CN106040291A - Preparation method and application for nuclearshell material catalyst - Google Patents
Preparation method and application for nuclearshell material catalyst Download PDFInfo
- Publication number
- CN106040291A CN106040291A CN201610495069.5A CN201610495069A CN106040291A CN 106040291 A CN106040291 A CN 106040291A CN 201610495069 A CN201610495069 A CN 201610495069A CN 106040291 A CN106040291 A CN 106040291A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- oxide
- core
- shell material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 67
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims abstract description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 22
- -1 Scia Chemical compound 0.000 claims description 21
- 230000004044 response Effects 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000010457 zeolite Substances 0.000 claims description 16
- 235000013877 carbamide Nutrition 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Chemical compound [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-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
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011824 nuclear material Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000011257 shell material Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000005809 transesterification reaction Methods 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 2
- 230000007704 transition Effects 0.000 abstract 2
- 238000000707 layer-by-layer assembly Methods 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 16
- 238000005253 cladding Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 13
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical group CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 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
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- PTENJNIBULCQNG-UHFFFAOYSA-N N.[Cl].[Zn] Chemical compound N.[Cl].[Zn] PTENJNIBULCQNG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7053—A-type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7607—A-type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7807—A-type
-
- B01J35/643—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
Abstract
The invention discloses a preparation method and application for a nuclear shell material catalyst and belongs to the technical field of the preparation of the nuclear shell material catalyst. A transition metallic oxide of the nuclear material of the catalyst is electrified after being modified with positive and negative polyelectrolyte; a layer of molecular sieve membrane coats the outer surface of the transition metallic oxide according to an electrostatic self-assembly method, namely, oxide is taken as the core, molecular sieve is taken as the shell and the compound is aliased as MalphaO beta@ molecular sieve (M is one of the transition metal elements and alpha and beta are valences); the compound reacts with ammonium chloride at certain concentration, so that M alpha O beta is converted into the corresponding chloride ammonium salt M(NH3)nCl beta(n is the number of ammonia molecule and is 1-8); the target catalyst structure after low-temperature baking and ammonia removal is MCl beta@ molecular sieve. The catalyst can be applied to the system of transesterification of urea or carbamic acid ester and phenol for generating diphenyl carbonate; the catalyst can perform new coordination absorption with the ammonia generated by the reaction system, so as to drive the reaction to move right; the yield of diphenyl carbonate product is above 90%; the catalytic effect after the catalyst is used for 5 times is still good.
Description
Technical field
The present invention relates to the preparation method and applications of a kind of core-shell material catalyst, belong to core-shell catalyst and prepare skill
Art field.
Background technology
" green " intermediate diphenyl carbonate (Diphenyl Carbonate, the letter of organic compound and macromolecular material
DPC) molecular formula is called C6H5OCOOC6H5, it being used primarily in plastics industry, its most significant purposes is entered with bisphenol-A exactly
Row polycondensation reaction polycarbonate synthesis (PC), Merlon possesses good optical property, the highest anti-Beating Strength, high-quality
The outstanding performance such as heat stability and be widely used, as in Sheet material for eyeglass, Aero-Space, automobile making, pesticide, medical treatment, building etc.
Application in field.The total quantity consumed of current PC is only second to polyamide (PA) in engineering plastics and occupies second.The whole world in 2005
Aggregate consumption is more than 4,500,000 tons.The consumption figure of PC will be more than PA from now on.But, phenomenon burning hot with PC consumption market is in not assisting
Readjust the distribution exhibition is domestic PC technological development state the most at a low ebb, and process units is had in the most only minority manufacturer,
Gross annual output ability about 5000 tons, and grade is low, it is difficult to meet the market demand, big from state's imports such as Japan, Korea S, the U.S. every year
Volume production product, domestic import PC in 2005 and PC alloy totally 63.48 ten thousand tons, imbalance between supply and demand is the most prominent.In addition, DPC also may be used
It is used in the some other chemical products of synthesis, such as p-Hydroxybenzoate, poly-arylcarbonic acid fat, monoisocyanates and diisocyanate
Deng, also act as the plasticizer etc. of polyamide, polyester, in recent years, close for reaction material with DPC and bisphenol-A with environmentally friendly
Becoming a large amount of exploitations of Merlon new technology, DPC becomes the compound got most of the attention.
The traditional approach of synthesis DPC with phosgene and phenol (PhOH) as raw material.But, phosgene has severe toxicity and to production equipment
Corrosivity is big, and this causes a lot of unfavorable factor to environmental conservation and production safety, and phosgenation uses substantial amounts of dichloromethane to make
Production equipment is caused to be corroded for solvent can produce substantial amounts of villaumite.These unfavorable factors comprehensive, people in the decades in past
The most constantly seek " green " synthetic method.Since eighties of last century the seventies, the most successively have developed more than ten plants non-light
Gas method diphenyl carbonate synthesis (DPC) technique.At present, the non-phosgene of synthesis DPC mainly has the oxidation carbonyl of ester-interchange method, phenol
Base method.Oxidation carbonylation method is to be directly synthesized carbonic acid two with phenol, carbon monoxide and oxygen under catalyst action for raw material
The reaction method of phenyl ester, but this synthetic method system is complicated and to use precious metal such as platinum high as major catalyst price
Expensive, by-product shipwreck removes and causes DPC hydrolysis, CO to be easily oxidized to CO2This feature cannot be put into production temporarily significantly etc. reason
Limit its process of industrialization；Ester-interchange method refers to dialkyl carbonate and phenol, dialkyl oxalate and phenol, carbonic acid two
Methyl ester (DMC) synthesizes the synthetic method of DPC with phenylacetate.Comprehensively getting off, current ester-interchange method is based primarily upon dimethyl carbonate
Being raw material reaction method under catalyst with phenol, this synthetic method " green ", invest little, but its obvious shortcoming is difficult
Make molecular balance move right to break the restriction of thermodynamical equilibrium, by-product carbinol forms azeotropic mixture with dimethyl carbonate,
It is difficult to separate.Therefore, this seminar selection carbamate and phenol carry out reaction and prepare diphenyl carbonate, product
Only ammonia, if the restriction just can broken thermodynamically can be adsorbed in time by the ammonia after reaction so that balance moves right.
So develop one or more excellent catalytic effect, cheap and easy to get and callable new catalyst is to advance diphenyl carbonate
The key of process of industrialization.
Summary of the invention
The technical problem to be solved is to overcome carbamate and phenol ester exchange process carbonate synthesis hexichol
Ester thermodynamics is difficult to the shortcoming broken, prepare a kind of cheap be easy to get, catalytic efficiency is high, reuse often for carbon
The core-shell material catalyst of diphenyl phthalate synthesis.
It is an object of the invention to provide the preparation method of a kind of core-shell material catalyst, specifically include following steps:
(1) transition metal oxide be impregnated in the positive/negative polyelectrolyte solution that mass percent concentration is 0.3～1.0 %
0.5～2 h, centrifugal filtration, residue washing (Electrostatic Absorption the solute of polyelectrolyte)；After washing, filtering residue repeats said process 2
～secondary, whole immerse during positive polyelectrolyte solution and negative polyelectrolyte solution be used alternatingly, the poly-electricity immersed i.e. for the first time
If solve matter positive polyelectrolyte solution, then second time is immersed with negative polyelectrolyte solution；
(2) in the ratio of 1 ~ 20 g/L, the filtering residue that step (1) obtains is transferred to nanometer A that mass percent concentration is 2% ~ 10%
(add deionized water makes molecular sieve solution mass fraction percent concentration be 2～10% and with ultrasonic to type zeolite molecular sieve suspension
Wavelength-division dissipates process and is allowed to disperse) middle process 0.5 ~ 12 h, make A-type nano zeolite molecular sieve pass through electrostatic interaction and adsorb equably
Oxide particle surface, filter, wash, dried solid is placed in molecular sieve primary response liquid 90 ~ 120 DEG C of Crystallizing treatment 1 ~
5 h(make it carry out secondary cladding and diauxic growth, make oxide surface obtain one layer of fine and close molecular screen membrane), filter, wash,
At 60 ~ 140 DEG C, carry out reacting 2 ~ 10h with the ammonium chloride solution that mass percent concentration is 10% ~ 90% again after vacuum drying and obtain M
(NH3)nClβ@molecular sieve, wherein n=1 ~ 8, for ammonia be coordinated number, filter, wash, be vacuum dried after low-temperature bake (make its take off
Except the ammonia in nuclear material and polyelectrolyte) prepare core-shell material catalyst MClβ@molecular sieve.
Preferably, transition metal oxide of the present invention be zinc oxide, copper oxide, Aska-Rid., nickel oxide, cobalt oxide,
In ferrum oxide, manganese oxide, chromium oxide, Scia, titanium oxide, vanadium oxide, lanthana, cerium oxide, praseodymium oxide, Dineodymium trioxide one
Kind.
Preferably, positive polyelectrolyte of the present invention is PDDA.
Preferably, negative polyelectrolyte of the present invention is poly-p styrene sulfonic acid.
Preferably, low-temperature bake of the present invention is process 0.5 ~ 2 h under the conditions of 250 ~ 300 DEG C.
The core-shell material catalyst that another object of the present invention is to the present invention be prepared is used for carbamide or amino first
Acid esters is with phenol reactant diphenyl carbonate synthesis, and reaction carries out 2 ~ 48 h at 190 DEG C ~ 210 DEG C.
A-type nano zeolite molecular sieve described in step of the present invention (2) is that existing method prepares；Step of the present invention (2)
Described in molecular sieve primary response liquid be system with molecular sieve for preparing standby during reactant liquor before crystallization.
Transition metal oxide of the present invention be conventional method prepare to have specific morphology (the most spherical, just
Square, rectangle, spheroid shape, cylindricality etc.) the transition metal oxide of a diameter of 1 ~ 5 micron or rare-earth oxide.
Catalyst prepared by the present invention generates carbonic acid two in the ester exchange reaction of carbamide (or carbamate) with phenol
During phenyl ester, nuclear material transition metal chloride by reaction coupling constantly adsorb ammonia until saturated then
Catalytic efficiency decreases, and the ammonia selecting the catalyst of suitable addition just can realize reaction system generation was all coordinated to
Cross in metal chloride thus promoted the forward of reaction to move, and then the production capacity of diphenyl carbonate is improved.
Beneficial effects of the present invention:
(1) improve the productivity of carbonate production by transesterification diphenyl ester, productivity is up to more than 90%；(2) catalyst of the present invention
Synthesis technique is simple, raw material is easy to get；The catalyst shell material prepared is fine and close NaA type molecular sieve film, and its aperture is at 0.4nm
Left and right, can effectively make ammonia passing hole channel that ester exchange reaction system generates and then be coordinated with nuclear material, stoping other big
Molecule such as phenol oxygen root is coordinated thus improves the conversion ratio of reaction；(4) catalyst morphology controllable, size tunable, is catalyzed after using 5 times
Effect is the best.(5) catalyst just can be made to regenerate by simple heat treated.
Detailed description of the invention
Below in conjunction with example, the present invention is described in further details, but protection scope of the present invention is not limited to described interior
Hold.
Embodiment 1
The method of the zinc chloride catalyst preparing molecular sieve cladding is as follows:
(1) with reference to " Easir A. Khan, the Preparation of metal that Enping Hu, Zhiping Lai etc. delivers
Oxide/zeolite core shell nanostructures " prepare the spherical alumina zinc powder body that particle diameter is 1～5 micron,
Conventional Zeta potential analyser is used to determine zinc oxide surface of solids positively charged；
(2) preparation of molecular sieve is with reference to " Mechanism of Zeolite A Nanocrystal Growth from
Colloids at Room Temperature”
1. SiO is pressed2:Al2O3:NaOH: (TMA)2O:H2The mol ratio of O is the ratio of 11.25:1.8:1.2:13.4:700, claims
Measure the reaction raw materials Ludox (30% in water) corresponding to above-mentioned substance, aluminum isopropylate., sodium hydroxide, tetramethyl hydroxide
Ammonium, deionized water, standby；
2. step (1) weighs deionized water 8.0 g, add Ludox 9.0 g under stirring at normal temperature, stir, preparation
Out solution A；
3. weigh deionized water 28 g, under room temperature magnetic agitation by 3.0 g aluminum isopropylate., 9.2 g (1M) NaOH solution and
20 g Tetramethylammonium hydroxide, are configured to solution B；
4. solution A is poured in B solution, uniformly ageing is stirred at room temperature and after 3 days, i.e. obtains molecular sieve primary response liquid；
5. being put into by molecular sieve primary response liquid in the hydrothermal reaction kettle of 100ml, 80 DEG C of crystallization 1 day, crystallization afterproduct is through ultrasonic
(150W, 5min), centrifugation (1000rpm, 30min), 80 DEG C are dried 12 h, i.e. obtain nano type A after 550 DEG C of calcining 2 h
Zeolite molecular sieve, selects Zeta potential analyser gained molecular sieve to carry out surface potential analysis to determine that its surface band is born
Electricity.
(3) step (1) zinc oxide solid 2g is immersed in the poly-p styrene sulfonic acid that 1 L mass percent concentration is 0.3%
(PSS) processing 0.5 h in solution, 6000rpm is centrifuged, and filters, and filtering residue is washed with deionized water 3 times；After washing, filtering residue is immersed in again
PDDA (PDDA) solution of mass percent concentration 0.3% processes 0.5 h, filters, wash
Wash solid, the most again with the PSS process of mass percent concentration 0.3%；
(4) after the solid particle that step (3) prepares being transferred to ultrasound wave dispersion process in the ratio of 1g/L, mass percent is dense
Degree be 2 % A-type nano zeolite molecular sieve suspension in process 2 h so that it is complete once to be coated with shape by electrostatic adsorption
Become core-shell material, filter, solid be placed in the most again molecular sieve primary response liquid (step 4. in the molecular sieve that obtains the most anti-
Answer liquid) in filter after 90 DEG C of crystallization 1 h, wash, be dried the zinc oxide core-shell material preparing molecular sieve cladding.
(5) core-shell material of step (4) gained molecular sieve coating zinc oxide being placed in percent mass Particle density is 10 %'s
Going to reactor in ammonium chloride solution makes nuclear material zinc oxide react generation chlorine ammonia zinc, and reaction condition is 140 DEG C, 2 h.
(6) by step (5) resulting materials Zn (NH3)2Cl2@molecular screen material is placed in 300 DEG C of roasting 0.5 h in Muffle furnace and obtains
Catalyst Z nCl2@molecular sieve.
Above-mentioned catalyst is applied in carbamide with phenol reactant diphenyl carbonate synthesis (reaction equation is as follows), reaction
Carrying out 2 h, conversion rate of urea 98.8% at 210 DEG C, diphenyl carbonate yield is 97.3%, and catalyst uses carbonic acid two after 5 times
Phenyl ester yield is that 93.8%(is shown in Table 1)；
。
Embodiment 2
The method of the Caddy (Cleary) catalyst preparing molecular sieve cladding is as follows:
(1) with reference to M Risti, " the Formation and properties of that S Popovi, S Musi etc. delivers
Cd (OH) 2And CdO particles " prepare the spherical alumina cadmium powder body that particle diameter is 1～5 micron, use conventional Zeta
Potentiometric analyzer determines that the Aska-Rid. surface of solids is electronegative；
(2) preparation of molecular sieve is with reference to " Investigations on hydrothermal synthesis parameters
in preparation of nanoparticles of LTA zeolite with the aid of TMAOH”
1. SiO is pressed2:Al2O3:Na2O: (TMA)2O:H2The mol ratio of O is the ratio of 6:1:0.32:7.27:350, weighs hydrogen-oxygen
Change sodium, Tetramethylammonium hydroxide, Ludox, aluminum isopropylate. and deionized water standby；
2. 0.26g NaOH and 53.01g (TMA)2O is dissolved in 19.68g deionized water；
3. the solution in 2. is divided into two parts of A, B；
4. in A, add 4.21g aluminum isopropylate. and stir, B add 7.21g Ludox and stirs, finally
B solution is poured in A and mix homogeneously obtains molecular sieve primary response liquid.
5. molecular sieve primary response liquid is put in the hydrothermal reaction kettle of 50 ml, 100 DEG C of crystallization 12 h, crystallization afterproduct
Through ultrasonic (150W, 5min), centrifugation (15000rpm, 25min), wash to pH < 9,80 DEG C of dry 12 h, 550 DEG C of calcinings 2
I.e. obtain A-type nano zeolite molecular sieve after h, select Zeta potential analyser that gained molecular sieve is carried out surface potential analysis with really
Make its surface electronegative.
(3) step (1) Aska-Rid. solid 4g is immersed in the phthalic acid diethyl that 1 L mass percent concentration is 0.5%
Processing 0.8 h in omega-diol diacrylate (PDDA) solution, 6000rpm is centrifuged, and filters, and filtering residue is washed with deionized water 3 times；Washing
Rear filtering residue is immersed in poly-p styrene sulfonic acid (PSS) solution of mass percent concentration 0.5% again and processes 0.8 h, filters, washes
Wash solid, the most again with the PDDA process of mass percent concentration 0.5%；
(4) after the solid particle that step (3) prepares being transferred to ultrasound wave dispersion process in the ratio of 5 g/L, mass percent is dense
Degree be 4% A-type nano zeolite molecular sieve suspension in process 1.8 h so that it is complete once to be coated with shape by electrostatic adsorption
Become core-shell material, filter, solid be placed in the most again molecular sieve primary response liquid (step 4. in the molecular sieve that obtains the most anti-
Answer liquid) in filter after 100 DEG C of crystallization 2 h, wash, be dried the Aska-Rid. core-shell material preparing molecular sieve cladding.
(5) core-shell material of step (4) gained molecular sieve cladding Aska-Rid. being placed in percent mass Particle density is 20 %'s
Going to reactor in ammonium chloride solution makes nuclear material Aska-Rid. react generation chlorine ammonia cadmium, and reaction condition is 120 DEG C, 4 h.
(6) by step (5) resulting materials Cd (NH3)2Cl2@molecular screen material is placed in 280 DEG C of roasting 1.5 h in Muffle furnace
Obtain catalyst CdCl2@molecular sieve.
Above-mentioned catalyst is applied in carbamide with phenol reactant diphenyl carbonate synthesis (reaction equation is as follows), reaction
Carrying out 12 h, conversion rate of urea 97.1% at 200 DEG C, diphenyl carbonate yield is 96.5%, and catalyst uses carbonic acid two after 5 times
Phenyl ester yield is that 90.5%(is shown in Table 1)；
。
Embodiment 3
The method of the cobalt-chloride catalyst preparing molecular sieve cladding is as follows:
(1) with reference to Y the Li, " Morphology-that J Zhang, Z Liu, M Liu, H Lin, R Che etc. delivers
dominant microwave absorption enhancement and electron tomography
Characterization of CoO self-assembly 3D nano-flowers " to prepare particle diameter be 1～5 micron
Spherical alumina cobalt powder body, uses conventional Zeta potential analyser to determine that the cobalt oxide surface of solids is electronegative；
(2) preparation of molecular sieve is with reference to " Synthesis and Characterization of High-Quality
Zeolite LTA and FAU Single Nanocrystals”
1. SiO is pressed2:Al2O3:NaCl: (TMA)2O:H2The mol ratio of O is the ratio of 3:1:0.007:1.5:276, weighs aluminum
Powder, tetraethyl orthosilicate, Tetramethylammonium hydroxide, sodium chloride and water are standby；
2. aluminium powder and sodium hydroxide being dissolved in the solution of Tetramethylammonium hydroxide, this solution is 0.2 micron by aperture again
Filter is to remove impurity；
The most under agitation tetraethyl orthosilicate is slowly dropped in above-mentioned clear liquor system, is aged two days after stirring to clarify
Molecular sieve primary response liquid；
4. being put into by molecular sieve primary response liquid in the hydrothermal reaction kettle of 250ml, 100 DEG C of crystallization 14 days, crystallization afterproduct is through super
Sound (150W, 5min), centrifugation (1000rpm, 30min), 80 DEG C are dried 12 h, i.e. obtain nanometer A after 550 DEG C of calcining 2 h
Type zeolite molecular sieve, selects Zeta potential analyser gained molecular sieve to carry out surface potential analysis to determine that its surface band is born
Electricity.
(3) step (1) cobalt oxide solid 6 g is immersed in the phthalic acid diethyl that 1L mass percent concentration is 0.6%
Processing 1 h in omega-diol diacrylate (PDDA) solution, 6000rpm is centrifuged, and filters, and filtering residue is washed with deionized water 3 times；After washing
Filtering residue is immersed in poly-p styrene sulfonic acid (PSS) solution of mass percent concentration 0.6% again and processes 1 h, filters, washs admittedly
Body, the most again with the PDDA process of mass percent concentration 0.6%；
(4) after the solid particle that step (3) prepares being transferred to ultrasound wave dispersion process in the ratio of 10g/L, mass percent is dense
Degree be 6% A-type nano zeolite molecular sieve suspension in process 0.8 h so that it is complete once to be coated with shape by electrostatic adsorption
Become core-shell material, filter, solid be placed in the most again molecular sieve primary response liquid (step 3. in the molecular sieve that obtains the most anti-
Answer liquid) in filter after 120 crystallization 1 h, wash, be dried the cobalt oxide core-shell material preparing molecular sieve cladding.
(5) core-shell material of step (4) gained molecular sieve cladding cobalt oxide being placed in percent mass Particle density is 50 %'s
Going to reactor in ammonium chloride solution makes nuclear material cobalt oxide react generation chlorine ammonia cobalt, and reaction condition is 100 DEG C, 5 h.
(6) by step (5) resulting materials Co (NH3)6Cl2@molecular screen material is placed in 250 DEG C of roasting 2 h in Muffle furnace and obtains
Catalyst CoCl2@molecular sieve.
Above-mentioned catalyst is applied in carbamide with phenol reactant diphenyl carbonate synthesis (reaction equation is as follows), reaction
Carrying out 48 h, conversion rate of urea 97.5% at 190 DEG C, diphenyl carbonate yield is 95.5%, and catalyst uses carbonic acid two after 5 times
Phenyl ester yield is that 90.1%(is shown in Table 1)；
。
Embodiment 4
The method of the nickel chloride catalyst agent preparing molecular sieve cladding is as follows:
(1) " the Highly Efficient Removal of delivered with reference to Ting Zhu, Jun Song Chen etc.
Organic Dyes from Waste Water Using Hierarchical NiO Spheres with High
Surface Area " for going out the spherical nickel oxide powder body that particle diameter is 1～5 micron, use conventional Zeta potential analyser to determine oxygen
Change manganese surface of solids positively charged；
(2) preparation of molecular sieve is with reference to " Layer-by-Layer preparation of zeolite coatings of
nanosized crystals”
1. SiO is pressed2:Al2O3:Na2O: (TMA)2O:H2The mol ratio of O is the ratio of 5:0.6::0.3:9:400, weighs above-mentioned thing
Reaction raw materials Ludox (30% in water), aluminum isopropylate., sodium hydroxide, Tetramethylammonium hydroxide corresponding to matter, go from
Sub-water, standby；
2. by NaOH and (TMA)2O is dissolved in deionized water；
3. the solution in 2. is divided into two parts of A, B；
4. in A, add aluminum isopropylate. and stir, B add Ludox and stirs, finally pouring B solution into A
In and mix homogeneously obtain molecular sieve primary response liquid.
5. molecular sieve primary response liquid is put in the hydrothermal reaction kettle of 100ml, 90 DEG C of crystallization 2 days, crystallization afterproduct warp
Ultrasonic (150W, 5min), centrifugation (1000rpm, 30min), 60 DEG C are dried 24 h, i.e. obtain nanometer after 550 DEG C of calcining 5 h
Type A zeolite molecular sieve, selects Zeta potential analyser gained molecular sieve to carry out surface potential analysis to determine its surface band
Negative electricity.
(3) step (1) manganese oxide solid 8 g is immersed in the poly-p styrene sulfonic acid that 1L mass percent concentration is 0.9%
(PSS) processing 1.5 h in solution, 6000rpm is centrifuged, and filters, and filtering residue is washed with deionized water 3 times；After washing, filtering residue is immersed in again
PDDA (PDDA) solution of mass percent concentration 0.9% processes 1.5 h, filters, wash
Wash solid, the most again with the PDDA process of mass percent concentration 0.9%；
(4) after the solid particle that step (3) prepares being transferred to ultrasound wave dispersion process in the ratio of 15g/L, mass percent is dense
Degree be 8% A-type nano zeolite molecular sieve suspension in process 1.3 h so that it is complete once to be coated with shape by electrostatic adsorption
Become core-shell material, filter, solid be placed in the most again molecular sieve primary response liquid (step 4. in the molecular sieve that obtains the most anti-
Answer liquid) in filter after 110 DEG C of crystallization 4 h, wash, be dried the nickel oxide core-shell material preparing molecular sieve cladding.
(5) core-shell material of step (4) gained molecular sieve cladding nickel oxide being placed in percent mass Particle density is 70 %'s
Going to reactor in ammonium chloride solution makes nuclear material nickel oxide react generation chlorine ammonia nickel, and reaction condition is 130 DEG C, 6 h.
(6) by step (5) resulting materials Ni (NH3)6Cl2@molecular screen material is placed in 250 DEG C of roasting 2 h in Muffle furnace and must urge
Agent MnCl2@molecular sieve.
Above-mentioned catalyst is applied in carbamide with phenol reactant diphenyl carbonate synthesis (reaction equation is as follows), reaction
Carrying out 36 h, conversion rate of urea 96.6% at 190 DEG C, diphenyl carbonate yield is 93.7%, and catalyst uses carbonic acid two after 5 times
Phenyl ester yield is that 90.5%(is shown in Table 1)；
。
Embodiment 5
The method of the lanthanum oxide catalyst preparing molecular sieve cladding is as follows:
(1) with reference to Z Xu, " the Preparation and that S Bian, J Wang, T Liu, L Wang, Y Gao etc. delivers
luminescence of La2O3: Ln3+(Ln3+= Eu3+, Tb3+, Dy3+, Sm3+, Er3+, Ho3+, Tm3+, Yb3+/Er3 +, Yb3+/Ho3+) microspheres " prepare the spherical alumina lanthanum powder body that particle diameter is 1～5 micron, use conventional Zeta electricity
Position analyser determines that the lanthana surface of solids is electronegative；
(2) preparation of molecular sieve is with reference to " Assembly of Nanozeolite Monolayers on the Gold
Substrates of Piezoeletric Sensors”
1. SiO is pressed2:Al2O3:Na2O: (TMA)2O:H2The mol ratio of O is the ratio of 11.9:1.9:0.4:14:700, in weighing
State the reaction raw materials Ludox (30% in water) corresponding to material, aluminum isopropylate., sodium hydroxide, Tetramethylammonium hydroxide,
Deionized water, standby；
2. deionized water 28 g is weighed, by 2.29 g aluminum isopropylate., 0.1 gNaOH and 15.04 g tetra-under room temperature magnetic agitation
Ammonium hydroxide is dissolved in 27.2g deionized water and stirs one day until clarification, is designated as solution A；
3. 7.04g Ludox is under agitation slowly dropped in solution A the solution B that stirs to obtain, and B is old through 72 hours room temperatures
Molecular sieve primary response liquid is obtained after change；
4. being put into by molecular sieve primary response liquid in the hydrothermal reaction kettle of 100ml, 60 DEG C of crystallization 1 day, crystallization afterproduct is through ultrasonic
(150W, 5min), centrifugation (1000rpm, 30min), 60 DEG C are dried 24 h, i.e. obtain nano type A after 500 DEG C of calcining 4 h
Zeolite molecular sieve, selects Zeta potential analyser gained molecular sieve to carry out surface potential analysis to determine that its surface band is born
Electricity.
(3) step (1) manganese oxide solid 10 g is immersed in the phthalic acid two that 1 L mass percent concentration is 1.0%
Processing 2h, 6000rpm in glycol diacrylate (PDDA) solution centrifugal, filter, filtering residue is washed with deionized water 3 times；Washing
Rear filtering residue is immersed in poly-p styrene sulfonic acid (PSS) solution of mass percent concentration 1.0% again and processes 2 h, filters, washs
Solid, the most again with the PDDA process of mass percent concentration 1.0%；
(4) in the ratio of 20 g/L by step (3) prepare solid particle transfer to ultrasound wave dispersion process after mass percent
Concentration be 10 % A-type nano zeolite molecular sieve suspension in process 9 h so that it is complete once to be coated with by electrostatic adsorption
Form core-shell material, filter, solid be placed in the most again molecular sieve primary response liquid (step 3. in the molecular sieve that obtains initial
Reactant liquor) in filter after 115 DEG C of crystallization 4.5 h, wash, be dried the lanthana core-shell material preparing molecular sieve cladding.
(5) core-shell material of step (4) gained molecular sieve cladding lanthana being placed in percent mass Particle density is 90 %'s
Going to reactor in ammonium chloride solution makes nuclear material lanthana react generation chlorine ammonia lanthanum, and reaction condition is 60 DEG C, 10 h.
(6) by step (5) resulting materials La (NH3)8Cl2@molecular screen material is placed in 250 DEG C of roasting 2 h in Muffle furnace and must urge
Agent LaCl3@molecular sieve.
Above-mentioned catalyst is applied in carbamide with phenol reactant diphenyl carbonate synthesis (reaction equation is as follows), reaction
Carrying out 18 h, conversion rate of urea 98.6% at 195 DEG C, diphenyl carbonate yield is 98.3%, and catalyst uses carbonic acid two after 5 times
Phenyl ester yield is that 93.2%(is shown in Table 1)；
。
From table 1, the catalyst prepared by the present invention is effective, remains to keep higher after reusing 5 times
Catalysis activity, the metal oronain salt formed after catalysis is used further to again catalysis after can making its deamination by simple heat treated, from
And achieve catalysis and the dual specially good effect coupled, it can be seen that, this catalyst can be additionally used in other similar reaction systems, it is achieved high
Effect catalysis.
Table 1: catalyst repeat performance
。
Claims (6)
1. the preparation method of a core-shell material catalyst, it is characterised in that specifically include following steps:
(1) determine surface positively charged or the negative electricity of transition metal oxide, transition metal oxide be impregnated in percent mass
Specific concentration be 0.3～1.0 % positive/negative polyelectrolyte solution in 0.5～2 h, centrifugal filtration, residue washing；Filtering residue after washing
Repeat said process 2～3 times, whole immerse during positive polyelectrolyte solution and negative polyelectrolyte solution be used alternatingly；
(2) in the ratio of 1 ~ 20 g/L, the filtering residue that step (1) obtains is transferred to nanometer A that mass percent concentration is 2% ~ 10%
Type zeolite molecular sieve suspension processes 0.5 ~ 12 h, filters, wash, dried solid is placed in molecular sieve primary response liquid
90 ~ 120 DEG C of Crystallizing treatment 1 ~ 5 h, filter, wash, be vacuum dried after be the ammonium chloride of 10% ~ 90% with mass percent concentration again
Solution carries out reacting 2 ~ 10h at 60 ~ 140 DEG C and obtains M (NH3)nClβ@molecular sieve, wherein n=1 ~ 8, be coordinated number, mistake for ammonia
Filter, wash, be vacuum dried after low-temperature bake prepare core-shell material catalyst MClβ@molecular sieve.
The preparation method of core-shell material catalyst the most according to claim 1, it is characterised in that: transition metal oxide is oxygen
Change zinc, copper oxide, Aska-Rid., nickel oxide, cobalt oxide, ferrum oxide, manganese oxide, chromium oxide, Scia, titanium oxide, vanadium oxide, oxygen
Change the one in lanthanum, cerium oxide, praseodymium oxide, Dineodymium trioxide.
The preparation method of core-shell material catalyst the most according to claim 1, it is characterised in that: positive polyelectrolyte is adjacent benzene
Dicarboxylic omega-diol diacrylate.
The preparation method of core-shell material catalyst the most according to claim 1, it is characterised in that: negative polyelectrolyte is for poly-right
Styrene sulfonic acid.
The preparation method of core-shell material catalyst the most according to claim 1, it is characterised in that: low-temperature bake be 250 ~
0.5 ~ 2 h is processed under the conditions of 300 DEG C.
6. the core-shell material catalyst that the preparation method of core-shell material catalyst according to any one of claim 1-5 prepares is closing
Become the application in diphenyl carbonate, it is characterised in that: this catalyst synthesizes carbon for carbamide or carbamate with phenol reactant
In diphenyl phthalate, reaction carries out 2 ~ 48 h at 190 DEG C ~ 210 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610495069.5A CN106040291B (en) | 2016-06-30 | 2016-06-30 | A kind of preparation method and applications of core-shell material catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610495069.5A CN106040291B (en) | 2016-06-30 | 2016-06-30 | A kind of preparation method and applications of core-shell material catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106040291A true CN106040291A (en) | 2016-10-26 |
| CN106040291B CN106040291B (en) | 2019-12-03 |
Family
ID=57167249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610495069.5A Active CN106040291B (en) | 2016-06-30 | 2016-06-30 | A kind of preparation method and applications of core-shell material catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106040291B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579795A (en) * | 2018-03-30 | 2018-09-28 | 昆明理工大学 | A kind of using transition metal salt is core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell and application |
| CN108745277A (en) * | 2018-06-07 | 2018-11-06 | 天津鼎芯膜科技有限公司 | A kind of three-dimensional assembly Core-shell structure material and its preparation method and application |
| CN108821350A (en) * | 2018-05-29 | 2018-11-16 | 昆明理工大学 | A kind of preparation method of transition metal salt amine complex |
| CN109622026A (en) * | 2018-12-05 | 2019-04-16 | 枣庄学院 | A kind of difunctional core-shell structure composite catalyst and its preparation method and application |
| CN110252274A (en) * | 2019-06-14 | 2019-09-20 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | The preparation method of ester exchange synthesizing diphenyl carbonate catalyst |
| CN112337504A (en) * | 2020-11-11 | 2021-02-09 | 昆明理工大学 | Core-shell catalyst, preparation method thereof and method for treating industrial tail gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012137138A4 (en) * | 2011-04-04 | 2013-04-04 | Universidade Do Porto | Method for hydrothermal preparation of metal oxide catalyst support, composite catalyst and applications for hydrogen production |
| CN105251526A (en) * | 2015-10-27 | 2016-01-20 | 昆明理工大学 | Preparing method and application of core-shell material catalyst |
| CN105268483A (en) * | 2015-11-05 | 2016-01-27 | 昆明理工大学 | Preparation method and application of core-shell material catalyst |
-
2016
- 2016-06-30 CN CN201610495069.5A patent/CN106040291B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012137138A4 (en) * | 2011-04-04 | 2013-04-04 | Universidade Do Porto | Method for hydrothermal preparation of metal oxide catalyst support, composite catalyst and applications for hydrogen production |
| CN105251526A (en) * | 2015-10-27 | 2016-01-20 | 昆明理工大学 | Preparing method and application of core-shell material catalyst |
| CN105268483A (en) * | 2015-11-05 | 2016-01-27 | 昆明理工大学 | Preparation method and application of core-shell material catalyst |
Non-Patent Citations (2)
| Title |
|---|
| DONG FENG，ET AL: "The preparation of core-shell structural ZnO@4A nano-materials", 《PROCEEDINGS OF THE 2015 INTERNATIONAL CONFERENCE ON ADVANCED ENGINEERING MATERIALS AND TECHNOLOGY》 * |
| 唐谟堂: "《配合物冶金理论与技术》", 31 October 2011, 中南大学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579795A (en) * | 2018-03-30 | 2018-09-28 | 昆明理工大学 | A kind of using transition metal salt is core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell and application |
| CN108821350A (en) * | 2018-05-29 | 2018-11-16 | 昆明理工大学 | A kind of preparation method of transition metal salt amine complex |
| CN108745277A (en) * | 2018-06-07 | 2018-11-06 | 天津鼎芯膜科技有限公司 | A kind of three-dimensional assembly Core-shell structure material and its preparation method and application |
| CN109622026A (en) * | 2018-12-05 | 2019-04-16 | 枣庄学院 | A kind of difunctional core-shell structure composite catalyst and its preparation method and application |
| CN110252274A (en) * | 2019-06-14 | 2019-09-20 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | The preparation method of ester exchange synthesizing diphenyl carbonate catalyst |
| CN112337504A (en) * | 2020-11-11 | 2021-02-09 | 昆明理工大学 | Core-shell catalyst, preparation method thereof and method for treating industrial tail gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106040291B (en) | 2019-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106040291B (en) | A kind of preparation method and applications of core-shell material catalyst | |
| CN106179515B (en) | A kind of preparation method of the catalyst of diphenyl carbonate synthesis | |
| CN110918126B (en) | Preparation method of flower-shaped molybdenum disulfide combined UiO-66 photocatalyst | |
| CN105268483B (en) | A kind of preparation method and application of core-shell material catalyst | |
| CN104903407B (en) | Semiconductor-oxides nanotubes-based composite particles useful for dye-removal and process thereof | |
| CN101623645B (en) | Preparation for p-n junction hollow sphere and application in photocatalytic hydrogen production by water decomposition | |
| CN104646001B (en) | A kind of visible-light response type bismuth ferrite bismuth oxide composite and preparation method thereof | |
| CN102302933A (en) | Method for preparing magnetic oxide hollow microsphere/titanium dioxide composite photocatalyst | |
| CN106391066B (en) | A kind of composite photo-catalyst and preparation method thereof of rapidly and efficiently rhodamine B degradation | |
| CN108311165A (en) | It is a kind of to prepare BiOCl/SrFe12-xCoxO19The method of composite magnetic catalysis material | |
| CN102241415A (en) | Bismuth oxybromide particles with three-dimensional flower-like microstructure and preparation method and use thereof | |
| Shekofteh-Gohari et al. | Ternary ZnO/Ag3VO4/Fe3O4 nanocomposites: Novel magnetically separable photocatalyst for efficiently degradation of dye pollutants under visible-light irradiation | |
| CN107658527A (en) | A kind of high-performance transition metal oxide hollow ball air electrode and preparation method thereof | |
| CN107511154A (en) | A kind of sea urchin shape CeO2/Bi2S3Composite visible light catalyst and preparation method thereof | |
| Yang et al. | Investigation of electron beam irradiation on In2S3-MxInySz (M= Bi or La) Z-scheme heterojunctions for efficient and stable degradation of water pollutants | |
| CN105772039A (en) | Fluorine and boron co-doped TiO2 nano-plate with crystal planes (001) and oxygen vacancy, method for preparing fluorine and boron co-doped TiO2 nano-plate and application thereof | |
| CN105251526B (en) | A kind of preparation method and applications of core-shell material catalyst | |
| CN108579795A (en) | A kind of using transition metal salt is core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell and application | |
| CN106748782B (en) | A kind of method of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing Methyl Ethyl Carbonate | |
| CN109622026A (en) | A kind of difunctional core-shell structure composite catalyst and its preparation method and application | |
| CN101947460A (en) | Synthesis method of nano-zinc sulfide/bamboo charcoal photocatalytic material by hydrothermal process | |
| CN103586013A (en) | Method for preparing wheat-ear-shaped nano ZnO photocatalyst | |
| CN109465037A (en) | The magnetic CDs-MoS of micropollutants in a kind of degradation water2-Fe3O4The green synthesis method of catalysis material | |
| CN111151242B (en) | Preparation method of cerium-manganese metal ion modified aluminate photocatalyst | |
| CN105214694B (en) | A kind of method that soft template method prepares BiOCl hollow shells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhao Wenbo Inventor after: Xu Zhiyong Inventor after: Feng Dong Inventor after: Chen Yuan Inventor after: Li Yanhong Inventor after: Wang Yang Inventor after: Zhao Qian Inventor before: Zhao Wenbo Inventor before: Feng Dong Inventor before: Chen Yuan Inventor before: Li Yanhong Inventor before: Wang Yang Inventor before: Zhao Qian |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |