AU5172593A - Hydroalkylation of aromatic hydrocarbons - Google Patents
Hydroalkylation of aromatic hydrocarbonsInfo
- Publication number
- AU5172593A AU5172593A AU51725/93A AU5172593A AU5172593A AU 5172593 A AU5172593 A AU 5172593A AU 51725/93 A AU51725/93 A AU 51725/93A AU 5172593 A AU5172593 A AU 5172593A AU 5172593 A AU5172593 A AU 5172593A
- Authority
- AU
- Australia
- Prior art keywords
- catalyst
- zsm
- catalyst according
- aromatic hydrocarbon
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 28
- 239000003054 catalyst Substances 0.000 claims description 70
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 34
- 239000002808 molecular sieve Substances 0.000 claims description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 239000010457 zeolite Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- 238000005342 ion exchange Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- -1 offretite Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims 2
- 150000003863 ammonium salts Chemical class 0.000 claims 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000010544 hydroalkylation process reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012457 nonaqueous media Substances 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940075554 sorbate Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 150000005201 tetramethylbenzenes Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000005199 trimethylbenzenes Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003738 xylenes Chemical group 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
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- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- C07C2529/12—Noble metals
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- C07C2529/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- C07C2529/22—Noble metals
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- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble metals
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the eroionite or offretite type, e.g. zeolite T
- C07C2529/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the eroionite or offretite type, e.g. zeolite T containing iron group metals, noble metals or copper
- C07C2529/54—Noble metals
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L
- C07C2529/61—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L containing iron group metals, noble metals or copper
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Description
HYDROALKYLATION OF AROMATIC HYDROCARBONS
The invention provides a new route for the production of specialty chemicals and specification grade jet and diesel fuel from highly aromatic materials, for example liquids derived from coal hydrogenation processes or petroleum reformates. It is also known that aromatic constituents are included in liquids from coal pyrolysis, some shale oils and in liquids derived from conversion of oxygenates and hydrocarbons over zeolite catalysts. Aromatics are considered excellent gasoline components because of their high octane number, however, they are considered too "smoky" for commercial jet fuel and give a low cetane number for diesel fuels. Further, aromatics emission from unburnt and combusted fuel has become an important issue environmentally with recent and indicated government legislation for the reduction of the aromatics content of gasoline and diesel fuels. Thus the saturation of the aromatics fraction or the development of alternative processing strategies such as their hydroalkylation to non-fused cycloalkanes, which are suitable distillate blendstocks, provide a viable option to refineries to meet existing and proposed legislative and environmental pressures to reduce the levels of aromatics in transport fuels. The hydroalkylation of aromatic compounds over dual function catalysts has been demonstrated previously and examples are incorporated herein for reference. Slaugh, L.H. and Leonard, J.A. in US Patent 3,412,165 have produced cyclohexylbenzene from benzene over a variety of transition metal catalysts including nickel/tungsten, palladium and platinum on zeolite and alumina supports.
Extensive investigations of benzene hydroalkylation have been reported by Crone, J.M. and Suggit, R.M. et al. in US Patents 3,760,018, 3,760,019, 3,839,477, 3,784,617, 3,837,477, 3,869,523 and 3,926,842. The use of nickel/tungsten and cobalt/tungsten catalyst systems together with some rare-earth metals have been investigated.
Murtha, T.P. and co-workers investigated hydroalkylation catalysts extensively. Their work is described in US Patents 4,094,918, 4,093,671, 4,094,920, 4,122,125, 4,118,434, 4,152,362, 4,219,689, 4,268,699 and 4,329,531. Aromatic hydrocarbons were contacted under hydroalkylation conditions and in the presence of hydrogen with a catalyst comprising a platinum compound or other Group VIII noble metal supported on a nickel and rare-earth treated crystalline zeolite which had been calcined to produce an acidic support. Finally in European Patent 0338734 Makkee, M. discloses a reductive alkylation (hydroalkylation) process in which a monocycloalkyl aromatic hydrocarbon or a substituted monocycloalkyl aromatic hydrocarbon is prepared by contacting, respectively, an aromatic hydrocarbon or alkyl substituted aromatic hydrocarbon with hydrogen in the presence of a catalyst comprising ruthenium and nickel supported on zeolite beta. Optionally the catalyst can also include a rare-earth metal or tungsten. The hydroalkylation occurs through the partial hydrogenation of the aromatic hydrocarbon to a cycloalkene. The cycloalkene then reacts with the aromatic hydrocarbon or alkyl substituted aromatic hydrocarbon to obtain the desired monocycloalkyl aromatic hydrocarbon or substituted monocycloalkyl aromatic hydrocarbon.
In a first aspect the present invention provides a catalyst for hydroalkylating an aromatic hydrocarbon, the catalyst comprising a molecular sieve material having an acid function, a hydrogenation component and a shape selective function wherein the molecular sieve material has a pore size that is capable of accommodating molecules of the products to be produced and excluding molecules of reactants that are too large. In a second aspect the present invention provides a process for hydroalkylating an aromatic hydrocarbon, the process comprising contacting an aromatic hydrocarbon with hydrogen in the presence of the catalyst. The specific size constraints of different molecular sieve framework structures limit the reactants and the size of product molecules through product selectivity and active site selectivity. The controlling function is the rate of diffusion of product away from the reactive sites, through the pores and out of the crystallite. Reactant selectivity is based on the exclusion of a potential reactant by its size and the size of the pore. Product shape is controlled by the volume available at the active site which precludes the formation of too bulky intermediates at the site.
The term "molecular sieve" is all inclusive in that it embraces all materials that exhibit shape selectivity, regardless of composition or degree of crystallinity. The molecular sieve characteristic of the material exists where the framework structure creates a porous regular array of apertures. The apertures are of a size as to be able to take up molecules into their porous structure whilst rejecting others on the basis of their larger
effective molecular dimensions.
Although zeolites are considered the primary molecular sieves [zeolites are crystalline aluminosilicates which are three dimensional structures arising from a framework of [SiO4]4- and [AlO4]5- coordinated polyhedra linked by their corner atoms] and are of major importance in the invention, other non-aluminosilicate materials, such as some carbons and silicas, have molecular sieve properties. Also an ever-increasing number of crystalline porous substances are being synthesised containing co-ordination polyhedra of elements other than just silicon or aluminium. Candidate elements for such isomorphous replacement are for example 6a, and B, close to A1 in Group III of the Periodic Table and Ge, close to Si in Group IV.
Other compounds based on the linkage of [PO4]3- coordination polyhedra are known. Typical examples are the "AlPO4" substances prepared by Union Carbide corporation's research laboratories. They are crystalline, have three dimensional structures, are porous and have been classed as molecular sieves. The overall framework charge of pure AlPO4's is neutral, they lack ion exchange properties and thus their catalytic activity is limited. However, other similar compounds designated SAPO's have structures of Si, Al and P in tetrahedral framework sites, have a negative charge and hence ion exchange properties. Further, the compounds have been extended to include MeAPOs (Me=metal), framework structures incorporating some metals from Groups III, IV, V, VI, VII and VIII of the Periodic Table of Elements. Studies have shown that some of these materials have high catalytic activity.
Also of interest are the large number of molecularly
engineered layer structures (MELS) and the pillared interlayered clays (PILC) that fill the pore size and activity gap between zeolites and the larger pore amorphous gel catalysts. They are high surface area solids with unique structures that have large pores more useful for forming the multi-ring aromatic or naphthenic molecules that are too large for small pore conventional zeolites. Materials have been developed for high thermal, reaction and regeneration stability with novel catalytic activity provided by the interlayer charged species in, for example, layered metal hydroxides or by the pillaring cations propping open the layers of sheet minerals or clays such as montmorillonite, smectite and hectorite. The molecular sieve sorption properties of these materials and their compositional diversity makes them a versatile group of potential catalysts.
Molecular sieves with an ion exchange capacity have an increased pore size control ability in that the exchange of ions may increase or reduce the pore dimensions to sizes comparable to the dimension of the reactant molecules and/or the potential product. Moreover ion exchanges can be used to place cations into specific framework sites so as to create active sites to which reactant molecules can be attracted thus promoting the bond distortion and rupture essential to molecular rearrangements. Another feature of ion exchange is that it provides a route for the introduction of metal cations which can subsequently be reduced to catalytically active metal particles. This introduces a bifunctional nature to the molecular sieve.
Molecular sieves derive their acidity or catalytic activity from the proton associated with the framework aluminium.
This Brønsted acid site arises from the creation of
"hydroxyls" within the pore structure which are usually formed by ammonium exchange followed by a calcination step. In high silica zeolites these "protonated" species can be made by direct exchange with mineral acids. In this form the hydroxyls are protons associated with negatively charged framework oxygen linked into alumina tetrahedra creating the Brønsted sites. These protons have great mobility particularly above 200°C, and at 550°C they lose water forming Lewis acid sites. The Lewis sites in turn are unstable, especially in the presence of water vapour and an annealing process occurs with the ejection of Al from the. framework which becomes more stable (dealumination). The size exclusion and steric inhibition together with the intermolecular forces between the constituents of the molecular sieve and the sorbate molecules offer opportunities for unique selectivities based on competitive sorption properties of various molecular sieves. Variables such as the silica to alumina ratio, the nature of the cation species and the geometry of the channels (unidimensional, multi-dimensional or interconnecting with super cages) are important considerations for the catalyst. They also contribute to catalyst's stability, reduce its coking propensity and increase its amenability to regeneration.
In the present invention the process feed or starting material for conversion to specialty chemicals and/or jet and diesel fuel boiling range products or blendstock is an aromatic or aromatic containing hydrocarbon, preferably containing benzene and/or an alkyl substituted aromatic hydrocarbon. The alkyl substitute may be less than 10 carbon atoms, preferably 1 to 5 carbon atoms. The most
preferred alkyl substituent is methyl. There may be one or more alkyl and/or aromatic substituents on the aromatic nucleus. Examples of suitable starting material include any or a mixture of benzene, toluene, ethyl benzene, the xylenes, trimethyl benzenes, tetramethyl benzenes, biphenyl and alkyl substituted biphenyls.
The starting material may contain an aromatic or mixture of aromatics in any other liquid or gas mixture which comprises 0 to 95 volume percent of the feed stream. The aromatic feed mass hourly space velocity (MHSV) may range between 0.1 and 100 hr-1, preferably between 1 and 50 hr-1.
In the aromatics hydroalkylation process the feed may be introduced to the catalyst in a reactor under a wide range of conditions. It is preferred that hydrogen be present at pressures between 1 and 200 atmospheres, more preferably between 1 and 100 atmospheres. Further, the hydrogen feed rate lies preferably in a range from 0.2 and 5 mole of hydrogen per mole of aromatic feed and more preferably between 0.2 and 1.5 mole/mole of aromatic feed.
The reaction temperature is not particularly critical, however, it preferably ranges from 80°C to 350°C.
The hydroalkylation process may be carried out in a fixed bed reactor with the aromatic feed and hydrogen contacting the catalyst in an upflow or downflow arrangement. It is also possible to use a countercurrent flow of hydrogen and the aromatic feedstock over the catalyst. Although a fixed bed reactor is described any other type of reactor may be used, for example, fluid bed, slurry phase stirred reactor etc.
The invention provides a catalyst comprising a molecular sieve support with a pore or channel structure of sufficient size for the entry of reactants and departure of products and an active site selectivity to aromatic hydroalkylation products. The molecular sieve desirably has, at least what is termed a medium to large pore size formed by the framework structure. The pores or channels of the molecular sieve structure should be greater than 5Å and should be preferably 2-dimensional and more preferably 3-dimensional in nature and preferably be interconnected. The molecular sieve support may be selected from the group of aluminosilicate zeolites consisting of zeolite beta, Nu-2, EU-1, ZSM-4, ZSM-5, ZSM-5/ZSM-11, ZSM-12, ZSM-20, ZSM-23, ZSM-35, ZSM-38, ZSM-47, ZSM-48, ZSM-50, Type X, Type Y, EMC-2, CSZ-1, ECR-30 mordenite, offretite, zeolite L, zeolite omega and zeolite PHI. It may also be selected from any metal substituted zeolite whereby some or all of the aluminium and/or the silicon of the above zeolites has been replaced by one or more elements from the Groups II to VIII of the Periodic Table of Elements for example Ga, B, Fe, Cr, Mn, V, Ti, Ge, As, Be etc. The molecular sieve support may be selected from the aluminophosphates (AlPO4's), silicoaluminophosphates (SAPOs), metalloaluminophosphates (MeAPOs) particularly VPI-5, AlPO-5, SAPO-5, SAPO-11, SAPO-31, SAPO-36, SAPO-37, SAPO-40, SAPO-41, CoAPO-50 and other metal substituted materials of similar structure e.g. BeGeAPO-11 and AsBeAPO-31 etc.
The molecular sieve used in the process of this invention may include, in the as synthesised form, exchangeable cations such as lithium, sodium, potassium, caesium, rubidium, beryllium, calcium, magnesium, strontium, barium etc. These cations may be partially or completely replaced with other different cations. Particularly preferred are
rare earth metal ions, transition metal ions (or mixtures of these ions) and other ions such as hydrogen and ammonium. The replacement of the initial ions should not alter the basic structure of the molecular sieve support and preferably the amount of ions exchanged onto the sieve is as much as can be achieved. The rare earth metal may be selected from the group consisting of cerium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium or mixtures thereof.
A preferred aspect of the molecular sieve is that it has an acidic function obtained by ion exchange and/or
impregnation by ammonium nitrate, ammonium fluoride, ammonium chloride, etc., followed by calcination in air at between 200°C and 800°C.
The molecular sieve may be used in the process as prepared or after calcining in air or after calcining and/or treatment by ion exchange, impregnation and/or by incipient wetness techniques with inorganic and/or organic metal or ammonium containing compounds. When treating the molecular sieve aqueous and/or non-aqueous solutions may be used. The preferred catalyst of this invention contains, after treatment an active metal or metals from Group Ib, IIb, IIIb, VIb, VIIb and VIII of the Periodic Table of Elements in quantities of from 0.1% to 25 wt% of the catalyst. Most preferred are those elements which impart a hydrogenation component to the support. Generally this includes one or more metals from copper, chromium, cobalt, nickel, tungsten, molybdenum and zinc.
The catalyst may contain an additional element or elements, from Groups V, VI, VII and VIII of the Periodic Table which
may act as a promoter. The promoter or promoters may be added by ion exchange, impregnation, and/or precipitation from aqueous and/or non-aqueous solutions of inorganic or organic compounds. Further the promoter may be also added by dry mixing an easily decomposable compound such as an acetate, nitrate, chloride, bromide, carbonyl, sulphide etc. The promoter may be from 0.001% to 10 wt% of the catalyst. The preferred promoters may be silver, copper, platinum, palladium, ruthenium, rhenium, iridium or rhodium or mixtures thereof.
The catalyst containing the metal compounds may be activated by reduction. This reduction may be carried out in a 5% to 100% hydrogen atmosphere at a temperature from 50° to 600°C at a pressure from 0 to 200 atmospheres and for 5 minutes to 24 hours.
The molecular sieve may be combined, dispersed or otherwise intimately mixed and pressed with an inorganic oxide matrix in proportions that result in a product containing 10 wt% to 100 wt% of catalyst in the final product. Matrices which impart desirable properties to the catalyst such as increased strength and attrition resistance to the catalyst and aid in dissipation of the heat of reaction are preferred. Oxides of silica, aluminium, zirconium, titanium, chromium, etc. may be used.
The present invention provides a catalyst and process for hydroalkylation of aromatic compounds. In a preferred form of the invention there is provided a catalyst comprising copper, nickel and a rare earth element supported on a molecular sieve having a medium to large interconnected 3-dimensional channel structure. The preferred molecular sieve may consist of zeolite Type X,
Type Y, ZSM 20 or zeolite beta, or any combination thereof. The copper content of the catalyst may lie in the range from 2 to 25 wt% of the catalyst, the nickel content from 1 to 25 wt% and the rare earth elements from 0.2 to 15 wt%.
The active metals may be promoted by an additional element or elements which further enhance the activity, selectivity, stability and/or regenerability of the catalyst. The preferred promoter is platinum or ruthenium and the content may lie in the range 0.001 to 2 wt% of the catalyst.
The process of the present invention may be used for hydroalkylating aromatic compounds, boiling in the gasoline range, to yield compounds boiling in the jet and/or diesel fuel range. This enhances the jet and diesel fuel fraction of a hydrocarbon stream and provides a method for reducing the benzene and total aromatic content of gasoline. The US "Clean Air Act of 15th November 1990 requires that benzene in gasoline be restricted to 1% by volume while the total aromatics are to be less than 25% by volume.
The process of the present invention may be used for hydroalkylating an essentially pure compound to obtain a more valuable product or specialty chemical, for example benzene may be hydroalkylated to cyclohexylbenzene.
In the process any hydroalkylated product or compounds from the hydroalkylation reactor may be further purified after separation from the unreacted feed. The feed may be recycled while the product may be further treated to a fully saturated product by feeding it, with hydrogen into a hydrogenation unit operating at conditions and with a catalyst familiar to those within the industry. For
example, the hydroalkylated product of benzene, cyclohexylbenzene may be further hydrogenated to bicyclohexyl. Purified product may be sold as specialty chemicals while less purified product may be used as a jet or diesel fuel boiling range product or blendstock.
To illustrate the invention the following examples have been included. The examples are not to be considered limiting on the scope of the invention.
Example 1
The following amounts of material were combined, well stirred and sealed in a stainless steel autoclave
Sodium aluminate 12.5g
Tetraethylammonium hydroxide (40%) 263g
Ludox™ HS (40% SiO2) 521 g
Water 188g The autoclave was heated to 150°C with stirring and held at that temperature for 6 days. The resulting crystalline material was identified as zeolite beta (XRD, US Patent 3,308,069) and after washing twice with water and calcining overnight at 600°C had a chemical composition of 2.4% Al2O3, 97.2% SiO2 and 0.01% Na2O.
40g of the zeolite beta was ion exchanged with ammonium nitrate three times and then exchanged with a nickel, rare earth solution (1 litre containing 29.1 g of Ni (NO3)2.6H2O and 0.5g of mischmetal dissolved in acid). The zeolite was collected, washed, dried and then impregnated with 11.8g of copper acetate, 12.4g of nickel nitrate and 0.1g of ruthenium chloride dissolved in 200g of water. The mixture was stirred until a firm paste was formed and then dried
overnight at 140°C, calcined at 550°C, pressed, crushed and sized to a -500 + 250 μm fraction.
Example 2
287g of rare earth exchanged zeolite Type Y (Strem) was further exchanged with nickel nitrate. This was dried and calcined at 550°C then added to a 1000 ml solution containing 79.16 g of copper acetate, 83.2g of nickel nitrate, 0.7g of ruthenium chloride. The mixture was heated and stirred to a paste, dried at 140°C, calcined at 550°C, pressed, crushed and sized to a -500 + 250 μm fraction. The above described catalysts were used in hydroalkylation trials of aromatic compounds in a pressure fixed bed, down flow reactor. The aromatic compounds used in trial 3 were derived from a reformate. The operating conditions as well as the results are listed in the Table. The trials indicate that the supporting molecular sieve with the ruthenium promoted copper, nickel and rare earth active metals is an active catalyst for hydroalkylation of aromatic feeds to higher boiling point compounds suitable for distillate feedstock or, if purified for specialty chemicals.
Claims (34)
1. A catalyst for hydroalkylating an aromatic hydrocarbon, the catalyst comprising a molecular sieve material having an acid function, a hydrogenation component and a shape selective function wherein the molecular sieve material has a pore size that is capable of accommodating molecules of the products to be produced and excluding molecules of reactants that are too large.
2. A catalyst according to claim 1 wherein the hydrogenation component comprises an active metal or metals selected from Groups IB, IIB, IIIB, VIB, VIIB and VIII of the Periodic Table of elements.
3. A catalyst according to claim 2 wherein the hydrogenation component is selected from a group consisting of copper, chromium, cobalt, nickel, tungsten, molybdenum and zinc.
4. A catalyst according to claim 3 wherein the hydrogenation component is copper, chromium, zinc or copper and nickel.
5. A catalyst according to claim 4 wherein the hydrogenation component comprises copper and nickel.
6. A catalyst according to any one of claims 1 to 5 wherein the hydrogenation component comprises from 0.1% to 25% by weight of the catalyst.
7. A catalyst according to any one of the preceding claims wherein the molecular sieve material is selected from a group of aluminosilicate zeolites consisting of zeolite beta, Nu-2, EU-1, ZSM-4, ZSM-5, ZSM-5/ZSM-11, ZSM-12, ZSM-20, ZSM-23, ZSM-35, ZSM-38, ZSM-47, ZSM-48, ZSM-50, Type X, Type Y, EMC-2, CSZ-1, ECR-30 mordenite, offretite, zeolite L, zeolite omega and zeolite PHI.
8. A catalyst according to any one of the preceding claims wherein the catalyst has pores having a size greater than 5A.
9. A catalyst according to any one of the preceding claims wherein exchangeable cations in the molecular sieve material are at least partially replaced with rare earth metal ions.
10. A catalyst according to claim 9 wherein the rare earth metal is selected from a group consisting of cerium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and mixtures thereof.
11. A catalyst according to any one of the preceding claims wherein the acid function is obtained by ion exchange and/or impregnation by a suitable ammonium salt followed by calcination in air at a temperature in a range from 200°C to 800°C.
12. A catalyst according to claim 11 wherein the ammonium salt is ammonium fluoride.
13. A catalyst according to any one of the preceding claims wherein the catalyst includes a suitable promoter selected from an element of Groups V, VI, VII and VIII of the Periodic Table.
14. A catalyst according to claim 13 wherein the promoter comprises from 0.001% to 10% by weight of the catalyst.
15. A catalyst according to claim 13 or claim 14 wherein the promoter is selected from a group consisting of silver, copper, platinum, palladium, ruthenium, rhenium, iridium, rhodium, and mixtures thereof.
16. A catalyst according to claim 15 wherein the promoter is ruthenium or platinum.
17. A catalyst for hydroalkylating an aromatic hydrocarbon, the catalyst comprising copper, nickel and a rare earth element supported on a molecular sieve material having a medium to large interconnected 3-dimensional channel structure.
18. A catalyst according to claim 17 wherein the molecular sieve material is selected from a group consisting of zeolite Type X, Type Y, ZSM-20, zeolite beta and combinations thereof.
19. A catalyst according to claim 17 or claim 18 wherein the copper comprises from 2 to 25 weight % of the catalyst, the nickel comprises from 1 to 25 weight % of the catalyst and the rare earth element from 0.2 to 15 weight % of the catalyst.
20. A catalyst according to any one of claims 17 to 19 wherein the catalyst includes from 0.001 to 2 weight % of a promoter based on the weight of catalyst.
21. A catalyst according to claim 20 wherein the promoter is ruthenium or platinum.
22. A process for hydroalkylating an aromatic hydrocarbon, the process comprising contacting an aromatic hydrocarbon with hydrogen in the presence of a catalyst according to any one of the preceding claims.
23. A process according to claim 22 wherein the aromatic hydrocarbon includes benzene.
24. A process according to claim 22 or claim 23 wherein the aromatic hydrocarbon includes an alkyl substituted aromatic hydrocarbon.
25. A process according to claim 24 wherein the alkyl substituent comprises less than 10 carbon atoms.
26. A process according to claim 25 wherein the alkyl substituent comprises from 1 to 5 carbon atoms.
27. A process according to claim 26 wherein the alkyl substituent is a methyl group.
28. A process according to claim 22 wherein the aromatic hydrocarbon is selected from a group consisting of benzene, toluene, ethyl benzene, a xylene, a trimethyl benzene, a tetramethyl benzene, biphenyl, an alkyl substituted biphenyl and mixtures thereof.
29. A process according to any one of claims 22 to 28 wherein the process comprises contacting a stream of aromatic hydrocarbons having a mass hourly velocity in a range from 0.2 to 100 hr-1 with hydrogen in the presence of the catalyst.
30. A process according to claim 29 wherein the mass hourly velocity lies in a range from 1 to 50 hr-1.
31. A process according to any one of claims 22 to 30 wherein the hydrogen is present at a pressure in a range from 1 to 200 atmospheres.
32. A process according to any one of claims 22 to 31 wherein the hydrogen is fed to a contact zone at a rate in a range from 0.2 to 5 mole per mole of aromatic hydrocarbon.
33. A process according to claim 32 wherein the hydrogen is fed to a contact zone at a rate in a range from 0.2 to 1.5 mole per mole of aromatic hydrocarbon.
34. A process according to any one of claims 22 to 33 wherein the aromatic hydrocarbon is contacted with hydrogen at a temperature in a range from 80 to 350°C.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPL527092 | 1992-10-15 | ||
AUPL5270 | 1992-10-15 | ||
PCT/AU1993/000531 WO1994008712A1 (en) | 1992-10-15 | 1993-10-15 | Hydroalkylation of aromatic hydrocarbons |
Publications (1)
Publication Number | Publication Date |
---|---|
AU5172593A true AU5172593A (en) | 1994-05-09 |
Family
ID=3776473
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU51725/93A Abandoned AU5172593A (en) | 1992-10-15 | 1993-10-15 | Hydroalkylation of aromatic hydrocarbons |
Country Status (4)
Country | Link |
---|---|
AU (1) | AU5172593A (en) |
IN (1) | IN180004B (en) |
NL (1) | NL9320046A (en) |
WO (1) | WO1994008712A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9725377B2 (en) * | 2013-03-14 | 2017-08-08 | Exxonmobil Chemical Patents Inc. | Hydroalkylation catalyst and process for use thereof |
WO2016053637A1 (en) * | 2014-09-29 | 2016-04-07 | Basf Corporation | Preparation and applications of hydrophobic materials |
US11078431B2 (en) * | 2019-12-16 | 2021-08-03 | Saudi Arabian Oil Company | Modified ultra-stable Y (USY) zeolite catalyst for deolefinization of hydrocarbon streams |
CN117511597A (en) * | 2022-08-04 | 2024-02-06 | 菲利普斯66公司 | Process for removing benzene from middle distillate reformate |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3760018A (en) * | 1971-05-17 | 1973-09-18 | Texaco Inc | Hydroalkylation catalyst and process |
US3784617A (en) * | 1972-12-06 | 1974-01-08 | R Suggitt | Hydroalkylation of mononuclear aromatic hydrocarbons |
US3926842A (en) * | 1973-01-02 | 1975-12-16 | Texaco Inc | Method of regenerating spent hydroalkylation catalyst containing an oxidizable group viii metal |
US4380683A (en) * | 1976-12-20 | 1983-04-19 | The Standard Oil Company | Hydroalkylation of benzene and analogs |
US4094920A (en) * | 1977-02-08 | 1978-06-13 | Phillips Petroleum Company | Hydroalkylation using multi metallic zeolite catalyst |
US4094918A (en) * | 1977-02-10 | 1978-06-13 | Phillips Petroleum Company | Hydroalkylation process using multi-metallic zeolite catalyst |
US4152362A (en) * | 1978-01-03 | 1979-05-01 | Phillips Petroleum Company | Hydroalkylation using a rhenium, nickel, rare earth zeolite |
US4268699A (en) * | 1978-07-21 | 1981-05-19 | Phillips Petroleum Company | Hydroalkylation using nickel-ruthenium catalyst on zeolite type support |
US4219689A (en) * | 1978-09-08 | 1980-08-26 | Phillips Petroleum Company | Aromatic hydroalkylation catalyst using iridium on zeolites |
US4447554A (en) * | 1980-05-29 | 1984-05-08 | Phillips Petroleum Company | Hydroalkylation catalyst and methods for producing and employing same |
US4923836A (en) * | 1987-07-16 | 1990-05-08 | Union Oil Company Of California | Ni/Cu absorbent/catalyst for desulfurization and isomerization of N-paraffins |
AU649586B2 (en) * | 1990-03-09 | 1994-05-26 | Tosoh Corporation | Catalyst and method for catalytically decomposing nitrogen oxides |
-
1993
- 1993-10-14 IN IN615CA1993 patent/IN180004B/en unknown
- 1993-10-15 WO PCT/AU1993/000531 patent/WO1994008712A1/en active Application Filing
- 1993-10-15 NL NL9320046A patent/NL9320046A/en not_active Application Discontinuation
- 1993-10-15 AU AU51725/93A patent/AU5172593A/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
NL9320046A (en) | 1995-11-01 |
IN180004B (en) | 1998-01-10 |
WO1994008712A1 (en) | 1994-04-28 |
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