CN111792909B - 一种磁性硅柱撑层状粘土球团的制备方法及应用 - Google Patents
一种磁性硅柱撑层状粘土球团的制备方法及应用 Download PDFInfo
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- CN111792909B CN111792909B CN202010556741.3A CN202010556741A CN111792909B CN 111792909 B CN111792909 B CN 111792909B CN 202010556741 A CN202010556741 A CN 202010556741A CN 111792909 B CN111792909 B CN 111792909B
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- layered clay
- magnetic silicon
- magnetic
- silicon pillared
- pellet
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- 239000004927 clay Substances 0.000 title claims abstract description 60
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 50
- 239000010703 silicon Substances 0.000 title claims abstract description 50
- 239000008188 pellet Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000012798 spherical particle Substances 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 7
- 150000002505 iron Chemical class 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
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- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims abstract description 3
- 238000005096 rolling process Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- -1 dodecyl quaternary ammonium salt Chemical class 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 6
- 229960001545 hydrotalcite Drugs 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001083 [(2R,3R,4S,5R)-1,2,4,5-tetraacetyloxy-6-oxohexan-3-yl] acetate Substances 0.000 claims description 3
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 claims description 3
- 229910001430 chromium ion Inorganic materials 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011790 ferrous sulphate Substances 0.000 claims description 2
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- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- YDCPQRQGABOSRY-UHFFFAOYSA-N iron;urea Chemical compound [Fe].NC(N)=O YDCPQRQGABOSRY-UHFFFAOYSA-N 0.000 claims description 2
- 229960002969 oleic acid Drugs 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 15
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- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
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- 239000002253 acid Substances 0.000 description 2
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
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- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
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- 238000011084 recovery Methods 0.000 description 2
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- JYVDPJQDVPRECD-UHFFFAOYSA-N [Fe+3].NC(=O)N Chemical compound [Fe+3].NC(=O)N JYVDPJQDVPRECD-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
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- 238000000975 co-precipitation Methods 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229940032950 ferric sulfate Drugs 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- SUOTZEJYYPISIE-UHFFFAOYSA-N iron(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SUOTZEJYYPISIE-UHFFFAOYSA-N 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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Abstract
本发明公开了一种磁性硅柱撑层状粘土球团的制备方法及应用。制备过程包括:将硅源、表面活性剂溶解于乙醇中,在氮气或氩气的气氛下加入铁盐和分散剂,将得到的混合溶液与层状粘土悬浮液搅拌,加入碱性溶液调整pH值,经过洗涤、磁分离、真空干燥、研磨,得到磁性硅柱撑结构的层状粘土;将硅溶胶、铝溶胶等无机成型剂以液膜形式覆盖在固体颗粒上,采用滚动成型法,在转盘成型机中形成球形颗粒,在N2气氛下焙烧制得磁性硅柱撑层状粘土球团,该材料在重金属离子吸附和有机废水催化降解领域有着广阔的应用前景。
Description
技术领域
本发明涉及一种磁性硅柱撑层状粘土球团的制备方法及应用,属于环境工程和材料工程技术领域。
背景技术
近年来,随着化工、制药、炼油、纺织和印染等行业的快速发展,所产生的重金属和有机工业废水严重威胁着环境和人类的生命健康,对这类工业废水的处理迫在眉睫。
粘土矿物因廉价易得而被广泛用于水处理材料的研究。中国专利CN201610470204.0报道了基于粘土矿物的高效类芬顿磁性催化剂及制备方法与应用,但该发明只是将粘土矿物作为催化剂载体,没有更好地利用到柱撑粘土矿物良好的吸附性能。中国专利CN201710059326.5报道了AlCe柱撑粘土的制备方法,增加了粘土的层间距和比表面积,有效提高了粘土的吸附性能,但材料缺乏磁性回收利用性能。中国专利CN201810236507.5报道了一种磁性多孔膨润土壳聚糖复合微球制备方法,证明了经过成型的材料可以增大材料的反应接触面积,提高吸附速率,然而材料中用到的壳聚糖耐酸性较差,影响材料使用的稳定性。
综上,目前制备的粘土矿物水处理材料中,存在材料磁性回收能力差、吸附能力弱、稳定性差等问题。
发明内容
本发明旨在提供一种磁性硅柱撑层状粘土球团的制备方法及应用,利用层状粘土矿物开发出一种工艺简单、低成本、绿色环保、高稳定的磁性硅柱撑层状粘土球团。
本发明的原理如下:硅源通过溶剂化嵌入表面活性剂中,与表面活性剂分子一同通过离子交换嵌入粘土夹层;在碱性环境中同时发生硅源水解和共沉淀反应形成磁性硅柱撑结构的层状粘土;分散剂的加入可以有效降低四氧化三铁的团聚程度,保证形成的磁性纳米颗粒高度分散;磁性硅柱撑层状粘土在无机成型剂的作用下,于转盘成型机中转动成型,经过洗涤、磁分离、干燥、高温煅烧得到磁性硅柱撑层状粘土球团。球团结构使得四氧化三铁稳定牢固的与载体结合,并且增大了材料的反应接触面积;煅烧后的材料中形成的介孔结构决定了材料具有高效吸附性,可以有效将污染物吸附于材料周围,进一步提高催化性能。
本发明提供了一种磁性硅柱撑层状粘土球团的制备方法,包括以下步骤:
(1)将层状粘土加入蒸馏水中混合得到粘土悬浮液;以表面活性剂为结构导向剂与硅源溶解于乙醇中,通入氮气或氩气,引入铁盐,加入分散剂更好地分散铁盐,搅拌0.5~3h,形成混合液;将上述混合液缓慢加入粘土悬浮液中,搅拌0.5~3 h,形成反应液,向上述反应液中缓慢滴入碱性溶液,将pH调至8~13,继续搅拌1~5 h,硅源水解和铁盐共沉淀形成二氧化硅和四氧化三铁,磁分离收集产品,在90~120℃下真空干燥6~12 h,研磨后得到中间产物磁性硅柱撑结构的层状粘土;
所述的层状粘土为膨润土、蒙脱石、高岭土、伊利石、水滑石中的一种或多种混合。所述的表面活性剂为长链季铵盐和非离子型表面活性剂形成的复配溶液。所述的硅源为偏硅酸钠、正硅酸乙酯其中之一。所述的铁盐为氯化亚铁、氯化铁、硫酸亚铁、硫酸铁、硝酸亚铁、硝酸铁、醋酸铁(Ⅱ)、尿素铁(Ⅲ)中的一种或多种。所述的分散剂为油酸、聚乙二醇400、聚乙二醇200、葡萄糖五乙酸酯中的一种。所述的碱性溶液为氨水、氢氧化钠溶液、碳酸钠溶液其中之一。
(2)将磁性硅柱撑结构的层状粘土放于转盘成型机中,连续喷入无机成型剂,使无机成型剂以液膜形式覆盖在固体颗粒表面,随盘滚动逐渐形成球形颗粒,在N2气氛下于300~450℃下焙烧2~18 h,最终得到磁性硅柱撑层状粘土球团。
所述的无机成型剂为硅溶胶、铝溶胶的其中之一。
优选地,步骤(1)中长链季铵盐包括十二烷基季铵盐、十六烷基季铵盐、十八烷基季铵盐中的一种。非离子型表面活性剂包括不饱和脂肪酰胺、聚醚型非离子表面活性剂中的一种。n(长链季铵盐):n(非离子型表面活性剂)=(0.6~3),n为摩尔数。
优选地,步骤(1)中n(层状粘土):n(表面活性剂):n(硅源):n(铁盐):n(分散剂):n(乙醇):n(水)=1:(1~5):(2~4):(0.2~4):(4~10):(20~50):250,n为摩尔数
优选地,步骤(1)中氨水的质量百分浓度为25%,所述氢氧化钠溶液的浓度为0.5~3mol/L,碳酸钠溶液的浓度为0.5~3mol/L。
优选地,步骤(1)中碱性溶液的滴加速率控制在60~100滴/min。
优选地,步骤(1)中洗涤与磁分离的步骤重复3~5次。
优选地,步骤(2)中硅溶胶中二氧化硅的质量分数为35~50%,铝溶胶中氧化铝的质量分数为20~25%。
优选地,步骤(2)中无机成型剂的用量按照V(水):V(无机成型剂)=1~10,V为体积。
优选地,步骤(2)中圆盘式容器的转速为50~200rpm。
本发明提供了上述磁性硅柱撑层状粘土球团在重金属离子吸附中的应用,制备出的材料可以用作吸附材料,用量为0.1~1g的材料能用于吸附50~200mL浓度为50~1000mg/L的重金属离子;所述的重金属离子为铜离子、镍离子、铬离子中的一种。
本发明提供了上述磁性硅柱撑层状粘土球团在有机污染物催化降解中的应用,制备出的材料可以用作类芬顿催化材料,用量为0.01~0.5g的材料能用于吸附50~200mL浓度为50~1000mg/L的有机污染物;所述的有机污染物为苯酚、双酚A、喹啉中的一种或多种。
本发明的有益效果:
(1)本发明利用廉价易得的层状粘土矿物制备的磁性硅柱撑层状粘土球团材料可以被简单的磁性设备吸引,具有良好的磁响应性,有利于材料回收,不会造成二次污染;
(2)本发明制备的材料吸附能力增强,可以将污染物快速吸附于材料上或材料周围,也使得催化效率显著提高;
(3)本发明制备的材料与单纯四氧化三铁分别都在pH=5的酸性溶液中浸泡2h后,装有单纯四氧化三铁的瓶子中溶液变黄,有铁离子浸出,而装有材料的瓶子中仍然是澄清溶液,说明制备出的磁性硅柱撑层状粘土球团材料耐酸性很强、耐腐蚀,可以有效拓宽材料的使用范围。
具体实施方式
下面通过实施例来进一步说明本发明,但不局限于以下实施例。
实施例1:
取10g蒙脱石于200mL的烧杯中,加入80mL蒸馏水形成蒙脱石悬浮液,将其转移至500mL的三口烧瓶中。取50mL的乙醇于200mL的烧杯中,向其中依次加入55mL正硅酸乙酯、2g油酸酰胺和2.5g十八烷基三甲基氯化铵,通入N2,加入8g硫酸铁、7g七水硫酸亚铁20mL聚乙二醇400,搅拌1h。将混合液缓慢加入蒙脱石悬浮液中,搅拌1 h。用氢氧化钠溶液(0.5mol/L)将混合液调至pH=12,搅拌1h。醇洗1次,水洗2次,经过磁分离得到的产物于90℃下真空干燥12h,研磨后将产物放于转盘成型机中,向其中连续喷入30mL硅溶胶(40%),随盘转动逐渐形成球形颗粒,转速为100rpm。在N2气氛下,300℃煅烧12h得到磁性硅柱撑层状粘土球团材料。
将0.5g本实施例所得材料用于100mL 1000mg/L模拟镍离子废水中吸附,用分光光度仪测定吸附前后的离子浓度,120min内镍离子吸附率达95%以上。
实施例2:取10g高岭土于200mL的烧杯中,加入80mL蒸馏水形成高岭土悬浮液,将其转移至500mL的三口烧瓶中。取45mL的乙醇于200mL的烧杯中,向其中依次加入70mL正硅酸乙酯、5g芥酸酰胺和6g十八烷基三甲基溴化铵,通入N2,加入9g九水合硝酸铁、5g六水合硝酸亚铁和25mL的聚乙二醇200,搅拌0.5h。将混合液缓慢加入高岭土悬浮液中,搅拌3h。用碳酸钠溶液(0.5mol/L)将混合液调至pH=9,搅拌1h。醇洗2次,水洗2次,经过磁分离得到的产物于120℃下真空干燥6h,研磨后将产物放于转盘成型机中,向其中连续喷入50mL硅溶胶(35%),随盘转动逐渐形成球形颗粒,转速为80rpm。在N2气氛下,400℃煅烧6h得到磁性硅柱撑层状粘土球团材料。
将0.5g本实施例所得材料用于100mL 1000mg/L模拟铜离子废水中吸附,用分光光度仪测定吸附前后的离子浓度,120min内铜离子吸附率达95%以上。
实施例3:取10g水滑石于200mL的烧杯中,加入80mL蒸馏水形成水滑石悬浮液,将其转移至500mL的三口烧瓶中。取30mL的乙醇于200mL的烧杯中,向其中依次加入65g偏硅酸钠、8g芥酸酰胺和15g十二烷基三甲基溴化铵,通入氩气,加入6g醋酸铁(Ⅱ)、10g尿素铁(Ⅲ)和25mL的油酸,搅拌3h。将混合液缓慢加入水滑石悬浮液中,搅拌1h。用氨水溶液(25%)将混合液调至pH=11,搅拌2h。醇洗2次,水洗1次,经过磁分离得到的产物于100℃下真空干燥15h,研磨后将产物放于转盘成型机中,向其中连续喷入60mL铝溶胶(25%),随盘转动逐渐形成球形颗粒,转速为90rpm。在氩气气氛下,350℃煅烧8h得到磁性硅柱撑层状粘土球团。
将0.6g本实施例所得材料用于100mL 800mg/L模拟铬离子离子废水中吸附,用分光光度仪测定吸附前后的离子浓度,120min内铜离子吸附率达90%以上。
实施例4:取10g膨润土和5g伊利石于200mL的烧杯中,加入100mL蒸馏水形成粘土悬浮液,将其转移至500mL的三口烧瓶中。取50mL的乙醇于200mL的烧杯中,向其中依次加入80g偏硅酸钠、4g油酸酰胺和5g十二烷基三甲基氯化铵,通入氩气,加入12g六水合氯化铁、8g四水合氯化亚铁和30mL葡萄糖五乙酸酯,搅拌1h。将混合液缓慢加入粘土悬浮液中,搅拌2h得到混合液。用碳酸钠溶液(2mol/L)将混合液调至pH=12,搅拌0.5h。醇洗2次,水洗3次,经过磁分离得到的产物于110℃下真空干燥12h,研磨后将产物放于转盘成型机中,向其中连续喷入60mL铝溶胶(20%),转动逐渐形成球形颗粒,转速为120rpm。在氩气气氛下,350℃煅烧15h得到磁性硅柱撑层状粘土球团。
将0.05g本实施例所得材料与3mL的过硫酸钠溶液(20%)用于100mL 1000mg/L模拟苯酚溶液中类芬顿催化降解,用高位液相色谱仪测定催化前后的苯酚浓度,50min内苯酚完全降解。
实施例5:取10g高岭土和10g水滑石于200mL的烧杯中,加入150mL蒸馏水形成粘土悬浮液,将其转移至500mL的三口烧瓶中。取50mL的乙醇于200mL的烧杯中,向其中依次加入90g偏硅酸钠、7g脂肪醇聚氧乙烯醚和9g十六烷基三甲基氯化铵,通入氩气,加入15g硫酸铁、10g七水硫酸亚铁和40mL聚乙二醇400,搅拌0.5h。将混合液缓慢加入粘土悬浮液中,搅拌2h得到混合液。用氢氧化钠溶液(1mol/L)将混合液调至pH=11,搅拌2h。醇洗2次,水洗3次,经过磁分离得到的产物于100℃下真空干燥15h,研磨后将产物放于转盘成型机中,向其中连续喷入80mL硅溶胶(40%),随盘转动逐渐形成球形颗粒,转速为115rpm。在氩气气氛下,400℃煅烧13h得到磁性硅柱撑层状粘土球团。
将0.06g本实施例所得材料与5mL过氧化氢溶液(30%)用于100mL 800mg/L模拟双酚A溶液中类芬顿催化降解,用高位液相色谱仪测定催化前后的双酚A浓度,40min内双酚A完全降解。
实施例6:取10g蒙脱石和10g高岭土于200mL的烧杯中,加入150mL蒸馏水形成粘土悬浮液,将其转移至500mL的三口烧瓶中。取50mL的乙醇于200mL的烧杯中,向其中依次加入70g偏硅酸钠、5g脂肪醇聚氧乙烯醚和10g十六烷基三甲基氯化铵,通入氩气,加入18g硫酸铁、12g七水硫酸亚铁和40mL聚乙二醇400,搅拌0.5h。将混合液缓慢加入粘土悬浮液中,搅拌2h得到混合液。用氢氧化钠溶液(1mol/L)将混合液调至pH=11,搅拌2h。醇洗2次,水洗3次,经过磁分离得到的产物于100℃下真空干燥10h,研磨后将产物放于转盘成型机中,向其中连续喷入50mL硅溶胶(30%),随盘转动逐渐形成球形颗粒,转速为120rpm。在氩气气氛下,400℃煅烧12h得到磁性硅柱撑层状粘土球团。
将0.05g本实施例所得材料与4mL过氧化氢溶液(30%)用于100mL 800mg/L模拟喹啉溶液中类芬顿催化降解,用高位液相色谱仪测定催化前后的喹啉浓度,30min内喹啉完全降解。
Claims (9)
1.一种磁性硅柱撑层状粘土球团的制备方法,其特征在于包括以下步骤:
(1)将层状粘土加入蒸馏水中混合得到粘土悬浮液;以表面活性剂为结构导向剂与硅源溶解于乙醇中,通入氮气或氩气,引入铁盐,加入分散剂更好地分散铁盐,搅拌0.5~3 h,形成混合液;将上述混合液缓慢加入粘土悬浮液中,搅拌0.5~3 h,形成反应液,向上述反应液中缓慢滴入碱性溶液,将pH调至8~13,继续搅拌1~5 h,硅源水解和铁盐共沉淀形成二氧化硅和四氧化三铁,磁分离收集产品,在90~120℃下真空干燥6~12 h,研磨后得到中间产物磁性硅柱撑结构的层状粘土;
(2)将磁性硅柱撑结构的层状粘土放于转盘成型机中,连续喷入无机成型剂,使无机成型剂以液膜形式覆盖在固体颗粒表面,随盘滚动逐渐形成球形颗粒,在N2气氛下于300~450℃下焙烧2~18 h,最终得到磁性硅柱撑层状粘土球团;
所述的层状粘土为膨润土、蒙脱石、高岭土、伊利石、水滑石中的一种或多种混合;所述的硅源为偏硅酸钠、正硅酸乙酯其中之一;所述的分散剂为油酸、聚乙二醇400、聚乙二醇200、葡萄糖五乙酸酯中的一种;所述的无机成型剂为硅溶胶、铝溶胶中的一种;n(层状粘土):n(表面活性剂):n(硅源):n(铁盐):n(分散剂):n(乙醇):n(水)=1:(1~5):(2~4):(0.2~4):(4~10):(20~50):250,n为摩尔数。
2.根据权利要求1所述的磁性硅柱撑层状粘土球团的制备方法,其特征在于:所述的表面活性剂为长链季铵盐和非离子型表面活性剂形成的复配溶液。
3.根据权利要求2所述的磁性硅柱撑层状粘土球团的制备方法,其特征在于:长链季铵盐包括十二烷基季铵盐、十六烷基季铵盐、十八烷基季铵盐中的一种;非离子型表面活性剂包括不饱和脂肪酰胺、聚醚型非离子表面活性剂中的一种;n(长链季铵盐):n(非离子型表面活性剂)=0.6~3,n为摩尔数。
4.根据权利要求1所述的磁性硅柱撑层状粘土球团的制备方法,其特征在于:所述的铁盐为氯化亚铁、氯化铁、硫酸亚铁、硫酸铁、硝酸亚铁、硝酸铁、醋酸铁(Ⅱ)、尿素铁(Ⅲ)中的一种或多种。
5.根据权利要求1所述的磁性硅柱撑层状粘土球团的制备方法,其特征在于:所述的碱性溶液为氨水、氢氧化钠溶液、碳酸钠溶液中的一种;所述氨水的质量百分浓度为25%,所述氢氧化钠溶液的浓度为0.5~3mol/L,碳酸钠溶液的浓度为0.5~3mol/L;
碱性溶液的滴加速率控制在60~100滴/min。
6.根据权利要求1所述的磁性硅柱撑层状粘土球团的制备方法,其特征在于:所述硅溶胶中二氧化硅的质量分数为35~50%,铝溶胶中氧化铝的质量分数为20~25%;
无机成型剂的用量按照体积比为:V(水):V(无机成型剂)=1~10,V为体积。
7.根据权利要求1所述的磁性硅柱撑层状粘土球团的制备方法,其特征在于:步骤(2)中转盘成型机的转速为50~200rpm。
8.一种权利要求1~7任一项所述的制备方法制得的磁性硅柱撑层状粘土球团在重金属离子吸附中的应用,其特征在于:所述的重金属离子为铜离子、镍离子、铬离子中的一种;每0.1~1g磁性硅柱撑层状粘土球团材料能用于吸附50~200mL浓度为50~1000mg/L的重金属离子。
9.一种权利要求1~7任一项所述的制备方法制得的磁性硅柱撑层状粘土球团在有机污染物催化降解中的应用,其特征在于:所述的有机污染物为苯酚、双酚A、喹啉中的一种或多种;每0.01~0.5g磁性硅柱撑层状粘土球团材料能用于吸附50~200mL浓度为50~1000mg/L的有机污染物。
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