CN112742415A - 一种TiO2纳米管复合铜基硅基催化剂、制备方法及其应用 - Google Patents
一种TiO2纳米管复合铜基硅基催化剂、制备方法及其应用 Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 120
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 91
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 44
- 239000010703 silicon Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002071 nanotube Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 65
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 55
- 239000007787 solid Substances 0.000 claims description 55
- 239000007864 aqueous solution Substances 0.000 claims description 50
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 49
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- -1 hydroxyl compound Chemical class 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002596 lactones Chemical class 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011368 organic material Substances 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 140
- 238000002156 mixing Methods 0.000 description 48
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 30
- 238000003756 stirring Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 239000011734 sodium Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 description 9
- 239000008139 complexing agent Substances 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 229920002463 poly(p-dioxanone) polymer Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- YXLXNENXOJSQEI-UHFFFAOYSA-L Oxine-copper Chemical group [Cu+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 YXLXNENXOJSQEI-UHFFFAOYSA-L 0.000 description 3
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical class [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 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 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 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
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000000622 polydioxanone Substances 0.000 description 2
- 239000004633 polyglycolic acid Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000002909 rare earth metal compounds Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- 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 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000012918 MOF catalyst Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- SQKWGPOIVHMUNF-UHFFFAOYSA-K cerium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Ce+3] SQKWGPOIVHMUNF-UHFFFAOYSA-K 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
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- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
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Abstract
本发明涉及一种TiO2纳米管复合铜基硅基催化剂、制备方法及其应用。所述催化剂中铜和助剂元素限域于TiO2纳米管和SiO2之间,成本低廉、对环境友好,具有表面积高,晶粒在反应过程中不易长大,寿命较长等优点。
Description
技术领域
本发明涉及一种TiO2纳米管复合铜基硅基催化剂。更具体而言,本发明涉及TiO2纳米管复合铜基硅基催化剂、制备方法。本发明还涉及TiO2纳米管复合铜基硅基催化剂在含羟基有机化合物脱氢形成内酯中的应用。
背景技术
铜基催化剂在工业加氢和脱氢方面有着较为广泛的用途,可用于一氧化碳加氢合成甲醇、硝基苯加氢合成苯胺、丁辛醛加氢合成丁辛醇、顺酐加氢到1,4-丁二醇、草酸酯加氢合成乙二醇、1,4-丁二醇脱氢生产γ-丁内酯,也可用于二乙二醇脱氢生产对二氧环己酮。在这些加氢及脱氢产物中,对二氧环己酮是一种非常昂贵的单体,主要用于生产聚对二氧环己酮。与聚乙醇酸(PGA)、乙交酯和丙交酯的共聚物、聚乳酸(PLA)和聚己内酯(PCL)等商品化聚酯较为相似,聚对二氧环己酮(PPDO)具有优异的生物相容性、生物可吸收性和生物可降解性,随着近年来绿色可再生能源及材料的快速发展,更加受到了学术界和工业界的关注。聚对二氧环己酮(PPDO)最早由美国 Ethicon公司于上世纪70 年代开发成功,经过近50年的技术开发,现主流商品命名为 PDS Ⅱ,由美国食品药品监督管理局(FDA)批准认证作为医用可吸收手术缝合线,适用于软组织的缝合,包括小儿心血管组织和眼科手术,尤其适合于需要可吸收缝线、且需要长时间伤口支持(长达六周)的部位。
对二氧环己酮,其最早起于上世纪30年代至50年代的报道,US2142033、US2807629、US2900395采用惰性的载体负载还原态的铜和铬作为活性组分,在反应温度为240-360℃的条件下,将二乙二醇通入到固定床反应器中进行脱氢和环化反应,最终经过分离纯化获得高纯度的对二氧环己酮固体,其产率仅为25%。Union Carbide Chemicals &Plastics Technology Corporation公司在US5675022专利中改性铜铬催化剂,并用于二乙二醇气相氧化生成对二氧环己酮,而后采熔融方式获得对二氧环己酮。US5310945专利和JP2000-351775专利中优化了铜铬催化剂,但催化二乙二醇脱氢的活性仍未达到较好水平,催化剂在反应140小时和100小时后因积碳和催化剂烧结而失活。韩国MEDICHEM CO LTD根据前期技术存在的问题,在WO2009017261专利中对铜铬催化剂进一步改性,高选择性地获得了对二氧环己酮混合液,而后采用异丙醇和C6-C7饱和烃作为重结晶溶剂,并在羟基阻聚剂和脱水剂存在的条件下得到对二氧环己酮产品,产品纯度可达99.99%,水分含量低于70ppm,总收率为78%-80%。ZL20051002120.3专利中披露了一种用于制备对二氧环己酮的催化剂,该催化剂包括惰性载体和负载于其上的由铜化合物、锌化合物以及催化助剂构成的活性组分,催化助剂由碱金属或碱土金属化合物与稀土金属化合物构成,以催化剂重量为基准,活性组分的含量为20~90%,其中锌化合物含量以与铜化合物的摩尔比计为0.3~3.0,催化助剂中的碱金属或碱土金属化合物含量以与铜化合物的摩尔比计为0.01~0.2,催化助剂中的稀土金属化合物含量以与铜化合物的摩尔比计为0.01~0.05,并采用共沉淀方法进行制备。
在已有的背景技术中,由于铜的熔点和Tammann温度较低(分别为1083℃和405℃),在高温焙烧、还原和反应过程中,铜纳米颗粒极易发生烧结。中国科学院福州物质结构所姚元根等采用溶胶-凝胶法在制备催化剂中引入Cu-MOF前驱体来调控最终催化剂中铜物种的尺寸及分散度,所得到的Cu/SiO2-MOF催化剂用于草酸二甲酯加氢是常规铜硅催化剂寿命的2倍(Synthesis of Robust MOF-Derived Cu/SiO2 Catalyst with Low CopperLoading via Sol–Gel Method for the Dimethyl Oxalate Hydrogenation Reaction,ACS Catalysis, 2018年8卷4期3382-3394页)。这项技术尽管解决了低铜含量铜分散好但包裹后活性低的难题,提高了低铜含量催化剂的活性和稳定性,但采用MOFs作为基体成本较高,工业化难度较大。
综上,制备一种颗粒尺寸小、分散度高,且热稳定性好的纳米铜催化剂是含羟基有机化合物脱氢形成内酯工业实施的关键。
发明内容
本发明人在现有技术的基础上经过刻苦的研究发现,通过使用TiO2纳米管作为原始基体,根据需要配合以适当的铜、硅及助剂元素,制备的催化剂具有良好的含羟基有机化合物脱氢形成内酯性能,由此完成了本发明。
第一方面,本发明提供了一种TiO2纳米管复合铜基硅基催化剂,其特征在于,该催化剂含有TiO2纳米管、负载于该TiO2上的铜组分和硅组分。
在一个实施方案中,对于所述催化剂,以CuO计,所述铜组分中大于或等于50wt%至90wt%的部分负载于所述TiO2纳米管内。
在一个实施方案中,该催化剂还含有除所述TiO2以外的其它氧组分和助剂元素,其中,所述助剂元素是选自碱金属、碱土金属、过渡元素、Cu以外的其它IB族金属、IIB族、IIIA族、IVA族和VA族的至少一种金属。
优选地,所述助剂元素是选自以下Li、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、Zr、Nb、W、Mn、Re、Fe、Ru、Co、Ni、Pd、Pt、Au、Zn、Cd、Al、Ga、In、Sn、Pb、Sb、Bi、La、Ce、Nd、V、Ag、Mo的至少一种金属,
在一个实施方案中,对于所述催化剂,基于所述催化剂的总重量,所述铜组分的含量(以CuO计)为2~40重量%,优选5~30重量%。在一个实施方案中,对于所述催化剂,所述硅组分的含量(以SiO2计)为1~18重量%,优选2~15重量%。在一个实施方案中,所述催化剂含义所述助剂,且所述助剂元素的含量(以助剂的氧化物计)为0~6.0重量%,优选0~5.9重量%,进一步优选0.001~5.0重量%,更优选0.1~4.0重量%,
在一个实施方案中,对于所述催化剂,基于所述催化剂的总重量,所述TiO2纳米管的含量为48~97重量%,优选50~92.9重量%,更优选余量。
在一个实施方案中,对于所述催化剂,其中,所述催化剂基本上由所述TiO2纳米管、所述铜组分、所述硅组分和所述助剂元素构成。
在一个实施方案中,对于所述催化剂,其中,所述TiO2纳米管复合铜基硅基催化剂BET比表面积为100~330m2g-1,优选110~230m2g-1,最可几孔径为9~16nm,孔容为0.4~1.2mlg-1,优选1.0~2.1mlg-1,N2O滴定法测得的铜比表面积为23~80 m2g-1。
铜的比表面积测定采用Antonella Gervasini等在Applied Catalysis A:General,2005年281卷(1-2期)199-205页“Dispersion and surface states of coppercatalysts by temperature-programmed-reduction of oxidized surfaces (s-TPR)”一文中所陈述的方法进行,包括:将铜催化剂预先还原,而后采用N2O氧化,再用H2在程序升温下进行还原,铜的比表面积计算采用MSA(m2g-1 Cu) = MolH2SF.A/104CMWCu 计算。
第二方面,本发明还提供了制备第一方面所述催化剂的方法,包括以下步骤:
(1)取TiO2粉末加入5-40wt%的碱液中,在100-180℃下水热反应12-48小时得到水热产物;
(2)将水热产物过滤、洗涤后,进行干燥,得到含有钛酸的固体;
(3)初级接触步骤:将步骤(2)中含有钛酸的固体与含有铜以及任选助剂金属元素的前驱体接触0.5-5小时,得到初级接触产物A;
(4)第二接触步骤:将步骤(3)的初级接触产物A与含有硅元素的前驱体接触0.5-5小时,得到第二接触产物;和
(5)将第二接触产物在夹带有机醇的空气气氛下焙烧,即得TiO2纳米管复合铜基硅基催化剂。
在一个实施方案中,步骤(1)中,所述碱液为NaOH水溶液或KOH水溶液。
在一个实施方案中,步骤(2)中,所述干燥温度为40-85℃,干燥时间为0.5-10小时。
在一个实施方案中,步骤(3)中,所述含有铜的前驱体优选铜的可溶性盐,进一步优选铜的水溶性盐,再进一步优选选自铜的硝酸盐、硫酸盐、亚硫酸盐、磷酸盐、卤化盐、磷酸氢盐、碳酸盐、碳酸氢盐、铵盐的的至少一种。
在一个实施方案中,步骤(3)中,所述含有助剂的物质优选助剂的可溶性盐,进一步优选助剂的硝酸盐、硫酸盐、亚硫酸盐、磷酸盐、卤化盐、磷酸氢盐、碳酸盐、碳酸氢盐、铵盐的的至少一种。
在一个实施方案中,步骤(3)中,为了保证钛酸的固体与含有铜的前驱体、助剂的前驱体充分接触,选择有机溶剂或者水作为溶剂。有机溶剂选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇或叔丁醇中的至少一种。
根据本发明,在所述步骤(3)的初级接触步骤中,对各原料组分(即,含钛酸固体、含有铜的前驱体、助剂组分前驱体)的接触接触顺序没有特别的限制。并且,根据本发明,对所述接触步骤的进行方式没有特别的限制,只要可以实现各原料组分的充分接触,并形成均匀的接触产物即可。比如,可以按照本领域已知的任何方式混合(必要时辅助搅拌)各原料组分至均匀即可。
如果有必要,为了使该接触更为均匀和充分,或者为了便于接触的进行,该接触步骤还可以在分散介质比如水的存在下进行。此时所获得的接触产物可能是浆液或糊状的形式。
在一个实施方案中,步骤(3)中,初级接触步骤可以在0℃至150℃的任何温度下进行,例如室温下进行。当温度高于分散介质的沸点时,可以在压力容器中进行,以使该压力下对应的沸点高于所述温度。从方便的角度而言,优选常温,但根据需要并不限于此。接触时间以获得均匀的初级接触产物为准,一般为0.5至5小时,根据需要也并不限于此。
根据本发明,步骤(3)中的所述初级接触产物在制备后,尤其是所述接触产物是浆液状时,根据需要还可以通过本领域已知的任何方式进行干燥,例如烘干(比如在60~150℃下,优选在70~120℃下)、晾干、风干,以除去在其制备过程中可能引入的任何分散介质(比如水),从而得到干燥的初级接触产物用于焙烧步骤。
根据本发明,步骤(3)中的所述接触可以在添加剂如金属络合剂(优选水溶性的金属络合剂)、稳定剂、pH调节剂等的存在下进行。
在一个实施方案中,步骤(4)中,所述含有硅的物质选自硅酸甲酯、硅酸乙酯、硅酸丙酯、硅酸丁酯、氨基丙基三乙氧基硅烷、硅酸钠中的至少任意一种。
根据本发明,在所述步骤(4)的第二接触步骤中,对各原料组分(即,含步骤(3)的初级接触产物或任选干燥的初级接触产物、硅组分前驱体)的接触顺序没有特别的限制。并且,根据本发明,对所述接触步骤的进行方式没有特别的限制,只要可以实现各原料组分的充分接触,并形成均匀的接触产物即可。比如,可以按照本领域已知的任何方式混合(必要时辅助搅拌)各原料组分至均匀即可。
任选地,为了使该接触更为均匀和充分,或者为了便于接触的进行,该第二接触步骤还可以在分散介质比如水的存在下进行。此时所获得的第二接触产物可能是浆液或糊状的形式。
该第二接触步骤可以在0℃至150℃的任何温度下进行,例如室温下进行。当温度高于分散介质的沸点时,可以在压力容器中进行,以使该压力下对应的沸点高于所述温度。从方便的角度而言,优选常温,但根据需要并不限于此。接触时间以获得均匀的接触产物为准,一般为0.5至5小时,根据需要也并不限于此。
根据本发明,所述第二接触产物在制备后,尤其是所述接触产物是浆液状时,根据需要还可以通过本领域已知的任何方式进行干燥,例如烘干(比如在60~150℃下,优选在70~120℃下)、晾干、风干,以除去在其制备过程中可能引入的任何分散介质(比如水)。根据本发明,将所述经过干燥的接触产物也简单地称为接触产物。
根据本发明,所述第二接触步骤可以在添加剂如金属络合剂(优选水溶性的金属络合剂)、稳定剂、pH调节剂等的存在下进行。
在一个实施方案中,本发明的制备方法中的所述初级和第二接触可各自在金属络合剂的存在下进行,并且所述金属络合剂与所述铜组分前驱体的重量比为0.4~2.0。
作为所述金属络合剂,比如可以举出多元羧酸、一元醇、多元醇和多元胺等。这些金属络合剂可以根据需要单独使用一种,也可以多种组合使用。在多种组合使用时,各金属络合剂的用量总和与所述钒组分前驱体的重量比符合前述规定,即,为0.4~2.0。
作为所述多元羧酸,比如可以举出带有2~10个(优选3~6个)羧基的C2-20烷烃,比如可以举出草酸、丁二酸、己二酸等。作为所述多元羧酸,还可以举出带有一个或多个羟基(比如1~6个)、同时带有2~10个(优选3~6个)羧基的C2-20烷烃,比如可以举出苹果酸、酒石酸、柠檬酸等。或者,作为所述多元羧酸,还可以是在前述的C2-20烷烃链中插入一个或多个N原子而获得的多羧基烷基(多)胺,比如可以举出次氮基三乙酸、乙二胺四乙酸等。
作为所述一元醇,比如可以举出带有1个羟基的C1-20烷烃,比如可以举出甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇。
作为所述多元醇,比如可以举出带有2~10个(优选3~6个)羟基的C2-20烷烃,比如可以举出乙二醇,或者可以举出该多元醇的聚合物,比如聚乙二醇等,或者还可以是在所述C2-20烷烃链中插入一个或多个N原子而获得的多羟基烷基(多)胺,比如可以举出一乙醇胺、三乙醇胺等。
作为所述多元胺,比如可以举出乙二胺、二乙三胺、三乙四胺等。
作为所述稳定剂,可以使用本领域已知的那些,比如可以举出氯化铵和硫酸铵等。作为所述pH调节剂,比如可以举出盐酸、氨水等。
在一个实施方案中,步骤(5)中,所述有机醇选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇或叔丁醇中的至少一种。
在一个实施方案中,步骤(5)中,夹带的有机醇的量与空气的重量比为1:100-1:800。
在一个实施方案中,步骤(5)中,焙烧温度为200-450℃。
本发明的还提供了所述催化剂用于含羟基有机化合物脱氢形成内酯的应用。
本发明可用的含羟基有机化合物是指在碳主链的两个或者多个碳原子上带有羟基的化合物,该有机物包括碳主链、氧、氢构成的化合物,也包括碳链中的碳原子被其他杂原子取代如硫、氮所取代的化合物,优选为两个碳原子上带有羟基的化合物,进一步优选为1,4-丁二醇,二乙二醇。
根据本发明的所述应用,使本发明的催化剂与含羟基有机化合物接触,通过催化脱氢反应而将羟基化合物脱氢成环形成内酯。
除了以下规定的反应条件以外,该接触反应可以按照本领域已知的任何方式(比如接触方式、反应容器、催化剂的进料方式、或含羟基有机化合物原料的进料方式等)进行。
根据本发明,所述催化脱氢反应的条件包括:反应温度为200~300℃,优选230~300℃,压力为常压至2 MPa,优选常压~0.2MPa,含羟基化合物的空速为0.1~1.2h-1,优选为0.1~0.8h-1,反应气氛为氢气、氮气、氦气、氩气、二氧化碳气氛中的至少一种,气体空速为1000-5000h-1。
根据需要,在与所述催化剂接触之前,所述含羟基有机化合物可以被预热至80~260℃,优选100~250℃。
有益效果
与现有技术(ACS Catalysis, 2018年8卷4期3382-3394页)等文献相比,本发明提供的催化剂制备方法简单可行,具有成本低廉和不含重金属铬、对环境友好等技术特点。与现有的含羟基化合物脱氢为内酯催化剂相比,本发明提供的催化剂中铜和助剂元素限域于TiO2纳米管和SiO2之间,具有表面积高,晶粒在反应过程中不易长大,寿命较长等优点。
实施例
以下采用实施例进一步详细地说明本发明,但本发明并不限于这些实施例。
实施例1
取TiO2粉末100重量份加入到500重量份重量分数为10%的NaOH水溶液,在120℃下水热反应24小时得到水热产物,将水热反应后的产物过滤、洗涤,60℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、5重量份的硝酸锰、3重量份的草酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物1-1,干燥产物1-1与9重量份的正硅酸乙酯的乙醇溶液混合,50℃干燥6小时,得到干燥产物1-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂A,测定催化剂的表面积为141m2g-1,其铜表面积为32m2g-1。测得其中Cu重量百分含量(以CuO计)为12.9%,Si重量百分含量(以SiO2计)为2.2%,Mn重量百分含量(以MnO2计)为2.4%,Na重量百分含量(以Na2O计)为0.3%。
对比例1
取TiO2粉末100重量份加入到500重量份重量分数为10%的NaOH水溶液,在120℃下水热反应24小时得到水热产物,将水热反应后的产物过滤、洗涤,60℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、5重量份的硝酸锰、3重量份的草酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物1-1,干燥产物1-1在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基催化剂A-C,测定催化剂的表面积为162m2g-1,其铜表面积为27m2g-1。测得其中Cu重量百分含量(以CuO计)为13.2%,Mn重量百分含量(以MnO2计)为2.5%,Na重量百分含量(以Na2O计)为0.3%。
实施例2
取TiO2粉末100重量份加400重量份重量分数为20%的KOH水溶液,在130℃下水热反应48小时得到水热产物,将水热反应后的产物过滤、洗涤,70℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与40重量份硝酸铜、8重量份的硝酸钠、12重量份的草酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物2-1,干燥产物2-1与15重量份的正硅酸乙酯乙醇溶液混合,50℃干燥6小时,得到干燥产物2-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂B,测定催化剂的表面积为134m2g-1,其铜表面积为31m2g-1。测得其中Cu重量百分含量(以CuO计)为16.1%,Si重量百分含量(以SiO2计)为4.0%,Na重量百分含量(以Na2O计)为2.3%。
实施例3
取TiO2粉末100重量份加400重量份重量分数为20%的KOH水溶液,在110℃下水热反应48小时得到水热产物,将水热反应后的产物过滤、洗涤,65℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与40重量份硝酸铜、8重量份的硝酸钾、20重量份的柠檬酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物3-1,干燥产物3-1与10重量份的正硅酸乙酯乙醇溶液混合,50℃干燥6小时,得到干燥产物3-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂C,测定催化剂的表面积为150m2g-1,其铜表面积为39m2g-1。测得其中Cu重量百分含量(以CuO计)为16.1%,Si重量百分含量(以SiO2计)为2.6%,K重量百分含量(以K2O计)为3.4%。
实施例4
取TiO2粉末100重量份加500重量份重量分数为5%的NaOH 水溶液,在150℃下水热反应20小时得到水热产物,将水热反应后的产物过滤、洗涤,60℃干燥8小时得到含有钛酸的固体。取干燥后的固体100重量份与45重量份硝酸铜、8重量份的硝酸镁、20重量份的柠檬酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物4-1,干燥产物4-1与21重量份的正硅酸乙酯乙醇溶液混合,50℃干燥6小时,得到干燥产物4-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂D,测定催化剂的表面积为111m2g-1,其铜表面积为41m2g-1。测得其中Cu重量百分含量(以CuO计)为17.1%,Si重量百分含量(以SiO2计)为5.2%,Mg重量百分含量(以MgO计)为2.0%。
实施例5
取TiO2粉末100重量份加300重量份重量分数为40%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,80℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与33重量份硝酸铜、3重量份的硝酸钡、20重量份的柠檬酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物5-1,干燥产物5-1与21重量份的正硅酸乙酯乙醇溶液混合,50℃干燥6小时,得到干燥产物5-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂E,测定催化剂的表面积为129m2g-1,其铜表面积为34m2g-1。测得其中Cu重量百分含量(以CuO计)为13.6%,Si重量百分含量(以SiO2计)为5.8%,Ba重量百分含量(以BaO计)为1.7%。
实施例6
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与33重量份硝酸铜、4重量份的硝酸锆、20重量份的柠檬酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物6-1,干燥产物6-1与21重量份的正硅酸乙酯乙醇溶液混合,50℃干燥6小时,得到干燥产物6-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂F,测定催化剂的表面积为118m2g-1,其铜表面积为39m2g-1。测得其中Cu重量百分含量(以CuO计)为13.0%,Si重量百分含量(以SiO2计)为5.6%,Zr重量百分含量(以ZrO2计)为1.4%。
实施例7
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与33重量份硝酸铜、4重量份的偏钨酸铵、20重量份的柠檬酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物7-1,干燥产物7-1与21重量份的正硅酸乙酯乙醇溶液混合,50℃干燥6小时,得到干燥产物7-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂G,测定催化剂的表面积为111m2g-1,其铜表面积为32m2g-1。测得其中Cu重量百分含量(以CuO计)为13.0%,Si重量百分含量(以SiO2计)为5.6%,W重量百分含量(以WO3计)为3.5%。
实施例8
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、4重量份的硝酸铼、20重量份的柠檬酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物8-1,干燥产物8-1与16重量份的正硅酸乙酯乙醇溶液混合,50℃干燥6小时,得到干燥产物8-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂H,测定催化剂的表面积为145m2g-1,其铜表面积为41m2g-1。测得其中Cu重量百分含量(以CuO计)为12.6%,Si重量百分含量(以SiO2计)为4.5%,Re重量百分含量(以Re2O3计)为2.3%。
实施例9
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与20重量份硝酸铜、8重量份的硝酸铁的水溶液混合,搅拌,80℃干燥2小时得到干燥产物9-1,干燥产物9-1与16重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物9-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂I,测定催化剂的表面积为123m2g-1,其铜表面积为45m2g-1。测得其中Cu重量百分含量(以CuO计)为8.9%,Si重量百分含量(以SiO2计)为4.3%,Fe重量百分含量(以Fe2O3计)为2.8%。
实施例10
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、5重量份的氯化钌的水溶液混合,搅拌,80℃干燥2小时得到干燥产物10-1,干燥产物10-1与16重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物10-2,在空气和正丙醇的混合气氛下400℃焙烧得到TiO2纳米管复合铜基硅基催化剂J,测定催化剂的表面积为114m2g-1,其铜表面积为37m2g-1。测得其中Cu重量百分含量(以CuO计)为12.7%,Si重量百分含量(以SiO2计)为4.3%,Ru重量百分含量(以Ru2O3计)为2.8%。
实施例11
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与40重量份硝酸铜、8重量份的硝酸镍的水溶液混合,搅拌,80℃干燥2小时得到干燥产物11-1,干燥产物11-1与16重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物11-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂K,测定催化剂的表面积为114m2g-1,其铜表面积为33m2g-1。测得其中Cu重量百分含量(以CuO计)为16.1%,Si重量百分含量(以SiO2计)为4.0%,Ni重量百分含量(以NiO计)为3.1%。
实施例12
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、3重量份的氯化钯的盐酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物12-1,干燥产物12-1与18重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物12-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂L,测定催化剂的表面积为127m2g-1,其铜表面积为43m2g-1。测得其中Cu重量百分含量(以CuO计)为12.6%,Si重量百分含量(以SiO2计)为4.9%,Pd重量百分含量(以PdO计)为2.1%。
实施例13
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、3重量份的氯化镓的盐酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物13-1,干燥产物13-1与18重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物13-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂M,测定催化剂的表面积为133m2g-1,其铜表面积为42m2g-1。测得其中Cu重量百分含量(以CuO计)为12.6%,Si重量百分含量(以SiO2计)为5.0%,Ga重量百分含量(以Ga2O3计)为1.7%。
实施例14
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、3重量份的氯化亚锡的盐酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物14-1,干燥产物14-1与18重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物14-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂N,测定催化剂的表面积为141m2g-1,其铜表面积为40m2g-1。测得其中Cu重量百分含量(以CuO计)为12.6%,Si重量百分含量(以SiO2计)为5.0%,Sn重量百分含量(以SnO2计)为2.3%。
实施例15
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、3重量份的氯化亚锡的盐酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物15-1,干燥产物15-1与18重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物15-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂O,测定催化剂的表面积为149m2g-1,其铜表面积为41m2g-1。测得其中Cu重量百分含量(以CuO计)为12.6%,Si重量百分含量(以SiO2计)为5.0%,Sb重量百分含量(以Sb2O3计)为1.9%。
实施例16
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、5重量份的硝酸铋的硝酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物16-1,干燥产物16-1与18重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物16-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂P,测定催化剂的表面积为141m2g-1,其铜表面积为43m2g-1。测得其中Cu重量百分含量(以CuO计)为12.3%,Si重量百分含量(以SiO2计)为5.0%,Bi重量百分含量(以Bi2O3计)为2.8%。
实施例17
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、5重量份的硝酸镧的草酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物17-1,干燥产物17-1与18重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物17-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂Q,测定催化剂的表面积为141m2g-1,其铜表面积为40m2g-1。测得其中Cu重量百分含量(以CuO计)为12.6%,Si重量百分含量(以SiO2计)为5.0%,La重量百分含量(以La2O3计)为2.4%。
实施例18
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与40重量份硝酸铜、4重量份的偏钒酸铵的草酸水溶液混合,搅拌,80℃干燥2小时得到干燥产物18-1,干燥产物18-1与15重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物18-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂R,测定催化剂的表面积为111m2g-1,其铜表面积为27m2g-1。测得其中Cu重量百分含量(以CuO计)为16.1%,Si重量百分含量(以SiO2计)为3.8%,V重量百分含量(以V2O5计)为2.8%。
实施例19
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与45重量份硝酸铜、4重量份的硝酸银的水溶液混合,搅拌,80℃干燥2小时得到干燥产物19-1,干燥产物19-1与19重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物19-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂S,测定催化剂的表面积为118m2g-1,其铜表面积为26m2g-1。测得其中Cu重量百分含量(以CuO计)为17.7%,Si重量百分含量(以SiO2计)为4.7%,Ag重量百分含量(以Ag2O计)为2.5%。
实施例20
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与45重量份硝酸铜、50重量份的钼酸铵的热水溶液混合,搅拌,80℃干燥2小时得到干燥产物20-1,干燥产物20-1与30重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物20-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂T,测定催化剂的表面积为121m2g-1,其铜表面积为26m2g-1。测得其中Cu重量百分含量(以CuO计)为17.3%,Si重量百分含量(以SiO2计)为7.1%,Mo重量百分含量(以MoO3计)为0.7%。
实施例21
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与40重量份硝酸铜、8重量份的硝酸铈的水溶液混合,搅拌,80℃干燥2小时得到干燥产物21-1,干燥产物21-1与18重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物21-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂U,测定催化剂的表面积为161m2g-1,其铜表面积为37m2g-1。测得其中Cu重量百分含量(以CuO计)为15.8%,Si重量百分含量(以SiO2计)为4.6%,Ce重量百分含量(以CeO2计)为3.9%。
实施例22
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、3重量份的硝酸钠和3重量份的硝酸锰水溶液混合,搅拌,80℃干燥2小时得到干燥产物22-1,干燥产物22-1与18重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物22-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂V,测定催化剂的表面积为159m2g-1,其铜表面积为44m2g-1。测得其中Cu重量百分含量(以CuO计)为12.6%,Si重量百分含量(以SiO2计)为4.7%,Na重量百分含量(以Na2O计)为1.1%,Mn重量百分含量(以MnO2计)为1.5%。
实施例23
取TiO2粉末100重量份加400重量份重量分数为20%的NaOH水溶液,在140℃下水热反应30小时得到水热产物,将水热反应后的产物过滤、洗涤,75℃干燥5小时得到含有钛酸的固体。取干燥后的固体100重量份与30重量份硝酸铜、3重量份的硝酸钠、3重量份的硝酸锰、3重量份的硝酸铋水溶液混合,搅拌,80℃干燥2小时得到干燥产物23-1,干燥产物23-1与18重量份的正硅酸乙酯丙醇溶液混合,50℃干燥6小时,得到干燥产物23-2,在空气和正丙醇的混合气氛下380℃焙烧得到TiO2纳米管复合铜基硅基催化剂W,测定催化剂的表面积为131m2g-1,其铜表面积为43m2g-1。测得其中Cu重量百分含量(以CuO计)为12.1%,Si重量百分含量(以SiO2计)为4.8%,Na重量百分含量(以Na2O计)为1.0%,Mn重量百分含量(以MnO2计)为1.4%,Bi重量百分含量(以Bi2O3计)为1.7%。
对比例:
根据四川大学ZL20051002120.3实施例6制备的催化剂,即称取的249.7克五水合硫酸铜(1mol)、86.3克七水合硫酸锌(0.3mol)、7.4克 二水合氯化钙(0.05mol)及14.2克六水合氯化铈(0.04mol)混合,加入2500mL去离子水溶解后,再加入1100克氧化铝及330克二氧化硅,在35℃、强搅拌下滴加碳酸铵至pH=7.0。沉淀完成后,在50℃下陈化50min,再进行过滤、洗涤,以除去可溶性金属化合物。将洗涤后的沉淀物在120℃下干燥12h,然后在700℃下煅烧3h,焙烧好的粒子与淀粉混合均匀后,压制成Φ5×5的圆柱状催化剂X。
实施例24
二乙二醇脱氢催化性能测试:
(1)将实施例1-23和对比例1-2中的催化剂分别装入固定床反应器,在250℃氢气条件下还原2小时,而后按0.5h-1的重量空速泵入二乙二醇,氢气的体积空速为1500h-1,反应压力为常压,反应温度为270℃,结果见表1所示。
表1 不同催化剂上二乙二醇脱氢生成对二氧环己酮结果
尽管在本文中参考示例性的实施方案详细描述了本发明,但是应当理解的是,本发明不限于所述实施方案。具有本领域普通技能且可获取本文教导的人员会认识到在本发明范围内的其它变化、修改和实施方案。因此,本发明应与后面所述的权利要求一致地被广义地解释。
Claims (12)
1.一种TiO2纳米管复合铜基硅基催化剂,其特征在于,该催化剂含有TiO2纳米管、负载于该TiO2上的铜组分和硅组分。
2.根据权利要求1所述的催化剂,其特征在于,以CuO计,所述铜组分中大于或等于50wt%至90wt%的部分负载于所述TiO2纳米管内。
3.根据权利要求1所述的催化剂,其特征在于,基于所述催化剂的总重量,所述铜组分的含量(以CuO计)为2~40重量%,优选5~30重量%;和/或所述硅组分的含量(以SiO2计)为1~18重量%,优选2~15重量%;和/或所述TiO2纳米管的含量为48~97重量%,优选50~92.9重量%,条件是该催化剂的所有组分含量之和为100%。
4.根据权利要求1所述的催化剂,其特征在于,该催化剂还含有除所述TiO2以外的其它氧组分和助剂元素,
其中,所述助剂元素是选自碱金属、碱土金属、过渡元素、Cu以外的其它IB族金属、IIB族、IIIA族、IVA族和VA族的至少一种金属。
5.根据权利要求4所述的催化剂,其特征在于,所述助剂元素是选自Li、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、Zr、Nb、W、Mn、Re、Fe、Ru、Co、Ni、Pd、Pt、Au、Zn、Cd、Al、Ga、In、Sn、Pb、Sb、Bi、La、Ce、Nd、V、Ag和Mo的至少一种金属。
6.根据权利要求4所述的催化剂,其特征在于,基于所述催化剂的总重量,所述铜组分的含量(以CuO计)为2~40重量%,优选5~30重量%;和/或所述硅组分的含量(以SiO2计)为1~18重量%,优选2~15重量%;和/或所述的助剂元素的含量(以助剂的氧化物计)为0~6.0重量%,优选0~5.9重量%,进一步优选0.001~5.0重量%,更优选0.1~4.0重量%;和/或所述TiO2纳米管的含量为48~97重量%,优选50~92.9重量%;条件是该催化剂的所有组分含量之和为100%。
7.根据权利要求6所述的催化剂,其中,所述催化剂基本上由所述TiO2纳米管、所述铜组分、所述硅组分和所述助剂元素构成。
8.根据权利要求1所述的催化剂,其中,所述催化剂的BET比表面积为100~330m2g-1,优选110~230m2g-1;和/或最可几孔径为9~16nm,孔容为0.4~1.2mlg-1,优选1.0~2.1mlg-1;和/或N2O滴定法测得的铜比表面积为23~80 m2g-1。
9.一种制备如权利要求1-8中任一项所述的催化剂的方法,包括以下步骤:
(1)取TiO2粉末加入5-40wt%的碱液中,在100-180℃下水热反应12-48小时得到水热产物;
(2)将水热产物过滤、洗涤后,进行干燥,得到含有钛酸的固体;
(3)初级接触步骤:将步骤(2)中含有钛酸的固体与含有铜和任选助剂金属元素的前驱体接触0.5-5小时,得到初级接触产物A;
(4)第二接触步骤:将步骤(3)的初级接触产物A与含有硅元素的前驱体接触0.5-5小时,得到第二接触产物;和
(5)将第二接触产物在夹带有机醇的空气气氛下焙烧,即得所述催化剂。
10. 权利要求9的制备方法,其中:
步骤(1)中,所述碱液为NaOH水溶液或KOH水溶液;和/或
步骤(2)中,所述干燥温度为40-85℃,干燥时间为0.5-10小时;和/或
步骤(5)中,所述有机醇选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇或叔丁醇中的至少一种;和/或
步骤(5)中,夹带有机醇的量与空气的重量比为1:100-1:800;和/或
步骤(5)中,焙烧温度为200-450℃。
11.权利要求1至8任一项所述的催化剂在使含羟基的有机物发生脱氢反应中的应用,其中该化合物的羟基进行脱氢形成内酯。
12.使用权利要求1至8任一项所述的催化剂实施使含羟基的有机物发生脱氢反应的方法,其中所述催化脱氢反应的条件包括:
反应温度为200~300℃,优选230~300℃;和/或
压力为常压至2 MPa,优选常压~0.2MPa;和/或
含羟基化合物的空速为0.1~1.2h-1,优选为0.1~0.8h-1;和/或
反应气氛为氢气、氮气、氦气、氩气、二氧化碳气氛中的至少一种;和/或
气体空速为1000-5000h-1。
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CN109395720A (zh) * | 2017-08-16 | 2019-03-01 | 中国石化扬子石油化工有限公司 | 一种Pd/TiO2-SiO2纳米管催化剂及其制备方法和应用 |
CN108704647A (zh) * | 2018-06-15 | 2018-10-26 | 华东理工大学 | 一种抗积碳型甲烷干气重整包覆型镍催化剂及制备方法 |
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