TWI457175B - 混合床聚合物催化劑及其用途 - Google Patents
混合床聚合物催化劑及其用途 Download PDFInfo
- Publication number
- TWI457175B TWI457175B TW100121362A TW100121362A TWI457175B TW I457175 B TWI457175 B TW I457175B TW 100121362 A TW100121362 A TW 100121362A TW 100121362 A TW100121362 A TW 100121362A TW I457175 B TWI457175 B TW I457175B
- Authority
- TW
- Taiwan
- Prior art keywords
- catalyst
- metal
- exchange resin
- mixed bed
- ion exchange
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 110
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 32
- 150000002576 ketones Chemical class 0.000 claims description 28
- 239000003456 ion exchange resin Substances 0.000 claims description 26
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 25
- 229920001577 copolymer Polymers 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000376 reactant Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- 239000003361 porogen Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- -1 tetralin peroxide Chemical class 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 229920006216 polyvinyl aromatic Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011325 microbead Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 150000003440 styrenes Chemical group 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetraline Natural products C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- BOJBAESURDTYEE-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyl carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OC(=O)OC1CCC(C(C)(C)C)CC1 BOJBAESURDTYEE-UHFFFAOYSA-N 0.000 description 1
- NWRZGFYWENINNX-UHFFFAOYSA-N 1,1,2-tris(ethenyl)cyclohexane Chemical compound C=CC1CCCCC1(C=C)C=C NWRZGFYWENINNX-UHFFFAOYSA-N 0.000 description 1
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical class C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- ZHKBLALOBMBJLL-UHFFFAOYSA-N 1-hexylperoxyhexane Chemical compound CCCCCCOOCCCCCC ZHKBLALOBMBJLL-UHFFFAOYSA-N 0.000 description 1
- JSWLXPQVSUEOJQ-UHFFFAOYSA-N 1-nonylperoxynonane Chemical compound CCCCCCCCCOOCCCCCCCCC JSWLXPQVSUEOJQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- DDBYLRWHHCWVID-UHFFFAOYSA-N 2-ethylbut-1-enylbenzene Chemical compound CCC(CC)=CC1=CC=CC=C1 DDBYLRWHHCWVID-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- OQYUFQVPURDFKC-UHFFFAOYSA-N 2-methylbut-1-enylbenzene Chemical compound CCC(C)=CC1=CC=CC=C1 OQYUFQVPURDFKC-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- FITCNIVIIJXTTC-UHFFFAOYSA-N 2-tert-butylperoxycarbonylbenzenecarboperoxoic acid Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OO FITCNIVIIJXTTC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XRERONKQLIQWGW-UHFFFAOYSA-N but-1-ene;styrene Chemical group CCC=C.C=CC1=CC=CC=C1 XRERONKQLIQWGW-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012607 strong cation exchange resin Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
本發明係關於混合床聚合物催化劑。更具體而言,本發明係關於摻雜金屬之離子交換樹脂催化劑及強陽離子交換樹脂催化劑的混合床。
於封裝之床中使用摻雜金屬之離子交換樹脂催化劑係已知者。舉例而言,於美國專利第6,977,314號中,摻雜金屬之多磺酸化(polysulfonated)陽離子交換樹脂催化劑形成催化劑之床,並用以製造酮。英國專利第GB 994137號及第GB1191113號也揭露了含有金屬之強酸性陽離子催化劑。英國專利第GB994137號也揭露了於封裝床內使用活性炭或活性氧化鋁。然而,難以於離子交換床中達成活性炭或氧化鋁之良好混合,因此導致低選擇性、由於小粒子之生成而造成之設備堵塞、以及於氫化反應製程中之壓力降。
本發明試圖藉由提供具有摻雜金屬之離子交換樹脂催化劑及強酸性離子交換樹脂催化劑兩者之混合床聚合物催化劑而改善當前技術領域,該混合床聚合物催化劑具有高度所欲之反應轉化率及於催化劑床中的均勻金屬分佈。本發明也允許相關於實驗條件如製程流速、溫度及其他條件調節金屬負載量。
於本發明之第一態樣,係提供一種混合床聚合物催化劑,其係包含:10至90重量%之具有其上負載有選自鈀、鉑、銥、銠、釕、銅、金及/或銀之金屬之離子交換樹脂的第一催化劑;以及,10至90重量%之具有不含金屬之強酸性離子交換樹脂的第二催化劑。該金屬係均勻地分佈於整個混合床中。
於本發明之第二態樣,係提供本發明之催化劑於炔類、烯類、醛類、酮類、醇類、腈類、胺類及硝基之氫化反應的用途。
於本發明之第三態樣,係提供一種製備酮之方法,係包含:提供聚合物催化劑之混合床,其具有10至90重量%之具有其上負載有選自鈀、鉑、銥、銠、釕、銅、金及銀之一者或多者之金屬之離子交換樹脂的第一催化劑;以及10至90重量%之具有不含金屬之強酸性離子交換樹脂的第二催化劑;該金屬係均勻地分佈於整個混合床中;將該金屬均勻地分佈於整個混合床中;以及合成該酮,以產生0.1至60%之產率。
本發明係關於混合床聚合物催化劑。該混合床催化劑包含第一催化劑及第二催化劑,其中,該第一催化劑含有金屬而該第二催化劑不含金屬。該第一催化劑為負載有金屬之離子交換樹脂。該第二催化劑為強酸性離子交換樹脂。“強酸性離子交換樹脂”中之“強酸性”係意指該樹脂於水中之pKa小於2。該強酸性離子交換樹脂包含具有濕度保持能力為自10%至90%、粒子尺寸為100微米(μm)至2000 μm及體積容量自0.5 meq/L(毫當量/公升)至7 meq/L的苯乙烯系強酸陽離子性樹脂。離子交換樹脂之實例係包括磺酸化不足(undersulfonated)之樹脂及多磺酸化之樹脂。於一較佳之具體實施態樣中,該離子交換樹脂包含多磺酸化之陽離子交換樹脂,其中,芳族/磺酸之範圍為自10:1至1:2。該1:2係磺酸化極限。可用於催化劑之其他樹脂包括丙烯酸系骨架樹脂,如弱酸陽離子樹脂、弱鹼陰離子樹脂、強鹼陰離子樹脂及強酸陽離子樹脂。
於該第一催化劑及第二催化劑兩者中之離子交換樹脂可為凝膠狀(gellular)樹脂形式或大孔微珠形式。較佳地,該離子交換樹脂催化劑係大孔球形微珠形式,其具有之平均直徑為100μm至2毫米(mm),更佳150μm至1.5 mm,最佳250μm至1 mm。當該離子交換樹脂為多磺酸化之陽離子交換樹脂時,該磺酸基之含量為,基於該多磺酸化之陽離子交換樹脂之乾重,較佳約5.0至7.0,更佳約5.1至6.5,最佳約5.2至6.0meq/g(毫當量/公克),且負載有,基於該多磺酸化陽離子交換樹脂之乾重,較佳約0.1至10%,更佳約0.5至5%,最佳約0.7至2%之金屬或金屬離子。
較佳地,該第一催化劑及第二催化劑兩者之該離子交換樹脂具有之表面積為約10至1000,更佳約15至500,最佳約0.1至50平方公尺/公克(m2
/g),所具有之總孔隙度較佳為約0.1至0.9,更佳約0.2至0.7,最佳約0.25至0.5立方公分/聚合物公克數(cm3
/g),其平均孔直徑較佳為約50之2,500埃,更佳約150至1,000埃。
可自經交聯之大孔共聚物製備該第一催化劑及第二催化劑兩者之離子交換樹脂,該經交聯之大孔共聚物係自含有至少1重量%(基於總單體重量)之多乙烯基不飽和單體的單體或單體混合物聚合之聚合物或共聚物。藉由在致孔劑(亦稱為“相增量劑”或“沉澱劑”),亦即為單體之溶劑但並非聚合物之溶劑,的存在下進行懸浮聚合將孔隙度引入該共聚物微珠中。
舉例而言,經交聯之大孔共聚物之製備可包括製備含有懸浮助劑(如分散劑、保護性膠體及緩衝劑)之連續水相溶液;之後與含有1至85%多乙烯基芳族單體的單體混合物、自由基起始劑以及較佳約0.2至5,更佳0.3至3,最佳0.4至1份(相對於每份單體)致孔劑(如甲苯、二甲苯、(C4
-C10
)-烷醇、(C6
-C12
)-飽和烴或多伸烷基二醇)混合。隨後於升高之溫度聚合該單體之混合物及致孔劑,並藉由多種手段將該致孔劑自所得聚合物微珠中移除,舉例而言,及可藉由蒸餾或溶劑洗滌移除甲苯、二甲苯及(C4
-C10
)-烷醇,可藉由水洗移除多伸烷基二醇。隨後藉由常規手段如脫水再乾燥來分離所得大孔共聚物。
可於該經交聯之共聚物之製備中使用的適當之多乙烯基芳族單體包括,舉例而言,選自二乙烯基苯、三乙烯基苯、二乙烯基甲苯、二乙烯基萘、二乙烯基二甲苯、及其混合物之一種或多種單體;應理解,前述交聯劑之每一種之多種位置異構物的任一者皆為適當者。於一較佳之具體實施態樣中,該多乙烯基芳族單體為二乙烯基苯。較佳地,該經交聯之共聚物包含約1至85%,更佳約5至55%,最佳約10至25%之多乙烯基芳族單體單元。
視需要,除了使用該多乙烯基芳族交聯劑之外,可使用非芳族交聯單體,如乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、二乙二醇二乙烯基醚、及三乙烯基環己烷。當使用時,基於用以形成該大孔共聚物之總單體重量,該非芳族交聯單體作為經聚合之單元較佳可佔約0至10%,更佳約0至5%,最佳約0至2%之大孔聚合物。
可於該經交聯之共聚物之製備中使用的適當之單不飽和乙烯基芳族單體包括,舉例而言,苯乙烯、α-甲基苯乙烯、經(C1
-C4
)烷基取代之苯乙烯、經鹵取代之苯乙烯(如二溴苯乙烯及三溴苯乙烯)、乙烯基萘及乙烯基蒽。較佳地,該單不飽和乙烯基芳族單體係選自苯乙烯、經(C1
-C4
)烷基取代之苯乙烯、及其混合物。適當之經(C1
-C4
)烷基取代之苯乙烯中所包括者為,舉例而言,乙基乙烯基苯、乙烯基甲苯、二乙基苯乙烯、乙基甲基苯乙烯及二甲基苯乙烯。應理解,前述乙烯基芳族單體之每一種之多種位置異構物的任一者皆為適當者。較佳地,該共聚物包含約15至99%,更佳約75至90%之單不飽和乙烯基芳族單體單元。
視需要,除了使用該乙烯基芳族單體之外,可使用非芳族單不飽和乙烯基單體,如脂肪族不飽和單體,舉例而言,氯乙烯、丙烯腈、(甲基)丙烯酸及(甲基)丙烯酸烷基酯。當使用時,基於用以形成該大孔共聚物之總單體重量,該非芳族單不飽和乙烯基單體作為經聚合之單元,較佳可佔約0至10%,更佳約0至5%,最佳約0至2%之大孔共聚物。
可用於製備大孔共聚物之致孔劑係包括疏水性致孔劑如(C7
-C10
)芳族烴及(C6
-C12
)飽和烴,以及親水性致孔劑如(C4
-C10
)烷醇及多伸烷基二醇。適當之(C7
-C10
)芳族烴類包括,舉例而言,甲苯、乙基苯、鄰二甲苯、間二甲苯及對二甲苯之一者或多者;應理解,前述烴類之每一種之多種位置異構物的任一者皆為適當者。較佳地,該芳族烴為甲苯、或二甲苯、或二甲苯之混合物、或甲苯與二甲苯之混合物。適當之(C6
-C12
)飽和烴係包括,舉例而言,己烷、庚烷、及異辛烷之一者或多者;較佳地,該飽和烴為異辛烷。適當之(C4
-C10
)烷醇係包括,舉例而言,異丁醇、第三戊醇、正戊醇、異戊醇、甲基異丁基甲醇(4-甲基-2-戊醇)、己醇及辛醇之一者或多者;較佳地,該烷醇係選自(C5
-C8
)烷醇之一種或多種如甲基異丁基甲醇及辛醇。
可用於製備共聚物之聚合反應起始劑係包括單體可溶解性(monomer-soluble)起始劑,如過氧化物、氫過氧化物及相關起始劑,如過氧化苯甲醯、氫過氧化第三丁基、過氧化異丙苯(cumene peroxide)、過氧化四氫萘(tetralin peroxide)、過氧化乙醯、過氧化己醯、過辛酸第三丁酯(亦稱為過氧化-2-乙基己酸第三丁酯)、過辛酸第三戊酯、過苯甲酸第三丁酯、二過氧鄰苯二甲酸第三丁酯、過氧二碳酸二環己酯、過氧二碳酸二(4-第三丁基環己基)酯、及過氧化甲乙酮。亦可用者係偶氮起始劑,如偶氮二異丁腈、偶氮二異丁醯胺、2,2’-偶氮-雙(2,4-二甲基戊腈)、偶氮-雙(α-甲基丁腈)、偶氮二甲基戊酸二甲酯、偶氮二甲基戊酸二乙酯及偶氮二甲基戊酸二丁酯。較佳之過氧化物起始劑為過氧化二醯基如過氧化苯甲醯,以及過氧化酯(peroxyester)如過辛酸第三丁酯及過氧苯甲酸第三丁酯;更佳地,該起始劑為過氧化苯甲醯。過氧化物起始劑之用量為,基於乙烯基單體之總重,較佳約0.3%至5%,更佳約0.5至3%,最佳約0.7%至2%。
較佳地,該經交聯之共聚物係選自二乙烯基苯共聚物、苯乙烯-二乙烯基苯共聚物、二乙烯基苯-乙基乙烯基苯共聚物及苯乙烯-乙基乙烯基苯-二乙烯基苯共聚物,用作該催化劑之基材。可根據發明領域中具有通常知識者已知之用於多磺酸化的常規製程使用強酸官能基將此等經交聯之共聚物予以官能化,如使用三氧化硫(SO3
)、冒煙之硫酸或發煙硫酸(含有三氧化硫之濃硫酸)以及氯磺酸予以磺酸化。或者,可對經單磺酸化之陽離子交換樹脂進行常規多磺酸化處理,以提供經多磺酸化之陽離子交換樹脂催化劑。
該第一催化劑中之例示性金屬係包括:鈀(Pd)、鉑(Pt)、銥(Ir)、銠(Rh)、釕(Ru)、銅(Cu)、金(Au)、銀(Ag)及其混合物。該催化劑可使用均質地分佈於該樹脂中之零價狀態的金屬作成。較佳地,該離子交換樹脂催化劑係含有,基於該催化劑之乾重,0.1至15%之金屬。
較佳地,該混合床聚合物催化劑係包含10至90重量%之該第一催化劑及10至90重量%之該第二催化劑。該第一催化劑可佔低至該混合床聚合物催化劑總重之1%,亦可佔高達該混合床聚合物催化劑總重之99%,取決於所欲之結果。然而,因為具有金屬之催化劑可能成本更高,較少量之該第一催化劑係較佳。更佳地,該混合床聚合物催化劑係包含15至25重量%之該第一催化劑及75至85重量%之該第二催化劑,最佳地,該混合床聚合物催化劑係包含19至21重量%之該第一催化劑及79至81重量%之該第二催化劑。
該混合床聚合物催化劑達成所欲之反應轉化率以及該雙官能催化劑(第一催化劑)及酸催化劑(第二催化劑)於該催化劑床中的均勻分佈。可調節實驗條件所需之金屬負載量。使用該混合床聚合物催化劑之可能反應係包括,但不限於,炔類、烯類、醛類、酮類、醇類、腈類、胺類及硝基之氫化反應,且可據之調節金屬負載量。
於一具體實施態樣中,該混合床聚合物催化劑係用以製備酮。該金屬係均勻地分佈於該第一催化劑及第二催化劑之整個混合床中,且以產生0.1至60%之產率合成該酮。
該混合床聚合物催化劑係達成約5至65%之產率及85至99%之選擇性。於一具體實施態樣中,該催化劑係達成30%之產率及97%之選擇性。產率係基於所產生之酮的量,而選擇性係基於相對於總產物所產生之酮的量。
於本發明之一較佳具體實施態樣中,該混合床聚合物催化劑為包含於容器內之物理形式微珠,該微珠形成催化劑床。於氫(作為獨立之餵料流)之存在下,將酮反應物或溶劑如丙酮之餵料流與該催化劑床接觸足以發生該酮之縮合反應的溫度與時間。自該催化劑床分離含有反應產物(飽和酮加成產物)、副產物(不飽和酮加成產物)以及可能存在之任何未反應之酮反應物的經縮合之液體流,藉由常規分離手段(如蒸餾)自該液體流中回收所欲之酮加成產物。
技術領域中具有通常技術者能選擇適宜之條件,如(1)於氫之存在下的批式操作,舉例而言,其中該催化劑床係負載有該液體流,或(2)更佳之連續操作,舉例而言,其中,以允許該液體流在該催化劑床中停留足夠之時間而使得所欲之反應發生的速率將該液體流(與氫一起)連續餵入柱反應器之一端,同時,自該床之另一端連續移除經縮合之液體流。同樣,基於本文所提供之指引以及技術領域中具有通常知識者已知之知識,可容易地選擇反應設備、反應物流通過該床之上行或下行方向的選擇、反應時間及溫度、特定之反應物、以及回收酮加成產物之方法。
可選擇柱反應器內之溫度及壓力,使得該酮反應物於該催化劑中係處於其沸點。該酮反應物之溫度/壓力的變更係用以提供所欲之反應溫度及條件的組合,從而使得縮合反應於該催化劑床中之液相中發生。可改變條件以提供該催化劑床之氣相條件,該條件可使得該縮合反應係於液相中施行。於一較佳之具體實施態樣中,係使用滴流床條件,其中,存在流經該催化劑床之液體及氣體。於一具體實施態樣中,該氣體為氫,且該平衡液體/蒸汽為丙酮。選擇較高之壓力可提供更多液體。
本發明之混合床聚合物催化劑可用於縮合反應中,其中,該酮反應物及氫可於批式反應條件下或於連續反應條件下接觸。於一具體實施態樣中,該方法係基於催化性蒸餾製程之連續製程,其中,將該酮反應物引入柱反應器的底部之緊鄰於再沸器階段之上方處;於此例中,將該產物餾分或產物流自蒸餾設備之再沸器部份連續抽出,以茲進行進一步處理。較佳地,將待進行縮合反應之酮反應物餵入並使其下行通過該催化劑床,且將氫流體以相同方向通過該反應區域。然而,可使用其他引入反應物餵料流的方法,如氫以並流或對流方向流動、溢流製程及氣相製程。
對於連續製程,相對於反應物之量,待使用之混合床聚合物催化劑之量典型係與藉由每單位時間內相對於催化劑之體積的反應物之LHSV(液時空速,liquid hourly space velocity)或液體流速表示的反應通量速率相關。對於使得設備使用率及產物生成最大化,高LHSV可係所欲者;然而,符合此目標必須與原材料之%轉化率及所欲之產物之%選擇性保持平衡。若LHSV太低,所欲之產物的生產速率(產率及選擇性)降低,且該製程可能不經濟。若LHSV太高,該催化劑之活性將不足以提供所欲水準之轉化率(該製程變為“動力學受限”)。LHSV之適當之值的範圍典型為,較佳0.5及10 h-1
,更佳1至8 h-1
,最佳2至4 h-1
。
該酮反應物可於該催化劑之存在下於65℃至200℃之溫度及1至100巴(0.1至10兆帕(MPa))之氫壓力下與氫接觸。典型地,該縮合反應係於氫/酮反應物莫耳比至少為1:1時予以實施。
於本發明之另一具體實施態樣中,該製程可為批式製程,其中,酮反應物係於催化蒸餾裝置之再沸器部位階段(與上揭者相似)引入反應器柱中。當於該再沸器部位達到所欲之酮加成產物之產物組成物時,可隨後終止該製程。或者,可將該縮合反應於批式高壓釜反應器中進行具體之時間段,之後冷卻,並藉由蒸餾或其他常規手段回收所欲之酮加成產物。
於本發明之一個例示性實施例中,自下述兩者形成混合床離子交換樹脂催化劑:其一為負載有0.7重量%之Pd的離子交換樹脂,另一者為呈純酸形式存在之離子交換樹脂。較低之整體Pd負載量有效降低了非所欲之異丙醇副產物的形成,同時,該催化劑混合物之高酸性有助於維持MIBK之高產率。此外,兩種催化劑皆具有相似之粒子尺寸分佈、比重及體積變化,從而允許如所欲般在該催化劑床中形成安定混合物或分層。因此,使用經Pd摻雜樹脂/酸樹脂催化劑的混合系統藉由降低IPA之形成而改善MIBK選擇性,於每個催化劑床中使用較少的Pd維持與具有較高Pd負載量之催化劑相當之高產率,並保持該金屬於整個催化劑床中的均勻分佈。
下述實施例係用以例示性說明本發明。於該等實施例中,使用下述縮寫。
GC:氣相色層分析術;IPA:異丙醇;MIBK:甲基異丁基酮;MPa:兆帕;rpm:每分鐘轉數;wt%及%-w:重量百分率;C:攝氏;mL:毫升;μL:微升;s:秒;min:分鐘;kg:公斤;mg/mL:毫克/毫升;m:公尺;以及,cm:公分。
測試方法
產率、轉化率及選擇性:將來自反應之產物注射入GC氣相色層分析儀中。分析並定量不同之反應產物。丙酮轉化率為發生反應製成產物之丙酮,產物產率為所獲得之所欲產物的量,且選擇性為藉由GC測定之目標產物與全部產物的比。
雙柱GC-FID方法說明:
載氣:來自高壓氮氣瓶之N2
注射器:0.2μL體積
入口:前方;模式:分流;溫度:250℃;壓力:5.4 psi(37 kPa)
分流比:50比1;分流流速:73.0 mL/min;總流速:76.6 mL/min
氣體回收器(Gas saver):20.0 mL/min@2.00分鐘
柱:
第1柱:Macherei Nagel 726600. Optima Wax. 30m×250μm×0.25μm;恒壓;入口:前方;出口:前方
氮氣流速:壓力5.4 psi(37 kPa),流速0.7 mL/min,平均速度:20cm/s
第2柱:Varian CP9151 VF1701MS Capillary 30.0×250μm×0.25μm;恒壓;入口:前方;出口:後方
氮氣流速:壓力5.4 psi(37 kPa),流速0.7mL/min,平均速度:20cm/s
爐:
設定點:40℃,保持時間:5min,第1次升溫:5.0℃/min至115℃,第2次升溫:15.0℃/min至240℃,最終時間:6.67min@240℃,總運行時間:35min
偵檢器:
前FID:加熱器250℃
流速:H2
:30mL/min,空氣:350mL/min,補充N2
:30mL/min
第1訊號:數據傳輸率20 Hz,峰寬:0.01min,開始時間:0,結束時間:35min
後FID:加熱器250℃
流速:H2
:30mL/min,空氣:350mL/min,補充N2
:30 mL/min
第2訊號:數據傳輸率20Hz,峰寬:0.01min,開始時間:0,結束時間:35min。
實施例
實施例1:於小規模批式反應器中之混合床催化劑篩
於AMBERLYSTTM
CH28(負載有Pd之離子交換樹脂)與AMBERLYSTTM
252H(不含Pd之強酸陽離子樹脂)之摻和物中使用不同之重量%比。使用批式反應器於200 psi(1.38 MPa)及110℃之條件下氫化4小時,同時以1000 rpm之速率攪拌來測試樹脂混合物。藉由GC分析測定產率並顯示於表1中。
如表1中所示,直至CH28:252H之比為20:80,MIBK之產率保持大致相等。僅於CH28之含量低於20%時,MIBK之產率下降。CH28含量自100%至20%提供IPA之形成的顯著降低,IPA係MIBK合成之最成問題的副產物之一。因此,使用浸漬較低水準之Pd之催化劑達成經改善之MIBK相對於IPA的選擇性,其亦表示,與使用純CH28催化劑相比,成本顯著下降(接近5倍)。對於最大化MIBK產率以及同時產生最少之可能出現的IPA,接近20%之CH28含量係最優者。
實施例2:得自批式反應器之選擇性數據
實施例3:比較結果
Claims (10)
- 一種混合床聚合物催化劑,係包含:10至90重量%之具有其上負載有選自鈀、鉑、銥、銠、釕、銅、金及銀之至少一者之金屬之離子交換樹脂的第一催化劑;以及10至90重量%之具有不含金屬之強酸性離子交換樹脂的第二催化劑;該金屬係均勻地分佈於整個混合床中。
- 如申請專利範圍第1項所述之催化劑,其中,該第一催化劑係包含,基於該第一催化劑之乾重,0.1至15%之分佈於其中之金屬離子。
- 如申請專利範圍第1項所述之催化劑,其中,該強酸性離子交換樹脂係包含具有濕度保持能力為自10%至90%、粒子尺寸為100μm至2000μm及體積容量自0.5meq/L至7meq/L的苯乙烯系強酸陽離子性樹脂。
- 如申請專利範圍第1項所述之催化劑,其中,該金屬物係包含零價金屬。
- 如申請專利範圍第1項所述之催化劑,其中,該第一催化劑係佔該混合床聚合物催化劑之15至25重量%。
- 如申請專利範圍第1項所述之催化劑,其中,該金屬物係包含鈀。
- 如申請專利範圍第1項所述之催化劑,其中,該第二催化劑係包含凝膠狀樹脂。
- 如申請專利範圍第1項所述之催化劑,其中,該第一催 化劑係包含100μm至2mm之粒子尺寸,且該第二催化劑係包含100μm至2mm之粒子尺寸。
- 一種申請專利範圍第1項所述之催化劑於酮類的氫化反應之用途。
- 如申請專利範圍第9項所述之用途,其中,該酮類之產率為0.1至60%。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US36029410P | 2010-06-30 | 2010-06-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201204462A TW201204462A (en) | 2012-02-01 |
TWI457175B true TWI457175B (zh) | 2014-10-21 |
Family
ID=44736124
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW100121362A TWI457175B (zh) | 2010-06-30 | 2011-06-20 | 混合床聚合物催化劑及其用途 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8471069B2 (zh) |
EP (1) | EP2402086B1 (zh) |
KR (1) | KR101283371B1 (zh) |
CN (1) | CN102309989B (zh) |
TW (1) | TWI457175B (zh) |
ZA (1) | ZA201104840B (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI457175B (zh) * | 2010-06-30 | 2014-10-21 | Dow Global Technologies Llc | 混合床聚合物催化劑及其用途 |
JP6042278B2 (ja) * | 2012-07-10 | 2016-12-14 | オルガノ株式会社 | 白金族金属担持接触水素化還元触媒及び接触水素化還元方法 |
JP6042277B2 (ja) * | 2012-07-10 | 2016-12-14 | オルガノ株式会社 | 白金族金属担持触媒及び反応装置 |
KR101369021B1 (ko) * | 2012-10-25 | 2014-02-28 | 한국화학연구원 | 수분 안정성이 향상된 유독성 가스 제거용 저온산화촉매 |
CN105188875B (zh) | 2013-03-13 | 2017-03-08 | 陶氏环球技术有限责任公司 | 用于圆柱形过滤元件的拼接纤维增强外壳 |
EP3515883A1 (en) * | 2016-09-20 | 2019-07-31 | Rohm and Haas Company | Method of hydrogenation of phenol |
JP7230309B2 (ja) | 2019-09-30 | 2023-03-01 | エルジー・ケム・リミテッド | 水素化反応用触媒及びその製造方法 |
MX2023001207A (es) * | 2020-07-29 | 2023-04-26 | Ddp Specialty Electronic Mat Us 8 Llc | Proceso para la preparacion de un alcohol de azucar. |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3574763A (en) * | 1966-07-07 | 1971-04-13 | Johannes Wollner | Production of saturated carbonyl compounds |
TW200301244A (en) * | 2001-12-19 | 2003-07-01 | Rohm & Haas | Metal-doped sulfonated ion exchange resin catalysts |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1193931B (de) | 1963-06-29 | 1965-06-03 | Rheinpreussen Ag | Verfahren zur einstufigen Herstellung von Methylisobutylketon |
US3953517A (en) * | 1967-09-08 | 1976-04-27 | Veba-Chemie Aktiengesellschaft | Process for preparing methyl isobutyl ketone and catalyst |
JPS4833724B1 (zh) * | 1968-06-14 | 1973-10-16 | ||
GB1280368A (en) | 1969-10-08 | 1972-07-05 | Showa Denko Kk | Process for the production of methyl isobutyl ketone |
JPS5126769B2 (zh) | 1972-07-25 | 1976-08-09 | ||
AU7839498A (en) * | 1997-06-18 | 2000-01-05 | Catalytic Distillation Technologies | Production of mibk using catalytic distillation technology |
ES2249839T3 (es) | 1997-08-01 | 2006-04-01 | Martek Biosciences Corporation | Composiciones nutritivas que contienen acido docasahexanoico y sus procedimientos de produccion. |
CN1114585C (zh) * | 1998-04-16 | 2003-07-16 | 中国石化金陵石油化工公司 | 双金属树脂型催化剂及其制备方法 |
CN1101269C (zh) * | 1999-09-17 | 2003-02-12 | 中国石油化工集团公司 | 丙酮合成甲基异丁基酮的催化剂及其制备方法 |
ZA200107297B (en) | 2000-09-15 | 2002-03-11 | Catalytic Distillation Tech | Production of methyl isobutyl ketone. |
CN1211160C (zh) * | 2002-05-15 | 2005-07-20 | 中国石油化工股份有限公司 | 一种钯/树脂催化剂的制备方法 |
US20060135793A1 (en) | 2004-11-26 | 2006-06-22 | Blessing Robert W | Process for the dimerisation of levulinic acid, dimers obtainable by such process and esters of such dimers |
KR100834963B1 (ko) | 2006-10-18 | 2008-06-19 | 금호피앤비화학 주식회사 | 금속이 도핑된 술폰화 양이온교환 수지 촉매 및 이를 이용한 메틸이소부틸케톤의 제조방법 |
TWI457175B (zh) * | 2010-06-30 | 2014-10-21 | Dow Global Technologies Llc | 混合床聚合物催化劑及其用途 |
-
2011
- 2011-06-20 TW TW100121362A patent/TWI457175B/zh not_active IP Right Cessation
- 2011-06-21 EP EP11170642.0A patent/EP2402086B1/en not_active Not-in-force
- 2011-06-28 CN CN201110192501.0A patent/CN102309989B/zh not_active Expired - Fee Related
- 2011-06-29 US US13/172,528 patent/US8471069B2/en not_active Expired - Fee Related
- 2011-06-29 KR KR1020110063356A patent/KR101283371B1/ko not_active IP Right Cessation
- 2011-06-30 ZA ZA2011/04840A patent/ZA201104840B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3574763A (en) * | 1966-07-07 | 1971-04-13 | Johannes Wollner | Production of saturated carbonyl compounds |
TW200301244A (en) * | 2001-12-19 | 2003-07-01 | Rohm & Haas | Metal-doped sulfonated ion exchange resin catalysts |
CN1426990A (zh) * | 2001-12-19 | 2003-07-02 | 罗姆和哈斯公司 | 金属掺杂的磺化离子交换树脂催化剂 |
Also Published As
Publication number | Publication date |
---|---|
US8471069B2 (en) | 2013-06-25 |
ZA201104840B (en) | 2012-03-28 |
EP2402086A1 (en) | 2012-01-04 |
KR20120002464A (ko) | 2012-01-05 |
TW201204462A (en) | 2012-02-01 |
EP2402086B1 (en) | 2016-11-02 |
US20120004467A1 (en) | 2012-01-05 |
CN102309989A (zh) | 2012-01-11 |
KR101283371B1 (ko) | 2013-07-08 |
CN102309989B (zh) | 2014-12-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI457175B (zh) | 混合床聚合物催化劑及其用途 | |
US8592340B2 (en) | Metal alloy catalyst composition | |
KR100940327B1 (ko) | 금속-도핑된 술폰화 이온교환 수지 촉매 | |
JP5349540B2 (ja) | 不均一系触媒を製造する方法 | |
US20120004466A1 (en) | Method for Preparing a Ketone | |
US8492594B2 (en) | Multireaction bifunctional polymeric catalyst | |
TWI642480B (zh) | 觸媒載體用乙烯吡啶樹脂、其製造方法及甲醇的羰基化反應用觸媒 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GD4A | Issue of patent certificate for granted invention patent | ||
MM4A | Annulment or lapse of patent due to non-payment of fees |