WO1998004498A1 - Preparation of y-type faujasite using an organic template - Google Patents
Preparation of y-type faujasite using an organic template Download PDFInfo
- Publication number
- WO1998004498A1 WO1998004498A1 PCT/US1997/012996 US9712996W WO9804498A1 WO 1998004498 A1 WO1998004498 A1 WO 1998004498A1 US 9712996 W US9712996 W US 9712996W WO 9804498 A1 WO9804498 A1 WO 9804498A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction mixture
- silica
- type faujasite
- sio
- water
- Prior art date
Links
- 239000012013 faujasite Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title description 2
- 239000011541 reaction mixture Substances 0.000 claims abstract description 94
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910001868 water Inorganic materials 0.000 claims abstract description 63
- 238000002425 crystallisation Methods 0.000 claims abstract description 55
- 230000008025 crystallization Effects 0.000 claims abstract description 55
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 114
- 239000010457 zeolite Substances 0.000 claims description 92
- 229910021536 Zeolite Inorganic materials 0.000 claims description 79
- 239000000377 silicon dioxide Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- -1 alkali metal cation Chemical class 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims 11
- 229910052906 cristobalite Inorganic materials 0.000 claims 11
- 229910052682 stishovite Inorganic materials 0.000 claims 11
- 229910052905 tridymite Inorganic materials 0.000 claims 11
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 230000032683 aging Effects 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
- 239000003039 volatile agent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 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 7
- 239000000843 powder Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229960004029 silicic acid Drugs 0.000 description 4
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004113 Sepiolite Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 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 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000329 aluminium sulfate 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
- 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000001889 high-resolution electron micrograph Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 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
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- 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
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/21—Faujasite, e.g. X, Y, CZS-3, ECR-4, Z-14HS, VHP-R
Definitions
- the present invention relates to a process for producing crystalline aluminosilicate Y-type faujasite from a reaction mixture which contains an organic templating agent capable of producing Y-type faujasite and only sufficient water to form the Y-type faujasite.
- Background Prior art methods of preparing crystalline Y zeolite typically produce finely divided crystals which must be separated from an excess of liquid in which the zeolite is crystallized. The liquid, in turn, must be treated for reuse or else be discarded, with potentially deleterious environmental consequences.
- Preparing commercially useful catalytic materials which contain the powdered zeolite also normally requires additional binding and forming steps.
- the zeolite powder as crystallized must be mixed with a binder material and then formed into shaped particles or agglomerates, using methods such as extruding, agglomeration, spray drying, and the like.
- binding and forming steps greatly increase the complexity of catalyst manufacture involving zeolitic materials.
- the additional steps may also have an adverse effect on the catalytic performance of the Y zeolite so bound and formed.
- 3,094,383, issued June 18, 1963 to Dzierzanowski et al. discloses a method for making type A zeolites in the form of coherent polycrystalline aggregates by forming reaction masses consisting of a mixture of sodium aiuminate, a siliceous material and water, wherein the H2 ⁇ /Na2 ⁇ mole ratio is 5 to 25.
- the mass is aged while maintaining it out of contact with an external aqueous liquid phase while preventing the mass from dehydrating.
- the aging step can include maintaining the mass at 100°F. ( 38°C.) for, e.g., 18 hours, followed by heating at 200°F (93°C.) for, e.g., 24 hours.
- Taggart et al. discloses a method for producing an aluminosilicate zeolite in a preformed body by providing an unreacted preformed body containing a reactive kaolin-type clay and alkali metal hydroxide, and reacting the preformed body in an aqueous reaction mixture until crystals of the zeolite are formed in the body.
- the aggregate of the preformed body and the aqueous reactant mixture has a H 2 O/Na 2 O mole ratio of at least 20. It is stated that Y zeolite can be made in this manner.
- U S Patent No 3,777,006, issued December 4, 1 73 to Rundell et al discloses a process for preparing zeolitic bodies having a size in excess of 200 microns, by preparing clay bodies in the desired size range, treating the clay bodies in a sodium silicate solution, and heating the formed bodies in the solution until crystallization is complete It is indicated that Y zeolite can be made in this manner U.S.
- Patent No 3,972,983, issued August 3, 1976 to Ciric discloses a faujasite-type zeolite designated ZSM-20 made by preparing a mixture containing sources of an alkali metal oxide, a tetraethylammonium oxide, an oxide of aluminum, an oxide of silicon and water and maintaining the mixture at a temperature of at least 50°C until crystals of the zeolite are formed
- the mole ratio of water to silica in the reaction mixture is disclosed to be 10-20
- U S Patent No 4,058,586, issued November 15, 1977 to Chi et al discloses a method for preparing zeolitic aluminosilicates, particularly those that are characterized by pores in the 4 to 10 Angstrom sizes that are designated Zeolites A and X, in which compacts of Zeolites A and X, metakaolin clay mixture undergo crystallization at a temperature of 200° to 700°F (93° to 371 °C ) The crystallization is carried out in a calciner or other drying equipment
- the reaction mixture is heated at crystallization conditions and in the absence of an external liquid phase, so that excess liquid need not be removed from the crystallized material prior to drying the crystals.
- GB 2, 160,517 A published December 24, 1985, relates to a preformed synthetic zeolite selected from the group consisting of Y, omega zeolite, offretite, erionite, L zeolite and ferrierite whose Si/Al atomic ratio ranges from 1.5 to 100, the preformed zeolite being obtained from a preformed aluminosilicic material whose Si/Al atomic ratio is lower than that of the product and ranges from 0.5 to 90 by treating the material with a silica-containing product in the presence of at least one organic or inorganic base.
- a method for preparing crystalline Y-type faujasite comprising preparing a reaction mixture comprising at least one active source of silica, at least one active source of alumina, and an organic tempiating agent capable of producing the Y-type faujasite in amounts sufficient to produce the Y-type faujasite, and sufficient water to produce the Y-type faujasite, and maintaining said reaction mixture at a temperature up to about 130°C. under crystallization conditions and in the absence of an added external liquid phase for sufficient time to form crystals of the Y-type faujasite.
- the present invention also provides a method for preparing crystalline Y-type faujasite, said method comprising preparing a reaction mixture comprising at least one active source of silica, at least one active source of alumina, and an organic templating agent capable of producing the Y-type faujasite in amounts sufficient to produce the Y-type faujasite, and sufficient water to shape said mixture, forming said reaction mixture into a shape, and maintaining said reaction mixture at a temperature up to about 130°C. under crystallization conditions and in the absence of an added external liquid phase for sufficient time to form crystals of the Y-type faujasite.
- the Y-type faujasite prepared in accordance with this invention has an X-ray diffraction pattern, after it has been calcined, containing the lines of Table I. It is important, in preparing the reaction mixture of the present process, that the amount of water present in the reaction mixture as prepared for the crystallization step be sufficient to produce the Y-type faujasite. Thus, the reaction mixture itself furnishes all the water needed to crystallize the zeolite. This amount of water is less than the amount of water required in conventional processes for preparing zeolites. It is an amount which is not substantially greater than that required to produce the Y- type faujasite.
- the amount of water used in the present invention is less than that required to dissolve the reaction mixture components, or, if they are not dissolved, less than that required to immerse the reaction mixture components in the water.
- there is no separate, added external liquid phase present which must be removed from the crystallized material at the end of the crystallization step by, for example filtering or decanting, prior to drying the crystals.
- This absence of an added external liquid phase distinguishes the present invention from methods for making Y-type faujasite wherein the Y-type faujasite crystals are formed from solution or where solid reactants are heated in an aqueous solution until crystals of Y-type faujasite form.
- the present invention is based on the discovery of a method for crystallizing the Y-type faujasite from a reaction mixture which contains an organic template capable of producing the Y-type faujasite and which contains only enough water to form the Y-type faujasite.
- the Y-type faujasite produced by this method has a silica to alumina mole ratio of greater than 6. Further, the Y-type faujasite prepared by the above described method is made as very small crystallites. DETAILED DESCRIPTION OF THE INVENTION PREPARING THE REACTION MIXTURE
- the reaction mixture from which and in which the Y-type faujasite is crystallized comprises at least one active source of silica, at least one active source of alumina, and sufficient water to form the Y-type faujasite. This amount of water is considerably less than that required in conventional processes for preparing the Y-type faujasite.
- the amount of water required in the reaction mixture of the present invention is that amount which is needed to adequately blend the mixture.
- a reaction mixture is prepared by mixing water with active sources of the zeolite to form a uniform mass having preferably a heavy paste-like consistency.
- the active sources will be in a form which can be easily blended into a uniform mass, and may be, for example, powders, hydrated particles, or concentrated aqueous solutions. Sufficient water is added to wet all the powders during the mixing and kneading steps. Alternatively, sufficient water is added that the powders may be kneaded into a uniform and generally homogeneous mixture which may be shaped. It is not necessary that all of the active sources be readily soluble in water during kneading, since the water added to the active sources will be insufficient to make a fluid-like mixture.
- the amount of water added depends on the mixing apparatus and on the active sources employed. Those familiar with the art can readily determine without undue experimentation the amount of liquid required to properly mix active sources of the zeolite. For example, hydrated sources of the zeolite may require relatively less water, and dried sources may require relatively more. Though it is preferred that the mixture be blended and kneaded until the mixture has a uniform, homogeneous appearance, the length of time devoted to kneading the mixture is not critical in the present invention. The water content of the reaction mixture after blending and kneading may be further adjusted, for example, by drying or by the addition of water.
- Typical sources of silicon oxide (SiO 2 ) include silicates, silica hydrogel, silicic acid, colloidal silica, fumed silica, tetraalkyl orthosilicates silica hydroxides, precipitated silica and clays.
- Typical sources of aluminum oxide include aluminates, alumina, and aluminum compounds such as AICI 3 , Al 2 (SO 4 ) 3 , aluminum hydroxide (Al(OH 3 )), and kaolin clays.
- AICI 3 Al 2 (SO 4 ) 3
- Al(OH 3 ) aluminum hydroxide
- kaolin clays kaolin clays.
- One advantage of the present invention is that the sources of silicon oxide and aluminum oxide can all be non-zeolitic. Salts, particularly alkali metal halides such as sodium chloride, can be added to or formed in the reaction mixture. They are disclosed in the literature as aiding the crystallization of zeolites while preventing silica occlusion in the lattice.
- the reaction mixture also contains one or more active sources of alkali metal oxide. Sources of lithium, sodium and potassium, are preferred.
- Any alkali metal compound which is not detrimental to the crystallization process is suitable here.
- Non-limiting examples include oxides, hydroxides, nitrates, sulfates, halogenides, oxalates, citrates and acetates.
- the alkali metal is generally employed in an amount so that the alkali metal/aluminum ratio is at least 1/1, preferably greater than 1/1.
- the reaction mixture also contains an organic templating agent capable of producing Y-type faujasite. These organic templating agents are typically quaternary ammonium cations such as tetraethylammonium, tetrapropylammonium, or tetrabutylammonium cations.
- Tetraethyl ammonium compounds are the preferred organic template.
- the counter ion for the quaternary ammonium compounds may be essentially any anion such as halide or hydroxide which is not detrimental to the formation of the Y-type faujasite.
- halide refers to the halogen anions, particularly fluorine, chlorine, bromine, iodine, and combinations thereof.
- representative anions include hydroxide, acetate, sulfate, carboxylate, tetrafluoroborate, and halides such as fluoride, chloride, bromide, and iodide. Hydroxide and iodide are particularly preferred as anions.
- the organic templating agent is used in an amount which is sufficient to produce the Y-type faujasite.
- the reaction mixture should contain the following components in the amounts indicated (expressed as mole ratios of oxides even though the actual starting materials may not be oxides):
- R/SiO 2 0.05-0.5 0.1-0.4 H 2 O/SiO 2 - 1-5 2-5 wherein M * is an alkali metal cation and R is the organic templating agent.
- the reaction mixture may be formed into a desired shape before the crystallization step, thereby reducing the number of process steps required to prepare catalytic materials containing the resulting zeolite.
- it may be necessary to change the liquid content of the reaction mixture, either by drying or by adding more liquid, in order to provide a formable mass which retains its shape.
- water will generally comprise from about 20 percent to about 60 percent by weight, and preferably from about 30 percent to about 50 percent by weight of the reaction mixture.
- the reaction mixture is formed into a shape, e.g., particles.
- Methods for preparing such shapes are well known in the art, and include, for example, extrusion, spray drying, granulation, agglomerization and the like.
- shape When the shape is in the form of particles, they are preferably of a size and shape desired for the ultimate catalyst, and may be in the form of, for example, extrudates, cylinders, spheres, granules, agglomerates and prills.
- the particles will generally have a cross sectional diameter between about 1/64 inch and about 1/2 inch, and preferably between about 1/32 inch and about 1/4 inch, i.e., the particles will be of a size to be retained on a 1/64 inch, and preferably on a 1/32 inch screen and will pass through a 1/2 inch, and preferably through a 1/4 inch screen.
- the shape prepared from the reaction mixture will contain sufficient water to retain a desired shape. Additional water is not required in the mixture in order to initiate or maintain crystallization within the shaped reaction mixture. Indeed, it may be preferable to remove some of the excess water from the shaped reaction mixture prior to crystallization.
- Conventional methods for drying wet solids can be used to dry the reaction mixture, and may include, for example drying in air or an inert gas such as nitrogen or helium at temperatures below about 200°C and at pressures from subatmospheric to about 5 atmospheres pressure. nitrogen or helium at temperatures below about 200°C and at pressures from subatmospheric to about 5 atmospheres pressure.
- Naturally occurring clays e.g., bentonite, kaolin, montmorillonite, sepiolite and attapulgite, are not required, but may be included in the reaction mixture prior to crystallization to provide a product having good crush strength.
- Such clays can be used in the raw state as originally mined or can be initially subjected to calcination, acid treatment or chemical modification.
- Microcrystalline cellulose has also been found to improve the physical properties of the particles.
- ZEOLITE CRYSTALLIZATION According to the present process, the zeolite is crystallized either within the reaction mixture or within the shape made from the reaction mixture. In either case, the composition of the mixture from which the zeolite is crystallized has the molar composition ranges stated above.
- the total volatiles content of the reaction mixture during crystallization be in the range of between about 20 wt.% and about 60 wt.% , and preferably between about 30 wt.% and about 60 wt.%, based on the weight of the reaction mixture, where the total volatiles content is the measure of total volatile liquid, including water, in the reaction mixture. It is a feature of the present process that no additional liquid beyond that required to produce the Y-type faujasite is required for zeolite crystallization. Crystallization of the zeolite takes place in the absence of an added external liquid phase, i.e., in the absence of a liquid phase separate from the reaction mixture.
- the present method provides a method of crystallizing the zeolite in such a way as to minimize the amount of water which must be treated and/or discarded following crystallization. To that end, the present method provides a zeolite synthesis method which requires no additional water for crystallization beyond a sufficient amount of liquid required to form the Y-type faujasite.
- the reaction mixture is preferably "aged" before the Y- type faujasite is crystallized.
- This aging is accomplished by maintaining the reaction mixture at a relatively low temperature (compared to the crystallization temperature) under conditions which will prevent dehydration of the reaction mixture (such as placing the mixture in a sealed container and/or exposing it to a small amount of water vapor).
- the reaction mixture is maintained at room temperature or a slightly higher temperature.
- the temperature at which the mixture is aged will be from about 25°C. to about 75C, preferably from about 25°C. to about 50°C. This temperature should be maintained for a time sufficient to provide the crystalline Y-type faujasite following the crystallization step.
- the aging should be continued long enough to allow Y- type faujasite nuclei to begin to form in the reaction mixture.
- the aging step will be at least 24 hours, preferably 2 days or longer (e.g., 2-4 days), with longer aging times leading to a more crystalline product.
- Crystallization is conducted after the aging step at an elevated temperature and usually in an autoclave so that the reaction mixture is subject to autogenous pressure until the crystals of zeolite are formed.
- the temperatures during the hydrothermal crystallization step are typically maintained from about 70°C. to about 130°C, preferably from about 80°C.
- the resulting product may be zeolite beta, not Y-type faujasite.
- the crystallization is conducted under conditions which will prevent dehydration of the reaction mixture. This may be accomplished by exposing the reaction mixture to a small amount of water vapor or steam during crystallization. It is believed it is well within the skill of one skilled in this art to determine a satisfactory crystallization time without undue experimentation.
- the crystallization time required to form crystals will typically range from about 1 day to about 10 days, and more frequently from about 1 day to about 4 days. If the crystallization period is too long, the zeolite formed will be zeolite Beta, not Y-type faujasite.
- the crystallized material collected following the crystallization step will typically comprise at least about 50 weight percent crystals. Crystallized material containing at least about 80 weight percent crystals, and even at least about 90 weight percent crystals, may also be prepared using the present method. Once the zeolite crystals have formed, the crystals may be water-washed and then dried, e.g., at 90°C. to 150°C. for from 8 to 24 hours. The drying step can be performed at atmospheric or subatmospheric pressures.
- the zeolite made by the present process is crystallized within the reaction mixture, which comprises amorphous reagents.
- Crystalline material i.e., "seed" crystals of Y-type faujasite
- seed crystals may be added to the mixture prior to the crystallization step, and methods for enhancing the crystallization of zeolites by adding "seed" crystals are well known.
- seed crystals is not a requirement of the present process. Indeed, it is an important feature of the present process that the zeolite can be crystallized within the reaction mixture in the absence of crystals added prior to the crystallization step.
- the Y-type faujasite prepared in accordance with this invention and calcined is characterized by the X-ray diffraction lines in Table I below.
- Table I d is the distance between two lattice planes, and I/Io is the ratio, expressed in percent, of the intensity of any given line (I) to the intensity of the most intense line (Io). The strongest line is assigned a value of 100.
- the intensities are indicated as W(weak - less than 20), M (medium - 20-40), S (strong - 40-60) and VS (very strong - greater than 60).
- Table IA actual relative intensities are shown.
- the silica/alumina mole ratio of the product zeolite can be determined from a corelation with the unit cell constant as calculated from X-ray diffraction analysis (see Sohn et al., Zeolites, 6, 225 (86)).
- the Y-type faujasites produced by the present application include zeolites such as ZSM-20, ECR-32 and ECR-35.
- ZEOLITE CRYSTALLITE SIZE Typically, the zeolite crystals are less than 10 microns in diameter as determined by Scanning Electron Microscopy. Since small crystals are desirable for certain catalytic applications, crystallization conditions can be tailored to produce zeolite crystals with diameters of less than 1.0 micron.
- the crystal size of the zeolite may be determined by, for example, grinding the shaped particles to separate the individual crystals. High resolution electron micrographs of the separated crystals can then be prepared, after which the average size of individual zeolite crystals can be determined by reference to calibrated length standards. An average crystal size may then be computed in various well-known ways, including: where rij is the number of zeolite crystals where minimum length falls within an interval Li. For purposes of this invention, average crystal size will be defined as a number average.
- zeolite crystal size is distinguished from what some manufacturers term "zeolite particle size," the latter being the average size of all particles, including both individual crystals and polycrystalline agglomerates, in the as-produced zeolite powder.
- zeolite particle size typically, the zeolite crystals are less than 10 microns in diameter as determined by Scanning Electron Microscopy. Since small crystals are desirable for certain catalytic applications, crystallization conditions can be tailored by, for example, reducing crystallization temperature, by increasing aluminum content in the reaction mixture, and/or by reducing the water content of the reaction mixture or the shaped particles prior to crystallization, to produce zeolite crystals with diameters of less than 1.0 micron.
- ZEOLITE POST-TREATMENT A crystallized material containing crystals of zeolite is prepared in the process as described above.
- the zeolite can be used as synthesized or can be thermally treated (calcined).
- the synthesis product can contain silica which is not incorporated in the zeolite structure. This excess silica can be removed by washing with dilute acid (e.g., 0.2M HNO 3 ) or dilute base (e.g., 0.0 IM NH4OH). This washing should be done prior to thermal treatment of the zeolite.
- dilute acid e.g., 0.2M HNO 3
- dilute base e.g., 0.0 IM NH4OH
- the zeolite can be leached with chelating agents, e.g., EDTA or dilute acid solutions, to increase the silica/alumina mole ratio. These methods or acidic ion-exchange resin treatment.
- the zeolite can also be steamed; steaming helps stabilize the crystalline lattice to attack from acids.
- the zeolite can be used in intimate combination with hydrogenating components, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as palladium or platinum, for those applications in which a hydrogenation/ dehydrogenation function is desired.
- Typical replacing cations can include metal cations, e.g., rare earth, Group IA, Group IIA and Group VIII metals, as well as their mixtures.
- metal cations e.g., rare earth, Group IA, Group IIA and Group VIII metals, as well as their mixtures.
- replacing metallic cations cations of metals such as rare earth, Mn, Ca, Mg, Zn, Ga, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, Fe and Co are particularly preferred.
- the hydrogen, ammonium, and metal components can be exchanged into the zeolite.
- the zeolite can also be impregnated with the metals, or, the metals can be physically intimately admixed with the zeolite using standard methods known to the art.
- the metals can also be occluded in the crystal lattice by having the desired metals present as ions in the reaction mixture from which the zeolite is prepared.
- Typical ion exchange techniques involve contacting the synthetic zeolite with a solution containing a salt of the desired replacing cation or cations. Although a wide variety of salts can be employed, chlorides and other halides, nitrates, and sulfates are particularly preferred. Representative ion exchange techniques are disclosed in a wide variety of patents including U.S. Patent Nos. 3,140,249; 3,140,251; and 3, 140,253. Ion exchange can take place either before or after the zeolite is calcined.
- the zeolite is typically washed with water and dried at temperatures ranging from 65°C. to about 315°C. After washing, the zeolite can be calcined in air or inert gas at temperatures ranging from about 200°C. to 820°C. for periods of time ranging from 1 to 48 hours, or more, to produce a catalytically active product especially useful in hydrocarbon conversion processes.
- the spatial arrangement of the atoms which form the basic crystal lattice of the zeolite remains essentially unchanged. The exchange of cations has little, if any, effect on the zeolite lattice structures.
- the zeolite may be used as a catalyst, without additional forming, if the reaction mixture has been formed into a shape which is of a size and shape desired for the ultimate catalyst.
- the zeolite can be composited with other materials resistant to the temperatures and other conditions employed in organic conversion processes, using techniques such as spray drying, extrusion, and the like.
- matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and metal oxides. The latter may occur naturally or may be in the form of gelatinous precipitates, sols, or gels, including mixtures of silica and metal oxides.
- an active material in conjunction with the synthetic zeolite tends to improve the conversion and selectivity of the catalyst in certain organic conversion processes.
- Inactive materials can suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically without using other means for controlling the rate of reaction.
- zeolite materials have been incorporated into naturally occurring clays, e.g., bentonite and kaolin. These materials, i.e., clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in petroleum refining the catalyst is often subjected to rough handling.
- Naturally occurring clays which can be composited with the synthetic zeolite of this invention include the montmorillonite and kaolin families, which families include the sub-bentonites and 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. Fibrous clays such as sepiolite and attapulgite can also be used as supports. Such clays can be used in the raw state as originally mined or can be initially subjected to calcination, acid treatment or chemical modification.
- the zeolite prepared by the present method can be composited with porous matrix materials and mixtures of matrix materials such as silica, alumina, titania, magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica titania, titania-zirconia as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
- the matrix can be in the form of a cogel.
- the zeolite can also be composited with other zeolites such as synthetic and natural faujasites (e.g., X), and erionites. They can also be composited with purely synthetic zeolites such as those of the ZSM, SSZ, KU, FU, and NU series. The combination of zeolites can also be composited in a porous inorganic matrix.
- the zeolite prepared in the present process is useful in hydrocarbon conversion reactions. Hydrocarbon conversion reactions are chemical and catalytic processes in which carbon containing compounds are changed to different carbon containing compounds.
- hydrocarbon conversion reactions include isomerization of Cs and C ⁇ compounds to increase the octane of gasoline, hydrocracking, fluid catalytic cracking, butane alkylation for fuels, aromatics alkylation, aromatics isomerization and olefin polymerization.
- EXAMPLES Example 1 150 Grams of silica (Hi-Sil 233, a hydrated silica manufacture by PPG) was placed in a Baker-Perkins mixer. 50 Grams of NaAl ⁇ 2 was added to the mixer and the two were mixed for about ten minutes.
- each of parts A, B, C and D was placed in its own one quart Teflon bottle with a hole in the cover, and each bottle was sealed in an autoclave which contained 12 cc water outside the bottles to prevent drying of the samples when heated (especially small samples in large autoclaves). At the end of crystallization, there was still about 12 cc water outside the bottles, so consumption of this water was negligible.
- the bottles were then left at room temperature for 24 hours
- the bottles containing parts A and C were then heated at 1 10°C. for two days, and the bottles containing parts B and D were heated at 110°C. for four days.
- the resulting crystalline extrudates were washed with deionized water, filtered, dried in a vacuum oven at 120°C.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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DE69701470T DE69701470T2 (en) | 1996-07-31 | 1997-07-22 | METHOD FOR PRODUCING Y-TYPE FAUJASITE BY MEANS OF AN ORGANIC TEMPLATE |
BR9710622-4A BR9710622A (en) | 1996-07-31 | 1997-07-22 | Process for the preparation of y-type crystalline faukasite. |
EP97935102A EP0915809B1 (en) | 1996-07-31 | 1997-07-22 | Preparation of y-type faujasite using an organic template |
AU38123/97A AU3812397A (en) | 1996-07-31 | 1997-07-22 | Preparation of y-type faujasite using an organic template |
JP50897998A JP4073958B2 (en) | 1996-07-31 | 1997-07-22 | Manufacture of Y-type faujasite using organic template |
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US08/690,683 US5716593A (en) | 1996-07-31 | 1996-07-31 | Preparation of Y-type faujasite using an organic template |
US08/690,683 | 1996-07-31 |
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US6270743B1 (en) * | 1995-05-24 | 2001-08-07 | Kuboto Corporation | Method of manufacturing crystalline microporous materials |
US5919430A (en) * | 1996-06-19 | 1999-07-06 | Degussa Aktiengesellschaft | Preparation of crystalline microporous and mesoporous metal silicates, products produced thereby and use thereof |
US6444865B1 (en) | 1997-12-01 | 2002-09-03 | Shell Oil Company | Process wherein a hydrocarbon feedstock is contacted with a catalyst |
US6756029B2 (en) | 1999-08-11 | 2004-06-29 | Petroleo Brasileiro S.A.-Petrobras | Molecular sieves of faujasite structure |
US6632415B2 (en) | 2001-04-09 | 2003-10-14 | Chevron U.S.A. Inc. | Methods for making molecular sieves |
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Also Published As
Publication number | Publication date |
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EP0915809A1 (en) | 1999-05-19 |
JP4073958B2 (en) | 2008-04-09 |
EP0915809B1 (en) | 2000-03-15 |
BR9710622A (en) | 2000-01-11 |
DE69701470D1 (en) | 2000-04-20 |
CN1226875A (en) | 1999-08-25 |
JP2001525781A (en) | 2001-12-11 |
US5716593A (en) | 1998-02-10 |
KR20000029697A (en) | 2000-05-25 |
DE69701470T2 (en) | 2000-07-06 |
AU3812397A (en) | 1998-02-20 |
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