WO2009062742A2 - Porous solid acid catalysts, methods of manufacturing the same, and methods of manufacturing organics molecules using the same - Google Patents
Porous solid acid catalysts, methods of manufacturing the same, and methods of manufacturing organics molecules using the same Download PDFInfo
- Publication number
- WO2009062742A2 WO2009062742A2 PCT/EP2008/009669 EP2008009669W WO2009062742A2 WO 2009062742 A2 WO2009062742 A2 WO 2009062742A2 EP 2008009669 W EP2008009669 W EP 2008009669W WO 2009062742 A2 WO2009062742 A2 WO 2009062742A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zeolite
- catalyst
- pore size
- crystalline
- range
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000011973 solid acid Substances 0.000 title claims abstract description 19
- 239000010457 zeolite Substances 0.000 claims abstract description 135
- 239000011148 porous material Substances 0.000 claims abstract description 96
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 114
- 229910021536 Zeolite Inorganic materials 0.000 claims description 106
- 238000006243 chemical reaction Methods 0.000 claims description 90
- 239000002253 acid Substances 0.000 claims description 31
- 239000000376 reactant Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000012038 nucleophile Substances 0.000 claims description 9
- 230000000269 nucleophilic effect Effects 0.000 claims description 9
- 239000012039 electrophile Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- 150000002118 epoxides Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 20
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000007344 nucleophilic reaction Methods 0.000 abstract description 4
- 239000011949 solid catalyst Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- -1 rare earth cations Chemical class 0.000 description 20
- 239000000543 intermediate Substances 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000012266 salt solution Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 8
- 239000002841 Lewis acid Substances 0.000 description 8
- 150000007517 lewis acids Chemical class 0.000 description 8
- 150000003863 ammonium salts Chemical class 0.000 description 7
- NYENCOMLZDQKNH-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)bismuthanyl trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F NYENCOMLZDQKNH-UHFFFAOYSA-K 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 238000005917 acylation reaction Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 3
- WNMKUSDJPFVKRD-UHFFFAOYSA-N 2-(4-methoxyanilino)cyclopentan-1-ol Chemical compound C1=CC(OC)=CC=C1NC1C(O)CCC1 WNMKUSDJPFVKRD-UHFFFAOYSA-N 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- QTJBUFUVRIBLJM-UHFFFAOYSA-N 2,3-dibutyl-1h-imidazol-3-ium;bromide Chemical compound [Br-].CCCC[NH+]1C=CN=C1CCCC QTJBUFUVRIBLJM-UHFFFAOYSA-N 0.000 description 1
- PVDAGKNKQFWQDO-UHFFFAOYSA-N 2-(2-bromophenoxy)oxane Chemical compound BrC1=CC=CC=C1OC1OCCCC1 PVDAGKNKQFWQDO-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ABSZYEUMTNJQPI-UHFFFAOYSA-N 2-anilinocyclohexan-1-ol Chemical compound OC1CCCCC1NC1=CC=CC=C1 ABSZYEUMTNJQPI-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- OSOZHQRKDGHSSC-UHFFFAOYSA-N 2-dodecoxyoxane Chemical compound CCCCCCCCCCCCOC1CCCCO1 OSOZHQRKDGHSSC-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- ZJCUUXGLZWBCIL-UHFFFAOYSA-N 4-(1h-indol-3-yl)butan-2-one Chemical compound C1=CC=C2C(CCC(=O)C)=CNC2=C1 ZJCUUXGLZWBCIL-UHFFFAOYSA-N 0.000 description 1
- AEQNFPABZYMPFO-UHFFFAOYSA-N 4-(2-methyl-1h-indol-3-yl)butan-2-one Chemical compound C1=CC=C2C(CCC(=O)C)=C(C)NC2=C1 AEQNFPABZYMPFO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000012834 electrophilic reactant Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ZNYIVYFFZCEWDY-UHFFFAOYSA-N methyl 3-[4-(3-methoxy-3-oxopropyl)piperazin-1-yl]propanoate Chemical compound COC(=O)CCN1CCN(CCC(=O)OC)CC1 ZNYIVYFFZCEWDY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000005708 tetrahydropyranylation reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- 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
-
- 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
- B01J29/084—Y-type faujasite
-
- B01J35/647—
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- C07D243/10—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
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- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- B01J2229/10—After treatment, characterised by the effect to be obtained
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- 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
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- C07C2601/14—The ring being saturated
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to solid acid catalysts suitable for the catalysis of organic synthesis reactions.
- the invention relates to porous solid acid catalysts whose porosity has been tailored to render the catalyst more efficient in the acid catalyzed nulceophilic reactions.
- the present invention also relates to methods of making the catalyst, and in particular methods for generating the porosity of the catalyst.
- the present invention further relates to methods of synthesizing organic molecules manufactured using the inventive catalysts.
- Bronsted acid- and Lewis acid-catalyzed reactions are amongst the most common and basic transformations in organic chemistry. See, for example, (a) Lewis Acids in Organic Synthesis, Vol. 1; Yamamoto, H., Ed.; Wiley VCH: Weinheim, 2000 and (b) Lewis Acids in Organic Synthesis, Vol. 2; Yamamoto, H., Ed.; Wiley VCH: Weinheim, 2000. While the activation of functional groups towards attack by a nucleophile constitutes a powerful synthetic strategy, noticeable disadvantages are encountered when ' using classical Bronsted or Lewis acids, especially on a large scale. Such acids are often .
- Zeolites have been proposed as suitable solid acid catalysts for use in organic reactions.
- US 2006/0041171 describes a zeolite-based solid acid catalyst for the production of acylated aromatic ethers.
- the patent application describes exchanging zeolite Y with rare earth cations in amounts ranging from 10 to 30 weight percent to make the catalysts more compatible with acylation reactions. It is noted that even when employing such catalysts, yields of the acylated compounds are not uniformly high.
- the catalyst described therein is a heterogeneous catalyst prepared by impregnating or exchanging zeolitic material with Lewis acidic metals, e.g., copper.
- Lewis acidic metals e.g., copper.
- the patent application describes that the Lewis acid metal containing catalysts can be extended to
- US Patent 6,669,924 describes porous zeolitic-based catalysts.
- the catalysts described therein are prepared in two stages. First a mesoporous silica having a stereoregular arrangement of uniformly-sized mesopores having diameters from 20 to 500 A is prepared or selected. Secondly, a porous nanocrystalline zeolite, e.g., ZSM5, is crystallized onto the walls of the silica precursor thereby resulting in a material having bimodal pore size distribution, wherein one mode of porosity is from the silica precursor and the second mode results from the nanocrystalline zeolite formed on the pore walls of the precursor.
- the patent is silent to particular reactions for which the catalyst is suitable, but generally mentions that the catalysts can be used in petroleum refining and organic synthesis. It is generally known that the zeolites described in this patent are often used in the petroleum refining industry.
- a problem known to occur using zeolites such as that described in the aforementioned '924 patent is the hindered diffusion of molecules in pore structures described in the 924 patent.
- the one dimensional mesoporous pore structure often result in low yields (J.P. Lourenco et al. / Microporous and Mesopo ⁇ ous Materials 94 (2006) 56-65).
- These structures also apparently have insufficient stability (J. Phys. Chem. 1995, 99, 10590-10593), thus hindering their thermal regeneration.
- This invention is a tailored highly porous catalyst for efficient, environmentally sustainable acid catalysis suitable for use in nucleophilic reactions employed in fine chemical and pharmaceutical organic synthesis.
- the catalyst has shown to affect relatively high yields and relatively high selectivities in such reactions.
- the catalyst has a tailored distribution of acid centers within the zeolite framework, relatively free access to active acid sites for the reactants, and structural stability. These features are obtained through a specialized stream treatment or chemical modification, such as, ion exchange, or acid or base treatment of starting materials such as crystalline zeolites.
- the tailor-made catalyst of this invention features a bi-modal or multimodal pore system. Surprisingly, this pore structure enables efficient diffusion of the reactants and products, which as mentioned above, enhances catalysis under solvent-free conditions.
- one aspect of this invention is a novel process for synthesizing organic molecules, the process comprising (a) combining a nucleophile reactant and electrophile reactant subject to reaction with a nucleophilic compound, (b) introducing a solid acid catalyst comprising a pore size distribution having at least two different modes, (c) conducting a reaction between the nucleophile and electrophile, and (d) recovering organic molecules as a product and separating the solid acid catalyst.
- Another aspect of the invention is a catalyst comprising crystalline acid zeolite having a pore size distribution having at least two different modes, the peak maximum pore size for each mode being in a range of 20 to 600 Angstroms, wherein the at least two different modes are present in the crystalline zeolite structure. It is preferable that the peak maximum pore size for each of the at least two different pore size modes is in the range of 20 to 200 Angstroms. It is especially preferable that the peak maximum pore size of at least one of the modes is at least 50 Angstroms and in the range of 50 to 200 Angstroms.
- Another aspect is therefore a method for manufacturing a solid acid catalyst, the method comprising selecting a crystalline acid zeolite having a microporous pore size, typically having an average pore size of 3 to 10 Angstroms, subjecting the crystalline acid zeolite to steam, and recovering a crystalline acid zeolite having the at least two different pore size modes described above.
- the Figure illustrates the pore size distribution of one embodiment of the invention, wherein the catalyst is prepared according to Example 1.
- the Figure illustrates a pore size distribution of pore sizes for a crystalline acid zeolite of this invention as measured using "Analysenmethode Nr. CE 46: " MESSUNG DER OBERFLACHE UND DER PORENGR ⁇ SSENVERTEILUNG MIT DEM TRISTAR 3000", dated August 17, 2005.
- the Figure shows pore volume [dV/d log (D)] for pores in the range of 10 to 1000 Angstroms in diameter. V is pore volume and D is pore diameter.
- the peak maximum pore size for one pore size mode is about 4 ⁇ A and the peak maximum pore size for the second pore size mode is about 9 ⁇ A.
- the Figure does not report all porosity of the zeolite, e.g., micropores less than 10 Angstroms, because the method was carried out to measure only those pores in the range of 10 to 1000 Angstroms.
- the catalyst of this invention is a "solid acid catalyst.”
- the acid sites on the catalysts e.g., alumina sites present on solid aluminosilicates, activate and/or otherwise facilitate reactions between the nucleophile and electrophile reactants described above. These reactions are called nucleophilic reactions, an example of which is illustrated below.
- the catalyst of the invention is a solid and therefore not substantially soluble in the phase of the medium in which the reaction of the nucleophile and electrophile occur.
- the solid phase of the catalyst enables one to more easily separate the catalyst from the reaction product, e.g., compared to liquid homogenous catalysts, thereby also allowing one to more readily recycle the catalyst for use in later reactions.
- the catalyst of this invention can be prepared from conventional aluminosilicate materials such as crystalline Y zeolites.
- the process used to prepare the catalyst creates a material having two or more modes of pore sizes.
- the mode of pore size refers to the area under a peak maximum pore size that is shown in pore distribution graphs generated by BET methods measuring pore size.
- the graphs generated from measuring pore size of this invention possess at least two such peak maximums.
- the peak maximum pore size for a mode is the largest pore size shown for a particular mode. This invention would have at least two such peak maximums.
- the pore size analysis used to measure pore size of this invention is known in the art. The Examples later below provide the specific conditions under which the porosity of the invention has been evaluated.
- the catalyst of this invention is preferably prepared from acid aluminosilicates such as acid zeolites.
- Suitable acid zeolites are those having a "framework" silicon to aluminum ratio of 3.1 to 4.8 as determined by the Breck-Flanigen equation described later below. The aforementioned range is based on zeolites have a unit cell size of 24.48- 24.60. These zeolites have cage structures possessing porosity and alumina sites possessing Lewis acidity.
- the zeolite employed in this invention is selected depending on the nature of the reactants and the reaction product.
- the zeolite may be selected from the group of structures with at least 10 ring apertures such as DAC, EPI, EUO, FER, HEU, LAU, MEL, . MFI, MFS, MTT, NES, NU-85, NU-86 and NU88, STI, TON, WEI, -PAR and - WEN and structures with 12-ring apertures such as *BEA, BOG, CAN, EMT, FAU, GME, LTL, MAZ, MEI, MOR, MTW, OFF and -RON.
- zeolitic materials include phosphate materials such as MeALPO and SAPO, and zeolitic titanosilicates, vanadosilicates, ferrisilicates and borosilicates. Full details of many of these structures may be found in the "Atlas of Zeolite Structure Types", W. M. Meier and D. H. Olson, 3 rd Revised Edition, 1992, Butterworth-Heinemann. It will be readily understood by those skilled in the art that zeolite structures may possess a range of framework compositions.
- composition of the zeolite for the purposes of the present invention should be such that it possesses cation-exchangeable sites within the framework
- this may be achieved using aluminosilicate zeolites having a silica:alumina ratio of at least 1 :2, more preferably 1:5.
- silica: alumina ratios can be used, the reduction in alumina sites (associated with aluminium in the framework) means that very high silica: alumina ratios are less preferred.
- the zeolite may be treated with an alkali metal compound, e.g. sodium hydroxide.
- the preferred zeolite structures are FAU and MFI.
- the FAU zeolite structure corresponds to zeolite X and zeolite Y whereas the aluminosilicate MFI structure corresponds to ZSM-5.
- the preferred zeolites are zeolite Y, e.g., USY, and ZSM-5.
- the zeolite is optionally further processed to possess a desired number of active Lewis acid sites on its structure.
- the acidity is a function of the number of aluminum (Al) atoms per unit cell size (UCS).
- Al aluminum
- UCS unit cell size
- the final acidity will depend on the type of reaction in which the catalyst will be used, but in general the acidity of the catalyst can be articulated as "N A i/ucs" and can be in the range of 24 to 47 based on the Breck-Flanigen relation.
- the zeolites suitable for making this invention typically have average pore sizes of 10 Angstroms or smaller.
- suitable zeolites have an average pore size of at least 3 Angstoms to no more than -10 Angstroms, and more typically in the range of 4.0 to 8,0 A.
- the porosities of conventional zeolites are typically monomodal in the sense that the pore size distribution graphs of these materials show a range of pore sizes having one predominant peak of 10 A or less.
- the pore size distribution for the preferred zeolites such as FAU and MFI zeolites are relatively narrow.
- FAU zeolites e.g., zeolite Y and zeolite X, have an average pore size of 4.7 Angstroms.
- MFI zeolites such as ZSM5
- ZSM5 have an average pore size of 5.1 x 5.3 Angstroms and 5.3 x 5.6 Angstroms.
- the pores for the MFI zeolites are considered oblong and the aforementioned sizes therefore reflect the average size of each dimension present in the oblong shaped pores.
- Two modes of micropores less than 6 Angstroms are typically present, and thus the aforementioned two average pore size measurements.
- the chosen zeolite's porosity is modified, i.e., "tailored", to create a catalyst having two or more pore size modes wherein the peak maximum pore size for each of the two or more modes is in the range of 20 to 600 Angstroms. Greater detail of the process is provided below, but the process is typically conducted to create at least one additional pore size mode wherein its peak maximum pore size is in the range of 20 to 600 A.
- the zeolites used to make this invention are preferably crystalline. Crystallinity of the zeolites is determined by conventional X-ray diffraction (XRD) methods. Crystalline zeolites are preferred because "isolated" Lewis acid sites are generated within their crystalline structures. The sites present in or within these structures are considered to have "super-acidity” because Al atoms are isolated within the zeolite framework.
- XRD X-ray diffraction
- the porosity of this invention is created by subjecting the zeolite to steam at temperatures and for a duration that depend on the desired pore size distribution.
- the zeolite is heated in an oven, e.g., calciner, and subjected to 80-100% steam for a duration of ten minutes to twenty hours; -
- the zeolite is generally heated to a temperature of at least 35O 0 C, and more specifically in a range of 350 to 900 0 C.
- the temperatures employed in this range are more typically greater than 400 0 C, and more preferably greater than 500 0 C.
- the residence time for steam treatment can be shorter at the higher temperatures at which the zeolite is heated and when larger amounts of steam are present in the oven.
- the steam treatment dealuminates the silica alumina structure of the zeolite thereby causing the alumina to redistribute along the zeolite structure. Redistribution of alumina under the above conditions alters the pore structure to create additional modes of pore size wherein the modes' peak maximum pore size is each within the range of 20 to 600 Angstroms.
- the addition of pore size modes is controlled through choice of the steam conditions and the duration of steaming and heating.
- acid sites on the alumina are also redistributed, thereby increasing the accessibility of such sites to reactants.
- the average pore size of at least one of the pore size modes should be ten times the molecule size of the proposed reactants in the nucleophilic reaction to enable effective diffusion.
- the molecules typically reacted are in the range of 5 - 25 A. Consequently, the pore sizes of the pores in the catalyst responsible for diffusion should be in the range of 20 to 600 Angstroms, and more preferably in the range of 50 - 200 A range. This mesoporous range of porosity is achieved by the tailored synthesis of the zeolitic catalysts described herein.
- the pore size distribution of the invention is measured by "Analysenmethode Nr. CE 46: " MESSUNG DER OBERFLACHE UND DER PORENGROSSENVERTEILUNG MlT DEM TRISTAR 3000", dated August 17, 2005.
- the zeolites having the aforementioned two or more pore size modes may be used in an organic synthesis reaction as is, or they can be incorporated into a formed material prepared by combining the zeolite with other materials.
- the zeolites mentioned above can be in the form of powder, granules, pellets, or extrudates. These formed materials can be prepared by techniques known to those skilled in the art, including pelletizing, extruding or spray drying.
- the catalysts of this invention may therefore contain other materials such as binders and other functional components that are useful in carrying -out the organic synthesis reactions of this invention.
- suitable binders are those typically used to bind zeolite crystals into particle form and include, but are not limited to, silica, alumina, silica-aluminas, and resinous binders. [0029] It is preferable to use the catalyst in powder form.
- zeolites that have yet to be treated according to the invention can be combined or incorporated with the aforementioned materials and formed into formed or shaped materials.
- the formed material is then subjected to the steam and other conditions previously described so that the zeolite in the formed materials possesses the two or more modes of pore size described earlier, i.e., the zeolites in the formed material have at least two modes of pore size distribution wherein the peak maximum pore size for each mode is in the range of 20 to 600 Angstroms, preferably, 50 to 200 Angstroms.
- optimized zeolites to combine high acidity by tailored distribution of the acid centers within the zeolite framework with free accessibility of the active centers for the substrates and maximum structural stability may be prepared by the following procedure.
- a sodium type Y zeolite (NaY) is exchanged with an ammonium salt solution to lower the soda (Na 2 O) content to below about 5 percent by weight.
- ammonium-exchanged zeolite (NH 4 NaY) is calcined in presence of 80 - 100% steam at a temperature of from 400 to 900 0 C.
- the calcined zeolite is then reacted with an acid-aluminium salt solution or aqueous NHj solution or ammonium salt solution to lower the soda content of the zeolite to below 1.5 percent by weight Na 2 O.
- the zeolite prepared by the above procedure may be combined with an inorganic oxide matrix either after the acid-aluminium salt exchange, i.e. after step (3), or after calcination, i.e. after step (2).
- the calcined zeolite of step (2) is combined with the matrix, the combined calcined zeolite/matrix mixture is treated with the acid aluminium salt solution or a silica solution.
- the ammonium salt solution which is used to reduce the sodium level of the initial sodium Y zeolite is preferably ammonium sulphate or aqueous NH3 solution. However, solutions of, e.g. ammonium chloride or ammonium nitrate may be used.
- the ammonium salt solution typically contains from about 3 to 10 percent by weight of the salt dissolved in water.
- the ammonium salt-solution is contacted with the sodium Y zeolite for a period of from about 10 to 120 minutes, preferably at a temperature ranging from about 25 to 100 °C.
- the sodium Y zeolite is typically contacted with from about 1 to 3 batches of the ammonium salt solution.
- the Na, NH+ 4 zeolite is heated, , at a temperature of from about 120 to 600 0 C.
- the calcination is conducted for a period of from about 1 sec to 120 min.
- the catalysts of this invention may be employed to manufacture a range of organic synthetic products and/or chemical intermediates.
- the catalysts are suitable for catalyzing acid catalyzed reactions between electrophilic reactant molecules, e.g., those organic compounds containing unsaturated carbon-carbon bonds, carbonyls and expoxide, and nucleophilic reactant molecules, e.g., those containing nitrogen-based functional groups, such as amines; oxygen-based functional groups, such as alcohols; and sulfur-based functional groups, such as thiols.
- the inventive catalyst may be used in acid-based catalysis of Michael type addition reactions.
- Such reactions include reactions between nucleophilic aliphatic amines and electrophilic ⁇ , ⁇ -unsaturated compounds. See for example, [ L. Ambroise, C. Chassagnard, G. Revial, J. d'Angelo; Tetrahedron: Asymmetry 1991, 6, 407-410, R. Varala, M.M. Alam, S.R. Adapa; Synlett 2003, 5, 720-721].
- Examplary aliphatic amines for use in these reactions include both cyclic and straight chain aliphatic amines, which can be primary or secondary.
- Aromatic compounds having nucleophilic nitrogen heteroatoms also serve as suitable nucleophiles for use with and activation by this invention.
- Unsaturated compounds suitable for use in Michael reactions include ⁇ , ⁇ - unsaturated ethylenic compounds, e.g., methyl methacrylate and acrylonitrile.
- Condensation reactions can also benefit from use of the solid catalyst of this invention. Examples of such reactions include, but are not limited to, reactions of phenyl diamines with unsaturated carbonyl compounds. [D.V. Jarikote, S.A. Siddiqui, R.
- the invention also has suitable application in epoxide ring-opening reactions.
- Such reactions include alcoholysis of epoxides (as the electrophile), e.g., meso-epoxides, with nucelophiles such as alcohols, water, acetic acid, and acetone.
- Such ring opening reactions are frequently carried out with primary, secondary and tertiary alcohols.
- Epoxide ring opening reactions are also commonly used to manufacture ⁇ -amino alcohols, which is an intermediate frequently used in the pharmaceutical industry.
- Such compounds are prepared through nucleophilic attack of the epoxide ring by reaction with anilines and/or other nucleophilic aromatic alcohols. [T. Ollevier, G. Lavie-Compin; Tetrahedron Letters 2004, 45, 49-52, F. Carree, R. Gil, J. Collin; Organic Letters 2005, 7(6), 1023-1026].
- the catalysts of this invention are also suitable for use in reactions described in US 2006/0041 171 (acylation of aromatic ethers), US 2005/0033100 (Diels Alder reactions with dienes), and US 7,074,960 (carbonyl-ene and iminoene reactions), the contents of which are incorporated herein by reference. [0040]
- the invention may also be used in catalytic tetrahydropyranylation of alcohols and phenols.
- the reactions above may be run neat, in water or in organic solvents.
- the solvents may be polar or non-polar. Examples include aromatic hydrocarbons such toluene or xylene. A suitable non-aromatic hydrocarbon is ethyl acetate.
- the catalyst is particularly suitable for neat reactions, thereby avoiding or reducing use of environmentally unfriendly solvents.
- the catalyst of this invention may be used under conditions typically employed in the reactions described above.
- the reaction temperature and pressure vary depending on the reactants and desired products yields.
- the catalysts are more readily removed from reaction medium.
- Catalysts of this invention containing crystalline zeolites are thermally stable at temperatures conventionally used to remove reaction contaminants and regenerate the catalysts. Therefore, the crystalline zeolite-based embodiments of this invention make recycling of the catalysts relatively more simple and manageable.
- any range of numbers recited in the specification or claims, such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited.
- a sodium type zeolite Y catalyst (NaY) exchanged with an ammonium salt solution to lower the soda (Na 2 O) content to below about 5 percent by weight was treated in an oven with 100% steam at 540 0 C for ninety minutes.
- the treated zeolite was measured for pore size using "Analysenmethode Nr. CE 46: " MESSUNG DER OBERFLACHE UND DER PORENGR ⁇ SSENVERTEILUNG MIT DEM TRISTAR 3000", dated August 17, 2005, and was shown to have the pore size distribution in Figure 1.
- the treated zeolite was added as is to a reaction between an acrylic acid ester and a primary amine to produce 3-isopropylamino-proprionic acid methyl ester. Such products are intermediates used to manufacture industrially useful products.
- 0.22 g [2.6mmole] of methyl aery late, 0.15g [2.6mmole] of isopropyl amine, and 260mg of the invention catalyst were combined neat and the reaction was run at room temperature for about twenty minutes. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product was weighed to measure yield. The yield and the yield reported for the reaction of the same reactants described in L. Ambroise, C.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an acrylic acid ester and a secondary amine to produce 3-diallylamino-propionic acid methyl ester. Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an unsaturated nitrile and a secondary amine to produce 3-diallylamino- proprionitrile. Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an acrylic acid ester and a heterocyclic amine to produce 3-[4-(2- Methoxycarbonyl-ethyl)-piperazin-l-yl]-propionic acid methyl ester.
- Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between a ⁇ , ⁇ -unsaturated compound and an nucleophilic indole to produce 4-(lH-Indol- 3-yl)-butan-2-one. Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between a ⁇ , ⁇ -unsaturated carbonyl compound and an nucleophilic indole to produce 4- (2-Methyl-lH-indol-3-yl)-butan-2-one. Such products are intermediates used to manufacture Industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between a cyclic ketone compound and an aromatic diamine to produce 11- Spirocyclohexyl-2,3,4,10,11,1 la-hexahydro-lH-diberizo[b,e][l,4]diacepine. Such products are intermediates used to manufacture industrially useful products.
- [0061] Specifically, 1.5 ml [14.5 mmole] of cyclohexanone, 0.1 Ig - [0.97mmole] of o- phenylene diamine and 257 mg of the invention were combined neat and the reaction was run at room temperature for about seventeen hours.
- the reaction mixture was then filtered through a glass frit to remove the catalyst and the product yield was measured.
- the yield and the yield reported for the reaction of the same reactants with dibutylimidazolium bromide homogenous catalyst described in D.V. Jarikote, S.A. Siddiqui, R. Rajagopal, T. Daniel, R.J. Lahoti, K. V. Srinivasan; Tetrahedron Letters 2003, 44, 1835-1838 are reported in Table 1.
- the invention had greater product yield compared to that reported for this reaction using a homogenous catalyst, but yielded product without solvent, and with a more manageable recovery of the catalyst.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an alcohol to produce ( ⁇ r ⁇ n.s)-2-Ethoxycyclopentanol. Such products are intermediates used to manufacture industrially useful products.
- 0.33g [3.91 mmole] of cyclopentene oxide, ImI [17.15 mmole] of ethanol and 391 mg of the invention were combined neat and the reaction was run at room temperature for about twelve hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product yield was measured. The yield and the yield reported for the reaction of the same reactants with iron (III) trifluroacetate homogenous catalyst described in N.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between a epoxyacetat compound and an alcohol to produce (£)-6-ethoxy-7-hydroxy-3,7- dimethyloct-2-enylacetate. Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an aromatic amine to produce _2-Phenylamino- cyclopentanol. Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an aromatic amine to produce 2-Phenylamino- cyclohexanol. Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an aromatic amine to produce 2-(4- Methoxyphenylamino)-cyclopentanol. Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an aromatic amine to produce 2-(4- Methoxyphenylamino)-cyclopentanol. Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between 3,4-Dihydro-2H-pyran and a phenol to produce 2-(2-Bromo-phenoxy)- tetrahydropyran. Such products are intermediates used to manufacture industrially useful products.
- Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between 3,4-Dihydro-2H-pyran and an aliphatic alcohol to produce 2-Dodecyloxy- tetrahydro-pyran. Such products are intermediates used to manufacture industrially useful products.
Abstract
This invention relates to a process for synthesizing organic molecules utilizing a novel porous acid catalyst. The inventive processes are generally nucleophilic reactions employing a solid acid catalyst that has a pore size distribution having at least two different modes. The properties of the catalysts allow for relatively high product yields while at the same time provide the benefits of other solid catalysts, these benefits being manageable catalyst recycle and reduction and/or elimination of environmentally unfriendly solvents. The novel catalyst can be prepared by steam treating conventional crystalline zeolites under conditions sufficient to produce tailored pore size distributions having two or more modes of average of pore sizes, and optionally forming them into catalyst forms and/or particles. Accordingly, this invention also relates to the manufacture of the catalyst.
Description
POROUS SOLID ACID CATALYSTS,
METHODS OF MANUFACTURING THE SAME, AND METHODS OF MANUFACTURING ORGANIC MOLECULES USING THE SAME
FIELD OF THE INVENTION
[0001] The present invention relates to solid acid catalysts suitable for the catalysis of organic synthesis reactions. In particular, the invention relates to porous solid acid catalysts whose porosity has been tailored to render the catalyst more efficient in the acid catalyzed nulceophilic reactions. The present invention also relates to methods of making the catalyst, and in particular methods for generating the porosity of the catalyst. The present invention further relates to methods of synthesizing organic molecules manufactured using the inventive catalysts.
BACKGROUND OF THE INVENTION
[0002] Bronsted acid- and Lewis acid-catalyzed reactions are amongst the most common and basic transformations in organic chemistry. See, for example, (a) Lewis Acids in Organic Synthesis, Vol. 1; Yamamoto, H., Ed.; Wiley VCH: Weinheim, 2000 and (b) Lewis Acids in Organic Synthesis, Vol. 2; Yamamoto, H., Ed.; Wiley VCH: Weinheim, 2000. While the activation of functional groups towards attack by a nucleophile constitutes a powerful synthetic strategy, noticeable disadvantages are encountered when' using classical Bronsted or Lewis acids, especially on a large scale. Such acids are often . highly corrosive, environmentally unfriendly, and sometimes expensive reagents, e.g., H2SO4, HF, TFOH, Triflouro-acetic acid . Such acids cannot be easily recovered after quenching the reaction mixture. For product isolation after reaction with conventional Lewis catalysts such as e.g. H2SO4, AlCl3, HF, TFOH, Triflouro-acetic acid, and ZnCl2, additional processing steps are employed to destroy the acid-base adduct, separate the used catalyst from the reaction mixture and purify the desired product. In numerous cases undesired by-products have to be removed. See for example, A. Corma, H. Garcia, Chem. Rev. 2003, 103, 4307 - 4365. This results in the production of undesired waste. [0003] The need for environmentally sustainable acid catalysts has been expressed in numerous publications, e.g., Anastas, P. T.; Kirchhoff, M. M. Ace. Chem. Res. 2002, 35, 686-694. The use of less corrosive solid acid catalysts has been sought as well. See, e.g., Wilson, K; Clark, J. H.; Pure Appl. Chem. 2000, 72, 1313-1319; Climent, M.; Corma, A.
Green Chem. 2002, 4, 565-569;and Corma, A.; Garcia, H. Chem. Rev. 2003, 103, 4307-
4365.
[0004] Industry has also sought performing reactions without solvent, or with relatively little solvent. Doing so not only avoids the environmentally issues mentioned above, but also results in high atom economy. See, e.g., Trost, B. M. Science 1991, 254, 1471-1477 and Trost, B. M. Angew. Chem. Int. Ed. Engl. 1995, 34, 259-281. Because solvent molecules compete with the substrate for the catalyst' s reactive sites, solvent-free conditions are clearly favorable. Solid heterogeneous catalyst have been developed to meet this need. The needs are more readily met if diffusion within a solid catalyst is not hindered by geometrical constraints such as pore size.
[0005] Zeolites have been proposed as suitable solid acid catalysts for use in organic reactions. For example, US 2006/0041171 describes a zeolite-based solid acid catalyst for the production of acylated aromatic ethers. The patent application describes exchanging zeolite Y with rare earth cations in amounts ranging from 10 to 30 weight percent to make the catalysts more compatible with acylation reactions. It is noted that even when employing such catalysts, yields of the acylated compounds are not uniformly high.
[0006] US 2005/0033100 describes zeolitic-based catalysts for Diels-Alder reactions.
The catalyst described therein is a heterogeneous catalyst prepared by impregnating or exchanging zeolitic material with Lewis acidic metals, e.g., copper. The patent application describes that the Lewis acid metal containing catalysts can be extended to
Diels Alders reactions, which can be more stereochemically demanding compared to aziridation reactions for which the catalysts described in the '100 patent have been previously been used. Such Lewis acid impregnated catalysts however are susceptible to leaching of metal ions, and therefore can present contamination issues when manufacturing molecules destined for use in health and environmental products.
[0007] US Patent 7,074,960 describes catalysts similar to those described in US
2005/0033100, but describes using such catalysts for performing carbonyl-ene and iminoene reactions.
[0008] US Patent 6,669,924 describes porous zeolitic-based catalysts. The catalysts described therein are prepared in two stages. First a mesoporous silica having a
stereoregular arrangement of uniformly-sized mesopores having diameters from 20 to 500 A is prepared or selected. Secondly, a porous nanocrystalline zeolite, e.g., ZSM5, is crystallized onto the walls of the silica precursor thereby resulting in a material having bimodal pore size distribution, wherein one mode of porosity is from the silica precursor and the second mode results from the nanocrystalline zeolite formed on the pore walls of the precursor. The patent is silent to particular reactions for which the catalyst is suitable, but generally mentions that the catalysts can be used in petroleum refining and organic synthesis. It is generally known that the zeolites described in this patent are often used in the petroleum refining industry.
[0009] A problem known to occur using zeolites such as that described in the aforementioned '924 patent is the hindered diffusion of molecules in pore structures described in the 924 patent. The one dimensional mesoporous pore structure often result in low yields (J.P. Lourenco et al. / Microporous and Mesopoτous Materials 94 (2006) 56-65). These structures also apparently have insufficient stability (J. Phys. Chem. 1995, 99, 10590-10593), thus hindering their thermal regeneration.
[0010] Even in light of the developments noted above, the demand for environmentally friendly yet highly efficient and effective solid acid catalysts has not yet been met. The need for environmentally friendly, i.e., a "green" heterogeneous Lewis acid catalyst, becomes even more important when conducting fine chemical and pharmaceutical synthesis.
SUMMARY OF THE INVENTION
[0011] This invention is a tailored highly porous catalyst for efficient, environmentally sustainable acid catalysis suitable for use in nucleophilic reactions employed in fine chemical and pharmaceutical organic synthesis. The catalyst has shown to affect relatively high yields and relatively high selectivities in such reactions. The catalyst has a tailored distribution of acid centers within the zeolite framework, relatively free access to active acid sites for the reactants, and structural stability. These features are obtained through a specialized stream treatment or chemical modification, such as, ion exchange, or acid or base treatment of starting materials such as crystalline zeolites. While
conventional zeolites suffer from diffusion limitations, e.g., see Kortunov, P.; Vasenkov, S.; Karger, J.; Valiullin, R.; Gottschalk, P.; Fe Elia, M.; Perez, M.; Stόcker, M.; Drescher, B.; McElhiney, G.; Berger, C; Glaser, R.; Weitkamp J. J. Am. Chem. Soc. 2005, 127, pp. 13055-13059, the tailor-made catalyst of this invention features a bi-modal or multimodal pore system. Surprisingly, this pore structure enables efficient diffusion of the reactants and products, which as mentioned above, enhances catalysis under solvent-free conditions. Moreover, no extensive washing or extraction is needed for product recovery, because less reaction product is retained within the pore structure of the catalyst. Consequently, a simple filtration is sufficient for product isolation. [0012] Therefore one aspect of this invention is a novel process for synthesizing organic molecules, the process comprising (a) combining a nucleophile reactant and electrophile reactant subject to reaction with a nucleophilic compound, (b) introducing a solid acid catalyst comprising a pore size distribution having at least two different modes, (c) conducting a reaction between the nucleophile and electrophile, and (d) recovering organic molecules as a product and separating the solid acid catalyst. [0013] Another aspect of the invention is a catalyst comprising crystalline acid zeolite having a pore size distribution having at least two different modes, the peak maximum pore size for each mode being in a range of 20 to 600 Angstroms, wherein the at least two different modes are present in the crystalline zeolite structure. It is preferable that the peak maximum pore size for each of the at least two different pore size modes is in the range of 20 to 200 Angstroms. It is especially preferable that the peak maximum pore size of at least one of the modes is at least 50 Angstroms and in the range of 50 to 200 Angstroms.
[0014] Another aspect is therefore a method for manufacturing a solid acid catalyst, the method comprising selecting a crystalline acid zeolite having a microporous pore size, typically having an average pore size of 3 to 10 Angstroms, subjecting the crystalline acid zeolite to steam, and recovering a crystalline acid zeolite having the at least two different pore size modes described above.
BRIEF DESCRIPTION OF THE DRAWING
[0015] The Figure illustrates the pore size distribution of one embodiment of the invention, wherein the catalyst is prepared according to Example 1. The Figure illustrates a pore size distribution of pore sizes for a crystalline acid zeolite of this invention as measured using "Analysenmethode Nr. CE 46: " MESSUNG DER OBERFLACHE UND DER PORENGRόSSENVERTEILUNG MIT DEM TRISTAR 3000", dated August 17, 2005. The Figure shows pore volume [dV/d log (D)] for pores in the range of 10 to 1000 Angstroms in diameter. V is pore volume and D is pore diameter. The peak maximum pore size for one pore size mode is about 4θA and the peak maximum pore size for the second pore size mode is about 9θA. The Figure does not report all porosity of the zeolite, e.g., micropores less than 10 Angstroms, because the method was carried out to measure only those pores in the range of 10 to 1000 Angstroms.
DETAILED DESCRIPTION
[0016] The catalyst of this invention is a "solid acid catalyst." The acid sites on the catalysts, e.g., alumina sites present on solid aluminosilicates, activate and/or otherwise facilitate reactions between the nucleophile and electrophile reactants described above. These reactions are called nucleophilic reactions, an example of which is illustrated below.
[0017] The catalyst of the invention is a solid and therefore not substantially soluble in the phase of the medium in which the reaction of the nucleophile and electrophile occur. The solid phase of the catalyst enables one to more easily separate the catalyst from the reaction product, e.g., compared to liquid homogenous catalysts, thereby also allowing one to more readily recycle the catalyst for use in later reactions.
[0018] As described below, the catalyst of this invention can be prepared from conventional aluminosilicate materials such as crystalline Y zeolites. The process used to prepare the catalyst creates a material having two or more modes of pore sizes. The mode of pore size refers to the area under a peak maximum pore size that is shown in pore distribution graphs generated by BET methods measuring pore size. The graphs generated from measuring pore size of this invention possess at least two such peak maximums. The peak maximum pore size for a mode is the largest pore size shown for a particular mode. This invention would have at least two such peak maximums. The pore
size analysis used to measure pore size of this invention is known in the art. The Examples later below provide the specific conditions under which the porosity of the invention has been evaluated.
[0019] The catalyst of this invention is preferably prepared from acid aluminosilicates such as acid zeolites. Suitable acid zeolites are those having a "framework" silicon to aluminum ratio of 3.1 to 4.8 as determined by the Breck-Flanigen equation described later below. The aforementioned range is based on zeolites have a unit cell size of 24.48- 24.60. These zeolites have cage structures possessing porosity and alumina sites possessing Lewis acidity.
(0020] The zeolite employed in this invention is selected depending on the nature of the reactants and the reaction product. The zeolite may be selected from the group of structures with at least 10 ring apertures such as DAC, EPI, EUO, FER, HEU, LAU, MEL, . MFI, MFS, MTT, NES, NU-85, NU-86 and NU88, STI, TON, WEI, -PAR and - WEN and structures with 12-ring apertures such as *BEA, BOG, CAN, EMT, FAU, GME, LTL, MAZ, MEI, MOR, MTW, OFF and -RON. Other suitable zeolitic materials include phosphate materials such as MeALPO and SAPO, and zeolitic titanosilicates, vanadosilicates, ferrisilicates and borosilicates. Full details of many of these structures may be found in the "Atlas of Zeolite Structure Types", W. M. Meier and D. H. Olson, 3rd Revised Edition, 1992, Butterworth-Heinemann. It will be readily understood by those skilled in the art that zeolite structures may possess a range of framework compositions. The composition of the zeolite for the purposes of the present invention should be such that it possesses cation-exchangeable sites within the framework For example this may be achieved using aluminosilicate zeolites having a silica:alumina ratio of at least 1 :2, more preferably 1:5. Although higher silica: alumina ratios can be used, the reduction in alumina sites (associated with aluminium in the framework) means that very high silica: alumina ratios are less preferred. Rather, if it is desired to reduce the number of acid sites in the zeolite, the zeolite may be treated with an alkali metal compound, e.g. sodium hydroxide. The preferred zeolite structures are FAU and MFI. The FAU zeolite structure corresponds to zeolite X and zeolite Y whereas the aluminosilicate MFI structure corresponds to ZSM-5. The preferred zeolites are zeolite Y, e.g., USY, and ZSM-5.
[0021] The zeolite is optionally further processed to possess a desired number of active Lewis acid sites on its structure. The acidity is a function of the number of aluminum (Al) atoms per unit cell size (UCS). A common method to calculate the Al atoms per UCS is the Breck-Flanigen relation:
Number of Al per UCS = 115.2 x (ao[l/A]-24.19l).
[0022] The final acidity will depend on the type of reaction in which the catalyst will be used, but in general the acidity of the catalyst can be articulated as "NAi/ucs" and can be in the range of 24 to 47 based on the Breck-Flanigen relation.
[0023] The zeolites suitable for making this invention typically have average pore sizes of 10 Angstroms or smaller. For example, suitable zeolites have an average pore size of at least 3 Angstoms to no more than -10 Angstroms, and more typically in the range of 4.0 to 8,0 A. The porosities of conventional zeolites are typically monomodal in the sense that the pore size distribution graphs of these materials show a range of pore sizes having one predominant peak of 10 A or less. The pore size distribution for the preferred zeolites such as FAU and MFI zeolites are relatively narrow. FAU zeolites, e.g., zeolite Y and zeolite X, have an average pore size of 4.7 Angstroms. While MFI zeolites, such as ZSM5, have an average pore size of 5.1 x 5.3 Angstroms and 5.3 x 5.6 Angstroms. The pores for the MFI zeolites are considered oblong and the aforementioned sizes therefore reflect the average size of each dimension present in the oblong shaped pores. Two modes of micropores less than 6 Angstroms are typically present, and thus the aforementioned two average pore size measurements.
[0024] In this invention, the chosen zeolite's porosity is modified, i.e., "tailored", to create a catalyst having two or more pore size modes wherein the peak maximum pore size for each of the two or more modes is in the range of 20 to 600 Angstroms. Greater detail of the process is provided below, but the process is typically conducted to create at least one additional pore size mode wherein its peak maximum pore size is in the range of 20 to 600 A.
[0025] While it is envisioned that one can use the inventive process to prepare amorphous catalyst having at least two pore size modes, the zeolites used to make this
invention are preferably crystalline. Crystallinity of the zeolites is determined by conventional X-ray diffraction (XRD) methods. Crystalline zeolites are preferred because "isolated" Lewis acid sites are generated within their crystalline structures. The sites present in or within these structures are considered to have "super-acidity" because Al atoms are isolated within the zeolite framework. On the other hand, isolated Lewis acid sites are not readily attained in the structure of low crystalline or amorphous materials because domains of Al2Ch and SiO2 are formed, and there are little or no discrete Al atoms within the material's framework. Consequently, the acidity of these materials is much weaker.
[0026] The porosity of this invention is created by subjecting the zeolite to steam at temperatures and for a duration that depend on the desired pore size distribution. The zeolite is heated in an oven, e.g., calciner, and subjected to 80-100% steam for a duration of ten minutes to twenty hours; -The zeolite is generally heated to a temperature of at least 35O0C, and more specifically in a range of 350 to 9000C. The temperatures employed in this range are more typically greater than 4000C, and more preferably greater than 5000C. The residence time for steam treatment can be shorter at the higher temperatures at which the zeolite is heated and when larger amounts of steam are present in the oven. Without being held to a particular theory, the steam treatment dealuminates the silica alumina structure of the zeolite thereby causing the alumina to redistribute along the zeolite structure. Redistribution of alumina under the above conditions alters the pore structure to create additional modes of pore size wherein the modes' peak maximum pore size is each within the range of 20 to 600 Angstroms. The addition of pore size modes is controlled through choice of the steam conditions and the duration of steaming and heating. In the process of redistributing alumina, acid sites on the alumina are also redistributed, thereby increasing the accessibility of such sites to reactants. Generally, and without being held to a particular theory, it is believed that the average pore size of at least one of the pore size modes should be ten times the molecule size of the proposed reactants in the nucleophilic reaction to enable effective diffusion. The molecules typically reacted are in the range of 5 - 25 A. Consequently, the pore sizes of the pores in the catalyst responsible for diffusion should be in the range of 20 to 600 Angstroms, and more preferably in the range of 50 - 200 A range. This mesoporous
range of porosity is achieved by the tailored synthesis of the zeolitic catalysts described herein.
[0027J As mentioned earlier, the pore size distribution of the invention is measured by "Analysenmethode Nr. CE 46: " MESSUNG DER OBERFLACHE UND DER PORENGROSSENVERTEILUNG MlT DEM TRISTAR 3000", dated August 17, 2005. [0028] The zeolites having the aforementioned two or more pore size modes may be used in an organic synthesis reaction as is, or they can be incorporated into a formed material prepared by combining the zeolite with other materials. For example, the zeolites mentioned above can be in the form of powder, granules, pellets, or extrudates. These formed materials can be prepared by techniques known to those skilled in the art, including pelletizing, extruding or spray drying. The catalysts of this invention may therefore contain other materials such as binders and other functional components that are useful in carrying -out the organic synthesis reactions of this invention. For example, suitable binders are those typically used to bind zeolite crystals into particle form and include, but are not limited to, silica, alumina, silica-aluminas, and resinous binders. [0029] It is preferable to use the catalyst in powder form.
[0030] In addition, zeolites that have yet to be treated according to the invention can be combined or incorporated with the aforementioned materials and formed into formed or shaped materials. The formed material is then subjected to the steam and other conditions previously described so that the zeolite in the formed materials possesses the two or more modes of pore size described earlier, i.e., the zeolites in the formed material have at least two modes of pore size distribution wherein the peak maximum pore size for each mode is in the range of 20 to 600 Angstroms, preferably, 50 to 200 Angstroms. [0031] According to the present invention optimized zeolites to combine high acidity by tailored distribution of the acid centers within the zeolite framework with free accessibility of the active centers for the substrates and maximum structural stability may be prepared by the following procedure.
(I) A sodium type Y zeolite (NaY) is exchanged with an ammonium salt solution to lower the soda (Na2O) content to below about 5 percent by weight.
(2) The ammonium-exchanged zeolite (NH4NaY) is calcined in presence of 80 - 100% steam at a temperature of from 400 to 9000C.
(3) The calcined zeolite is then reacted with an acid-aluminium salt solution or aqueous NHj solution or ammonium salt solution to lower the soda content of the zeolite to below 1.5 percent by weight Na2O.
[0032] The zeolite prepared by the above procedure may be combined with an inorganic oxide matrix either after the acid-aluminium salt exchange, i.e. after step (3), or after calcination, i.e. after step (2). When the calcined zeolite of step (2) is combined with the matrix, the combined calcined zeolite/matrix mixture is treated with the acid aluminium salt solution or a silica solution.
[0033] The ammonium salt solution which is used to reduce the sodium level of the initial sodium Y zeolite is preferably ammonium sulphate or aqueous NH3 solution. However, solutions of, e.g. ammonium chloride or ammonium nitrate may be used. The ammonium salt solution typically contains from about 3 to 10 percent by weight of the salt dissolved in water. The ammonium salt-solution is contacted with the sodium Y zeolite for a period of from about 10 to 120 minutes, preferably at a temperature ranging from about 25 to 100 °C. In order to obtain the desired level of soda removal, e.g., reduction of the Na2O content to below 5 percent by weight, preferably below 3 percent by weight, the sodium Y zeolite is typically contacted with from about 1 to 3 batches of the ammonium salt solution.
[0034] After contact with the ammonium salt solution, the Na, NH+4 zeolite is heated, , at a temperature of from about 120 to 600 0C. Preferably the calcination is conducted for a period of from about 1 sec to 120 min.
[0035] The catalysts of this invention may be employed to manufacture a range of organic synthetic products and/or chemical intermediates. Generally, the catalysts are suitable for catalyzing acid catalyzed reactions between electrophilic reactant molecules, e.g., those organic compounds containing unsaturated carbon-carbon bonds, carbonyls and expoxide, and nucleophilic reactant molecules, e.g., those containing nitrogen-based functional groups, such as amines; oxygen-based functional groups, such as alcohols; and sulfur-based functional groups, such as thiols.
[0036] For example, the inventive catalyst may be used in acid-based catalysis of Michael type addition reactions. Such reactions include reactions between nucleophilic aliphatic amines and electrophilic α,β-unsaturated compounds. See for example, [ L.
Ambroise, C. Chassagnard, G. Revial, J. d'Angelo; Tetrahedron: Asymmetry 1991, 6, 407-410, R. Varala, M.M. Alam, S.R. Adapa; Synlett 2003, 5, 720-721]. Examplary aliphatic amines for use in these reactions include both cyclic and straight chain aliphatic amines, which can be primary or secondary. Aromatic compounds having nucleophilic nitrogen heteroatoms also serve as suitable nucleophiles for use with and activation by this invention. [M.M. Alam, R. Varala, S.R. Adapa; Tetrahedron Letters 2003, 44, 5115- 5119]. Unsaturated compounds suitable for use in Michael reactions include α,β- unsaturated ethylenic compounds, e.g., methyl methacrylate and acrylonitrile. [0037] Condensation reactions can also benefit from use of the solid catalyst of this invention. Examples of such reactions include, but are not limited to, reactions of phenyl diamines with unsaturated carbonyl compounds. [D.V. Jarikote, S.A. Siddiqui, R. Rajagopal, T. Daniel, R.J. Lahoti, K.V. Srinivasan; Tetrahedron Letters 2003, 44, 1835- 1838]. Condensation reactions such as acylation of amino acids with aromatic acid chlorides, cyclization of β-amino alcohols with carboxylic acids into oxazoline derivatives and synthesis of imidiazoline and benzoxazole derivatives can each be catalytically activated by the invention. [A. Hegedils, J. Vigh, Z. Hell; Synthetic Communications 2004, 4145-4152].
[0038] The invention also has suitable application in epoxide ring-opening reactions. Such reactions include alcoholysis of epoxides (as the electrophile), e.g., meso-epoxides, with nucelophiles such as alcohols, water, acetic acid, and acetone. Such ring opening reactions are frequently carried out with primary, secondary and tertiary alcohols. Epoxide ring opening reactions are also commonly used to manufacture β-amino alcohols, which is an intermediate frequently used in the pharmaceutical industry. Such compounds are prepared through nucleophilic attack of the epoxide ring by reaction with anilines and/or other nucleophilic aromatic alcohols. [T. Ollevier, G. Lavie-Compin; Tetrahedron Letters 2004, 45, 49-52, F. Carree, R. Gil, J. Collin; Organic Letters 2005, 7(6), 1023-1026].
[0039J The catalysts of this invention are also suitable for use in reactions described in US 2006/0041 171 (acylation of aromatic ethers), US 2005/0033100 (Diels Alder reactions with dienes), and US 7,074,960 (carbonyl-ene and iminoene reactions), the contents of which are incorporated herein by reference.
[0040] The invention may also be used in catalytic tetrahydropyranylation of alcohols and phenols.
[0041] The manufacture of other compounds, e.g., β-amino-ester, indol derivatives, semi- acetals, tetrahydropyrane-ether, amino-alcohols, may also be benefit from the use of the invention.
[0042] The reactions above may be run neat, in water or in organic solvents. Although use of solvents is not preferable, when using solvents with this invention, the solvents may be polar or non-polar. Examples include aromatic hydrocarbons such toluene or xylene. A suitable non-aromatic hydrocarbon is ethyl acetate. In any event, the catalyst is particularly suitable for neat reactions, thereby avoiding or reducing use of environmentally unfriendly solvents.
[0043] The catalyst of this invention may be used under conditions typically employed in the reactions described above. The reaction temperature and pressure vary depending on the reactants and desired products yields. In addition to reducing or eliminating the need for organic reaction solvents, the catalysts are more readily removed from reaction medium. Catalysts of this invention containing crystalline zeolites are thermally stable at temperatures conventionally used to remove reaction contaminants and regenerate the catalysts. Therefore, the crystalline zeolite-based embodiments of this invention make recycling of the catalysts relatively more simple and manageable.
[0044] The scope of the invention is not in any way intended to be limited by the examples set forth below. The examples are given as specific illustrations of the claimed invention. It should be understood, however, that the invention is not limited to the specific details set forth in the examples.
[0045] All parts and percentages in the examples, as well as the remainder of the specification which refers to solid compositions or concentrations, are by weight unless otherwise specified. Concentrations of gaseous mixtures are by volume unless otherwise specified.
[0046] Further, any range of numbers recited in the specification or claims, such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or
otherwise, any number falling within such range, including any subset of numbers within any range so recited.
EXAMPLES Example 1
[0047] A sodium type zeolite Y catalyst (NaY) exchanged with an ammonium salt solution to lower the soda (Na2O) content to below about 5 percent by weight was treated in an oven with 100% steam at 5400C for ninety minutes. The treated zeolite was measured for pore size using "Analysenmethode Nr. CE 46: " MESSUNG DER OBERFLACHE UND DER PORENGRόSSENVERTEILUNG MIT DEM TRISTAR 3000", dated August 17, 2005, and was shown to have the pore size distribution in Figure 1.
[0048] The treated zeolite was added as is to a reaction between an acrylic acid ester and a primary amine to produce 3-isopropylamino-proprionic acid methyl ester. Such products are intermediates used to manufacture industrially useful products. [0049] Specifically, 0.22 g [2.6mmole] of methyl aery late, 0.15g [2.6mmole] of isopropyl amine, and 260mg of the invention catalyst were combined neat and the reaction was run at room temperature for about twenty minutes. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product was weighed to measure yield. The yield and the yield reported for the reaction of the same reactants described in L. Ambroise, C. Chassagnard, G. Revial, J. d'Angelo; Tetrahedron: Asymmetry 1991, 6, 407-410 are reported in Table 1. The invention not only had a greater than 95% product yield compared to 80% for the homogenous catalyst, but also yielded product in much shorter reaction time, and with a more manageable recovery of the catalyst.
Example 2
[0050] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an acrylic acid ester and a secondary amine to produce 3-diallylamino-propionic
acid methyl ester. Such products are intermediates used to manufacture industrially useful products.
[0051] Specifically, 0.2Og [2.33mmole] of methylacrylate, 0.22g [2.33mmole] of dipropenyl amine, and 233mg of the invention were combined neat and the reaction was run at room temperature for about fifteen minutes. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product was weighed to measure yield. The yield and the yield reported for the reaction of the same reactants with a homogenous bismuth triflate catalyst described in R. Varala, M.M. Alam, S.R. Adapa; Synleit 2003, 5, 720-721 are reported in Table 1. The invention not only had a greater than 95% product yield compared to 90% for the homogenous catalyst, but also yielded product in a shorter reaction, without solvent, and with a more manageable recovery of the catalyst.
Example 3
[0052] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an unsaturated nitrile and a secondary amine to produce 3-diallylamino- proprionitrile. Such products are intermediates used to manufacture industrially useful products.
[0053] Specifically, 0.17g [3.24mmole] of acrylonitrile, 0.31 g [3.24mmole] of dipropenyl amine, and 324mg of the invention were combined neat and the reaction was run at room temperature for about fifteen minutes. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product was weighed for product yield. The product yield and the yield reported for the reaction of the same reactants with no catalyst described in N.O. Brace; J. Org. Chem. 1971, 21, 3187-3191 are reported in Table 1. The invention not only had a greater than 95% yield compared to 84% with no catalyst, but also yielded product in a shorter reaction, and with a more manageable recovery of the catalyst.
Example 4
[0054] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an acrylic acid ester and a heterocyclic amine to produce 3-[4-(2- Methoxycarbonyl-ethyl)-piperazin-l-yl]-propionic acid methyl ester. Such products are intermediates used to manufacture industrially useful products.
[0055] Specifically, 0.41g [4.8mmole] of methylacrylate, 0.21g [2.4mmole] of piperazine, and 240mg of the invention were combined neat and the reaction was run at room temperature for about fifteen minutes. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product was weighed for product yield. The yield and the yield reported for the reaction of the same reactants with a homogenous bismuth triflate catalyst described in R. Varala, M.M. Λlam, S.R. Adapa; Synlett 2003, 5, 720-721 are reported in Table 1. The invention had an equivalent product yield to that reported for this reaction using a homogenous catalyst, but yielded product in a shorter reaction, without solvent, and with a more manageable recovery of the catalyst.
Example 5
[0056] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between a α,β-unsaturated compound and an nucleophilic indole to produce 4-(lH-Indol- 3-yl)-butan-2-one. Such products are intermediates used to manufacture industrially useful products.
[00571 Specifically, 0.08g [l .Bmmole] of methyl vinyl ketone, 0,l3g [1.13mmole] of indole (2,3-benzopyrrole) and 113mg of the invention were combined neat and the reaction was run at room temperature for about four hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product was weighed for product yield. The yield and the yield reported for the reaction of the same reactants with a homogenous bismuth triflate catalyst described in M.M. Alam, R. Varala, S.R. Adapa; Tetrahedron Letters 2003, 44, 5115-51 19 are reported in Table 1. The invention had greater product yield to that reported for this reaction using a homogenous catalyst, but yielded product without solvent, and with a more manageable recovery of the catalyst.
Example 6
[0058] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between a α,β-unsaturated carbonyl compound and an nucleophilic indole to produce 4- (2-Methyl-lH-indol-3-yl)-butan-2-one. Such products are intermediates used to manufacture Industrially useful products.
[0059] Specifically, 0.29g [4.2mmole] of methyl vinyl ketone, 0.55g [4.2mmole] of 2- Methyl-indole (2,3-benzo-l -methyl- pyrrole) and 420mg of the invention were combined neat and the reaction was run at room temperature - for about four hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product yield was measured. The yield and the yield reported for the reaction of the same reactants with a homogenous bismuth triflate catalyst described in M.M. Alam, R. Varala, S.R. Adapa; Tetrahedron Letters 2003, 44, 5115-5119 are reported in Table 1. The invention had greater product yield compared to that reported for this reaction using a homogenous
catalyst, but yielded product without solvent, and with a more manageable recovery of the catalyst.
Example 7
[0060] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between a cyclic ketone compound and an aromatic diamine to produce 11- Spirocyclohexyl-2,3,4,10,11,1 la-hexahydro-lH-diberizo[b,e][l,4]diacepine. Such products are intermediates used to manufacture industrially useful products. [0061] Specifically, 1.5 ml [14.5 mmole] of cyclohexanone, 0.1 Ig - [0.97mmole] of o- phenylene diamine and 257 mg of the invention were combined neat and the reaction was run at room temperature for about seventeen hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product yield was measured. The yield and the yield reported for the reaction of the same reactants with dibutylimidazolium bromide homogenous catalyst described in D.V. Jarikote, S.A. Siddiqui, R. Rajagopal, T. Daniel, R.J. Lahoti, K. V. Srinivasan; Tetrahedron Letters 2003, 44, 1835-1838 are reported in Table 1. The invention had greater product yield compared to that reported for this reaction using a homogenous catalyst, but yielded product without solvent, and with a more manageable recovery of the catalyst.
Example 8
[0062] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an alcohol to produce (ϊrαn.s)-2-Ethoxycyclopentanol. Such products are intermediates used to manufacture industrially useful products. [0063] Specifically, 0.33g [3.91 mmole] of cyclopentene oxide, ImI [17.15 mmole] of ethanol and 391 mg of the invention were combined neat and the reaction was run at room temperature for about twelve hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product yield was measured. The yield and the yield reported for the reaction of the same reactants with iron (III) trifluroacetate homogenous catalyst described in N. Iranpoor, Η. Adibi; Bull. Chem. Soc. Jpn. 2000, 73, 675-680 are reported in Table 1. The invention had greater product yield compared to
that reported for this reaction using a homogenous catalyst, but yielded product without solvent, and with a more manageable recovery of the catalyst.
Example 9
[0064] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between a epoxyacetat compound and an alcohol to produce (£)-6-ethoxy-7-hydroxy-3,7- dimethyloct-2-enylacetate. Such products are intermediates used to manufacture industrially useful products.
[0065] Specifically, 0.49g [2.29mmole] of epoxynerylacetate, ImI [17.15 mmole] of ethanol and 229 mg of the invention were combined neat and the reaction was run at room temperature for about twelve hours. The reaction mixture was then filtered through llass frit to remove the catalyst and the product yield was measured.
Example 10
[0066] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an aromatic amine to produce _2-Phenylamino- cyclopentanol. Such products are intermediates used to manufacture industrially useful products.
[0067] Specifically, 0.44g [5.23 mmole] of cyclopentene oxide, 0.4 Ig [4.4 mmole] of aniline and 406 mg of the invention were combined in 0.3 ml of acetate and the reaction was run at room temperature for about three hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product was weight to measure yield. The yield and the yield reported for the reaction of the same reactants with bismuth triflate homogenous catalyst described in T. Ollevier, G. Lavie-Compin; Tetrahedron Letters 2004, 45, 49-52 are reported in Table 1. The invention not only had substantially greater product yield compared to that reported for this reaction using a homogenous catalyst (>95% vs 68%), but yielded product with relatively less solvent, and with a more manageable recovery of the catalyst.
Example 11
[0068J Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an aromatic amine to produce 2-Phenylamino- cyclohexanol. Such products are intermediates used to manufacture industrially useful products.
[0069] Specifically, 0.43g [4.4 romole] of cyclohexene oxide, 0.34 g [3.6 mmole] of aniline and 338 mg of the invention were combined in 0.3 ml of water and the reaction was run at room temperature for about three hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product yield was measured by scale. The yield and the yield reported for the reaction of the same reactants with bismuth triflate homogenous catalyst described in T. OUevier, G. Lavie-Compin; Tetrahedron Letters 2004, 45, 49-52 are reported in Table 1. The invention not only had greater product yield compared to that reported for this reaction using a homogenous catalyst (>95% vs 68%), but yielded product with relatively less solvent, and with a more manageable recovery of the catalyst.
Example 12
[0070] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an aromatic amine to produce 2-(4- Methoxyphenylamino)-cyclopentanol. Such products are intermediates used to manufacture industrially useful products.
[0071] Specifically, 0.22g [2.6 mmole] of cyclopentene oxide, 0.27 g [2.2 mmole] of para-methoxy aniline and 270 mg of the invention were combined in 0.3 ml of water and the reaction was run at room temperature for about three hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product yield was measured by scale. The yield and the yield reported for the reaction of the same reactants with a Lanthanide iodo binaphtholates catalyst described in F. Carree, R. Gil, J. Collin; Organic Letters 2005, 7(6), 1023-1026 are reported in Table 1. The invention had a
greater product yield compared to that reported for this reaction using the reported zeolite catalyst (88% vs 77%), but yielded product with relatively less solvent.
Example 13
[0072] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between an epoxide compound and an aromatic amine to produce 2-(4- Methoxyphenylamino)-cyclopentanol. Such products are intermediates used to manufacture industrially useful products.
[0073] Specifically, 0.37g [3.8 mmole] of cyclohexene oxide, 0.39 g 3.2mmole] oϊpara- methoxy aniline and 393 mg of the invention were combined in 0.3 ml [??] of water and the reaction was run at room temperature for about three hours. The reaction mixture was then filtered through a glass frit to remove- the catalyst and the product yield was measured by scale. The yield and the yield reported for the reaction of the same reactants with bismuth triflate homogenous catalyst described in T. Ollevier, G. Lavie-Compin; Tetrahedron Letters 2004, 45, 49-52 are reported in Table 1. The invention not only had greater product yield compared to that reported for this reaction using a homogenous catalyst, but yielded product with relatively less solvent, and with a more manageable recovery of the catalyst.
Example 14
[0074] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between 3,4-Dihydro-2H-pyran and a phenol to produce 2-(2-Bromo-phenoxy)- tetrahydropyran. Such products are intermediates used to manufacture industrially useful products.
[0075] Specifically, 1.68g [20 mmole] of 3,4-Dihydro-2H-pyran, 1.73g [10 mmole] of o- bromophenol and 650 mg of the invention were combined neat and the reaction was run at room temperature for about four hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product yield was measured by scale. The yield and the yield reported for the reaction of the same reactants with TFA homogenous
catalyst described in F.-W. Ulrich, E. Breitmaier; Synthesis 1987, 951-953 are reported in Table 1. The invention had less product yield compared to that reported for this reaction using a homogenous catalyst (88% vs 89%), but yielded product without solvent, DHP also as solvent], and with a more manageable recovery of the catalyst.
Example 15
[0076] Zeolite Y catalyst prepared according to Example 1 was added as is to a reaction between 3,4-Dihydro-2H-pyran and an aliphatic alcohol to produce 2-Dodecyloxy- tetrahydro-pyran. Such products are intermediates used to manufacture industrially useful products.
[0077] Specifically, 1.49g [I7.7mmole] of 3,4-Dihydro-2H-pyran , 0.93g [5 mmole] of Dodecanol and 477 mg of the.inyention were combined neat and the reaction was run at room temperature for about four hours. The reaction mixture was then filtered through a glass frit to remove the catalyst and the product yield was measured by scale. The yield and the yield reported foτ the reaction of the same reactants with a zeolite based heterogeneous catalyst described in A. Ηegedϋs, J. Vigh, Z. Hell; Synthetic Communications 2004, 4145-4152 are reported in Table 1. The invention had greater product yield compared to that reported for this reaction using a prior art solid catalyst. The invention also had greater product yield utilizing less amount of catalyst.
Claims
1. Process for synthesizing organic molecules, the process comprising
(a) combining a nucleophile reactant and electrophile reactant subject to reaction with a nucleophilic compound,
(b) introducing a solid acid catalyst to the combination in (a) wherein the solid acid catalyst comprises a pore size distribution having at least two different modes,
(c) conducting a reaction between nucleophile and organic electrophile, and
(d) recovering organic molecules as a product from the reaction in (c) and separating the solid acid catalyst.
2. A process according to claim 1, wherein the electrophile comprises a functional group selected from the group consisting of carbonyls, epoxide and unsaturated carbon-carbon bonds.
3. A process according to claim 1, wherein the nucleophile comprises a functional group selected from the group consisting of amine, alcohol, and thiol.
4. A process according to claim 1 wherein the solid acid catalyst comprises crystalline compounds.
5. A process according to claim 4 wherein the solid acid catalyst comprises crystalline zeolite.
6. A process according to claim 5 wherein the crystalline zeolite is a member of the group consisting of USY zeolite, beta zeolite, and ZSM5.
7. A process according to claim 5 wherein the crystalline zeolite is USY zeolite.
8. A process according to claim 1 wherein a peak maximum pore size of each of the at least two different modes is in the range of 20 to 600 Angstroms.
9. A process according to claim 1 wherein the peak maximum pore size of each of the at least different pore size modes is in the range of 20 to 200 Angstroms.
10. A process according to claim 1 wherein the peak maximum pore size of at least one of the at least two different pore size modes is in the range of 50 to 200 Angstroms.
11. A catalyst comprising crystalline acid zeolite having a pore size distribution of at least two different modes, the peak maximum pore size of the at least two different modes being in the range of 20 to 600 Angstroms, wherein the at least two of the different pore modes are present in the crystalline zeolite structure.
12. A catalyst according to claim 11, wherein the crystalline zeolite is selected from the group consisting of Y zeolite, beta zeolite, and ZSM5.
13. A catalyst according to claim 11 wherein the crystalline zeolite consists essentially of USY zeolite.
14. A catalyst according to claim 11 wherein the peak maximum pore sizes of each of the at least two different modes is in of the range of 20 to 200 Angstroms.
15. A catalyst according to claim 11 wherein the peak maximum pore size of at least one of the at least two different modes is in of the range of 50 to 200 Angstroms.
16. A catalyst according to claim 11 wherein the crystalline zeolite has been treated with steam.
17. A catalyst according to claim 11 wherein the crystalline zeolite is selected from the group consisting of USY zeolite, beta zeolite, and ZSM5.
18. A catalyst according to claim U wherein the crystalline zeolite consists essentially of USY zeolite.
19. A catalyst according to claim 14, wherein the crystalline zeolite is selected from the group consisting of Y zeolite, beta zeolite, and ZSM5.
20. A catalyst according to claim 15, wherein the crystalline zeolite is selected from the group consisting of Y zeolite, beta zeolite, and ZSM5.
21. A catalyst according to claim 14 wherein the crystalline zeolite consists essentially of USY zeolite.
22. A catalyst according to claim 15 wherein the crystalline zeolite consists essentially of USY zeolite.
23. A catalyst according to claim 11 wherein the crystalline zeolite comprises USY zeolite, and the peak maximum pore size of at least one of the at least two different modes is in of the range of 50 to 200 Angstroms.
24. A method for manufacturing a solid acid catalyst, the method comprising
(a) selecting a crystalline acid zeolite having a pore size distribution in the range of 4 to 10 Angstroms,
(b) subjecting the crystalline acid zeolite to steam under conditions sufficient to create at least two modes of pore size distribution each having a peak maximum pore size in the range of 20 to 600 Angstroms, and (c) recovering a crystalline acid zeolite having at least two different pore size modes, wherein the peak maximum pore size for the at least two different modes is in the range of 20 to 600 Angstroms.
25. A method according to claim 24 wherein the crystalline acid zeolite is selected from the group consisting of USY zeolite, beta zeolite, and ZSM5.
26. A method according to claim 24 wherein the crystalline acid zeolite is subject to 80 to 100% steam at a temperature in the range of 350 to 9000C for a time period in the range of ten minutes up to twenty hours.
27. A method according to claim 24 wherein the recovered crystalline acid zeolite of (c) has at least two different modes of pore sizes, each mode having a peak maximum pore size in of the range of 20 to 200 Angstroms.
28. A method according to claim 24 wherein the peak maximum pore size of at least one of the at least two different pore size modes of the recovered crystalline acid zeolite in (c) is in of the range of 50 to 200 Angstroms.
29. A method according to claim 24 wherein the crystalline acid zeolite selected in (a) comprises USY zeolite, and the peak maximum pore size of at least one of the at least two different pore size modes for the crystalline acid zeolite recovered in (c) is in of the range of 50 to 200 Angstroms.
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WO2010033202A1 (en) * | 2008-09-18 | 2010-03-25 | Exxonmobil Research And Engineering Company | Extra mesoporous y zeolite |
WO2010072976A1 (en) * | 2008-12-22 | 2010-07-01 | Total Raffinage Marketing | Modified y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof |
WO2011112644A1 (en) * | 2010-03-11 | 2011-09-15 | Exxonmobil Research And Engineering Company | Low small mesoporous peak cracking catalyst and method of using |
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US9242234B2 (en) | 2008-12-22 | 2016-01-26 | Centre National De La Recherche Scientifique | Modified Y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof |
CN106517233A (en) * | 2016-10-25 | 2017-03-22 | 浙江大学 | Method for synthesizing B body-enriched Beta zeolite molecular sieve by fluoride-free solvent-free route |
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WO2010033202A1 (en) * | 2008-09-18 | 2010-03-25 | Exxonmobil Research And Engineering Company | Extra mesoporous y zeolite |
JP2012502876A (en) * | 2008-09-18 | 2012-02-02 | 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 | Super mesoporous Y zeolite |
US8361434B2 (en) | 2008-09-18 | 2013-01-29 | Exxonmobil Research And Engineering Company | Extra mesoporous Y zeolite |
US8932454B2 (en) | 2008-09-18 | 2015-01-13 | Exxonmobile Research And Engineering Co. | Mesoporous Y hydrocracking catalyst and associated hydrocracking processes |
WO2010072976A1 (en) * | 2008-12-22 | 2010-07-01 | Total Raffinage Marketing | Modified y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof |
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US9242234B2 (en) | 2008-12-22 | 2016-01-26 | Centre National De La Recherche Scientifique | Modified Y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof |
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WO2011112644A1 (en) * | 2010-03-11 | 2011-09-15 | Exxonmobil Research And Engineering Company | Low small mesoporous peak cracking catalyst and method of using |
US8715487B2 (en) | 2010-03-11 | 2014-05-06 | Exxonmobil Research And Engineering Company | Low small mesoporous peak cracking catalyst and method of using |
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