CN108855122A - The new application of manganese nodule and the preparation method of stratiform intercalation composite titania material - Google Patents
The new application of manganese nodule and the preparation method of stratiform intercalation composite titania material Download PDFInfo
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- CN108855122A CN108855122A CN201810543701.8A CN201810543701A CN108855122A CN 108855122 A CN108855122 A CN 108855122A CN 201810543701 A CN201810543701 A CN 201810543701A CN 108855122 A CN108855122 A CN 108855122A
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- China
- Prior art keywords
- manganese nodule
- mineral
- titanium dioxide
- layer mineral
- preparation
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000011572 manganese Substances 0.000 title claims abstract description 81
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 78
- 238000009830 intercalation Methods 0.000 title claims abstract description 45
- 230000002687 intercalation Effects 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 98
- 239000011707 mineral Substances 0.000 claims abstract description 98
- 239000010410 layer Substances 0.000 claims abstract description 72
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 37
- 239000011229 interlayer Substances 0.000 claims abstract description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 150000001298 alcohols Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000013535 sea water Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- 206010013786 Dry skin Diseases 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000002525 ultrasonication Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- -1 Alkyl dimethyl ammonium chloride Chemical compound 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- GTDHYNXLIKNVTJ-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(C)(C)CO GTDHYNXLIKNVTJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 3
- UUYQSLQNSVVXCC-UHFFFAOYSA-N CN.C(C=C)(=O)OCCN(C)C Chemical compound CN.C(C=C)(=O)OCCN(C)C UUYQSLQNSVVXCC-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 claims description 2
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- MLGWTHRHHANFCC-UHFFFAOYSA-N prop-2-en-1-amine;hydrochloride Chemical compound Cl.NCC=C MLGWTHRHHANFCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 1
- 241000446313 Lamella Species 0.000 claims 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 claims 1
- 125000005456 glyceride group Chemical group 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000002002 slurry Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 7
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PWEDSNYOIUQQAP-UHFFFAOYSA-J OCCO.Cl[Ti](Cl)(Cl)Cl Chemical compound OCCO.Cl[Ti](Cl)(Cl)Cl PWEDSNYOIUQQAP-UHFFFAOYSA-J 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- GFORUURFPDRRRJ-UHFFFAOYSA-N [Na].[Mn] Chemical compound [Na].[Mn] GFORUURFPDRRRJ-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PFKRTWCFCOUBHS-UHFFFAOYSA-N dimethyl(octadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH+](C)C PFKRTWCFCOUBHS-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BKEOXUSOEGMVTL-UHFFFAOYSA-N trimethyl-$l^{3}-bromane Chemical compound CBr(C)C BKEOXUSOEGMVTL-UHFFFAOYSA-N 0.000 description 1
- 201000008827 tuberculosis Diseases 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the preparation methods of a kind of new application of manganese nodule and stratiform intercalation composite titania material.It is material first with ocean manganese nodule raw ore, is handled using reagents such as strong oxidizer, persulfates, synthesizes manganese nodule layer mineral；Then organically-modified to the layer mineral progress of synthesis, modified layered mineral are made；TiO 2 precursor and alcohols material are mixed, slurry is made, modified layered mineral are mixed with the slurry, TiO 2 precursor is made to introduce layer mineral interlayer, after hydrolysis, calcination processing, stratiform intercalation composite titania material is made.Nano-titanium dioxide is intercalation into Manganese nodules interlayer by the present invention, titanium dioxide partial size is reduced using the interlayer confinement effect of manganese nodule layer mineral, inhibit the reunion of nano particle, and change the exposure crystal face feature of intercalation titanium dioxide, compared to nano-titanium dioxide, cost is relatively low, and has preferably absorption and photocatalysis performance.
Description
Technical field
The present invention relates to the preparation method of compound more particularly to the new applications and stratiform intercalation titanium dioxide of a kind of manganese nodule
The preparation method of titanium composite material.
Background technique
Ocean manganese nodule is a kind of Deep Sea Minerals abundant, and reserves are big, and distribution is wide, has important strategic importance.
Recently as electron microscope, powder x-ray diffraction, the development of the new technologies such as neutron diffraction, the non-traditional utilization of manganese nodule
Value, such as good adsorption capacity, high catalytic property and excellent photoelectric characteristic gradually show.It is extracted from ocean manganese nodule
Layer mineral remains the pore structure of manganese nodule, has good catalytic performance and absorption property.Layer mineral such as water simultaneously
Sodium manganese ore etc. itself has good photocatalysis performance, is a kind of preferable photochemical catalyst.Using the physics of manganese nodule itself, change
Feature makes it as functional material, and it is more meaningful using method to extract metal merely than tradition, as CN1183650A is disclosed
A kind of a kind of new application of manganese nodule and the manufacturing method of manganese series cell anode.
Titanium dioxide has extensive use in functional paint, photocatalysis field, and chemical property is stable, nontoxic and pollution-free,
It is the photochemical catalyst of the various aspects such as wastewater treatment, air cleaning first choice.It prepares nano-titanium dioxide technology complexity and cost is higher；
In addition, the reuniting effect of nano particle will lead to its reduced performance.Once someone carried titanium dioxide using natural minerals, but only will
Carrier of the surface of natural minerals as nano-titanium dioxide urges its light although cost can be reduced to a certain extent
It is little to change performance influence.
Summary of the invention
For overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of new application of manganese nodule and stratiform intercalations
The preparation method of composite titania material.
Technical solution of the present invention：
A kind of new application of manganese nodule, prepares layer mineral from ocean manganese nodule, and nano-titanium dioxide is inserted into layer mineral
Lattice interlayer, to obtain stratiform intercalation composite titania material.
The layer mineral is birnessite, like one in manganite, vernadite, vernadite, lithiophorite
Kind is a variety of.
The nano-titanium dioxide is magnetic metal particle of the partial size in 1 ~ 500 nm.
A kind of stratiform intercalation composite titania material, nano-titanium dioxide are inserted into the lattice interlayer of layer mineral, institute
The layer mineral stated is the mineral for the lamellar structure formed with Mn oxide being prepared by raw material of ocean manganese nodule.
, steps are as follows：
1）After ocean manganese nodule raw ore is impregnated 1 ~ 7 d in seawater or simulated seawater, crushing grinding, ultrasonication 1 ~
60 min keep its fully dispersed, and 1 ~ 30 min is centrifugated under 500 ~ 15000 rpm rates, collect lower layer's granular precipitate
Substance, dry 2 ~ 48 h obtain dry powdered manganese nodule raw ore at 25 ~ 150 DEG C；
2）Take dry powdered manganese nodule raw ore and strong oxidizer in mass ratio 0.1：1~10：1 mixing is added organic reagent and grinds
Mill is uniformly mixed it, and mixture calcines 1 ~ 12 h at 500 ~ 1500 DEG C, and calcined product is put into and fills 0.1 ~ 2 mol/L
In container in persulfate solution, 10 ~ 120 min are stirred, filters, clean after reaction, by filter residue in 60 ~ 150 DEG C of constant temperature
Layer mineral is made in 0.5 ~ 24 h；
3）After the dispersion of layer mineral ultrasonic wave, layer mineral is added in the organic modifiers of 0.5 ~ 2 times of ion exchange capacity,
Constant temperature is stirred to react 0.5 ~ 12 h under 40 ~ 90 DEG C of water-baths, continues 1 ~ 24 h of aging under water-bath, is made and changes after washing, drying
Property layer mineral, prepare 50 ~ 500 mL, 0.5 ~ 10 mmol/L TiO 2 precursor alcohol solution, stir 10 ~ 120 min
After mix, modified layered mineral are added into solution in the ratio of 0.01 ~ 1 g/mL, continuing to be stirred to react 1 ~ 24 h must mix
Object；
4）It removes ionized water and is slowly dropped into step 3）Mixture in, while be added dropwise while stir, stand 6 ~ 24 h, wash, after filtering
50 ~ 150 DEG C of dryings, 100 ~ 800 DEG C of 1 ~ 12 h of calcining, products therefrom is stratiform intercalation composite titania material.
The preparation method, step 2）Described in strong oxidizer be potassium permanganate, potassium manganate, potassium nitrate, potassium hyperchlorate
One of or it is a variety of；
The preparation method, step 2）Described in organic reagent be that oleic acid, stearic acid, palmitic acid, stearmide, vinyl are double
One of stearmide, glyceryl tristearate are a variety of.
The preparation method, step 2）Described in persulfate be ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, over cure
One of potassium hydrogen phthalate is a variety of.
The preparation method, step 3）Described in organic modifiers be hexadecylpyridinium chloride, cetyl front three
Base ammonium bromide, dodecyl trimethyl ammonium bromide, octadecyltrimethylammonium chloride, octadecyldimethyl ammonium chloride, 12
Sodium alkyl benzene sulfonate, hexadecyldimethyl benzyl ammonium allyl ammonium chloride, in dimethylaminoethyl acrylate methyl ammonia ethyl ester trimethyl ammonium chloride
It is one or more.
The preparation method, step 3）Described in TiO 2 precursor be butyl titanate, isopropyl titanate, glycerol metatitanic acid
In ester, titanium sulfate, titanium tetrachloride it is one or more
The preparation method, step 3）Described in alcohols be one of methanol, ethyl alcohol, ethylene glycol, propylene glycol, glycerine or
It is a variety of.
Effective achievement of the invention：
The stratiform intercalation composite titania material preparation method of the slave ocean manganese nodule mineral preparation proposed, raw material are ocean manganese
Tuberculosis, abundance, the reaction principle being related to can be realized with process flow by easy reaction instrument, operating condition energy-saving ring
It protects, to provide new thinking using manganese nodule.The composite material of preparation is protected simultaneously not only with the absorption property of manganese nodule
The photocatalysis performance for having stayed layer mineral and titanium dioxide reduces titanium dioxide partial size using confinement effect, inhibits nanometer
The reunion of particle simultaneously changes exposed crystal face feature, finally effectively increases composite material to the absorption degradation ability of pollutant,
It effectively improves it in the fields such as wastewater treatment, photocatalysis performance, expands its application prospect.
Detailed description of the invention
Fig. 1 is laminar titanium dioxide intercalation composite material prepared by the slave ocean manganese nodule mineral of the embodiment of the present invention 1
XRD spectrum；
Fig. 2 is the transmission electron microscope photo of the laminar titanium dioxide intercalation composite material of the embodiment of the present invention 1, illustrates composite material
Pattern under different resolution；
Fig. 3 is the transmission electron microscope photo of the laminar titanium dioxide intercalation composite material of the embodiment of the present invention 1, illustrates 5 nm resolution
Photo under rate；
Fig. 4 is photocatalysis of the laminar titanium dioxide intercalation composite material of the embodiment of the present invention 1 to positive decene petroleum hydrocarbon contaminant
Degradation effect, and the degradation effect being simply mixed with manganese nodule raw ore, titanium dioxide, manganese nodule raw ore and titanium dioxide compare
Figure.
Specific embodiment
The invention proposes a kind of new applications of manganese nodule, prepare layer mineral from ocean manganese nodule, by nanometer titanium dioxide
Titanium is inserted into the lattice interlayer of layer mineral, to obtain stratiform intercalation composite titania material.
The layer mineral is birnessite, like one in manganite, vernadite, vernadite, lithiophorite
Kind is a variety of.
The nano-titanium dioxide is magnetic metal particle of the partial size in 1 ~ 500 nm.
A kind of stratiform intercalation composite titania material, nano-titanium dioxide are inserted into the lattice interlayer of layer mineral, institute
The layer mineral stated is the lamellar structure formed with Mn oxide being prepared by raw material of ocean manganese nodule.
The preparation method of the stratiform intercalation composite titania material, steps are as follows：
The first step is pre-processed to ocean manganese nodule.Blocky manganese nodule is crushed, the powdered manganese nodule ground is former
Mine is easier to carry out next reaction；
Second step is to extract layer mineral from manganese nodule raw ore.It prepares manganese knot under the strong oxidizer high-temperature calcination of layer mineral
Impure mineral corrosion oxidation in core, and the sodium ion in potassium ion exchange manganese nodule is provided；After persulfate reacts, strong oxygen
Oxide or hydroxide in agent treated sintered product largely dissolve, and purer layer mineral is made；
Third step is the layer mineral for preparing TiO 2 precursor intercalation.The modified layer mineral interlayer of organic modifiers is by parent
It is aqueous to become lipophilic, simultaneously because pillared effect interlamellar spacing becomes larger.TiO 2 precursor/alcohols material mixture slurry is added
Afterwards, due to interlayer oleophylic, the presoma TiO 2 precursor of titanium dioxide is introduced into layer mineral interlayer；
4th step is to prepare the stratiform intercalation composite titania material prepared from ocean manganese nodule mineral.Distilled water is added to react
Afterwards, TiO 2 precursor is hydrolyzed in layer mineral interlayer, titanium dioxide in interlayer by confinement acting growth, partial size it is smaller and
It is not easy to reunite.Solid product is recycled, it is multiple that the stratiform intercalation titanium dioxide prepared from ocean manganese nodule mineral is obtained after calcining
Condensation material.
The present invention is further illustrated with reference to embodiments.
Embodiment 1
1）After ocean manganese nodule raw ore is impregnated 7 d in simulated seawater, crushing grinding.60 min of ultrasonication makes it sufficiently
Dispersion, and 30 min are centrifugated under 15000 rpm rates, lower layer's granular precipitate substance is collected, it is dry at 150 DEG C
48 h；
2）Take manganese nodule and a certain amount of potassium permanganate in mass ratio 10 after handling：1 mixing, a small amount of oleic acid grinding, which is added, makes its mixing
Uniformly, mixture calcines 12 h at 1500 DEG C.Calcined product is put into the taper filled in 2 mol/L ammonium persulfate solutions
In bottle, 120 min are stirred.It filters, cleans after reaction, by filter residue in 150 DEG C of 24 h of constant temperature, layer mineral is made；
3）After the dispersion of layer mineral ultrasonic wave, layer mineral is added the cetyl trimethyl bromine of 2 times of ion exchange capacities
Change in ammonium, constant temperature is stirred to react 12 h under 90 DEG C of water-baths, continues 24 h of aging under water-bath, is made and is modified after washing, drying
Layer mineral.The butyl titanate ethanol solution of 500 mL, 10 mmol/L is prepared, is mixed after stirring 120 min, by 1 g/mL's
Modified layered mineral are added into solution for ratio, continue to be stirred to react 24 h；
4）It takes certain volume deionized water to be slowly dropped into said mixture, is stirred when being added dropwise, stand 24 h, wash, filtering
150 DEG C of dryings afterwards.800 DEG C of 12 h of calcining, products therefrom are the stratiform intercalation titanium dioxide prepared from ocean manganese nodule mineral
Composite material.
Fig. 1 is laminar titanium dioxide intercalation composite material prepared by the slave ocean manganese nodule mineral of the embodiment of the present invention 1
XRD spectrum.As seen from the figure, titanium dioxide in XRD spectrum（2θ=25.28°,37.80°,48.05°,53.89°,55.06°,
62.69°）Diffraction maximum it is very sharp, with standard PDF card compare（JCPDF 21-1272）, illustrate that the titanium dioxide generated is
Anatase.Diffraction maximum in XRD spectrum simultaneously containing layer mineral birnessite（2θ=12.38°,24.90°,34.92°）.
Illustrate that the stratiform intercalation composite titania material prepared from ocean manganese nodule mineral is successfully made in embodiment 1.
Fig. 2 is the transmission electron microscope photo of the laminar titanium dioxide intercalation composite material of the embodiment of the present invention 1, is illustrated compound
Pattern under material different resolution, it is seen that it is hexagonal prism shape under small scale, is spherical aggregate under large scale.100 nm
Photo of the visible black color titanium dioxide intercalation in light birnessite interlayer under resolution ratio.
Fig. 3 is the transmission electron microscope photo of the laminar titanium dioxide intercalation composite material of the embodiment of the present invention 1, illustrates 5 nm
Photo under resolution ratio, it is seen that three groups of lattice fringes, and fringe spacing is all 0.34 nm.Birnessite and Anatase dioxy
Change diffraction maximum of the titanium all containing 0.34 nm, therefore speculate that both possible is intercalation relationship, i.e., embodiment 1 is successfully made from ocean
The stratiform intercalation composite titania material of Manganese nodules preparation.
Fig. 4 is light of the laminar titanium dioxide intercalation composite material to positive decene petroleum hydrocarbon contaminant of the embodiment of the present invention 1
Catalytic degradation effect, and the degradation effect pair being simply mixed with manganese nodule raw ore, titanium dioxide, manganese nodule raw ore and titanium dioxide
Than figure.
Embodiment 2
1）After ocean manganese nodule raw ore is impregnated 1 d in simulated seawater, crushing grinding.1 min of ultrasonication makes it sufficiently
Dispersion, and 1 min is centrifugated under 500 rpm rates, lower layer's granular precipitate substance is collected, dry 2 h at 25 DEG C；
2）Take manganese nodule and a certain amount of potassium nitrate in mass ratio 0.1 after handling：1 mixing, a small amount of stearic acid grinding, which is added, keeps it mixed
It closes uniformly, mixture calcines 1 h at 500 DEG C.Calcined product is put into the cone filled in 0.1mol/L potassium persulfate solution
In shape bottle, 10 min are stirred.It filters, cleans after reaction, by filter residue in 60 DEG C of 0.5 h of constant temperature, layer mineral is made.
3）After the dispersion of layer mineral ultrasonic wave, layer mineral is added the Cetyl Chloride of 0.5 times of ion exchange capacity
Change in pyridine, constant temperature is stirred to react 0.5 h under 40 DEG C of water-baths, continues aging 1h under water-bath, is made and changes after washing, drying
Property layer mineral.0.5 mmol/L isopropyl titanate methanol solution of 50mL is prepared, is mixed after stirring 10 min, by 0.01 g/mL's
Modified layered mineral are added into solution for ratio, continue to be stirred to react 1 h；
4）It takes certain volume deionized water to be slowly dropped into said mixture, is stirred when being added dropwise, stand 6 h, washing, after filtering
50 DEG C of dryings.100 DEG C of 1 h of calcining, the stratiform intercalation titanium dioxide that products therefrom is prepared from ocean manganese nodule mineral are compound
Material.
Embodiment 3
1）After ocean manganese nodule raw ore is impregnated 1 d in simulated seawater, crushing grinding.60 min of ultrasonication fills it
Dispersion, and 30 min are centrifugated under 500 rpm rates, lower layer's granular precipitate substance is collected, it is dry at 25 DEG C
48 h；
2）Take manganese nodule and a certain amount of potassium manganate in mass ratio 0.1 after handling：1 mixing, is added a small amount of stearmide and stearic acid
Grinding is uniformly mixed it, and mixture calcines 1 h at 1500 DEG C.Calcined product is put into to fill 2 mol/L sodium peroxydisulfates molten
In conical flask in liquid, 10 min are stirred.It filters, cleans after reaction, by filter residue in 150 DEG C of 0.5 h of constant temperature, layered minerals are made
Object；
3）After the dispersion of layer mineral ultrasonic wave, layer mineral is added the trimethyl bromine of 2 times of ion exchange capacities
Change in ammonium, constant temperature is stirred to react 12 h under 40 DEG C of water-baths, continues aging 1h under water-bath, modified layer is made after washing, drying
Shape mineral.By 50 mL, 10 mmol/L glycerol titanate esters propylene glycol solution is prepared, mixed after stirring 120 min, by 0.01 g/
Modified layered mineral are added into solution for the ratio of mL, continue to be stirred to react 24 h；
4）It takes certain volume deionized water to be slowly dropped into said mixture, is stirred when being added dropwise, stand 6 h, washing, after filtering
150 DEG C of dryings.200 DEG C of 12 h of calcining, products therefrom are that the stratiform intercalation titanium dioxide prepared from ocean manganese nodule mineral is answered
Condensation material.
Embodiment 4
1）After ocean manganese nodule raw ore is impregnated 7 d in simulated seawater, crushing grinding.1 min of ultrasonication makes it sufficiently
Dispersion, and 1 min is centrifugated under 15000 rpm rates, lower layer's granular precipitate substance is collected, dry 2 at 150 DEG C
h；
2）Take manganese nodule and a certain amount of potassium hyperchlorate in mass ratio 10 after handling：1 mixing, a small amount of stearmide grinding, which is added, makes it
It is uniformly mixed, mixture calcines 12 h at 500 DEG C.Calcined product is put into and is filled in 0.1 mol/L ammonium persulfate solution
Conical flask in, stir 120 min.It filters, cleans after reaction, by filter residue in 60 DEG C of 24 h of constant temperature, layer mineral is made；
3）After the dispersion of layer mineral ultrasonic wave, layer mineral is added the octadecyldimethyl of 0.5 times of ion exchange capacity
In ammonium chloride and octadecyltrimethylammonium chloride, constant temperature is stirred to react 0.5 h under 90 DEG C of water-baths, continues under water-bath old
Change 24 h, modified layered mineral are made after washing, drying.Prepare 500 mL, 0.5 mmol/L titanium sulfate methanol solution, stirring 10
It is mixed after min, modified layered mineral is added into solution in the ratio of 1 g/mL, continue to be stirred to react 1 h；
4）It takes certain volume deionized water to be slowly dropped into said mixture, is stirred when being added dropwise, stand 24 h, wash, filtering
50 DEG C of dryings afterwards.400 DEG C of 1 h of calcining, products therefrom are that the stratiform intercalation titanium dioxide prepared from ocean manganese nodule mineral is answered
Condensation material.
Embodiment 5
1）After ocean manganese nodule raw ore is impregnated 7 d in simulated seawater, crushing grinding.30 min of ultrasonication fills it
Dispersion, and 30 min are centrifugated under 500 rpm rates, lower layer's granular precipitate substance is collected, it is dry at 100 DEG C
2 h；
2）Take manganese nodule and a certain amount of potassium permanganate in mass ratio 10 after handling：The double stearic grindings of a small amount of vinyl are added in 1 mixing
It is uniformly mixed it, mixture calcines 1 h at 1000 DEG C.Calcined product is put into fill 2 mol/L potassium hydrogen persulfates and
In conical flask in potassium persulfate solution, 60 min are stirred.It filters, cleans after reaction, by filter residue in 60 DEG C of 24 h of constant temperature, system
Obtain layer mineral；
3）After the dispersion of layer mineral ultrasonic wave, layer mineral is added the dimethylaminoethyl acrylate methyl ammonia of 1 times of ion exchange capacity
In ethyl ester trimethyl ammonium chloride, constant temperature is stirred to react 12 h under 40 DEG C of water-baths, continues 12 h of aging under water-bath, and washing is done
Modified layered mineral are made after dry.500 mL, 0.5 mmol/L butyl titanate glycerin solution is prepared, is mixed after stirring 60 min
It is even, modified layered mineral are added into solution in the ratio of 0.01 g/mL, continue to be stirred to react 24 h；
4）It takes certain volume deionized water to be slowly dropped into said mixture, is stirred when being added dropwise, stand 12 h, wash, filtering
50 DEG C of dryings afterwards.300 DEG C of 6 h of calcining, products therefrom are that the stratiform intercalation titanium dioxide prepared from ocean manganese nodule mineral is answered
Condensation material.
Embodiment 6
1）After ocean manganese nodule raw ore is impregnated 1 d in simulated seawater, crushing grinding.30 min of ultrasonication fills it
Dispersion, and 1 min is centrifugated under 5000 rpm rates, lower layer's granular precipitate substance is collected, it is dry at 90 DEG C
36 h；
2）Take manganese nodule and a certain amount of potassium manganate in mass ratio 10 after handling：1 mixing, a small amount of oleic acid grinding, which is added, keeps its mixing equal
Even, mixture calcines 8 h at 500 DEG C.Calcined product is put into the conical flask filled in 2 mol/L sodium peroxydisulfate solution
In, stir 10 min.It filters, cleans after reaction, by filter residue in 90 DEG C of 24 h of constant temperature, layer mineral is made；
3）After the dispersion of layer mineral ultrasonic wave, layer mineral is added the octadecyl trimethyl of 0.5 times of ion exchange capacity
In ammonium chloride, constant temperature is stirred to react 12 h under 60 DEG C of water-baths, continues 1 h of aging under water-bath, is made and changes after washing, drying
Property layer mineral.5 mmol/L, 400 mL titanium tetrachloride ethylene glycol solution is prepared, is mixed after stirring 30 min, by 0.5 g/mL
Ratio modified layered mineral are added into solution, continue to be stirred to react 1 h；
4）It takes certain volume deionized water to be slowly dropped into said mixture, is stirred when being added dropwise, stand 12 h, wash, filtering
50 DEG C of dryings afterwards.500 DEG C of 8 h of calcining, products therefrom are that the stratiform intercalation titanium dioxide prepared from ocean manganese nodule mineral is answered
Condensation material.
Embodiment 7
1）After ocean manganese nodule raw ore is impregnated 5 d in simulated seawater, crushing grinding.20 min of ultrasonication makes it sufficiently
Dispersion, and 15 min are centrifugated under 700 rpm rates, lower layer's granular precipitate substance is collected, dry 40 at 100 DEG C
h；
2）Take manganese nodule and a certain amount of potassium nitrate in mass ratio 1 after handling：1 mixing, a small amount of palmitic acid grinding, which is added, makes its mixing
Uniformly, mixture calcines 12 h at 1000 DEG C.Calcined product is put into the cone filled in 2 mol/L hydrogen persulfate potassium solutions
In shape bottle, 120 min are stirred.It filters, cleans after reaction, by filter residue in 80 DEG C of 24 h of perseverance, layer mineral is made；
3）After the dispersion of layer mineral ultrasonic wave, layer mineral is added the hexadecyldimethyl benzyl ammonium alkene of 2 times of ion exchange capacities
In propyl ammonium chloride, constant temperature is stirred to react 12 h under 80 DEG C of water-baths, continues 24 h of aging under water-bath, makes after washing, drying
Obtain modified layered mineral.50 mL, 10 mmol/L isopropyl titanate ethanol solution is prepared, is mixed after stirring 110 min, by 0.1 g/
Modified layered mineral are added into solution for the ratio of mL, continue to be stirred to react 8 h；
4）It takes certain volume deionized water to be slowly dropped into said mixture, is stirred when being added dropwise, stand 12 h, wash, filtering
90 DEG C of dryings afterwards.600 DEG C of 12 h of calcining, products therefrom are that the stratiform intercalation titanium dioxide prepared from ocean manganese nodule mineral is answered
Condensation material.
Stratiform intercalation composite titania material is to petroleum hydrocarbon contaminant（By taking positive decene as an example）Photocatalytic degradation effect evaluation
Experiment
It prepares the positive decene suspension of 1.19 g/L, optic catalytic composite material by the preparation of 1 condition of above-described embodiment is added to 2
G/L irradiates under 175 W high-pressure sodium lamp, 365 nm ultraviolet source, concussion reaction 0.25 h, 0.5 h, 1 h, 2 h, 3 h,
It is sampled after 4 h.N-hexane extraction is used after sampling, GC-MS method measures residual concentration.The result shows that composite material is to just in 1 h
The degradation rate of decene is 82.9%, and in 4 h, composite material is 93.9% to the degradation rate of positive decene.Take National Bureau of Oceanography second
The manganese nodule raw ore powder of research institute inventory, compares experiment under the same conditions, and degradation rate is 76.4% when 1 h, when 4 h
It is 79.6%.It takes butyl titanate ethanol solution that water is added to hydrolyze 500 DEG C and calcines titania powder obtained, under the same conditions
Compare experiment, degradation rate is 69.5% when degradation rate is 41.8%, 4h when 1h.Take above-mentioned manganese nodule and titanium dioxide by matter
Measure ratio 1：1 mixing, compares test under the same conditions, and degradation rate is 83.2% when degradation rate is 65.8%, 4h when 1h.It is attached
Fig. 4 is experimental result, it is seen that light of the stratiform intercalation composite titania material prepared from ocean manganese nodule mineral to positive decene
Catalytic degradation effect is better than manganese nodule raw ore and titanium dioxide, while mixing better than manganese nodule raw ore and the simple of titanium dioxide
It closes.Illustrate the stratiform intercalation composite titania material prepared from ocean manganese nodule mineral while there is preferable absorption and light to urge
Change ability, and intercalation is overlapped mutually in the titanium dioxide of interlayer and the photo-catalysis capability of layer mineral itself, obtains material group
The addition effect of conjunction, has been obviously improved the performance of product.
Claims (10)
1. a kind of new application of manganese nodule, which is characterized in that prepare layer mineral from ocean manganese nodule, nano-titanium dioxide is inserted
Enter the lattice interlayer to layer mineral, to obtain stratiform intercalation composite titania material.
2. new application according to claim 1, which is characterized in that the layer mineral be birnessite, like manganite,
One of vernadite, vernadite, lithiophorite are a variety of.
3. new application according to claim 1, which is characterized in that the nano-titanium dioxide is partial size in 1 ~ 500 nm
Titanium dioxide granule.
4. a kind of stratiform intercalation composite titania material, which is characterized in that nano-titanium dioxide is inserted into the crystalline substance of layer mineral
Between compartment, the layer mineral is the lamella knot formed with Mn oxide being prepared by raw material of ocean manganese nodule
Structure.
5. a kind of preparation method of stratiform intercalation composite titania material according to claim 4, which is characterized in that step
It is rapid as follows：
1）After ocean manganese nodule raw ore is impregnated 1 ~ 7 d in seawater or simulated seawater, crushing grinding, ultrasonication 1 ~
60 min keep its fully dispersed, and 1 ~ 30 min is centrifugated under 500 ~ 15000 rpm rates, collect lower layer's granular precipitate
Substance, dry 2 ~ 48 h obtain dry powdered manganese nodule raw ore at 25 ~ 150 DEG C；
2）Take dry powdered manganese nodule raw ore and strong oxidizer in mass ratio 0.1：1~10：1 mixing is added organic reagent and grinds
Mill is uniformly mixed it, and mixture calcines 1 ~ 12 h at 500 ~ 1500 DEG C, and calcined product is put into and fills 0.1 ~ 2 mol/L
In container in persulfate solution, 10 ~ 120 min are stirred, filters, clean after reaction, by filter residue in 60 ~ 150 DEG C of constant temperature
Layer mineral is made in 0.5 ~ 24 h；
3）After the dispersion of layer mineral ultrasonic wave, layer mineral is added in the organic modifiers of 0.5 ~ 2 times of ion exchange capacity,
Constant temperature is stirred to react 0.5 ~ 12 h under 40 ~ 90 DEG C of water-baths, continues 1 ~ 24 h of aging under water-bath, is made and changes after washing, drying
Property layer mineral, prepare 50 ~ 500 mL, 0.5 ~ 10 mmol/L TiO 2 precursor alcohol solution, stir 10 ~ 120 min
After mix, modified layered mineral are added into solution in the ratio of 0.01 ~ 1 g/mL, continuing to be stirred to react 1 ~ 24 h must mix
Object；
4）It removes ionized water and is slowly dropped into step 3）Mixture in, while be added dropwise while stir, stand 6 ~ 24 h, wash, after filtering
50 ~ 150 DEG C of dryings, 100 ~ 800 DEG C of 1 ~ 12 h of calcining, products therefrom is stratiform intercalation composite titania material.
6. preparation method according to claim 5, it is characterised in that step 2）Described in strong oxidizer be potassium permanganate, manganese
One of sour potassium, potassium nitrate, potassium hyperchlorate are a variety of；
Step 2）Described in organic reagent be oleic acid, it is stearic acid, palmitic acid, stearmide, vinyl bis-stearamides, three stearic
One of acid glyceride is a variety of.
7. preparation method according to claim 5, which is characterized in that step 2）Described in persulfate be ammonium persulfate,
One of potassium peroxydisulfate, sodium peroxydisulfate, potassium hydrogen persulfate are a variety of.
8. preparation method according to claim 5, which is characterized in that step 3）Described in organic modifiers be cetyl
Pyridinium chloride, cetyl trimethylammonium bromide, dodecyl trimethyl ammonium bromide, octadecyltrimethylammonium chloride, 18
Alkyl dimethyl ammonium chloride, neopelex, hexadecyldimethyl benzyl ammonium allyl ammonium chloride, dimethylaminoethyl acrylate methyl ammonia
One of ethyl ester trimethyl ammonium chloride is a variety of.
9. preparation method according to claim 5, which is characterized in that step 3）Described in TiO 2 precursor be metatitanic acid
Butyl ester, isopropyl titanate, glycerol titanate esters, in titanium sulfate, titanium tetrachloride it is one or more.
10. preparation method according to claim 5, which is characterized in that step 3）Described in alcohols be methanol, ethyl alcohol, second
One of glycol, propylene glycol, glycerine are a variety of.
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| CN100998933A (en) * | 2006-01-11 | 2007-07-18 | 中国科学院化学研究所 | Organic clay loaded with nanometer anatase type titanium dioxide and its preparation method and use |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100998933A (en) * | 2006-01-11 | 2007-07-18 | 中国科学院化学研究所 | Organic clay loaded with nanometer anatase type titanium dioxide and its preparation method and use |
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| ZONG-HUAI LIU等: "Swelling and Delamination Behaviors of Birnessite-Type Manganese Oxide by Intercalation of Tetraalkylammonium Ions", 《LANGMUIR》 * |
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