WO2017158415A1 - Tetraethyl ammonium hydroxide templated meapso molecular sieve catalysts for conversion of alkyl chlorides to olefins - Google Patents
Tetraethyl ammonium hydroxide templated meapso molecular sieve catalysts for conversion of alkyl chlorides to olefins Download PDFInfo
- Publication number
- WO2017158415A1 WO2017158415A1 PCT/IB2016/057900 IB2016057900W WO2017158415A1 WO 2017158415 A1 WO2017158415 A1 WO 2017158415A1 IB 2016057900 W IB2016057900 W IB 2016057900W WO 2017158415 A1 WO2017158415 A1 WO 2017158415A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- templated
- alkyl halide
- olefins
- teaoh
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 164
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 80
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 55
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 title claims description 63
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 title claims description 63
- 239000002808 molecular sieve Substances 0.000 title abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title abstract description 9
- 150000001348 alkyl chlorides Chemical class 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 67
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 60
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 35
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005977 Ethylene Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims description 49
- 239000000047 product Substances 0.000 claims description 41
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 40
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 38
- -1 olefin hydrocarbon Chemical class 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 239000011135 tin Substances 0.000 claims description 23
- 239000011572 manganese Substances 0.000 claims description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 229910052718 tin Inorganic materials 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 229940050176 methyl chloride Drugs 0.000 claims description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 15
- 239000002178 crystalline material Substances 0.000 claims description 15
- 229910052748 manganese Inorganic materials 0.000 claims description 15
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 11
- 229910052732 germanium Inorganic materials 0.000 claims description 11
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052702 rhenium Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 229940086542 triethylamine Drugs 0.000 claims description 4
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002002 slurry Substances 0.000 description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000013078 crystal Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 11
- 239000008119 colloidal silica Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000004809 Teflon Substances 0.000 description 9
- 229920006362 Teflon® Polymers 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 235000010210 aluminium Nutrition 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 241000269350 Anura Species 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 229940102396 methyl bromide Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000408939 Atalopedes campestris Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 241001455273 Tetrapoda Species 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical group [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010961 commercial manufacture process Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
- C07C19/03—Chloromethanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the invention generally concerns the use of tetraethyl ammonium hydroxide templated metal incorporated silicoaluminophosphate (MeAPSO) molecular sieve catalysts to catalyze the reaction of alkyl halides to light olefins.
- MeAPSO silicoaluminophosphate
- FIGS. 1 A and IB provide examples of products generated from ethylene (FIG. 1 A) and propylene (FIG. IB).
- SAPO catalysts have an open microporous structure with regularly sized channels, pores or "cages.” These materials are sometimes referred to as “molecular sieves” in that they have the ability to sort molecules or ions based primarily on the size of the molecules or ions. SAPO materials are both microporous and crystalline, and have a three-dimensional crystal framework of P0 4 + , A10 4 " and Si0 4 tetrahedra. SAPO-34 and MeSAPO-34 catalysts have been prepared by a range of methods. Various synthetic methods using templates have been employed to prepare SAPO molecular sieves and metal incorporated SAPO molecular sieves. By way of example, Razavian et al.
- MnAPSO made using triethylamine as a templating agent has been used in chloromethane to olefin reactions ⁇ See, for example, Wei et al., in "Study of Mn incorporation into SAPO framework: Synthesis characterization and catalysis in chloromethane conversion to light olefins", Microporous and Mesoporous Materials 2006, Vol. 90, pp. 188-197). The produced crystals in Wei et al. were larger than SAPO-34 crystals prepared under the same conditions. This catalyst suffered from loss of activity after sixty minutes of time on stream.
- the discovery is premised on a metal incorporated SAPA-34 (MeAPSO-34, where Me is the total metal) catalyst prepared using tetraethylammonium hydroxide (TEAOH) as the templating agent, which results in a catalyst having a small particle size ⁇ e.g., 200 nm to 1000 nm or 200 nm to 500 nm, or less than 1000 nm) when compared with MeAPSO-34 made using other amine templating agents or mixtures of templating agents.
- TEAOH tetraethylammonium hydroxide
- the catalysts of the present invention offer a more efficient and scalable product for the alkyl halide to light olefin (e.g., C 2 to C 4 olefins) reaction process.
- a method for converting an alkyl halide to an olefin includes contacting a tetraethylammonium hydroxide (TEAOH) templated metal silicoaluminophosphate-34 (MeAPSO-34) catalyst with a feed including an alkyl halide (e.g., methyl halide or methyl chloride) under reaction conditions sufficient to produce an olefin hydrocarbon product that includes olefins.
- TEAOH tetraethylammonium hydroxide
- MeAPSO-34 templated metal silicoaluminophosphate-34
- the metal in the MeAPSO-34 is incorporated into the SAPO-34 framework.
- the metal can be manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof, preferably manganese, tin, manganese and iron, manganese and germanium, manganese and tin, or tin and iron.
- the TEOH templated MeAPSO-34 catalyst can be the reaction product of heat treatment of a synthesis mixture having a molar composition of: aAl:6Si:cP:i3 ⁇ 40:eTEAOH:/ e x O y where 0 ⁇ ⁇ 1, 0 ⁇ 6 ⁇ 1, 0 ⁇ c ⁇ 1, d is 30 to 80, 0 ⁇ e ⁇ 4; 0 ⁇ f ⁇ 1, x is 1 to 2, and_y is 1 to 3.
- a is 1, b is 0.4, c is 1, d is 60, e is 2 and / is 0.05 or 0.1.
- Heat treatment can include (a) heating the synthesis mixture to obtain a crystalline material; and (b) calcining the crystalline material.
- the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt.% alcohol, or preferably is alcohol free.
- the olefins can include C 2 -C 4 olefins and the maximum combined selectivity of ethylene and propylene can be at least 70%, preferably at least 80%), or more preferably 90%> to 98%>, the maximum combined space time yield of ethylene and propylene can be at least 1/hr or 1/hr to 3/hr; and the maximum conversion of alkyl halide can be at least 80%> or 85%> to 100%>.
- the produced olefin hydrocarbon product can be collected, stored, transported, or combinations thereof.
- Reaction conditions for the conversion of an alkyl halide to olefins can include an average temperature from 300 °C to 500 °C, an average pressure of 0.5 MPa or less, and a weighted hourly space velocity (WHSV) of 0.5 to 10 h "1 .
- WHSV weighted hourly space velocity
- the reaction for converting an alkyl halide to an olefin occurs in a fluid catalytic cracking (FCC) process or reactor or fluidized circulating bed process or reactor.
- the method can further include collecting or storing the produced olefin hydrocarbon product and using the produced olefin hydrocarbon product to produce a petrochemical or a polymer.
- the method can also include regenerating the used/deactivated catalyst in a continuous process such as a FCC-type process or reactor or a circulating catalyst bed process or reactor.
- a catalyst capable of catalyzing an alkyl halide to olefin reaction is described.
- the catalyst can have the general formula of e TEAOH(Me Si a Al 3 ⁇ 4 P c )0 2 , where: Me is manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof and Me is incorporated into the framework of the catalyst; e is the molar amount of tetraethylammonium hydroxide (TEOH) per mole of (Me Si a Al3 ⁇ 4P c )0 2 ; and a, b, and c are the molar fractions of metal, silicon, aluminum, and phosphorous respectively, where 0 ⁇ e ⁇ 4, 0 ⁇ / ⁇ l, 0 ⁇ ⁇ ⁇ 1, 0 ⁇ ⁇ ⁇ 1, 0 ⁇ c ⁇ l, and the sum off, a, b, and c is equal to 1.
- Me is manganese, magnesium, cobalt, nickel, iron, copper, zinc,
- the catalyst can be in particulate form and have an average particle size of 200 to 1000 nm or 200 nm to 500 nm. Surprisingly, it was found that the TEAOH templated catalyst had a particle size less than the particle size of a triethyl amine templated MeAPSO-34 catalyst or SAPO-34 catalyst.
- the catalyst can have a formula of (Sn / Si a Al 3 ⁇ 4 P c )0 2 , where a, b, and c are the molar fractions of tin, silicon, aluminum, and phosphorous respectively, where 0 ⁇ / ⁇ l, 0 ⁇ a ⁇ l, 0 ⁇ 0 ⁇ l, 0 ⁇ c ⁇ l, and the sum off, a, b, and c is equal to 1.
- a method can include (a) heating a synthesis mixture having has a molar composition of: aAl:6Si:cP: ⁇ 3 ⁇ 40:eTEAOH:/ e x O y where 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, d is 30 to 80, 0 ⁇ e ⁇ 4; 0 ⁇ / ⁇ l, is l to 2 and y is 1 to 3 to obtain a crystalline material; and (b) calcining the crystalline material (e.g., heating the crystalline material in air at a temperature of 450 °C to 600 °C). Heating the synthesis mixture can include hydrothermally crystallizing the synthesis mixture at 180 °C to 210 °C for 18 to 48 hours under autogenous pressure; and drying the mixture at 90 °C to 110 °C.
- a system for producing olefins can include an inlet for a feed including the alkyl halide, a reaction zone that is configured to be in fluid communication with the inlet, and an outlet configured to be in fluid communication with the reaction zone to remove an olefin hydrocarbon product from the reaction zone.
- the reaction zone can include the feed and the TEAOH templated MeAPSO-34 catalyst described above and in the specification.
- the reaction zone can further include a FCC-type reactor or a circulating catalyst bed reactor, and a collection device that is capable of collecting the olefin hydrocarbon product.
- Embodiment 1 describes a method for converting an alkyl halide to an olefin.
- the method can include contacting a tetraethylammonium hydroxide (TEAOH) templated metal silicoaluminophosphate-34 (MeAPSO-34) catalyst with a feed comprising an alkyl halide under reaction conditions sufficient to produce an olefin hydrocarbon product comprising olefins, wherein the metal (Me) is incorporated into the SAPO-34 framework.
- TEAOH tetraethylammonium hydroxide
- MeAPSO-34 metal silicoaluminophosphate-34
- Embodiment 2 is the method of embodiment 1, wherein the incorporated metal (Me) is manganese (Mn), magnesium (Mg), cobalt (Co), nickel (Ni), iron (Fe), copper (Cu), zinc (Zn), tin (Sn), germanium (Ge), titanium (Ti), rhenium (Re), or any combination thereof, preferably manganese, tin, manganese and iron, manganese and germanium, manganese and tin, or tin and iron.
- Embodiment 3 is the method of any one of embodiments 1 to 2, wherein the olefins are C 2 to C 4 olefins.
- Embodiment 4 is the method of embodiment 3, wherein the maximum combined selectivity of ethylene and propylene is at least 70%, preferably at least 80%, or more preferably 90% to 98%, the maximum combined space time yield of ethylene and propylene is at least 1/hr or 1/hr to 3/hr, and the maximum conversion of alkyl halide is at least 80% or 85% to 100%.
- Embodiment 5 is the method of embodiment 4, wherein the maximum selectivity of ethylene is 40% to 55%, and the maximum selectivity of propylene is 30% to 45%.
- Embodiment 6 is the method of any one of embodiments 1 to 5, wherein the reaction conditions include a temperature from 300 °C to 500 °C, a pressure of 0.5 MPa or less, and a weighted hourly space velocity (WHSV) of 0.5 to 10 h "1 .
- the reaction conditions include a temperature from 300 °C to 500 °C, a pressure of 0.5 MPa or less, and a weighted hourly space velocity (WHSV) of 0.5 to 10 h "1 .
- WHSV weighted hourly space velocity
- Embodiment 7 is the method of any one of embodiments 1 to 5, wherein the TEAOH templated MeAPSO-34 catalyst is the reaction product of heat treatment of a synthesis mixture having a molar composition of: aAl 2 0 3 :6Si0 2 :cP 2 0 5 : ⁇ 2 0:eTEAOH:/ e x O y; where 0 ⁇ ⁇ 1, 0 ⁇ 6 ⁇ 1, 0 ⁇ c ⁇ 1, d is 30 to 80, 0 ⁇ e ⁇ 4; 0 ⁇ f ⁇ 1, x is 1 to 2, and y is 1 to 3.
- Embodiment 8 is the method of embodiment 7, wherein a is 1, b is 0.4, c is I, d is 60, e is 2 and /is 0.05 or 0.1.
- Embodiment 9 is the method of embodiment 7, wherein the heat treatment comprises: (a) heating the synthesis mixture to obtain a crystalline material; and (b) calcining the crystalline material.
- Embodiment 10 is the method of any one of embodiments 1 to 9, wherein the alkyl halide is a methyl halide, preferably methyl chloride.
- Embodiment 1 1 is the method of any one of embodiments 1 to 10, wherein the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt. % alcohol, or preferably is alcohol free.
- Embodiment 12 is the method of any one of embodiments 1 to 11, wherein the reaction occurs in a fixed feed reactor, a fluid catalytic cracking (FCC) reactor or fluidized circulating bed reactor.
- Embodiment 13 is the method of any one of embodiments 1 to 12, further comprising collecting or storing the produced olefin hydrocarbon product.
- Embodiment 15 is the catalyst of embodiment 14, having an average particle size of 200 nm to 1000 nm or 200 nm to 500 nm.
- Embodiment 16 is the catalyst of any one of embodiments 14 to 15, wherein the particle size of the catalyst is less than the particle size of a triethyl amine templated catalyst and/or a mixed templated catalyst.
- Embodiment 17 is a system for producing olefins, the system comprising: an inlet for a feed comprising an alkyl halide; a reaction zone that is configured to be in fluid communication with the inlet, wherein the reaction zone comprises the feed and the catalyst of any one of embodiments 14 to 16; and an outlet configured to be in fluid communication with the reaction zone to remove an olefin hydrocarbon product from the reaction zone.
- Embodiment 18 is the system of embodiment 17, wherein the reaction zone includes a fluid catalytic cracking (FCC)-type reactor or a circulating catalyst bed reactor.
- Embodiment 19 is the system of any one of embodiments 17 to 18, further comprising a collection device that is capable of collecting the olefin hydrocarbon product.
- FCC fluid catalytic cracking
- Embodiment 20 is a method of making the catalyst of any one of embodiments 14 to 16, the method comprising: (a) heating a synthesis mixture to obtain a crystalline material; and (b) calcining the crystalline material, wherein the synthesis mixture has a molar composition of aAl 2 03:*Si02:cP 2 05: ⁇ iH20:eTEAOH ⁇ Me x O y where 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, d is 30 to 80, 0 ⁇ e ⁇ 4; 0 ⁇ f ⁇ 1, x is 1 to 2, and ⁇ is 1 to 3.
- Catalyst means a substance which alters the rate of a chemical reaction.
- Catalytic means having the properties of a catalyst.
- conversion means the mole fraction (i.e., percent) of a reactant converted to a product or products.
- selectivity refers to the percent of converted reactant that went to a specified product, for example C2-C4 olefin selectivity is the % of alkyl halide that formed C2-C4 olefins.
- wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component.
- 10 grams of component in 100 grams of the material is 10 wt.% of component.
- the catalysts of the present invention can "comprise,” “consist essentially of,” or “consist of particular ingredients, components, compositions, etc. disclosed throughout the specification.
- a basic and novel characteristic of the catalysts of the present invention are their size ⁇ e.g., 200 nm to 1000 nm or 200 nm to 500 nm, or less than 1000 nm) as well as their ability to selectivity produce light olefins, and in particular, ethylene and propylene, from alkyl halides ⁇ e.g., methyl chloride).
- FIGS 1A and IB depict illustrations of various chemicals and products that can be produced from ethylene (FIG. 1 A) and propylene (FIG. IB).
- FIG. 2 depicts a system for producing olefins from alkyl halides using the catalyst of the present invention.
- FIGS. 3A and 3B are SEM images of crystals of TEAOH templated MnAPSO-34 catalyst of the present invention at various magnifications.
- FIG. 4 is an SEM image of crystals of TEAOH templated FeAPSO-34 catalyst of the present invention.
- FIG. 5 is an SEM image of crystals of TEA templated MnAPSO-34 catalyst of the prior art.
- FIG. 6 shows graphs of percent CH 3 C1 conversion of the TEAOH templated catalysts of present invention and the comparative catalyst (SAPO-34).
- FIG. 7 shows graphs of percent CH 3 CI conversion of the TEAOH templated catalysts 2 and 3 (MnAPSO-34) of present invention and the comparative catalyst (SAPO- 34).
- FIG. 8 shows graphs of CH 3 CI conversion, ethylene selectivity, propylene selectivity and methane selectivity of the catalyst 2 (MnAPSO-34) of present invention and the comparative catalyst (SAPO-34).
- FIG. 9 shows graphs of CH 3 CI conversion, ethylene selectivity, and propylene selectivity of the catalyst 8 (SnAPSO-34) of present invention and the comparative catalyst (SAPO-34).
- FIG. 10 shows graphs of CH 3 CI conversion, ethylene selectivity, and propylene selectivity of the catalyst 10 (TiAPSO-34) of present invention and the comparative catalyst (SAPO-34).
- FIG. 11 shows graphs of CH 3 CI conversion, ethylene selectivity, and propylene selectivity of the catalyst 1 1 (ReAPSO-34) of present invention and the comparative catalyst (SAPO-34).
- catalysts used in the methods and systems of the current invention have been shown to have maximum combined selectivity of ethylene and propylene of at least 70% or ranging from 90% to 98%.
- the MeAPSO-34 catalysts of the present invention are prepared as TEAOH templated SAPO-34 catalysts using TEAOH in the hydrothermal crystallization process of making the catalyst.
- the metal atom is incorporated into the SAPO-34 framework.
- the addition of a structure-directing or template agent/ion effects the pre-organization provided by the coordination sphere and can results in significant modification of physical/chemical/electronic properties of the template complex formed. It was surprisingly found that the addition of TEAOH as the structure-directing or template agents resulted in a profound effect on the resultant crystal morphology (size, shape, dispersion, surface area, distribution) and surface Bransted acidity of the MeAPSO-34 catalyst formed. This is illustrated in non-limiting examples in FIGS. 1-4 as well as comparative FIG. 5.
- MeAPSO catalysts of the present invention are provided in the Examples section.
- MeAPSO catalysts are prepared using a gel containing aluminum (Al), phosphorus (P), silicon (Si) compounds, and metal precursors with structure-directing agents under crystallization conditions.
- a general non-limiting method of making the MeAPSO catalysts includes preparing an aqueous mixture of aluminum z ' so-propoxide with phosphoric acid and, optionally hydrochloric acid. Colloidal silica can be added to the aluminum/phosphorous mixture with agitation followed by the metal precursor, and then addition of tetraethylammonium hydroxide (TEAOH).
- TEAOH tetraethylammonium hydroxide
- the metal precursor can be salts (e.g., acetate or nitrate salts) of the desired metal.
- metal salts include acetate or nitrate salts of manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, and rhenium metals.
- salt solutions of two or more metals can be used.
- manganese and iron salt solution(s), manganese and germanium salt solution(s), manganese and tin salt solution(s), or tin and iron salt solution(s) can be used.
- the synthesis mixture can have molar composition of: ⁇ 1 2 0 3 : b Si0 2 : cP 2 0 5 :dH 2 0 : eTE AOH: Me x O y where 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, d is 30 to 80, 0 ⁇ e ⁇ 4; 0 ⁇ f ⁇ 1, x is 1 to 2, and y is 1 to 3.
- Non-limiting nano-crystal MeAPSO-34 catalysts can include a molar ratio where a is 1, b is
- c is l, 50-70, e is 2 and /is 0.05; a is 1, b is 0.4, c is 1, ⁇ i is 50-70, e is 2 and /is 0.1; a is 1, b is 0.4, c is 1, d is 50-70, e is 3 and /is 0.05; a is 1, b is 0.4, c is 1, d is 50-70, e is 3 and is 0.1; a is 1, b is 0.4, c is 1, ⁇ f is 50-70, e is 4 and /is 0.05; a is 1, 6 is 0.4, c is 1, ⁇ f is 50-70, e is 4 and /is 0.1; a is 1, b is 0.35, c is 1, d is 50-70, e is 2 and /is 0.05; a is 1, b is 0.35, c is 1, d is 50-70, e is 2 and /is 0.05; a is 1, b is 0.35
- d is 50-70, e is 2 and /is 0.1; a is 1, Ms 0.35, c is 1, d is 50-70, e is 3 and /is 0.05; a is 1, b is 0.35, c is 1, d is 50-70, e is 3 and /is 0.1; a is 1, is 0.35, c is I, d is 50-70, e is 4 and /is 0.05; a is 1, is 0.35, c is 1, ⁇ iis 50-70, e is 4 and /is 0.1; a is 1, Ms 0.45, c is 1, ⁇ i is 50-70, e is 2 and /is 0.05; a is 1, £ is 0.45, c is 1, d s 50-70, e is 2 and /is 0.1; a is 1, £ is 0.45, c is 1, d s 50-70, e is 2 and /is 0.1; a is 1, £ is 0.45, c is 1, d
- the synthesis mixture can then be heat treated to form a crystalline material.
- Crystal growth can be performed in a pressure vessel, such as an autoclave using autogenous pressure, by a temperature-difference method, temperature-reduction method, or a metastable-phase technique.
- the crystal growth can be performed in an autoclave.
- the heat treatment can be performed at 150 °C to 250 °C, preferably 175 °C to 225 °C, or more preferably at 180 °C to 210 °C for a desired amount of time ⁇ e.g., 18 to 48 hours, or 24 hours) in an heated high pressure reactor ⁇ e.g., autoclave) with or without agitation.
- Average crystallization temperatures can range from 180 °C to 210 °C, and all temperatures there between including 181 °C , 182 °C , 183 °C , 184 °C , 185 °C, 186 °C, 187 °C, 188 °C, 189 °C, 190 °C, 191 °C, 192 °C, 193 °C, 194 °C, 195 °C, 196 °C, 197 °C, 198 °C, or 199 °C, 200 °C, 201 °C, 202 °C, 203 °C, 204 °C, 205 °C, 206 °C, 207 °C, 208 °C, or 209 °C.
- Heating can be performed for 12 hours to 36 hours and all periods of time there between including 12 hours, 15 hours, 20 hours, 25 hours, 30 hours, or 35 hours.
- the crystalline material can be separated and washed with water, and dried at about 90 °C and then calcined to remove any remaining templating agent.
- the calcining step can be performed in air at 400 °C to 700 °C, preferably 450 °C to 650 °C, or more preferably from 500 °C to 600 °C, for a sufficient period of time ⁇ e.g., 3 to 10 hours).
- MeAPSO-34 catalysts prepared using a TEAOH as a structure-directing agent provides effects on the chemical composition, morphology, and surface acidity that benefit the methods and systems for converting alkyl halides to olefins as currently disclosed.
- the MeAPSO-34 crystal produced using the methods above and in the Examples above can have any type of morphology.
- Non-limiting examples of morphologies include a wire, a particle, a sphere, a rod, a tetrapod, a hyper-branched structure, a tube, a cube, a plate, or mixtures thereof.
- the crystalline MeAPSO-34 catalysts can have an average particle size of 200 nm to 1000 nm or 200 nm to 500 nm.
- the average particle size of 200 nm to 1000 nm includes all average particle sizes between 200 nm to 1000 nm, for instance 200 nm, 225 nm, 250 nm, 275 nm, 300 nm, 325 nm, 350 nm, 375 nm, 400 nm, 425 nm, 450 nm, 475 nm, 500 nm, 525 nm, 550 nm, 575 nm, 600 nm, 625 nm, 650 nm, 675 nm, 700 nm, 725 nm, 750 nm, 775 nm, 800 nm, 825 nm, 850 nm, 875 nm, 900 nm, 925 nm, 950 nm, 975 nm, 1000 nm, and all values and ranges in between.
- Particle size can be determined using Scanning Electron Microscopy (SEM) or Transmission Electron
- the TEAOH templated MeAPSO catalysts of the present invention help to catalyze the conversion of alkyl halides to C 2 -C 4 olefins such as ethylene, propylene and butene (butylene).
- Butene can include 1-butene, (Z -but-2-ene, (J3 ⁇ 4)-but-2-ene, 2- methylpropene, and combinations thereof.
- the following non-limiting two-step process is an example of conversion of methane to methyl chloride and conversion of methyl chloride to ethylene, propylene and butene. Equation (II) illustrates the reactions that are believed to occur in the context of the present invention:
- reaction may produce byproducts such as methane, C 5 olefins, C 2 -C 5 alkanes and aromatic compounds such as benzene, toluene and xylene.
- Conditions sufficient for olefin production include temperature, time, alkyl halide concentration, space velocity, and pressure.
- the temperature range for olefin production may range from about 300 °C to 500 °C, preferably ranging 350 °C to 450 °C.
- a weight hourly space velocity (WHSV) of alkyl halide higher than 0.5 h "1 can be used, preferably between 1.0 and 10 h "1 , more preferably between 2.0 and 3.5 h "1 .
- the conversion of alkyl halide is carried out at a pressure less than 145 psig (1 MPa) and preferably less than 73 psig (0.5 MPa), or at atmospheric pressure.
- the conditions for olefin production may be varied based on the type of the reactor.
- the methods and system disclosed herein also include the ability to regenerate used/deactivated catalyst in a continuous process such as in a fluid catalytic cracking (FCC)- type process or reactor or a circulating catalyst bed process or reactor.
- the method and system can further include collecting or storing the produced olefin hydrocarbon product along with using the produced olefin hydrocarbon product to produce a petrochemical or a polymer.
- the system 100 can include an alkyl halide source 102, a reactor 104, and a collection device 106.
- the alkyl halide source 102 can be configured to be in fluid communication with the reactor 104 via an inlet 108 on the reactor.
- the alkyl halide source can be configured such that it regulates the amount of alkyl halide feed entering the reactor 104.
- the reactor 104 can include a reaction zone 110 having the TEAOH templated MeAPSO-34 catalyst 112 of the present invention.
- reactors that can be used include fixed-bed reactors, fluidized bed reactors, bubbling bed reactors, slurry reactors, rotating kiln reactors, or any combinations thereof when two or more reactors are used.
- reactor 104 is a fluid catalytic cracking (FCC)-type reactor or a circulating catalyst bed reactor that permits the regeneration of used/deactivated catalyst in a continuous process.
- the reactor 104 can include an outlet 114 for products produced in the reaction zone 110.
- the products produced can include ethylene, propylene and butylene.
- the collection device 106 can be in fluid communication with the reactor 104 via the outlet 114. Both the inlet 108 and the outlet 114 can be open and closed as desired.
- the collection device 106 can be configured to store, further process, or transfer desired reaction products ⁇ e.g., C2-C4 olefins) for other uses.
- FIG. 1 provides non-limiting uses of ethylene and propylene produced from the catalysts and processes of the present invention.
- the system 100 can also include a heating source 1 18.
- the heating source 1 18 can be configured to heat the reaction zone 18 to a temperature sufficient (e.g., 300 to 500 °C or 325 to 375 °C) to convert the alkyl halides in the alkyl halide feed to olefin hydrocarbon products.
- a heating source 1 18 can be a temperature controlled furnace, tube-in-shell heat exchangers, heaters, and the like. Additionally, any unreacted alkyl halide can be recycled and included in the alkyl halide feed to further maximize the overall conversion of alkyl halide to olefin products.
- Catalytic activity as measured by alkyl halide conversion can be expressed as the % moles of the alkyl halide converted with respect to the moles of alkyl halide fed.
- the combined selectivity of ethylene and propylene is at least 70%, preferably at least 80%>, more preferably at least 90%, or most preferably 90% to 98% under certain reaction conditions, wherein the maximum combined space time yield (STY) of ethylene and propylene is at least 1/hr or 1/hr to 3/hr, and/or wherein the maximum conversion of alkyl halide is at least 65% or 70% to 80%.
- the selectivity of ethylene is about 40% or higher and the selectivity of propylene is about 30% or higher, wherein the maximum selectivity of ethylene is 50% to 60% and the maximum selectivity of propylene is 35% to 45%.
- chloromethane (CH 3 C1) is used here to define conversion and maximum selectivity of products by the following equations (III)-(VII):
- Maximum selectivity for butylene may be expressed as: 4(C 4 H 8 )
- numerator is the carbon adjusted mole of butylene and the denominator is the moles of carbon converted.
- denominator is the moles of carbon converted.
- MeAPSO catalysts are made from silicon (Si), aluminum (Al), and phosphorous (P) in various molar ratios.
- silicon sources include colloidal silica, fumed silica, tetramethyl orthosilicate, tetraethyl orthosilicate, or tetraisopropyl orthosilicate.
- aluminum sources include aluminum methoxide, aluminum ethoxide, aluminum isopropoxide, or aluminums tert-butoxide.
- Non-limiting examples of phosphorus sources include phosphoric acid. These compounds can be obtained from various commercial sources, of which Sigma Aldrich® (U.S. A) is a non-limiting example.
- Templating agents can be used to direct crystal growth, pore size and the like.
- the templating agent, tetraethyl ammonium hydroxide (TEAOH) is available from commercial sources, for example, Sigma Aldrich® (U.S. A) or SACHEM, Inc., (USA) under the tradename ZeoGenTM.
- the metal or metal oxide denoted "Me” in the MeASPO materials can include metals or metal oxides from Columns 2, 4, 7 to 12, and 14 of the Periodic Table or combinations thereof.
- Non-limiting examples of metals include manganese (Mn), magnesium (Mg), copper (Cu), cobalt (Co), iron (Fe), nickel (Ni), germanium (Ge), tin (Sn), titanium (Ti), rhenium (Re), or zinc (Zn).
- the metals or metal oxides or metal precursors can be purchased from commercial manufactures such as Sigma-Aldrich®. 2. Alkyl Halide Feed
- the alkyl halide feed includes one or more alkyl halides.
- the alkyl halide feed may contain alkyl monohalides, alkyl dihalides, alkyl trihalides, preferably alkyl monohalide with less than 10 mol.% of other halides relative to the total halides.
- the alkyl halide feed may also contain nitrogen, helium, steam, and so on as inert compounds.
- the alkyl halide in the feed may have the following structure: C n H(2 n +2)-m m, where n and m are integers, n ranges from 1 to 5, preferably 1 to 3, even more preferably 1, m ranges 1 to 3, preferably 1, X is Br, F, I, or CI.
- the feed may include about 10, 15, 20, 40, 50 mol.% or more of the alkyl halide.
- the feed contains up to 10 mol.% or more of a methyl halide.
- the methyl halide is methyl chloride, methyl bromide, methyl fluoride, or methyl iodide, or any combination thereof.
- the feed stream can also include alcohol.
- the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt.% alcohol, or preferably is alcohol free, and in one instance that alcohol is methanol.
- alkyl halide particularly of methyl chloride (CH 3 C1) is commercially produced by thermal chlorination of methane at 400 °C to 450 °C and at a raised pressure. Catalytic oxychlorination of methane to methyl chloride is also known.
- methyl chloride is industrially made by reaction of methanol and HC1 at 180 °C to 200 °C using a catalyst.
- methyl halides are commercially available from a wide range of sources (e.g., Praxair, Danbury, CT; Sigma-Aldrich Co. LLC, St. Louis, Mo.; BOC Sciences USA, Shirley, NY).
- methyl chloride and methyl bromide can be used alone or in combination.
- Comparative Catalyst 1 was synthesized using the following molar ratios lAl 2 O3:0.4SiO 2 : lP 2 O 5 :60H 2 O:2TEAOH.
- Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring.
- the slurry was allowed to stir for an additional 1 hour.
- Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes.
- TEAOH was then added and the final mixture was stirred for 30 minutes.
- the slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave.
- the sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL DI water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours.
- the SAPO-34 had a Si/Al ratio of 0.18 and a Al/P ratio of 1.34. The material was confirmed to be SAPO-34 by X-ray diffraction (XRD).
- Catalysts 2 and 3 were synthesized using the following molar ratios 1 Al 2 O 3 :0.4SiO 2 : 1 ⁇ 2 ⁇ 5 :60 ⁇ 2 ⁇ :2 ⁇ :0.05 ⁇ and lAl 2 O 3 :0.4SiO 2 : lP 2 O 5 :60H 2 O:2TEAOH:0.1MnO, respectively.
- Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour.
- Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes.
- TEAOH was added to the mixture and then manganese acetate was added.
- the final mixture was stirred for 30 minutes.
- the slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours.
- Catalyst 2 had a Si/Al ratio of 0.16, a Al/P ratio of 1.19 and contained 1.31 wt.% of Mn based on the total weight of the catalyst.
- Catalyst 3 had a Si/Al ratio of 0.16, a Al/P ratio of 1.10 and contained 2.34 wt.% of Mn based on the total weight of the catalyst. The material was confirmed to be of the CHA structure by XRD.
- Catalyst 4 was synthesized using the following molar ratios lAl 2 O 3 :0.4SiO 2 : lP 2 O 5 :60H 2 O:2TEAOH:0.05Fe 2 O 3 .
- Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and iron nitrate were then added and the final mixture was stirred for 30 minutes.
- the slurry was added to a Teflon liner and placed in a 300 mL Pan- autoclave.
- the sample was crystallized hydrothermally at 190 °C for 24 hours.
- After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times.
- the final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours.
- the material was confirmed to be of the CHA structure by XRD.
- Catalyst 5 was synthesized using the following molar ratios lAl 2 O3:0.4SiO 2 : lP 2 O 5 :60H 2 O:2TEAOH:0.05CoO.
- Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes.
- TEAOH and cobalt acetate tetrahydrate were then added and the final mixture was stirred for 30 minutes.
- the slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave.
- the sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times.
- the final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.
- Catalyst 6 was synthesized using the following molar ratios lAl 2 O 3 :0.4SiO 2 : lP 2 O 5 :60H 2 O:2TEAOH:0.05CuO.
- Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and copper acetate monohydrate were then added and the final mixture was stirred for 30 minutes.
- the slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave.
- the sample was crystallized hydrothermally at 190 °C for 24 hours.
- After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times.
- the final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours.
- the material was confirmed to be of the CHA structure by XRD.
- Catalyst 7 was synthesized using the following molar ratios lAl 2 O3:0.4SiO 2 : lP 2 O 5 :60H 2 O:2TEAOH:0.05MgO.
- Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and magnesium acetate tetrahydrate were then added and the final mixture was stirred for 30 minutes.
- the slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave.
- the sample was crystallized hydrothermally at 190 °C for 24 hours.
- After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times.
- the final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours.
- the material was confirmed to be of the CHA structure by XRD.
- Catalyst 8 was synthesized using the following molar ratios lAl 2 O 3 :0.4SiO 2 : lP 2 O 5 :60H 2 O:2TEAOH:0.05SnO.
- Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and tin oxide were then added and the final mixture was stirred for 30 minutes.
- Catalyst 9 was synthesized using the following molar ratios lAl 2 O3:0.4SiO 2 : lP 2 O 5 :60H 2 O:2TEAOH:0.05TiO.
- Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and titanium ethoxide were then added and the final mixture was stirred for 30 minutes.
- Catalyst 10 was synthesized using the following molar ratios lAl 2 O 3 :0.4SiO 2 : lP 2 O 5 :60H 2 O:2TEAOH:0.05ReO.
- Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and ammonium perrhenate were then added and the final mixture was stirred for 30 minutes.
- the slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave.
- the sample was crystallized hydrothermally at 190-200 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times.
- the final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.
- FIG. 3A is a SEM image of the catalyst of Example 2 at magnification of 2 kx, viewing field of 12.8 micrometers.
- FIG. 3B is a SEM image of the catalyst of Example 2 at magnification of 19.999 kx, viewing field of 12.8 micrometers.
- FIG. 3B is a SEM image of the catalyst of Example 2 at magnification of 20.001 kx, viewing field of 12.8 micrometers.
- FIG. 4 is a SEM image of the crystals of Example 3 at a scale of 4 ⁇ . From the SEM, it was determined that regular cubed shaped nanoparticles of FeAPSO-34 having average dimension of 500 nm were formed.
- FIG. 5 is a SEM image of crystals from a TEA templated MnAPSO-34 catalyst of the prior art at 2 kx magnification taken at 20 kV (See, Wei et al), which has a particles of approximately 4-5 microns (4000 to 5000 nm).
- the catalyst powder was pressed and then crushed and sized between 20 and 40 mesh screens.
- a fresh load of sized (20-40 mesh) catalyst (1.0 g) was loaded in a stainless steel tubular (1/2-inch outer diameter) reactor.
- the catalyst was dried at 200 °C under N 2 flow (100 cm 3 /min) for an hour and then temperature was raised to 450 °C at which time N 2 was replaced by methyl chloride feed (100 cm 3 /min) containing 20 mol% CH 3 C1 in N 2 .
- the weight hourly space velocity (WHSV) of CH 3 C1 was about 0.8 h "1 to 3.0 h "1 and reactor inlet pressure was about 0 MPa.
- the percent CH 3 C1 conversion, C 2 percent selectivity, C 3 percent selectivity of the catalyst of present invention and the comparative catalyst are listed in Table 3 at 3 h "1 , 450 °C, and 0 psig. Selectivities were based on methyl chloride and are carbon-based.
- FIG. 6 shows graphs of percent CH 3 C1 conversion of catalysts 1, 2, and 4-7 listed in Table 2 of present invention and the comparative catalyst (SAPO-34).
- FIG. 7 shows graphs of percent CH 3 C1 conversion of the catalysts 2 and 3 (MnAPSO-34) of present invention and the comparative catalyst (SAPO-34).
- FIG. 8 shows graphical representations of the data in Table 3 for MnAPSO-34.
- the graphs show CH 3 C1 conversion, ethylene selectivity, propylene selectivity and methane selectivity of the catalyst 2 (MnAPSO-34) of present invention and the comparative catalyst (SAPO-34).
- FIGS. 9-11 show graphical representations of the data for catalysts 8-10 in Table 3 respectively.
- the graphs show the CH 3 C1 conversion, ethylene selectivity, and propylene selectivity of separately catalyst 8 (SnAPSO-34), catalyst 9 (TiAPSO-34), and catalyst 10 (ReAPSO-34) of present invention and the comparative catalyst (SAPO-34).
- the higher ethylene selectivity of the TEAOH templated MeAPSO-34 catalysts was attributed to higher acidity of the catalyst due to the presence of the Lewis acid metal.
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Abstract
Disclosed are methods and systems of catalyzing the reaction of alkyl halides to light olefins using a TEAOH templated MeAPSO-34 molecular sieve catalyst. These methods and systems have been shown to have maximum combined selectivity of ethylene and propylene of at least 70% or 90% to 98%.
Description
TETRAETHYL AMMONIUM HYDROXIDE TEMPLATED MeAPSO MOLECULAR SIEVE CATALYSTS FOR CONVERSION OF ALKYL CHLORIDES TO OLEFINS
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority of U.S. Provisional Patent Application No. 62/309, 130 filed March 16, 2016, and U.S. Provisional Patent Application No. 62/366,894 filed July 26, 2016. The entire contents of each of the above-referenced disclosures are specifically incorporated herein by reference without disclaimer.
BACKGROUND OF THE INVENTION
A. Field of the Invention [0002] The invention generally concerns the use of tetraethyl ammonium hydroxide templated metal incorporated silicoaluminophosphate (MeAPSO) molecular sieve catalysts to catalyze the reaction of alkyl halides to light olefins.
B. Description of Related Art
[0003] Light olefins such as ethylene and propylene are used by the petrochemical industry to produce a variety of key chemicals that are then used to make numerous downstream products. By way of example, both of these olefins are used to make a multitude of plastic products that are incorporated into many articles of manufacture. FIGS. 1 A and IB provide examples of products generated from ethylene (FIG. 1 A) and propylene (FIG. IB).
[0004] Methane activation to higher hydrocarbons, especially to light olefins, has been the subject of great interest over many decades. Recently, the conversion of methane to light olefins via a two-step process that includes conversion of methane to methyl halide {e.g., methyl chloride) followed by conversion of the methyl halide to light olefins has attracted great attention. Micro pore zeolite {e.g., ZSM-5) or zeolite type catalysts {e.g., SAPO-34) have been commonly employed for methyl chloride (or other methyl halide) conversion reactions. However, the selectivity to a desired olefin {e.g., propylene), rapid catalyst deactivation due to carbon deposition (coking), and the synthesis cost of the catalyst remain the major challenges for scale-up and commercial success of the reaction.
[0005] SAPO catalysts have an open microporous structure with regularly sized channels, pores or "cages." These materials are sometimes referred to as "molecular sieves" in that
they have the ability to sort molecules or ions based primarily on the size of the molecules or ions. SAPO materials are both microporous and crystalline, and have a three-dimensional crystal framework of P04 +, A104 " and Si04 tetrahedra. SAPO-34 and MeSAPO-34 catalysts have been prepared by a range of methods. Various synthetic methods using templates have been employed to prepare SAPO molecular sieves and metal incorporated SAPO molecular sieves. By way of example, Razavian et al. in "Recent Advances in Silicoaluminophosphate Nanocatalysts Synthesis Techniques and Their Effects on Particle Size Distribution, Reviews on Advancement of Material Science, 2011, Vol. 29, pp. 83-99 describes various templating agents to make SAPO-34 catalysts. MeAPSO molecular sieves with a RHO framework for a gas absorption process are described in U.S. Patent Application Publication No. 20150147269 to Tian et al. Other references that use amines as the templating agent to make MeAPSO molecular sieves include Chinese Patent No. 100448537 to Wei et al. and U.S. Patent Application Publication No. 20100310440 to Bull et al. The templating agent used in each of these references was morpholine or mixtures that include morpholine.
[0006] MnAPSO made using triethylamine as a templating agent has been used in chloromethane to olefin reactions {See, for example, Wei et al., in "Study of Mn incorporation into SAPO framework: Synthesis characterization and catalysis in chloromethane conversion to light olefins", Microporous and Mesoporous Materials 2006, Vol. 90, pp. 188-197). The produced crystals in Wei et al. were larger than SAPO-34 crystals prepared under the same conditions. This catalyst suffered from loss of activity after sixty minutes of time on stream.
SUMMARY OF THE INVENTION
[0007] A discovery has been made that addresses the problems {e.g., low catalytic activity and fast deactivation) associated with using SAPO-34 catalysts in alkyl halide to olefin reactions. The discovery is premised on a metal incorporated SAPA-34 (MeAPSO-34, where Me is the total metal) catalyst prepared using tetraethylammonium hydroxide (TEAOH) as the templating agent, which results in a catalyst having a small particle size {e.g., 200 nm to 1000 nm or 200 nm to 500 nm, or less than 1000 nm) when compared with MeAPSO-34 made using other amine templating agents or mixtures of templating agents. Surprisingly, using TEAOH resulted in catalyst particles of comparatively smaller size than the prior art (see, e.g., FIGS. 3-5). Further, these smaller sized catalysts of the present
invention had commercially relevant activity and conversion and selectivity properties when used in the alkyl halide to light olefin reaction process. Therefore, the catalysts of the present invention offer a more efficient and scalable product for the alkyl halide to light olefin (e.g., C2 to C4 olefins) reaction process. [0008] In one aspect of the present invention, there is disclosed a method for converting an alkyl halide to an olefin, the method includes contacting a tetraethylammonium hydroxide (TEAOH) templated metal silicoaluminophosphate-34 (MeAPSO-34) catalyst with a feed including an alkyl halide (e.g., methyl halide or methyl chloride) under reaction conditions sufficient to produce an olefin hydrocarbon product that includes olefins. The metal in the MeAPSO-34 is incorporated into the SAPO-34 framework. The metal can be manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof, preferably manganese, tin, manganese and iron, manganese and germanium, manganese and tin, or tin and iron. The TEOH templated MeAPSO-34 catalyst can be the reaction product of heat treatment of a synthesis mixture having a molar composition of: aAl:6Si:cP:i¾0:eTEAOH:/ exOy where 0 < α≤1, 0 < 6≤1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 <f< 1, x is 1 to 2, and_y is 1 to 3. In one instance, a is 1, b is 0.4, c is 1, d is 60, e is 2 and / is 0.05 or 0.1. Heat treatment can include (a) heating the synthesis mixture to obtain a crystalline material; and (b) calcining the crystalline material. In some aspects, the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt.% alcohol, or preferably is alcohol free. The olefins can include C2-C4 olefins and the maximum combined selectivity of ethylene and propylene can be at least 70%, preferably at least 80%), or more preferably 90%> to 98%>, the maximum combined space time yield of ethylene and propylene can be at least 1/hr or 1/hr to 3/hr; and the maximum conversion of alkyl halide can be at least 80%> or 85%> to 100%>. Maximum selectivity of ethylene can be 40%) to 55%) and the maximum selectivity of propylene can be 30%> to 45%>. The produced olefin hydrocarbon product can be collected, stored, transported, or combinations thereof. Reaction conditions for the conversion of an alkyl halide to olefins can include an average temperature from 300 °C to 500 °C, an average pressure of 0.5 MPa or less, and a weighted hourly space velocity (WHSV) of 0.5 to 10 h"1.
[0009] In certain aspects of the method, the reaction for converting an alkyl halide to an olefin occurs in a fluid catalytic cracking (FCC) process or reactor or fluidized circulating bed process or reactor. The method can further include collecting or storing the produced
olefin hydrocarbon product and using the produced olefin hydrocarbon product to produce a petrochemical or a polymer. The method can also include regenerating the used/deactivated catalyst in a continuous process such as a FCC-type process or reactor or a circulating catalyst bed process or reactor. [0010] In some embodiments, a catalyst capable of catalyzing an alkyl halide to olefin reaction is described. The catalyst can have the general formula of eTEAOH(Me SiaAl¾Pc)02, where: Me is manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof and Me is incorporated into the framework of the catalyst; e is the molar amount of tetraethylammonium hydroxide (TEOH) per mole of (Me SiaAl¾Pc)02; and a, b, and c are the molar fractions of metal, silicon, aluminum, and phosphorous respectively, where 0 < e < 4, 0 </< l, 0 < α <1, 0 < ό < 1, 0 < c < l, and the sum off, a, b, and c is equal to 1. The catalyst can be in particulate form and have an average particle size of 200 to 1000 nm or 200 nm to 500 nm. Surprisingly, it was found that the TEAOH templated catalyst had a particle size less than the particle size of a triethyl amine templated MeAPSO-34 catalyst or SAPO-34 catalyst. In one embodiment, the catalyst can have a formula of (Sn/SiaAl¾Pc)02, where a, b, and c are the molar fractions of tin, silicon, aluminum, and phosphorous respectively, where 0 </< l, 0 < a <l, 0 < 0 < l, 0 < c < l, and the sum off, a, b, and c is equal to 1.
[0011] Methods of making the catalyst of the present invention are also described. A method can include (a) heating a synthesis mixture having has a molar composition of: aAl:6Si:cP:<¾0:eTEAOH:/ exOy where 0 < a < 1, 0 < b < 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 </< l, is l to 2 and y is 1 to 3 to obtain a crystalline material; and (b) calcining the crystalline material (e.g., heating the crystalline material in air at a temperature of 450 °C to 600 °C). Heating the synthesis mixture can include hydrothermally crystallizing the synthesis mixture at 180 °C to 210 °C for 18 to 48 hours under autogenous pressure; and drying the mixture at 90 °C to 110 °C.
[0012] In another embodiment of the present invention there is disclosed a system for producing olefins. The system can include an inlet for a feed including the alkyl halide, a reaction zone that is configured to be in fluid communication with the inlet, and an outlet configured to be in fluid communication with the reaction zone to remove an olefin hydrocarbon product from the reaction zone. The reaction zone can include the feed and the TEAOH templated MeAPSO-34 catalyst described above and in the specification. During
use, the reaction zone can further include a FCC-type reactor or a circulating catalyst bed reactor, and a collection device that is capable of collecting the olefin hydrocarbon product.
[0013] In the context of the present invention 20 embodiments are described. Embodiment 1 describes a method for converting an alkyl halide to an olefin. The method can include contacting a tetraethylammonium hydroxide (TEAOH) templated metal silicoaluminophosphate-34 (MeAPSO-34) catalyst with a feed comprising an alkyl halide under reaction conditions sufficient to produce an olefin hydrocarbon product comprising olefins, wherein the metal (Me) is incorporated into the SAPO-34 framework. Embodiment 2 is the method of embodiment 1, wherein the incorporated metal (Me) is manganese (Mn), magnesium (Mg), cobalt (Co), nickel (Ni), iron (Fe), copper (Cu), zinc (Zn), tin (Sn), germanium (Ge), titanium (Ti), rhenium (Re), or any combination thereof, preferably manganese, tin, manganese and iron, manganese and germanium, manganese and tin, or tin and iron. Embodiment 3 is the method of any one of embodiments 1 to 2, wherein the olefins are C2 to C4 olefins. Embodiment 4 is the method of embodiment 3, wherein the maximum combined selectivity of ethylene and propylene is at least 70%, preferably at least 80%, or more preferably 90% to 98%, the maximum combined space time yield of ethylene and propylene is at least 1/hr or 1/hr to 3/hr, and the maximum conversion of alkyl halide is at least 80% or 85% to 100%. Embodiment 5 is the method of embodiment 4, wherein the maximum selectivity of ethylene is 40% to 55%, and the maximum selectivity of propylene is 30% to 45%. Embodiment 6 is the method of any one of embodiments 1 to 5, wherein the reaction conditions include a temperature from 300 °C to 500 °C, a pressure of 0.5 MPa or less, and a weighted hourly space velocity (WHSV) of 0.5 to 10 h"1. Embodiment 7 is the method of any one of embodiments 1 to 5, wherein the TEAOH templated MeAPSO-34 catalyst is the reaction product of heat treatment of a synthesis mixture having a molar composition of: aAl203:6Si02:cP205:^20:eTEAOH:/ exOy; where 0 < α≤ 1, 0 < 6≤ 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 < f < 1, x is 1 to 2, and y is 1 to 3. Embodiment 8 is the method of embodiment 7, wherein a is 1, b is 0.4, c is I, d is 60, e is 2 and /is 0.05 or 0.1. Embodiment 9 is the method of embodiment 7, wherein the heat treatment comprises: (a) heating the synthesis mixture to obtain a crystalline material; and (b) calcining the crystalline material. Embodiment 10 is the method of any one of embodiments 1 to 9, wherein the alkyl halide is a methyl halide, preferably methyl chloride. Embodiment 1 1 is the method of any one of embodiments 1 to 10, wherein the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt. % alcohol, or preferably is alcohol free. Embodiment 12 is the
method of any one of embodiments 1 to 11, wherein the reaction occurs in a fixed feed reactor, a fluid catalytic cracking (FCC) reactor or fluidized circulating bed reactor. Embodiment 13 is the method of any one of embodiments 1 to 12, further comprising collecting or storing the produced olefin hydrocarbon product. [0014] Embodiment 14 is a catalyst capable of catalyzing an alkyl halide to an olefin reaction, the catalyst having a general formula of eTEAOH(Me/SiaAl¾Pc)02, where Me is manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof and Me is incorporated into the framework of the catalyst, e is the molar amount of tetraethylammonium hydroxide (TEAOH) per mole of (Me SiaAl¾Pc)02 and a, b, and c are the molar fractions of metal, silicon, aluminum, and phosphorous respectively and 0 < e < 4, 0 <f< 1, 0 < a < 1, 0 < b < 1, 0 < c < 1, and f+a+b+c = 1, wherein the catalyst is capable of catalyzing an alkyl halide to olefin reaction. Embodiment 15 is the catalyst of embodiment 14, having an average particle size of 200 nm to 1000 nm or 200 nm to 500 nm. Embodiment 16 is the catalyst of any one of embodiments 14 to 15, wherein the particle size of the catalyst is less than the particle size of a triethyl amine templated catalyst and/or a mixed templated catalyst.
[0015] Embodiment 17 is a system for producing olefins, the system comprising: an inlet for a feed comprising an alkyl halide; a reaction zone that is configured to be in fluid communication with the inlet, wherein the reaction zone comprises the feed and the catalyst of any one of embodiments 14 to 16; and an outlet configured to be in fluid communication with the reaction zone to remove an olefin hydrocarbon product from the reaction zone. Embodiment 18 is the system of embodiment 17, wherein the reaction zone includes a fluid catalytic cracking (FCC)-type reactor or a circulating catalyst bed reactor. Embodiment 19 is the system of any one of embodiments 17 to 18, further comprising a collection device that is capable of collecting the olefin hydrocarbon product. Embodiment 20 is a method of making the catalyst of any one of embodiments 14 to 16, the method comprising: (a) heating a synthesis mixture to obtain a crystalline material; and (b) calcining the crystalline material, wherein the synthesis mixture has a molar composition of aAl203:*Si02:cP205:<iH20:eTEAOH^MexOy where 0 < a < 1, 0 < b < 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 <f< 1, x is 1 to 2, and^ is 1 to 3.
[0016] The following includes definitions of various terms and phrases used throughout this specification.
[0017] The term "catalyst" means a substance which alters the rate of a chemical reaction. "Catalytic" means having the properties of a catalyst.
[0018] The term "conversion" means the mole fraction (i.e., percent) of a reactant converted to a product or products. [0019] The term "selectivity" refers to the percent of converted reactant that went to a specified product, for example C2-C4 olefin selectivity is the % of alkyl halide that formed C2-C4 olefins.
[0020] The term "about" or "approximately" are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
[0021] The term "substantially" and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.
[0022] The terms "wt.%", "vol.%", or "mol.%" refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.
[0023] The terms "inhibiting" or "reducing" or "preventing" or "avoiding" or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.
[0024] The term "effective," as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.
[0025] The use of the words "a" or "an" when used in conjunction with any of the terms "comprising," "including," "containing," or "having" in the claims or the specification may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."
[0026] The words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and
any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
[0027] The catalysts of the present invention can "comprise," "consist essentially of," or "consist of particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase "consisting essentially of," in one non- limiting aspect, a basic and novel characteristic of the catalysts of the present invention are their size {e.g., 200 nm to 1000 nm or 200 nm to 500 nm, or less than 1000 nm) as well as their ability to selectivity produce light olefins, and in particular, ethylene and propylene, from alkyl halides {e.g., methyl chloride).
[0028] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIGS 1A and IB depict illustrations of various chemicals and products that can be produced from ethylene (FIG. 1 A) and propylene (FIG. IB).
[0030] FIG. 2 depicts a system for producing olefins from alkyl halides using the catalyst of the present invention.
[0031] FIGS. 3A and 3B are SEM images of crystals of TEAOH templated MnAPSO-34 catalyst of the present invention at various magnifications. [0032] FIG. 4 is an SEM image of crystals of TEAOH templated FeAPSO-34 catalyst of the present invention.
[0033] FIG. 5 is an SEM image of crystals of TEA templated MnAPSO-34 catalyst of the prior art.
[0034] FIG. 6 shows graphs of percent CH3C1 conversion of the TEAOH templated catalysts of present invention and the comparative catalyst (SAPO-34).
[0035] FIG. 7 shows graphs of percent CH3CI conversion of the TEAOH templated catalysts 2 and 3 (MnAPSO-34) of present invention and the comparative catalyst (SAPO- 34).
[0036] FIG. 8 shows graphs of CH3CI conversion, ethylene selectivity, propylene selectivity and methane selectivity of the catalyst 2 (MnAPSO-34) of present invention and the comparative catalyst (SAPO-34).
[0037] FIG. 9 shows graphs of CH3CI conversion, ethylene selectivity, and propylene selectivity of the catalyst 8 (SnAPSO-34) of present invention and the comparative catalyst (SAPO-34).
[0038] FIG. 10 shows graphs of CH3CI conversion, ethylene selectivity, and propylene selectivity of the catalyst 10 (TiAPSO-34) of present invention and the comparative catalyst (SAPO-34). [0039] FIG. 11 shows graphs of CH3CI conversion, ethylene selectivity, and propylene selectivity of the catalyst 1 1 (ReAPSO-34) of present invention and the comparative catalyst (SAPO-34).
DETAILED DESCRIPTION OF THE INVENTION
[0040] While currently available SAPO-34 catalysts, and some TEA templated MeAPSO-34 catalysts, show high activity for alkyl halide conversion with selectivity to light olefins (e.g., ethylene and propylene), they deactivate quickly. A discovery has been made that provides a solution to the deactivation of the catalyst. The discovery is premised on forming a microporous catalyst having a small crystal size and desirable surface Bransted acidity using tetraethylammonium hydroxide as the templating agent. The catalyst is capable of converting alkyl halides to olefins with less deactivation than SAPO-34 catalysts made with the same templating agent. Further, the catalysts used in the methods and systems of the current invention have been shown to have maximum combined selectivity of ethylene and propylene of at least 70% or ranging from 90% to 98%.
[0041] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.
A. Methods of Making TEAOH Templated MeAPSO-34 Catalysts
[0042] The MeAPSO-34 catalysts of the present invention are prepared as TEAOH templated SAPO-34 catalysts using TEAOH in the hydrothermal crystallization process of making the catalyst. The metal atom is incorporated into the SAPO-34 framework. The addition of a structure-directing or template agent/ion effects the pre-organization provided by the coordination sphere and can results in significant modification of physical/chemical/electronic properties of the template complex formed. It was surprisingly found that the addition of TEAOH as the structure-directing or template agents resulted in a profound effect on the resultant crystal morphology (size, shape, dispersion, surface area, distribution) and surface Bransted acidity of the MeAPSO-34 catalyst formed. This is illustrated in non-limiting examples in FIGS. 1-4 as well as comparative FIG. 5.
[0043] Non-limiting examples of making MeAPSO catalysts of the present invention are provided in the Examples section. Generally, MeAPSO catalysts are prepared using a gel containing aluminum (Al), phosphorus (P), silicon (Si) compounds, and metal precursors with structure-directing agents under crystallization conditions. A general non-limiting method of making the MeAPSO catalysts includes preparing an aqueous mixture of aluminum z'so-propoxide with phosphoric acid and, optionally hydrochloric acid. Colloidal silica can be added to the aluminum/phosphorous mixture with agitation followed by the metal precursor, and then addition of tetraethylammonium hydroxide (TEAOH). The metal precursor can be salts (e.g., acetate or nitrate salts) of the desired metal. Non-limiting examples of metal salts include acetate or nitrate salts of manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, and rhenium metals. In some embodiments, salt solutions of two or more metals can be used. For example, manganese and iron salt solution(s), manganese and germanium salt solution(s), manganese and tin salt solution(s), or tin and iron salt solution(s) can be used. The synthesis mixture can have molar composition of: αΑ1203 : b Si02 : cP205 :dH20 : eTE AOH: MexOy where 0 < a < 1, 0 < b < 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 <f< 1, x is 1 to 2, and y is 1 to 3.
Non-limiting nano-crystal MeAPSO-34 catalysts can include a molar ratio where a is 1, b is
0.4, c is l, 50-70, e is 2 and /is 0.05; a is 1, b is 0.4, c is 1, <i is 50-70, e is 2 and /is 0.1; a is 1, b is 0.4, c is 1, d is 50-70, e is 3 and /is 0.05; a is 1, b is 0.4, c is 1, d is 50-70, e is 3 and is 0.1; a is 1, b is 0.4, c is 1, <f is 50-70, e is 4 and /is 0.05; a is 1, 6 is 0.4, c is 1, <f is 50-70, e is 4 and /is 0.1; a is 1, b is 0.35, c is 1, d is 50-70, e is 2 and /is 0.05; a is 1, b is 0.35, c is
1, d is 50-70, e is 2 and /is 0.1; a is 1, Ms 0.35, c is 1, d is 50-70, e is 3 and /is 0.05; a is 1, b is 0.35, c is 1, d is 50-70, e is 3 and /is 0.1; a is 1, is 0.35, c is I, d is 50-70, e is 4 and /is 0.05; a is 1, is 0.35, c is 1, <iis 50-70, e is 4 and /is 0.1; a is 1, Ms 0.45, c is 1, <i is 50-70, e is 2 and /is 0.05; a is 1, £ is 0.45, c is 1, d s 50-70, e is 2 and /is 0.1; a is 1, £ is 0.45, c is 1, d is 50-70, e is 3 and /is 0.05; a is 1, b is 0.45, c is 1, d is 50-70, e is 3 and /is 0.1 ; a is 1, b is 0.50, c is 1, i/ is 50-70, e is 2 and /is 0.05; a is 1, is 0.5, c is 1, d \s 50-70, e is 2 and /is 0.1; a is 1, £ is 0.4, c is 1, d is 60, e is 2 and /is 0.05; a is 1, b is 0.4, c is 1, d is 60, e is 2 and /is 0.1.
[0044] The synthesis mixture can then be heat treated to form a crystalline material. Crystal growth can be performed in a pressure vessel, such as an autoclave using autogenous pressure, by a temperature-difference method, temperature-reduction method, or a metastable-phase technique. In a particular embodiment, the crystal growth can be performed in an autoclave. The heat treatment can be performed at 150 °C to 250 °C, preferably 175 °C to 225 °C, or more preferably at 180 °C to 210 °C for a desired amount of time {e.g., 18 to 48 hours, or 24 hours) in an heated high pressure reactor {e.g., autoclave) with or without agitation. Average crystallization temperatures can range from 180 °C to 210 °C, and all temperatures there between including 181 °C , 182 °C , 183 °C , 184 °C , 185 °C, 186 °C, 187 °C, 188 °C, 189 °C, 190 °C, 191 °C, 192 °C, 193 °C, 194 °C, 195 °C, 196 °C, 197 °C, 198 °C, or 199 °C, 200 °C, 201 °C, 202 °C, 203 °C, 204 °C, 205 °C, 206 °C, 207 °C, 208 °C, or 209 °C. Heating can be performed for 12 hours to 36 hours and all periods of time there between including 12 hours, 15 hours, 20 hours, 25 hours, 30 hours, or 35 hours. After heating, the crystalline material can be separated and washed with water, and dried at about 90 °C and then calcined to remove any remaining templating agent. The calcining step can be performed in air at 400 °C to 700 °C, preferably 450 °C to 650 °C, or more preferably from 500 °C to 600 °C, for a sufficient period of time {e.g., 3 to 10 hours). Without wishing to be bound by theory, it is believed that MeAPSO-34 catalysts prepared using a TEAOH as a structure-directing agent provides effects on the chemical composition, morphology, and
surface acidity that benefit the methods and systems for converting alkyl halides to olefins as currently disclosed.
B. Structural Characteristics of the TEAOH Templated MeAPSO-34 Catalysts
[0045] The MeAPSO-34 crystal produced using the methods above and in the Examples above can have any type of morphology. Non-limiting examples of morphologies include a wire, a particle, a sphere, a rod, a tetrapod, a hyper-branched structure, a tube, a cube, a plate, or mixtures thereof. The crystalline MeAPSO-34 catalysts can have an average particle size of 200 nm to 1000 nm or 200 nm to 500 nm. The average particle size of 200 nm to 1000 nm includes all average particle sizes between 200 nm to 1000 nm, for instance 200 nm, 225 nm, 250 nm, 275 nm, 300 nm, 325 nm, 350 nm, 375 nm, 400 nm, 425 nm, 450 nm, 475 nm, 500 nm, 525 nm, 550 nm, 575 nm, 600 nm, 625 nm, 650 nm, 675 nm, 700 nm, 725 nm, 750 nm, 775 nm, 800 nm, 825 nm, 850 nm, 875 nm, 900 nm, 925 nm, 950 nm, 975 nm, 1000 nm, and all values and ranges in between. Particle size can be determined using Scanning Electron Microscopy (SEM) or Transmission Electron Spectroscopy (TEM). C. Olefin Production
1. Methods and Systems
[0046] The TEAOH templated MeAPSO catalysts of the present invention help to catalyze the conversion of alkyl halides to C2-C4 olefins such as ethylene, propylene and butene (butylene). Butene can include 1-butene, (Z -but-2-ene, (J¾)-but-2-ene, 2- methylpropene, and combinations thereof. The following non-limiting two-step process is an example of conversion of methane to methyl chloride and conversion of methyl chloride to ethylene, propylene and butene. Equation (II) illustrates the reactions that are believed to occur in the context of the present invention:
CH4 + X2 ► CH3X + HX (I) MeAPSO-34
9CH3X C2H4 + C3H6 + C4H8 + 9HX (II)
Besides the C2-C4 olefins the reaction may produce byproducts such as methane, C5 olefins, C2-C5 alkanes and aromatic compounds such as benzene, toluene and xylene.
[0047] Conditions sufficient for olefin production (e.g., ethylene, propylene and butylene as shown in Equation (II)) include temperature, time, alkyl halide concentration, space
velocity, and pressure. The temperature range for olefin production may range from about 300 °C to 500 °C, preferably ranging 350 °C to 450 °C. A weight hourly space velocity (WHSV) of alkyl halide higher than 0.5 h"1 can be used, preferably between 1.0 and 10 h"1, more preferably between 2.0 and 3.5 h"1. The conversion of alkyl halide is carried out at a pressure less than 145 psig (1 MPa) and preferably less than 73 psig (0.5 MPa), or at atmospheric pressure. The conditions for olefin production may be varied based on the type of the reactor.
[0048] The methods and system disclosed herein also include the ability to regenerate used/deactivated catalyst in a continuous process such as in a fluid catalytic cracking (FCC)- type process or reactor or a circulating catalyst bed process or reactor. The method and system can further include collecting or storing the produced olefin hydrocarbon product along with using the produced olefin hydrocarbon product to produce a petrochemical or a polymer.
[0049] Referring to FIG. 2, a system 100 is illustrated, which can be used to convert alkyl halides to olefin hydrocarbon products with the TEAOH templated MeAPSO catalysts of the present invention. The system 100 can include an alkyl halide source 102, a reactor 104, and a collection device 106. The alkyl halide source 102 can be configured to be in fluid communication with the reactor 104 via an inlet 108 on the reactor. As explained above, the alkyl halide source can be configured such that it regulates the amount of alkyl halide feed entering the reactor 104. The reactor 104 can include a reaction zone 110 having the TEAOH templated MeAPSO-34 catalyst 112 of the present invention. The amounts of the alkyl halide feed and the catalyst 112 used can be modified as desired to achieve a given amount of product produced by the system 100. Non-limiting examples of reactors that can be used include fixed-bed reactors, fluidized bed reactors, bubbling bed reactors, slurry reactors, rotating kiln reactors, or any combinations thereof when two or more reactors are used. In preferred aspects, reactor 104 is a fluid catalytic cracking (FCC)-type reactor or a circulating catalyst bed reactor that permits the regeneration of used/deactivated catalyst in a continuous process. The reactor 104 can include an outlet 114 for products produced in the reaction zone 110. The products produced can include ethylene, propylene and butylene. The collection device 106 can be in fluid communication with the reactor 104 via the outlet 114. Both the inlet 108 and the outlet 114 can be open and closed as desired. The collection device 106 can be configured to store, further process, or transfer desired reaction products {e.g., C2-C4
olefins) for other uses. By way of example only, FIG. 1 provides non-limiting uses of ethylene and propylene produced from the catalysts and processes of the present invention. Still further, the system 100 can also include a heating source 1 18. The heating source 1 18 can be configured to heat the reaction zone 18 to a temperature sufficient (e.g., 300 to 500 °C or 325 to 375 °C) to convert the alkyl halides in the alkyl halide feed to olefin hydrocarbon products. Non-limiting examples of a heating source 1 18 can be a temperature controlled furnace, tube-in-shell heat exchangers, heaters, and the like. Additionally, any unreacted alkyl halide can be recycled and included in the alkyl halide feed to further maximize the overall conversion of alkyl halide to olefin products. Further, certain products or byproducts such as butylene, C5+ olefins and C2+ alkanes can be separated and used in other processes to produce commercially valuable chemicals (e.g., propylene). This increases the efficiency and commercial value of the alkyl halide conversion process of the present invention.
2. Catalyst Activity/Selectivity
[0050] Catalytic activity as measured by alkyl halide conversion can be expressed as the % moles of the alkyl halide converted with respect to the moles of alkyl halide fed. In particular aspects, the combined selectivity of ethylene and propylene is at least 70%, preferably at least 80%>, more preferably at least 90%, or most preferably 90% to 98% under certain reaction conditions, wherein the maximum combined space time yield (STY) of ethylene and propylene is at least 1/hr or 1/hr to 3/hr, and/or wherein the maximum conversion of alkyl halide is at least 65% or 70% to 80%. In certain instances, the selectivity of ethylene is about 40% or higher and the selectivity of propylene is about 30% or higher, wherein the maximum selectivity of ethylene is 50% to 60% and the maximum selectivity of propylene is 35% to 45%.
[0051] As an example, chloromethane (CH3C1) is used here to define conversion and maximum selectivity of products by the following equations (III)-(VII):
(CH3C1)° - (CH3CI)
% CH3CI Conversion x 100, (III)
(CH3C1)° where, (CH3CI)0 and (CH3C1) are moles of methyl chloride in the feed and reaction product, respectively.
[0052] Maximum selectivity is defined as C-mole% and are defined for ethylene, propylene, and so on as follows:
2(C2H4)
% Ethylene Selectivity = x 100, (IV)
(CH3C1)° - (CH3CI) where the numerator is the carbon adjusted mole of ethylene and the denominator is the moles of carbon converted.
[0053] Maximum selectivity for propylene may be expressed as:
3(C3H6)
% Propylene Selectivity = x 100, (V)
(CH3C1)° - (CH3CI) where the numerator is the carbon adjusted mole of propylene and the denominator is the moles of carbon converted.
[0054] Maximum selectivity for butylene may be expressed as: 4(C4H8)
% Butylene Selectivity = x 100, (VI)
(CH3C1)° - (CH3CI)
where the numerator is the carbon adjusted mole of butylene and the denominator is the moles of carbon converted. [0055] Selectivity for aromatic compounds may be expressed as:
6(C6H6) + 7(C7H8) + 8(C8H10)
% Aromatics Selectivity = x 100 (VII)
(CH3C1)° - (CH3CI) where the numerator is the carbon adjusted mole of aromatic compounds and the denominator is the moles of carbon converted.
D. Materials
1. MeAPSO Materials
[0056] MeAPSO catalysts are made from silicon (Si), aluminum (Al), and phosphorous (P) in various molar ratios. Non-limiting examples of silicon sources include colloidal silica, fumed silica, tetramethyl orthosilicate, tetraethyl orthosilicate, or tetraisopropyl orthosilicate.
Non-limiting examples of aluminum sources include aluminum methoxide, aluminum ethoxide, aluminum isopropoxide, or aluminums tert-butoxide. Non-limiting examples of phosphorus sources include phosphoric acid. These compounds can be obtained from various commercial sources, of which Sigma Aldrich® (U.S. A) is a non-limiting example. Templating agents can be used to direct crystal growth, pore size and the like. The templating agent, tetraethyl ammonium hydroxide (TEAOH) is available from commercial sources, for example, Sigma Aldrich® (U.S. A) or SACHEM, Inc., (USA) under the tradename ZeoGen™.
[0057] The metal or metal oxide denoted "Me" in the MeASPO materials can include metals or metal oxides from Columns 2, 4, 7 to 12, and 14 of the Periodic Table or combinations thereof. Non-limiting examples of metals include manganese (Mn), magnesium (Mg), copper (Cu), cobalt (Co), iron (Fe), nickel (Ni), germanium (Ge), tin (Sn), titanium (Ti), rhenium (Re), or zinc (Zn). The metals or metal oxides or metal precursors can be purchased from commercial manufactures such as Sigma-Aldrich®. 2. Alkyl Halide Feed
[0058] The alkyl halide feed includes one or more alkyl halides. The alkyl halide feed may contain alkyl monohalides, alkyl dihalides, alkyl trihalides, preferably alkyl monohalide with less than 10 mol.% of other halides relative to the total halides. The alkyl halide feed may also contain nitrogen, helium, steam, and so on as inert compounds. The alkyl halide in the feed may have the following structure: CnH(2n+2)-m m, where n and m are integers, n ranges from 1 to 5, preferably 1 to 3, even more preferably 1, m ranges 1 to 3, preferably 1, X is Br, F, I, or CI. In particular aspects, the feed may include about 10, 15, 20, 40, 50 mol.% or more of the alkyl halide. In particular embodiments, the feed contains up to 10 mol.% or more of a methyl halide. In preferred aspects, the methyl halide is methyl chloride, methyl bromide, methyl fluoride, or methyl iodide, or any combination thereof. The feed stream can also include alcohol. In a particular embodiment, the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt.% alcohol, or preferably is alcohol free, and in one instance that alcohol is methanol.
[0059] The production of alkyl halide, particularly of methyl chloride (CH3C1) is commercially produced by thermal chlorination of methane at 400 °C to 450 °C and at a raised pressure. Catalytic oxychlorination of methane to methyl chloride is also known. In addition, methyl chloride is industrially made by reaction of methanol and HC1 at 180 °C to
200 °C using a catalyst. Alternatively, methyl halides are commercially available from a wide range of sources (e.g., Praxair, Danbury, CT; Sigma-Aldrich Co. LLC, St. Louis, Mo.; BOC Sciences USA, Shirley, NY). In preferred aspects, methyl chloride and methyl bromide can be used alone or in combination.
EXAMPLES
[0060] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results. The materials used in the following examples are described in Table 1, and were used as-described unless specifically stated otherwise.
Table 1
EXAMPLE 1
(Preparation of Comparative SAPO-34 Catalyst)
[0061] Comparative Catalyst 1 was synthesized using the following molar ratios lAl2O3:0.4SiO2: lP2O5:60H2O:2TEAOH. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes.
TEAOH was then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL DI water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The SAPO-34 had a Si/Al ratio of 0.18 and a Al/P ratio of 1.34. The material was confirmed to be SAPO-34 by X-ray diffraction (XRD).
EXAMPLE 2
(Preparation of TEAOH Templated MnAPSO-34 Catalysts) [0062] Catalysts 2 and 3 were synthesized using the following molar ratios 1 Al2O3:0.4SiO2: 1Ρ2Ο5:60Η2Ο:2ΤΕΑΟΗ:0.05ΜηΟ and lAl2O3:0.4SiO2: lP2O5:60H2O:2TEAOH:0.1MnO, respectively. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH was added to the mixture and then manganese acetate was added. The final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. Catalyst 2 had a Si/Al ratio of 0.16, a Al/P ratio of 1.19 and contained 1.31 wt.% of Mn based on the total weight of the catalyst. Catalyst 3 had a Si/Al ratio of 0.16, a Al/P ratio of 1.10 and contained 2.34 wt.% of Mn based on the total weight of the catalyst. The material was confirmed to be of the CHA structure by XRD.
EXAMPLE 3
(Preparation of TEAOH Templated FeAPSO-34 Catalyst)
[0063] Catalyst 4 was synthesized using the following molar ratios lAl2O3:0.4SiO2: lP2O5:60H2O:2TEAOH:0.05Fe2O3. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred
for 30 minutes. TEAOH and iron nitrate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Pan- autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.
EXAMPLE 4
(Preparation of TEAOH Templated CoAPSO-34 Catalyst) [0064] Catalyst 5 was synthesized using the following molar ratios lAl2O3:0.4SiO2: lP2O5:60H2O:2TEAOH:0.05CoO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and cobalt acetate tetrahydrate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.
EXAMPLE 5
(Preparation of TEAOH Templated CuAPSO-34 Catalyst)
[0065] Catalyst 6 was synthesized using the following molar ratios lAl2O3:0.4SiO2: lP2O5:60H2O:2TEAOH:0.05CuO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and copper acetate monohydrate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by
centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.
EXAMPLE 6
(Preparation of TEAOH Templated MgAPSO-34 Catalyst)
[0066] Catalyst 7 was synthesized using the following molar ratios lAl2O3:0.4SiO2: lP2O5:60H2O:2TEAOH:0.05MgO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and magnesium acetate tetrahydrate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.
EXAMPLE 7
(Preparation of TEAOH Templated SnAPSO-34 Catalyst) [0067] Catalyst 8 was synthesized using the following molar ratios lAl2O3:0.4SiO2: lP2O5:60H2O:2TEAOH:0.05SnO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and tin oxide were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 200 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.
EXAMPLE 8
(Preparation of TEAOH Templated TiAPSO-34 Catalyst)
[0068] Catalyst 9 was synthesized using the following molar ratios lAl2O3:0.4SiO2: lP2O5:60H2O:2TEAOH:0.05TiO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and titanium ethoxide were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190-200 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD. EXAMPLE 9
(Preparation of TEAOH Templated ReAPSO-34 Catalyst)
[0069] Catalyst 10 was synthesized using the following molar ratios lAl2O3:0.4SiO2: lP2O5:60H2O:2TEAOH:0.05ReO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and ammonium perrhenate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190-200 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.
EXAMPLE 10
(MeSAPO-34 Catalyst Characterization)
[0070] Scanning Electron Microscopy (SEM) analysis. SEM analysis was performed on the comparative Example 1 and inventive sample from Examples 2 and 3 using a JSM-
7800F-PRIME scanning electron microscope operating at 5kV. FIG. 3A is a SEM image of the catalyst of Example 2 at magnification of 2 kx, viewing field of 12.8 micrometers. FIG. 3B is a SEM image of the catalyst of Example 2 at magnification of 19.999 kx, viewing field of 12.8 micrometers. FIG. 3B is a SEM image of the catalyst of Example 2 at magnification of 20.001 kx, viewing field of 12.8 micrometers. From the SEM, it was determined that regular cubed shaped nanoparticles of MnAPSO-34 having average dimension of 500 nm were formed. FIG. 4 is a SEM image of the crystals of Example 3 at a scale of 4 μπι. From the SEM, it was determined that regular cubed shaped nanoparticles of FeAPSO-34 having average dimension of 500 nm were formed. FIG. 5 is a SEM image of crystals from a TEA templated MnAPSO-34 catalyst of the prior art at 2 kx magnification taken at 20 kV (See, Wei et al), which has a particles of approximately 4-5 microns (4000 to 5000 nm).
EXAMPLE 11
(Methyl chloride Conversion Reactions)
[0071] The TEAOH templated MeAPSO-34 catalysts shown in Table 2 and the comparative SAPO-34 catalyst were tested for methyl chloride conversion by using a fixed- bed tubular reactor at about 450 °C for a period of 6 h. The MeAPSO-34 catalysts were made using the same procedure as in Examples 2 and 3 using the various materials in Table 1.
Table 2
The catalyst powder was pressed and then crushed and sized between 20 and 40 mesh screens. In each test, a fresh load of sized (20-40 mesh) catalyst (1.0 g) was loaded in a stainless steel tubular (1/2-inch outer diameter) reactor. The catalyst was dried at 200 °C
under N2 flow (100 cm3/min) for an hour and then temperature was raised to 450 °C at which time N2 was replaced by methyl chloride feed (100 cm3/min) containing 20 mol% CH3C1 in N2. The weight hourly space velocity (WHSV) of CH3C1 was about 0.8 h"1 to 3.0 h"1 and reactor inlet pressure was about 0 MPa. The percent CH3C1 conversion, C2 percent selectivity, C3 percent selectivity of the catalyst of present invention and the comparative catalyst are listed in Table 3 at 3 h"1, 450 °C, and 0 psig. Selectivities were based on methyl chloride and are carbon-based. FIG. 6 shows graphs of percent CH3C1 conversion of catalysts 1, 2, and 4-7 listed in Table 2 of present invention and the comparative catalyst (SAPO-34). FIG. 7 shows graphs of percent CH3C1 conversion of the catalysts 2 and 3 (MnAPSO-34) of present invention and the comparative catalyst (SAPO-34). FIG. 8 shows graphical representations of the data in Table 3 for MnAPSO-34. The graphs show CH3C1 conversion, ethylene selectivity, propylene selectivity and methane selectivity of the catalyst 2 (MnAPSO-34) of present invention and the comparative catalyst (SAPO-34). FIGS. 9-11 show graphical representations of the data for catalysts 8-10 in Table 3 respectively. The graphs show the CH3C1 conversion, ethylene selectivity, and propylene selectivity of separately catalyst 8 (SnAPSO-34), catalyst 9 (TiAPSO-34), and catalyst 10 (ReAPSO-34) of present invention and the comparative catalyst (SAPO-34). The higher ethylene selectivity of the TEAOH templated MeAPSO-34 catalysts was attributed to higher acidity of the catalyst due to the presence of the Lewis acid metal. From the data, it was determined that the TEAOH templated MeAPSO-34 catalysts had better conversion, STY, C2-C3 selectivity, C3 selectivity and activity as compared to the TEAOH templated SAPO-34 (see, for example Wei et al). Without wishing to be bound by theory, it is believed that the smaller particle size of the catalyst attributed to the higher activity and overall selectivity of the MeAPSO-34 catalysts of the present invention as compared to TEAOH templated SAPO-34 catalysts.
Table 3
* Space time yield = Tonnes Ethylene&Propylene/Tonne Catalyst/hr. STY is calculated based on carbon-based selectivities.
Claims
1. A method for converting an alkyl halide to an olefin, the method comprising contacting a tetraethylammonium hydroxide (TEAOH) templated metal silicoaluminophosphate-34 (MeAPSO-34) catalyst with a feed comprising an alkyl halide under reaction conditions sufficient to produce an olefin hydrocarbon product comprising olefins, wherein the metal (Me) is incorporated into the SAPO-34 framework.
2. The method of claim 1, wherein the incorporated metal (Me) is manganese (Mn), magnesium (Mg), cobalt (Co), nickel (Ni), iron (Fe), copper (Cu), zinc (Zn), tin (Sn), germanium (Ge), titanium (Ti), rhenium (Re), or any combination thereof, preferably manganese, tin, manganese and iron, manganese and germanium, manganese and tin, or tin and iron.
3. The method of claim 1, wherein the olefins are C2 to C4 olefins.
4. The method of claim 3, wherein: the maximum combined selectivity of ethylene and propylene is at least 70%, preferably at least 80%, or more preferably 90% to 98%, the maximum combined space time yield of ethylene and propylene is at least 1/hr or 1/hr to 3/hr; and the maximum conversion of alkyl halide is at least 80% or 85% to 100%.
5. The method of claim 4, wherein the maximum selectivity of ethylene is 40% to 55%, and the maximum selectivity of propylene is 30% to 45%.
6. The method of any one of claims 1 to 5, wherein the reaction conditions include a temperature from 300 °C to 500 °C, a pressure of 0.5 MPa or less, and a weighted hourly space velocity (WHSV) of 0.5 to 10 h"1.
7. The method of any one of claims 1 to 5, wherein the TEAOH templated MeAPSO-34 catalyst is the reaction product of heat treatment of a synthesis mixture having a molar composition of:
aAl203:6Si02:cP205:^20:eTEAOH:/ exOy where 0 < a < 1, 0 < b <1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 <f< 1, x is 1 to 2, and y is 1 to 3.
8. The method of claim 7, wherein a is 1, b is 0.4, c is I , d is 60, e is 2 and /is 0.05 or 0.1.
9. The method of claim 7, wherein the heat treatment comprises:
(a) heating the synthesis mixture to obtain a crystalline material; and
(b) calcining the crystalline material.
10. The method of claim 1 , wherein the alkyl halide is a methyl halide, preferably methyl chloride.
1 1. The method of claim 1, wherein the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt. % alcohol, or preferably is alcohol free.
12. The method of claim 1, wherein the reaction occurs in a fixed feed reactor, a fluid catalytic cracking (FCC) reactor or fluidized circulating bed reactor.
13. The method of claim 1, further comprising collecting or storing the produced olefin hydrocarbon product.
14. A catalyst capable of catalyzing an alkyl halide to an olefin reaction, the catalyst having a general formula of: eTEAOH(Me/SiaAl5Pc)02,
where:
Me is manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof and Me is incorporated into the framework of the catalyst;
e is the molar amount of tetraethylammonium hydroxide (TEAOH) per mole of (Me SiaAl¾Pc)02 and a, b, and c are the molar fractions of metal, silicon, aluminum, and phosphorous respectively;
0 < e < 4, 0 <f< 1, 0 < a < 1, 0 < b < 1, 0 < c < 1, and f+a+b+c = 1,
wherein the catalyst is capable of catalyzing an alkyl halide to olefin reaction.
15. The catalyst of claim 14, having an average particle size of 200 nm to 1000 nm or 200 nm to 500 nm.
16. The catalyst of claim 14, wherein the particle size of the catalyst is less than the particle size of a triethyl amine templated catalyst and/or a mixed templated catalyst.
17. A system for producing olefins, the system comprising: an inlet for a feed comprising an alkyl halide; a reaction zone that is configured to be in fluid communication with the inlet, wherein the reaction zone comprises the feed and the catalyst of claim 14; and an outlet configured to be in fluid communication with the reaction zone to remove an olefin hydrocarbon product from the reaction zone.
18. The system of claim 17, wherein the reaction zone includes a fluid catalytic cracking (FCC)-type reactor or a circulating catalyst bed reactor.
19. The system of claim 17, further comprising a collection device that is capable of collecting the olefin hydrocarbon product.
20. A method of making the catalyst of claim 14, the method comprising:
(a) heating a synthesis mixture to obtain a crystalline material; and
(b) calcining the crystalline material,
wherein the synthesis mixture has a molar composition of: aAl203:6Si02:cP205:^20:eTEAOH:/ exOy where 0 < a <1, 0 < b < 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 < f<\, x is 1 to 2, and .y is 1 to 3.
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WO2016022340A1 (en) * | 2014-08-05 | 2016-02-11 | Sabic Global Technologies B.V. | Stable silicoaluminophosphate catalysts for conversion of alkyl halides to olefins |
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