CN116889879A - Composition for catalytic degradation of terramycin and preparation method thereof - Google Patents
Composition for catalytic degradation of terramycin and preparation method thereof Download PDFInfo
- Publication number
- CN116889879A CN116889879A CN202310852229.7A CN202310852229A CN116889879A CN 116889879 A CN116889879 A CN 116889879A CN 202310852229 A CN202310852229 A CN 202310852229A CN 116889879 A CN116889879 A CN 116889879A
- Authority
- CN
- China
- Prior art keywords
- biochar
- parts
- composition
- stirring
- catalytic degradation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000015556 catabolic process Effects 0.000 title claims abstract description 33
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 30
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 title claims abstract description 17
- 229940063650 terramycin Drugs 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 16
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000000084 colloidal system Substances 0.000 claims abstract description 8
- 229920005615 natural polymer Polymers 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 44
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 42
- 239000004100 Oxytetracycline Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 34
- 229960000625 oxytetracycline Drugs 0.000 claims description 34
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 claims description 34
- 235000019366 oxytetracycline Nutrition 0.000 claims description 34
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims description 28
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 229960000583 acetic acid Drugs 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 239000012362 glacial acetic acid Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical group [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 241001070941 Castanea Species 0.000 claims description 10
- 235000014036 Castanea Nutrition 0.000 claims description 10
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 235000010489 acacia gum Nutrition 0.000 claims description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 241000416162 Astragalus gummifer Species 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 240000007472 Leucaena leucocephala Species 0.000 claims description 2
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 2
- 229920001615 Tragacanth Polymers 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 229940079101 sodium sulfide Drugs 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000196 tragacanth Substances 0.000 claims description 2
- 235000010487 tragacanth Nutrition 0.000 claims description 2
- 229940116362 tragacanth Drugs 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003242 anti bacterial agent Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229940088710 antibiotic agent Drugs 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 2
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000022 bacteriostatic agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002509 fulvic acid Substances 0.000 description 2
- 229940095100 fulvic acid Drugs 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241000187419 Streptomyces rimosus Species 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000001775 anti-pathogenic effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 210000003763 chloroplast Anatomy 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 231100000024 genotoxic Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012009 microbiological test Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000041 toxicology testing Toxicity 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of catalytic oxidation, in particular to a composition for catalytic degradation of terramycin and a preparation method thereof. The composition for the catalytic degradation of terramycin comprises the following raw materials in parts by weight: 5-15 parts of chemical modified biochar, 15-45 parts of ferrous salt, 10-30 parts of metal sulfide, 5-15 parts of natural polymer colloid, 4-8 parts of tin-based metal carbide or titanium-based metal carbide and 1-2 parts of polyethyleneimine. According to the composition for the catalytic degradation of terramycin, which is prepared by the invention, the biochar is acetylated to enable the biochar to be loaded with more active functional groups, so that the capacity of oxidative degradation of OTC by H2O2 is improved. The prepared composition for the catalytic degradation of terramycin has the advantages that the biochar is loaded with tin-based and titanium-based metal substances, the oxidative degradation capacity of H2O2 in low-concentration OTC can be obviously enhanced, and the oxidative degradation capacity of H2O2 in high-concentration OTC can be further improved.
Description
Technical Field
The invention relates to the technical field of catalytic oxidation, in particular to a composition for catalytic degradation of terramycin and a preparation method thereof.
Background
Oxytetracycline (OTC) is a broad-spectrum antibiotic synthesized by streptomyces rimosus itself, has broad-spectrum anti-pathogenic microorganism effect, is a fast bacteriostatic agent, and has bactericidal effect on certain bacteria at high concentration. The characteristics of low cost, wide application range and the like are widely used as antibacterial and bacteriostatic agents, feed additives, growth factors and the like in the pharmaceutical treatment, animal husbandry, agriculture and aquaculture. With the wide range of production and use of oxytetracycline, the amount and dependence of human oxytetracycline on day increases. However, due to the structural characteristics and special properties of oxytetracycline, oxytetracycline in sewage cannot be effectively removed by conventional sewage treatment processes, and the oxytetracycline finally enters the human body through a food chain to influence human health. Toxicity studies report that antibiotics in water cause resistance and are toxic to many microorganisms. In addition, a large number of experimental results show that the microorganism can produce toxic effects when being contacted with antibiotics for a long time. Studies on the toxic effects of antibiotics clearly show that antibiotics are potentially genotoxic agents, which have been demonstrated by animal and microbiological tests. Antibiotics also typically inhibit chloroplast formation, chlorophyll production, and protein synthesis, thereby adversely affecting photosynthetic capacity of microalgae, proliferation and growth of cells. The main methods for removing antibiotics currently include the following: adsorption, oxidation, membrane separation, biodegradation, etc. The oxidation method is to generate high-activity free radicals in a system by using light, electricity, ultrasonic waves, an oxidant and the like, and then remove organic pollutants through the free radicals. The advanced oxidation technology mainly comprises a Fenton oxidation method, an ozone oxidation method, a photochemical oxidation method (photocatalysis method), an electrochemical oxidation method, an ultrasonic oxidation method, a catalytic wet oxidation method and the like. The advanced oxidation technology has a plurality of characteristics of (1) good oxidation effect, high efficiency and high reaction speed; (2) the reaction condition is easy to control, and the stability is good; (3) Has wide application range and can be used for treating various pollutantsThe removing effect is good; (4) Can be used in combination with other procedures to improve this effect and reduce costs; and (5) the operation is simple and easy to manage. Wherein the ozone oxidation is to add O into the sewage and wastewater 3 By O 3 The strong oxidizing property of (a) causes the cleavage of certain functional groups of the antibiotic, thereby performing degradation oxidation and removal. Electrochemical oxidation is the oxidation of antibiotics by electrolytically generated hydroxyl groups, ozone and other oxidizing functionalities, or the removal of antibiotics directly by electrode reactions. Fenton oxidation is carried out by H 2 O 2 With Fe 2+ Hydroxyl radicals (-OH) and other highly reactive oxygen species generated by the combined system degrade and remove the antibody. The catalyst is a key factor in determining the Fenton oxidation effect. Biochar shows incomparable advantages as a catalyst due to its rich oxygen-containing functional groups, persistent free radicals and low cost.
Biochar (biochar) refers to solid substances generated by pyrolysis of biomass materials in a high-temperature environment, and has the characteristics of stable structure, complex pore structure, large specific surface area, high oxygen-containing active group degree and the like, has good adsorption capacity on heavy metals, organic pollutants and ammonia nitrogen pollutants in environments such as water, soil and the like, is simple in manufacturing method, and is commonly used for removing pollutants in natural environments. At present, the method for preparing the biochar mainly comprises high-temperature pyrolysis, wherein in the high-temperature pyrolysis process, a biomass material is dried and dehydrated at the temperature of 0-200 ℃, chemical bonds in the biomass material are changed in the temperature range of 200-400 ℃, lignin and cellulose are continuously decomposed, amorphous carbon is further formed, and more carbon materials with aromatic ring structures are generated along with the further increase of the temperature (> 400 ℃). The characteristics of the biochar include rich functional groups, developed pores and various components, and various pollutants in the environment are removed by using the biochar as an adsorbent. At present, researchers at home and abroad repair and improve the environment by using biochar as an adsorption material. However, the activated performance of biochar is limited, and it is necessary to modify biochar. Common modification methods of the biochar at present comprise physical modification, chemical modification and biological modification. The chemical modification method is one of the common methods for researchers, and the chemical modification refers to the modification of the physicochemical properties of the biochar material by adding some acid-base or redox reagents, so as to improve the pollutant removal capability of the biochar.
Based on the above circumstances, the invention provides a composition for catalytic degradation of oxytetracycline and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a composition for catalytic degradation of terramycin and a preparation method thereof.
In order to achieve the above purpose, the invention provides a composition for the catalytic degradation of terramycin, which consists of the following raw materials in parts by weight: 5-15 parts of chemical modified biochar, 15-45 parts of ferrous salt, 10-30 parts of metal sulfide, 5-15 parts of natural polymer colloid, 4-8 parts of tin-based metal carbide or titanium-based metal carbide and 1-2 parts of polyethyleneimine.
The invention also provides a preparation method of the composition for the catalytic degradation of terramycin, which comprises the following steps:
(1) Ferrous salt is mixed according to the mass-liquid ratio of 1g: mixing 0.5L with water, adding natural polymer colloid under stirring at 200-300 rpm, adding chemical modified biochar after mixing uniformly, and finally adding metal sulfide solution at the rate of 2-3 drops per second, wherein the metal sulfide is prepared by the following steps of: mixing 20ml of the solution with water, continuously stirring for 3 hours after the metal sulfide solution is added dropwise, completing the whole process in nitrogen atmosphere, standing for 10-12 hours after stirring, and drying to obtain the biochar carrying the metal sulfide;
(2) Tin-based metal carbide or titanium-based metal carbide and absolute ethyl alcohol are mixed according to a mass-liquid ratio of 1g: 50-55 ml of the mixture is uniformly mixed and stirred, then biochar of metal sulfide is added, stirring is carried out for 30-35 min at 30-40 ℃ in the protection atmosphere of nitrogen, then polyethyleneimine is added, stirring is continuously carried out for 2-2.5 h at 60-70 ℃, suction filtration is carried out, washing is carried out for three times by deionized water, and vacuum freeze drying is carried out for 10-12 h, thus obtaining the catalyst.
Preferably, the ferrous salt comprises one of ferrous oxide, ferrous hydroxide, ferrous sulfate, and ferrous chloride. In one embodiment, the ferrous salt is ferrous sulfate heptahydrate.
Preferably, the metal sulfide includes one of sodium sulfide and potassium sulfide. In one embodiment, the metal sulfide is sodium sulfide nonahydrate.
Preferably, the chemically modified biochar comprises one of acidified biochar, alkalized biochar, acetylated biochar, oxidized biochar. In one embodiment, the chemically modified biochar is an acetylated biochar.
Preferably, the acetylated biochar is prepared by the following method:
(1) Crushing the cleaned and dried chestnut shells by using a crusher, passing through 40 meshes, then placing the chestnut shells in a protective atmosphere of nitrogen in a tube furnace, heating to a set temperature at 10 ℃/min < -1 > for pyrolysis, preserving heat for 2.0-2.5 h after the set temperature is reached, setting the temperature to 700-750 ℃, and cooling to room temperature to obtain a biochar precursor;
(2) Taking a biochar precursor according to the mass-liquid ratio of 1g: 10-12 ml of mixed solution of glacial acetic acid/acetic anhydride is added, and the volume ratio of glacial acetic acid to acetic anhydride is 1:1, after fully swelling for 30-40 min, adding 2% sulfuric acid according to the mass-liquid ratio of 1:0.5-0.8 ml with the biochar precursor, stirring and refluxing for reaction for 5-6 h, then carrying out suction filtration, washing with deionized water to be neutral, and drying in an oven at 65+/-5 ℃ until the weight is constant, thus obtaining the acetylated biochar.
Preferably, the tin-based metal carbide or titanium-based metal carbide is tin titanium carbide, the chemical formula is Ti 2 SnC, wherein the grain diameter of the tin titanium carbide is 200-300 meshes, and the purity is more than or equal to 98%.
Preferably, the natural polymer colloid comprises one of acacia, tragacanth, xanthan gum and guar gum. In one embodiment, the natural polymeric colloid is acacia gum.
Preferably, the composition for the catalytic degradation of oxytetracycline consists of the following raw materials in parts by weight: 5-15 parts of acetylated biochar, 15-45 parts of ferrous sulfate heptahydrate, 10-30 parts of sodium sulfide nonahydrate, 5-15 parts of Arabic gum, 4-8 parts of tin titanium carbide and 1-2 parts of polyethyleneimine.
Preferably, the preparation method of the composition for the catalytic degradation of oxytetracycline comprises the following steps:
(1) Crushing the cleaned and dried chestnut shells by using a crusher, sieving with 40 meshes, and placing in a tube furnace under the protection atmosphere of nitrogen at a speed of 10 ℃/min -1 Heating to a set temperature for pyrolysis, preserving heat for 2.0-2.5 h after reaching the set temperature, setting the temperature to 700-750 ℃, and cooling to room temperature to obtain a biochar precursor;
(2) Taking a biochar precursor according to the mass-liquid ratio of 1g: 10-12 ml of mixed solution of glacial acetic acid/acetic anhydride is added, and the volume ratio of glacial acetic acid to acetic anhydride is 1:1, after fully swelling for 30-40 min, adding 2% sulfuric acid according to the mass-liquid ratio of 1:0.5-0.8 ml with the biochar precursor, stirring and refluxing for reaction for 5-6 h, then carrying out suction filtration, washing with deionized water to be neutral, and drying in a drying oven at 65+/-5 ℃ until the weight is constant, thus obtaining the acetylated biochar;
(3) Ferrous sulfate heptahydrate is prepared according to a mass-to-liquid ratio of 1g: mixing 0.5L with water, adding Arabic gum under stirring at 200-300 rpm, adding acetylated biochar after uniformly mixing, and finally adding sodium sulfide nonahydrate solution at a rate of 2-3 drops per second, wherein the sodium sulfide nonahydrate solution is prepared by mixing sodium sulfide nonahydrate with 1g of sodium sulfide nonahydrate according to a mass-liquid ratio of 1g: mixing 20ml of the solution with water, continuously stirring for 3 hours after the sodium sulfide nonahydrate solution is added dropwise, completing the whole process in nitrogen atmosphere, standing for 10-12 hours after stirring is finished, and drying to obtain the biochar carrying ferrous sulfide;
(4) Tin titanium carbide and absolute ethyl alcohol are mixed according to the mass-liquid ratio of 1g: 50-55 ml of the raw materials are mixed and stirred uniformly, then biochar carrying ferrous sulfide is added, stirring is carried out for 30-35 min at 30-40 ℃ in a nitrogen protection atmosphere, then polyethyleneimine is added, stirring is carried out continuously for 2-2.5 h at 60-70 ℃, suction filtration is carried out, washing is carried out for three times by deionized water, and vacuum freeze drying is carried out for 10-12 h, thus obtaining the product.
Compared with the prior art, the invention has the following beneficial effects:
1. the composition for terramycin catalytic degradation prepared by the invention can load more active functional groups by acetylating the biochar, thereby improving H 2 O 2 Oxidative degradation ability of OTC.
2. The prepared composition for the catalytic degradation of terramycin has the advantages that the biochar is loaded with tin-based and titanium-based metal substances at the same time, and the H in the low-concentration OTC can be obviously enhanced 2 O 2 Oxidative degradation ability and further improvement of H at high concentration of OTC 2 O 2 Oxidative degradation capability.
3. The raw materials of the invention are abundant in China and have proper price, so that the large-scale production of the invention has no high cost limit; meanwhile, the composition for the catalytic degradation of terramycin is simple, has low overall production cost, and is beneficial to industrial mass production.
Detailed Description
Example 1
The specific raw materials are weighed according to table 1, and the preparation steps are as follows:
(1) Crushing the cleaned and dried chestnut shells by using a crusher, sieving with 40 meshes, and placing in a tube furnace under the protection atmosphere of nitrogen at a speed of 10 ℃/min -1 Heating to a set temperature for pyrolysis, preserving heat for 2.0h after reaching the set temperature, setting the temperature to 750 ℃, and cooling to room temperature to obtain a biochar precursor;
(2) Taking a biochar precursor according to the mass-liquid ratio of 1g:10ml of a mixed solution of glacial acetic acid/acetic anhydride was added, the volume ratio of glacial acetic acid to acetic anhydride being 1:1, after fully swelling for 30min, adding 2% sulfuric acid according to the mass-liquid ratio of 1:0.5ml with the biochar precursor, stirring and refluxing for reaction for 5h, then carrying out suction filtration, washing with deionized water to be neutral, and drying in a drying oven at 65+/-5 ℃ to constant weight to obtain the acetylated biochar;
(3) Ferrous sulfate heptahydrate is prepared according to a mass-to-liquid ratio of 1g: mixing 0.5L with water, adding Arabic gum under stirring at 200rpm, adding acetylated biochar after uniformly mixing, and finally adding sodium sulfide nonahydrate solution at a rate of 2-3 drops per second, wherein the sodium sulfide nonahydrate solution is prepared by mixing sodium sulfide nonahydrate with 1g of sodium sulfide nonahydrate according to a mass-liquid ratio of 1g: mixing 20ml of the solution with water, continuously stirring for 3 hours after the sodium sulfide nonahydrate solution is added dropwise, completing the whole process in nitrogen atmosphere, standing for 10 hours after stirring is finished, and drying to obtain the biochar carrying ferrous sulfide;
(4) Tin titanium carbide and absolute ethyl alcohol are mixed according to the mass-liquid ratio of 1g:50ml of the mixture is mixed and stirred uniformly, then biochar carrying ferrous sulfide is added, stirring is carried out for 35min at 30 ℃ in a nitrogen protection atmosphere, then polyethylenimine is added, stirring is carried out for 2.5h at 60 ℃, suction filtration is carried out, washing is carried out for three times by deionized water, and vacuum freeze drying is carried out for 10h, thus obtaining the product.
Example 2
The specific raw materials are weighed according to table 1, and the preparation steps are as follows:
(1) Crushing the cleaned and dried chestnut shells by using a crusher, sieving with 40 meshes, and placing in a tube furnace under the protection atmosphere of nitrogen at a speed of 10 ℃/min -1 Heating to a set temperature for pyrolysis, preserving heat for 2.5h after reaching the set temperature, setting the temperature to 700 ℃, and cooling to room temperature to obtain a biochar precursor;
(2) Taking a biochar precursor according to the mass-liquid ratio of 1g:12ml of a mixed solution of glacial acetic acid/acetic anhydride was added, the volume ratio of glacial acetic acid to acetic anhydride being 1:1, after fully swelling for 40min, adding 2% sulfuric acid according to the mass-liquid ratio of 1:0.8ml with the biochar precursor, stirring and refluxing for reaction for 6h, then carrying out suction filtration, washing with deionized water to be neutral, and drying in a drying oven at 65+/-5 ℃ to constant weight to obtain the acetylated biochar;
(3) Ferrous sulfate heptahydrate is prepared according to a mass-to-liquid ratio of 1g: mixing 0.5L with water, adding Arabic gum under stirring at 300rpm, adding acetylated biochar after uniformly mixing, and finally adding sodium sulfide nonahydrate solution at a rate of 2-3 drops per second, wherein the sodium sulfide nonahydrate solution is prepared by mixing sodium sulfide nonahydrate with 1g of sodium sulfide nonahydrate according to a mass-liquid ratio of 1g: mixing 20ml of the solution with water, continuously stirring for 3 hours after the sodium sulfide nonahydrate solution is added dropwise, completing the whole process in nitrogen atmosphere, standing for 12 hours after stirring is finished, and drying to obtain the biochar carrying ferrous sulfide;
(4) Tin titanium carbide and absolute ethyl alcohol are mixed according to the mass-liquid ratio of 1g: mixing 55ml, stirring uniformly, adding biochar carrying ferrous sulfide, stirring at 40 ℃ for 30min in a nitrogen protection atmosphere, adding polyethylenimine, stirring at 70 ℃ continuously for 2h, filtering, washing with deionized water for three times, and vacuum freeze-drying for 12 h.
Example 3
The specific raw materials are weighed according to table 1, and the preparation steps are as follows:
(1) Crushing the cleaned and dried chestnut shells by using a crusher, sieving with 40 meshes, and placing in a tube furnace under the protection atmosphere of nitrogen at a speed of 10 ℃/min -1 Heating to a set temperature for pyrolysis, preserving heat for 2.5h after reaching the set temperature, setting the temperature to 750 ℃, and cooling to room temperature to obtain a biochar precursor;
(2) Taking a biochar precursor according to the mass-liquid ratio of 1g:12ml of a mixed solution of glacial acetic acid/acetic anhydride was added, the volume ratio of glacial acetic acid to acetic anhydride being 1:1, after fully swelling for 40min, adding 2% sulfuric acid according to the mass-liquid ratio of 1:0.8ml with the biochar precursor, stirring and refluxing for reaction for 6h, then carrying out suction filtration, washing with deionized water to be neutral, and drying in a drying oven at 65+/-5 ℃ to constant weight to obtain the acetylated biochar;
(3) Ferrous sulfate heptahydrate is prepared according to a mass-to-liquid ratio of 1g: mixing 0.5L with water, adding Arabic gum under stirring at 300rpm, adding acetylated biochar after uniformly mixing, and finally adding sodium sulfide nonahydrate solution at a rate of 2-3 drops per second, wherein the sodium sulfide nonahydrate solution is prepared by mixing sodium sulfide nonahydrate with 1g of sodium sulfide nonahydrate according to a mass-liquid ratio of 1g: mixing 20ml of the solution with water, continuously stirring for 3 hours after the sodium sulfide nonahydrate solution is added dropwise, completing the whole process in nitrogen atmosphere, standing for 12 hours after stirring is finished, and drying to obtain the biochar carrying ferrous sulfide;
(4) Tin titanium carbide and absolute ethyl alcohol are mixed according to the mass-liquid ratio of 1g: mixing 55ml, stirring uniformly, adding biochar carrying ferrous sulfide, stirring at 40 ℃ for 35min in a nitrogen protection atmosphere, adding polyethylenimine, stirring at 70 ℃ continuously for 2.5h, filtering, washing with deionized water for three times, and vacuum freeze-drying for 12 h.
Comparative example 1
Specific raw materials were weighed according to Table 1, except that titanium dioxide was used instead of tin titanium carbide, and the remaining preparation steps were the same as in example 3.
Comparative example 2
Specific raw materials were weighed according to table 1, except that tin dioxide was used instead of tin titanium carbide, and the rest of the preparation procedure was the same as in example 3.
Comparative example 3
Specific raw materials were weighed according to table 1, except that a mixture of tin dioxide and titanium dioxide was used instead of tin titanium carbide, wherein the mass ratio of tin dioxide to titanium dioxide was 2:6, and the rest of the preparation steps were the same as in example 3.
Comparative example 4
Specific raw materials were weighed according to Table 1, except that H was used in example 3 2 O 2 The oxidized biochar replaces the acetylated biochar, wherein the step (2): mixing the prepared biochar precursor with 30% H at a mass-liquid ratio of 5g to 40ml 2 O 2 Mixing, reacting for 8 hours in dark condition, filtering, and flushing with deionized water three times. Drying in oven at 80deg.C for 24 hr, and storing in sealed bag to obtain H 2 O 2 And (5) oxidizing the biochar. The remaining preparation steps were the same as in example 3.
Comparative example 5
Specific raw materials were weighed according to table 1, except that hydrochloric acid activated biochar was used instead of acetylated biochar, in which step (2) was: adding 1mol/L HCl solution into the prepared biochar precursor for immersing, fully mixing for 24 hours, and then flushing with deionized water for three times. Drying in an oven at 80 ℃ for 24 hours, and storing in a sealed bag for standby, namely the hydrochloric acid activated biochar. The remaining preparation steps were the same as in example 3.
Comparative example 6
Specific raw materials were weighed according to table 1, except that sodium hydroxide activated biochar was used instead of acetylated biochar, in which step (2): in order to immerse the prepared biochar precursor, 1mol/L NaOH solution is added, and after fully mixing for 24 hours, deionized water is used for flushing three times. Drying in an oven at 80 ℃ for 24 hours, and storing in a sealed bag for standby, namely the sodium hydroxide activated biochar. The remaining preparation steps were the same as in example 3.
TABLE 1
Evaluation of Performance
10mg of each of examples 1 to 3 and comparative examples 1 to 5 was weighed into a 100mL wide-mouth conical flask, and 30mL of OTC solution having a concentration of 50, 100, 200, 300, 400mg/L was added thereto. At ph=3, 0.050mL H was added 2 O 2 Standing at room temperature for 3h. After the reaction is completed, the solution is filtered, and the OTC content in the filtrate is measured by an ultraviolet spectrophotometer. Each treatment was repeated 3 times. Wherein, OTC removal rate%: k= (C 0 -C e )/C 0 X 100%; wherein: k (%) is the OTC removal rate; c (C) 0 (mg/L) is the initial concentration of OTC; c (C) e (mg/L) is the concentration of OTC in the system after the reaction. The specific results are shown in Table 2.
Effect of coexisting ions on OTC degradation: na with ion concentration of 100, 200, 400mg/L respectively 2 CO 3 Preparing a solution and a NaCl solution, wherein the concentration of fulvic acid is respectively 10 mg/L, 20 mg/L and 40mg/L, and adding OTC into each concentration solution to ensure that the concentration of OTC is 200mg/L; 10mg of each of example 3, comparative example 3 and comparative example 4 was weighed into a 100mL wide-mouth conical flask, 30mL of the mixed solution was added, and 0.050mL of H was added at pH=2 2 O 2 Standing at room temperature for 2h. After the reaction was completed, the filtrate was filtered and the OTC content was measured at 354nm with an ultraviolet spectrophotometer. Each treatment was repeated 3 times. Specific results are shown in tables 3 to 5.
TABLE 2 effect on OTC degradation rate results
| 50mg/L | 100mg/L | 200mg/L | 300mg/L | 400mg/L | |
| Example 1 | 91.12％ | 91.36％ | 93.45％ | 93.28％ | 94.35％ |
| Example 2 | 93.82％ | 94.27％ | 94.58％ | 95.16％ | 96.57％ |
| Example 3 | 95.23％ | 95.48％ | 96.35％ | 97.63％ | 97.88％ |
| Comparative example 1 | 42.75％ | 68.31％ | 81.42％ | 85.86％ | 92.36％ |
| Comparative example 2 | 44.26％ | 69.74％ | 82.33％ | 87.18％ | 93.13％ |
| Comparative example 3 | 61.48％ | 76.33％ | 85.62％ | 90.66％ | 93.68％ |
| Comparative example 4 | 80.54％ | 81.67％ | 83.51％ | 84.94％ | 85.26％ |
| Comparative example 5 | 54.85％ | 56.92％ | 55.33％ | 57.62％ | 58.61％ |
| Comparative example 6 | 71.18％ | 72.49％ | 74.78％ | 75.16％ | 77.35％ |
Table 3 Na 2 CO 3 Effect of concentration on OTC degradation Rate
| / | 100mg/L | 200mg/L | 400mg/L | |
| Example 3 | 96.35％ | 92.41％ | 86.42％ | 73.13％ |
| Comparative example 3 | 85.62％ | 76.93％ | 65.84％ | 52.64％ |
| Comparative example 4 | 83.51％ | 78.67％ | 72.58％ | 61.76％ |
TABLE 4 influence of NaCl concentration on the degradation rate of OTC
| / | 100mg/L | 200mg/L | 400mg/L | |
| Example 3 | 96.35％ | 94.72％ | 90.37％ | 87.75％ |
| Comparative example 3 | 85.62％ | 81.46％ | 73.58％ | 65.28％ |
| Comparative example 4 | 83.51％ | 80.15％ | 76.30％ | 72.34％ |
TABLE 5 influence of fulvic acid concentration on OTC degradation rate
| / | 100mg/L | 200mg/L | 400mg/L | |
| Example 3 | 96.35％ | 95.18％ | 92.32％ | 88.39％ |
| Comparative example 3 | 85.62％ | 83.69％ | 81.65％ | 75.81％ |
| Comparative example 4 | 83.51％ | 79.86％ | 73.21％ | 66.29％ |
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The composition for the catalytic degradation of the oxytetracycline is characterized by comprising the following raw materials in parts by weight: 5-15 parts of chemical modified biochar, 15-45 parts of ferrous salt, 10-30 parts of metal sulfide, 5-15 parts of natural polymer colloid, 4-8 parts of tin-based metal carbide or titanium-based metal carbide and 1-2 parts of polyethyleneimine.
2. The composition for the catalytic degradation of oxytetracycline of claim 1, wherein the ferrous salt comprises one of ferrous oxide, ferrous hydroxide, ferrous sulfate, ferrous chloride.
3. The composition for the catalytic degradation of oxytetracycline of claim 1, wherein the metal sulfide comprises one of sodium sulfide and potassium sulfide.
4. The composition for the catalytic degradation of terramycin according to claim 1, wherein the natural polymeric colloid comprises one of acacia, tragacanth, xanthan gum, guar gum.
5. The composition for the catalytic degradation of terramycin according to claim 1, wherein the chemically modified biochar comprises one of acidified biochar, alkalized biochar, acetylated biochar, oxidized biochar.
6. The composition for the catalytic degradation of terramycin according to claim 5, wherein the acetylated biochar is prepared by the following method:
(1) Crushing the cleaned and dried chestnut shells by using a crusher, passing through 40 meshes, then placing the chestnut shells in a protective atmosphere of nitrogen in a tube furnace, heating to a set temperature at 10 ℃/min < -1 > for pyrolysis, preserving heat for 2.0-2.5 h after the set temperature is reached, setting the temperature to 700-750 ℃, and cooling to room temperature to obtain a biochar precursor;
(2) Taking a biochar precursor according to the mass-liquid ratio of 1g: 10-12 ml of mixed solution of glacial acetic acid/acetic anhydride is added, and the volume ratio of glacial acetic acid to acetic anhydride is 1:1, after fully swelling for 30-40 min, adding 2% sulfuric acid according to the mass-liquid ratio of 1:0.5-0.8 ml with the biochar precursor, stirring and refluxing for reaction for 5-6 h, then carrying out suction filtration, washing with deionized water to be neutral, and drying in an oven at 65+/-5 ℃ until the weight is constant, thus obtaining the acetylated biochar.
7. The composition for the catalytic degradation of terramycin according to claim 1, wherein the tin-based metal carbide or titanium-based metal carbide is tin titanium carbide, the particle size of which is 200-300 mesh, and the purity is not less than 98%.
8. The composition for the catalytic degradation of oxytetracycline according to claim 7, consisting of the following raw materials in parts by weight: 5-15 parts of acetylated biochar, 15-45 parts of ferrous sulfate heptahydrate, 10-30 parts of sodium sulfide nonahydrate, 5-15 parts of Arabic gum, 4-8 parts of tin titanium carbide and 1-2 parts of polyethyleneimine.
9. A process for preparing the composition for the catalytic degradation of oxytetracycline according to claim 1, comprising the steps of:
(1) Ferrous salt is mixed according to the mass-liquid ratio of 1g: mixing 0.5L with water, adding natural polymer colloid under stirring at 200-300 rpm, adding chemical modified biochar after mixing uniformly, and finally adding metal sulfide solution at the rate of 2-3 drops per second, wherein the metal sulfide is prepared by the following steps of: mixing 20ml of the solution with water, continuously stirring for 3 hours after the metal sulfide solution is added dropwise, completing the whole process in nitrogen atmosphere, standing for 10-12 hours after stirring, and drying to obtain the biochar carrying the metal sulfide;
(2) Tin-based metal carbide or titanium-based metal carbide and absolute ethyl alcohol are mixed according to a mass-liquid ratio of 1g: 50-55 ml of the mixture is uniformly mixed and stirred, then biochar of metal sulfide is added, stirring is carried out for 30-35 min at 30-40 ℃ in the protection atmosphere of nitrogen, then polyethyleneimine is added, stirring is continuously carried out for 2-2.5 h at 60-70 ℃, suction filtration is carried out, washing is carried out for three times by deionized water, and vacuum freeze drying is carried out for 10-12 h, thus obtaining the catalyst.
10. A method of preparing the composition for the catalytic degradation of oxytetracycline of claim 8, wherein the composition for the catalytic degradation of oxytetracycline is prepared by a method comprising the steps of:
(1) Crushing the cleaned and dried chestnut shells by using a crusher, passing through 40 meshes, then placing the chestnut shells in a protective atmosphere of nitrogen in a tube furnace, heating to a set temperature at 10 ℃/min < -1 > for pyrolysis, preserving heat for 2.0-2.5 h after the set temperature is reached, setting the temperature to 700-750 ℃, and cooling to room temperature to obtain a biochar precursor;
(2) Taking a biochar precursor according to the mass-liquid ratio of 1g: 10-12 ml of mixed solution of glacial acetic acid/acetic anhydride is added, and the volume ratio of glacial acetic acid to acetic anhydride is 1:1, after fully swelling for 30-40 min, adding 2% sulfuric acid according to the mass-liquid ratio of 1:0.5-0.8 ml with the biochar precursor, stirring and refluxing for reaction for 5-6 h, then carrying out suction filtration, washing with deionized water to be neutral, and drying in a drying oven at 65+/-5 ℃ until the weight is constant, thus obtaining the acetylated biochar;
(3) Ferrous sulfate heptahydrate is prepared according to a mass-to-liquid ratio of 1g: mixing 0.5L with water, adding Arabic gum under stirring at 200-300 rpm, adding acetylated biochar after uniformly mixing, and finally adding sodium sulfide nonahydrate solution at a rate of 2-3 drops per second, wherein the sodium sulfide nonahydrate solution is prepared by mixing sodium sulfide nonahydrate with 1g of sodium sulfide nonahydrate according to a mass-liquid ratio of 1g: mixing 20ml of the solution with water, continuously stirring for 3 hours after the sodium sulfide nonahydrate solution is added dropwise, completing the whole process in nitrogen atmosphere, standing for 10-12 hours after stirring is finished, and drying to obtain the biochar carrying ferrous sulfide;
(4) Tin titanium carbide and absolute ethyl alcohol are mixed according to the mass-liquid ratio of 1g: 50-55 ml of the raw materials are mixed and stirred uniformly, then biochar carrying ferrous sulfide is added, stirring is carried out for 30-35 min at 30-40 ℃ in a nitrogen protection atmosphere, then polyethyleneimine is added, stirring is carried out continuously for 2-2.5 h at 60-70 ℃, suction filtration is carried out, washing is carried out for three times by deionized water, and vacuum freeze drying is carried out for 10-12 h, thus obtaining the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310852229.7A CN116889879A (en) | 2023-07-12 | 2023-07-12 | Composition for catalytic degradation of terramycin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310852229.7A CN116889879A (en) | 2023-07-12 | 2023-07-12 | Composition for catalytic degradation of terramycin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116889879A true CN116889879A (en) | 2023-10-17 |
Family
ID=88313150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310852229.7A Pending CN116889879A (en) | 2023-07-12 | 2023-07-12 | Composition for catalytic degradation of terramycin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116889879A (en) |
-
2023
- 2023-07-12 CN CN202310852229.7A patent/CN116889879A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021227213A1 (en) | Catalyst for use in removing antibiotics in water body by activating peroxymonosulfate, preparation method therefor, and application thereof | |
| Wang et al. | Enhanced nitrate, manganese, and phenol removal by polyvinyl alcohol/sodium alginate with biochar gel beads immobilized bioreactor: Performance, mechanism, and bacterial diversity | |
| US20230150850A1 (en) | Method for removing organic pollutants from water bodies by activating persulfate with nutrient-enhanced soybean sprout-based biochar | |
| CN111974400A (en) | Composite nano material based on layered double hydroxides and preparation and application thereof | |
| CN109179554A (en) | Utilize the method for fortimicin in manganese dioxide load biological carbon materials removal water body | |
| CN114917943B (en) | Nitrogen-doped magnetic biochar material and preparation method and application thereof | |
| CN113042004B (en) | Preparation method and application of modified carbon-based material | |
| CN112316967A (en) | Preparation method of nitrogen-sulfur double-doped biochar material for degrading phenol in water | |
| CN112111211B (en) | Environment-friendly coating | |
| CN115025773A (en) | Method for preparing carbon/palladium composite material for efficiently degrading p-nitrophenol by using carbon dots as reducing agent | |
| CN116889879A (en) | Composition for catalytic degradation of terramycin and preparation method thereof | |
| CN112517046A (en) | Universal preparation method of hierarchical-pore nitrogen-doped carbon-oxygen reduction catalyst based on double-pore-foaming agent synthesis | |
| CN114377696B (en) | Biofilm-based BiOCl x Br (1-x) /Au/MnO 2 Composite material, preparation method and application thereof | |
| CN112121771A (en) | Biomass adsorbent for removing refractory organic pollutants, preparation method and application method thereof | |
| CN113198432B (en) | Preparation method of biomass activated carbon | |
| CN111115729A (en) | Composite material for industrial wastewater treatment tubular membrane filter layer | |
| CN113477228B (en) | Preparation method and application of grafted load modified biochar | |
| CN115646526A (en) | Preparation method and application of nitrogen-doped charcoal-embedded cobalt-based catalyst | |
| CN116786082B (en) | Specific adsorbent for oxytetracycline and preparation method thereof | |
| CN115140846A (en) | Composite treating agent, preparation method and application thereof in wastewater purification | |
| CN114950494A (en) | Photocatalytic material for catalyzing and degrading tetracycline and preparation method thereof | |
| CN111548803B (en) | Soil conditioner and preparation method and application thereof | |
| CN113845207A (en) | Cellulose magnetic carrier and preparation method thereof, anaerobic granular sludge containing cellulose magnetic carrier and preparation method thereof | |
| CN112427025A (en) | Preparation method and application of waste gas and waste water treating agent | |
| CN111620389A (en) | Application of amorphous alloy in catalytic degradation of antibiotic pollutants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |