US20080146825A1 - Direct epoxidation catalyst - Google Patents
Direct epoxidation catalyst Download PDFInfo
- Publication number
- US20080146825A1 US20080146825A1 US11/641,271 US64127106A US2008146825A1 US 20080146825 A1 US20080146825 A1 US 20080146825A1 US 64127106 A US64127106 A US 64127106A US 2008146825 A1 US2008146825 A1 US 2008146825A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- diatomaceous earth
- palladium
- zeolite
- gold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000005909 Kieselgur Substances 0.000 claims abstract description 32
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 claims abstract description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 150000003624 transition metals Chemical class 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 34
- 239000010931 gold Substances 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 21
- 229910052737 gold Inorganic materials 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000872 buffer Substances 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 10
- 239000007787 solid Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 13
- -1 titanium silicates Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229940080262 sodium tetrachloroaurate Drugs 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical class COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical class COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005112 continuous flow technique Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 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
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000011514 vinification Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B01J35/19—
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- B01J35/40—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
Definitions
- the invention relates to a catalyst comprising a noble metal supported on a diatomaceous earth and a transition metal zeolite.
- the catalyst is used to produce an epoxide by reacting an olefin, hydrogen, and oxygen.
- the reaction may be performed in the presence of a catalyst comprising gold and a titanium-containing support (see, e.g., U.S. Pat. Nos. 5,623,090, 6,362,349, and 6,646,142), or a catalyst containing palladium and a titanium zeolite (see, e.g., JP 4-352771).
- a catalyst comprising gold and a titanium-containing support
- a catalyst containing palladium and a titanium zeolite see, e.g., JP 4-352771.
- Example 13 of JP 4-352771 describes the use of a mixture of titanosilicate and Pd-on-carbon for propylene epoxidation.
- U.S. Pat. No. 6,008,388 describes a catalyst comprising a noble metal and a titanium or vanadium zeolite, but additionally teaches that the Pd can be incorporated into a support before mixing with the zeolite.
- the catalyst supports disclosed include silica, alumina, and activated carbon.
- U.S. Pat. No. 6,498,259 discloses the epoxidation of an olefin with hydrogen and oxygen in a solvent containing a buffer in the presence of a catalyst mixture containing a titanium zeolite and a noble metal catalyst.
- liquid and/or gas product streams need to be separated from the solid catalyst particles.
- titanium zeolites and the supported noble metal catalyst into large enough particles (e.g., >1 ⁇ m) to make such separation (e.g., filtration) practically viable.
- the invention is a catalyst comprising a noble metal supported on a diatomaceous earth and a transition metal zeolite.
- the catalyst is used in an epoxidation process comprising reacting an olefin, hydrogen, and oxygen.
- Diatomaceous earth is readily available and can be easily separated from a liquid and/or gas effluent.
- the invention is a catalyst comprising a transition metal zeolite.
- Zeolites are microporous crystalline solids with well-defined structures. Generally they contain one or more of Si, Ge, Al, B, P, or the like, in addition to oxygen. Many zeolites occur naturally as minerals and are extensively mined in many parts of the world. Others are synthetic and are made commercially for specific uses. Zeolites have the ability to act as catalysts for chemical reactions which take place mostly within the internal cavities of the zeolites.
- Transition metal zeolites are zeolites comprising transition metals in framework. A transition metal is a Group 3-12 element. The first row of them are from Sc to Zn. Preferred transition metals are Ti, V, Mn, Fe, Co, Cr, Zr, Nb, Mo, and W. More preferred are Ti, V, Mo, and W. Most preferred is Ti.
- Preferred titanium zeolites are titanium silicates (titanosilicates). Preferably, they contain no element other than titanium, silicon, and oxygen in the lattice framework (see R. Szostak, “Non-aluminosilicate Molecular Sieves,” in Molecular Sieves: Principles of Synthesis and Identification (1989), Van Nostrand Reinhold, pp. 205-82). Small amounts of impurities, e.g., boron, iron, aluminum, phosphorous, copper, and the like, and mixtures thereof, may be present in the lattice. The amount of impurities is preferably less than 0.5 wt. %, more preferably less than 0.1 wt. %.
- Preferred titanium silicates will generally have a composition corresponding to the following empirical formula: xTiO 2 ⁇ (1—x)SiO 2 , where x is between 0.0001 and 0.5000. More preferably, the value of x is from 0.01 to 0.125.
- the molar ratio of Si to Ti in the lattice framework of the zeolite is advantageously from 9.5:1 to 99:1, most preferably from 9.5:1 to 60:1.
- Particularly preferred titanium zeolites are titanium silicalites (see Catal. Rev .- Sci. Eng., 39(3) (1997) 209).
- TS-1 titanium silicalite-1, a titanium silicalite having an MFI topology analogous to that of the ZSM-5 aluminosilicate
- TS-2 having an MEL topology analogous to that of the ZSM-11 aluminosilicate
- TS-3 as described in Belgian Pat. No. 1,001,038.
- Titanium zeolites having framework structures isomorphous to zeolite beta, mordenite, and ZSM-12 are also suitable for use. The most preferred is TS-1.
- the catalyst comprises a noble metal.
- Suitable noble metals include gold, silver, platinum, palladium, iridium, ruthenium, osmium, rhenium, rhodium, and mixtures thereof.
- Preferred noble metals are Pd, Pt, Au, Re, Ag, and mixtures thereof. Palladium, gold, and their mixtures are particularly desirable.
- the amount of noble metal present in the catalyst will be in the range of from 0.01 to 20 wt. %, preferably 0.1 to 5 wt. %.
- the catalyst comprises a diatomaceous earth.
- Diatomaceous earth also known as kieselguhr, or diatomite, is a naturally occurring, highly structured, fine hydrous silica powder made up of the remains of planktonic algae. Many different types of diatomaceous earth are available commercially. Diatomaceous earth is used in many applications as the uniquely porous nature of each particle gives diatomite high surface area, low bulk density, high permeability, high water absorption, and low abrasion. Diatomaceous earth filter aids are used to prevent blinding of filter elements and are used to clarify liquids in brewing, water treatment, wine making, sugar refining, fruit juice production, and in industrial chemicals processing.
- Diatomaceous earth functional fillers are used in paints, rubber, plastics, pharmaceuticals, toothpastes, polishes, and chemicals where performance is improved by the unique properties of diatomaceous earth.
- Diatomaceous earth can also be used as catalyst support. See Kenneth R. Engh, “Diatomite,” Kirk - Othmer Encyclopedia of Chemical Technology online edition, 2006. See also U.S. Pat. Nos. 4,297,241, 4,285,927, and 6,746,597
- Diatomaceous earth gives many advantages as a catalyst or a catalyst support.
- diatomaceous earth is easy to filter. When a solid catalyst is used in a slurry reaction, it is usually necessary to separate the catalyst from a liquid and/or gas reaction effluent. In a continuous slurry reaction, a liquid and/or gas effluent needs to be continuously withdrawn from the reactor. In either case, the ease of filtration improves the operation.
- commercially available diatomaceous earth materials can be used in slurry reactions without the need of particle enlargement. For example, diatomaceous earth materials available from EaglePicher Filtration & Minerals, Inc.
- the noble metal is supported on the diatomaceous earth.
- the manner in which the noble metal is incorporated in a diatomaceous earth is not critical.
- the noble metal may be supported on the diatomaceous earth by impregnation, ion-exchange, adsorption, precipitation, or the like.
- Suitable compounds include nitrates, sulfates, halides (e.g., chlorides, bromides), carboxylates (e.g., acetate), and amine or phosphine complexes of noble metals (e.g., palladium(II) tetraammine bromide, tetrakis(triphenylphosphine) palladium(0)).
- halides e.g., chlorides, bromides
- carboxylates e.g., acetate
- amine or phosphine complexes of noble metals e.g., palladium(II) tetraammine bromide, tetrakis(triphenylphosphine) palladium(0).
- the oxidation state of the noble metal is not critical. Palladium, for instance, may be in an oxidation state anywhere from 0 to +4 or any combination of such oxidation states. To achieve the desired oxidation state or combination of oxidation states, the noble metal compound after being introduced on the diatomaceous earth may be fully or partially pre-reduced. Satisfactory catalytic performance can, however, be attained without any pre-reduction.
- the weight ratio of the transition metal zeolite to noble metal is not particularly critical. However, a transition metal zeolite to noble metal weight ratio of from 10:1 to 5000:1 (grams of transition metal zeolite per gram of noble metal) is preferred.
- the catalyst may comprise a promoter.
- a promoter helps to improve the catalyst performance (e.g., activity, selectivity, life of the catalyst).
- Preferred promoters include lead, zinc, alkaline earth metals, lanthanide metals, and the like. Lead is particularly preferred.
- the promoter may be added on the transition metal zeolite and/or the diatomaceous earth. Preferably it is added to the diatomaceous earth. While the choice of compound used as the promoter source is not critical, suitable compounds include metal carboxylates. (e.g., acetate), halides (e.g., chlorides, bromides, iodides), nitrates, sulfate, and the like.
- the typical amount of promoter metal present in the catalyst will be in the range of from about 0.001 to 5 weight percent, preferably 0.001 to 2 weight percent relative to the catalyst.
- the diatomaceous earth has preferably a mass median particle size in the range of 1 to 200 ⁇ m, more preferably in the range of 10 to 100 ⁇ m.
- the mass median particle diameter is the diameter that divides half of the mass (“Particle Size Measurement,” Kirk - Othmer Encyclopedia of Chemical Technology online edition, 2006).
- the invention also includes an epoxidation process comprising reacting an olefin, hydrogen, and oxygen in the presence of the catalyst of the invention.
- Suitable olefins include any olefin having at least one carbon-carbon double bond, and generally from 2 to 60 carbon atoms.
- the olefin is an acyclic alkene of from 2 to 30 carbon atoms; the process is particularly suitable for epoxidizing C 2 -C 6 olefins. More than one double bond may be present in the olefin molecule, as in a diene or triene.
- the olefin may be a hydrocarbon or may contain functional groups such as halogen, carboxyl, hydroxyl, ether, carbonyl, cyano, or nitro groups, or the like.
- the olefin is propylene and the epoxide is propylene oxide.
- Oxygen and hydrogen are required. Although any sources of oxygen and hydrogen are suitable, molecular oxygen and molecular hydrogen are preferred.
- the molar ratio of oxygen to olefin is usually 1:1 to 1:20, and preferably 1:1.5 to 1:10. Relatively high oxygen to olefin molar ratios (e.g., 1:1 to 1:3) may be advantageous for certain olefins.
- an inert gas is preferably used in the process. Any desired inert gas can be used. Suitable inert gases include nitrogen, helium, argon, and carbon dioxide. Saturated hydrocarbons with 1-8, especially 1-6, and preferably 1-4 carbon atoms, e.g., methane, ethane, propane, and n-butane, are also suitable. Nitrogen and saturated C 1 -C 4 hydrocarbons are preferred inert gases. Mixtures of inert gases can also be used. The molar ratio of olefin to gas is usually in the range of 100:1 to 1:10 and especially 20:1 to 1:10.
- the process may be performed in a continuous flow, semi-batch, or batch mode.
- a continuous flow process is preferred.
- the catalyst is preferably in a slurry or a fixed bed.
- the catalyst is preferably formed into extrudates, tablets, granules, and the like.
- the process is carried out at a temperature effective to achieve the desired olefin epoxidation, preferably at temperatures in the range of 0-200° C., more preferably, 20-150° C.
- a portion of the reaction mixture is a liquid under the reaction conditions.
- a reaction solvent is preferably used in the process.
- Suitable reaction solvents are liquid under the reaction conditions. They include, for example, oxygen-containing hydrocarbons such as alcohols, aromatic and aliphatic solvents such as toluene and hexane, nitriles such as acetonitrile, carbon dioxide, and water.
- Suitable oxygenated solvents include alcohols, ethers, esters, ketones, carbon dioxide, water, and the like, and mixtures thereof.
- Preferred oxygenated solvents include water and lower aliphatic C 1 -C 4 alcohols such as methanol, ethanol, isopropanol, tert-butanol, and mixtures thereof. Fluorinated alcohols can be used.
- a buffer is employed in the reaction to inhibit the formation of glycols or glycol ethers during the epoxidation, and it can improve the reaction rate and selectivities.
- the buffer is typically added to the solvent to form a buffer solution, or the solvent and the buffer are added separately.
- Useful buffers include any suitable salts of oxyacids, the nature and proportions of which in the mixture are such that the pH of their solutions preferably ranges from 3 to 12, more preferably from 4 to 10, and most preferably from 5 to 9.
- Suitable salts of oxyacids contain an anion and a cation.
- the anion may include phosphate, carbonate, bicarbonate, sulfate, carboxylates (e.g., acetate), borate, hydroxide, silicate, aluminosilicate, or the like.
- the cation may include ammonium, alkylammonium (e.g., tetraalkylammoniums, pyridiniums), alkylphosphonium, alkali metal, and alkaline earth metal ions, or the like. Examples include NH 4 , NBu 4 , NMe 4 , Li, Na, K, Cs, Mg, and Ca cations.
- the preferred buffer comprises an anion selected from the group consisting of phosphate, carbonate, bicarbonate, sulfate, hydroxide, and acetate; and a cation selected from the group consisting of ammonium, alkylammonium, alkylphosphonium, alkali metal, and alkaline earth metal ions.
- Buffers may preferably contain a combination of more than one suitable salt. Typically, the concentration of the buffer in the solvent is from 0.0001 M to 1 M, preferably from 0.0005 M to 0.3 M.
- Diatomaceous earth FN-1 (EaglePicher Filtration and Minerals, Inc., 30 g) is added to a solution made from deionized water (120 g), aqueous sodium tetrachloroaurate solution (20.74 wt. % gold, 0.795 g), and disodium tetrachloropalladate (from Aldrich Chemical, 0.825 g).
- Sodium bicarbonate powder is added to the slurry until the pH reaches 7.24. The slurry is allowed to react for 4 h at 50° C., then filtered. The solid is washed with deionized water (7 ⁇ 80 g). The solid is then calcined in air at 110° C.
- the calcined solid is then transferred to a quartz tube and treated with a gas containing 4 vol. % hydrogen in nitrogen at 100° C. for 1 h (flow rate 100 mL/h) and then purged with nitrogen for 1 h.
- the final solid (Catalyst A) contains 1.0 wt. % palladium and 0.44 wt. % gold.
- Example 2 The procedure of Example 1 is repeated except that the solid is calcined at 550° C. before hydrogen reduction.
- the solid obtained (Catalyst B) contains 1.0 wt. % palladium and 0.44 wt. % gold.
- Example 1 The procedure of Example 1 is repeated except that the solid is calcined at 650° C. before hydrogen reduction.
- the solid obtained (Catalyst C) contains 1.0 wt. % palladium and 0.44 wt. % gold.
- Example 1 The procedure of Example 1 is repeated except that diatomaceous earth FP-3 (EaglePicher Filtration and Minerals, Inc., 30 g) is used instead of FN-1.
- the solid obtained (Catalyst D) contains 0.75 wt. % palladium and 0.35 wt. % gold.
- Example 4 The procedure of Example 4 is repeated except that the solid is calcined at 550° C. before hydrogen reduction.
- the solid obtained (Catalyst E) contains 0.75 wt. % palladium and 0.35 wt. % gold.
- Example 1 The procedure of Example 1 is repeated except that diatomaceous earth FW-14 (EaglePicher Filtration and Minerals, Inc., 30 g) is used instead of FN-1.
- the solid obtained (Catalyst F) contains 0.81 wt. % palladium and 0.33 wt. % gold.
- a spray-dried anatase (average diameter 35 ⁇ m, air calcined at 700° C. for 4 h, surface area 40 m 2 /g, 20 g) is added to a solution made from deionized water (80 g), an aqueous sodium tetrachloroaurate solution (20.74 wt. % gold, 0.53 g), and disodium tetrachloropalladate (19.75 wt. % Pd, 1.01 g).
- Sodium bicarbonate powder is added to the slurry until the pH reaches 7.24. The slurry is allowed to react for 4 h at 50° C., then filtered. The solid is washed with deionized water (7 ⁇ 80 g).
- the solid is then calcined in air at 110° C. for 4 h (at a rate of 10° C./min from room temperature to 110° C.) and at 550° C. for 4 h (at a rate of 2° C./min from 110° C. to 550° C.).
- the calcined solid is transferred to a quartz tube and treated with a gas containing 4 vol. % hydrogen in nitrogen at 100° C. for 1 h (flow rate 100 mL/h) and then purged with nitrogen for 1 h.
- the final solid (Catalyst G) contains 1.0 wt. % palladium and 0.42 wt. % gold.
- Titanium silicalite-1 (TS-1) is prepared by following procedures disclosed in U.S. Pat. Nos. 4,410,501 and 4,833,260, and calcined in air at 550° C.
- ammonium phosphate buffer solution (0.1 M, pH 6) is prepared as follows. Ammonium dihydrogen phosphate (11.5 g) is dissolved in deionized water (900 g). Aqueous ammonium hydroxide (30 wt. % NH 4 OH) is added to the solution until the pH reads 6 via a pH meter. The volume of the solution is then increased to exactly 1000 mL with additional deionized water.
- a 300-mL stainless steel reactor is charged with Catalyst A (0.07 g), TS-1 powder (0.63 g), the buffer solution prepared above (13 g), and methanol (100 g).
- the reactor is then charged to 300 psig with a feed gas consisting of 2 volume percent (vol. %) hydrogen, 4 vol. % oxygen, 5 vol. % propylene, 0.5 vol. % methane, and the balance nitrogen.
- the pressure in the reactor is maintained at 300 psig via a back pressure regulator with the feed gases pass continuously through the reactor at 1600 mL/min (measured at 23° C. and 1 atmosphere pressure).
- the oxygen, nitrogen and propylene feeds are passed through a 2-L stainless steel vessel (saturator) preceding the reactor containing 1.5 L of methanol.
- the reaction mixture is heated to 60° C. while it is stirred at 1500 rpm.
- the gaseous effluent is analyzed by an online gas chromatograph (GC) every hour.
- the liquid is analyzed by offline GC at the end of the 18 h run.
- the products formed include propylene oxide (PO), propane, and derivatives of propylene oxide such as propylene glycol, propylene glycol monomethyl ethers, dipropylene glycol, and dipropylene glycol methyl ethers.
- the calculated results are shown in Table 1.
- the catalyst productivity is defined as the grams of PO formed (including PO which is subsequently reacted to form PO derivatives) per gram of catalyst per hour.
- POE (mole) moles of PO+moles of PO units in the PO derivatives.
- PO/POE (moles of PO)/(moles of POE) ⁇ 100.
- Propylene to POE selectivity (moles of POE)/(moles of propane formed+moles of POE) ⁇ 100.
- Example 8 The procedure of Example 8 is repeated except that Catalysts B, C, D, E, F, G are used respectively instead of Catalyst A. Results are shown in Table 1.
Abstract
Description
- The invention relates to a catalyst comprising a noble metal supported on a diatomaceous earth and a transition metal zeolite. The catalyst is used to produce an epoxide by reacting an olefin, hydrogen, and oxygen.
- Direct epoxidation of higher olefins (containing three or more carbons) such as propylene with oxygen and hydrogen has been the focus of recent efforts. For example, the reaction may be performed in the presence of a catalyst comprising gold and a titanium-containing support (see, e.g., U.S. Pat. Nos. 5,623,090, 6,362,349, and 6,646,142), or a catalyst containing palladium and a titanium zeolite (see, e.g., JP 4-352771).
- Mixed catalyst systems for olefin epoxidation with hydrogen and oxygen have also been disclosed. For example, Example 13 of JP 4-352771 describes the use of a mixture of titanosilicate and Pd-on-carbon for propylene epoxidation. U.S. Pat. No. 6,008,388 describes a catalyst comprising a noble metal and a titanium or vanadium zeolite, but additionally teaches that the Pd can be incorporated into a support before mixing with the zeolite. The catalyst supports disclosed include silica, alumina, and activated carbon. U.S. Pat. No. 6,498,259 discloses the epoxidation of an olefin with hydrogen and oxygen in a solvent containing a buffer in the presence of a catalyst mixture containing a titanium zeolite and a noble metal catalyst.
- In a slurry epoxidation process using the mixed catalyst systems, liquid and/or gas product streams need to be separated from the solid catalyst particles. Generally it is necessary to make titanium zeolites and the supported noble metal catalyst into large enough particles (e.g., >1 μm) to make such separation (e.g., filtration) practically viable.
- The invention is a catalyst comprising a noble metal supported on a diatomaceous earth and a transition metal zeolite. The catalyst is used in an epoxidation process comprising reacting an olefin, hydrogen, and oxygen. Diatomaceous earth is readily available and can be easily separated from a liquid and/or gas effluent.
- The invention is a catalyst comprising a transition metal zeolite. Zeolites are microporous crystalline solids with well-defined structures. Generally they contain one or more of Si, Ge, Al, B, P, or the like, in addition to oxygen. Many zeolites occur naturally as minerals and are extensively mined in many parts of the world. Others are synthetic and are made commercially for specific uses. Zeolites have the ability to act as catalysts for chemical reactions which take place mostly within the internal cavities of the zeolites. Transition metal zeolites are zeolites comprising transition metals in framework. A transition metal is a Group 3-12 element. The first row of them are from Sc to Zn. Preferred transition metals are Ti, V, Mn, Fe, Co, Cr, Zr, Nb, Mo, and W. More preferred are Ti, V, Mo, and W. Most preferred is Ti.
- Preferred titanium zeolites are titanium silicates (titanosilicates). Preferably, they contain no element other than titanium, silicon, and oxygen in the lattice framework (see R. Szostak, “Non-aluminosilicate Molecular Sieves,” in Molecular Sieves: Principles of Synthesis and Identification (1989), Van Nostrand Reinhold, pp. 205-82). Small amounts of impurities, e.g., boron, iron, aluminum, phosphorous, copper, and the like, and mixtures thereof, may be present in the lattice. The amount of impurities is preferably less than 0.5 wt. %, more preferably less than 0.1 wt. %. Preferred titanium silicates will generally have a composition corresponding to the following empirical formula: xTiO2·(1—x)SiO2, where x is between 0.0001 and 0.5000. More preferably, the value of x is from 0.01 to 0.125. The molar ratio of Si to Ti in the lattice framework of the zeolite is advantageously from 9.5:1 to 99:1, most preferably from 9.5:1 to 60:1. Particularly preferred titanium zeolites are titanium silicalites (see Catal. Rev.-Sci. Eng., 39(3) (1997) 209). Examples of these include TS-1 (titanium silicalite-1, a titanium silicalite having an MFI topology analogous to that of the ZSM-5 aluminosilicate), TS-2 (having an MEL topology analogous to that of the ZSM-11 aluminosilicate), and TS-3 (as described in Belgian Pat. No. 1,001,038). Titanium zeolites having framework structures isomorphous to zeolite beta, mordenite, and ZSM-12 are also suitable for use. The most preferred is TS-1.
- The catalyst comprises a noble metal. Suitable noble metals include gold, silver, platinum, palladium, iridium, ruthenium, osmium, rhenium, rhodium, and mixtures thereof. Preferred noble metals are Pd, Pt, Au, Re, Ag, and mixtures thereof. Palladium, gold, and their mixtures are particularly desirable. Typically, the amount of noble metal present in the catalyst will be in the range of from 0.01 to 20 wt. %, preferably 0.1 to 5 wt. %.
- The catalyst comprises a diatomaceous earth. Diatomaceous earth, also known as kieselguhr, or diatomite, is a naturally occurring, highly structured, fine hydrous silica powder made up of the remains of planktonic algae. Many different types of diatomaceous earth are available commercially. Diatomaceous earth is used in many applications as the uniquely porous nature of each particle gives diatomite high surface area, low bulk density, high permeability, high water absorption, and low abrasion. Diatomaceous earth filter aids are used to prevent blinding of filter elements and are used to clarify liquids in brewing, water treatment, wine making, sugar refining, fruit juice production, and in industrial chemicals processing. Diatomaceous earth functional fillers are used in paints, rubber, plastics, pharmaceuticals, toothpastes, polishes, and chemicals where performance is improved by the unique properties of diatomaceous earth. Diatomaceous earth can also be used as catalyst support. See Kenneth R. Engh, “Diatomite,” Kirk-Othmer Encyclopedia of Chemical Technology online edition, 2006. See also U.S. Pat. Nos. 4,297,241, 4,285,927, and 6,746,597
- Diatomaceous earth gives many advantages as a catalyst or a catalyst support. First, diatomaceous earth is easy to filter. When a solid catalyst is used in a slurry reaction, it is usually necessary to separate the catalyst from a liquid and/or gas reaction effluent. In a continuous slurry reaction, a liquid and/or gas effluent needs to be continuously withdrawn from the reactor. In either case, the ease of filtration improves the operation. Second, commercially available diatomaceous earth materials can be used in slurry reactions without the need of particle enlargement. For example, diatomaceous earth materials available from EaglePicher Filtration & Minerals, Inc. have median particle sizes of 10-80 μm (Technical Data Sheet, http://www.eaglepicher.com). In comparison, other catalyst supports (e.g., silica, alumina, and titania) would generally need to be processed (e.g., spray-dried) to obtain particles of such sizes.
- The noble metal is supported on the diatomaceous earth. The manner in which the noble metal is incorporated in a diatomaceous earth is not critical. For example, the noble metal may be supported on the diatomaceous earth by impregnation, ion-exchange, adsorption, precipitation, or the like.
- There are no particular restrictions regarding the choice of the noble metal compound or complex used as the source of the noble metal. Suitable compounds include nitrates, sulfates, halides (e.g., chlorides, bromides), carboxylates (e.g., acetate), and amine or phosphine complexes of noble metals (e.g., palladium(II) tetraammine bromide, tetrakis(triphenylphosphine) palladium(0)).
- Similarly, the oxidation state of the noble metal is not critical. Palladium, for instance, may be in an oxidation state anywhere from 0 to +4 or any combination of such oxidation states. To achieve the desired oxidation state or combination of oxidation states, the noble metal compound after being introduced on the diatomaceous earth may be fully or partially pre-reduced. Satisfactory catalytic performance can, however, be attained without any pre-reduction.
- The weight ratio of the transition metal zeolite to noble metal is not particularly critical. However, a transition metal zeolite to noble metal weight ratio of from 10:1 to 5000:1 (grams of transition metal zeolite per gram of noble metal) is preferred.
- The catalyst may comprise a promoter. A promoter helps to improve the catalyst performance (e.g., activity, selectivity, life of the catalyst). Preferred promoters include lead, zinc, alkaline earth metals, lanthanide metals, and the like. Lead is particularly preferred. The promoter may be added on the transition metal zeolite and/or the diatomaceous earth. Preferably it is added to the diatomaceous earth. While the choice of compound used as the promoter source is not critical, suitable compounds include metal carboxylates. (e.g., acetate), halides (e.g., chlorides, bromides, iodides), nitrates, sulfate, and the like. The typical amount of promoter metal present in the catalyst will be in the range of from about 0.001 to 5 weight percent, preferably 0.001 to 2 weight percent relative to the catalyst.
- When the catalyst is used in a slurry, the diatomaceous earth has preferably a mass median particle size in the range of 1 to 200 μm, more preferably in the range of 10 to 100 μm. The mass median particle diameter is the diameter that divides half of the mass (“Particle Size Measurement,” Kirk-Othmer Encyclopedia of Chemical Technology online edition, 2006).
- The invention also includes an epoxidation process comprising reacting an olefin, hydrogen, and oxygen in the presence of the catalyst of the invention.
- An olefin is used in the process. Suitable olefins include any olefin having at least one carbon-carbon double bond, and generally from 2 to 60 carbon atoms. Preferably the olefin is an acyclic alkene of from 2 to 30 carbon atoms; the process is particularly suitable for epoxidizing C2-C6 olefins. More than one double bond may be present in the olefin molecule, as in a diene or triene. The olefin may be a hydrocarbon or may contain functional groups such as halogen, carboxyl, hydroxyl, ether, carbonyl, cyano, or nitro groups, or the like. In a particularly preferred process, the olefin is propylene and the epoxide is propylene oxide.
- Oxygen and hydrogen are required. Although any sources of oxygen and hydrogen are suitable, molecular oxygen and molecular hydrogen are preferred. The molar ratio of hydrogen to oxygen can usually be varied in the range of H2:O2=1:100 to 5:1 and is especially favorable at 1:5 to 2:1. The molar ratio of oxygen to olefin is usually 1:1 to 1:20, and preferably 1:1.5 to 1:10. Relatively high oxygen to olefin molar ratios (e.g., 1:1 to 1:3) may be advantageous for certain olefins.
- In addition to the olefin, oxygen, and hydrogen, an inert gas is preferably used in the process. Any desired inert gas can be used. Suitable inert gases include nitrogen, helium, argon, and carbon dioxide. Saturated hydrocarbons with 1-8, especially 1-6, and preferably 1-4 carbon atoms, e.g., methane, ethane, propane, and n-butane, are also suitable. Nitrogen and saturated C1-C4 hydrocarbons are preferred inert gases. Mixtures of inert gases can also be used. The molar ratio of olefin to gas is usually in the range of 100:1 to 1:10 and especially 20:1 to 1:10.
- The process may be performed in a continuous flow, semi-batch, or batch mode. A continuous flow process is preferred. The catalyst is preferably in a slurry or a fixed bed. For a fixed-bed process, the catalyst is preferably formed into extrudates, tablets, granules, and the like.
- It is advantageous to work at a pressure of 1-200 bars. The process is carried out at a temperature effective to achieve the desired olefin epoxidation, preferably at temperatures in the range of 0-200° C., more preferably, 20-150° C. Preferably, at least a portion of the reaction mixture is a liquid under the reaction conditions.
- A reaction solvent is preferably used in the process. Suitable reaction solvents are liquid under the reaction conditions. They include, for example, oxygen-containing hydrocarbons such as alcohols, aromatic and aliphatic solvents such as toluene and hexane, nitriles such as acetonitrile, carbon dioxide, and water. Suitable oxygenated solvents include alcohols, ethers, esters, ketones, carbon dioxide, water, and the like, and mixtures thereof. Preferred oxygenated solvents include water and lower aliphatic C1-C4 alcohols such as methanol, ethanol, isopropanol, tert-butanol, and mixtures thereof. Fluorinated alcohols can be used.
- Where a reaction solvent is used, it may be advantageous to use a buffer. The buffer is employed in the reaction to inhibit the formation of glycols or glycol ethers during the epoxidation, and it can improve the reaction rate and selectivities. The buffer is typically added to the solvent to form a buffer solution, or the solvent and the buffer are added separately. Useful buffers include any suitable salts of oxyacids, the nature and proportions of which in the mixture are such that the pH of their solutions preferably ranges from 3 to 12, more preferably from 4 to 10, and most preferably from 5 to 9. Suitable salts of oxyacids contain an anion and a cation. The anion may include phosphate, carbonate, bicarbonate, sulfate, carboxylates (e.g., acetate), borate, hydroxide, silicate, aluminosilicate, or the like. The cation may include ammonium, alkylammonium (e.g., tetraalkylammoniums, pyridiniums), alkylphosphonium, alkali metal, and alkaline earth metal ions, or the like. Examples include NH4, NBu4, NMe4, Li, Na, K, Cs, Mg, and Ca cations. The preferred buffer comprises an anion selected from the group consisting of phosphate, carbonate, bicarbonate, sulfate, hydroxide, and acetate; and a cation selected from the group consisting of ammonium, alkylammonium, alkylphosphonium, alkali metal, and alkaline earth metal ions. Buffers may preferably contain a combination of more than one suitable salt. Typically, the concentration of the buffer in the solvent is from 0.0001 M to 1 M, preferably from 0.0005 M to 0.3 M. The buffer may include ammonium hydroxide which can be formed by adding ammonia gas to the reaction system. For instance, one may use a pH=12-14 solution of ammonium hydroxide to balance the pH of the reaction system. More preferred buffers include alkali metal phosphates, ammonium phosphate, and ammonium hydroxide. The ammonium phosphate buffer is particularly preferred.
- Following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.
- Diatomaceous earth FN-1 (EaglePicher Filtration and Minerals, Inc., 30 g) is added to a solution made from deionized water (120 g), aqueous sodium tetrachloroaurate solution (20.74 wt. % gold, 0.795 g), and disodium tetrachloropalladate (from Aldrich Chemical, 0.825 g). Sodium bicarbonate powder is added to the slurry until the pH reaches 7.24. The slurry is allowed to react for 4 h at 50° C., then filtered. The solid is washed with deionized water (7×80 g). The solid is then calcined in air at 110° C. for 4 h (10° C./min from room temperature to 110° C.) and at 300° C. for 4 h (2° C./min from 110° C. to 300° C.). The calcined solid is then transferred to a quartz tube and treated with a gas containing 4 vol. % hydrogen in nitrogen at 100° C. for 1 h (flow rate 100 mL/h) and then purged with nitrogen for 1 h. The final solid (Catalyst A) contains 1.0 wt. % palladium and 0.44 wt. % gold.
- The procedure of Example 1 is repeated except that the solid is calcined at 550° C. before hydrogen reduction. The solid obtained (Catalyst B) contains 1.0 wt. % palladium and 0.44 wt. % gold.
- The procedure of Example 1 is repeated except that the solid is calcined at 650° C. before hydrogen reduction. The solid obtained (Catalyst C) contains 1.0 wt. % palladium and 0.44 wt. % gold.
- The procedure of Example 1 is repeated except that diatomaceous earth FP-3 (EaglePicher Filtration and Minerals, Inc., 30 g) is used instead of FN-1. The solid obtained (Catalyst D) contains 0.75 wt. % palladium and 0.35 wt. % gold.
- The procedure of Example 4 is repeated except that the solid is calcined at 550° C. before hydrogen reduction. The solid obtained (Catalyst E) contains 0.75 wt. % palladium and 0.35 wt. % gold.
- The procedure of Example 1 is repeated except that diatomaceous earth FW-14 (EaglePicher Filtration and Minerals, Inc., 30 g) is used instead of FN-1. The solid obtained (Catalyst F) contains 0.81 wt. % palladium and 0.33 wt. % gold.
- A spray-dried anatase (average diameter 35 μm, air calcined at 700° C. for 4 h, surface area 40 m2/g, 20 g) is added to a solution made from deionized water (80 g), an aqueous sodium tetrachloroaurate solution (20.74 wt. % gold, 0.53 g), and disodium tetrachloropalladate (19.75 wt. % Pd, 1.01 g). Sodium bicarbonate powder is added to the slurry until the pH reaches 7.24. The slurry is allowed to react for 4 h at 50° C., then filtered. The solid is washed with deionized water (7×80 g). The solid is then calcined in air at 110° C. for 4 h (at a rate of 10° C./min from room temperature to 110° C.) and at 550° C. for 4 h (at a rate of 2° C./min from 110° C. to 550° C.). The calcined solid is transferred to a quartz tube and treated with a gas containing 4 vol. % hydrogen in nitrogen at 100° C. for 1 h (flow rate 100 mL/h) and then purged with nitrogen for 1 h. The final solid (Catalyst G) contains 1.0 wt. % palladium and 0.42 wt. % gold.
- Titanium silicalite-1 (TS-1) is prepared by following procedures disclosed in U.S. Pat. Nos. 4,410,501 and 4,833,260, and calcined in air at 550° C.
- An ammonium phosphate buffer solution (0.1 M, pH 6) is prepared as follows. Ammonium dihydrogen phosphate (11.5 g) is dissolved in deionized water (900 g). Aqueous ammonium hydroxide (30 wt. % NH4OH) is added to the solution until the pH reads 6 via a pH meter. The volume of the solution is then increased to exactly 1000 mL with additional deionized water.
- A 300-mL stainless steel reactor is charged with Catalyst A (0.07 g), TS-1 powder (0.63 g), the buffer solution prepared above (13 g), and methanol (100 g). The reactor is then charged to 300 psig with a feed gas consisting of 2 volume percent (vol. %) hydrogen, 4 vol. % oxygen, 5 vol. % propylene, 0.5 vol. % methane, and the balance nitrogen. The pressure in the reactor is maintained at 300 psig via a back pressure regulator with the feed gases pass continuously through the reactor at 1600 mL/min (measured at 23° C. and 1 atmosphere pressure). In order to maintain a constant solvent level in the reactor during the run, the oxygen, nitrogen and propylene feeds are passed through a 2-L stainless steel vessel (saturator) preceding the reactor containing 1.5 L of methanol. The reaction mixture is heated to 60° C. while it is stirred at 1500 rpm. The gaseous effluent is analyzed by an online gas chromatograph (GC) every hour. The liquid is analyzed by offline GC at the end of the 18 h run. The products formed include propylene oxide (PO), propane, and derivatives of propylene oxide such as propylene glycol, propylene glycol monomethyl ethers, dipropylene glycol, and dipropylene glycol methyl ethers. The calculated results are shown in Table 1. The catalyst productivity is defined as the grams of PO formed (including PO which is subsequently reacted to form PO derivatives) per gram of catalyst per hour. POE (mole)=moles of PO+moles of PO units in the PO derivatives. PO/POE=(moles of PO)/(moles of POE)×100. Propylene to POE selectivity=(moles of POE)/(moles of propane formed+moles of POE)×100.
- The procedure of Example 8 is repeated except that Catalysts B, C, D, E, F, G are used respectively instead of Catalyst A. Results are shown in Table 1.
-
TABLE 1 Epoxidation of Propylene Example 8 9 10 11 12 13 14 Pd—Au Catalyst A B C D E F G Support FN-1 FN-1 FN-1 FP-3 FP-3 FW-14 Anatase Support Surface Area (m2/g) 24 24 24 2 2 0.4 28 Calcination Temperature (° C.) 300 550 650 300 550 300 550 Catalyst Productivity, 0.57 0.49 0.46 0.46 0.43 0.43 0.47 g POE/g cat/h PO/POE, 88 90 91 90 90 91 90 % (mole/mole) Propylene to POE Selectivity, 56 77 84 63 75 65 80 % (mole/mole) Hydrogen to POE Selectivity, 18 23 27 25 29 21 34 % (mole/mole) Oxygen to POE Selectivity, 37 45 43 38 42 31 38 % (mole/mole)
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