WO2017202495A1 - A synthetic zeolite comprising a catalytic metal - Google Patents
A synthetic zeolite comprising a catalytic metal Download PDFInfo
- Publication number
- WO2017202495A1 WO2017202495A1 PCT/EP2017/000621 EP2017000621W WO2017202495A1 WO 2017202495 A1 WO2017202495 A1 WO 2017202495A1 EP 2017000621 W EP2017000621 W EP 2017000621W WO 2017202495 A1 WO2017202495 A1 WO 2017202495A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zeolite
- pore size
- small pore
- synthetic zeolite
- size synthetic
- Prior art date
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 296
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 281
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 261
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 161
- 239000002184 metal Substances 0.000 title claims abstract description 161
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 108
- 239000011148 porous material Substances 0.000 claims abstract description 159
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 47
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 47
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 47
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 47
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 25
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 24
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 23
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 10
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 101
- 230000015572 biosynthetic process Effects 0.000 claims description 90
- 238000000034 method Methods 0.000 claims description 75
- 238000003786 synthesis reaction Methods 0.000 claims description 74
- 230000008569 process Effects 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 62
- 239000003054 catalyst Substances 0.000 claims description 59
- 239000002245 particle Substances 0.000 claims description 53
- 239000003446 ligand Substances 0.000 claims description 46
- -1 HAuBr4 xH20 Inorganic materials 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 37
- 229910001868 water Inorganic materials 0.000 claims description 35
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000004873 anchoring Methods 0.000 claims description 29
- 239000011541 reaction mixture Substances 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- 229910052732 germanium Inorganic materials 0.000 claims description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- 150000004760 silicates Chemical class 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052790 beryllium Inorganic materials 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 3
- 229910021640 Iridium dichloride Inorganic materials 0.000 claims description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 3
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 3
- 239000012084 conversion product Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- 239000002594 sorbent Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- UAIHPMFLFVHDIN-UHFFFAOYSA-K trichloroosmium Chemical compound Cl[Os](Cl)Cl UAIHPMFLFVHDIN-UHFFFAOYSA-K 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 2
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 claims description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 abstract description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 116
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000010948 rhodium Substances 0.000 description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 32
- 239000000463 material Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000000499 gel Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 22
- 238000011282 treatment Methods 0.000 description 22
- 239000002105 nanoparticle Substances 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 17
- 238000007669 thermal treatment Methods 0.000 description 17
- 238000004627 transmission electron microscopy Methods 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 13
- 238000000634 powder X-ray diffraction Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 238000000386 microscopy Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000004876 x-ray fluorescence Methods 0.000 description 9
- 229920006362 Teflon® Polymers 0.000 description 8
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 8
- 229910052676 chabazite Inorganic materials 0.000 description 8
- 239000002923 metal particle Substances 0.000 description 8
- 239000004809 Teflon Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- 238000001144 powder X-ray diffraction data Methods 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 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 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005216 hydrothermal crystallization Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000012229 microporous material Substances 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000011369 resultant mixture Substances 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910018879 Pt—Pd Inorganic materials 0.000 description 3
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012925 reference material Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000004475 Arginine Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 229910021076 Pd—Pd Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 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
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000001483 mobilizing effect Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- AJPPAKACCOFNEN-UHFFFAOYSA-K tetraethylazanium;phosphate Chemical compound [O-]P([O-])([O-])=O.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC AJPPAKACCOFNEN-UHFFFAOYSA-K 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 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
- B01J29/72—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
- B01J29/74—Noble metals
- B01J29/743—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
-
- 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
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
- B01J29/505—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
- B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
-
- 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
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
- B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
- B01J29/54—Noble metals
-
- 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
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
- B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
- B01J29/56—Iron group metals or copper
-
- 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
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
- B01J29/58—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
-
- 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
- B01J29/7049—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
- B01J29/7065—CHA-type, e.g. Chabazite, LZ-218
-
- 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
-
- 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
- B01J29/7207—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
- B01J29/723—CHA-type, e.g. Chabazite, LZ-218
-
- 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
- B01J29/74—Noble metals
-
- 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
- B01J29/74—Noble metals
- B01J29/7407—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
-
- 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
- B01J29/72—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
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- 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
-
- 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
-
- 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
- B01J29/783—CHA-type, e.g. Chabazite, LZ-218
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J29/86—Borosilicates; Aluminoborosilicates
-
- 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
- B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
-
- 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
- B01J29/88—Ferrosilicates; Ferroaluminosilicates
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Definitions
- the present invention relates to a small pore synthetic zeolite comprising a catalytic metal and to processes for making the small pore synthetic zeolite.
- Zeolites are a class of crystalline microporous oxide materials with well-defined pores and cavities. Although their chemical composition was first limited to aluminosilicate polymorphs, many more heteroatoms such as B, P, As, Sn, Ti, Fe, Ge, Ga, Be and Zn, among others, can now be introduced into zeolitic frameworks in addition to Si and Al.
- Zeolites both natural and synthetic, have been demonstrated in the past to be useful as adsorbents and to have catalytic properties for various types of hydrocarbon conversion reactions.
- Zeolites are ordered, porous crystalline materials having a definite crystalline structure as determined by X-ray diffraction (XRD).
- XRD X-ray diffraction
- T Si, Al, P, Ti, etc.
- the tetrahedra are cross-linked by the sharing of oxygen atoms with the electrovalence of the tetrahedra containing trivalent element (e.g., aluminum or boron) or divalent element (e.g., Be or Zn) being balanced by the inclusion in the crystal of a cation, for example, a proton, an alkali metal or an alkaline earth metal cation.
- trivalent element e.g., aluminum or boron
- divalent element e.g., Be or Zn
- Zeolites that find application in catalysis include any of the naturally occurring or synthetic crystalline zeolites. Examples of these zeolites include large pore zeolites, intermediate pore size zeolites, and small pore zeolites. These zeolites and their isotypes are described in "Atlas of Zeolite Framework Types", eds, Ch. Baerlocher, L.B. McCusker, D.H. Olson, Elsevier, Sixth Revised Edition, 2007, which is hereby incorporated by reference.
- a large pore zeolite generally has a pore size of at least about 6.0 A to 8 A and includes LTL, MAZ, FAU, OFF, *BEA, and MOR framework type zeolites (IUPAC Commission of Zeolite Nomenclature).
- large pore zeolites include mazzite, offretite, zeolite L, zeolite Y, zeolite X, omega, and beta.
- An intermediate pore size zeolite generally has a pore size from more than 4.5 A to less than about 7 A and includes, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites (IUPAC Commission of Zeolite Nomenclature).
- Examples of intermediate pore size zeolites include ZSM-5, ZSM- 1 1 , ZSM-22, MCM-22, silicalite 1 , and silicalite 2.
- a small pore size zeolite has a pore size from about 3 A to less than about 5.0 A and includes, for example, CHA, ERI, KFI, LEV, SOD, and LTA framework type zeolites (IUPAC Commission of Zeolite Nomenclature).
- Examples of small pore zeolites include ZK-4, SAPO-34, SAPO-35, ZK- 14, SAPO-42, ZK-21 , ZK-22, ZK-5, ZK-20, zeolite A, chabazite, zeolite T, and ALPO- 17.
- Synthesis of zeolites typically involves the preparation of a synthesis mixture which comprises sources of all the elements present in the zeolite, often with a source of hydroxide ion to adjust the pH.
- a structure directing agent SDA
- Structure directing agents are compounds which are believed to promote the formation of zeolite frameworks and which are thought to act as templates around which certain zeolite structures can form and which thereby promote the formation of the desired zeolite.
- Various compounds have been used as structure directing agents including various types of quaternary ammonium cations.
- zeolites The synthesis of zeolites is a complicated process. There are a number of variables that need to be controlled in order to optimize the synthesis in terms of purity, yield and quality of the zeolite produced. A particularly important variable is the choice of synthesis template (structure directing agent), which usually determines which framework type is obtained from the synthesis. Quaternary ammonium ions are typically used as the structure directing agents in the preparation of zeolite catalysts. For example, zeolite MCM- 68 may be made from quaternary ammonium ions as is described in US 6,049,01 8.
- zeolites that are typically produced using quaternary ammonium ions include ZSM- 25, ZSM-48, ZSM-57, ZS -58, and ECR-34, as described in US 4,247,416, US 4,585,747, US 4,640,829, US 4,698,21 8, and US 5,455,020.
- the "as-synthesized" zeolite will contain the structure directing agent in its pores, and is usually subjected to a calcination step to burn out the structure directing agent and free up the pores.
- metal cations such as metal cations of Groups 2 to 1 5 of the Periodic Table of the Elements within the zeolite structure. This is typically accomplished by ion exchange treatment.
- Zeolites are often used in industrial catalysts as supports for catalytic metals.
- Metals also play an important role in palliating catalyst deactivation by coke in acid catalyzed processes, using hydrogen to maintain the catalyst surface clean of heavy hydrocarbons.
- a major problem emerges due to gradual reorganization of the metal into the form of larger (thermodynamically more stable) metal particles, which implies a loss in the effective number of sites available for catalysis.
- hydroprocessing catalysts often require periodic regeneration routines to eliminate residual heavy hydrocarbons from the catalyst surface, using air and high temperatures to complete the combustion process. The use of H 2 /0 2 cycles along the catalyst lifetime aggravates the metal sintering problem.
- metal catalysts supported on zeolites are prepared by ion exchange or incipient wetness impregnation of the support. In each case the goal is to place the metal inside the pores of the support without an agglomeration of metal particles on the external surface of the support. Since the metals are typically introduced as cation precursors, they can ion exchange with the cations associated with the ionic framework, in particular with the trivalent elements, such as Al in an aluminosilicate material, or tetravalent elements such as Si in a silicoaluminophosphate material.
- the invention provides a small pore size synthetic zeolite having a degree of crystallinity of at least 80% and comprising at least 0.01 wt%, based on the weight of the zeolite, of at least one catalytic metal selected from the group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Mo, W, Re, Co, Ni, Zn, Cr, Mn, Ce, Ga, and combinations thereof, wherein at least 80% of the catalytic metal is encapsulated in the zeolite, wherein if the zeolite is an aluminosilicate then the aluminosilicate has a Si02:Ah0 3 molar ratio of greater than 6: 1 , preferably greater than 12: 1 , in particular greater than 30: 1 .
- the invention provides a small pore size synthetic aluminosilicate zeolite having a Si0 2 :A l 2 0 3 molar ratio of greater than 6: 1 , preferably greater than 12: 1 , in particular greater than 30: 1 , and a degree of crystallinity of at least 80% which comprises at least 0.01 wt%, based on the weight of the zeolite, of at least one catalytic metal selected from the group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Mo, W, Re, Co, Ni, Zn, Cr, Mn, Ce, Ga, and combinations thereof, wherein at least 80% of the catalytic metal is encapsulated in the zeolite.
- the invention provides a small pore size synthetic zeolite having a degree of crystallinity of at least 80% and comprising at least 0.01 wt%, based on the weight of the zeolite, of at least one catalytic metal selected from the group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Mo, W, Re, Co, Ni, Zn, Cr, Mn, Ce, Ga, and combinations thereof, wherein at least a portion of the catalytic metal is encapsulated in zeolite such that if the zeolite is used to catalyze the conversion of a feed stream containing a first reactant compound which is sufficiently small that it can enter the pores of the zeolite (e.g.
- the ratio of the rate of conversion of the second reactant to the rate of conversion of the first reactant is reduced by at least 80% as compared to the same reaction carried out under the same conditions using the same feed stream over a catalyst comprising the same catalytic metal supported on the surface of an amorphous support, wherein if the zeolite is an aluminosilicate then the aluminosilicate has a Si0 2 :A l 203 molar ratio of greater than 6: 1 , preferably greater than 12: 1 , in particular greater than 30: 1.
- the invention also provides, in a yet further aspect, a process for the preparation of the small pore size synthetic zeolite of the invention comprising:
- the invention in a yet further aspect, also provides a process for the preparation of a small pore size synthetic zeolite of the invention comprising:
- a) providing a reaction mixture comprising a synthesis mixture capable of forming the small pore size synthetic zeolite framework, at least one anchoring agent, and at least one catalytic metal precursor, wherein the anchoring agent includes at least one amine and/or thiol group and at least one alkoxysilane group and the catalytic metal precursor includes at least one ligand capable of being exchanged by the at least one amine group and/or thiol group of the anchoring agent;
- the crystals of the small pore size synthetic zeolite recovered from the reaction mixture will include the SDA in the pores and cavities of the zeolite (that is, in "as made” form).
- the processes for the preparation of the small pore size synthetic zeolite of the invention may further include a step of subjecting the small pore size synthetic zeolite recovered from the reaction mixture to a calcination step.
- the calcination step removes the structure directing agent and provides the zeolite in calcined form.
- the calcination step also removes the ligands or anchoring agents used to stabilize the metal during the crystallization step.
- the invention provides use of an active form of the small pore size synthetic zeolite of the invention as a sorbent or as a catalyst.
- active form is meant a calcined material that has been ion-exchanged with protons and is therefore acidic.
- the invention provides a process for converting a feedstock comprising an organic compound to a conversion product which comprises the step of contacting said feedstock at organic compound conversion conditions with a catalyst comprising a small pore size synthetic zeolite according to the invention.
- Figure 1 shows PXRD patterns of the metal-containing high-silica small pore zeolites synthesized according to Examples 1 and 4 to 10.
- Figure 2 shows TEM images and particle size distributions of the sample synthesized according to Example 1 , after being calcined at 550 °C and treated with H 2 at 400 °C ( Figures 2A and 2C), and after additional thermal treatment by calcination with air at 650 °C and subsequent reduction with H 2 at 400 °C ( Figures 2B and 2D).
- Figure 3 shows the XANES and EXAFS spectra of the sample synthesized according to Example 1 .
- Figure 3A shows XANES spectra of the sample synthesized according to Example 1 (after being calcined at 550 °C and treated with H 2 at 400 °C) (time zero, bottom spectrum), as the sample is further treated with 5% 0 2 and the temperature is raised from 20 to 500 °C.
- Figure 3B shows EXAFS spectra (not phase-corrected) of the oxidised sample after the oxidation detailed for Fig 3A (bottom line), and its comparison with the material of Example 1 (calcined at 550 °C and treated with H 2 at 400 °C) (middle line), and a reference platinum foil (top line).
- Figure 4 shows STEM images and particle size distributions of the sample synthesized according to Comparative Example 2 after being calcined at 400 °C and treated with H 2 at 400 °C ( Figures 4A and 4C), and after additional thermal treatment by calcination with air at 650 °C and, finally, with H 2 at 400 °C ( Figures 4B and 4D).
- Figure 5 shows the initial reaction rates obtained for the hydrogenation of model alkenes (ethylene and propylene) using the materials synthesized according to Example 1 and Comparative Example 2 as catalysts.
- Figure 6 shows TEM images of the sample synthesized according to Example 4, after calcination at 550 °C followed by treatment with H 2 at 400 °C.
- Figure 6A is representative of the majority of the areas evaluated, showing small metal nanoparticles.
- Figure 6B shows an area where a big metal nanoparticle is observed in addition to the small metal nanoparticles (the abundance of the larger particles is ⁇ 0.1 % by number).
- Figure 7 shows TEM images and particle size distribution of the sample synthesized according to Example 5, after being calcined at 600 °C and treated with H 2 at 400 °C ( Figure 7A), and after additional thermal treatment by calcination with air at 650 °C and subsequent reduction with H 2 at 400 °C ( Figures 7B and 7C).
- Figure 8 shows the Fourier-Transform EXAFS spectra (not phase-corrected) at the Rh K-Edge of the sample synthesized according to Example 6 after treatment with 5% 0 2 at 500 °C.
- Figure 9 shows TEM images of the sample synthesized according to Example 8, after being calcined at 500 °C and treated with H 2 at 400 °C ( Figure 9A), and after additional thermal treatment by calcination with air at 650 °C and subsequent reduction with H 2 at 400 °C ( Figure 9B).
- Figure 10 shows TEM images and particle size distribution of the sample synthesized according to Example 9, after being calcined at 560 °C and treated with H 2 at 400 °C ( Figure 10A), and after additional thermal treatment by calcination with air at 650 °C and subsequent reduction with H 2 at 400 °C ( Figure 10B and 10C).
- Figure 1 1 shows a STEM image and particle size distribution of a microtomed sample synthesized according to Example 10, after being calcined at 550 °C and treated with H 2 at 400 °C ( Figures 1 1 A and 1 1 B).
- Figures 12 and 13 show a STEM image and EXAFS spectra of the sample synthesized according to Example 1 1 , after being calcined at 550 °C and treated with H 2 at 400 °C.
- Figure 13 shows the Fourier-Transform EXAFS spectra (not phase-corrected) at the Pt LIIl-Edge ( Figure 1 3A top) and Pd K-Edge ( Figure 13A bottom) of said sample and the EXAFS spectra (not phase-corrected) at the Pt LIII-Edge ( Figure 13B top) and Pd K-Edge ( Figure 1 3B bottom) of said sample after treatment with 50 2 at 500 °C.
- Figure 14 shows a STEM image of the sample synthesized according to Example 12, after being calcined at 550 °C and treated with H 2 at 400 °C.
- Figure 1 5 shows SEM (retro-dispersed electrons) images of the sample synthesized according to Example 1 (top) and Comparative Example 13 (bottom) after calcination at 550 °C (left) and after subsequent treatment in steam at 600 °C (right).
- Figure 16 shows PXRD patterns of sample synthesized according to Example 1 (top) and Comparative Example 1 3 (bottom) after calcination at 550 °C (left) and after subsequent treatment in steam at 600 °C.
- the present inventors have found that it is possible to synthesize small pore size zeolites, in particular silicates and aluminosilicates, having a catalytic metal present in encapsulated form inside the pores and/or cavities of the zeolite.
- the inventors believe that the encapsulation of the catalytic metal within the small pore size synthetic zeolites, in particular within the pores and/or cavities of small pore size synthetic zeolites, limits the growth of the catalytic metal species to small particles, for example, catalytic metal particles having a biggest dimension of less than 4.0 nm, for instance a biggest dimension in the range between 0.1 and 3.0 nm, such as between 0.5 and 1 .0 nm, and prevents significant growth of those particles thereby providing an improved resistance to sintering.
- the size of the particles of catalytic metal (at least in terms of biggest dimension) is typically larger than the pore window size of the zeolite, and so the metal can be considered to be occluded within the cavities in the zeolite crystals rather than being present in the small pore windows of the zeolite.
- Conventional noble metal catalysts on silica supports in contrast, generally exhibit sintering and therefore growth of the metal particles under high temperature cycles of reduction and oxidation which leads to a reduction in the number of catalytic sites and the activity of the catalyst.
- the zeolites of the invention may have advantages in selectivity in organic conversion reactions and in resistance to catalyst poisons.
- synthetic zeolite should be understood to refer to a zeolite which has been prepared from a synthesis mixture as opposed to being a naturally occurring zeolite which has been obtained by mining or quarrying or similar processes from the natural environment.
- small pore size synthetic zeolite refers to a synthetic zeolite wherein the pores of the zeolite have a size in the range of from 3.0 A to less than 5.0 A.
- the small pore size synthetic zeolite will generally have an 8-membered ring framework structure but some 9- or 10-membered ring zeolites are known to have distorted rings which have a size in the range of from 3.0 to 5.0 A and fall within the scope of the term "small pore size synthetic zeolite” as used herein.
- the small pore size synthetic zeolite is an 8-membered ring zeolite.
- the small pore size synthetic zeolite is of framework type AEI, AFT, AFX, CHA, CDO, DDR, EDI, ERI, IHW, ITE, ITW, KFI, MER, MTF, MWF, LEV, LTA, PAU, PWY, RHO, SFW or UFI, more preferably of framework type CHA, AEI, AFX, RHO, KFI or LTA.
- the small pore synthetic zeolite is of framework type CHA or AFX.
- CHA is an especially preferred framework type.
- the zeolite framework type may optionally be a framework type which can be synthesized without requiring the presence of a structure directing agent.
- the small pore size synthetic zeolite may be of a framework type which requires the presence of a structure directing agent in the synthesis mixture.
- the small pore size synthetic zeolite is one in which the zeolite framework contains one or more elements selected from the group consisting of Si, Al, P, As, Ti, Ge, Sn, Fe, B, Ga, Be and Zn; preferably in which the zeolite framework contains at least one tetravalent element X selected from the group consisting of Si, Ge, Sn and Ti and/or at least one trivalent element Y selected from the group consisting of Al, B, Fe and Ga, optionally one pentavalent element Z selected from the group consisting of P and As, and optionally one divalent element W selected from the group consisting of Be and Zn; more preferably in which the zeolite framework contains at least Si and/or Al and optionally P.
- the zeolite framework contains at least one tetravalent element X selected from the group consisting of Si, Ge, Sn and Ti and optionally at least one trivalent element Y selected from the group consisting of Al, B, Fe and Ga; most preferably the zeolite framework contains Si and optionally Al and/or B; especially the zeolite framework contains Si and optionally Al.
- the zeolite framework contains a metal, such as Fe
- the catalytic metal and transition metal will be other than the metal contained in the framework.
- the catalytic metal is extra-framework metal, that is, the catalytic metal generally does not form part of the framework of the synthetic zeolite, i.e. of the three-dimensional framework of tetrahedra of the synthetic zeolite.
- the small pore size synthetic zeolite is selected from the group consisting of silicates, aluminosilicates, borosilicates, aluminophosphates (ALPOs), and silicoaluminophosphates (SAPOs); preferably from silicates, aluminosilicates and borosilicates, especially from silicates and aluminosilicates.
- the small pore size synthetic zeolite may optionally be a crystalline aluminophosphate or silicoaluminophosphate.
- Aluminophosphate molecular sieves are porous frameworks containing alternating aluminum and phosphorous tetrahedral atoms connected by bridging oxygen atoms.
- silicoaluminophosphate molecular sieves some of the phosphorous, or pairs of aluminum and phosphorous atoms can be substituted with tetrahedral silicon atoms.
- Those materials may be represented by the formula, on an anhydrous basis:
- x is greater than 0 in the case of silicoaluminophosphate molecular sieves and optionally, x is in the range of from greater than 0 to about 0.3 1.
- the range of y is from 0.25 to 0.5, and z is in the range of from 0.25 to 0.5 and preferably y and z are in the range 0.4 to 0.5.
- the small pore size synthetic zeolite is preferably a silicate or an aluminosilicate. If the small pore size synthetic zeolite is an aluminosilicate, it contains Si and Al and has a Si0 2 :Al 2 0 3 molar ratio of greater than 6: 1 , preferably greater than 8: 1 , more preferably greater than 10: 1 , most preferably greater than 1 2: 1 , in particular greater than 30: 1 , such as greater than 100: 1 , or even greater than 150: 1 .
- the small pore size synthetic zeolite is a silicate, it has an Al 2 03:Si0 2 molar ratio that is 0 or a Si0 2 :Al 2 03 molar ratio that is infinite (i.e. no A1 2 0 3 ). While the presence of aluminum within the zeolite framework structure does contribute acidic sites to the catalyst it also is associated with a reduction in thermal stability of the zeolite. Many industrial organic feedstock conversion processes are carried out at temperatures which require the use of zeolite supports having a Si0 2 :Al 2 0 3 molar ratio of greater than 6: 1 or even greater than 10: 1 , such as greater than 12: 1 or greater than 30: 1 or greater than 100: 1 or greater than 150: 1.
- the small pore size synthetic zeolite has a degree of crystallinity of at least 80%, optionally at least 90%, preferably at least 95% and most preferably at least 98%.
- the small pore size synthetic zeolite is essentially pure crystalline material.
- the degree of crystallinity may be calculated via x-ray diffraction (XRD) by comparison with a reference material of known 100% crystalline material of the same framework type, the same composition, the same or similar particle size and containing the same amount of metals prepared by an incipient wetness technique.
- the catalytic metal is primarily extra-framework metal and is in the form of metal particles that will tend to scatter x-rays. Therefore in order to obtain fully comparable results to calculate the degree of crystallinity it is important that the reference material contains the same amount of the same metals as present in the small pore size synthetic zeolite.
- the small pore size synthetic zeolite comprises at least 0.01 wt% of catalytic metal, based on the weight of the zeolite.
- the amount of metal is determined by X-ray fluorescence (XRF) or inductively coupled plasma (ICP) and is expressed as wt% of the metal (based on the elemental form of the metal, and not, for example, the oxide form) in the total sample.
- the small pore size synthetic zeolite comprises at least 0.05 wt%, preferably from 0.05 to 5 wt% of the catalytic metal, preferably from 0.1 to 3 wt%, more preferably from 0.5 to 2.5 wt%, most preferably from 1 to 2 wt%.
- the weight percentage of the catalytic metal which is encapsulated in the zeolite can be calculated by carrying out an organic conversion reaction involving a mixed feed having at least one feed compound which is small enough to enter the pores of the zeolite and at least one feed compound which is too large to enter the pores of the zeolite and by comparing the results with an equivalent reaction carried out using a catalyst having an equivalent metal loading in which the metal is not encapsulated, for example one in which the metal is supported on amorphous silica.
- the weight percentage of the catalytic metal which is encapsulated in the zeolite may be measured by hydrogenation of a mixed feed comprising a feed compound, such as ethylene, which is small enough to enter the pores of the zeolite and a feed compound, such as propylene, which is too large to enter the pores of the zeolite.
- a feed compound such as ethylene
- propylene which is too large to enter the pores of the zeolite.
- the smaller compound (e.g. ethylene) and larger compound (e.g. propylene) may be reacted independently rather than as a mixed feed comprising both. This preferred embodiment is advantageous in that it avoids competitive adsorption and diffusion effects that may occur when the smaller and larger compounds are co-fed. Such a procedure is described in detail in Example 3 below.
- the conversion of the larger molecule for example propylene
- the conversion of the smaller molecule for example ethylene
- the degree of difference can be used to calculate the percentage of catalytic metal which is encapsulated.
- this method only takes into account the catalytic metal present in the zeolite of the invention, i.e. the extra-framework metal that has a catalytic activity.
- the bulk metal inside any large metal particles present or any catalytic metal covered under dense Si0 2 layers will not take part in the reaction and so will not influence the selectivity and the product mix obtained.
- the words "at least 80% of the catalytic metal is encapsulated in the zeolite” and similar expressions should be taken to mean “at least 80% of the catalytically active portion of the catalytic metal is encapsulated in the zeolite", it being understood that in many cases the catalytically active portion of the catalytic metal will be all or substantially all of the catalytic metal.
- the percentage of the active catalytic metal that is encapsulated in the zeolite (a) is determined by the following formula:
- a is the percentage of catalytic metal encapsulated in the zeolite
- PR is the propylene reaction rate expressed as mol of propylene converted per mol of catalytic metal per second
- ER is the ethylene reaction rate expressed as mol of ethylene converted per mol of catalytic metal per second
- PR zeolite and ER zeolite are to be understood as the propylene and ethylene rates of the catalyst to be tested
- PR Si0 2 " and "ER Si0 2 " are to be understood as the propylene and ethylene rates of a catalyst having an equivalent metal loading in which the metal is supported on amorphous silica.
- a is the percentage of catalytic metal encapsulated in the zeolite based on the total amount of catalytic metal whether it is present in the zeolite or on the zeolite surface
- a is an absolute percentage number regardless of whether the amount of metal in the zeolite or on the zeolite surface is expressed as amounts in weight or mole.
- an a of at least 80 % corresponds to a ethylene hydrogenation rate that is at least 5 times greater than that of propylene for metals that hydrogenate both ethylene and propylene at identical rates when supported on Si0 2 .
- the catalytic metal is encapsulated in the zeolite of the present invention.
- at least 90%, more particularly at least 95% of the catalytic metal is encapsulated in the zeolite of the present invention.
- the catalytic metal may be selected from group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Mo, W, Re, Co, Ni, Zn, Cr, Mn, Ce, Ga, and combinations thereof; more preferably from the group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Re, and combinations thereof; most preferably from the group consisting of Pt, Rh, Pd and Au and combinations thereof, especially from the Pt, Pd and/or Rh. Pt and Rh are especially preferred catalytic metals.
- the catalytic metal will be present in the form of metal particles, which includes metal clusters as well as site-isolated single metal atoms (the catalytic metal may be present in the particles and/or clusters as elemental metal or as the metal oxide).
- the catalytic metal is present in the form of particles wherein at least 80% of the particles by number have a biggest dimension of less than 4 nm as measured by transmission electron microscopy (TEM).
- TEM transmission electron microscopy
- at least 80% of the particles by number have a biggest dimension in the range of from 0.1 to 3.0 nm, for instance from 0.5 to 1 nm, as measured by TEM.
- the expression “percentage of the particles by number” refers to the arithmetic average of number of particles having the required characteristic out of 100 particles, this value being determined on the basis of a population of at least one thousand particles.
- the expression “biggest dimension” when discussing metal particle size means the biggest dimension as measured by TEM. In the case of substantially spherical particles, the biggest dimension of a particle will correspond to its diameter. In the case of rectangular particles, the biggest dimension of a particle will correspond to the diagonal of the rectangle drawn by the particle.
- the catalytic metal after thermal treatment of the small pore size synthetic zeolite of the present invention by calcination in air at 650°C for two hours and treatment with H 2 at 400°C for two hours, the catalytic metal will still be present in the form of particles wherein at least 80% of the particles by number have a biggest dimension of less than 4 nm as measured by TEM, in particular at least 80% of the particles by number will still have a biggest dimension in the range of from 0.1 to 3.0 nm, for instance from 0.5 to 1 nm, as measured by TEM.
- the small pore size synthetic zeolite may further comprise one or more metals other than the catalytic metal.
- the small pore size synthetic zeolite comprises at least 0.01 wt%, optionally from 0.05 to 5 wt%, such as from 0.1 to 5 wt% of a transition metal selected from the group consisting of Cu, Fe, Ti, Zr, Nb, Hf, Ta and combinations thereof.
- this transition metal is primarily extra-framework metal.
- the small pore size synthetic zeolite is a silicate or an aluminosilicate having a Si0 2 :Al 2 0 3 molar ratio of greater than 6: 1 , preferably greater than 12: 1 , in particular greater than 30: 1 , wherein the catalytic metal is selected from the group consisting of Pt, Rh, Pd and Au, and combinations thereof, in particular Pt, Pd and/or Rh, and wherein the zeolite is of framework type CHA, AEI, AFX, RHO, KFI or LTA, in particular CHA or AFX.
- the small pore size synthetic zeolite is in as-synthesized form and comprises a structure directing agent (SDA), in particular an organic structure directing agent (OSDA), within its pores.
- SDA structure directing agent
- OSDA organic structure directing agent
- the small pore size synthetic zeolite does not comprise a structure directing agent.
- the small pore size synthetic zeolite may be in calcined form.
- the invention provides a process for the preparation of the small pore synthetic zeolite of the invention comprising:
- the inventors believe, without wishing to be bound by theory, that the ligands L stabilize the metal complex in the synthesis mixture, which is generally highly alkaline, such that it does not become part of the zeolite framework or precipitate from the solution to form large particles which cannot be encapsulated.
- the ligand L may be a O-containing ligand, such as oxalate ion or acetylacetonate ion.
- the ligand L may be a P-containing ligand, such as phosphine, for example, triphenylphosphine.
- the ligand L is a N-containing ligand, in particular an amine such as NH 3 , ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylene pentamine, preferably selected from the group consisting of NH 3 and bidentate amines such as ethylene diamine and combinations thereof.
- the ligand L should be chosen such that the catalytic metal precursor is stable in the highly alkaline conditions of the synthesis mixture, or in a fluoride media. In particular, the catalytic metal precursor should be stable against precipitation at the pH of the synthesis mixture under the conditions used to form the small pore synthetic zeolite.
- the catalytic metal precursor is selected from the group consisting of [Pt(NH 3 ) 4 ]Cl 2 , [Pt(NH 3 ) 4 ](N0 3 ) 2 , [Pd(NH 2 CH 2 CH 2 NH 2 ) 2 ]Cl 2 , [Rh(NH 2 CH 2 CH 2 NH 2 ) 3 ]Cl 3 , [Ir(NH 3 ) 5 Cl]Cl 2 , [Re(NH 2 CH 2 CH 2 NH 2 ) 2 0 2 ]Cl, [Ag(NH 2 CH 2 CH 2 NH 2 )]N0 3 , [Ru(NH 3 ) 6 ]Cl 3 , [Ir(NH 3 ) 6 ]Cl 3 , [Ir(NH 3 ) 6 ](N0 3 ) 3 , [Ir(NH 3 ) 5 N0 3 ](N0 3 ) 2 .
- the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetravalent element X and/or a source of a trivalent element Y, and optionally a source of a pentavalent element Z, and the molar ratio of the catalytic metal precursor (in terms of metal) : (X0 2 + Y 2 0 3 + Z 2 0 5 ) in the synthesis mixture is in the range of from 0.00001 to 0.015, preferably from 0.0001 to 0.010, more preferably from 0.001 to 0.008.
- the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetravalent element X and optionally a source of a trivalent element Y, and the molar ratio of the catalytic metal precursor (in terms of metal) : (X0 2 + Y2O3) in the synthesis mixture is in the range of from 0.00001 to 0.015, preferably from 0.0001 to 0.010, more preferably from 0.001 to 0.008.
- the invention provides a process for the preparation of the small pore size synthetic zeolite of the invention comprising the steps of
- the anchoring agent reacts with the catalytic metal precursor and also with the framework of the zeolite to anchor the catalytic metal precursor in the zeolite as the framework forms.
- the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetravalent element X and/or a source of a trivalent element Y, and optionally a source of a pentavalent element Z, and the molar ratio of anchoring agent : (X0 2 + Y 2 0 3 + Z 2 0 5 ) is in the range of from 0.001 to 0.020, preferably in the range of from 0.002 to 0.015.
- the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetravalent element X and optionally a source of a trivalent element Y, and the molar ratio of anchoring agent : (X0 2 + Y 2 0 3 ) is in the range of from 0.001 to 0.020, preferably in the range of from 0.002 to 0.015.
- the molar ratio of catalytic metal precursor (in terms of metal) : (X0 2 + Y20 3 + Z 2 0 5 ) or more particularly the molar ratio of catalytic metal precursor (in terms of metal) : (X0 2 + Y2O3) is in the range of from 0.0001 to 0.001 , preferably from 0.0002 to less than 0.001 , more preferably from 0.0002 to 0.0005.
- the catalytic metal precursor can be any suitable catalytic metal complex which includes at least one Iigand capable of being exchanged by the at least one amine group and/or thiol group of the anchoring agent.
- the catalytic metal precursor is selected from the group consisting of H 2 PtCl 6 , H 2 PtBr 6 , Pt(NH 3 )4CI 2 , Pt(NH3) 4 (N0 3 ) 2 , RuCl 3 xH 2 0, RuBr 3 xH 2 0, RhCl 3 xH 2 0, Rh(N0 3 ) 3 2 H 2 0, RhBr 3 xH 2 0, PdCl 2 xH 2 0, Pd(NH 3 )4Cl 2 , Pd(NH 3 ) 4 B4 2 , Pd(NH 3 )(N0 3 ) 2 , AuCl 3 , HAuBr 4 -xH 2 0, HAuCU, HAu(N0 3 ) 4 xH 2 0, Ag(N0 3 ) 2 , ReCl 3 , Re 2 0 7 , OsCl 3 , Os0 , IrBr 3 -4H 2 0, IrCl 2 , IrCl 2
- the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetr choice element X and/or a source of a trivalent element Y, optionally a source of a pentavalent element Z, optionally a source of a divalent element W, optionally a source of an alkali metal M, a source of hydroxide ions and/or a source of halide ions, a source of a structure directing agent (SDA) (in particular a source of an organic structure directing agent (OSDA)), and water.
- SDA structure directing agent
- OSDA organic structure directing agent
- the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetr choice element X, optionally a source of a trivalent element Y, optionally a source of an alkali metal M, a source of hydroxide ions and/or a source of halide ions, a source of a structure directing agent (SDA) (in particular a source of an organic structure directing agent (OSDA)), and water.
- SDA structure directing agent
- OSDA organic structure directing agent
- the tetr candidate element X is most often one or more of Si, Ge, Sn and Ti, preferably Si or a mixture of Si and Ti or Ge, most preferably Si.
- suitable sources of silicon (Si) that can be used to prepare the synthesis mixture include silica; colloidal suspensions of silica, for example that sold by E.I. du Pont de Nemours under the tradename Ludox®; precipitated silica; alkali metal silicates such as potassium silicate and sodium silicate; tetraalkyl orthosilicates; and fumed silicas such as Aerosil and Cabosil.
- the trivalent element Y is most often one or more of B, Al, Fe, and Ga, preferably B, Al or a mixture of B and Al, most preferably Al.
- Suitable sources of trivalent element Y that can be used to prepa e the synthesis mixture depend on the element Y that is selected (e.g., boron, aluminum, iron and gallium).
- sources of boron include boric acid, sodium tetraborate and potassium tetraborate. Sources of boron tend to be more soluble than sources of aluminum in hydroxide-mediated synthesis systems.
- the trivalent element Y is aluminum, and the aluminum source includes aluminum sulfate, aluminum nitrate, aluminum hydroxide, hydrated alumina, such as boehmite, gibbsite, and pseudoboehmite, and mixtures thereof.
- Other aluminum sources include, but are not limited to, other water-soluble aluminum salts, sodium aluminate, aluminum alkoxides, such as aluminum isopropoxide, or aluminum metal, such as aluminum in the form of chips.
- sources containing both Si and Al elements can also be used as sources of Si and Al.
- suitable sources containing both Si and Al elements include amorphous silica-alumina gels, kaolin, metal-kaolin, and zeolites, in particular aluminosilicates such as synthetic faujasite and ultrastable faujasite, for instance USY.
- Suitable sources of pentavalent elements Z depend on the element Z that is selected.
- Z is phosphorus.
- Suitable sources of phosphorus include one or more sources selected from the group consisting of phosphoric acid; organic phosphates, such as triethyl phosphate, tetraethyl-ammonium phosphate; aluminophosphates; and mixtures thereof.
- the synthesis mixture also contains a source of a divalent element W.
- W is selected from the group consisting of Be and Zn.
- the synthesis mixture also contains a source of halide ions, which may be selected from the group consisting of chloride, bromide, iodide or fluoride, preferably fluoride.
- the source of halide ions may be any compound capable of releasing halide ions in the molecular sieve synthesis mixture.
- Non-limiting examples of sources of halide ions include hydrogen fluoride; salts containing one or several halide ions, such as metal halides, preferably where the metal is sodium, potassium, calcium, magnesium, strontium or barium; ammonium fluoride; or tetraalkylammonium fluorides such as tetramethylammonium fluoride or tetraethylammonium fluoride. If the halide ion is fluoride, a convenient source of halide ion is HF or NH 4 F.
- the synthesis mixture also contains a source of alkali metal M + .
- the alkali metal M + is preferably selected from the group consisting of sodium, potassium and mixtures of sodium and potassium.
- the sodium source may be a sodium salt such as NaC l , NaBr, or NaN0 3 ; sodium hydroxide or sodium aluminate.
- the potassium source may be potassium hydroxide or potassium halide such as KC 1 or NaBr or potassium nitrate.
- the synthesis mixture also contains a source of hydroxide ions, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
- Hydroxide can also be present as a counter ion of the (organic) structure directing agent or by the use of sodium aluminate or potassium aluminate as a source of Y, or by the use of sodium silicate or potassium silicate as the source of X.
- Sodium or potassium aluminate and silicate can also be used as the source of alkali metal M + .
- the synthesis mixture optionally further comprises a structure directing agent (SDA), in particular an organic structure directing agent (OSDA).
- SDA structure directing agent
- OSDA organic structure directing agent
- the nature of the SDA (or OSDA) will depend upon the desired framework type. Many such structure directing agents are known to the skilled person.
- the structure directing agent may be present in any suitable form, for example as a salt of a halide such as a chloride, iodide or bromide, as a hydroxide or as a nitrate.
- the structure directing agent will generally be cationic and preferably be an organic structure directing agent, for example, a nitrogen-containing cation such as a quaternary ammonium cation.
- the OSDA may optionally be N,N,N-trimethyI- l - adamantammonium hydroxide or iodide (TMAdA) where it is desired to produce a zeolite of framework type CHA or l , -(hexane-l ,6-diyl)bis(l -methylpiperidinium) where it is desired to produce a zeolite of framework type AFX.
- TMAdA N,N,N-trimethyI- l - adamantammonium hydroxide or iodide
- the synthesis mixture can have any composition which is suitable for preparing the desired zeolite framework.
- the following ranges are given as examples of desirable and preferred ranges for each pair of components in the synthesis mixture.
- the molar ratio of X0 2 : Y2O3 in the synthesis mixture may be in the range of from 1 to infinity (i.e. no Y), in particular from 1 tol OO, preferably from 4 to 50.
- the molar ratio of SDA : (X0 2 + Y2O3 + Z 2 0 5 ) is in the range of from 0.04 to 0.5, preferably from 0.08 to 0.3.
- the molar ratio of H 2 0 : (X0 2 + Y 2 0 3 ) is in the range of from 1 to 100, preferably from 10 to 60.
- the molar ratio of M + : (X0 2 + Y 2 0 3 + Z 2 0 5 ) is in the range of from 0 to 0.45, preferably from 0 to 0.20.
- the molar ratio of OH " : (X0 2 + Y2O3 + Z2O5) is in the range of from 0 to 1 .0, preferably from 0.2 to 0.4.
- the molar ratio of halide " : (X0 2 + Y2O3 + Z 2 0 5 ) is in the range of from 0 to 1 , preferably from 0 to 0.5.
- no Z is present and the molar ratio of X0 2 : Y2O3 in the synthesis mixture may be in the range of from 1 to infinity (i.e. no Y when the zeolite is a silicate), in particular from 1 to 100, preferably from 4 to 50, e.g.
- the synthesis may be performed with or without added nucleating seeds. If nucleating seeds are added to the synthesis mixture, the seeds are suitably present in an amount from about 0.01 ppm by weight to about 10,000 ppm by weight, based on the synthesis mixture, such as from about 100 ppm by weight to about 5,000 ppm by weight of the synthesis mixture.
- the seeds can for instance be of any suitable zeolite, in particular of a zeolite having the same framework as the zeolite to be obtained.
- Crystallization can be carried out under either static or stirred conditions in a suitable reactor vessel, such as for example, polypropylene jars or Teflon® lined or stainless steel autoclaves.
- the crystallization is typically carried out at a temperature of about 100°C to about 200°C, such as about 1 50°C to about 170°C, for a time sufficient for crystallization to occur at the temperature used, e.g. , from about 1 day to about 100 days, in particular from 1 to 50 days, for example from about 2 days to about 40 days.
- the synthesized crystals are separated from the mother liquor and recovered.
- the product is typically activated before use in such a manner that the organic part of the structure directing agent is at least partially removed from the zeolite.
- the activation process is typically accomplished by calcining, more particularly by heating the zeolite at a temperature of at least about 200 °C, preferably at least about 300 °C, more preferably at least about 370 °C for at least 1 minute and generally not longer than 20 hours. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is usually desired for reasons of convenience.
- the thermal treatment can be performed at a temperature up to about 925 °C. For instance, the thermal treatment can be conducted at a temperature of from 400 to 600 °C, for instance from 500 to 550 °C, in the presence of an oxygen-containing gas, for example in air.
- the small pore size synthetic zeolite of the present invention or manufactured by the process of the present invention may be used as an adsorbent or as a catalyst to catalyze a wide variety of organic compound conversion processes including many of present commercial/industrial importance.
- Examples of preferred chemical conversion processes which can be effectively catalyzed by the zeolite of the present invention or manufactured by the process of the present invention, by itself or in combination with one or more other catalytically active substances including other crystalline catalysts, include those requiring a catalyst with acid activity or hydrogenation activity.
- Examples of organic conversion processes which may be catalyzed by zeolite of the present invention or manufactured by the process of the present invention include cracking, hydrocracking, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, adsorption, alkylation, transalkylation, dealkylation, hydrodecylization, disproportionation, oligomerization, dehydrocyclization and combinations thereof.
- the conversion of hydrocarbon feeds can take place in any convenient mode, for example in fluidized bed, moving bed, or fixed bed reactors depending on the types of process desired.
- the zeolite of the present disclosure when employed either as an adsorbent or as a catalyst in an organic compound conversion process should be dehydrated, at least partially. This can be done by heating to a temperature in the range of about 100 °C to about 500 °C, such as about 200 °C to about 370 °C in an atmosphere such as air, nitrogen, etc., and at atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes and 48 hours. Dehydration can also be performed at room temperature merely by placing the molecular sieve in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
- the zeolite Once the zeolite has been synthesized, it can be formulated into a catalyst composition by combination with other materials, such as binders and/or matrix materials that provide additional hardness or catalytic activity to the finished catalyst. These other materials can be inert or catalytically active materials.
- zeolite of the present invention may be desirable to incorporate with another material that is resistant to the temperatures and other conditions employed in organic conversion processes.
- materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina.
- the latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
- Naturally occurring clays which may be used include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite.
- Such clays can be used in the raw state as originally mined or after being subjected to calcination, acid treatment or chemical modification.
- These binder materials are resistant to the temperatures and other conditions, e.g. , mechanical attrition, which occur in various hydrocarbon conversion processes.
- the zeolites of the present invention or manufactured by the process of the present invention may be used in the form of an extrudate with a binder. They are typically bound by forming a pill, sphere, or extrudate. The extrudate is usually formed by extruding the zeolite, optionally in the presence of a binder, and drying and calcining the resulting extrudate.
- Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained in an economic and orderly manner without employing other means for controlling the rate of reaction.
- These materials may be incorporated into naturally occurring clays, e.g. , bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions.
- the zeolite can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
- a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
- the relative proportions of zeolite and inorganic oxide matrix may vary widely, with the molecular sieve content ranging from about 1 to about 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight percent of the composite.
- a suitable XRD method involved a Bruker D4 diffractometer using Cu Ka radiation at 35 kV/45 mA, 0.20° divergence slit, and a Vantec detector. Data was collected from 2 to 50° 2-theta, 0.018° step size, and 0.2 sec/step counting time using Bragg-Brentano geometry.
- the degree of crystallinity was >95%.
- the absence of any amorphous material was determined by the absence of a broad diffraction peak in the 2-theta range of 1 8 - 25° and by the absence of a second amorphous phase in the SEM pictures.
- This example illustrates successful preparation of a sintering-resistant platinum catalyst according to the present invention.
- TMAdA N,N,N-trimethyl- l -adamantammonium hydroxide
- the gel was transferred to an autoclave with a Teflon liner, and heated at 90 °C for 7 days, and later, at 160 °C for 2 days under dynamic conditions.
- the sample after the hydrothermal crystallization was filtered and washed with abundant distilled water, and finally dried at 100 °C.
- the solid was characterized by Powder X-ray Diffraction (PXRD), obtaining the characteristic PXRD pattern of the CHA material (see Example 1 in Figure 1 ). Elemental analysis by ICE-AES of the resultant solid indicated a Si/Al of 8.5 (Si0 :Al 2 0 3 molar ratio of 17: 1 ) and analysis by XRF gave a Pt content of 0.21 wt%.
- PXRD Powder X-ray Diffraction
- the Pt-containing CHA was calcined at 550 °C in air in order to remove the organic moieties included inside the microporous material during the crystallization process.
- the calcined sample was treated with H 2 at 400 °C for 2 hours.
- TEM microscopy (see Figure 2A) reveals the formation of very small Pt nanoparticles.
- These Pt nanoparticles are substantially spherical and have a particle size (biggest dimension, i.e. diameter) in the range of 1 to 3 nm within the high-silica CHA structure.
- the particle size distribution (diameter vs. abundance expressed as a percentage of the particles by number) for this sample is shown in Figure 2C.
- X-Ray Absorption Near Edge Structure was recorded as the sample, previously reduced with H 2 at 400 °C, was treated with 5% 0 2 at increasing temperatures (from 20 to 500 °C).
- the spectra show a gradual decrease of the first absorption peak (white line intensity), which is ascribed to gradual oxidation of the metal nanoparticles ( Figure 3A).
- the observation of isosbestic point in the spectra indicate simple stoichiometric transformation of one species into another, consistent with a fine control of the catalytic structures and their uniformity.
- EXAFS Extended X-Ray Fine Structure
- Figure 3B shows the EXAFS spectrum of a platinum foil (upper line), and that corresponding to the sample of Example 1 (calcined at 550 °C and treated with H 2 at 400 °C) (middle line in Fig 3B - note that the Pt-Pt peak intensity in the sample is small compared to the reference foil, an additional proof of the smallness of the nanoparticles).
- a catalyst consisting of platinum nanoparticles supported on amorphous silica (reference material) was prepared according to the process of WO201 1/096999. In this procedure, 1 .784 g of tetraammine platinum hydroxide was mixed with 12.2 g of deionized water. 0.6 g of arginine was added to this solution so that the arginine to Pt molar ratio was 8: 1 . The solution was added by incipient wetness onto 10.0 g of Davison silica (grade 62, 60- 200 mesh, 150 Angstrom pore diameter from Sigma-Aldrich). The sample was dried at 120 °C for 2 hrs.
- the dried sample was placed in a tube furnace with an active air flow of 300 seem of air, with the heating rates being maintained at 3 °C/min to 400 °C and then maintaining the temperature at 400 °C for 16 hrs.
- the catalyst Prior to the hydrogenation experiment, the catalyst was reduced in situ in a flow of hydrogen (50 mL/min) at 400 °C for 4 h. The reactor was then cooled down to the selected reaction temperature (80 °C). With the catalyst bed at 80 ⁇ 1 °C, a mixture of ethylene (or propylene) (4 mL/min), hydrogen (20 mL/min), and nitrogen (100 mL/min) was flowed through the reactor, and the reacted gas mixture was analyzed at various times on stream.
- Figure 5 shows the catalytic activity of the fresh CHA-encapsulated platinum (Example 1 ) and the Pt Si0 2 (Example 2) catalysts for each alkene, expressed as mol of reactant converted per mol of platinum per second.
- the gel was transferred to an autoclave with a Teflon liner, and heated at 90 °C for 7 days, and later, at 160 °C for 2 days under dynamic conditions.
- the sample after the hydrothermal crystallization was filtered and washed with abundant distilled water, and finally dried at 100 °C.
- the solid was characterized by Powder X-ray Diffraction (PXRD), obtaining the characteristic PXRD pattern of the CHA material (see Example 4 in Figure 1 ).
- the chemical analysis of the resultant solid indicated a Si/Al ratio of 8 (Si0 2 /Al 2 0 3 molar ratio of 16: 1 ) and a Pt content of 0.46wt%.
- the Pt-containing CHA was calcined at 550 °C in air in order to remove the organic moieties included inside of the microporous material during the crystallization process, and subsequently reduced in flow of H 2 at 400 °C for 2 h.
- TEM Figure 6
- Approximately 5 % of the images include at least one big nanoparticle in addition to the small ones (as illustrated in Figure 6B).
- the percentage of Pt encapsulated in the zeolite (a) was determined to be 90%.
- a synthesis gel was prepared with the composition:
- TEM microscopy (see Figure 7A) reveals the formation of very small Pt nanoparticles within the high-silica CHA structure.
- the above reduced sample was subjected to an additional thermal treatment. It was oxidized in air at 650 °C for 2 hours (50 seem of pure 0 2 at atmospheric pressure to treat 200 mg of catalyst), followed by a 1 hour purge with N 2 (50 seem of pure N 2 at atmospheric pressure to treat 200 mg of catalyst), and later, reduced again with H 2 at 400 °C for 2 hours (50 seem of pure H 2 at atmospheric pressure to treat 200 mg of catalyst).
- a synthesis gel was prepared with the composition:
- SDAOH 0.064 Rh(C 2 H 4 N 2 ) Cl 3 : 10 Na 2 0: A1 2 0 3 : 34 Si0 2 : 1000 H 2 0, where SDAOH is N,N,N-trimethyl-l -adamantammonium hydroxide (TMAdA).
- TMAdA N,N,N-trimethyl-l -adamantammonium hydroxide
- EMD sodium silicate
- 28.2wt% Si0 9.3wt% Na 2 0
- de-ionized water 43.74 g de-ionized water.
- Rh(N0 3 ) 3 10.1 wt% Rh
- deionized water 0.241 g
- the dried chabazite was quickly added and the mixture kneaded by hand for 2 minutes with a ceramic spatula and then mixed for 4 minutes in a dual asymmetric centrifuge (FlackTec DAC600 SpeedMixer).
- the sample was dried at 1 15 °C and then ramped to 350 °C at 0.5 °C/min in air and then held at 350 °C in air for two hours.
- the percentage of Rh encapsulated in the zeolite (a) was determined to be 20%.
- a synthesis gel was then prepared with the composition, 2.2 SDAOH: 0.1 5 Pt: 0.15 Rh(C2H 4 N2) 3 Cl3: 7 Na 2 0: A1 2 0 3 : 25 S1O2: 715 H2O, where SDAOH is ⁇ , ⁇ , ⁇ -trimethyl- 1 -adamantammonium hydroxide (TMAdA).
- TMAdA ⁇ , ⁇ , ⁇ -trimethyl- 1 -adamantammonium hydroxide
- Teflon-lined autoclave was added 9.5 g 25wt% SDAOH, 1 .0 g 50wt% NaOH, 20.1 g of sodium silicate (EMD, 28.2wt% S1O2, 9.3wt% Na 2 0), and 44.6 g de-ionized water.
- Phase analysis by powder XRJD showed the sample to be pure chabazite (see Example 8 in Figure 1 ).
- the sample was calcined to remove the SDA by heating in a muffle furnace from 25 °C to 500 °C in two hours in air and then holding at 500 °C for 3 hours in air.
- Analysis by X F gave 0.64wt% Rh and 1.02wt% Pt.
- the calcined sample was treated with H 2 at 400 °C for 2 hours.
- TEM microscopy (see Figure 9A) reveals the formation of very small Pt nanoparticles within the high-silica CHA structure.
- the above reduced sample was oxidized in air at 650 °C for 2 hours, and later, reduced again with H 2 at 400 °C for 2 hours.
- TEM microscopy (see Figure 9B) reveals that the small Pt nanoparticles within the high-silica CHA structure remain stable and have not sintered into larger particles after the redox treatments.
- the percentage of Rh/Pt encapsulated in the zeolite (a) was determined to be 95%.
- a synthesis gel was prepared with the composition, 12 SDA(OH) 2 : 0.25 Pvh(C 2 H N 2 ) 3 Cl 3 : 6 Na 2 0: A1 2 0 3 : 40 Si0 2 : 1200 H 2 0, where SDA is l ,l '-(hexane-l ,6- diyl)bis(l -methylpiperidinium).
- SDA is l ,l '-(hexane-l ,6- diyl)bis(l -methylpiperidinium).
- colloidal silica Lidox LS-30
- 57.3 g 22.6wt% SDA(OH) 2 57.3 g 22.6wt% SDA(OH) 2
- 6.4 g de-ionized water de-ionized water.
- the autoclave was mounted on a rotating shelf (25 rpm) in a 160 °C oven for 6 days.
- the product was recovered by vacuum filtration, washed with de-ionized water and dried in a 1 15 °C oven.
- Phase analysis by powder XRD showed the sample to be pure AFX zeolite (see Example 9 in Figure 1 ).
- the sample was calcined to remove the SDA by heating in a muffle furnace from 25 °C to 560 °C in two hours in air and then holding for 3 hours in air.
- TMAdA N,N,N-trimethyl-l -adamantammonium iodide
- TEOS tetraethylorthosilicate
- FIG. 1 A shows a STEM image of the solid after being calcined at 550°C in air and reduced with H 2 at 400°C for 2 hours. The sample was microtomed prior to acquisition of the STEM image. The particle size distribution (diameter vs. abundance expressed as a percentage of the particles by number) for this sample is shown in Figure 1 I B.
- the gel was transferred to an autoclave with a Teflon liner, and heated at 90 °C for 7 days, and later, at 160 °C for 2 days under dynamic conditions.
- the sample after the hydrothermal crystallization was filtered and washed with abundant distilled water, and finally dried at 100 °C.
- the Pt/Pd-containing CHA was calcined at 550 °C in air in order to remove the organic moieties included inside the microporous material during the crystallization process.
- the calcined sample was treated with H 2 at 400 °C for 2 hours.
- STEM microscopy (see Figure 12) reveals the formation of very small metallic nanoparticles. These metallic nanoparticles are substantially spherical and have a particle size (biggest dimension, i.e. diameter) in the range of 1 to 3 nm within the high-silica CHA structure.
- EXAFS spectra of the preceding sample after subsequent treatment in 0 2 at 500 °C shows the lack of Pt-Pt, Pt-Pd, Pt-O-Pt, Pt-O-Pd, and Pd-Pd, Pd-Pt, Pd-O-Pd, Pd-O-Pt moieties in the Pt and Pd edges, respectively, and the exclusive presence of Pt-0 and Pd-0 interaction ( Figure l 3B), evidencing the formation of site-isolated single metal atoms after the high temperature oxidative treatment.
- EXAMPLE 12 Pt/Fe Encapsulated in High Silica CHA Zeolite using TMSH as anchoring agent
- 640 mg of sodium hydroxide (99wt%, Sigma-Aldrich) was dissolved in 8 g of water. Then, 680 mg of a l wt% aqueous solution of chloroplatinic acid (H 2 PtCl6, 37.50wt% Pt basis, Sigma-Aldrich) and 42 mg of (3-mercaptopropyl)trimethoxysilane (TMSH, 95%, Sigma-Aldrich) were added to the above solution, and the mixture was stirred for 30 minutes.
- chloroplatinic acid H 2 PtCl6, 37.50wt% Pt basis, Sigma-Aldrich
- TMSH (3-mercaptopropyl)trimethoxysilane
- TMAdA N,N,N-trimethyl-l -adamantammonium hydroxide
- the gel was transferred to an autoclave with a Teflon liner, and heated at 90 °C for 7 days, and later, at 160 °C for 2 days under dynamic conditions.
- the sample after the hydrothermal crystallization was filtered and washed with abundant distilled water, and finally dried at 100 °C.
- the solid was characterized by Powder X-ray Diffraction (PXRD), obtaining the characteristic PXRD pattern of the CHA material. Elemental analysis by ICE-AES of the resultant solid indicated a Si/Al of 8.0 (Si0 2 :Al 2 0 3 molar ratio of 16: 1 ) and a Si/Fe of 56, and analysis by XRF gave a Pt content of 0.15wt%.
- PXRD Powder X-ray Diffraction
- the Fe-Pt-containing CHA was calcined at 550 °C in air in order to remove the organic moieties included inside the microporous material during the crystallization process.
- the calcined sample was treated with H 2 at 400 °C for 2 hours.
- STEM microscopy (see Figure 14) reveals the formation of very small metallic nanoparticles. These metallic nanoparticles are substantially spherical and have a particle size (biggest dimension, i.e. diameter) in the range of 1 to 3 nm within the high-silica CHA structure.
- EXAMPLE 13 Pt Encapsulated in a Low Si/Al Ratio LTA Zeolite - comparative example
- a Pt-containing Al-rich LTA material was synthesized following the methodology described by M. Choi et al. ("Mercaptosilane-assisted synthesis of metal clusters within zeolites and catalytic consequences of encapsulation", JACS, 2010, 132, 9129-91 37) for comparison purposes.
- the gel was transferred to an autoclave with a Teflon liner, and heated at 100°C for 24 hours under dynamic conditions.
- the sample after the hydrothermal crystallization was filtered and washed with abundant distilled water, and finally dried at 100°C. After the synthesis procedure, the obtained solid showed the crystalline structure of the LTA material.
- the invention relates to:
- Embodiment 1 A small pore size synthetic zeolite having a degree of crystallinity of at least 80% and comprising at least 0.01 wt%, based on the weight of the zeolite, of at least one catalytic metal selected from the group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Mo, W, Re, Co, Ni, Zn, Cr, Mn, Ce, Ga, and combinations thereof, wherein at least 80% of the catalytic metal is encapsulated in the zeolite, wherein if the zeolite is an aluminosilicate it has a Si02:Al 2 03 molar ratio of greater than 6: 1 .
- Embodiment 2 The small pore size synthetic zeolite according to embodiment 1 which is an 8-membered ring zeolite, preferably of framework type AEI, AFT, AFX, CHA, CDO, DDR, EDI, ERI, IHW, ITE, ITW, KFI, MER, MTF, MWF, LEV, LTA, PAU, PWY, RHO, SFW or UFI, more preferably of framework type CHA, AEI, AFX, RHO, KFI or LTA, most preferably CHA or AFX.
- Embodiment 3 The small pore size synthetic zeolite of embodiment 1 or 2 in which the zeolite framework contains one or more elements selected from the group consisting of Si, Al, P, As, Ti, Ge, Sn, Fe, B, Ga, Be and Zn; preferably in which the zeolite framework contains at least one tetravalent element X selected from the group consisting of Si, Ge, Sn and Ti and optionally at least one trivalent element Y selected from the group consisting of Al, B, Fe and Ga; more preferably in which the zeolite framework contains at least Si and optionally Al and/or B; most preferably in which the zeolite framework contains at least Si and optionally Al.
- the zeolite framework contains one or more elements selected from the group consisting of Si, Al, P, As, Ti, Ge, Sn, Fe, B, Ga, Be and Zn; preferably in which the zeolite framework contains at least one tetravalent element X selected from the group consisting of Si, Ge, Sn
- Embodiment 4 The small pore size synthetic zeolite of any one of the preceding embodiments which is selected from the group consisting of silicates, aluminosilicates and borosilicates, preferably from the group consisting of silicates and aluminosilicates.
- Embodiment 5 The small pore size synthetic zeolite of any one of the preceding embodiments which contains Si and Al and having a Si0 2 :Al 2 0 3 molar ratio of greater than 8: 1 , preferably greater than 10: 1 , more greater than 12: 1 , in particular greater than 30: 1 , more particularly greater than 100: 1 , most particularly greater than 150: 1 .
- Embodiment 6 The small pore size synthetic zeolite of any one of the preceding embodiments which further comprises at least 0.01 wt%, preferably from 0.05 to 5 wt% of a transition metal selected from the group consisting of Cu, Fe, Ti, Zr, Nb, Hf, Ta and combinations thereof, in particular wherein said transition metal is extra-framework metal.
- Embodiment 7 The small pore size synthetic zeolite of any one of the preceding embodiments having a degree of crystallinity of at least 95%.
- Embodiment 8 The small pore size synthetic zeolite of any one of the preceding embodiments which comprises from 0.05 to 5 wt% of the catalytic metal, preferably from 0.1 to 3 wt%, more preferably from 0.5 to 2.5 wt%, most preferably from 1 to 2 wt%.
- Embodiment 9 The small pore size synthetic zeolite of any one of the preceding embodiments wherein at least 80%, more preferably at least 90%, preferably at least 95%, and most preferably at least 98% of the catalytic metal is encapsulated in zeolite.
- Embodiment 10 The small pore size synthetic zeolite of any one of the preceding embodiments in which the catalytic metal is selected from the group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Re, and combinations thereof; most preferably from the group consisting of Pt, Rh, Pd and Au and combinations thereof, in particular Pt, Pd and/or Rh.
- the catalytic metal is selected from the group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Re, and combinations thereof; most preferably from the group consisting of Pt, Rh, Pd and Au and combinations thereof, in particular Pt, Pd and/or Rh.
- Embodiment 1 1 The small pore size synthetic zeolite of any one of the preceding embodiments wherein the catalytic metal is present in the form of particles wherein at least 80% of the particles by number have a biggest dimension of less than 4 nm as measured by TEM.
- Embodiment 12 The small pore size synthetic zeolite of any one of the preceding embodiments which is a silicate or an aluminosihcate having a Si02:Al 2 0 3 molar ratio of greater than 6: 1 , preferably greater than 12: 1 , in particular greater than 30: 1 , wherein the catalytic metal is selected from the group consisting of Pt, Rh, Pd and Au and combinations thereof, preferably Pt, Pd and/or Rh, and wherein the zeolite is of framework type CHA, AEI, AFX, RHO, KFI or LTA, preferably CHA or AFX.
- the catalytic metal is selected from the group consisting of Pt, Rh, Pd and Au and combinations thereof, preferably Pt, Pd and/or Rh
- the zeolite is of framework type CHA, AEI, AFX, RHO, KFI or LTA, preferably CHA or AFX.
- Embodiment 13 The small pore size synthetic zeolite of any one of the preceding embodiments which is in as-synthesized form and further comprises a structure directing agent (SDA), in particular an organic structure directing agent (OSDA).
- SDA structure directing agent
- OSDA organic structure directing agent
- Embodiment 14 The small pore size synthetic zeolite of any one of the preceding embodiments in calcined form prepared by subjecting the small pore size zeolite of embodiment 13 to a calcining step.
- Embodiment 1 5 A process for the preparation of the small pore size synthetic zeolite of any one of the preceding embodiments comprising: a) providing a reaction mixture comprising a synthesis mixture capable of forming the small pore size synthetic zeolite framework and at least one catalytic metal precursor, wherein the catalytic metal precursor includes metal complexes stabilized by ligands L selected from the group consisting of N-containing ligands, O-containing ligands, S- containing ligands, and P-containing ligands,
- Embodiment 16 The process of embodiment 1 5 wherein the ligand L is a N-containing ligand, in particular an amine, preferably selected from the group consisting of NH 3 and bidentate amines and combinations thereof; more particularly selected from the group consisting of NH 3 and ethylenediamine.
- the ligand L is a N-containing ligand, in particular an amine, preferably selected from the group consisting of NH 3 and bidentate amines and combinations thereof; more particularly selected from the group consisting of NH 3 and ethylenediamine.
- Embodiment 17 The process of embodiment 1 5 or 16 wherein the catalytic metal precursor is selected from the group consisting of [Pt(NH 3 )4]Cl 2 , [Pt(NH 3 ) 4 ](N0 3 ) 2 , [Pd(NH 2 CH 2 CH 2 NH 2 ) 2 ]Cl 2 , [Rh(NH 2 CH 2 CH 2 NH 2 ) 3 ]Cl 3 , [Ir(NH 3 ) 5 Cl]Cl 2 , [Re(NH 2 CH 2 CH 2 NH 2 ) 2 0 2 ]Cl, [Ag(NH 2 CH 2 CH 2 NH 2 )]N0 3 , [Ru(NH 3 ) 6 ]Cl 3 , [Ir(NH 3 ) 6 ]Cl 3 , [Ir(NH 3 ) 5 ](N0 3 ) 3 , [Ir(NH 3 ) 5 N0 3 ](N0 3 ) 2 .
- the catalytic metal precursor is selected
- Embodiment 1 8 The process of any one of embodiments ] 5 to 17 wherein the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetravalent element X and optionally a source of a trivalent element Y, and wherein the molar ratio of the catalytic metal precursor (in terms of metal) : (X0 2 + Y 2 0 3 ) in the synthesis mixture is in the range of from 0.00001 to 0.015, preferably from 0.0001 to 0.010, more preferably from 0.001 to 0.008.
- Embodiment 19 A process for the preparation of the small pore size synthetic zeolite of any one of embodiments 1 to 14 comprising:
- Embodiment 22 The process of any one of embodiments 19 to 21 wherein the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetravalent element X and optionally a source of a trivalent element Y, in which the molar ratio of anchoring agent : (X0 2 + Y 2 0 3 ) is in the range of from 0.001 to 0.02, preferably from 0.002 to 0.015.
- Embodiment 23 The process of any of embodiments 19 to 22 wherein the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetravalent element X and optionally a source of a trivalent element Y, and wherein the molar ratio of catalytic metal precursor (in terms of metal) : (X0 2 + Y 2 0 3 ) is in the range of from 0.0001 to 0.001 , preferably from 0.0002 to less than 0.001 , more preferably from 0.0002 to 0.0005.
- Embodiment 24 The process of any one of embodiments 19 to 23 wherein the catalytic metal precursor is selected from the group consisting of H 2 PtCI 6 , H 2 PtBr 6 , Pt(NH 3 )4Cl 2 , Pt(NH 3 ) 4 (N0 3 ) 2) RuCl 3 xH 2 0, RuBr 3 xH 2 0, RhCl 3 xH 2 0, Rh(N0 3 ) 3 - 2 H 2 0, RhBr 3 xH 2 0, PdCl 2 xH 2 0, Pd(NH 3 )4Cl 2 , Pd(NH 3 )4B 42 , Pd(NH 3 )(N0 3 ) 2 , AuCI 3 , HAuBr 4 xH 2 0, HAuC , HAu(N0 3 ) 4 xH 2 0, Ag(N0 3 ) 2 , ReCl 3 , Re 2 0 7 , OsCl 3 , Os0 , IrBr
- Embodiment 25 The process of any one of embodiments 15 to 19 wherein the synthesis mixture capable of forming the small pore size synthetic zeolite framework comprises a source of a tetravalent element X and optionally a source of a trivalent element Y, optionally a source of an alkali metal M, a source of hydroxide ions and/or a source of halide ions, a source of an organic structure directing agent (OSDA), and water.
- OSDA organic structure directing agent
- Embodiment 26 The process of any one of embodiments 1 5 to 25 in which said synthesis mixture has a composition including the following molar ratios:
- X0 2 : Y 2 0 3 1 to 00 preferably 1 to 100
- Embodiment 27 The process of any one of embodiments 1 5 to 26 in which X is Si and Y is Al and/or B, preferably in which X is Si and Y is Al.
- Embodiment 28 The process of any one of embodiments 1 5 to 27 in which the crystallization conditions include heating the synthesis mixture at a temperature in the range of from 100 °C to 200 °C.
- Embodiment 29 A process for the preparation of a small pore size synthetic zeolite in calcined form according to embodiment 14 which comprises subjecting the small pore size synthetic zeolite in as-synthesized form of embodiment 13 or the crystals of small pore size synthetic zeolite recovered in the process of any of embodiments 15 to 23 to a calcination step.
- Embodiment 30 The process of embodiment 29 in which the calcination step is carried out at a temperature of equal to or greater than 500 °C for a period of at least 1 hour.
- Embodiment 31 Use of an active form of the small pore size synthetic zeolite of any one of embodiments 1 to 14 as a sorbent or as a catalyst.
- Embodiment 32 A process for converting a feedstock comprising an organic compound to a conversion product which comprises the step of contacting said feedstock at organic compound conversion conditions with a catalyst comprising a small pore size synthetic zeolite of any one of embodiments 1 to 14.
- Embodiment 33 The process of embodiment 32 which is a hydrogenation process.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201780031578.5A CN109475850A (en) | 2016-05-24 | 2017-05-24 | Synthetic zeolite comprising catalytic metal |
EP17739865.8A EP3463652A1 (en) | 2016-05-24 | 2017-05-24 | A synthetic zeolite comprising a catalytic metal |
RU2018144855A RU2740186C2 (en) | 2016-05-24 | 2017-05-24 | Synthetic zeolite containing catalytic metal |
BR112018070992A BR112018070992A2 (en) | 2016-05-24 | 2017-05-24 | synthetic zeolite comprising a catalytic metal |
KR1020187037232A KR20190009806A (en) | 2016-05-24 | 2017-05-24 | Synthetic zeolites containing catalytic metals |
US16/097,775 US20190168197A1 (en) | 2016-05-24 | 2017-05-24 | Synthetic Zeolite Comprising A Catalytic Metal |
SG11201808679WA SG11201808679WA (en) | 2016-05-24 | 2017-05-24 | A synthetic zeolite comprising a catalytic metal |
JP2018559877A JP2019516655A (en) | 2016-05-24 | 2017-05-24 | Synthetic zeolite containing catalyst metal |
CA3024570A CA3024570A1 (en) | 2016-05-24 | 2017-05-24 | A synthetic zeolite comprising a catalytic metal |
ZA2018/06586A ZA201806586B (en) | 2016-05-24 | 2018-10-04 | A synthetic zeolite comprising a catalytic metal |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662340768P | 2016-05-24 | 2016-05-24 | |
US62/340,768 | 2016-05-24 | ||
EP16183679 | 2016-08-11 | ||
EP16183679.6 | 2016-08-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017202495A1 true WO2017202495A1 (en) | 2017-11-30 |
Family
ID=56686671
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2017/000621 WO2017202495A1 (en) | 2016-05-24 | 2017-05-24 | A synthetic zeolite comprising a catalytic metal |
Country Status (5)
Country | Link |
---|---|
KR (1) | KR20190009806A (en) |
BR (1) | BR112018070992A2 (en) |
CA (1) | CA3024570A1 (en) |
SG (1) | SG11201808679WA (en) |
WO (1) | WO2017202495A1 (en) |
Cited By (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019154081A1 (en) * | 2018-02-07 | 2019-08-15 | Basf Se | Process for preparing a zeolitic material comprising ti and having framework type cha |
JP2019523204A (en) * | 2016-05-25 | 2019-08-22 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Zeolite material with encapsulated binary metal clusters |
WO2019224088A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for synthesizing an afx-structure zeolite of very high purity in the presence of an organic nitrogen-containing structuring agent |
WO2019224081A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Direct synthesis of a catalyst comprising an afx-structure zeolite and at least one transition metal for selective reduction of nox |
WO2019224082A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst comprising an afx-structure zeolite prepared from a mixture of fau zeolites and at least one transition metal for selective reduction of nox |
WO2019224087A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for preparing an afx-structure zeolite by synthesis in the presence of an organic nitrogen-containing structuring agent |
WO2019224093A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for preparing a zeolite composite containing copper and a mixture of zeolites of afx structural type and bea structural type |
WO2019224089A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst containing an aluminosilicate composite material comprising copper and a mixture of afx- and bea-structure zeolites, for selective reduction of nox |
WO2019224091A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for synthesizing a composite material consisting of a mixture of afx- and bea-structure zeolites in the presence of an organic nitrogen-containing structuring agent |
WO2019224090A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst comprising a mixture of an afx-structure zeolite and a bea-structure zeolite and at least one transition metal for selective reduction of nox |
WO2019224083A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst comprising an afx-structure zeolite of high purity and at least one transition metal for selective reduction of nox |
WO2019224086A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst comprising an afx-structure zeolite of very high purity and at least one transition metal for selective reduction of nox |
WO2019224084A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for preparing a high-purity afx structural zeolite with a nitrogen-containing organic structuring agent |
WO2019224085A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for synthesizing an afx-structure zeolite from a mixture of fau zeolites in the presence of an organic nitrogen-containing structuring agent |
US10703986B1 (en) | 2019-01-30 | 2020-07-07 | Exxonmobil Research And Engineering Company | Selective oxidation using encapsulated catalytic metal |
WO2020212354A1 (en) * | 2019-04-19 | 2020-10-22 | IFP Energies Nouvelles | Rapid synthesis of a catalyst comprising a zeolite having an afx structure and at least one transition metal for selective nox reduction |
WO2020212356A1 (en) | 2019-04-19 | 2020-10-22 | IFP Energies Nouvelles | Method for fast synthesis of an afx-structure zeolite with a faujasite source |
WO2020212355A1 (en) | 2019-04-19 | 2020-10-22 | IFP Energies Nouvelles | Method for rapidly synthesising an afx-structure zeolite by synthesis in the presence of an organic nitrogenous structuring agent |
FR3101258A1 (en) | 2019-09-30 | 2021-04-02 | IFP Energies Nouvelles | LOW TEMPERATURE SYNTHESIS OF HIGH PURE ZEOLITHE AFX |
FR3101259A1 (en) | 2019-09-30 | 2021-04-02 | IFP Energies Nouvelles | LOW TEMPERATURE SYNTHESIS OF A ZEOLITHE AFX BASED CATALYST AND ITS APPLICATION IN NH3-SCR |
CN113019434A (en) * | 2021-03-17 | 2021-06-25 | 成都科特瑞兴科技有限公司 | Coated catalyst for low-temperature hydrogen deoxidation and preparation method and application thereof |
CN113042034A (en) * | 2021-03-25 | 2021-06-29 | 湖南省尤利威科技有限公司 | Double-effect manganese catalyst for sterilizing and removing aldehyde as well as preparation method and application thereof |
CN113198520A (en) * | 2021-05-19 | 2021-08-03 | 中国石油大学(华东) | One-pot preparation method of molecular sieve supported palladium carbon catalyst and application of molecular sieve supported palladium carbon catalyst in synthesis of dimethyl carbonate by gas phase method |
CN113457727A (en) * | 2021-06-17 | 2021-10-01 | 西安交通大学 | Au/ZSM-5 catalyst with hierarchical pores regulated by alkali metal, and synthesis method and application thereof |
US11148124B2 (en) | 2019-12-04 | 2021-10-19 | Saudi Arabian Oil Company | Hierarchical zeolite Y and nano-sized zeolite beta composite |
WO2021216176A1 (en) * | 2020-04-23 | 2021-10-28 | Exxonmobil Research And Engineering Company | Conversion of heavy aromatics to lighter aromatics with low ring saturation and hydrocarbon cracking |
FR3111886A1 (en) | 2020-06-29 | 2021-12-31 | IFP Energies Nouvelles | DIRECT SYNTHESIS OF A ZEOLITH AFX-BASED CATALYST CONTAINING COPPER FOR SELECTIVE NOX REDUCTION |
US11225416B2 (en) | 2019-11-26 | 2022-01-18 | Saudi Arabian Oil Company | Dry gel synthesis of nano-sized ZSM-5 |
US11247196B2 (en) | 2019-12-04 | 2022-02-15 | Saudi Arabian Oil Company | Zeolite with encapsulated platinum |
JP2022518700A (en) * | 2019-01-16 | 2022-03-16 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Sintering resistant metal species in zeolite |
WO2022144802A1 (en) * | 2020-12-30 | 2022-07-07 | Chevron U.S.A. Inc. | Selective hydrocracking of normal paraffins |
WO2022144803A1 (en) * | 2020-12-30 | 2022-07-07 | Chevron U.S.A. Inc. | Selective hydrocracking of normal paraffins |
WO2022243164A1 (en) | 2021-05-21 | 2022-11-24 | IFP Energies Nouvelles | Synthesis of a palladium-bearing afx zeolite catalyst for nox adsorption |
CN115475652A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Catalyst for alkane dehydrogenation and preparation method and application thereof |
US11753492B2 (en) | 2019-12-09 | 2023-09-12 | Saudi Arabian Oil Company | Acryloyl based polymers with active end cap as corrosion inhibitors |
US11878293B2 (en) * | 2018-09-11 | 2024-01-23 | Basf Corporation | Process for preparing a zeolitic material having framework type AEI |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024080412A1 (en) * | 2022-10-12 | 2024-04-18 | 주식회사 그라젬 | Method for preparing functional cosmetic composition, using gold zeolite, and functional cosmetic composition prepared thereby |
CN115770606B (en) * | 2022-12-14 | 2024-09-10 | 吉林大学 | Supported palladium carbide catalyst and preparation method and application thereof |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4247416A (en) | 1979-02-28 | 1981-01-27 | Mobil Oil Corporation | Crystalline zeolite ZSM-25 |
US4299686A (en) * | 1978-04-26 | 1981-11-10 | Mobil Oil Corporation | Shape selective catalyst from zeolite alpha and use thereof |
US4585747A (en) | 1984-06-27 | 1986-04-29 | Mobil Oil Corporation | Synthesis of crystalline silicate ZSM-48 |
US4640829A (en) | 1984-04-16 | 1987-02-03 | Mobil Oil Corporation | Synthesis of crystalline silicate ZSM-50 using dibenzyldimethylammonium ions and the product produced |
US4698218A (en) | 1983-12-19 | 1987-10-06 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and the apparatus for the production of silicon hydrides |
US5455020A (en) | 1994-06-24 | 1995-10-03 | Exxon Research & Engineering Co. | Gallium silicate having 12-ring pores (ECR-34) and a method for its preparation |
US5529964A (en) * | 1993-02-17 | 1996-06-25 | Degussa Aktiengesellschaft | Modified molecular sieves by means of solid ion exchange |
US6049018A (en) | 1999-01-21 | 2000-04-11 | Mobil Corporation | Synthetic porous crystalline MCM-68, its synthesis and use |
WO2011096999A2 (en) | 2010-02-05 | 2011-08-11 | Exxonmobil Chemical Patents Inc. | Cyclohexanone dehydrogenation catalyst and process |
JP2015044720A (en) * | 2013-08-29 | 2015-03-12 | 三菱樹脂株式会社 | Metal-containing copper-sapo zeolite |
US20150218007A1 (en) * | 2011-06-27 | 2015-08-06 | Mitsubishi Plastics, Inc. | Transition-metal-containing zeolite |
-
2017
- 2017-05-24 SG SG11201808679WA patent/SG11201808679WA/en unknown
- 2017-05-24 BR BR112018070992A patent/BR112018070992A2/en not_active IP Right Cessation
- 2017-05-24 KR KR1020187037232A patent/KR20190009806A/en not_active Application Discontinuation
- 2017-05-24 WO PCT/EP2017/000621 patent/WO2017202495A1/en unknown
- 2017-05-24 CA CA3024570A patent/CA3024570A1/en not_active Abandoned
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4299686A (en) * | 1978-04-26 | 1981-11-10 | Mobil Oil Corporation | Shape selective catalyst from zeolite alpha and use thereof |
US4247416A (en) | 1979-02-28 | 1981-01-27 | Mobil Oil Corporation | Crystalline zeolite ZSM-25 |
US4698218A (en) | 1983-12-19 | 1987-10-06 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and the apparatus for the production of silicon hydrides |
US4640829A (en) | 1984-04-16 | 1987-02-03 | Mobil Oil Corporation | Synthesis of crystalline silicate ZSM-50 using dibenzyldimethylammonium ions and the product produced |
US4585747A (en) | 1984-06-27 | 1986-04-29 | Mobil Oil Corporation | Synthesis of crystalline silicate ZSM-48 |
US5529964A (en) * | 1993-02-17 | 1996-06-25 | Degussa Aktiengesellschaft | Modified molecular sieves by means of solid ion exchange |
US5455020A (en) | 1994-06-24 | 1995-10-03 | Exxon Research & Engineering Co. | Gallium silicate having 12-ring pores (ECR-34) and a method for its preparation |
US6049018A (en) | 1999-01-21 | 2000-04-11 | Mobil Corporation | Synthetic porous crystalline MCM-68, its synthesis and use |
WO2011096999A2 (en) | 2010-02-05 | 2011-08-11 | Exxonmobil Chemical Patents Inc. | Cyclohexanone dehydrogenation catalyst and process |
US20150218007A1 (en) * | 2011-06-27 | 2015-08-06 | Mitsubishi Plastics, Inc. | Transition-metal-containing zeolite |
JP2015044720A (en) * | 2013-08-29 | 2015-03-12 | 三菱樹脂株式会社 | Metal-containing copper-sapo zeolite |
Non-Patent Citations (9)
Title |
---|
"Atlas of Zeolite Framework Types", 2007, ELSEVIER |
CHEN H ET AL: "Contribution of hydrogen spillover to the hydrogenation of naphthalene over diluted Pt/RHO catalysts", APPLIED CATALYSIS A: GENERAL, ELSEVIER, AMSTERDAM, NL, vol. 358, no. 2, 1 May 2009 (2009-05-01), pages 103 - 109, XP026076721, ISSN: 0926-860X, [retrieved on 20090220], DOI: 10.1016/J.APCATA.2008.12.045 * |
GARCIA R ET AL: "Nickel Amine Complexes as Structure-Directing Agents for Aluminophosphate Molecular Sieves: A New Route to Supported Nickel Catalysts", TOPICS IN CATALYSIS, KLUWER ACADEMIC PUBLISHERS-PLENUM PUBLISHERS, NE, vol. 24, no. 1-4, 1 October 2003 (2003-10-01), pages 115 - 124, XP019291976, ISSN: 1572-9028 * |
LIMIN REN ET AL: "Design and Synthesis of a Catalytically Active Cu-SSZ-13 Zeolite from a Copper-Amine Complex Template", CHINESE JOURNAL OF CATALYSIS, vol. 33, no. 1, 1 January 2012 (2012-01-01), pages 92 - 105, XP055109007, ISSN: 1872-2067, DOI: 10.1016/S1872-2067(10)60280-X * |
M. CHOI ET AL.: "Mercaptosilane-assisted synthesis of metal clusters within zeolites and catalytic consequences of encapsulation", JACS, vol. 132, 2010, pages 9129 - 9137, XP055032621, DOI: doi:10.1021/ja102778e |
MINKEE CHOI ET AL: "Mercaptosilane-Assisted Synthesis of Metal Clusters within Zeolites and Catalytic Consequences of Encapsulation", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 132, no. 26, 7 July 2010 (2010-07-07), pages 9129 - 9137, XP055032621, ISSN: 0002-7863, DOI: 10.1021/ja102778e * |
MISSOK KANG: "Methanol conversion on metal-incorporated SAPO-34s (MeAPSO-34s)", 1 January 2000 (2000-01-01), pages 437 - 444, XP055027454, Retrieved from the Internet <URL:http://144.206.159.178/FT/616/20531/370338.pdf> [retrieved on 20120516], DOI: 10.1016/S1381-1169(00)00281-8 * |
NURIA MARTÍN ET AL: "High yield synthesis of high-silica chabazite by combining the role of zeolite precursors and tetraethylammonium: SCR of NOx", CHEMICAL COMMUNICATIONS - CHEMCOM., vol. 51, no. 49, 1 January 2015 (2015-01-01), pages 9965 - 9968, XP055249886, ISSN: 1359-7345, DOI: 10.1039/C5CC02670A * |
YANG H ET AL: "Incorporating platinum precursors into a NaA-zeolite synthesis mixture promoting the formation of nanosized zeolite", MICROPOROUS AND MESOPOROUS MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 117, no. 1-2, 1 January 2009 (2009-01-01), pages 33 - 40, XP025658742, ISSN: 1387-1811, [retrieved on 20080614], DOI: 10.1016/J.MICROMESO.2008.06.009 * |
Cited By (82)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7060523B2 (en) | 2016-05-25 | 2022-04-26 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Zeolite material with enclosed binary metal clusters |
JP2019523204A (en) * | 2016-05-25 | 2019-08-22 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Zeolite material with encapsulated binary metal clusters |
WO2019154081A1 (en) * | 2018-02-07 | 2019-08-15 | Basf Se | Process for preparing a zeolitic material comprising ti and having framework type cha |
FR3081349A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | DIRECT SYNTHESIS OF A CATALYST COMPRISING AFX STRUCTURAL TYPE ZEOLITE AND AT LEAST ONE TRANSITION METAL FOR SELECTIVE NOX REDUCTION |
WO2019224093A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for preparing a zeolite composite containing copper and a mixture of zeolites of afx structural type and bea structural type |
WO2019224087A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for preparing an afx-structure zeolite by synthesis in the presence of an organic nitrogen-containing structuring agent |
FR3081351A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | CATALYST COMPRISING AN AFX STRUCTURAL TYPE ZEOLITE PREPARED FROM A MIXTURE OF FAU AND AT LEAST ONE TRANSITIONAL METAL FOR THE SELECTIVE REDUCTION OF NOX |
WO2019224089A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst containing an aluminosilicate composite material comprising copper and a mixture of afx- and bea-structure zeolites, for selective reduction of nox |
WO2019224091A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for synthesizing a composite material consisting of a mixture of afx- and bea-structure zeolites in the presence of an organic nitrogen-containing structuring agent |
WO2019224090A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst comprising a mixture of an afx-structure zeolite and a bea-structure zeolite and at least one transition metal for selective reduction of nox |
WO2019224083A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst comprising an afx-structure zeolite of high purity and at least one transition metal for selective reduction of nox |
WO2019224086A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst comprising an afx-structure zeolite of very high purity and at least one transition metal for selective reduction of nox |
WO2019224084A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for preparing a high-purity afx structural zeolite with a nitrogen-containing organic structuring agent |
WO2019224085A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for synthesizing an afx-structure zeolite from a mixture of fau zeolites in the presence of an organic nitrogen-containing structuring agent |
FR3081344A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | PROCESS FOR THE SYNTHESIS OF AN AFX STRUCTURAL TYPE ZEOLITE FROM A MIXTURE OF ZEOLITES IN THE PRESENCE OF AN ORGANIC NITROGEN STRUCTURANT |
FR3081339A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | CATALYST COMPRISING A HIGH-PURITY AFX STRUCTURAL TYPE ZEOLITE AND AT LEAST ONE TRANSITION METAL FOR SELECTIVE NOX REDUCTION |
FR3081342A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | PROCESS FOR THE SYNTHESIS OF A COMPOSITE MATERIAL COMPRISING A MIXTURE OF AFX STRUCTURAL TYPE ZEOLITES AND BEA STRUCTURAL TYPE IN THE PRESENCE OF AN ORGANIC NITROGEN STRUCTURANT |
FR3081347A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | PROCESS FOR THE PREPARATION OF A HIGH PURITY AFX STRUCTURAL TYPE ZEOLITH WITH AN ORGANIC NITROGEN STRUCTURANT |
FR3081338A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | CATALYST BASED ON A COMPOSITE ALUMINOSILICATE MATERIAL COMPRISING COPPER AND A MIXTURE OF STRUCTURAL TYPE AFX AND BEA STRUCTURAL TYPE ZEOLITES FOR THE SELECTIVE REDUCTION OF NOX |
FR3081346A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | PROCESS FOR THE PREPARATION OF A ZEOLITHIC COMPOSITE MATERIAL CONTAINING COPPER AND A MIXTURE OF STRUCTURAL TYPE ZEOLITHS AFX AND BEA STRUCTURAL TYPE |
FR3081348A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | CATALYST COMPRISING A VERY HIGH PURITY AFX STRUCTURAL TYPE ZEOLITE AND AT LEAST ONE TRANSITION METAL FOR SELECTIVE NOX REDUCTION |
FR3081345A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | PROCESS FOR THE SYNTHESIS OF A ZEOLITE OF STRUCTURAL AFX TYPE OF VERY HIGH PURITY IN THE PRESENCE OF AN ORGANIC NITROGEN STRUCTURANT |
JP2021524430A (en) * | 2018-05-24 | 2021-09-13 | イエフペ エネルジ ヌヴェルIfp Energies Nouvelles | A method for synthesizing a composite material composed of a mixture of AFX-structured and BEA-structured zeolites in the presence of an organic nitrogen-containing structuring agent. |
JP2021524431A (en) * | 2018-05-24 | 2021-09-13 | イエフペ エネルジ ヌヴェルIfp Energies Nouvelles | Method for synthesizing high-purity AFX-structured zeolite in the presence of organic nitrogen-containing structuring agent |
WO2019224082A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Catalyst comprising an afx-structure zeolite prepared from a mixture of fau zeolites and at least one transition metal for selective reduction of nox |
FR3081340A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | CATALYST COMPRISING A MIXTURE OF AFX STRUCTURAL TYPE ZEOLITE AND A BEA STRUCTURAL TYPE ZEOLITE AND AT LEAST ONE TRANSITION METAL FOR SELECTIVE NOX REDUCTION |
JP7493461B2 (en) | 2018-05-24 | 2024-05-31 | イエフペ エネルジ ヌヴェル | Method for the synthesis of high purity AFX structured zeolites in the presence of organic nitrogen-containing structuring agents |
JP7422091B2 (en) | 2018-05-24 | 2024-01-25 | イエフペ エネルジ ヌヴェル | Method for synthesizing a composite material consisting of a mixture of AFX and BEA structured zeolites in the presence of an organic nitrogen-containing structuring agent |
JP2021524373A (en) * | 2018-05-24 | 2021-09-13 | イエフペ エネルジ ヌヴェルIfp Energies Nouvelles | A catalyst containing a very high purity AFX-structured zeolite and at least one transition metal for the selective reduction of NOx. |
CN112188928B (en) * | 2018-05-24 | 2023-12-05 | Ifp新能源公司 | Method for synthesizing composite material composed of AFX and BEA structure zeolite mixture in presence of organic nitrogen-containing structuring agent |
JP7355762B2 (en) | 2018-05-24 | 2023-10-03 | イエフペ エネルジ ヌヴェル | Method for producing high purity AFX structured zeolite using nitrogen-containing organic structuring agent |
JP7319302B2 (en) | 2018-05-24 | 2023-08-01 | イエフペ エネルジ ヌヴェル | A catalyst comprising a mixture of AFX structure zeolites, BEA structure zeolites and at least one transition metal for the selective reduction of NOx |
US11691134B2 (en) | 2018-05-24 | 2023-07-04 | IFP Energies Nouvelles | Catalyst comprising a mixture of an AFX-structure zeolite and a BEA-structure zeolite and at least one transition metal for selective reduction of NOx |
US11643332B2 (en) | 2018-05-24 | 2023-05-09 | IFP Energies Nouvelles | Method for preparing a high-purity AFX structural zeolite with a nitrogen-containing organic structuring agent |
CN112188927A (en) * | 2018-05-24 | 2021-01-05 | Ifp新能源公司 | Method for preparing high-purity AFX structure zeolite by using nitrogen-containing organic structuring agent |
CN112188928A (en) * | 2018-05-24 | 2021-01-05 | Ifp新能源公司 | Method for synthesizing a composite material consisting of a mixture of AFX and BEA structure zeolites in the presence of an organic nitrogen-containing structuring agent |
CN112203763A (en) * | 2018-05-24 | 2021-01-08 | Ifp新能源公司 | Process for the synthesis of very high purity AFX-structured zeolites in the presence of an organic nitrogen-containing structuring agent |
US11560317B2 (en) | 2018-05-24 | 2023-01-24 | IFP Energies Nouvelles | Method for synthesizing an AFX-structure zeolite of very high purity in the presence of an organic nitrogen-containing structuring agent |
WO2019224081A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Direct synthesis of a catalyst comprising an afx-structure zeolite and at least one transition metal for selective reduction of nox |
WO2019224088A1 (en) * | 2018-05-24 | 2019-11-28 | IFP Energies Nouvelles | Method for synthesizing an afx-structure zeolite of very high purity in the presence of an organic nitrogen-containing structuring agent |
US11148953B2 (en) | 2018-05-24 | 2021-10-19 | IFP Energies Nouvelles | Method for synthesizing a composite material consisting of a mixture of AFX- and BEA-structure zeolites in the presence of an organic nitrogen-containing structuring agent |
JP2021525170A (en) * | 2018-05-24 | 2021-09-24 | イエフペ エネルジ ヌヴェルIfp Energies Nouvelles | A catalyst containing an AFX-structured zeolite, a mixture of BEA-structured zeolites, and at least one transition metal for the selective reduction of NOX. |
JP2021524432A (en) * | 2018-05-24 | 2021-09-13 | イエフペ エネルジ ヌヴェルIfp Energies Nouvelles | Method for producing high-purity AFX-structured zeolite using a nitrogen-containing organic structuring agent |
US20210206650A1 (en) * | 2018-05-24 | 2021-07-08 | IFP Energies Nouvelles | Method for preparing a high-purity afx structural zeolite with a nitrogen-containing organic structuring agent |
FR3081343A1 (en) * | 2018-05-24 | 2019-11-29 | IFP Energies Nouvelles | PROCESS FOR THE PREPARATION OF AN AFX STRUCTURAL TYPE ZEOLITE BY SYNTHESIS IN THE PRESENCE OF A NITROGEN ORGANIC STRUCTURANT |
US11878293B2 (en) * | 2018-09-11 | 2024-01-23 | Basf Corporation | Process for preparing a zeolitic material having framework type AEI |
JP2022518700A (en) * | 2019-01-16 | 2022-03-16 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Sintering resistant metal species in zeolite |
JP7449948B2 (en) | 2019-01-16 | 2024-03-14 | エクソンモービル テクノロジー アンド エンジニアリング カンパニー | Sintering-resistant metal species in zeolite |
WO2020159634A1 (en) | 2019-01-30 | 2020-08-06 | Exxonmobil Research And Engineering Company | Selective oxidation using encapsulated catalytic metal |
US10703986B1 (en) | 2019-01-30 | 2020-07-07 | Exxonmobil Research And Engineering Company | Selective oxidation using encapsulated catalytic metal |
FR3095199A1 (en) | 2019-04-19 | 2020-10-23 | IFP Energies Nouvelles | Process for the rapid synthesis of an AFX-structural-type zeolite with a source of faujasite |
WO2020212355A1 (en) | 2019-04-19 | 2020-10-22 | IFP Energies Nouvelles | Method for rapidly synthesising an afx-structure zeolite by synthesis in the presence of an organic nitrogenous structuring agent |
FR3095130A1 (en) * | 2019-04-19 | 2020-10-23 | IFP Energies Nouvelles | QUICK SYNTHESIS OF A CATALYST INCLUDING AN AFX STRUCTURAL TYPE ZEOLITH AND AT LEAST ONE TRANSITION METAL FOR SELECTIVE NOX REDUCTION |
WO2020212354A1 (en) * | 2019-04-19 | 2020-10-22 | IFP Energies Nouvelles | Rapid synthesis of a catalyst comprising a zeolite having an afx structure and at least one transition metal for selective nox reduction |
CN113710360A (en) * | 2019-04-19 | 2021-11-26 | Ifp新能源公司 | Rapid synthesis of zeolites containing structure of AFX and for selective NOXCatalysis of reduced at least one transition metalAgent for chemical treatment |
CN113748087A (en) * | 2019-04-19 | 2021-12-03 | Ifp新能源公司 | Method for quickly synthesizing AFX structure zeolite by using faujasite source |
US11851338B2 (en) | 2019-04-19 | 2023-12-26 | IFP Energies Nouvelles | Method for fast synthesis of an AFX-structure zeolite with a FAUjasite source |
FR3095131A1 (en) | 2019-04-19 | 2020-10-23 | IFP Energies Nouvelles | RAPID SYNTHESIS PROCESS OF AN AFX STRUCTURAL TYPE ZEOLITH BY SYNTHESIS IN THE PRESENCE OF AN ORGANIC NITROGEN STRUCTURING |
WO2020212356A1 (en) | 2019-04-19 | 2020-10-22 | IFP Energies Nouvelles | Method for fast synthesis of an afx-structure zeolite with a faujasite source |
US20220193645A1 (en) * | 2019-04-19 | 2022-06-23 | IFP Energies Nouvelles | Rapid synthesis of a catalyst comprising a zeolite having an afx structure and at least one transition metal for selective nox reduction |
FR3101259A1 (en) | 2019-09-30 | 2021-04-02 | IFP Energies Nouvelles | LOW TEMPERATURE SYNTHESIS OF A ZEOLITHE AFX BASED CATALYST AND ITS APPLICATION IN NH3-SCR |
FR3101258A1 (en) | 2019-09-30 | 2021-04-02 | IFP Energies Nouvelles | LOW TEMPERATURE SYNTHESIS OF HIGH PURE ZEOLITHE AFX |
WO2021063705A1 (en) | 2019-09-30 | 2021-04-08 | IFP Energies Nouvelles | Low-temperature synthesis of high-purity afx zeolite |
WO2021063704A1 (en) | 2019-09-30 | 2021-04-08 | IFP Energies Nouvelles | Low-temperature synthesis of catalyst based on zeolite afx and application thereof in nh3-scr |
US11225416B2 (en) | 2019-11-26 | 2022-01-18 | Saudi Arabian Oil Company | Dry gel synthesis of nano-sized ZSM-5 |
US11247196B2 (en) | 2019-12-04 | 2022-02-15 | Saudi Arabian Oil Company | Zeolite with encapsulated platinum |
US11148124B2 (en) | 2019-12-04 | 2021-10-19 | Saudi Arabian Oil Company | Hierarchical zeolite Y and nano-sized zeolite beta composite |
US11753492B2 (en) | 2019-12-09 | 2023-09-12 | Saudi Arabian Oil Company | Acryloyl based polymers with active end cap as corrosion inhibitors |
WO2021216176A1 (en) * | 2020-04-23 | 2021-10-28 | Exxonmobil Research And Engineering Company | Conversion of heavy aromatics to lighter aromatics with low ring saturation and hydrocarbon cracking |
FR3111886A1 (en) | 2020-06-29 | 2021-12-31 | IFP Energies Nouvelles | DIRECT SYNTHESIS OF A ZEOLITH AFX-BASED CATALYST CONTAINING COPPER FOR SELECTIVE NOX REDUCTION |
WO2022144803A1 (en) * | 2020-12-30 | 2022-07-07 | Chevron U.S.A. Inc. | Selective hydrocracking of normal paraffins |
WO2022144802A1 (en) * | 2020-12-30 | 2022-07-07 | Chevron U.S.A. Inc. | Selective hydrocracking of normal paraffins |
CN113019434A (en) * | 2021-03-17 | 2021-06-25 | 成都科特瑞兴科技有限公司 | Coated catalyst for low-temperature hydrogen deoxidation and preparation method and application thereof |
CN113042034B (en) * | 2021-03-25 | 2022-04-26 | 湖南省尤利威科技有限公司 | Double-effect manganese catalyst for sterilizing and removing aldehyde as well as preparation method and application thereof |
CN113042034A (en) * | 2021-03-25 | 2021-06-29 | 湖南省尤利威科技有限公司 | Double-effect manganese catalyst for sterilizing and removing aldehyde as well as preparation method and application thereof |
CN113198520A (en) * | 2021-05-19 | 2021-08-03 | 中国石油大学(华东) | One-pot preparation method of molecular sieve supported palladium carbon catalyst and application of molecular sieve supported palladium carbon catalyst in synthesis of dimethyl carbonate by gas phase method |
CN113198520B (en) * | 2021-05-19 | 2022-07-19 | 中国石油大学(华东) | One-pot preparation method of molecular sieve supported palladium carbon catalyst and application of molecular sieve supported palladium carbon catalyst in synthesis of dimethyl carbonate by gas phase method |
WO2022243164A1 (en) | 2021-05-21 | 2022-11-24 | IFP Energies Nouvelles | Synthesis of a palladium-bearing afx zeolite catalyst for nox adsorption |
FR3123006A1 (en) | 2021-05-21 | 2022-11-25 | IFP Energies Nouvelles | SYNTHESIS OF A CATALYST BASED ON ZEOLITH AFX CONTAINING PALLADIUM FOR NOX ADSORPTION |
CN115475652A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Catalyst for alkane dehydrogenation and preparation method and application thereof |
CN115475652B (en) * | 2021-06-16 | 2024-05-28 | 中国石油化工股份有限公司 | Catalyst for alkane dehydrogenation and preparation method and application thereof |
CN113457727A (en) * | 2021-06-17 | 2021-10-01 | 西安交通大学 | Au/ZSM-5 catalyst with hierarchical pores regulated by alkali metal, and synthesis method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
KR20190009806A (en) | 2019-01-29 |
SG11201808679WA (en) | 2018-12-28 |
BR112018070992A2 (en) | 2019-01-29 |
CA3024570A1 (en) | 2017-11-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017202495A1 (en) | A synthetic zeolite comprising a catalytic metal | |
US20190168197A1 (en) | Synthetic Zeolite Comprising A Catalytic Metal | |
US10745285B2 (en) | Process for preparing a molecular sieve | |
US20220016611A1 (en) | Sinter Resistant Metal Species In Zeolites | |
JP5162249B2 (en) | ITQ-27, a novel crystalline microporous material | |
CN108622915B (en) | Method for synthesizing IZM-2 zeolite in presence of template 1, 6-bis (methylpiperidinium) hexane dibromide | |
KR102172784B1 (en) | Emm-25 molecular sieve material, its synthesis and use | |
JP5862807B2 (en) | Molecular sieve materials, their synthesis and use | |
JP7085375B2 (en) | Method for synthesizing IZM-2 zeolite in the presence of template 1,6-bis (methylpiperidinium) hexanedihydroxydo | |
EP3323785A1 (en) | Crystalline zeolites with eri/cha intergrowth framework type | |
JP6422488B2 (en) | Method for producing molecular sieve | |
CN112638825A (en) | Method for making molecular sieves | |
KR20180136501A (en) | Method for producing AFX-containing molecular chain SAPO-56 | |
JP2017202951A (en) | Manufacturing method of aei type aluminosilicate, manufacturing method of propylene and linear butene using the aei type aluminosilicate | |
WO2020159634A1 (en) | Selective oxidation using encapsulated catalytic metal | |
US10183285B2 (en) | Process for preparing a molecular sieve | |
US11299444B2 (en) | Selective hydrogen removal | |
WO2023168174A1 (en) | Emm-73 molecular sieve compositions, syntheses, and uses |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112018070992 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 2018559877 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 3024570 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17739865 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20187037232 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2017739865 Country of ref document: EP Effective date: 20190102 |
|
ENP | Entry into the national phase |
Ref document number: 112018070992 Country of ref document: BR Kind code of ref document: A2 Effective date: 20181011 |