared montmorillonite particles has an excellent adsorption effect on phenol, can completely degrade phenol with the concentration not higher than 10mg/L, and has a higher-level degradation effect on phenol with higher concentration.
Description
Technical Field
The invention relates to a phenol pollution degradation agent, in particular to a degradation agent for removing phenol pollution of underground water, a preparation method and application thereof.
Background
Phenolic compounds are widely used in the production of phenolic resins, insecticides, dyes, pesticides and pharmaceuticals as a basic raw material in the organic chemical industry. The phenolic compounds belong to organic pollutants with strong toxicity and are one of the main pollutants in the environment, and six phenolic pollutants, namely phenol, m-cresol, 2, 4-chlorophenol, 2,4, 6-chlorophenol, pentachlorophenol and p-nitrophenol, are listed in the blacklist of the water environment priority control pollution in China. The phenol compounds in the surface water mainly come from industrial wastewater of oil refining, gas washing, coking, paper making, synthetic ammonia, wood preservation, chemical industry and the like. The phenol compound has the simplest structure, the strongest toxicity and the biological toxicity, and if the phenol compound enters a human body, the phenol compound can cause 'three causes' -teratogenesis, carcinogenesis and mutagenicity. Phenol is widely applied to industries such as oil refining, coking, chemical industry, medicine and the like, and the pollution of soil, surface water and groundwater environment can be caused by the wide use of chemical raw materials containing phenol and the improper storage or nonstandard discharge of the chemical raw materials. Groundwater is an important source of water for drinking and irrigation, and the contamination of groundwater with phenol poses a great hazard to humans and crops. Therefore, the research on the economic and efficient underground water phenol degradation technology has very important significance.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention aims to provide a degrading agent for removing phenol pollution of underground water, a preparation method and application thereof, wherein phenol and monochromatic blue light irradiation are combined to domesticate spherical red bacteria to strengthen the phenol degrading effect of the spherical red bacteria, and the degrading agent formed by loading the spherical red bacteria into carbon quantum dot doped titanium pillared montmorillonite particles has an excellent adsorption effect on phenol, can completely degrade phenol with the concentration not higher than 10mg/L, and has a higher-level degradation effect on phenol with higher concentration.
The technical solutions adopted by the present invention to achieve the above objects include the following aspects.
In a first aspect of the application, a degradation agent for removing phenol pollution of underground water is provided, the degradation agent comprises carbon quantum dot doped titanium pillared montmorillonite particles adsorbed with spherical rhodobacter sphaeroides fermentation liquor,
wherein the rhodobacter sphaeroides strain is rhodopseudomonas sphaeroides;
the adsorption capacity of the rhodobacter sphaeroides is 109～1010cells/100g carbon quantum dots are doped with titanium pillared montmorillonite particles.
The utility model provides a spherical red bacterial fermentation liquid generates a class of glycolipid biosurfactant in fermentation degradation process, because it has stronger emulsification, solubilization, wetting and osmosis, not only improved its load and gone into the ability that carbon quantum dot mixes titanium pillared montmorillonite granule, still improved spherical red bacterial to phenol and other alkane compound's degradation efficiency, carbon quantum dot mixes titanium pillared montmorillonite granule and makes finally formed degradant have higher adsorption characteristic and further degradation characteristic to phenol, the concrete performance is: the phenol with the concentration not higher than 10mg/L can be completely degraded in an anoxic and even anaerobic and/or low-temperature environment, and the phenol degrading agent can be used for degrading phenol pollution under the anoxic and even anaerobic and/or low-temperature conditions of underground water; the phenol with the concentration higher than 10mg/L can be degraded and removed at a higher level under the low temperature and/or anoxic condition, and the phenol degrading agent can be used for degrading phenol pollution of underground water under the low temperature and/or anoxic condition; in addition, after the microorganism fermentation liquor is fixed by adopting an immobilization means, the degradation agent can play a role in buffering the change of the external environment, can provide a stable degradation environment, is more suitable for a toxic environment, treats groundwater phenol pollution with higher concentration, and prolongs the service time and the frequency of the degradation agent.
In a second aspect of the present application, there is provided a method for preparing the degradation agent for removing phenol contamination of groundwater according to the first aspect, comprising the steps of:
-preparing carbon quantum dot doped titanium pillared montmorillonite particles;
-obtaining a rhodobacter sphaeroides fermentation broth;
and doping titanium pillared montmorillonite particles with carbon quantum dots to adsorb the spherical rhodobacter bacteria liquid.
In the summary and the preferred embodiment of the application, the method for preparing the carbon quantum dot doped titanium pillared montmorillonite particles comprises the following steps:
1) weighing glucose solid and ethylenediamine into a proper amount of distilled water, uniformly stirring, reacting in a constant-temperature drying oven at 200-220 ℃ for 10-12 h, naturally cooling to room temperature, filtering the obtained solution with a 0.22 mu m filter membrane, dialyzing in distilled water environment for 2-5 d, and freeze-drying to obtain powdery carbon quantum dots;
2) mixing tetrabutyl titanate, glacial acetic acid and absolute ethyl alcohol uniformly to obtain a solution I; mixing 0.1mol/L hydrochloric acid and another absolute ethyl alcohol uniformly to obtain a solution II; dropping the solution II into the solution I at the speed of 1-2 drops/s while stirring, stopping dropping when yellow transparent sol appears, adding 0.8-1.0 mol/L sodium hydroxide solution, stirring uniformly, and standing to obtain a titanium pillaring agent;
3) slowly dripping a titanium pillaring agent into a sodium-based montmorillonite suspension with the mass concentration of 1% under the condition of stirring, continuously stirring for 6 hours at room temperature at 120-180 r/min, centrifugally filtering, and washing away Cl-Drying, grinding after drying, sieving with a 200-300 mesh sieve, grinding after high-temperature roasting, and repeatedly sieving to obtain the titanium pillared montmorillonite;
4) adding polyvinyl alcohol and sodium alginate into sufficient distilled water, stirring while heating, dissolving, adding titanium pillared montmorillonite and carbon quantum dots, stirring uniformly, stopping heating and stirring when the mixture in the cup is viscous, cooling to room temperature, and uniformly extruding the mixture into 2.5-2.8% CaCl by using an injection syringe2Preparing carbon quantum dot doped titanium pillared montmorillonite particles in the solution, soaking for 12h, washing with distilled water, filtering and drying to obtain the carbon quantum dot doped titanium pillared montmorillonite particles.
Further, the ratio of the glucose solid to the ethylenediamine in the step 1) is 1.6-1.8: 1(g: mL).
Further, the volume ratio of the tetrabutyl titanate, the glacial acetic acid, the absolute ethyl alcohol, the hydrochloric acid, the other absolute ethyl alcohol and the sodium hydroxide solution in the step 2) is 5:1:5:12:3: 4.
Further, the stirring in the step 2) is 120-180 r/min.
Further, the standing time in the step 2) is 6-8 h.
Further, the high-temperature roasting temperature in the step 3) is 320-350 ℃, and the roasting time is 3-5 hours.
Further, the weight ratio of the polyvinyl alcohol, the sodium alginate, the titanium pillared montmorillonite and the carbon quantum dots in the step 4) is 0.6-1: 1: 20-40: 0.03-0.05.
Further, the temperature in step 4) does not exceed 50 ℃ at the most.
The invention takes sodium-based montmorillonite as a matrix material and tetrabutyl titanate as a titanium source to prepare titanium pillared montmorillonite; then preparing carbon quantum dot doped titanium pillared montmorillonite particles from polyvinyl alcohol, sodium alginate, titanium pillared montmorillonite and powdery carbon quantum dots prepared from glucose and ethylenediamine according to a certain mass ratio, wherein the carbon quantum dot doped titanium pillared montmorillonite particles have an excellent adsorption effect on phenolic substances, particularly phenol, and can adsorb phenol in underground water and further degrade the phenol by spherical red bacteria fermentation liquor, so that the aim of removing phenol pollution of the underground water is fulfilled.
In the summary and preferred embodiment of the present application, the method for obtaining rhodobacter sphaeroides fermentation broth comprises the following steps:
1) inoculating 12-14% (m/m) of activated rhodobacter sphaeroides into an acclimatization culture medium containing 80-120 mg/L of phenol, irradiating with monochromatic blue light, and culturing and acclimatizing at 28-30 ℃ for 5-6 periods to obtain an acclimatized seed solution;
2) inoculating the domesticated seed solution into a fermentation culture medium in an inoculation amount of 8-10% (v/v), and performing shaking culture at 30-32 ℃ for 48-72 h at 120-200 r/min to obtain the rhodobacter sphaeroides fermentation liquor.
Further, the rhodobacter sphaeroides is rhodopseudomonas sphaeroides.
Further, the acclimatization cultureThe nutrient medium contains: 2.5-4.0 g/L malic acid, 1.0-1.2 g/L yeast extract, (NH)4)2SO41.5～1.8g/L、MgSO40.3～0.5g/L、CaCl20.1～0.15g/L、K2HPO41.0-1.5 g/L, 80-120 mg/L phenol, and the balance of distilled water, and sterilizing at 121 ℃ for 20min under natural pH.
Furthermore, the illumination intensity of the monochromatic blue light irradiation is 3500-4000 Lux, and the wavelength of the blue light is 420-465 nm.
Further, the fermentation medium contains: 35-40 g/L glucose, 3-5 g/L corn steep liquor dry powder, 2.5-2.8 g/L sodium glutamate, 2.3-2.5 g/L NaCl2, (NH)4)2SO43.0～3.5g/L、KH2PO43.0～3.5g/L，MgSO410.5-11.0 g/L, 2.5-3.0 mL/L auxiliary liquid, and the balance of distilled water; sterilizing at a temperature of 121 ℃ for 20min at a pH of 7.2-7.4.
Particularly further, the auxiliary liquid contains: 1.5g/L thiamine hydrochloride, 0.02g/L biotin, 1.5g/L nicotinic acid and the balance of distilled water.
According to the application, the domestication culture medium containing phenol and the monochromatic blue light irradiation are jointly domesticated, so that the spherical red bacteria can generate a glycolipid biosurfactant in the fermentation degradation process, and the glycolipid biosurfactant has stronger emulsification, solubilization, wetting and osmosis effects, so that the capacity of loading carbon quantum dots doped with titanium pillared montmorillonite particles is improved, the degradation efficiency of the spherical red bacteria on phenol and other alkane compounds is improved, the finally formed degradation agent, namely the carbon quantum dots doped titanium pillared montmorillonite particles with the spherical red bacteria has higher adsorption property and degradation property on phenol, the phenol with the concentration not higher than 10mg/L can be completely degraded under the anoxic condition or even the anaerobic condition, and the phenol can be used for degrading phenol pollution under the low-temperature condition of underground water; the phenol with the concentration not higher than 10mg/L can be completely degraded in a low-temperature environment, and the phenol degradation agent can be used for degrading phenol pollution under the low-temperature condition of underground water; can carry out higher-level degradation removal on phenol with the concentration higher than 10mg/L under low temperature and/or anoxic conditions, and can be used for degrading phenol pollution of underground water.
In the summary and preferred embodiments of the present application, the rhodobacter sphaeroides strain is rhodopseudomonas sphaeroides.
In the summary and the preferred embodiment of the present application, the adsorption amount of the rhodobacter sphaeroides is 109～1010cells/100g carbon quantum dots are doped with titanium pillared montmorillonite particles.
In a third aspect of the present application, there is provided the use of a degradation agent for removing phenol contamination of groundwater, the use comprising contacting the degradation agent with groundwater contaminated with phenol and removing phenol from the groundwater;
the degrading agent is any one of the degrading agents for removing phenol pollution of underground water described in the first aspect of the application or any one of the degrading agents prepared by any one of the methods described in the second aspect of the application.
The invention has the beneficial effects that:
1) the carbon quantum dot doped titanium pillared montmorillonite particles have excellent adsorption effect on phenols, particularly phenol, and can adsorb phenol in underground water and further degrade the phenol by spherical red bacterium fermentation liquor, so that the aim of removing phenol pollution of the underground water is fulfilled;
2) the carbon quantum dot doped titanium pillared montmorillonite particles also have the effect of adsorbing heavy metal ions, can further remove and degrade the heavy metal ions in the underground polluted water, and purify underground water resources;
3) the domestication culture medium containing phenol and the monochromatic blue light irradiation are jointly domesticated, so that the spherical red bacteria can generate a glycolipid biosurfactant in the fermentation degradation process, and the glycolipid biosurfactant has stronger emulsification, solubilization, wetting and penetration effects, so that the capacity of loading carbon quantum dot doped titanium column montmorillonite particles is improved, and the degradation efficiency of the spherical red bacteria on phenol and other alkane compounds is improved;
4) after the microorganism fermentation liquor is fixed by adopting an immobilization means, the degradation agent can buffer the change of the external environment, can provide a stable degradation environment, is more suitable for a toxic environment, treats groundwater phenol pollution with higher concentration, and prolongs the service time and the times of the degradation agent;
5) the degradation agent has higher adsorption property and degradation property to phenol, can completely degrade phenol with concentration not higher than 10mg/L under anoxic or even anaerobic condition, and can be used for degrading phenol pollution under underground water low-temperature condition; the phenol with the concentration not higher than 10mg/L can be completely degraded in a low-temperature environment, and the phenol degradation agent can be used for degrading phenol pollution under the low-temperature condition of underground water; can carry out higher-level degradation removal on phenol with the concentration higher than 10mg/L under low temperature and/or anoxic conditions, and can be used for degrading phenol pollution of underground water.
The invention adopts the technical scheme to provide the model essay, makes up the defects of the prior art, and has reasonable design and convenient operation.
Drawings
In order to make the aforementioned and other objects, features, and advantages of the invention, as well as others which will become apparent, reference is made to the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic diagram showing the degradation effect of the degradation agent of the present invention on water contaminated with 20mg/L phenol;
FIG. 2 is a schematic diagram showing the degradation effect of the degradation agent of the present invention on water contaminated with 10mg/L phenol.
Detailed Description
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The present invention uses the methods and materials described herein; other suitable methods and materials known in the art may be used. The materials, methods, and examples described herein are illustrative only and are not intended to be limiting. All publications, patent applications, patents, provisional applications, database entries, and other references mentioned herein, and the like, are incorporated by reference herein in their entirety. In case of conflict, the present specification, including definitions, will control.
Example 1:
first, the present example provides a degradation agent for removing phenol pollution from groundwater, the degradation agent comprises titanium-doped pillared montmorillonite particles with carbon quantum dots adsorbed with rhodobacter sphaeroides fermentation broth,
wherein the rhodobacter sphaeroides strain is rhodopseudomonas sphaeroides;
the adsorption capacity of the rhodobacter sphaeroides is 5 x 109cells/100g carbon quantum dots are doped with titanium pillared montmorillonite particles.
Secondly, the embodiment also provides a method for preparing the degradation agent for removing the phenol pollution of the groundwater, which comprises the following steps:
-preparing carbon quantum dot doped titanium pillared montmorillonite particles;
-obtaining a rhodobacter sphaeroides fermentation broth;
and doping titanium pillared montmorillonite particles with carbon quantum dots to adsorb the spherical rhodobacter bacteria liquid.
In the preferred embodiment, the method for preparing the carbon quantum dot doped titanium pillared montmorillonite particles comprises the following steps:
1) weighing glucose solid and ethylenediamine into a proper amount of distilled water, uniformly stirring, reacting in a constant-temperature drying oven at 202 ℃ for 10 hours, naturally cooling to room temperature, filtering the obtained solution with a 0.22 mu m filter membrane, dialyzing in a distilled water environment for 3 days, and freeze-drying to obtain powdery carbon quantum dots;
2) mixing tetrabutyl titanate, glacial acetic acid and absolute ethyl alcohol uniformly to obtain a solution I; mixing 0.1mol/L hydrochloric acid and another absolute ethyl alcohol uniformly to obtain a solution II; dropping the solution II into the solution I at the speed of 1 drop/s under stirring, stopping dropping when yellow transparent sol appears, adding 1mol/L sodium hydroxide solution, stirring uniformly, and standing to obtain a titanium pillaring agent;
3) slowly dripping a titanium pillaring agent into sodium-based montmorillonite suspension with the mass concentration of 1% under the condition of stirring, continuously stirring for 6 hours at room temperature at 120r/min, centrifugally filtering, and washing away Cl-Drying, grinding after drying, sieving with a 240-mesh sieve, grinding after high-temperature roasting, and repeatedly sieving to obtain the titanium pillared montmorillonite;
4) adding polyvinyl alcohol and sodium alginate into sufficient distilled water, heating while stirring, dissolving, adding titanium column montmorillonite and carbon quantum dots, stirring, stopping heating and stirring when the mixture in the cup is viscous,after cooling to room temperature, the mixture was uniformly extruded into 2.6% CaCl using a syringe2Preparing carbon quantum dot doped titanium pillared montmorillonite particles in the solution, soaking for 12h, washing with distilled water, filtering and drying to obtain the carbon quantum dot doped titanium pillared montmorillonite particles.
The method for preparing the carbon quantum dot doped titanium pillared montmorillonite particles further comprises the following limiting factors:
1) the ratio of glucose solids to ethylenediamine in step 1) is 1.6:1(g: mL);
2) the volume ratio of the tetrabutyl titanate, the glacial acetic acid, the absolute ethyl alcohol, the hydrochloric acid, the other absolute ethyl alcohol and the sodium hydroxide solution in the step 2) is 5:1:5:12:3: 4;
3) the stirring in the step 2) is 120 r/min;
4) the standing time in the step 2) is 6 h;
5) the high-temperature roasting temperature in the step 3) is 320 ℃, and the roasting time is 4 hours;
6) the weight ratio of the polyvinyl alcohol, the sodium alginate, the titanium pillared montmorillonite and the carbon quantum dots in the step 4) is 1:1:30: 0.05;
7) the temperature in step 4) does not exceed 50 ℃ at the most.
In the preferred embodiment, the method for obtaining rhodobacter sphaeroides fermentation broth comprises the following steps:
1) inoculating activated rhodobacter sphaeroides to an acclimatization culture medium containing 100mg/L phenol in an amount of 12% (m/m), irradiating with monochromatic blue light, and culturing and acclimatizing at 30 ℃ for 6 periods to obtain an acclimatized seed solution;
2) inoculating the domesticated seed solution into a fermentation culture medium with an inoculum size of 10% (v/v), and performing shake culture at 32 ℃ for 60h at 200r/min to obtain the rhodobacter sphaeroides fermentation liquor.
The method for obtaining the rhodobacter sphaeroides fermentation broth further comprises the following limiting factors:
1) the rhodobacter sphaeroides is rhodopseudomonas sphaeroides;
2) the acclimatization culture medium contains: malic acid 3g/L, yeast extract 1.2g/L, (NH)4)2SO41.6g/L、MgSO40.4g/L、CaCl20.12g/L、K2HPO41.2g/L, 100mg/L phenol, and the balance of distilled water, and sterilizing at 121 ℃ for 20min under natural pH;
3) the illumination intensity of the monochromatic blue light irradiation is 3800Lux, and the wavelength of the blue light is 450 nm;
4) the fermentation medium contains: 38g/L glucose, 4g/L corn steep liquor dry powder, 2.6g/L sodium glutamate, NaCl2.3g/L, (NH)4)2SO43.2g/L、KH2PO43.5g/L，MgSO411g/L, 3mL/L auxiliary liquid and the balance of distilled water; sterilizing at pH7.2 and 121 deg.C for 20 min;
5) the auxiliary liquid contains: 1.5g/L thiamine hydrochloride, 0.02g/L biotin, 1.5g/L nicotinic acid and the balance of distilled water.
In this preferred embodiment, the rhodobacter sphaeroides strain is rhodopseudomonas sphaeroides.
In the preferred embodiment, the amount of adsorbed rhodobacter sphaeroides is 5X 109cells/100g carbon quantum dots are doped with titanium pillared montmorillonite particles.
Thirdly, the embodiment also provides the application of the degradation agent for removing phenol pollution of underground water, wherein the application comprises the steps of contacting the degradation agent with the underground water polluted by phenol and removing the phenol in the underground water;
wherein, the degradation agent is the degradation agent for removing phenol pollution of groundwater described in the first part of this embodiment or the degradation agent prepared by the method described in the second part of this embodiment.
Comparative example 2:
the technical scheme of the degradation agent for removing phenol pollution of underground water is basically the same as that of the degradation agent in the embodiment 1, and the difference is that carbon quantum dots are not added when the carbon quantum dot doped titanium pillared montmorillonite particles are prepared in the comparative example 2.
Comparative example 3:
the technical scheme of the degradation agent for removing phenol pollution of underground water is basically the same as that of the embodiment 1, and the difference is that phenol is not added into the acclimation culture medium when the rhodobacter sphaeroides fermentation liquor is obtained in the comparative example 3.
Comparative example 4:
the technical scheme of the degradation agent for removing the phenol pollution of underground water is basically the same as that of the embodiment 1, and the difference is that white light with equal illumination intensity is used for replacing monochromatic blue light in the culture acclimation process when the spherical rhodobacter sphaeroides fermentation liquid is obtained in the comparative example 4.
Comparative example 5:
the technical scheme is basically the same as that of the embodiment 1, except that when the spherical rhodobacter sphaeroides fermentation broth is obtained in the comparative example 5, phenol is not added into the domestication culture medium, and monochromatic blue light is not irradiated in the culture domestication process, but white light with equal illumination intensity is used for replacing the monochromatic blue light.
Comparative example 6:
the technical scheme of the degradation agent for removing phenol pollution of underground water is basically the same as that of the degradation agent in the embodiment 1, and the difference is that rhodopseudomonas capsulata is used for replacing rhodopseudomonas sphaeroides when rhodobacter sphaeroides fermentation liquor is obtained in the comparative example 6.
Experimental example 1: degradation detection of the degradation agent with different technical schemes on the polluted water containing 20mg/L phenol:
testing water containing 20mg/L of phenol is prepared, a degradation agent is added according to the amount of 10g/L of the testing water, the degradation effect of the degradation agent on the phenol in different technical schemes of example 1 and comparative examples 2-6 is tested respectively, and the statistical result is shown in figure 1. As can be seen from the graph of FIG. 1, the degradation agent in example 1 of the preferred embodiment of the present application can achieve a phenol degradation rate of 80% or more at 6 hours, and it can be seen that the degradation agent of the present application performs a higher level of degradation removal on phenol with a concentration higher than 10 mg/L.
Experimental example 2: degradation detection of the degradation agent with different technical schemes on the polluted water containing 10mg/L phenol:
the test in experimental example 1 was diluted with water to a phenol concentration of 10mg/L, the degradation effect of the degradation agents of the different technical solutions of example 1 and comparative examples 2-6 on lower concentration phenol was tested according to the method of experimental example 1, and the statistical result is shown in fig. 2. As can be seen from the graph of FIG. 2, the degradation agent of example 1 in the preferred embodiment of the present application can complete the degradation of phenol-contaminated water of 10mg/L within 3 hours, indicating that the degradation agent for removing phenol contamination of groundwater of the present application can be used for the degradation of phenol contamination of groundwater.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
While the above detailed description has shown, described, and pointed out novel features as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or method illustrated may be made without departing from the spirit of the disclosure. In addition, the various features and methods described above may be used independently of one another, or may be combined in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure. Many of the embodiments described above include similar components, and thus, these similar components are interchangeable in different embodiments. While the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosure of preferred embodiments herein.
Claims (10)
1. A degradation agent for removing phenol pollution of underground water is characterized in that the degradation agent comprises titanium pillared montmorillonite particles which are doped with carbon quantum dots of spherical rhodobacter fermentation liquor,
wherein the rhodobacter sphaeroides strain is rhodopseudomonas sphaeroides;
the adsorption capacity of the rhodobacter sphaeroides is 109～1010cells/100g carbon quantum dots are doped with titanium pillared montmorillonite particles.
2. A method for preparing the degradation agent for removing phenol pollution of groundwater according to claim 1, characterized by comprising the steps of:
-preparing carbon quantum dot doped titanium pillared montmorillonite particles;
-obtaining a rhodobacter sphaeroides fermentation broth;
and doping titanium pillared montmorillonite particles with carbon quantum dots to adsorb the spherical rhodobacter bacteria liquid.
3. The method of claim 2, wherein: the method for preparing the carbon quantum dot doped titanium pillared montmorillonite particles comprises the following steps of:
1) weighing glucose solid and ethylenediamine into a proper amount of distilled water, uniformly stirring, reacting in a constant-temperature drying oven at 200-220 ℃ for 10-12 h, naturally cooling to room temperature, filtering the obtained solution with a 0.22 mu m filter membrane, dialyzing in distilled water environment for 2-5 d, and freeze-drying to obtain powdery carbon quantum dots;
2) mixing tetrabutyl titanate, glacial acetic acid and absolute ethyl alcohol uniformly to obtain a solution I; mixing 0.1mol/L hydrochloric acid and another absolute ethyl alcohol uniformly to obtain a solution II; dropping the solution II into the solution I at the speed of 1-2 drops/s while stirring, stopping dropping when yellow transparent sol appears, adding 0.8-1.0 mol/L sodium hydroxide solution, stirring uniformly, and standing to obtain a titanium pillaring agent;
3) slowly dripping a titanium pillaring agent into a sodium-based montmorillonite suspension with the mass concentration of 1% under the condition of stirring, continuously stirring for 6 hours at room temperature at 120-180 r/min, centrifugally filtering, and washing away Cl-Drying, grinding after drying, sieving with a 200-300 mesh sieve, grinding after high-temperature roasting, and repeatedly sieving to obtain the titanium pillared montmorillonite;
4) adding polyvinyl alcohol and sodium alginate into sufficient distilled water, stirring while heating, dissolving, adding titanium pillared montmorillonite and carbon quantum dots, stirring uniformly, stopping heating and stirring when the mixture in the cup is viscous, cooling to room temperature, and uniformly extruding the mixture into 2.5-2.8% CaCl by using an injection syringe2Preparing carbon quantum dot doped titanium pillared montmorillonite particles in the solution, soaking for 12h, washing with distilled water, filtering and drying to obtain the carbon quantum dot doped titanium pillared montmorillonite particles.
4. The method of claim 3, wherein: the volume ratio of the tetrabutyl titanate, the glacial acetic acid, the absolute ethyl alcohol, the hydrochloric acid, the other absolute ethyl alcohol and the sodium hydroxide solution in the step 2) is 5:1:5:12:3: 4.
5. The method of claim 3, wherein: the high-temperature roasting temperature in the step 3) is 320-350 ℃, and the roasting time is 3-5 h.
6. The method of claim 3, wherein: the weight ratio of the polyvinyl alcohol, the sodium alginate, the titanium pillared montmorillonite and the carbon quantum dots in the step 4) is 0.6-1: 1: 20-40: 0.03-0.05.
7. The method of claim 2, wherein: the method for obtaining the rhodobacter sphaeroides fermentation liquid comprises the following steps:
1) inoculating 12-14% (m/m) of activated rhodobacter sphaeroides into an acclimatization culture medium containing 80-120 mg/L of phenol, irradiating with monochromatic blue light, and culturing and acclimatizing at 28-30 ℃ for 5-6 periods to obtain an acclimatized seed solution;
2) inoculating the domesticated seed solution into a fermentation culture medium in an inoculation amount of 8-10% (v/v), and performing shaking culture at 30-32 ℃ for 48-72 h at 120-200 r/min to obtain the rhodobacter sphaeroides fermentation liquor.
8. The method of claim 7, wherein: the acclimatization culture medium contains: 2.5-4.0 g/L malic acid, 1.0-1.2 g/L yeast extract, (NH)4)2SO41.5～1.8g/L、MgSO40.3～0.5g/L、CaCl20.1～0.15g/L、K2HPO41.0-1.5 g/L, 80-120 mg/L phenol, and the balance of distilled water, and sterilizing at 121 ℃ for 20min under natural pH.
9. The method of claim 7, wherein: the illumination intensity of the monochromatic blue light irradiation is 3500-4000 Lux, and the wavelength of the blue light is 420-465 nm.
10. The application of the degradation agent for removing the phenol pollution of the underground water is characterized in that
The application comprises contacting the degrading agent with groundwater contaminated with phenol and removing phenol from the groundwater;
the degradation agent is the degradation agent for removing phenol pollution of underground water according to claim 1 or the degradation agent prepared by the method according to any one of claims 2 to 9.
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