CN112939005A - 一种-clo结构超大孔磷酸铝和杂原子磷酸铝分子筛的合成方法 - Google Patents
一种-clo结构超大孔磷酸铝和杂原子磷酸铝分子筛的合成方法 Download PDFInfo
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- CN112939005A CN112939005A CN202110341963.8A CN202110341963A CN112939005A CN 112939005 A CN112939005 A CN 112939005A CN 202110341963 A CN202110341963 A CN 202110341963A CN 112939005 A CN112939005 A CN 112939005A
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- Prior art keywords
- chloride
- sulfate
- nitrate
- oxide
- acetate
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 52
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 47
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 27
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- 239000011148 porous material Substances 0.000 title description 27
- 239000011541 reaction mixture Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 37
- 238000002425 crystallisation Methods 0.000 claims description 31
- 230000008025 crystallization Effects 0.000 claims description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 14
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 14
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 3
- 229910000346 scandium sulfate Inorganic materials 0.000 claims description 3
- QHYMYKHVGWATOS-UHFFFAOYSA-H scandium(3+);trisulfate Chemical compound [Sc+3].[Sc+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QHYMYKHVGWATOS-UHFFFAOYSA-H 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- IHLDFUILQQSDCQ-UHFFFAOYSA-L C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] IHLDFUILQQSDCQ-UHFFFAOYSA-L 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 2
- 229910000011 cadmium carbonate Inorganic materials 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 2
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 claims description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 claims description 2
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 2
- 229940044658 gallium nitrate Drugs 0.000 claims description 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 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 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 2
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- CZDSWLXAULJYPZ-UHFFFAOYSA-J molybdenum(4+);dicarbonate Chemical compound [Mo+4].[O-]C([O-])=O.[O-]C([O-])=O CZDSWLXAULJYPZ-UHFFFAOYSA-J 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 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
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 2
- IIDYTZRUUWUVQF-UHFFFAOYSA-D niobium(5+) pentasulfate Chemical compound [Nb+5].[Nb+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IIDYTZRUUWUVQF-UHFFFAOYSA-D 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- DBTMQFKUVICLQN-UHFFFAOYSA-K scandium(3+);triacetate Chemical compound [Sc+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBTMQFKUVICLQN-UHFFFAOYSA-K 0.000 claims description 2
- NYMLCLICEBTBKR-UHFFFAOYSA-H scandium(3+);tricarbonate Chemical compound [Sc+3].[Sc+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NYMLCLICEBTBKR-UHFFFAOYSA-H 0.000 claims description 2
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 235000014692 zinc oxide Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- LQURNKRHPRARRS-UHFFFAOYSA-N zirconium(4+);tetrahypochlorite Chemical compound [Zr+4].Cl[O-].Cl[O-].Cl[O-].Cl[O-] LQURNKRHPRARRS-UHFFFAOYSA-N 0.000 claims description 2
- 229940001007 aluminium phosphate Drugs 0.000 claims 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- -1 quaternary ammonium cations Chemical class 0.000 abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010457 zeolite Substances 0.000 abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 abstract description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052732 germanium Inorganic materials 0.000 abstract description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052738 indium Inorganic materials 0.000 abstract description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 239000011733 molybdenum Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 2
- 239000010955 niobium Substances 0.000 abstract description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000154 gallium phosphate Inorganic materials 0.000 description 2
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical compound [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 0.000 description 2
- 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 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种具有国际沸石协会确认的‑CLO结构超大孔磷酸铝和杂原子(硅、镁、钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、镓、锗、锆、铌、钼、镉、铟、锡、镧或铈)磷酸铝分子筛的合成方法。该合成方法采用浓胶水热法，并以低量简单季铵阳离子为模板剂，具体合成步骤是将磷源、铝源、杂原子源(合成杂原子磷酸铝分子筛时加入)、季铵模板剂、氟源混合均匀得到初始反应混合物，再将初始反应混合物在密闭反应器中在一定温度条件下晶化一定时间，晶化后的产物经过滤、洗涤、干燥处理，得到具有‑CLO结构的磷酸铝或杂原子磷酸铝分子筛原粉。本发明合成方法具有合成过程简单、产量高、合成成本低、对环境友好等优点。
Description
技术领域
本发明涉及磷酸铝和杂原子磷酸铝超大孔分子筛的合成方法，更具体地说是一种采用浓胶水热法，以低量简单季铵阳离子为模板剂，合成具有-CLO结构磷酸铝和杂原子磷酸铝超大孔分子筛的方法。
背景技术
分子筛是一种具有规则孔道、独特表面性质的晶体多孔材料，因此被广泛用于离子交换、催化、吸附、分离等化工领域。分子筛的孔径是影响分子筛性能的一个重要因素，目前已经实现工业应用的分子筛材料孔径都小于0.75nm，这极大地限制了它们对大尺寸反应物分子的处理能力，为了克服传统分子筛在此方面的缺点，人们尝试合成更大孔径的分子筛材料。1988年，Davis等人成功合成出了首个具有十八元环的超大孔磷酸铝分子筛VPI-5，其孔径可达到1.2nm，后来人们又开发出许多新型超大孔分子筛材料，在1991年，Estermann等人报道了一种在水热条件下合成的具有20元环的超大微孔磷酸镓分子筛Cloverite(Nature,1991,352,320-323)，国际沸石协会指定该分子筛的拓扑结构代码为-CLO，其包括两套非交叉的三维8元环和20元环孔道。之后一段时间，人们相继成功合成了几种不同组成的-CLO型结构分子筛，有硅锗酸盐PKU-12(Dalton Trans.,2013,42,1360-1363)和磷酸铝DNL-1(CN201010102897.0；CN201010566760.0；Angew.Chem.Int.Ed.,2010,49,5367-5370；J.Colloid Interf.Sci.,2015,451,117-124；Chem.Eur.J.2018,24,2410-2417；Angew.Chem.Int.Ed.,2020,59,3455-3459；Solid State Sci.,2020,100,106118)，杂原子磷酸铝分子筛(CN201310334711.8；CN201310335637.1；CN201410816503.6；MicroporousMesoporous Mater.,2014,198,153-160；Microporous Mesoporous Mater.,2021,315,110915)。与磷酸镓和硅锗分子筛相比，磷酸铝和杂原子磷酸铝分子筛具有优异的稳定性能和较低的合成成本，因此-CLO结构超大孔磷酸铝和杂原子磷酸铝分子筛在催化、吸附和分离等领域展现出广阔的应用前景。然而，目前-CLO结构磷酸铝和杂原子磷酸铝超大孔分子筛的合成均采用离子热或溶剂热法，以大量的离子液体、低共熔混合物、有机胺、表面活性剂等为溶剂和模板剂，这不可避免的带来环境污染和合成成本昂贵的问题。浓胶水热法合成分子筛具有模板剂用量少、晶化时间短、分子筛产率高、合成过程环境友好等优势，因此被认为是一种绿色的分子筛合成方法。
发明内容
本发明旨在公开一种国际沸石协会确认的-CLO结构磷酸铝和杂原子磷酸铝分子筛的合成方法。-CLO结构具有两套非交叉的三维8元环和20元环孔道，磷酸铝分子筛骨架由磷原子和铝原子通过氧原子桥接而成，杂原子磷酸铝分子筛为磷酸铝分子筛中部分的磷或铝原子被硅、镁、钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、镓、锗、锆、铌、钼、镉、铟、锡、镧或铈等杂原子取代。
本发明的目的通过以下技术方案实现：
采用浓胶水热法，以低量简单季铵阳离子为模板剂合成-CLO结构磷酸铝和杂原子磷酸铝分子筛，其合成步骤如下：
(a)将磷源、铝源、杂原子源(合成杂原子磷酸铝分子筛时加入)、季铵模板剂、氟源搅拌混合均匀得到浓胶初始反应混合物，混合物中磷源：铝源：杂原子源：氟源：季铵模板剂：水的摩尔比为1：0.8-1.2：0-1.0：0.1-2.0：0.1-1.0：0-4；
(b)将步骤(a)所得的浓胶初始反应混合物在一定温度下晶化一定时间；
(c)步骤(b)结束后，将产物进行洗涤、过滤和干燥，即可得-CLO结构超大孔磷酸铝或杂原子磷酸铝分子筛原粉。
上述合成方法步骤(a)所述的磷源为磷酸、磷酸一氢铵、磷酸二氢铵、磷酸铵中的一种或几种；
上述合成方法步骤(a)所述的铝源为异丙醇铝、拟薄水铝石、乙酸铝、硝酸铝、硫酸铝、氢氧化铝、氯化铝、氧化铝、高岭土中的一种或几种；
上述合成方法步骤(a)所述的杂原子源为正硅酸四乙酯、正硅酸四甲酯、白炭黑、硅溶胶、乙酸镁、硝酸镁、硫酸镁、氯化镁、碳酸镁、氧化镁、乙酸钪、硝酸钪、硫酸钪、氯化钪、碳酸钪、氧化钪、钛酸四乙酯、钛酸四甲酯、硝酸钛、硫酸钛、氯化钛、氧化钛、硝酸钒、硫酸钒、氯化钒、氧化钒、乙酸铬、硝酸铬、硫酸铬、氯化铬、碳酸铬、氧化铬、乙酸锰、硝酸锰、硫酸锰、氯化锰、碳酸锰、氧化锰、乙酸铁、硝酸铁、硫酸铁、氯化铁、碳酸铁、氧化铁、乙酸钴、硝酸钴、硫酸钴、氯化钴、碳酸钴、氧化钴、乙酸镍、硝酸镍、硫酸镍、氯化镍、碳酸镍、氧化镍、乙酸铜、硝酸铜、硫酸铜、氯化铜、碳酸铜、氧化铜、乙酸锌、硝酸锌、硫酸锌、氯化锌、碳酸锌、氧化锌、乙酸镓、硝酸镓、硫酸镓、氯化镓、碳酸镓、氧化镓、乙酸锗、氯化锗、氧化锗、乙酸锆、硝酸锆、硫酸锆、氯化锆、次氯酸锆、碳酸锆、氧化锆、硝酸铌、硫酸铌、氯化铌、氧化铌、乙酸钼、硝酸钼、硫酸钼、氯化钼、碳酸钼、氧化钼、乙酸镉、硝酸镉、硫酸镉、氯化镉、碳酸镉、氧化镉、乙酸铟、硝酸铟、硫酸铟、氯化铟、氧化铟、乙酸锡、硫酸锡、氯化锡、氧化锡、乙酸镧、硝酸镧、硫酸镧、氯化镧、碳酸镧、氧化镧、乙酸铈、硝酸铈、硫酸铈、氯化铈、碳酸铈、氧化铈中的一种或几种；
上述合成方法步骤(a)所述的季铵模板剂为四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、四甲基氯化铵、四乙基氯化铵、四丙基氯化铵、四丁基氯化铵、四甲基溴化铵、四乙基溴化铵、四丙基溴化铵、四丁基溴化铵中的一种或几种；
上述合成方法步骤(a)所述的氟源为氢氟酸、氟化铵、氟化钠中的一种或几种；
上述合成方法步骤(b)的晶化温度为130～300℃，晶化时间为1分钟～5天，晶化过程的加热方式采用烘箱加热或油浴加热；
本发明公开的一种以低量简单季铵阳离子为模板剂，浓胶水热法合成-CLO结构磷酸铝和杂原子磷酸铝分子筛的合成方法，与离子热和溶剂热法合成-CLO结构分子筛相比，浓胶水热法合成分子筛具有模板剂用量少、晶化时间短、分子筛产率高、合成成本低、合成过程简单安全、对环境友好等优势，有利于-CLO结构磷酸铝和杂原子磷酸铝分子筛的工业化生产。
附图说明
图1是本发明实施例1中样品的XRD谱图；
图2是本发明实施例2中样品的XRD谱图；
图3是本发明实施例3中样品的XRD谱图；
图4是本发明实施例4中样品的XRD谱图；
图5是本发明实施例5中样品的XRD谱图；
图6是本发明实施例6中样品的XRD谱图；
图7是本发明实施例7中样品的XRD谱图；
图8是本发明实施例8中样品的XRD谱图；
图9是本发明实施例9中样品的XRD谱图；
图10是本发明实施例10中样品的XRD谱图；
图11是本发明实施例11中样品的XRD谱图；
图12是本发明实施例12中样品的XRD谱图。
具体实施方式
下面结合实施例与附图对本发明进一步地描述，但本发明的实施方式不限于此，不能理解为对本发明保护范围的限制。
实施例1
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图1。
实施例2
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入645μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图2。
实施例3
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，0.49g的硝酸钛，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图3。
实施例4
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，0.56g的硝酸锆，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图4。
实施例5
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，125μl正硅酸四乙酯，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图5。
实施例6
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，375μl正硅酸四乙酯，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图6。
实施例7
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，625μl正硅酸四乙酯，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图7。
实施例8
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，0.65g的九水合硝酸铬，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图8。
实施例9
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，0.3g的硝酸镍，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图9。
实施例10
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，0.29g的硝酸锰，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图10。
实施例11
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，0.3g的硝酸钴，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图11。
实施例12
将374μl磷酸(浓度为85wt％)加入到50ml玻璃烧杯中，在保持110℃及搅拌的条件下，加入968μl四乙基氢氧化铵(浓度为25wt％)，242μl氢氟酸(浓度为40wt％)，1.12g的异丙醇铝，0.4g的硝酸铁，将初始反应混合物保持在110℃的条件下继续搅拌30min，使初始反应混合物呈纯白色固体。再将此纯白色固体置于装有聚四氟乙烯内衬的不锈钢反应釜中，密封好后放入180℃烘箱中晶化4小时。
晶化结束后将反应釜取出，冷却至室温，将产物用去离子水洗涤、过滤，分离所得产物在90℃烘箱中干燥3小时，即可得到白色粉末产物。产物经XRD分析，结果表明得到的产物具有-CLO拓扑结构的磷酸铝基超大孔分子筛，样品的XRD谱图见附图12。
Claims (10)
1.一种采用浓胶水热法，以低量简单季铵阳离子为模板剂，合成具有国际沸石协会确认的-CLO结构超大孔磷酸铝和杂原子磷酸铝分子筛的合成方法。
2.一种权利要求1所述-CLO结构超大孔磷酸铝和杂原子磷酸铝分子筛的合成方法，其合成步骤如下：
(a)将磷源、铝源、杂原子源(合成杂原子磷酸铝分子筛时加入)、季铵模板剂、氟源搅拌混合均匀得到浓胶初始反应混合物，混合物中磷源：铝源：杂原子源：氟源：季铵模板剂：水的摩尔比为1：0.8-1.2：0-1.0：0.1-2.0：0.1-1.0：0-4；
(b)将步骤(a)所得的浓胶初始反应混合物在一定温度下晶化一定时间；
(c)步骤(b)结束后，将产物进行洗涤、过滤和干燥，所得固体粉末即为-CLO结构磷酸铝或杂原子磷酸铝分子筛原粉。
3.根据权利要求2所述的方法，其特征在于：步骤(a)中的季铵模板剂为四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、四甲基氯化铵、四乙基氯化铵、四丙基氯化铵、四丁基氯化铵、四甲基溴化铵、四乙基溴化铵、四丙基溴化铵、四丁基溴化铵中的一种或几种。
4.根据权利要求2所述的方法，其特征在于：步骤(a)中的磷源为磷酸、磷酸一氢铵、磷酸二氢铵、磷酸铵中的一种或几种。
5.根据权利要求2所述的方法，其特征在于：步骤(a)中的铝源为异丙醇铝、拟薄水铝石、乙酸铝、硝酸铝、硫酸铝、氢氧化铝、氯化铝、氧化铝、高岭土中的一种或几种。
6.根据权利要求2所述的方法，其特征在于：步骤(a)中的杂原子源为正硅酸四乙酯、正硅酸四甲酯、白炭黑、硅溶胶、乙酸镁、硝酸镁、硫酸镁、氯化镁、碳酸镁、氧化镁、乙酸钪、硝酸钪、硫酸钪、氯化钪、碳酸钪、氧化钪、钛酸四乙酯、钛酸四甲酯、硝酸钛、硫酸钛、氯化钛、氧化钛、硝酸钒、硫酸钒、氯化钒、氧化钒、乙酸铬、硝酸铬、硫酸铬、氯化铬、碳酸铬、氧化铬、乙酸锰、硝酸锰、硫酸锰、氯化锰、碳酸锰、氧化锰、乙酸铁、硝酸铁、硫酸铁、氯化铁、碳酸铁、氧化铁、乙酸钴、硝酸钴、硫酸钴、氯化钴、碳酸钴、氧化钴、乙酸镍、硝酸镍、硫酸镍、氯化镍、碳酸镍、氧化镍、乙酸铜、硝酸铜、硫酸铜、氯化铜、碳酸铜、氧化铜、乙酸锌、硝酸锌、硫酸锌、氯化锌、碳酸锌、氧化锌、乙酸镓、硝酸镓、硫酸镓、氯化镓、碳酸镓、氧化镓、乙酸锗、氯化锗、氧化锗、乙酸锆、硝酸锆、硫酸锆、氯化锆、次氯酸锆、碳酸锆、氧化锆、硝酸铌、硫酸铌、氯化铌、氧化铌、乙酸钼、硝酸钼、硫酸钼、氯化钼、碳酸钼、氧化钼、乙酸镉、硝酸镉、硫酸镉、氯化镉、碳酸镉、氧化镉、乙酸铟、硝酸铟、硫酸铟、氯化铟、氧化铟、乙酸锡、硫酸锡、氯化锡、氧化锡、乙酸镧、硝酸镧、硫酸镧、氯化镧、碳酸镧、氧化镧、乙酸铈、硝酸铈、硫酸铈、氯化铈、碳酸铈、氧化铈中的一种或几种。
7.根据权利要求2所述的方法，其特征在于：步骤(a)中的氟源为氢氟酸、氟化铵、氟化钠中的一种或几种。
8.根据权利要求2所述的方法，其特征在于：步骤(a)所得的浓胶初始反应混合物中的少量水可由反应原料引入或额外加入。
9.根据权利要求2所述的方法，其特征在于：步骤(b)晶化温度为130～300℃。
10.根据权利要求2所述的方法，其特征在于：步骤(b)晶化时间为:1分钟～5天。
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