CN108097330A - A kind of cage granular object and preparation method for sewage purification - Google Patents
A kind of cage granular object and preparation method for sewage purification Download PDFInfo
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- CN108097330A CN108097330A CN201711469120.6A CN201711469120A CN108097330A CN 108097330 A CN108097330 A CN 108097330A CN 201711469120 A CN201711469120 A CN 201711469120A CN 108097330 A CN108097330 A CN 108097330A
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- China
- Prior art keywords
- cage
- preparation
- parts
- aerosil
- granular object
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000010865 sewage Substances 0.000 title claims abstract description 33
- 238000000746 purification Methods 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910002012 Aerosil® Inorganic materials 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 27
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 26
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 23
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004794 expanded polystyrene Substances 0.000 claims abstract description 20
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 claims abstract description 19
- 239000004814 polyurethane Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 239000004793 Polystyrene Substances 0.000 claims abstract description 9
- 229920002223 polystyrene Polymers 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 76
- 229910001868 water Inorganic materials 0.000 claims description 58
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 39
- 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 36
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 30
- 239000005864 Sulphur Substances 0.000 claims description 30
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 27
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052750 molybdenum Inorganic materials 0.000 claims description 27
- 239000011733 molybdenum Substances 0.000 claims description 27
- 239000004094 surface-active agent Substances 0.000 claims description 27
- 230000002378 acidificating effect Effects 0.000 claims description 26
- 230000035484 reaction time Effects 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 238000005253 cladding Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000033228 biological regulation Effects 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 4
- -1 sodium alkyl benzene Chemical class 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005187 foaming Methods 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 235000013339 cereals Nutrition 0.000 description 42
- 238000004064 recycling Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000011084 recovery Methods 0.000 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 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B01J35/398—
-
- B01J35/50—
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0248—Coatings comprising impregnated particles
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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 present invention provides a kind of cage granular objects and preparation method for sewage purification.By preparing silicon dioxide gel, and it removes polystyrene after wrapping up expanded polystyrene (EPS) and cage aerosil bulky grain is made, further hydro-thermal method prepares nanometer zinc ferrite inside particle, hydro-thermal method prepares molybdenum disulfide and is coated on ferrous acid zinc surface again, obtain cage granular object, last spraying polyurethane thin layer fixes particle, you can for sewage disposal.This method utilizes cage aerosil bulky grain network catalyzing nano-particles; it realizes nano-photo catalytic particle and purification is contacted with wastewater efficient; expand waste water area; effectively increase dispersiveness of the catalyst in sewage; it is easy to use and be easily recycled while being obviously improved photocatalysis and carrying out the effect of sewage purification, and preparation method is relatively simple; cost is relatively low, is suitble to large-scale promotion application.
Description
Technical field
The present invention relates to sewage treatment fields, and in particular to realizes efficient catalytic and recycling by cage granular object, especially
It is to be related to a kind of cage granular object and preparation method for sewage purification.
Background technology
As world industry develops, water pollution getting worse, the pollutant in water also shows diversified trend, often
The pollutant seen includes toxic heavy metal, natural toxin, drug, organic pollution etc..Common purification techniques has chlorine, smelly
Oxygen and disinfection by ultraviolet light and filtering, absorption, standing etc., but these methods are frequently not to have very much to newborn pollutant
Effect, and secondary pollution may be caused.Due to photocatalysis technology it is pollution-free, safe the features such as, using photocatalysis technology handle with
Degradation of contaminant has become the research hotspot of environmental area.
The photocatalysis technology can be operated without other electron acceptor, and the condition of operation is easier to control, knot
Structure is also fairly simple, and oxidability is very strong, while secondary pollution not yet.It can be complete the organic pollution included in water
Either inorganic pollution has been reduced into harmless object or has been aoxidized the full water that is degraded by carbon dioxide etc., photocatalysis skill
The degradation of art treated sewage is thorough, and the substance removed is difficult in many difficult degradations such as greasy dirt sewage, papermaking wastewater or with other methods,
Such as chloroform, Polychlorinated biphenyls, organic phosphorus compound, polycyclic aromatic hydrocarbon can utilize this method to remove, and required photochemical catalyst whether there is
The advantages that poison, cheap, stabilization and use that can be repeated.
In Photocatalyst, typically using semi-conducting materials such as titanium dioxide as catalyst, these semiconductor particles
Band structure be generally made of the valence band and empty higher energy conduction band for filling up electronics, there are forbidden band between valence band and conduction band, when with
When the illumination that energy is equal to or more than energy gap is mapped to semiconductor, the electricity (e-) in valence band, which is excited, transits to conduction band shape
Into light induced electron (e-), hole (h+) is generated in valence band, and moves to particle surface, photoproduction respectively under electric field action
Electronics (e-) is easily captured by oxidizing substances such as oxygen in water, and hole is because of the ability with extremely strong acquisition electronics
And with very strong oxidability, it can be by the organic matter of its adsorption or OH- and H2O molecular oxidations are free into OH
Base, OH free radicals are almost without selectively aoxidizing Organic substance in water.From the mechanism of photocatalytic degradation, catalyst and dirt
The contact surface of water largely affects catalytic effect, in addition because current photocatalysis progress sewage purification is mainly suspension method and solid
Determine method, catalyst in itself can have some impact on water environment, therefore it is also an important research contents to recycle.
Chinese invention patent application number 200510095463.1 discloses a kind of synthesis of magnet carried photocatalyst composite particle
Technique and effluent purification method and device belong to industrial sewage purification method and device.The synthesis technology is to utilize chemical coprecipitation
Method synthesis nano magnetic matrix ferroso-ferric oxide is magnetic core, is synthesized in its surface coated silica, then carried titanium dioxide
Composite nanometer particle.
Chinese invention patent application number 201710721831.1 discloses a kind of diatomite/(GR+TiO2) composite photocatalyst
The preparation method of agent, using, as carrier, butyl titanate is titanium source, by mixing by the diatomite of fine purification and pore structure transformation
Miscellaneous graphene is prepared into diatomite/(GR+TiO2) composite photo-catalyst.
Chinese invention patent application number 201510478901.6 discloses a kind of molybdenum disulfide/silver vanadate visible ray complex light
Class graphene molybdenum disulfide is placed in ultrasonic disperse in aqueous solution, obtains class graphene by catalyst and preparation method thereof, the invention
The dispersion liquid A of molybdenum disulfide；Silver nitrate solid particle is added in gained dispersion liquid A, in the case of water-bath temperature control, shading is stirred
It mixes to silver nitrate and fully dissolves, obtain dispersion liquid B；It is scattered that the vanadic acid sodium water solution prepared is slowly added into gained dropwise
Continue shading stirring in liquid B, after being added dropwise to complete, obtain product.
Chinese invention patent application number 201510028480.7 discloses a kind of molybdenum disulfide/zinc oxide nanometer composite material
Preparation method, preparation method specifically includes：Using sodium molybdate and thiocarbamide as raw material, using citric acid as additive, it is configured to mix
Solution at a certain temperature, carries out hydro-thermal reaction, then the product utilization centrifuge after hydro-thermal reaction is carried out separation of solid and liquid, and
Gained presoma is repeatedly washed with deionized water and ethyl alcohol, obtains the microballoon that sheet molybdenum disulfide assembles.Into
And gained molybdenum disulfide is scattered in the settled solution obtained by zinc chloride and sodium hydroxide, by hydro-thermal reaction i.e. available two
Molybdenum sulfide/zinc oxide nanometer composite material.
According to above-mentioned, extremely low for the photochemical catalyst and waste water probability of sewage purification in existing scheme, clean-up effect
Unobvious, and when photochemical catalyst is completely dispersed in water, the recycling of catalyst becomes problem, it is therefore desirable to which exploitation is using just
Profit, high catalytic efficiency, the sewage disposal photochemical catalyst being easily recycled, in consideration of it, the present invention proposes a kind of being used for for novelty
The cage granular object and preparation method of sewage purification, can effectively solve above-mentioned technical problem.
The content of the invention
It is low with waste water probability for the wider photochemical catalyst of current application, cause catalytic efficiency low, clean-up effect is not
Substantially, when catalyst is completely dispersed with water, cause recycling difficult, use cost is high, and the present invention proposes a kind of for dirt
The cage granular object and preparation method of Water warfare so as to effectively increase photocatalysis efficiency, while ensure that catalyst recycling
It is convenient.
Specific technical solution of the present invention is as follows：
A kind of preparation method of cage granular object for sewage purification, is characterized in that, specific preparation method comprises the following steps：
（1）Ethyl orthosilicate with absolute ethyl alcohol is mixed, is stirred strongly using magnetic stirring apparatus, while acidic catalyst is added dropwise
Agent and the mixed liquor of deionized water, heating stirring flows back after liquid feeding, and heating temperature is 60~70 DEG C, heating time for 2~
Then 4h is cooled down, add in n,N-Dimethylformamide, continue 15~20min of stirring, and silicon dioxide gel is made；
（2）To step（1）Expanded polystyrene (EPS) is added in silicon dioxide gel obtained, is sufficiently stirred, colloidal sol is made to be covered with polyphenyl
The surface of ethylene spherical macro utilizes solvent to remove polystyrene after dry, and the cage that hollow, spherical, surface is micropore is made
Formula aerosil bulky grain；
（3）Ferric nitrate and zinc nitrate is soluble in water, add in step（2）Cage granular object obtained adds in sodium hydroxide solution
The pH value of regulation system carries out hydro-thermal reaction to 11~12, and hydrothermal temperature is 170~180 DEG C, and the reaction time is 5~7h,
Nanometer zinc ferrite is formed in particle cage；
（4）Molybdenum source mixture and sulphur source mixture is soluble in water, 10~15min is stirred, adds in step（3）System in, add
Enter the pH value of hydrochloric acid regulation system to 0.5~2, add surfactant, carry out hydro-thermal reaction, hydrothermal temperature 180
~200 DEG C, the reaction time for 16~for 24 hours, generate molybdenum disulfide, while molybdenum disulfide cladding zinc ferrite, obtain with nano particle
Deposit is kernel, using cage aerosil as the sewage-treating agent of shell；
（5）In the surface spraying polyurethane thin layer of aerosil bulky grain, fix bulky grain, you can be made for dirt
The cage granular object of Water warfare.
Preferably, the acidic catalyst is one kind in nitric acid, hydrochloric acid, acetic acid or sulfuric acid.
Preferably, step（1）In each parts by weight of raw materials be：6~10 parts of ethyl orthosilicate, 12~15 parts of absolute ethyl alcohol, acid
1~2 part of catalyst of property, 43~71 parts of deionized water, 10~30 parts of N,N-dimethylformamide.
Preferably, step（2）Described in expanded polystyrene (EPS) density be 1.02~1.05g/cm3, coefficient of foaming 30
~50 times.
Preferably, the solvent is one kind in perchloroethylene, ethylene glycol ether, styrene or ethyl acetate.
Preferably, the mass ratio of the silicon dioxide gel and expanded polystyrene (EPS) is 3:1~4:1.
Preferably, step（3）In each parts by weight of raw materials be：18~22 parts of ferric nitrate, 20~25 parts of zinc nitrate, cage dioxy
5~10 parts of SiClx aeroge bulky grain, 0.5~1 part of sodium hydroxide, 42~56.5 parts of water.
Preferably, the molybdenum source mixture is one kind in ammonium paramolybdate, sodium molybdate or molybdenum chloride.
Preferably, the sulphur source mixture is one kind in thiocarbamide, thioacetamide, sodium thiosulfate or ammonium sulfide.
Preferably, the surfactant is cetyl trimethylammonium bromide, neopelex or polyethylene
One kind in pyrrolidones.
Preferably, step（4）In each parts by weight of raw materials be：15~20 parts of molybdenum source mixture, 15~20 parts of sulphur source mixture,
1~2 part of surfactant, coat nanometer zinc ferrite 1~2 part of 10~20 parts of cage aerosil bulky grain, hydrochloric acid,
36~58 parts of water.
Preferably, step（5）Described in polyurethane thin layer thickness be 0.1~0.3mm.
The present invention also provides a kind of cage granular objects for sewage purification that a kind of above-mentioned preparation method is prepared.
By cage granular object catalyst prepared by the present invention and common molybdenum disulfide catalyst, common molybdenum disulfide catalyst
It is compared, on the rate of recovery, recycling complexity, waste water area, treatment effeciency and ease of use, is had apparent
Advantage, as shown in table 1.
Table 1：
The present invention provides a kind of cage granular objects and preparation method for sewage purification, compared with prior art, protrude
The characteristics of and excellent effect be：
1st, propose and the preparation of bulky grain cage network catalyzing nano-particles is made for sewage purification using aerosil
Cage granular object method.
2nd, using the microporous properties of aerosil, a hollow bulky grain cage is formed it into so that nanometer
Catalysed particulate is by cage network in cage, and during for sewage disposal, sewage enters cage and contacted with catalyzing nano-particles, expands
Waste water area effectively increases dispersiveness of the catalyst in sewage, has been obviously improved photocatalysis and has carried out sewage purification
Effect.
3rd, catalyzing nano-particles are not lost in cage in the present invention, not only easy to use, and are easily recycled.
4th, preparation method of the invention is relatively simple, and cost is relatively low, is suitble to large-scale promotion application.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Scope be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Preparation process is：
（1）Ethyl orthosilicate with absolute ethyl alcohol is mixed, is stirred strongly using magnetic stirring apparatus, while acidic catalyst is added dropwise
Agent and the mixed liquor of deionized water, heating stirring flows back after liquid feeding, and reaction temperature is 65 DEG C, reaction time 3h；Then
It is cooled down, adds in n,N-Dimethylformamide, continued to stir 18min, silicon dioxide gel is made；Acidic catalyst is nitre
Acid；Each group is divided into：Ethyl orthosilicate 8kg, absolute ethyl alcohol 13kg, acidic catalyst 1kg, deionized water 58kg, N, N- dimethyl
Formamide 20kg；
（2）To step（1）Expanded polystyrene (EPS) is added in silicon dioxide gel obtained, is sufficiently stirred, colloidal sol is made to be covered with polyphenyl
The surface of ethylene spherical macro utilizes solvent to remove polystyrene after dry, and the cage that hollow, spherical, surface is micropore is made
Formula aerosil bulky grain；Solvent is perchloroethylene；The mass ratio of silicon dioxide gel and expanded polystyrene (EPS) is
3:1；
（3）Ferric nitrate and zinc nitrate is soluble in water, add in step（2）Cage granular object obtained adds in sodium hydroxide solution
The pH value of regulation system is to 11, and heating carries out hydro-thermal reaction, and heating temperature is 175 DEG C, reaction time 6h；The shape in particle cage
Into nanometer zinc ferrite；Each group is divided into：Ferric nitrate 20kg, zinc nitrate 23kg, cage aerosil bulky grain 7kg, hydrogen-oxygen
Change sodium 0.5kg, water 49.5kg；
（4）Molybdenum source and sulphur source compound is soluble in water, 13min is stirred, adds in step（3）System in, add in hydrochloric acid adjust
The pH value of system adds surfactant to 1, and heats carry out hydro-thermal reaction, and heating temperature is 190 DEG C, and the reaction time is
20h；The molybdenum disulfide cladding zinc ferrite of generation, obtains using nano particle deposit as kernel, with cage aerosil
For the sewage-treating agent of shell；Molybdenum source mixture is ammonium paramolybdate；Sulphur source mixture is thiocarbamide；Surfactant is cetyl
Trimethylammonium bromide；Each group is divided into：Molybdenum source mixture 18kg, sulphur source mixture 17kg, surfactant 1kg, cladding Nanoscale Iron
Cage aerosil bulky grain 15kg, hydrochloric acid 1kg, the water 48kg of sour zinc；
（5）In the surface spraying polyurethane thin layer of aerosil bulky grain, fix bulky grain, you can be made for dirt
The cage granular object of Water warfare；The thickness of polyurethane thin layer is 0.2mm；
Cage granular object prepared by embodiment 1, the rate of recovery, recycling complexity, waste water area, treatment effeciency and use
Convenience is as shown in table 2.
Embodiment 2
Preparation process is：
（1）Ethyl orthosilicate with absolute ethyl alcohol is mixed, is stirred strongly using magnetic stirring apparatus, while acidic catalyst is added dropwise
Agent and the mixed liquor of deionized water, heating stirring flows back after liquid feeding, and reaction temperature is 60 DEG C, reaction time 4h；Then
It is cooled down, adds in n,N-Dimethylformamide, continue 15~20min of stirring, silicon dioxide gel is made；Acidic catalyst is
Hydrochloric acid；Each group is divided into：Ethyl orthosilicate 6kg, absolute ethyl alcohol 12kg, acidic catalyst 2kg, deionized water 70kg, N, N- diformazans
Base formamide 10kg；
（2）To step（1）Expanded polystyrene (EPS) is added in silicon dioxide gel obtained, is sufficiently stirred, colloidal sol is made to be covered with polyphenyl
The surface of ethylene spherical macro utilizes solvent to remove polystyrene after dry, and the cage that hollow, spherical, surface is micropore is made
Formula aerosil bulky grain；Solvent is ethylene glycol ether；The mass ratio of silicon dioxide gel and expanded polystyrene (EPS)
Example is 4:1；
（3）Ferric nitrate and zinc nitrate is soluble in water, add in step（2）Cage granular object obtained adds in sodium hydroxide solution
The pH value of regulation system is to 12, and heating carries out hydro-thermal reaction, and heating temperature is 170 DEG C, reaction time 7h；The shape in particle cage
Into nanometer zinc ferrite；Each group is divided into：Ferric nitrate 18kg, zinc nitrate 22kg, cage aerosil bulky grain 5kg, hydrogen-oxygen
Change sodium 1kg, water 54kg；
（4）Molybdenum source and sulphur source compound is soluble in water, 10min is stirred, adds in step（3）System in, add in hydrochloric acid adjust
The pH value of system adds surfactant to 0.5, and heats carry out hydro-thermal reaction, and heating temperature is 180 DEG C, the reaction time
For for 24 hours；The molybdenum disulfide cladding zinc ferrite of generation, obtains using nano particle deposit as kernel, with cage silica airsetting
Glue is the sewage-treating agent of shell；Molybdenum source mixture is sodium molybdate；Sulphur source mixture is thioacetamide；Surfactant is ten
Dialkyl benzene sulfonic acids sodium；Each group is divided into：Molybdenum source mixture 15kg, sulphur source mixture 16kg, surfactant 2kg, cladding nanometer
Cage aerosil bulky grain 10kg, hydrochloric acid 1kg, the water 56kg of zinc ferrite；
（5）In the surface spraying polyurethane thin layer of aerosil bulky grain, fix bulky grain, you can be made for dirt
The cage granular object of Water warfare；The thickness of polyurethane thin layer is 0.1mm；
Cage granular object prepared by embodiment 2, the rate of recovery, recycling complexity, waste water area, treatment effeciency and use
Convenience is as shown in table 2.
Embodiment 3
Preparation process is：
（1）Ethyl orthosilicate with absolute ethyl alcohol is mixed, is stirred strongly using magnetic stirring apparatus, while acidic catalyst is added dropwise
Agent and the mixed liquor of deionized water, heating stirring flows back after liquid feeding, and reaction temperature is 70 DEG C, reaction time 2h；Then
It is cooled down, adds in n,N-Dimethylformamide, continued to stir 20min, silicon dioxide gel is made；Acidic catalyst is vinegar
Acid；Each group is divided into：Ethyl orthosilicate 10kg, absolute ethyl alcohol 15kg, acidic catalyst 1kg, deionized water 44kg, N, N- dimethyl
Formamide 30kg；
（2）To step（1）Expanded polystyrene (EPS) is added in silicon dioxide gel obtained, is sufficiently stirred, colloidal sol is made to be covered with polyphenyl
The surface of ethylene spherical macro utilizes solvent to remove polystyrene after dry, and the cage that hollow, spherical, surface is micropore is made
Formula aerosil bulky grain；Solvent is styrene；The mass ratio of silicon dioxide gel and expanded polystyrene (EPS) is 4:
1；
（3）Ferric nitrate and zinc nitrate is soluble in water, add in step（2）Cage granular object obtained adds in sodium hydroxide solution
The pH value of regulation system is to 11, and heating carries out hydro-thermal reaction, and heating temperature is 180 DEG C, reaction time 5h；The shape in particle cage
Into nanometer zinc ferrite；Each group is divided into：Ferric nitrate 22kg, zinc nitrate 25kg, cage aerosil bulky grain 8kg, hydrogen-oxygen
Change sodium 1kg, water 44kg；
（4）Molybdenum source and sulphur source compound is soluble in water, 15min is stirred, adds in step（3）System in, add in hydrochloric acid adjust
The pH value of system adds surfactant to 2, and heats carry out hydro-thermal reaction, and heating temperature is 200 DEG C, and the reaction time is
16h；The molybdenum disulfide cladding zinc ferrite of generation, obtains using nano particle deposit as kernel, with cage aerosil
For the sewage-treating agent of shell；Molybdenum source mixture is ammonium paramolybdate；Sulphur source mixture is ammonium sulfide；Surfactant is ten poly- second
Alkene pyrrolidone；Each group is divided into：Molybdenum source mixture 20kg, sulphur source mixture 20kg, surfactant 1kg, cladding nanometer ferrous acid
Cage aerosil bulky grain 18kg, hydrochloric acid 2kg, the water 39kg of zinc；
（5）In the surface spraying polyurethane thin layer of aerosil bulky grain, fix bulky grain, you can be made for dirt
The cage granular object of Water warfare；The thickness of polyurethane thin layer is 0.3mm；
Cage granular object prepared by embodiment 3, the rate of recovery, recycling complexity, waste water area, treatment effeciency and use
Convenience is as shown in table 2.
Embodiment 4
Preparation process is：
（1）Ethyl orthosilicate with absolute ethyl alcohol is mixed, is stirred strongly using magnetic stirring apparatus, while acidic catalyst is added dropwise
Agent and the mixed liquor of deionized water, heating stirring flows back after liquid feeding, and reaction temperature is 63 DEG C, reaction time 2.5h；So
After cooled down, add in n,N-Dimethylformamide, continue stir 16min, be made silicon dioxide gel；Acidic catalyst is nitre
Acid；Each group is divided into：Ethyl orthosilicate 7kg, absolute ethyl alcohol 13kg, acidic catalyst 1kg, deionized water 57kg, N, N- dimethyl
Formamide 22kg；
（2）To step（1）Expanded polystyrene (EPS) is added in silicon dioxide gel obtained, is sufficiently stirred, colloidal sol is made to be covered with polyphenyl
The surface of ethylene spherical macro utilizes solvent to remove polystyrene after dry, and the cage that hollow, spherical, surface is micropore is made
Formula aerosil bulky grain；Solvent is ethyl acetate；The mass ratio of silicon dioxide gel and expanded polystyrene (EPS) is
3:1；
（3）Ferric nitrate and zinc nitrate is soluble in water, add in step（2）Cage granular object obtained adds in sodium hydroxide solution
The pH value of regulation system is to 12, and heating carries out hydro-thermal reaction, and heating temperature is 172 DEG C, reaction time 5.5h；In particle cage
Form nanometer zinc ferrite；Each group is divided into：Ferric nitrate 19kg, zinc nitrate 24kg, cage aerosil bulky grain 8kg, hydrogen
Sodium oxide molybdena 0.6kg, water 48.4kg；
（4）Molybdenum source and sulphur source compound is soluble in water, 14min is stirred, adds in step（3）System in, add in hydrochloric acid adjust
The pH value of system adds surfactant to 1.5, and heats carry out hydro-thermal reaction, and heating temperature is 190 DEG C, the reaction time
For 19h；The molybdenum disulfide cladding zinc ferrite of generation, obtains using nano particle deposit as kernel, with cage silica airsetting
Glue is the sewage-treating agent of shell；Molybdenum source mixture is ammonium paramolybdate；Sulphur source mixture is ammonium sulfide；Surfactant is 16
Alkyl trimethyl ammonium bromide；Each group is divided into：Molybdenum source mixture 16kg, sulphur source mixture 17kg, surfactant 2kg, cladding are received
Cage aerosil bulky grain 15kg, hydrochloric acid 2kg, the water 48kg of rice zinc ferrite；
（5）In the surface spraying polyurethane thin layer of aerosil bulky grain, fix bulky grain, you can be made for dirt
The cage granular object of Water warfare；The thickness of polyurethane thin layer is 0.2mm.
Embodiment 4 prepare cage granular object, the rate of recovery, recycling complexity, waste water area, treatment effeciency and
Ease of use is as shown in table 2.
Embodiment 5
Preparation process is：
（1）Ethyl orthosilicate with absolute ethyl alcohol is mixed, is stirred strongly using magnetic stirring apparatus, while acidic catalyst is added dropwise
Agent and the mixed liquor of deionized water, heating stirring flows back after liquid feeding, and reaction temperature is 66 DEG C, reaction time 3.5h；So
After cooled down, add in n,N-Dimethylformamide, continue stir 18min, be made silicon dioxide gel；Acidic catalyst is nitre
Acid；Each group is divided into：Ethyl orthosilicate 9kg, absolute ethyl alcohol 14kg, acidic catalyst 2kg, deionized water 53kg, N, N- dimethyl
Formamide 22kg；
（2）To step（1）Expanded polystyrene (EPS) is added in silicon dioxide gel obtained, is sufficiently stirred, colloidal sol is made to be covered with polyphenyl
The surface of ethylene spherical macro utilizes solvent to remove polystyrene after dry, and the cage that hollow, spherical, surface is micropore is made
Formula aerosil bulky grain；Solvent is perchloroethylene；The mass ratio of silicon dioxide gel and expanded polystyrene (EPS) is
3:1；
（3）Ferric nitrate and zinc nitrate is soluble in water, add in step（2）Cage granular object obtained adds in sodium hydroxide solution
The pH value of regulation system is to 11, and heating carries out hydro-thermal reaction, and heating temperature is 178 DEG C, reaction time 6.5h；In particle cage
Form nanometer zinc ferrite；Each group is divided into：Ferric nitrate 21kg, zinc nitrate 24kg, cage aerosil bulky grain 7kg, hydrogen
Sodium oxide molybdena 1kg, water 47kg；
（4）Molybdenum source and sulphur source compound is soluble in water, 14min is stirred, adds in step（3）System in, add in hydrochloric acid adjust
The pH value of system adds surfactant to 1, and heats carry out hydro-thermal reaction, and heating temperature is 190 DEG C, and the reaction time is
20h；The molybdenum disulfide cladding zinc ferrite of generation, obtains using nano particle deposit as kernel, with cage aerosil
For the sewage-treating agent of shell；Molybdenum source mixture is sodium molybdate；Sulphur source mixture is thiocarbamide；Surfactant is detergent alkylate
Sodium sulfonate；Each group is divided into：Molybdenum source mixture 17kg, sulphur source mixture 17kg, surfactant 2kg, cladding nanometer zinc ferrite
Cage aerosil bulky grain 17kg, hydrochloric acid 1kg, water 46kg；
（5）In the surface spraying polyurethane thin layer of aerosil bulky grain, fix bulky grain, you can be made for dirt
The cage granular object of Water warfare；The thickness of polyurethane thin layer is 0.2mm；
Cage granular object prepared by embodiment 5, the rate of recovery, recycling complexity, waste water area, treatment effeciency and use
Convenience is as shown in table 2.
Embodiment 6
Preparation process is：
（1）Ethyl orthosilicate with absolute ethyl alcohol is mixed, is stirred strongly using magnetic stirring apparatus, while acidic catalyst is added dropwise
Agent and the mixed liquor of deionized water, heating stirring flows back after liquid feeding, and reaction temperature is 70 DEG C, reaction time 2h；Then
It is cooled down, adds in n,N-Dimethylformamide, continued to stir 20min, silicon dioxide gel is made；Acidic catalyst is sulphur
Acid；Each group is divided into：Ethyl orthosilicate 10kg, absolute ethyl alcohol 12kg, acidic catalyst 2kg, deionized water 46kg, N, N- dimethyl
Formamide 30kg；
（2）To step（1）Expanded polystyrene (EPS) is added in silicon dioxide gel obtained, is sufficiently stirred, colloidal sol is made to be covered with polyphenyl
The surface of ethylene spherical macro utilizes solvent to remove polystyrene after dry, and the cage that hollow, spherical, surface is micropore is made
Formula aerosil bulky grain；Solvent is ethyl acetate；The mass ratio of silicon dioxide gel and expanded polystyrene (EPS) is
3:1；
（3）Ferric nitrate and zinc nitrate is soluble in water, add in step（2）Cage granular object obtained adds in sodium hydroxide solution
The pH value of regulation system is to 11, and heating carries out hydro-thermal reaction, and heating temperature is 170 DEG C, reaction time 5h；The shape in particle cage
Into nanometer zinc ferrite；Each group is divided into：Ferric nitrate 18kg, zinc nitrate 20kg, cage aerosil bulky grain 10kg, hydrogen-oxygen
Change sodium 1kg, water 51kg；
（4）Molybdenum source and sulphur source compound is soluble in water, 10min is stirred, adds in step（3）System in, add in hydrochloric acid adjust
The pH value of system adds surfactant to 2, and heats carry out hydro-thermal reaction, and heating temperature is 180 DEG C, and the reaction time is
24h；The molybdenum disulfide cladding zinc ferrite of generation, obtains using nano particle deposit as kernel, with cage aerosil
For the sewage-treating agent of shell；Molybdenum source mixture is ammonium paramolybdate；Sulphur source mixture is thioacetamide；Surfactant is ten
Six alkyl trimethyl ammonium bromides；Each group is divided into：Molybdenum source mixture 20kg, sulphur source mixture 20kg, surfactant 2kg, cladding
Cage aerosil bulky grain 15kg, hydrochloric acid 1kg, the water 42kg of nanometer zinc ferrite；
（5）In the surface spraying polyurethane thin layer of aerosil bulky grain, fix bulky grain, you can be made for dirt
The cage granular object of Water warfare；The thickness of polyurethane thin layer is 0.2mm；
Cage granular object prepared by embodiment 6, the rate of recovery, recycling complexity, waste water area, treatment effeciency and use
Convenience is as shown in table 2.
Comparative example 1
Preparation process is：
（1）Ethyl orthosilicate with absolute ethyl alcohol is mixed, is stirred strongly using magnetic stirring apparatus, while acidic catalyst is added dropwise
Agent and the mixed liquor of deionized water, heating stirring flows back after liquid feeding, and reaction temperature is 70 DEG C, reaction time 2h；Then
It is cooled down, adds in n,N-Dimethylformamide, continued to stir 20min, silicon dioxide gel is made；Acidic catalyst is sulphur
Acid；Each group is divided into：Ethyl orthosilicate 10kg, absolute ethyl alcohol 12kg, acidic catalyst 2kg, deionized water 46kg, N, N- dimethyl
Formamide 30kg；
（2）To step（1）Expanded polystyrene (EPS) is added in silicon dioxide gel obtained, is sufficiently stirred, colloidal sol is made to be covered with polyphenyl
Aerosil bulky grain is made in the surface of ethylene spherical macro；
（3）Ferric nitrate and zinc nitrate is soluble in water, add in step（2）Particulate matter obtained adds in sodium hydroxide solution and adjusts
The pH value of system is to 11, and heating carries out hydro-thermal reaction, and heating temperature is 170 DEG C, reaction time 5h；Form nanometer zinc ferrite；
Each group is divided into：Ferric nitrate 18kg, zinc nitrate 20kg, aerosil bulky grain 10kg, sodium hydroxide 1kg, water 51kg；
（4）Molybdenum source and sulphur source compound is soluble in water, 10min is stirred, adds in step（3）System in, add in hydrochloric acid adjust
The pH value of system adds surfactant to 2, and heats carry out hydro-thermal reaction, and heating temperature is 180 DEG C, and the reaction time is
24h；The molybdenum disulfide cladding zinc ferrite of generation, obtains sewage-treating agent；Molybdenum source mixture is ammonium paramolybdate；Sulphur source mixture is
Thioacetamide；Surfactant is cetyl trimethylammonium bromide；Each group is divided into：Molybdenum source mixture 20kg, sulphur source mixing
Object 20kg, surfactant 2kg, aerosil bulky grain 15kg, hydrochloric acid 1kg, the water 42kg for coating nanometer zinc ferrite；
（5）In the surface spraying polyurethane thin layer of aerosil bulky grain, fix bulky grain, you can be made for dirt
The particulate matter of Water warfare；The thickness of polyurethane thin layer is 0.2mm；
Particulate matter prepared by comparative example 1, the rate of recovery, recycling complexity, waste water area, treatment effeciency and easy-to-use
Property is as shown in table 2.
Table 2：
Claims (10)
1. the preparation method of a kind of cage granular object for sewage purification, which is characterized in that specific preparation method includes following
Step：
（1）Ethyl orthosilicate with absolute ethyl alcohol is mixed, is stirred strongly using magnetic stirring apparatus, while acidic catalyst is added dropwise
Agent and the mixed liquor of deionized water, heating stirring flows back after liquid feeding, and heating temperature is 60~70 DEG C, heating time for 2~
Then 4h is cooled down, add in n,N-Dimethylformamide, continue 15~20min of stirring, and silicon dioxide gel is made；
（2）To step（1）Expanded polystyrene (EPS) is added in silicon dioxide gel obtained, is sufficiently stirred, colloidal sol is made to be covered with polyphenyl
The surface of ethylene spherical macro utilizes solvent to remove polystyrene after dry, and the cage that hollow, spherical, surface is micropore is made
Formula aerosil bulky grain；
（3）Ferric nitrate and zinc nitrate is soluble in water, add in step（2）Cage aerosil bulky grain obtained, adds
Enter the pH value of sodium hydroxide solution regulation system to 11~12, carry out hydro-thermal reaction, hydrothermal temperature is 170~180 DEG C, instead
It is 5~7h between seasonable, nanometer zinc ferrite is formed in particle cage；
（4）Molybdenum source mixture and sulphur source mixture is soluble in water, 10~15min is stirred, adds in step（3）System in, add
Enter the pH value of hydrochloric acid regulation system to 0.5~2, add surfactant, carry out hydro-thermal reaction, hydrothermal temperature 180
~200 DEG C, the reaction time for 16~for 24 hours, generate molybdenum disulfide, while molybdenum disulfide cladding zinc ferrite, obtain with nano particle
Deposit is kernel, using cage aerosil as the sewage-treating agent of shell；
（5）In the surface spraying polyurethane thin layer of aerosil bulky grain, fix bulky grain, you can be made for dirt
The cage granular object of Water warfare.
2. a kind of preparation method of cage granular object for sewage purification according to claim 1, it is characterised in that：It is described
Acidic catalyst is one kind in nitric acid, hydrochloric acid, acetic acid or sulfuric acid.
3. a kind of preparation method of cage granular object for sewage purification according to claim 1, it is characterised in that：Step
（1）In each parts by weight of raw materials be：6~10 parts of ethyl orthosilicate, 12~15 parts of absolute ethyl alcohol, 1~2 part of acidic catalyst, go from
Sub- 43~71 parts of water, 10~30 parts of N,N-dimethylformamide.
4. a kind of preparation method of cage granular object for sewage purification according to claim 1, it is characterised in that：Step
（2）Described in expanded polystyrene (EPS) density be 1.02~1.05g/cm3, coefficient of foaming is 30~50 times；The solvent is complete
One kind in vinyl chloride, ethylene glycol ether, styrene or ethyl acetate.
5. according to a kind of preparation method of the cage granular object for sewage purification of claim 1 or 4, it is characterised in that：
The mass ratio of the silicon dioxide gel and expanded polystyrene (EPS) is 3:1~4:1.
6. a kind of preparation method of cage granular object for sewage purification according to claim 1, it is characterised in that：Step
（3）In each parts by weight of raw materials be：18~22 parts of ferric nitrate, 20~25 parts of zinc nitrate, cage aerosil bulky grain 5~
10 parts, 0.5~1 part of sodium hydroxide, 42~56.5 parts of water.
7. a kind of preparation method of cage granular object for sewage purification according to claim 1, it is characterised in that：Step
（4）Described in molybdenum source mixture be one kind in ammonium paramolybdate, sodium molybdate or molybdenum chloride；The sulphur source mixture is thiocarbamide, sulphur
For one kind in acetamide, sodium thiosulfate or ammonium sulfide；The surfactant is cetyl trimethylammonium bromide, 12
One kind in sodium alkyl benzene sulfonate or polyvinylpyrrolidone.
8. a kind of preparation method of cage granular object for sewage purification according to claim 1, it is characterised in that：Step
（4）In each parts by weight of raw materials be：15~20 parts of molybdenum source mixture, 15~20 parts of sulphur source mixture, 1~2 part of surfactant, bag
Cover 36~58 parts of 1~2 part of 10~20 parts of cage aerosil bulky grain, hydrochloric acid, the water of nanometer zinc ferrite.
9. a kind of preparation method of cage granular object for sewage purification according to claim 1, it is characterised in that：Step
（5）Described in polyurethane thin layer thickness be 0.1~0.3mm.
10. a kind of cage granular object for sewage purification that any one of claim 1~9 preparation method is prepared.
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| CN109351294A (en) * | 2018-12-19 | 2019-02-19 | 华北水利水电大学 | A kind of preparation method of the modified aerogels for sewage treatment |
| CN114833189A (en) * | 2022-03-25 | 2022-08-02 | 包禾欣 | Purifying agent and preparation process and application thereof |
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