CN109647533A - A kind of floatable magnetic high-molecular composite material and preparation method and application - Google Patents
A kind of floatable magnetic high-molecular composite material and preparation method and application Download PDFInfo
- Publication number
- CN109647533A CN109647533A CN201811325406.1A CN201811325406A CN109647533A CN 109647533 A CN109647533 A CN 109647533A CN 201811325406 A CN201811325406 A CN 201811325406A CN 109647533 A CN109647533 A CN 109647533A
- Authority
- CN
- China
- Prior art keywords
- composite material
- source
- concentration
- zinc
- molecular composite
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 30
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010865 sewage Substances 0.000 claims abstract description 28
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 23
- -1 iron sulphur compound Chemical class 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 97
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052725 zinc Inorganic materials 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 239000005864 Sulphur Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 8
- 235000018417 cysteine Nutrition 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 5
- 239000002689 soil Substances 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000001722 carbon compounds Chemical class 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000012719 thermal polymerization Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 63
- 238000010521 absorption reaction Methods 0.000 description 38
- 239000002351 wastewater Substances 0.000 description 30
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000005286 illumination Methods 0.000 description 18
- 230000010355 oscillation Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 15
- 229940012189 methyl orange Drugs 0.000 description 15
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 14
- 239000011651 chromium Substances 0.000 description 13
- 239000000975 dye Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical group C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 9
- 238000001027 hydrothermal synthesis Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 6
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 6
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- 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 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 239000000661 sodium alginate Substances 0.000 description 4
- 235000010413 sodium alginate Nutrition 0.000 description 4
- 229940005550 sodium alginate Drugs 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 2
- 239000010919 dye waste Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940059701 methylene blue 10 mg Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000737 potassium alginate Substances 0.000 description 1
- 235000010408 potassium alginate Nutrition 0.000 description 1
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
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- B01J35/33—
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- B01J35/39—
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- 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
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- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to polymer composites and technical field of sewage, and in particular to a kind of floatable magnetic high-molecular composite material and preparation method and application.The composite material is made of magnetic Nano iron oxide or Magnetic nano iron sulphur compound and the compound of nano-zinc sulfide or nano-zinc sulfide.Wherein, magnetic Nano material recycle the composite material can by irony sieve directly after use, remove removing heavy metals from the root, facilitate the recycling of composite material；Nano-zinc sulfide or its composite material have biggish specific surface area, composite material can be widened to the response range of visible light, promote the separation of light induced electron and hole, in addition composite material may float on the water surface, the oxygen in sunlight and air can be made full use of, therefore the composite material has stronger photocatalysis degradation organic contaminant ability.The composite material and preparation method thereof is simple, at low cost, has wide range of applications, can directly biodegrade in the environment after use.
Description
Technical field
The invention belongs to polymer composites and technical field of sewage, and in particular to a kind of floatable magnetic high
Molecular composite material and the preparation method and application thereof.The magnetic high-molecular composite material can remove the heavy metal in water body simultaneously simultaneously
Organic pollutant in photocatalytic degradation water body.
Background technique
In recent years, water body environment pollution caused by organic matter and heavy metal has had resulted in severe global crisis, seriously
Threaten the ecological balance and human health.It all kinds of organic dye waste waters that are discharged of industrial productions such as especially prints and dyes and weaves, with
And the waste water of China's heavy industries processing generation occupies the sizable scale of construction of sewage and therefore contains organic matter and heavy metal
Sewage treatment become current scientific research personnel's urgent need to resolve the problem of.
Organic dye waste water is mainly characterized by toxicity greatly and complicated composition, has thereby resulted in exploitation waste water treatment process
Problem, the feasibility for causing specific aim to be administered are smaller.Currently, industrially frequently with sewage water treatment method include physical absorption
Method and chemical deposition method etc., but these methods all only remove organic pollutant from waste water, not by organic pollutant
Degradation, to really play the role of removing pollutant.
Heavy metal in sewage has the characteristics that difficult to degrade, Yi Fuji, toxicity are big.When the waste water containing heavy metal is without place
Reason is untreated up to standard when just arranging to natural environment, and soil, surface water and groundwater will receive different degrees of pollution, Jin Ertong
The amplification for crossing food chain is enriched in aquatic products or crops body by thousands of times of ground, eventually enters into human body.These are heavy
Metal almost can seldom be excreted, and can accumulate in human organ, cause the nervous system, circulatory system, digestive system, big
The serious destruction of brain, kidney and bone etc., even results in death.Currently, the processing mode of the heavy metal in water body mainly have it is heavy
Shallow lake method, oxidation-reduction method, absorption method and bioanalysis etc., wherein being most widely used is the precipitation method, and this method turns heavy metal
Become indissoluble object to leave in the environment, the indissoluble object is unstable, and (such as pH variation) can discharge again again under given conditions
Heavy metal ion out again leads to the pollution of environment, therefore this method still cannot fundamentally solve the pollution problem of heavy metal.
Therefore, developing a kind of can degrade simultaneously dirty organic pollutants and goes the method for removing heavy metals particularly significant.
Summary of the invention
It is in order to overcome the shortcomings of the prior art and insufficient, the primary purpose of the present invention is that providing a kind of floatable magnetic high
The preparation method of molecular composite material.
Another object of the present invention is to provide the floatable magnetic high-molecular composite woods obtained by above-mentioned preparation method
Material.The polymer composite can degrade the organic pollutant in water body simultaneously, and remove the heavy metal in water removal.
A further object of the present invention is to provide the applications of above-mentioned floatable magnetic high-molecular composite material.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of floatable magnetic high-molecular composite material, includes the following steps:
(1) source of iron is obtained into magnetic Nano iron oxide through solvent heat treatment, or by source of iron and sulphur source through solvent heat at
Reason obtains Magnetic nano iron sulphur compound；
(2) be added into water zinc source and sulphur source or zinc source, carbonitride and sulphur source or zinc source, manganese source and sulphur source or zinc source,
Copper source and sulphur source, add strong alkali hydroxides, obtain reaction solution, and reaction prepares nano-zinc sulfide or nano-zinc sulfide
Compound；
(3) the magnetic Nano iron oxide or Magnetic nano iron sulphur compound that prepare in step (1) are added into macromolecule
It in solution, is uniformly dispersed, obtains reaction system A, with solidify liquid curing molding, the nano-sulfur prepared in step (2) is then added
The compound for changing zinc or nano-zinc sulfide, obtains reaction system B, solidifies again, be finally freeze-dried and float to get to described
Floating magnetic high-molecular composite material.
Preferably, source of iron described in step (1) is in iron chloride, ferric sulfate, ferric nitrate, ferric acetate and ferric acetyl acetonade
One or more.
Preferably, sulphur source described in step (1) is nine water vulcanized sodium, thiocarbamide, thioacetamide, cysteine and 12
One or more of mercaptan.
Preferably, when solvent heat treatment described in step (1), solvent uses deionized water, methanol, ethylene glycol and ethyl alcohol
One or more of, reaction temperature is 140~220 DEG C, when reaction a length of 6~for 24 hours.
Preferably, when solvent heat treatment described in step (1), the concentration of source of iron in a solvent is 1~3wt.%.
Preferably, when solvent heat treatment described in step (1), the concentration of sulphur source in a solvent is 0.5~3wt.%.
Preferably, zinc source described in step (2) is zinc chloride, zinc sulfate, zinc acetate, zinc acetylacetonate, biphosphate
One or more of zinc and zinc nitrate.
Preferably, the concentration in zinc source is 0.1~0.4wt.% in reaction solution described in step (2).
Preferably, the preparation method of carbonitride described in step (2) is, using rich nitrogen and carbon compound as presoma,
It is prepared through thermal polymerization.
It is furthermore preferred that the rich nitrogen and carbon compound are melamine or urea, the temperature of heat polymerization is 500
~600 DEG C, when reaction a length of 3~5h.
Preferably, when zinc source and carbonitride is added described in step (2) into water, the concentration of carbonitride in reaction solution
Less than 0.05wt.%.
Preferably, manganese source described in step (2) is manganese chloride or manganese sulfate.
Preferably, when zinc source and manganese source is added described in step (2) into water, the concentration of manganese source is less than in reaction solution
0.02wt.%
Preferably, copper source described in step (2) is copper chloride or copper sulphate.
Preferably, when zinc source, copper source and sulphur source is added described in step (2) into water, copper source is dense in reaction solution
Degree is less than 0.02wt.%.
Preferably, sulphur source described in step (2) is vulcanized sodium, thiocarbamide, thioacetamide, cysteine and lauryl mercaptan
One or more of.
Preferably, when zinc source, copper source and sulphur source is added described in step (2) into water, sulphur source is dense in reaction solution
Degree is 0.1~0.4wt.%.
Preferably, strong alkali hydroxides described in step (2) are sodium hydroxide or potassium hydroxide.
Preferably, the concentration of the strong alkali hydroxides in reaction solution described in step (2) is 15~30wt.%.
Preferably, the temperature of reaction described in step (2) is 70~90 DEG C, reaction when it is a length of 0.5~for 24 hours.
Preferably, the compound of nano-zinc sulfide described in step (2) is nanometer g-C3N4/ ZnS, nanometer ZnS/MnS or
Nanometer ZnS/CuS.
Preferably, Polymer Solution described in step (3) is that alginate solution, cellulosate solution and chitosan are molten
One or more of liquid.
Preferably, the concentration of Polymer Solution described in step (3) is 1~4wt.%.
Preferably, when the Polymer Solution described in step (3) is two kinds of high scores molecular mixed solution, two kinds of height
The mass ratio of molecule is 1:2~1:1.
Preferably, magnetic Nano iron oxide or Magnetic nano iron vulcanization are closed in reaction system A described in step (3)
The concentration of object is 0.5~1wt.%.
Preferably, solidify liquid described in step (3) is ionic calcium soln and/or glutaraldehyde solution.
Preferably, the concentration of solidify liquid described in step (3) is 1~5wt.%.
Preferably, in reaction system B described in step (3) compound of nano-zinc sulfide or nano-zinc sulfide concentration
For 0.1~0.3wt.%.
Preferably, when a length of 12~48h of freeze-drying described in step (3).
The present invention further provides the floatable magnetic high-molecular composite materials obtained by above-mentioned preparation method.
The present invention further provides above-mentioned floatable magnetic high-molecular composite material is organic in photocatalytic degradation sewage
Application in pollutant.
Preferably, the organic pollutant is methylene blue, methyl orange or rhodamine b.
Preferably, the method for the photocatalytic degradation dirt organic pollutants is, by floatable magnetic high-molecular
Composite material is added in the sewage containing organic pollutant, and light-catalyzed reaction is carried out under the irradiation of sunlight, can be realized
The degradation of dirty organic pollutants.
It is furthermore preferred that when floatable magnetic high-molecular composite material is added in the sewage containing organic pollutant,
The solid-to-liquid ratio of high molecular material and sewage is 1:100g/mL.
The present invention further provides above-mentioned floatable magnetic high-molecular composite materials to remove the weight in sewage or soil
Application in metal.
Preferably, the heavy metal is cadmium or chromium.
Preferably, the method for the removal sewage or the heavy metal in soil is to answer floatable magnetic high-molecular
Condensation material is added in the sewage or soil containing heavy metal, takes out after certain time length.
It is furthermore preferred that when floatable magnetic high-molecular composite material is added in the sewage containing heavy metal, high score
The solid-to-liquid ratio of sub- material and sewage is 0.5:100g/mL.
Compared with prior art, the present invention having the following advantages and benefits:
The present invention uses cheap and safe and non-toxic raw material, is prepared for floatable magnetic high-molecular composite material.The material
The catalytic degradation of the removal of heavy metal and organic pollutant in sewage can be achieved at the same time in material.Preparation method is simple, wants to equipment
Ask lower, it is at low cost, it has wide range of applications, it can directly biodegrade in the environment after use.The material is used for sewage treatment
When, it is suitable for the water body environment of the wide scope of pH=3.0~9.0.Nano-zinc sulfide and its compound in material have widened material
To the response range of visible light, and because having biggish specific surface area to provide more reaction sites, to promote photoproduction electric
The separation of son and hole, material may float on the water surface in addition, can make full use of the oxygen in sunlight and air, therefore material has
There is stronger photocatalysis degradation organic contaminant ability.Magnetic Nano iron oxide or Magnetic nano iron vulcanization in material close
Object can directly be recycled after adsorbing heavy metal in water body with magnetism, therefore material by the irony sieve of downstream water outlet, from
And the material for removing the heavy metal in water body from the root, and recycling can be recycled by being re-activated after De contamination.
Detailed description of the invention
Fig. 1 is the hysteresis loop figure of floatable magnetic high-molecular composite material prepared by embodiment 1.
Fig. 2 is the photo in kind of floatable magnetic high-molecular composite material prepared by embodiment 1.
Fig. 3 is that floatable magnetic high-molecular composite material prepared by embodiment 1,2,4 and 7 is used for photocatalytic degradation water
In methyl orange degradation situation map, Blank curve represents the blank control for not adding catalyst in solution.
Fig. 4 is that floatable magnetic high-molecular composite material prepared by embodiment 1,2,4 and 7 is used for photocatalytic degradation water
In methyl orange kinetics linear analogue curve.
Fig. 5 is to be used to adsorb by floatable magnetic high-molecular composite material prepared by embodiment 1,2,5 and 6 to remove in water
The adsorption effect of hexavalent chromium with the reaction time variation diagram.
Fig. 6 is to be used to adsorb by floatable magnetic high-molecular composite material prepared by embodiment 1,2,5 and 6 to remove in water
The absorption situation of hexavalent chromium.
Specific embodiment
Below with reference to examples and drawings, invention is further described in detail, but embodiments of the present invention are not limited to
This.For not specifically specified technological parameter, routine techniques progress can refer to.
Embodiment 1
The present embodiment provides a kind of floatable magnetic high-molecular composite material and preparation methods and application.
(1) using volume ratio for 1:1 ethylene glycol-water as reaction dissolvent, iron chloride and hydrazine hydrate is added, it is dense to obtain iron chloride
The reaction solution that degree is 1wt.% and concentration of hydrazine hydrate is 0.05wt.%, reacts 8h at 160 DEG C in hydrothermal reaction kettle, from
The heart, it is dry to get magnetic Nano iron oxide；
(2) zinc chloride, sodium hydroxide and vulcanized sodium are added into water, obtaining zinc oxide concentration is 0.4wt.%, hydroxide
Na concn is 30wt.% and vulcanizes the reaction solution that na concn is 0.4wt.%, and 4h is reacted at 80 DEG C, is centrifuged, it is dry to get
Nano-zinc sulfide with photocatalysis；
(3) magnetic Nano iron oxide ultrasonic disperse is obtained into magnetic Nano in the sodium alginate soln of 1wt.%
Iron oxide concentration is the reaction system A of 0.5wt.%, instills the CaCl that concentration is 5wt.%2Solution keeps reaction system A solid
Change completely, nano-zinc sulfide is then added, obtains the reaction system B that nano-zinc sulfide concentration is 0.1wt.%, be further dropped into dense
Degree is the CaCl of 5wt.%2Reaction system B is fully cured in solution, is freeze-dried 12h to get the floatable magnetic is arrived
Property polymer composite.
The organic dyestuff methyl orange that above-mentioned magnetic high-molecular composite material is used in photocatalytic degradation sewage: preparation is contained
The floatable magnetic high-molecular composite material of 1g, dark processing 30min is added in the simulated wastewater 100mL of methyl orange 20mg/L.So
It is placed under sunlight and irradiates 5h, with the extinction of the maximum absorption band before ultraviolet-uisible spectrophotometer measurement illumination and after illumination
Degree, by calculating, the degradation rate of methyl orange is 55.1%.
Above-mentioned magnetic high-molecular composite material is used for the heavy metal Cr in absorption effluent6+: compound concentration is 100mg/L's
Containing Cr6+Simulated wastewater 100mL, simulated wastewater pH is adjusted to 3.0 with the hydrochloric acid solution of 0.1mol/L, it is floatable that 0.5g is added
Magnetic high-molecular composite material, at 25 DEG C, oscillation absorption is for 24 hours (hunting speed 50rpm).Oscillation finishes, and takes supernatant liquor,
Residue Cr is measured with atomic absorption photometer6+Content.By calculating, Cr6+Adsorption rate be 82.3%.
Embodiment 2
The present embodiment provides a kind of floatable magnetic high-molecular composite material and preparation methods and application.
(1) using ethylene glycol as reaction dissolvent, ferric sulfate and sodium thiosulfate is added, obtain sulfuric acid concentration of iron be 1wt.% and
Concentration of sodium thiosulfate is the reaction solution of 0.5wt.%, reacts for 24 hours, is centrifuged at 220 DEG C in hydrothermal reaction kettle, dry,
Up to Magnetic nano iron sulphur compound.
(2) it takes 10g urea to be placed in 50mL crucible, reacts 5h in Muffle furnace 550 DEG C, obtain carbonitride.Xiang Shuizhong
Zinc sulfate, carbonitride, sodium hydroxide and thiocarbamide is added, obtaining sulfuric acid zinc concentration is 0.1wt.%, and nitridation concentration of carbon is
The reaction solution that 0.05wt.%, naoh concentration are 15wt.% and thiourea concentration is 0.2wt.% reacts at 90 DEG C
12h, centrifugation are dry to get the nanometer g-C with photocatalysis3N4/ZnS。
(3) Magnetic nano iron sulphur compound ultrasonic disperse is obtained into Magnetic nano iron in the chitosan solution of 4wt.%
Sulfur compound concentration is the reaction system A of 0.75wt.%, instills the glutaraldehyde solution that concentration is 4wt.%, keeps reaction system A solid
Change completely, nanometer g-C is then added3N4/ ZnS obtains a nanometer g-C3N4/ ZnS concentration is the reaction system B of 0.25wt.%, then
It is secondary to instill the CaCl that concentration is 5wt.%2Reaction system B is fully cured in solution, be freeze-dried 16h to get to it is described can
The magnetic high-molecular composite material of floating.
The organic dyestuff methyl orange that above-mentioned magnetic high-molecular composite material is used in photocatalytic degradation sewage: preparation is contained
The floatable magnetic high-molecular composite material of 1g, dark processing 30min is added in the simulated wastewater 100mL of methyl orange 20mg/L.So
It is placed under sunlight and irradiates 5h, with the extinction of the maximum absorption band before ultraviolet-uisible spectrophotometer measurement illumination and after illumination
Degree, by calculating, the degradation rate of methyl orange is 95.5%.
Above-mentioned magnetic high-molecular composite material is used for the heavy metal Cr in absorption effluent6+: compound concentration is 100mg/L's
Containing Cr6+Simulated wastewater 100mL, simulated wastewater pH is adjusted to 3.0 with the hydrochloric acid solution of 0.1mol/L, it is floatable that 0.5g is added
Magnetic high-molecular composite material, at 25 DEG C, oscillation absorption is for 24 hours (hunting speed 50rpm).Oscillation finishes, and takes supernatant liquor,
Residue Cr is measured with atomic absorption photometer6+Content.By calculating, Cr6+Adsorption rate be 84.2%.
Embodiment 3
The present embodiment provides a kind of floatable magnetic high-molecular composite material and preparation methods and application.
(1) using ethyl alcohol as reaction dissolvent, ferric acetate and nine aqueous sodium persulfates are added, obtaining acetic acid concentration of iron is 2wt.% and nine
Aqueous sodium persulfate concentration is the reaction solution of 0.5wt.%, reacts 10h at 120 DEG C in hydrothermal reaction kettle, is centrifuged, dry, i.e.,
Obtain Magnetic nano iron sulphur compound.
(2) it takes 10g urea to be placed in 50mL crucible, reacts 4h in Muffle furnace 500 DEG C, obtain carbonitride.Xiang Shuizhong
Zinc nitrate, carbonitride, potassium hydroxide and sodium thiosulfate is added, obtaining nitric acid zinc concentration is 0.1wt.%, and nitridation concentration of carbon is
The reaction solution that 0.025wt.%, concentration of potassium hydroxide are 12wt.% and concentration of sodium thiosulfate is 0.1wt.%, at 80 DEG C
For 24 hours, centrifugation is dry to get the nanometer g-C with photocatalysis for reaction3N4/ZnS。
(3) Magnetic nano iron sulphur compound ultrasonic disperse is obtained into magnetic in the carboxymethylcellulose sodium solution of 1wt.%
Property Nanoscale Iron sulfur compound concentration be 0.5wt.% reaction system A, instill the glutaraldehyde solution that concentration is 1.5wt.%, make anti-
System A completion of cure is answered, nanometer g-C is then added3N4/ ZnS obtains a nanometer g-C3N4/ ZnS concentration is the reaction of 0.3wt.%
System B is further dropped into the glutaraldehyde solution that concentration is 1wt.%, reaction system B is fully cured, and is freeze-dried 48h to get arriving
The floatable magnetic high-molecular composite material.
The organic dyestuff methylene blue that above-mentioned magnetic high-molecular composite material is used in photocatalytic degradation sewage: preparation is contained
There is the simulated wastewater 100mL of methylene blue 20mg/L, the floatable magnetic high-molecular composite material of 1g, dark processing is added
30min.It is subsequently placed under sunlight and irradiates 5h, with the absorption maximum before ultraviolet-uisible spectrophotometer measurement illumination and after illumination
The absorbance at peak, by calculating, the degradation rate of methylene blue is 97.4%.
Above-mentioned magnetic high-molecular composite material is used for the heavy metal Cr in absorption effluent6+: compound concentration is 50mg/L's
Containing Cr6+Simulated wastewater 100mL, simulated wastewater pH is adjusted to 9.0 with the hydrochloric acid solution of 0.1mol/L, it is floatable that 0.5g is added
Magnetic high-molecular composite material, at 25 DEG C, oscillation absorption 16h (hunting speed 50rpm).Oscillation finishes, and takes supernatant liquor,
Residue Cr is measured with atomic absorption photometer6+Content.By calculating, Cr6+Adsorption rate be 64.3%.
Embodiment 4
The present embodiment provides a kind of floatable magnetic high-molecular composite material and preparation methods and application.
(1) using deionized water as reaction dissolvent, ferric acetyl acetonade and hydrazine hydrate is added, obtaining acetylacetone,2,4-pentanedione concentration of iron is
The reaction solution that 3wt.% and concentration of hydrazine hydrate are 0.1wt.%, reacts 8h at 140 DEG C in hydrothermal reaction kettle, is centrifuged, and does
It is dry to get magnetic Nano iron oxide.
(2) zinc dihydrogen phosphate, manganese chloride, potassium hydroxide and thioacetamide are added into water, it is dense to obtain zinc dihydrogen phosphate
Degree is 0.2wt.%, and manganese chloride concentration is 0.02wt.%, concentration of potassium hydroxide is 15wt.% and thioacetyl amine concentration is
The reaction solution of 0.3wt.% reacts 8h at 70 DEG C, centrifugation, dry to get nanometer ZnS/MnS with photocatalysis.
(3) sodium alginate-sodium carboxymethylcellulose by magnetic Nano iron oxide ultrasonic disperse in 2wt.% mixes
In solution (mass ratio of sodium alginate and sodium carboxymethylcellulose is 1:1), obtaining magnetic Nano iron oxide concentration is
The reaction system A of 1wt.% instills the glutaraldehyde solution that concentration is 5wt.%, makes reaction system A completion of cure, is then added and receives
Rice ZnS/MnS obtains the reaction system B that nanometer ZnS/MnS concentration is 0.1wt.%, is further dropped into penta 2 that concentration is 5wt.%
Reaction system B is fully cured in aldehyde solution, freeze-drying for 24 hours to get arrive the floatable magnetic high-molecular composite wood
Material.
The organic dyestuff methyl orange that above-mentioned magnetic high-molecular composite material is used in photocatalytic degradation sewage: preparation is contained
The floatable magnetic high-molecular composite material of 1g, dark processing is added in the simulated wastewater 100mL of methyl orange dye 20mg/L
30min.It is subsequently placed under sunlight and irradiates 5h, with the absorption maximum before ultraviolet-uisible spectrophotometer measurement illumination and after illumination
The absorbance at peak, by calculating, the degradation rate of methyl orange is 90.1%.
Above-mentioned magnetic high-molecular composite material is used for the heavy metal Cr in absorption effluent6+: compound concentration is 100mg/L's
Containing Cr6+Simulated wastewater 100mL, simulated wastewater pH is adjusted to 6.0 with the hydrochloric acid solution of 0.1mol/L, it is floatable that 0.5g is added
Magnetic high-molecular composite material, at 25 DEG C, oscillation absorption 36h (hunting speed 50rpm).Oscillation finishes, and takes supernatant liquor,
Residue Cr is measured with atomic absorption photometer6+Content.By calculating, Cr6+Adsorption rate be 89.2%.
Embodiment 5
The present embodiment provides a kind of floatable magnetic high-molecular composite material and preparation methods and application.
(1) using ethylene glycol as reaction dissolvent, iron chloride and lauryl mercaptan is added, obtaining ferric chloride concn is 1wt.% and ten
Two concentrations of mercaptans are the reaction solution of 0.5wt.%, react 12h at 240 DEG C in hydrothermal reaction kettle, are centrifuged, it is dry to get
Magnetic nano iron sulphur compound.
(2) zinc acetylacetonate, manganese sulfate, potassium hydroxide and vulcanized sodium are added into water, obtaining acetylacetone,2,4-pentanedione zinc concentration is
0.3wt.%, manganese sulfate concentration is 0.01wt.%, concentration of potassium hydroxide is 30wt.% and vulcanization na concn is 0.4wt.%'s
Reaction solution reacts 0.5h at 70 DEG C, centrifugation, dry to get nanometer ZnS/MnS with photocatalysis.
(3) Magnetic nano iron sulphur compound ultrasonic disperse is obtained into magnetic Nano in the potassium alginate solution of 2wt.%
Iron sulfur compound concentration is the reaction system A of 0.75wt.%, instills the calcium chloride solution that concentration is 3wt.%, makes reaction system A
Then nanometer ZnS/MnS is added in completion of cure, obtain the reaction system B that nanometer ZnS/MnS concentration is 0.15wt.%, drip again
Enter concentration be 5wt.% calcium chloride solution, reaction system B is fully cured, freeze-drying for 24 hours to get arrive the floatability
Magnetic high-molecular composite material.
The organic dyestuff methylene blue that above-mentioned magnetic high-molecular composite material is used in photocatalytic degradation sewage: preparation is contained
There is the simulated wastewater 100mL of methylene blue 10mg/L, the floatable magnetic high-molecular composite material of 1g, dark processing is added
30min.It is subsequently placed under sunlight and irradiates 5h, with the absorption maximum before ultraviolet-uisible spectrophotometer measurement illumination and after illumination
The absorbance at peak, by calculating, the degradation rate of methylene blue is 94.4%.
Above-mentioned magnetic high-molecular composite material is used for the heavy metal Cr in absorption effluent6+: compound concentration is 100mg/L's
Containing Cr6+Simulated wastewater 100mL, simulated wastewater pH is adjusted to 3.0 with the hydrochloric acid solution of 0.1mol/L, it is floatable that 0.5g is added
Magnetic high-molecular composite material, at 25 DEG C, oscillation absorption is for 24 hours (hunting speed 50rpm).Oscillation finishes, and takes supernatant liquor,
Residue Cr is measured with atomic absorption photometer6+Content.By calculating, Cr6+Adsorption rate be 98.2%.
Embodiment 6
The present embodiment provides a kind of floatable magnetic high-molecular composite material and preparation methods and application.
(1) using ethylene glycol as reaction dissolvent, ferric nitrate and cysteine is added, obtaining iron nitrate concentration is 2wt.% and half
Cystine concentration is the reaction solution of 0.5wt.%, reacts 12h at 220 DEG C in hydrothermal reaction kettle, is centrifuged, it is dry to get
Magnetic nano iron sulphur compound.
(2) zinc sulfate, copper chloride, potassium hydroxide and thiocarbamide are added into water, obtaining sulfuric acid zinc concentration is 0.1wt.%, chlorine
Change copper concentration be 0.01wt.%, the reaction solution that concentration of potassium hydroxide is 20wt.% and thiourea concentration is 0.1wt.%, 75
8h is reacted at DEG C, is centrifuged, it is dry to get nanometer ZnS/CuS with photocatalysis.
(3) Magnetic nano iron sulphur compound ultrasonic disperse is obtained into magnetic in the carboxymethylcellulose sodium solution of 3wt.%
Property Nanoscale Iron sulfur compound concentration be 0.5wt.% reaction system A, instill the calcium chloride solution that concentration is 1.5wt.%, make anti-
System A completion of cure is answered, nanometer ZnS/CuS is then added, obtains the reaction system B that nanometer ZnS/CuS concentration is 0.3wt.%,
It is further dropped into the calcium chloride solution that concentration is 3wt.%, reaction system B is fully cured, freeze-drying is described to get arriving for 24 hours
Floatable magnetic high-molecular composite material.
The organic dyestuff methylene blue that above-mentioned magnetic high-molecular composite material is used in photocatalytic degradation sewage: preparation is contained
There is the simulated wastewater 100mL of methylene blue 20mg/L, the floatable magnetic high-molecular composite material of 0.2g, dark processing is added
30min.It is subsequently placed under sunlight and irradiates 5h, with the absorption maximum before ultraviolet-uisible spectrophotometer measurement illumination and after illumination
The absorbance at peak, by calculating, the degradation rate of methylene blue is 60.3%.
Above-mentioned magnetic high-molecular composite material is used for the heavy metal Cr in absorption effluent6+: compound concentration is 100mg/L's
Containing Cr6+Simulated wastewater 100mL, simulated wastewater pH is adjusted to 3.0 with the hydrochloric acid solution of 0.1mol/L, it is floatable that 0.5g is added
Magnetic high-molecular composite material, at 25 DEG C, oscillation absorption is for 24 hours (hunting speed 50rpm).Oscillation finishes, and takes supernatant liquor,
Residue Cr is measured with atomic absorption photometer6+Content.By calculating, Cr6+Adsorption rate be 99.2%.
Embodiment 7
The present embodiment provides a kind of floatable magnetic high-molecular composite material and preparation methods and application.
(1) using ethylene glycol as reaction dissolvent, ferric acetyl acetonade and cysteine is added, obtaining acetylacetone,2,4-pentanedione concentration of iron is
The reaction solution that 1.5wt.% and semicystinol concentration are 0.5wt.%, reacts 16h at 200 DEG C in hydrothermal reaction kettle, from
The heart, it is dry to get Magnetic nano iron sulphur compound.
(2) zinc acetylacetonate, copper sulphate, sodium hydroxide and cysteine are added into water, obtains acetylacetone,2,4-pentanedione zinc concentration
For 0.4wt.%, concentration of copper sulfate 0.02wt.%, naoh concentration are 30wt.% and semicystinol concentration is
The reaction solution of 0.4wt.% reacts for 24 hours at 80 DEG C, centrifugation, dry to get nanometer ZnS/CuS with photocatalysis.
(3) Magnetic nano iron sulphur compound ultrasonic disperse is obtained into magnetic Nano in the chitosan solution of 2.5wt.%
Iron sulfur compound concentration is the reaction system A of 1wt.%, instills the glutaraldehyde solution that concentration is 2.5wt.%, makes reaction system A
Then nanometer Zn s/CuS is added in completion of cure, obtain the reaction system B that nanometer Zn s/CuS concentration is 0.1wt.%, drip again
Enter concentration be 1wt.% glutaraldehyde solution, reaction system B is fully cured, freeze-drying for 24 hours to get arrive the floatability
Magnetic high-molecular composite material.
The organic dyestuff methyl orange that above-mentioned magnetic high-molecular composite material is used in photocatalytic degradation sewage: preparation is contained
The floatable magnetic high-molecular composite material of 1g, dark processing 30min is added in the simulated wastewater 100mL of methyl orange 20mg/L.So
It is placed under sunlight and irradiates 5h, with the extinction of the maximum absorption band before ultraviolet-uisible spectrophotometer measurement illumination and after illumination
Degree, by calculating, the degradation rate of methyl orange is 88.1%.
Above-mentioned magnetic high-molecular composite material is used for the heavy metal Cd in absorption effluent2+: compound concentration is 20mg/L's
Containing Cd2+Simulated wastewater 100mL, simulated wastewater pH is adjusted to 5.0 with the hydrochloric acid solution of 0.1mol/L, it is floatable that 0.4g is added
Magnetic high-molecular composite material, at 25 DEG C, oscillation absorption 18h (hunting speed 50rpm).Oscillation finishes, and takes supernatant liquor,
Residue Cd is measured with atomic absorption photometer2+Content.By calculating, Cd2+Adsorption rate be 85.2%.
Embodiment 8
The present embodiment provides a kind of floatable magnetic high-molecular composite material and preparation methods and application.
(1) using methanol as reaction dissolvent, ferric acetate and lauryl mercaptan is added, obtaining acetic acid concentration of iron is 1wt.% and 12
Concentrations of mercaptans is the reaction solution of 3wt.%, reacts 12h at 140 DEG C in hydrothermal reaction kettle, is centrifuged, dry to get magnetism
Nanoscale Iron sulphur compound.
(2) it takes 10g melamine to be placed in 50mL crucible, reacts 3h in Muffle furnace 600 DEG C up to carbonitride.Xiang Shui
Middle addition zinc acetylacetonate, carbonitride, sodium hydroxide and thiocarbamide, obtaining acetylacetone,2,4-pentanedione zinc concentration is 0.3wt.%, and carbonitride is dense
Degree be 0.05wt.%, the reaction solution that naoh concentration is 20wt.% and thiourea concentration is 0.2wt.%, at 90 DEG C instead
8h is answered, is centrifuged, it is dry to get the nanometer g-C with photocatalysis3N4/ZnS。
(3) it by Magnetic nano iron sulphur compound ultrasonic disperse in the sodium alginate soln of 2.5wt.%, obtains magnetism and receives
The reaction system A that rice iron sulfur compound concentration is 0.5wt.% instills the glutaraldehyde that concentration is 1.5wt.%, makes reaction system A
Then nanometer g-C is added in completion of cure3N4/ ZnS obtains a nanometer g-C3N4/ ZnS concentration is the reaction system B of 0.2wt.%, then
It is secondary to instill the CaCl that concentration is 1.5wt.%2Reaction system B is fully cured in solution, and it is described to get arriving to be freeze-dried 48h
Floatable magnetic high-molecular composite material.
The organic dyestuff rhodamine b that above-mentioned magnetic high-molecular composite material is used in photocatalytic degradation sewage: preparation is contained
There is a simulated wastewater 100mL of rhodamine b dyestuff 20mg/L, be added the floatable magnetic high-molecular composite material of 0.1g, at dark
Manage 30min.It is subsequently placed under sunlight and irradiates 5h, with the maximum suction before ultraviolet-uisible spectrophotometer measurement illumination and after illumination
The absorbance for receiving peak, by calculating, the degradation rate of rhodamine b is 98.5%.
Above-mentioned magnetic high-molecular composite material is used for the heavy metal Cd in absorption effluent2+: compound concentration is 10mg/L's
Containing Cd2+Simulated wastewater 100mL, simulated wastewater pH is adjusted to 8.0 with the hydrochloric acid solution of 0.1mol/L, it is floatable that 0.6g is added
Magnetic high-molecular composite material, at 25 DEG C, oscillation absorption is for 24 hours (hunting speed 50rpm).Oscillation finishes, and takes supernatant liquor,
Residue Cd is measured with atomic absorption photometer2+Content.By calculating, Cd2+Adsorption rate be 88.1%.
Embodiment 9
The present embodiment provides a kind of floatable magnetic high-molecular composite material and preparation methods and application.
(1) using ethylene glycol as reaction dissolvent, ferric acetyl acetonade and thiocarbamide is added, obtaining acetylacetone,2,4-pentanedione concentration of iron is
The reaction solution that 0.75wt.% and thiourea concentration are 0.5wt.%, reacts 10h at 180 DEG C in hydrothermal reaction kettle, is centrifuged,
Drying is to get Magnetic nano iron sulphur compound.
(2) zinc nitrate, sodium hydroxide and cysteine are added into water, obtaining nitric acid zinc concentration is 0.4wt.%, hydrogen-oxygen
Change the reaction solution that na concn is 20wt.% and semicystinol concentration is 0.4wt.%, 12h is reacted at 80 DEG C, be centrifuged, does
It is dry to get the nano-zinc sulfide with photocatalysis.
(3) sodium alginate-sodium carboxymethylcellulose by Magnetic nano iron sulphur compound ultrasonic disperse in 2wt.% mixes
In solution (mass ratio of sodium alginate and sodium carboxymethylcellulose is 1:2), obtaining Magnetic nano iron sulfur compound concentration is
The reaction system A of 0.8wt.%, instill concentration be 1.5wt.% glutaraldehyde solution, make reaction system A completion of cure, then plus
Enter nano-zinc sulfide, obtain the reaction system B that nano-zinc sulfide concentration is 0.1wt.%, being further dropped into concentration is 3wt.%'s
CaCl2Reaction system B is fully cured in solution, is freeze-dried 48h to get compound to the floatable magnetic high-molecular
Material.
The organic dyestuff rhodamine b that above-mentioned magnetic high-molecular composite material is used in photocatalytic degradation sewage: preparation is contained
There is the simulated wastewater 100mL of rhodamine b (concentration 20mg/L), the floatable magnetic high-molecular composite material of 0.4g is added, it is dark
Handle 30min.It is subsequently placed under sunlight and irradiates 5h, with the maximum before ultraviolet-uisible spectrophotometer measurement illumination and after illumination
The absorbance of absorption peak, by calculating, the degradation rate of rhodamine b is 79.5%.
Above-mentioned magnetic high-molecular composite material is used for the heavy metal Cd in absorption effluent2+: compound concentration is 50mg/L's
Containing Cd2+Simulated wastewater 100mL, simulated wastewater pH is adjusted to 4.0 with the hydrochloric acid solution of 0.1mol/L, it is floatable that 0.5g is added
Magnetic high-molecular composite material, at 25 DEG C, oscillation absorption 12h (hunting speed 50rpm).Oscillation finishes, and takes supernatant liquor,
Residue Cd is measured with atomic absorption photometer2+Content.By calculating, Cd2+Adsorption rate be 89.4%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of floatable magnetic high-molecular composite material, which comprises the steps of:
(1) source of iron is obtained into magnetic Nano iron oxide through solvent heat treatment, or source of iron and sulphur source is obtained through solvent heat treatment
To Magnetic nano iron sulphur compound；
(2) zinc source and sulphur source or zinc source, carbonitride and sulphur source or zinc source, manganese source and sulphur source or zinc source, copper source are added into water
And sulphur source, strong alkali hydroxides are added, obtain reaction solution, reaction prepares the compound of nano-zinc sulfide or nano-zinc sulfide
Object；
(3) the magnetic Nano iron oxide or Magnetic nano iron sulphur compound that prepare in step (1) are added into Polymer Solution
In, it is uniformly dispersed, obtains reaction system A, with solidify liquid curing molding, the nano-zinc sulfide prepared in step (2) is then added
Or the compound of nano-zinc sulfide, reaction system B is obtained, is solidified again, is finally freeze-dried to get to described floatable
Magnetic high-molecular composite material.
2. the preparation method of floatable magnetic high-molecular composite material according to claim 1, it is characterised in that:
Polymer Solution described in step (3) is one of alginate solution, cellulosate solution and chitosan solution
Or it is two or more；
Solidify liquid described in step (3) is one or both of ionic calcium soln, glutaraldehyde solution.
3. the preparation method of floatable magnetic high-molecular composite material according to claim 1, it is characterised in that:
The concentration of Polymer Solution described in step (3) is 1~4wt.%；
The concentration of magnetic Nano iron oxide or Magnetic nano iron sulphur compound is in reaction system A described in step (3)
0.5~1wt.%；
The concentration of solidify liquid described in step (3) is 1~5wt.%；
In reaction system B described in step (3) concentration of the compound of nano-zinc sulfide or nano-zinc sulfide be 0.1~
0.3wt.%.
4. the preparation method of floatable magnetic high-molecular composite material according to claim 1, it is characterised in that:
Source of iron described in step (1) is one of iron chloride, ferric sulfate, ferric nitrate, ferric acetate and ferric acetyl acetonade or two
Kind or more；
Sulphur source described in step (1) is one in nine water vulcanized sodium, thiocarbamide, thioacetamide, cysteine and lauryl mercaptan
Kind is two or more；
Zinc source described in step (2) is in zinc chloride, zinc sulfate, zinc acetate, zinc acetylacetonate, zinc dihydrogen phosphate and zinc nitrate
One or more；
Manganese source described in step (2) is manganese chloride or manganese sulfate；
Copper source described in step (2) is copper chloride or copper sulphate；
Sulphur source described in step (2) be one of vulcanized sodium, thiocarbamide, thioacetamide, cysteine and lauryl mercaptan or
It is two or more；
Strong alkali hydroxides described in step (2) are sodium hydroxide or potassium hydroxide；
The compound of nano-zinc sulfide described in step (2) is nanometer g-C3N4/ ZnS, nanometer ZnS/MnS or nanometer ZnS/
CuS。
5. the preparation method of floatable magnetic high-molecular composite material according to claim 1, it is characterised in that:
When solvent heat treatment described in step (1), the concentration of source of iron in a solvent is 1~3wt.%；
When solvent heat treatment described in step (1), the concentration of sulphur source in a solvent is 0.5~3wt.%.
6. the preparation method of floatable magnetic high-molecular composite material according to claim 1, it is characterised in that:
The concentration in zinc source is 0.1~0.4wt.% in reaction solution described in step (2)；
When zinc source and carbonitride is added described in step (2) into water, the concentration of carbonitride is less than in reaction solution
0.05wt.%；
When zinc source and manganese source is added described in step (2) into water, the concentration of manganese source is less than 0.02wt.% in reaction solution；
When zinc source, copper source and sulphur source is added described in step (2) into water, the concentration of copper source is less than in reaction solution
0.02wt.%；
Zinc source, copper source is added described in step (2) into water and when sulphur source, in reaction solution the concentration of sulphur source be 0.1~
0.4wt.%；
The concentration of strong alkali hydroxides in reaction solution described in step (2) is 15~30wt.%.
7. the preparation method of floatable magnetic high-molecular composite material according to claim 1, it is characterised in that:
When solvent heat treatment described in step (1), solvent using one of deionized water, methanol, ethylene glycol and ethyl alcohol or
Two or more, reaction temperature is 140~220 DEG C, when reaction a length of 6~for 24 hours；
The temperature of reaction described in step (2) is 70~90 DEG C, reaction when it is a length of 0.5~for 24 hours.
8. the preparation method of floatable magnetic high-molecular composite material according to claim 1, it is characterised in that: step
(2) preparation method of the carbonitride described in is, using rich nitrogen and carbon compound as presoma, to be prepared through thermal polymerization,
Wherein, rich nitrogen and carbon compound are melamine or urea, and the temperature of heat polymerization is 500~600 DEG C, and when reaction is a length of
3~5h.
9. a kind of floatable magnetic high-molecular composite material, which is characterized in that by system according to any one of claims 1 to 8
Preparation Method obtains.
10. the application of floatable magnetic high-molecular composite material as claimed in claim 9, it is characterised in that: can by described
The magnetic high-molecular composite material of floating is used for the organic pollutant in photocatalytic degradation sewage, or for removing sewage or soil
In heavy metal.
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| CN110692630A (en) * | 2019-09-23 | 2020-01-17 | 南京高正农用化工有限公司 | Floating carrier for floating large granules and preparation method thereof |
| CN112295583A (en) * | 2020-10-23 | 2021-02-02 | 南昌航空大学 | Preparation method and application of zinc sulfide/boronized graphite phase carbon nitride visible-light-induced photocatalyst |
| CN112520807A (en) * | 2020-12-11 | 2021-03-19 | 东莞理工学院 | Preparation method and application of floating MXene assembly photo-thermal conversion material |
| CN114602508A (en) * | 2022-04-02 | 2022-06-10 | 吉林化工学院 | Preparation and application of MnS @ ZnS core-shell hollow sphere with photocatalytic performance |
| CN114685801A (en) * | 2022-03-08 | 2022-07-01 | 清华大学 | Precious metal recovery organic polymer and preparation method and application thereof |
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| CN110692630A (en) * | 2019-09-23 | 2020-01-17 | 南京高正农用化工有限公司 | Floating carrier for floating large granules and preparation method thereof |
| CN110692630B (en) * | 2019-09-23 | 2021-05-07 | 南京高正农用化工有限公司 | Floating carrier for floating large granules and preparation method thereof |
| CN112295583A (en) * | 2020-10-23 | 2021-02-02 | 南昌航空大学 | Preparation method and application of zinc sulfide/boronized graphite phase carbon nitride visible-light-induced photocatalyst |
| CN112520807A (en) * | 2020-12-11 | 2021-03-19 | 东莞理工学院 | Preparation method and application of floating MXene assembly photo-thermal conversion material |
| CN115282969A (en) * | 2022-01-04 | 2022-11-04 | 榆林学院 | Magnetic NiFe 2 O 4 Preparation method and application of nanosphere |
| CN115282969B (en) * | 2022-01-04 | 2024-03-08 | 榆林学院 | Magnetic NiFe 2 O 4 Preparation method and application of nanospheres |
| CN114685801A (en) * | 2022-03-08 | 2022-07-01 | 清华大学 | Precious metal recovery organic polymer and preparation method and application thereof |
| CN114602508A (en) * | 2022-04-02 | 2022-06-10 | 吉林化工学院 | Preparation and application of MnS @ ZnS core-shell hollow sphere with photocatalytic performance |
| CN114602508B (en) * | 2022-04-02 | 2023-08-04 | 吉林化工学院 | Preparation and application of MnS@ZnS core-shell hollow sphere catalyst with photocatalytic performance |
| CN114702086A (en) * | 2022-04-07 | 2022-07-05 | 费县塞达新材料技术中心 | Water body purification material for drinking water |
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