US20120022224A1 - Particles Including Zeolite Catalysts And Their Use In Oligomerization Processes - Google Patents
Particles Including Zeolite Catalysts And Their Use In Oligomerization Processes Download PDFInfo
- Publication number
- US20120022224A1 US20120022224A1 US13/156,824 US201113156824A US2012022224A1 US 20120022224 A1 US20120022224 A1 US 20120022224A1 US 201113156824 A US201113156824 A US 201113156824A US 2012022224 A1 US2012022224 A1 US 2012022224A1
- Authority
- US
- United States
- Prior art keywords
- spheroid
- particle
- olefin
- inch
- quadrulobe
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 239000002245 particle Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 87
- 230000008569 process Effects 0.000 title claims abstract description 75
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000010457 zeolite Substances 0.000 title claims abstract description 57
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 51
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 92
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims description 82
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000000126 substance Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000005563 spheronization Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 18
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- -1 for example Chemical class 0.000 description 14
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 14
- 239000000571 coke Substances 0.000 description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 11
- 239000006057 Non-nutritive feed additive Substances 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical class CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 239000001282 iso-butane Substances 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000013844 butane Nutrition 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- ZERULLAPCVRMCO-UHFFFAOYSA-N sulfure de di n-propyle Natural products CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005225 deoligomerization reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Chemical group 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- IOPLHGOSNCJOOO-UHFFFAOYSA-N methyl 3,4-diaminobenzoate Chemical compound COC(=O)C1=CC=C(N)C(N)=C1 IOPLHGOSNCJOOO-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- XLTBPTGNNLIKRW-UHFFFAOYSA-N methyldisulfanylethane Chemical compound CCSSC XLTBPTGNNLIKRW-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 210000004681 ovum Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7026—MFS-type, e.g. ZSM-57
-
- B01J35/40—
-
- B01J35/50—
-
- B01J35/51—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
- C10G2300/1092—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/22—Higher olefins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Embodiments of an invention disclosed herein relate to particles made from zeolite catalysts and their use in oligomerization processes. In particular, shaped particles (for example, spheroid particles) are made from compositions including the contact product of at least one zeolite catalyst and at least one binder.
Description
- This application claims the benefit of Ser. No. 61/366,704, filed Jul. 22, 2010, and EP 10174865.5, filed Sep. 11, 2010, the disclosures of which are incorporated by reference in their entireties.
- The invention relates to particles comprising zeolite catalysts and their use in oligomerization processes. In particular, shaped particles (for example, spheres, cylinders, tablets, lobed particles etc.) are made from compositions comprising the contact product of at least one zeolite catalyst and at least one binder. In several classes of embodiments, improvements may be observed in catalyst life, olefin selectivity, and/or coke deposition on the particle during olefin oligomerization.
- The condensation reaction of an olefin or a mixture of olefins over an acid catalyst to form higher molecular weight products is a widely used commercial process. This type of condensation reaction may be referred to as an oligomerization reaction, and the products are generally low molecular weight oligomers that are formed by the condensation of up to 12, typically 2, 3, or 4, but up to 5, 6, 7, or even 8 olefin molecules with each other. For example, low molecular weight olefins (such as, for example, propene, 2-methylpropene, 1-butene, 2-butenes, pentenes, and hexenes) may be converted by oligomerization processes using zeolite catalysts to a produce oligomers. Exemplary uses of such oligomers include high-octane gasoline blending stocks, starting material for the production of chemical intermediates, and other end-products. Such chemical intermediates and end-products include alcohols, acids, detergents, and esters such as plasticizer esters and synthetic lubricants.
- Industrial oligomerization processes employing zeolite catalysts typically run for several weeks before a catalyst change is required or a decommissioning of the reactor is needed. In industrial processes, zeolite catalysts are generally delivered as an extrudate of the zeolite catalyst and a binder. Extrudates may have many shapes and may be distinguished by their shape or number of lobes of each extrudate, for example, cylindrical (solid or hollow), trilobe, quadrulobe, (or simply multilobe).
- The feedstocks for the reactions are generally obtained from refining activities such as a stream derived from catalytic or steam cracking that may have been subjected to fractionation. The nature of such refining activities is such that there will be variations in the constituents of the feedstocks. In addition, it may be desirable to change the nature of the feed during a reactor run. Thus, the catalyst activity and the reaction conditions vary according to the composition of the feedstock. As a result, the ideal catalyst provides not only the ability to run a long time as referred to in terms of catalyst life, catalyst activity, or catalyst stability but is also able to oligomerize selectively to produce desired end products using a variety of heterogeneous feedstocks that may contain isomers, poisons, and saturated and unsaturated molecules. Furthermore, the reactions are exothermic and the size of the exotherm also depends upon the nature and amount of the constituents of the feedstock. For example, if isobutylene and propylene are present, they are particularly reactive generating a large amount of heat of reaction.
- The high temperatures generated may lead to carbonaceous deposits on the catalyst caused by a build up of condensed, heavy hydrocarbons similar to asphalt. Such deposits are commonly termed “coke” and lead to deactivation of the zeolite catalyst. In general, the higher the concentration of olefin in the feed, the higher will be the rate of heat release from the catalyzed reaction, and thus, the higher the temperatures reached. Consequently, there will be a higher rate of coke formation and deposition of coke on the catalyst particle. As a result, this has placed a limit on the maximum concentration of olefin that can be tolerated in the feed.
- Useful feed streams containing olefins such as C3 and C4 olefins may be refinery streams derived from steam cracking or catalytic cracking and the composition of the stream will depend upon the raw material from which it is produced and the production technology employed. For example, propylene refinery streams may typically contain up to 75 wt % propylene with the balance being predominantly propane. Similarly butene refinery streams may typically contain up to 70 wt % butenes with the balance being predominantly butanes. Poisons, such as, for example, nitrogen containing compounds (e.g., nitriles) and sulfur containing compounds, and isomeric equivalents are also most likely present. Thus, the reactivity of the olefins in oligomerization processes with zeolite catalysts varies according to the nature of the olefin, its concentration in the feedstock, and other variable constituents.
- Background references include U.S. Pat. Nos. 3,960,978, 4,016,218, 4,021,502 4,381,255, 4,560,536, 4,919,896, 5,446,222, 5,464,593, 5,672,800, 6,143,942, 6,403,853, 6,517,807, 6,884,914, 7,374,662, U.S. Patent Application Publication Nos. 2005/0054516, 2006/0199987, 2009/0216056,
EP 0 220 933 A, EP 746 538 A,EP 2 095 866 A, WO 1994/12452, WO 2005/118512, WO 2005/118513, WO 2007/006398, WO 2008/088452,GB 1 418 445 A, JP 2004 238209 A, Interaction of Acetonitrile with Olefins and Alcohols in Zeolite H-ZSM-5: In Situ Solid-State NMR Characterization of the Reaction Products, Alexander G. Stepanov, Mikhail V. Luzgin, Chem. Eur. J., 1997, 3, No. 1, pp. 47-56, and Analysis of Coke Deposition Profiles in Commercial Spent Hydroprocessing Catalysts Using Raman Spectroscopy, Bas M. Vogelaar et al., Fuel 86 (2007), pp. 1122-1129. - Therefore, there remains a need for improvements in particles comprising zeolite catalysts that provide for extended production runs yielding desired end products. Additionally, there remains a need for the particles to be able to oligomerize in presence of higher concentrations of catalyst poisons and yet yield higher concentrations of the desired end product. It will be appreciated that in large scale industrial processes, small increases in production (such as ≧1%) have highly significant value.
- In a class of embodiments, the invention provides for a particle made from a composition comprising the contact product of: (1) at least one zeolite catalyst; and (2) at least one binder; wherein the particle is a spheroid particle. The particle may be utilized in a process for the oligomerization of C3-C15 olefins.
- In any of the embodiments described herein, the at least one zeolite catalyst may be selected from one or more family members belonging to a TON structure, MFI structure, MFS structure, MWW structure, and mixtures thereof.
- In any of the embodiments described herein, the at least one zeolite catalyst may be selected from at least one of ZSM-5, ZSM-22, ZSM-57, MCM-22, MCM-48, and mixtures thereof.
- In any of the embodiments described herein, the spheroid particle may have an average particle size of from 0.1 mm to 5.0 mm (BS 1796-1: 1989).
- In any of the embodiments described herein, the spheroid particle may have an average particle size of from 0.1 mm to 4.0 mm (BS 1796-1: 1989).
- In any of the embodiments described herein, the spheroid particle may have an average particle size of from 0.3 mm to 3.0 mm (BS 1796-1: 1989).
- In any of the embodiments described herein, the spheroid particle may have an average particle size of from 0.5 mm to 1.5 mm (BS 1796-1: 1989).
- In any of the embodiments described herein, the composition may comprise from 25 to 99 wt % of the at least one zeolite catalyst based upon the total weight of the composition.
- In any of the embodiments described herein, the composition may comprise from 45 to 80 wt % of the at least one zeolite catalyst based upon the total weight of the composition.
- In any of the embodiments described herein, the composition may comprise from 50 to 75 wt % of the at least one zeolite catalyst based upon the total weight of the composition.
- In another class of embodiments, the invention provides for a process for producing the spheroid particle comprising producing the spheroid particle by the spherical granulation of the composition by a vibrational dropping process.
- In yet another class of embodiments, the invention provides for a process for producing the spheroid particle by a spheronization process.
- And yet in another class of embodiments, the invention provides for a process for the oligomerization of olefins, the process comprising: contacting at least one spheroid particle under oligomerization conditions with a feedstock comprising at least one C3-C15 olefin or a mixture thereof to form at least one oligomer product.
-
FIG. 1 is a plot at the conversion shown of the catalyst life of various examples. -
FIG. 2 is a plot showing the C8 selectivity of various examples during n-butene conversion. -
FIG. 3 is a plot at the conversion shown of the catalyst life of various examples. -
FIG. 4 is a plot showing the C9 selectivity of various examples during propylene conversion. - Before the present compounds, components, compositions, and/or methods are disclosed and described, it is to be understood that unless otherwise indicated this invention is not limited to specific compounds, components, compositions, reactants, reaction conditions, structures, or the like, as such may vary, unless otherwise specified. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.
- It must also be noted that, as used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless otherwise specified.
- Oligomerization processes described herein employ spheroid particles made from a composition comprising the contact product of at least one zeolite catalyst and at least one binder. The composition may include or be made with optional processing aids or other optional components. Embodiments of inventive processes may exhibit improved catalyst life and/or improved olefin selectivity that result in higher oligomer yield, and/or the ability to oligomerize in the presence of higher catalyst poisons or contaminants.
- The catalysts utilized in the oligomerization processes of embodiments of the invention, i.e., at least one zeolite catalyst, may be any suitable zeolite catalyst(s) capable of oligomerizing olefins. Zeolites are the aluminosilicate members of the family of microporous solids known as “molecular sieves.” The term molecular sieve refers to a particular property of these materials, i.e., the ability to selectively sort molecules based primarily on a size exclusion process. This is due to a very regular pore structure of molecular dimensions. The maximum size of the molecular or ionic species that can enter the pores of a zeolite is controlled by the dimensions of the channels. These are conventionally defined by the ring size of the aperture, where, for example, the term “8-ring” refers to a closed loop that is built from 8 tetrahedrally coordinated silicon or aluminum atoms and 8 oxygen atoms. These rings are not always perfectly symmetrical due to a variety of effects, including strain induced by the bonding between units that are needed to produce the overall structure, or coordination of some of the oxygen atoms of the rings to cations within the structure. Therefore, the pores in many zeolites may not be cylindrical.
- In an embodiment, the at least one zeolite catalyst may include a medium pore size molecular sieve having a Constraint Index of about 1 to about 12. Constraint Index and a method of its determination are described in, for example, U.S. Pat. No. 4,016,218.
- Examples of the at least one zeolite catalyst include those of the TON structure type (for example, ZSM-22, ISI-1, Theta-1, Nu-10, and KZ-2), those of the MTT structure type (for example, ZSM-23 and KZ-1), those of the MFI structure type (for example, ZSM-5), those of the MFS structure type (for example, ZSM-57), those of the MEL-structure type (for example, ZSM-11), those of the MTW structure type (for example, ZSM-12), those of the EUO structure type (for example, EU-1), those of the AEL structure type (for example, SAPO-11), members of the ferrierite family (for example, ZSM-35) and members of the ZSM-48 family of molecular sieves (for example, ZSM-48). Other examples include MWW (e.g., MCM-22, MCM-48), MOR, or beta type catalysts. As used herein, the term “structure type” is used as described in the Structure Type Atlas, Zeolites 17, 1996.
- In an embodiment, the at least one zeolite catalyst is selected from at least one of ZSM-5, ZSM-11, ZSM-12, ZSM-18, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50, ZSM-57, and mixtures thereof.
- In a class of embodiments, the at least one zeolite catalyst comprises molecular sieves having pores formed by 10-membered rings of tetrahedrally coordinated atoms, such as molecular sieves having the TON or MFS structure type.
- Mixtures of two or more of catalysts may be used in the processes. For example, the mixture may include ZSM-22 and ZSM-57 or ZSM-22 and ZSM-5 or ZSM-57 and ZSM-5. The at least one zeolite catalyst may also be combined with other catalysts such as a solid phosphoric acid (sPa) catalyst.
- In a class of embodiments, the at least one zeolite catalyst is used in its H— or acid form.
- The at least one zeolite catalyst may have an average crystallite or particle size of up to 15 μm, such as within the range of from 0.01 to 6 μm, alternatively, from 0.05 to 5 μm, and alternatively, from 0.1 to 3 μm. As used herein, “average particle size” refers to the arithmetic average of the diameter distribution of the crystals on a volume basis.
- In several embodiments, an as-synthesized molecular sieve is advantageously converted to its acid form, for example, by acid treatment, e.g., by HCl, acetic acid, etc. or by ion exchange, for example, ammonium ion exchange. Subsequently, it may undergo calcination before use. The calcined materials may be post-treated, such as by steaming.
- For example, the at least one zeolite catalyst may be produced by any suitable method. One technique includes heating a reaction mixture containing a source of silicon oxide, a source of aluminum oxide and, if appropriate, an organic promoter, for example, a nitrogen or phosphorus-containing organic base, together optionally, with an alkali metal base, and separating the porous aluminosilicate crystals (zeolite precursor crystals) formed. The precursor crystals are then calcined in air or oxygen at a temperature exceeding or about 500° C., for example, at a temperature of 550° C. for about 10 to about 20 hours. As recognized in the art, calcination temperatures and durations may vary depending on the type of zeolite catalyst or combination of zeolite catalysts selected. In one embodiment, the calcined material is exchanged with ammonium ions (NH4+) and subjected to conditions under which the ammonium ions decompose, with the formation of ammonia and a proton, thus, producing an acidic form of the at least one zeolite catalyst. Alternatively, the acidic form of the catalyst may be obtained by acid exchange with hydrochloric acid, acetic acid, etc. If desired, however, the calcined material may be used as a catalyst without first being exchanged with ammonium ions, since the material already possesses acidic sites.
- Ammonium exchanged and calcined mono-dimensional 10-rings zeolites (e.g., ZSM-22 and ZSM-23) may be treated to selectivate their surface, thereby, forming a selectivated catalyst. This selectivation may be achieved in numerous ways. In an embodiment, the at least one zeolite catalyst may be titrated with an organic nitrogen base, such as collidine. See, for example, U.S. Pat. No. 5,026,933. Another example is by depositing a crystalline Si:Al layer on a core of zeolite where this layer has a higher Si:Al ratio than the untreated zeolite. See, for example, U.S. Pat. No. 6,013,851.
- Although much of the discussion above is directed to aluminosilicate zeolites, it is possible to use material in which silicon and aluminum have been replaced in whole or in part by other elements, for example, any one or more of a
Group 2 to Group 15 atom. For example, silicon may be replaced by or contacted with germanium and aluminum or may be replaced with boron, gallium, chromium, and iron. As used herein, these materials containing such replacement lattice elements may also be termed zeolites. - Exemplary catalyst materials and processes for making and using may also be found in U.S. Pat. Nos. 3,960,978, 4,016,218, 4,021,502, 4,381,255, 4,560,536, 4,919,896, 5,446,222, 5,672,800, 6,143,942, 6,517,807, 6,884,914, U.S. Patent Application Publication No. 2006/0199987, EP 746 538 A, WO 1994/12452, WO 2005/118512, WO 2005/118513, WO 2007/006398, and WO 2008/088452. See also “Atlas of Zeolite Structure Types,” Eds. W. H. Meier, D. H. Olson and Ch. Baerlocher, Elsevier, Fourth Edition, 1996.
- The at least one zeolite catalyst may be contacted with at least one binder to form a composition that may be formed into a spheroid particle discussed in more detail below. The at least one binder may be a metal oxide and/or a clay. Suitable exemplary binder materials include at least one of alumina, silica, an aluminosilicate, clay, and mixtures thereof. In an embodiment, the binder is aluminum oxide (Al2O3) or commonly referred to as alumina.
- For example, in an embodiment, the composition to be fashioned into a spheroid particle may comprise alumina and ZSM-22 or the composition may comprise alumina and ZSM-57.
- In a class of embodiments, the composition to be fashioned into a spheroid particle may comprise from 10:90 to 90:10, alternatively, from 20:80 to 80:20, of the at least zeolite catalyst to the at least one binder by weight.
- In an alternative class of embodiments, the composition may comprise from 1 to 99 wt % of the at least one zeolite catalyst based upon the total weight of the composition, alternatively, from 20 to 80 wt % of the at least one zeolite catalyst based upon the total weight of the composition, alternatively, from 25 to 75 wt % of the at least one zeolite catalyst based upon the total weight of the composition, alternatively, from 30 to 75 wt % of the at least one zeolite catalyst based upon the total weight of the composition, and alternatively, from 40 to 75 wt % of the at least one zeolite catalyst based upon the total weight of the composition. The remainder of the composition may be or comprise of one or more binders and/or one or more other additives or processing aids.
- The composition may be produced through any method known in the art. Mixing may be performed with conventional methods and equipment. In some embodiments, mixing may be performed in the presence of solvents or water.
- The composition to be formed into a spheroid particle may be mixed or contacted with at least one processing aid and/or comprise other components. Processing aids help the mixing, mulling, and extruding operation, and may improve the mechanical and/or physical properties of the composition or resulting particle. For example, a processing aid may promote bridging of inorganic particles during the kneading, molding, drying, and calcination, and/or ensure the mechanical stability of the composition. The processing aids may also help disperse solvents, if used, more homogeneously throughout the composition. Processing aids are usually removed during calcination. When a metal carboxylate is used as a processing aid, the metal (e.g., its oxide) is generally incorporated into the composition during calcination.
- The composition may comprise other components, including, for example, amines, alkyl amines, carboxylic acids, alkyl ammonium compounds, amino alcohols, cellulose, cellulose ethers, fillers, starch, polyacrylates, polymethacrylates, polyvinyl alcohols, poly(vinylpyrrolidone)s, poly(amino acid)s, polyethers, poly(tetrahydrofuran)s, metal carboxylates, and mixtures thereof.
- Examples of cellulose ethers include sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, and derivatives thereof. Examples of poly(alkylene oxide)s are poly(ethylene oxide)s, polypropylene oxide)s, or copolymers of ethylene oxide and propylene oxide.
- In some embodiments, the composition to be shaped into a spheroid particle may include one or more emulsifiers and/or one or more materials described above to modify the properties of the particle.
- The composition comprising the contact product of the at least one zeolite catalyst and the at least one binder may formed into a spheroid particle by any process that is capable of producing a spheroid structure from the compositions described above. As used herein, “spheroid particle” may refer to any ellipsoid structure. As used herein, “ellipsoid” may be described as an ellipse that has been rotated about at least one of its axis. In a class of embodiments, the spheroid particle may have two equal semi-diameters. The spheroid particle may be one or more of a prolated spheroid (elongated), oblate spheroid (flattened), and sphere itself. As used herein, “spheroid particle” may also refer to two or three dimensional ovoid particles, for example, an ovum (egg). As used herein, “particle(s)” refers to discrete units of material structure as discussed in Hawley's Condensed Chemical Dictionary, Richard J. Lewis Sr., 13th ed., 1997, John Wiley & Sons, Inc., page 840. For the sake of brevity, when spheroid particle is used it may refer to any definition as defined herein as well as refer to one or more of the spheroid particles defined herein. In a class of embodiments, the spheroid particle is not a cylinder. In another class of embodiment, the spheroid particle is not an extrudate. In a class of embodiments, the spheroid particle is not produced using a spray-dried method.
- In a class of embodiments, the spheroid particle may be produced by the spherical granulation of a composition by a vibrational dropping process. This technology is commercially available from Brace GmbH, Alzenau, Germany. In general, the technology introduces a liquefied composition through a vibrating nozzle system wherein the exiting stream breaks up into uniform droplets. When dropped or released from the system, the surface tension of the droplets shapes them into a spheroid. Following, the droplets undergo a solidification step. Solidification may be achieved in a gaseous medium through cooling, drying, and/or in liquid medium. The resulting materials are spheroid particles.
- In another class of embodiments, the spheroid particle may be produced by a spheronization process. One such process or technology is known as the MARUMERIZER™ process (developed by Fuji Paudal of Osaka, Japan) and is available from LCI Corp., Charlotte, N.C. In general, the process involves the formation of marumes or spheronizing noodles of a given composition. The composition is then fed into a MARUMIZER apparatus which operates by centrifugal force on the noodles to form them into spheronized particles or spheroid particles.
- See also WO 97/22680, WO 02/24755,
EP 0 046 535 A,EP 2 095 866 A,GB 1 418 445 A, U.S. Pat. Nos. 3,277,520, 3,584,334, 3,741,703, 3,743,464, 5,464,593, 6,923,984, and U.S. Patent Application Publication No. 2005/0054516 for more information and details as to how to produce spheroid particles under several embodiments of the invention. - In several embodiments, the spheroid particles may exhibit one or more of the following properties: free flowing, comprise embedded agents, have high porosity, have precise fitting diameters, carry a coating, have a high density, and be activated/doped.
- As used herein, “average particle size” with reference to the spheroid particle refers to the arithmetic average of the diameter distribution of the spheroid particles. The spheroid particle may have an average particle size of at least about or from 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, or 0.5 mm up to and including 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm, 4.0 mm, or 5.0 mm, including any range disclosed therein. Methods of measuring the spheroid particle are known and any suitable method may be used. Examples include electron microscopy or sieving using a mesh size in accordance with ASTM 16. Methods of measurement and definitions of particle diameters are presented in Table 2.1 of Powder Sample and Particle Size Determination by Terence Allen, 2003, Elsevier Science and Technology Books, ISBN 9780444515643, and are applied herein. In a class of embodiments, a sieving method is applied including using one or more mesh screens to concentrate particles having particular average particle sizes. A preferred method of measurement is provided in British Standard (BS) 1796-1: 1989 cross-referenced as ISO 2591-1: 1988. This method is applied unless otherwise stated given its ease and convenience on a commercial scale to quickly concentrate a large volume of particles having a particular average particle size.
- In several classes of embodiments, the spheroid particles may exhibit improved bulk densities as compared to conventional catalyst particles. For example, spheroid particles may have may have a bulk density 0.50 gram/cc or more, alternatively, a bulk density of 0.55 gram/cc or more, alternatively, a bulk density of 0.60 gram/cc or more, and alternatively, a bulk density of 0.65 gram/cc or more. Bulk densities are important features of these embodiments because the bulk densities as describe above provide for more mass of catalyst per reactor volume resulting in higher product yields.
- In other classes of embodiments, hexane uptake may be used to measure the available micro-pore volume of the catalyst particles. For example, the spheroid particle may exhibit a hexane uptake of 40 mg hexane/gram catalyst or more, alternatively, a hexane uptake of 45 mg hexane/gram catalyst or more, alternatively, a hexane uptake of 50 mg hexane/gram catalyst or more, and alternatively, a hexane uptake of 55 mg hexane/gram catalyst or more.
- In another class of embodiments, the bulk crush strength may be used to measure the resistance to fracturing of the catalyst particles. For example, the spheroid particle may have a bulk crush strength according to ASTM D7048 of 15 psig or more, alternatively, 20 psig or more, alternatively, 25 psig or more, and alternatively, 30 psig or more. These are important characteristics when loading and unloading catalyst particles into and out of a reactor.
- In a class of embodiments, for a given population of spheroid particles, not all members need to be uniform and the given population may comprise non-uniform members in shape taking into account irregularities that may result in the manufacturing process, handling/transport, defects that develop during use or regeneration, contaminants, etc. As used herein, “uniform” refers to having the same form. In general classes of embodiments, a given class of spheroid particles comprises 30% or more uniform members, alternatively, 40% or more uniform members, alternatively, 50% or more uniform members, alternatively, 60% or more uniform members, alternatively, 70% or more uniform me alternatively, 80% or more uniform members, and, alternatively, 90% or more uniform members, based upon the total given population.
- The feedstock typically comprises olefins having from about 2 to about 15 carbon atoms, such as, for example, from about 2 to about 6 carbon atoms. Additionally, in several embodiments, the feedstock may comprise an oligomer, such as, for example, a dimer, especially one provided by recycling a part of a product stream.
- In class of embodiments, the feedstock comprises one or more of propene, butenes, pentenes, hexenes, their isomers, and mixtures thereof. The process is especially useful for the oligomerization of feedstocks comprising propene, butenes, other components, and mixtures thereof.
- As used herein, “oligomer(s)” or “oligomer product” refers to a polymer molecule (or a mixture of polymer molecules) made from a few monomer units such as, for example, a dimer, a trimer, a tetramer, a mixture thereof, etc. In a class of embodiments, “oligomer(s)” refers to a polymer molecule (or a mixture of polymer molecules) having 20 carbon atoms or less, alternatively, 15 carbon atoms or less, alternatively, 10 carbon atoms or less, alternatively, 9 carbon atoms or less, and alternatively, 8 carbon atoms or less. As used herein, “oligomerization process” refers to any process of catalytically joining monomer units to form the oligomer(s) as defined above. In a class of embodiments, oligomerization process is used synonymously with “polymerization process.” As used herein, the term “oligomerization conditions” refers to any and all those variations of equipment, conditions (e.g., temperatures, pressures, etc.), materials, and reactor schemes that are suitable to conduct the oligomerization process to produce the oligomer(s) as known and applied in the art and discussed more below.
- In an embodiment, the oligomerization process may consist essentially of one or more single-step oligomerization processes.
- In a class of embodiments, the feedstock may contain 30 wt % or more olefins, alternatively, 40 wt % or more olefins, alternatively, 50 wt % or more olefins, alternatively, 60 wt % or more olefins, alternatively, 70 wt % or more olefins, and alternatively, 80 wt % or more olefins, based upon the total weight of the feed. The olefins to be oligomerized may be one or more of C3-C15 olefins or mixtures thereof, alternatively, C3-C6 olefins or mixtures thereof, and alternatively, C3-C5 olefins or mixtures thereof.
- The feedstock may also comprise other hydrocarbons such as, for example, at least one saturated hydrocarbon (e.g., at least one alkane) having the same or different number of carbon atoms as the olefin(s) in the feedstock.
- Additionally, the feedstock may comprise isomers of any of the constituents found therein. As used herein, “isomer” refers to compounds having the same molecular formula but different structural formula. Examples may be structural isomers, stereoisomers, enantiomers, geometrical isomers, etc. Typically, the feedstock may comprise at least one isomer of the olefin(s) in the feedstock.
- In a class of embodiments, the feedstock may also comprise contaminants or compounds that may hinder catalyst life or productivity. These may include nitrogen, sulfur, chlorine, or compounds incorporating the aforementioned elements, and mixtures thereof. Ethers such as di-isopropylether (DIPE) may also be a contaminant that may be removed from the feedstock.
- Examples of nitrogen containing compounds include acetonitrile, ammonia, amines, propionitriles and mixtures thereof. Examples of sulphur containing compounds include mercaptans such as, for example, methyl mercaptan, ethyl mercaptan, propyl mercaptan, dimethyl sulfide, diethyl sulfide, ethyl methyl sulfide, n-propyl sulfide, 1-propane thiol, 2-propane thiol, 1-butane thiol, 1,1-methylethyl thiol, ethylmethyl disulfide, dimethyl disulfide, tetrahydrothiopene, and mixtures thereof.
- Examples of suitable feedstocks include untreated refinery streams such as Fluidized Catalytic Cracking (FCC), coker, and pygas streams as well as aromatics-containing streams, such as, for example, reformates.
- Other examples include Raffinate-1 (RAF-1) and/or Raffinate-2 (RAF-2). Typically, Raffinate-1 and Raffinate-2 may be regarded as stages in the processing of crude, generally, C4 streams. These streams are usually from olefin steam crackers but may also come from refinery cat-crackers in which case they generally contain the same components but in different proportions. The first stage of the process is to remove, by generally solvent extraction or hydrogenation, the butadiene which may be 40-45% of the stream. The remaining product is Raffinate-1. It generally consists of isobutylene, the two normal isomers, butene-1 and butene-2, and smaller quantities of butanes and other compounds. Removal of the isobutylene, usually by reaction with methanol to produce MTBE, leaves Raffinate-2. Raffinate 3 (RAF-3) is less common but may also be used.
Raffinate 3 may be obtained after separation of 1-butene fromRaffinate 2 with a residual 1-butene content of about 1%. - In another embodiment, the feedstock comprises an FCC light olefin stream that typically comprises ethane, ethylene, propane, propylene, isobutane, n-butane, butenes, pentanes, and other optional components. A specific example of such a feedstock may comprise the following:
-
Wt % Mol % Ethane 3.3 5.1 Ethylene 0.7 1.2 Propane 4.5 15.3 Propylene 42.5 46.8 Isobutane 12.9 10.3 n-Butane 3.3 2.6 Butenes 22.1 18.32 Pentanes 0.7 0.4 - In several classes of embodiments the feedstock may comprise a diluent. The diluent may comprise any suitable hydrocarbon such as alkanes. The alkanes may be represented the general formula: CnH2n+2, wherein n is a number from 1 to 20, alternatively, from 1 to 10, alternatively, from 1 to 5, and alternatively, from 3 to 4. Examples may include methane, ethane, propane, butane, pentane, and mixtures thereof. In a class of embodiments and when the diluent is present, the feedstock may comprise at least 10%, at least 25%, at least 30%, at least 35%, or at least 40% of the diluent, for example, the alkane such as propane and/or butane, based upon the total volume of the feedstock. Alternatively stated, the diluent may be present in the feedstock in the range from 10% to 40%, alternatively, from 10% to 35%, and alternatively, from 20% to 35% based upon the total volume of the feedstock. The diluent may also be delivered to the reactor(s) through separate feedstreams. When fed separately, the diluent may be fed in amounts to be equivalent to the embodiments wherein the diluent is co-fed with the feedstock. These amounts may not necessarily be the same as the ranges stated above given that more or less of the diluent may necessary when fed separately to provide an equivalent.
- Additionally, the feedstock may undergo further processing and purification steps prior to being introduced in the oligomerization reactor(s).
- In several classes of embodiments and prior to oligomerization, the feedstock may be hydrated (i.e., contacted with water) and in an embodiment sufficient water may be added to saturate the feedstock. In particular, the feedstock may comprise from about 0.01 to about 0.25, alternatively, from about 0.02 to about 0.20, and alternatively, from about 0.03 to about 0.10, mol % water based on the total hydrocarbon content of the feedstock. If desired and by way of example, the water content of the feedstock may be increased by passage through a thermostatted water saturator.
- The reaction system may include one or more of a fixed bed reactor, a packed bed reactor, a tubular reactor, a fluidized bed reactor, a slurry reactor, and/or a continuous catalyst regeneration reactor. They may be operated in any combination such as, for example, in series and/or parallel sequence. In several embodiments, they may be operated in continuous or batch mode.
- The oligomerization conditions may include operating temperatures from about 80° C. to about 350° C. Close to and above the upper end of the range, deoligomerization rates increase and may predominate over the oligomerization reaction providing an upper limit to practical operation. More typically, the reaction temperature is from about 130° C. to about 320° C., alternatively, from about 135° C. to about 310° C., and alternatively, from about 160° C. to about 270° C.
- The pressure may be in the range of from about 400 psig to about 4000 psig (2860 to 27680 kPa), and alternatively, from about 500 psig to about 1500 psig (3550 to 10440 kPa).
- The olefin weight hourly space velocity may be in the range of from about 0.1 hr−1 to about 20 hr−1 or from about 0.5 hr−1 to about 5 hr−1.
- In one embodiment, process is conducted at a temperature of 80-350° C.; an olefin weight hourly space velocity of 0.1-20 hr−1; and a pressure of 2860−27680 kPa.
- In another embodiment, the process is conducted at a temperature of 130-320° C.; an olefin weight hourly space velocity of 0.5-5 hr−1; and a pressure of 3550−10440 kPa.
- In a class of embodiments, the oligomer product may include a hydrocarbon composition comprising at least 80 wt %, alternatively, at least 90 wt % based upon the total weight of the reactor effluent (the final reactor effluent if one or more reactors are utilized) of C8 to C20 olefin or a mixture thereof.
- The oligomer product is useful in many applications and is the starting material for further processes. For example, the oligomer product may be polymerized to produce polyolefins that have application in the plastic industry and synthetic basestocks for lubricants. The oligomer product may undergo hydroformylation and subsequently hydrogenation to produce alcohols. The alcohols may be used in industry such as, for example, solvents. The alcohols may further be used in many other areas of industry such as, for example, undergoing esterification to produce esters that have application as plasticizers.
- As used herein, “catalyst life” (Tpdt/Tcat) describes the number of tons of product produced per ton of formulated catalyst. It may be plotted against a setpoint temperature at a given space velocity and at a given olefin conversion rate. For example, a plot may provide a comparison between oligomerization processes using spheroid particles and extrudates (for example, 1/16th inch (1.5875 mm) and 1/20th inch (1.2700 mm) quadrulobe extrudates).
- In a class of embodiments, the spheroid particles provide for a longer catalyst life (for example, as represented by Tpdt/Tcat) at a desirable conversion. For example, these embodiments may enjoy an increase in catalyst life as compared to extrudates of the same chemical composition, of 10% or greater, alternatively, 20% or greater, alternatively, 30% or greater, alternatively, 40% or greater, alternatively, 50% or greater, alternatively, 75% or greater, alternatively, 100% or greater, alternatively, 150% or greater, and alternatively, 200% or greater, at oligomerization temperatures of from 180° C. to 320° C., alternatively, 210° C. to 300° C., alternatively, 210° C. to 250° C., and alternatively, 210° C. to 240° C., at an olefin constant conversion rate of from 60 to 99 wt % based upon the total weight of olefins, alternatively, from 70 to 95 wt %, alternatively, from 75 to 99 wt %, alternatively, from 75 to 95 wt %, and alternatively, at about 75 wt %. The space velocity for the aforementioned embodiments may be in the range of 1 to 20 h−1. In an embodiment, the space velocity is 12 h−1.
- In another class of embodiments, the spheroid particles provide for a longer catalyst life and at desirable olefin conversion rates. For example, these embodiments may enjoy an increase in catalyst life of from 2750 Tpdt/Tcat or greater, alternatively, 3000 Tpdt/Tcat or greater, alternatively, 3100 Tpdt/Tcat or greater, alternatively, 3500 Tpdt/Tcat or greater, alternatively, 4000 Tpdt/Tcat or greater, alternatively, 5000 Tpdt/Tcat or greater, alternatively, 6000 Tpdt/Tcat or greater, alternatively, 7000 Tpdt/Tcat or greater, and alternatively, 8000 Tpdt/Tcat or greater, (alternatively stated, from any one of the aforementioned numerical values to 25,000 Tpdt/Tcat to provide a closed numerical range) at oligomerization temperatures from 180° C. to 320° C., alternatively, 210° C. to 300° C., alternatively, 210° C. to 250° C., and alternatively, 210° C. to 240° C., at an olefin constant conversion rate of from 60 to 99 wt % based upon the total weight of olefins, alternatively, from 70 to 95 wt %, alternatively, from 75 to 99 wt %, alternatively, from 75 to 95 wt %, and alternatively, at about 75 wt %. The space velocity for the aforementioned embodiments may be any one of 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20 h−1. In an embodiment, the space velocity is 12 h−1.
- Embodiments described herein may exhibit improvements in olefin selectivity at given conversion rates that result in higher oligomer yield. Olefin selectivity may be defined as the weight of olefins having a given carbon number divided by the total weight of the product. For example, olefin selectivities may increase by 1 wt % or greater, alternatively, 2 wt % or greater, 3 wt % or greater, alternatively, 4 wt % or greater, alternatively, 5 wt % or greater, alternatively, 6 wt % or greater, alternatively, 7 wt % or greater, alternatively, 8 wt % or greater, alternatively, 9 wt % or greater, and alternatively, 10 wt % or greater, based upon the total weight of the product at an olefin constant conversion rate of from 60 to 99 wt % based upon the total weight of olefins in feed, alternatively, from 70 to 95 wt %, alternatively, from 75 to 99 wt %, alternatively, from 75 to 95 wt %, and alternatively, at about 75 wt %, and at oligomerization temperatures from 180° C. to 320° C., alternatively, 210° C. to 300° C., alternatively, 210° C. to 250° C., and alternatively, 210° C. to 240° C. The space velocity for the aforementioned embodiments may be any one of 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20 h−1. In an embodiment, the space velocity is 12 h−1. In several classes of embodiments, olefin selectivity may directed to the production of C6-C16 oligomers or mixtures thereof from C3-C6 feedstocks or mixtures thereof, alternatively, C7-C8-C9 oligomers or mixtures thereof from C3-C4 feedstocks or mixtures thereof
- Embodiments described herein may exhibit improvements in coke deposition, especially during longer oligomerization process runs, as compared to extrudates. As previously explained, high temperatures generated may lead to carbonaceous deposits on the catalyst caused by a build up of condensed, heavy hydrocarbons similar to asphalt. Such deposits are commonly termed “coke” and lead to deactivation of the catalyst. In general, the higher the concentration of olefin in the feed, the higher will be the rate of heat release from the catalyzed reaction, and thus, the higher the temperatures reached. Additionally, the oligomerization temperature is typically increased when catalyst activity begins to decrease. Consequently, there will be a higher rate of coke formation when measured at the end of the reactor run. In embodiments disclosed herein, coke deposition may be much less than that of processes using extrudates. For example, coke deposition for inventive spheroid particles and their corresponding oligomerization processes may be 15 wt % or less, alternatively, 9 wt % or less, alternatively, 8 wt % or less, alternatively, 7 wt % or less, alternatively, 6 wt % or less, based upon the total weight of the catalyst. Without being bound to theory, the improvements associated with the reduction of coke deposition on the catalyst particle may be at least partially responsible for or related to the improvements in longer catalyst life and/or olefin selectivity.
- It is to be understood that while the invention has been described in conjunction with the specific embodiments thereof, the foregoing description is intended to illustrate and not limit the scope of the invention. Other aspects, advantages and modifications will be apparent to those skilled in the art to which the invention pertains.
- Therefore, the following examples are put forth so as to provide those skilled in the art with a complete disclosure and description and are not intended to limit the scope of that which the inventors regard as their invention.
- Olefin oligomerizations were conducted at different space velocities utilizing butene and propylene feeds. The butene runs ran at space velocities of 2, 6, 12 or 18 h−1 and the propylene runs ran at space velocities of 1, 2, 4, 6 and 12 h−1 over a range of conversion levels of 70 to 90% for butene and 90 to 96% for propylene. For these runs, the reaction temperature was adjusted to maintain the target conversion. As the catalyst deactivated, the reaction temperature was raised as shown in the figures. This process is monitored by plotting the temperature to achieve target conversion at a given WHSV against time. It is desirable to track the stability of catalyst between and within individual runs by using different feed rates. Therefore, the time was replaced by a cumulative amount of product produced by the catalyst expressed as weight units of product produced per weight unit of catalyst.
- ZSM-57/alumina extrudates ( 1/16th inch (1.5875 mm) quadrulobes) were used to process 65 wt % n-butenes/25 wt % n-butane/10 wt % isobutane feedstock. Reaction conditions were 7000 kPa (70 bar), WHSV between 6 and 18 hr−1, and at 170 to 240° C. feedstock inlet temperature. The temperature required to maintain 75% of olefin conversion is shown in
FIG. 1 (triangles) as a function of catalyst life (weight product/weight catalyst). A catalyst life of 3000 T product/T catalyst (Tpdt/Tcat) was reached at ˜240° C. C8 selectivity data at 12 WHSV are plotted (triangles) inFIG. 2 . At 75% conversion the C8 selectivity is ˜80 wt %. - ZSM-57/alumina extrudates ( 1/20th inch (1.2700 mm) quadrulobes) were used to process 65 wt % n-butenes/25 wt % n-butane/10 wt % isobutane feedstock. Reaction conditions were 7000 kPa (70 bar), WHSV between 6 and 18 hr−1, and at 170 to 220° C. feedstock inlet temperature. The temperature required to maintain 75% of olefin conversion is shown in
FIG. 1 as a function of catalyst life (weight product/weight catalyst). A catalyst life of 3000 T product/T catalyst (Tpdt/Tcat) was reached at ˜220° C. C8 selectivity data at 12 WHSV are plotted (squares) inFIG. 2 . At 75% conversion the C8 selectivity is ˜86 wt %. - ZSM-57/alumina spheroids particles (sieved on ASTM 16 (mesh size)=1.2 mm) were used to process 65 wt % n-butenes/25 wt % n-butane/10 wt % isobutane feedstock. Reaction conditions were 7000 kPa (70 bar), WHSV=12 hr−1, and at 170 to 210° C. feedstock inlet temperature. The temperature required to maintain 75% of olefin conversion is shown in
FIG. 1 as a function of catalyst life (weight product/weight catalyst). A catalyst life of 3000 T product/T catalyst (Tpdt/Tcat) was reached at ˜200° C. C8 selectivity data at WHSV=12 hr−1 are plotted (diamonds) inFIG. 2 . At 75% conversion the C8 selectivity is ˜88 wt %. - ZSM-57/alumina extrudates ( 1/16th inch (1.5875 mm) quadrulobes) were used to process 50 wt % propylene/22.5 wt % propane/22.5 wt % n-butane/5 wt % isobutane feedstock. Reaction conditions were 7000 kPa (70 bar), WHSV between 4 and 12 hr−1, and at 175 to 215° C. feedstock inlet temperature. The temperature required to maintain 75% of olefin conversion is shown in
FIG. 3 as a function of catalyst life (weight product/weight catalyst). A catalyst life of 2000 T product/T catalyst (Tpdt/Tcat) was reached at ˜215° C. C9 selectivity data at WHSV=4 hr−1 are plotted (diamonds) inFIG. 4 . At 90% conversion the C9 selectivity is ˜60-62 wt %. - ZSM-57/alumina spheroids particles (sieved on ASTM 16 (mesh size)=1.2 mm) were used to process 50 wt % propylene/22.5 wt % propane/22.5 wt % n-butane/5 wt % isobutane feedstock. Reaction conditions were 7000 kPa (70 bar), WHSV=4 hr−1, and at 175 to 215° C. feedstock inlet temperature. The temperature required to maintain 75% of olefin conversion is shown in
FIG. 3 as a function of catalyst life (weight product/weight catalyst). A catalyst life of 2000 T product/T catalyst (Tpdt/Tcat) was reached at ˜205° C. C9 selectivity data at WHSV=4 hr−1 are plotted (squares) inFIG. 4 . At 90% conversion the C9 selectivity is ˜66-68 wt %. - In
FIGS. 1 and 3 , the weight unit chosen is “ton” (1 ton=1000 kg), denoted as T in the drawing. The longer a reactor runs at constant conditions within the practical temperature range of the unit expressed whether as days on stream or T product/T catalyst, the more stable the catalyst. Example 3 shows that the spheroid particles are much more stable in butene oligomerization than the extrudates of Examples 1 and 2. Example 5 shows that the spheroid particles are much more stable in propylene oligomerization than the extrudates of Example 4.FIG. 2 shows that the spheroid particles of Example 3 are more C8 selective than the extrudates of Examples 1 and 2 at a given conversion.FIG. 4 shows that the spheroid particles of Example 5 are more C9 selective than the extrudates of Example 4. - The phrases, unless otherwise specified, “consists essentially of” and “consisting essentially of” do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the invention, additionally, they do not exclude impurities and variances normally associated with the elements and materials used. For example, in any of the embodiments described herein, the process may consist essentially of one or more single-step oligomerization processes. As used here, “consist essentially” would exclude the multi-step processes disclosed in U.S. Pat. No. 7,374,662.
- For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
- All priority documents are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted and to the extent such disclosure is consistent with the description of the present invention. Further, all documents and references cited herein, including testing procedures, publications, patents, journal articles, etc. are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted and to the extent such disclosure is consistent with the description of the present invention.
- While the invention has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the invention as disclosed herein.
Claims (25)
1. A particle for the oligomerization of olefins and made from a composition comprising the contact product of:
(1) at least one zeolite catalyst; and
(2) at least one binder;
wherein the particle is a spheroid particle and has an average particle size of from 0.1 mm to 5.0 mm.
2. The spheroid particle of claim 1 , wherein the spheroid particle is shaped not utilizing a sprayed-dried process.
3. The spheroid particle of claim 1 , wherein the at least one zeolite catalyst is selected from one or more family members belonging to a TON structure, MFI structure, MFS structure, MWW structure, and mixtures thereof.
4. The spheroid particle of claim 1 , wherein the at least one zeolite catalyst is selected from at least one of ZSM-5, ZSM-22, ZSM-57, MCM-22, MCM-48, and mixtures thereof.
5. The spheroid particle of claim 1 , wherein the spheroid particle has an average particle size of from 0.1 mm to 4.0 mm.
6. The spheroid particle of claim 1 , wherein the spheroid particle has an average particle size of from 0.3 mm to 3.0 mm.
7. The spheroid particle of claim 1 , wherein the spheroid particle has an average particle size of from 0.5 mm to 1.5 mm.
8. The spheroid particle of claim 1 , wherein the at least one binder is selected from at least one of alumina, silica, an aluminosilicate, clay, and mixtures thereof.
9. The spheroid particle of claim 1 , wherein the at least one binder is aluminum oxide (Al2O3).
10. The spheroid particle of claim 1 , wherein the composition comprises from 25 to 99 wt % of the at least one zeolite catalyst based upon the total weight of the composition.
11. The spheroid particle of claim 1 , the composition comprises from 45 to 80 wt % of the at least one zeolite catalyst based upon the total weight of the composition.
12. The spheroid particle of claim 1 , wherein the composition comprises from 50 to 75 wt % of the at least one zeolite catalyst based upon the total weight of the composition.
13. A process for producing the spheroid particle of claim 1 , the process comprising producing the spheroid particle by the spherical granulation of the composition by a vibrational dropping process.
14. A process for producing the spheroid particle of claim 1 , the process comprising producing the spheroid particle by a spheronization process.
15. A process for the oligomerization of olefins, the process comprising:
contacting at least one spheroid particle in accordance with claim 1 , under oligomerization conditions with a feedstock comprising at least one C3-C15 olefin or a mixture thereof to form at least one oligomer product.
16. The process of claim 15 , wherein the feedstock comprises at least one C3-C6 olefin, preferably, at least one C3-C5 olefin, or a mixture thereof.
17. The process of claim 15 , wherein the mixture comprises one or more of a C3-C6 alkane, an isomeric equivalent of the olefin, or a mixture thereof.
18. The process of claim 15 , wherein the process comprises a catalyst life of 10% or greater as compared to an extrudate of the same chemical composition in the shape of a ( 1/16th inch (1.5875 mm) quadrulobe or 1/20th inch (1.2700 mm) quadrulobe); at oligomerization temperatures of from 180° C. to 320° C.; at an olefin constant per pass conversion rate of from 60 to 99 wt % based upon the total weight of olefins; and at a space velocity of from 1 to 20 h−1.
19. The process of claim 15 , wherein the process comprises a catalyst life of 30% or greater as compared to an extrudate of the same chemical composition in the shape of a ( 1/16th inch (1.5875 mm) quadrulobe or 1/20th inch (1.2700 mm) quadrulobe); at oligomerization temperatures of from 180° C. to 320° C.; at an olefin constant per pass conversion rate of from 60 to 99 wt % based upon the total weight of olefins; and at a space velocity of from 1 to 20 h−1.
20. The process of claim 15 , wherein the process comprises a catalyst life of 50% or greater as compared to an extrudate of the same chemical composition in the shape of a ( 1/16th inch (1.5875 mm) quadrulobe or 1/20th inch (1.2700 mm) quadrulobe); at oligomerization temperatures of from 180° C. to 320° C.; at an olefin constant per pass conversion rate of from 60 to 99 wt % based upon the total weight of olefins; and at a space velocity of from 1 to 20 h−1.
21. The process of claim 15 , wherein the process comprises a catalyst life of 75% or greater as compared to an extrudate of the same chemical composition in the shape of a ( 1/16th inch (1.5875 mm) quadrulobe or 1/20th inch (1.2700 mm) quadrulobe); at oligomerization temperatures of from 180° C. to 320° C.; at an olefin constant per pass conversion rate of from 60 to 99 wt % based upon the total weight of olefins; and at a space velocity of from 1 to 20 h−1.
22. The process of claim 15 , wherein the process comprises an olefin selectivity increase of 1 wt % or greater as compared to an extrudate of the same chemical composition in the shape of a ( 1/16th inch (1.5875 mm) quadrulobe or 1/20th inch (1.2700 mm) quadrulobe); at oligomerization temperatures of from 180° C. to 320° C.; at an olefin constant per pass conversion rate of from 60 to 99 wt % based upon the total weight of olefins; and at a space velocity of from 1 to 20 h−1.
23. The process of claim 15 , wherein the process comprises an olefin selectivity increase of 2 wt % or greater as compared to an extrudate of the same chemical composition in the shape of a ( 1/16th inch (1.5875 mm) quadrulobe or 1/20th inch (1.2700 mm) quadrulobe); at oligomerization temperatures of from 180° C. to 320° C.; at an olefin constant per pass conversion rate of from 60 to 99 wt % based upon the total weight of olefins; and at a space velocity of from 1 to 20 h−1.
24. The process of claim 15 , wherein the process comprises an olefin selectivity increase of 3 wt % or greater as compared to an extrudate of the same chemical composition in the shape of a ( 1/16th inch (1.5875 mm) quadrulobe or 1/20th inch (1.2700 mm) quadrulobe); at oligomerization temperatures of from 180° C. to 320° C.; at an olefin constant per pass conversion rate of from 60 to 99 wt % based upon the total weight of olefins; and at a space velocity of from 1 to 20 h−1.
25. A composition comprising the spheroid particle of claim 1 and a feedstock comprising one or more olefins.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/156,824 US20120022224A1 (en) | 2010-07-22 | 2011-06-09 | Particles Including Zeolite Catalysts And Their Use In Oligomerization Processes |
US15/096,639 US10138175B2 (en) | 2010-07-22 | 2016-04-12 | Particles including zeolite catalysts and their use in oligomerization processes |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US36670410P | 2010-07-22 | 2010-07-22 | |
EP10174865 | 2010-09-01 | ||
EP10174865.5 | 2010-09-11 | ||
US13/156,824 US20120022224A1 (en) | 2010-07-22 | 2011-06-09 | Particles Including Zeolite Catalysts And Their Use In Oligomerization Processes |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/096,639 Division US10138175B2 (en) | 2010-07-22 | 2016-04-12 | Particles including zeolite catalysts and their use in oligomerization processes |
Publications (1)
Publication Number | Publication Date |
---|---|
US20120022224A1 true US20120022224A1 (en) | 2012-01-26 |
Family
ID=43403806
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/156,824 Abandoned US20120022224A1 (en) | 2010-07-22 | 2011-06-09 | Particles Including Zeolite Catalysts And Their Use In Oligomerization Processes |
US15/096,639 Expired - Fee Related US10138175B2 (en) | 2010-07-22 | 2016-04-12 | Particles including zeolite catalysts and their use in oligomerization processes |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/096,639 Expired - Fee Related US10138175B2 (en) | 2010-07-22 | 2016-04-12 | Particles including zeolite catalysts and their use in oligomerization processes |
Country Status (1)
Country | Link |
---|---|
US (2) | US20120022224A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016150529A1 (en) | 2015-03-20 | 2016-09-29 | Exxonmobil Chemical Patents Inc. | Process for converting an olefin containing hydrocarbon feed into an oligomerization product or a hydrogenated oligomerization product |
WO2016166526A1 (en) * | 2015-04-14 | 2016-10-20 | Johnson Matthey Public Limited Company | Shaped catalyst particle |
US20160312133A1 (en) * | 2015-04-24 | 2016-10-27 | Uop Llc | Process for the production of jet-range hydrocarbons |
US20160312134A1 (en) * | 2015-04-24 | 2016-10-27 | Uop Llc | Process for the production of jet-range hydrocarbons |
WO2019011582A1 (en) | 2017-07-13 | 2019-01-17 | Exxonmobil Chemical Patents Inc. | Process for the removal of nitrogen-containing compounds from a hydrocarbon feed |
US20210355048A1 (en) * | 2018-10-17 | 2021-11-18 | Exxonmobil Chemical Patents Inc. | Oligomerization of Olefins |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2620314A (en) * | 1950-03-08 | 1952-12-02 | Universal Oil Prod Co | Spheroidal alumina |
US5183790A (en) * | 1991-01-24 | 1993-02-02 | Mobil Oil Corp. | Use of ZSM-57 in catalytic cracking for gasoline octane improvement and co-production of light olefins |
US5397455A (en) * | 1993-08-11 | 1995-03-14 | Mobil Oil Corporation | Gasoline upgrading process |
US5558851A (en) * | 1992-12-16 | 1996-09-24 | Chevron U.S.A. Inc. | Preparation of aluminosilicate zeolites |
US5962735A (en) * | 1998-03-06 | 1999-10-05 | Uop Llc | Method for treating an organic liquid contaminated with an iodide compound |
US20020072467A1 (en) * | 2000-09-29 | 2002-06-13 | Tosoh Corporation | Molded catalyst for production of triethylenediamine, method for its production, and method for producing triethylenediamine |
US20060199987A1 (en) * | 2005-01-31 | 2006-09-07 | Kuechler Keith H | Olefin Oligomerization |
US20060224030A1 (en) * | 2004-04-05 | 2006-10-05 | Patrick Euzen | Process for the production of phenylalkanes that use a zeolitic catalyst that is based on silica-alumina |
US20080188694A1 (en) * | 2006-12-29 | 2008-08-07 | Schmidt Robert J | Solid Acid Catalyst and Process for Decomposition of Cumene Hydroperoxide |
US20090118556A1 (en) * | 2004-12-23 | 2009-05-07 | Patrick Euzen | Zeolitic catalyst with a controlled doping element content, and improved process for processing hydrocarbon feeds |
US7737315B2 (en) * | 2006-03-10 | 2010-06-15 | Exxonmobil Chemical Patents Inc. | Oligomerization of isobutene-containing feedstocks |
US7834229B2 (en) * | 2004-06-01 | 2010-11-16 | Exxonmobil Chemical Patents Inc. | Olefin oligomerization process |
US20110042270A1 (en) * | 2008-01-04 | 2011-02-24 | Ifp | Catalyst comprising at least one particular zeolite and at least one silica-alumina, and process for hydrocracking hydrocarbon feeds using said catalyst |
US8450233B2 (en) * | 2008-01-25 | 2013-05-28 | Total Petrochemicals Research Feluy | Process for obtaining catalyst composites comprising MeAPO and their use in conversion of organics to olefins |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2223306B1 (en) | 1973-03-27 | 1975-08-22 | Rhone Progil | |
US3960978A (en) | 1974-09-05 | 1976-06-01 | Mobil Oil Corporation | Converting low molecular weight olefins over zeolites |
US4021502A (en) | 1975-02-24 | 1977-05-03 | Mobil Oil Corporation | Converting low molecular weight olefins over zeolites |
US4016218A (en) | 1975-05-29 | 1977-04-05 | Mobil Oil Corporation | Alkylation in presence of thermally modified crystalline aluminosilicate catalyst |
US4381255A (en) | 1981-01-14 | 1983-04-26 | W. R. Grace & Co. | Binderless zeolite extrudates and method of producing |
US4560536A (en) | 1983-08-26 | 1985-12-24 | Mobil Oil Corporation | Catalytic conversion with catalyst regeneration sequence |
NZ217874A (en) | 1985-10-25 | 1989-01-27 | Mobil Oil Corp | Quadrulobe catalysts |
US4919896A (en) | 1987-12-28 | 1990-04-24 | Mobil Oil Corporation | Multistage catalytic reactor system for production of heavy hydrocarbons |
EP0507122B1 (en) | 1991-03-11 | 1995-01-11 | Mitsubishi Oil Co., Ltd. | Process for producing spherical zeolite catalyst and apparatus for producing the same |
EP0757976A3 (en) | 1992-01-30 | 1998-01-28 | Exxon Chemical Patents Inc. | Alkene oligomerisation with crystals of H-ZSM or ZSM catalysts |
GB9225183D0 (en) | 1992-12-02 | 1993-01-20 | British Petroleum Co Plc | Process for the production of branched olefins |
EP0746538B1 (en) | 1994-02-22 | 1999-01-27 | Exxon Chemical Patents Inc. | Oligomerization and catalysts therefor |
US5446222A (en) | 1994-06-17 | 1995-08-29 | Mobil Oil Corporation | Oligomers of cyclopentadiene and process for making them |
WO2000017105A1 (en) | 1998-09-22 | 2000-03-30 | Exxon Chemical Patents Inc. | Preparation of high silica zeolites bound by zeolite and use thereof |
US6787023B1 (en) * | 1999-05-20 | 2004-09-07 | Exxonmobil Chemical Patents Inc. | Metal-containing macrostructures of porous inorganic oxide, preparation thereof, and use |
US7112711B2 (en) * | 2000-04-28 | 2006-09-26 | Exxonmobil Chemical Patents Inc. | Alkene oligomerization process |
US7102038B2 (en) * | 2000-05-08 | 2006-09-05 | Shell Oil Company | Phosphorous removal and diene removal, when using diene sensitive catalyst, during conversion of olefins to branched primary alcohols |
US6649802B1 (en) * | 2000-09-21 | 2003-11-18 | Uop Llc | Layered oligomerization catalyst system |
US6403853B1 (en) | 2000-09-21 | 2002-06-11 | Uop Llc | Olefin oligomerization using surface modified molecular sieve catalyst |
US6875899B2 (en) | 2001-02-01 | 2005-04-05 | Exxonmobil Chemical Patents Inc. | Production of higher olefins |
FR2837213B1 (en) | 2002-03-15 | 2004-08-20 | Inst Francais Du Petrole | PROCESS FOR THE JOINT PRODUCTION OF PROPYLENE AND GASOLINE FROM A RELATIVELY HEAVY LOAD |
JP4526760B2 (en) | 2002-12-11 | 2010-08-18 | 日揮触媒化成株式会社 | Zeolite microsphere compact |
US20050054516A1 (en) | 2003-09-05 | 2005-03-10 | Vaughn Stephen Neil | Processes for formulating catalyst compositions having desirable particle size characteristics |
GB0412151D0 (en) | 2004-06-01 | 2004-06-30 | Exxonmobil Chem Patents Inc | Olefin oligomerization process |
GB0512377D0 (en) | 2005-06-17 | 2005-07-27 | Exxonmobil Chem Patents Inc | Oligomerisation of olefins with zeolite catalyst |
US7741526B2 (en) * | 2006-07-19 | 2010-06-22 | Exxonmobil Chemical Patents Inc. | Feedstock preparation of olefins for oligomerization to produce fuels |
US7825204B2 (en) | 2006-12-19 | 2010-11-02 | Lyondell Chemical Technology, L.P. | Inorganic oxide extrudates |
US8343335B2 (en) | 2008-02-21 | 2013-01-01 | Exxonmobil Research And Engineering Company | Production of shaped silica bodies |
EP2335812B1 (en) | 2008-02-25 | 2016-12-07 | JGC Catalysts and Chemicals Ltd. | Exhaust gas treatment apparatus |
US8575410B2 (en) * | 2009-03-31 | 2013-11-05 | Uop Llc | Process for oligomerizing dilute ethylene |
-
2011
- 2011-06-09 US US13/156,824 patent/US20120022224A1/en not_active Abandoned
-
2016
- 2016-04-12 US US15/096,639 patent/US10138175B2/en not_active Expired - Fee Related
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2620314A (en) * | 1950-03-08 | 1952-12-02 | Universal Oil Prod Co | Spheroidal alumina |
US5183790A (en) * | 1991-01-24 | 1993-02-02 | Mobil Oil Corp. | Use of ZSM-57 in catalytic cracking for gasoline octane improvement and co-production of light olefins |
US5558851A (en) * | 1992-12-16 | 1996-09-24 | Chevron U.S.A. Inc. | Preparation of aluminosilicate zeolites |
US5397455A (en) * | 1993-08-11 | 1995-03-14 | Mobil Oil Corporation | Gasoline upgrading process |
US5962735A (en) * | 1998-03-06 | 1999-10-05 | Uop Llc | Method for treating an organic liquid contaminated with an iodide compound |
US20020072467A1 (en) * | 2000-09-29 | 2002-06-13 | Tosoh Corporation | Molded catalyst for production of triethylenediamine, method for its production, and method for producing triethylenediamine |
US20060224030A1 (en) * | 2004-04-05 | 2006-10-05 | Patrick Euzen | Process for the production of phenylalkanes that use a zeolitic catalyst that is based on silica-alumina |
US7834229B2 (en) * | 2004-06-01 | 2010-11-16 | Exxonmobil Chemical Patents Inc. | Olefin oligomerization process |
US20090118556A1 (en) * | 2004-12-23 | 2009-05-07 | Patrick Euzen | Zeolitic catalyst with a controlled doping element content, and improved process for processing hydrocarbon feeds |
US20060199987A1 (en) * | 2005-01-31 | 2006-09-07 | Kuechler Keith H | Olefin Oligomerization |
US7737315B2 (en) * | 2006-03-10 | 2010-06-15 | Exxonmobil Chemical Patents Inc. | Oligomerization of isobutene-containing feedstocks |
US20080188694A1 (en) * | 2006-12-29 | 2008-08-07 | Schmidt Robert J | Solid Acid Catalyst and Process for Decomposition of Cumene Hydroperoxide |
US20110042270A1 (en) * | 2008-01-04 | 2011-02-24 | Ifp | Catalyst comprising at least one particular zeolite and at least one silica-alumina, and process for hydrocracking hydrocarbon feeds using said catalyst |
US8450233B2 (en) * | 2008-01-25 | 2013-05-28 | Total Petrochemicals Research Feluy | Process for obtaining catalyst composites comprising MeAPO and their use in conversion of organics to olefins |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016150529A1 (en) | 2015-03-20 | 2016-09-29 | Exxonmobil Chemical Patents Inc. | Process for converting an olefin containing hydrocarbon feed into an oligomerization product or a hydrogenated oligomerization product |
GB2541052B (en) * | 2015-04-14 | 2019-10-16 | Johnson Matthey Plc | Shaped catalyst particle |
WO2016166526A1 (en) * | 2015-04-14 | 2016-10-20 | Johnson Matthey Public Limited Company | Shaped catalyst particle |
US10913057B2 (en) | 2015-04-14 | 2021-02-09 | Johnson Matthey Public Limited Company | Shaped catalyst particle |
GB2541052A (en) * | 2015-04-14 | 2017-02-08 | Johnson Matthey Plc | Shaped catalyst particle |
CN107530696A (en) * | 2015-04-14 | 2018-01-02 | 庄信万丰股份有限公司 | The catalyst granules of shaping |
AU2016250205B2 (en) * | 2015-04-14 | 2020-07-30 | Johnson Matthey Public Limited Company | Shaped catalyst particle |
RU2701190C2 (en) * | 2015-04-14 | 2019-09-25 | Джонсон Мэтти Паблик Лимитед Компани | Catalyst particle of certain shape |
US20160312134A1 (en) * | 2015-04-24 | 2016-10-27 | Uop Llc | Process for the production of jet-range hydrocarbons |
US20160312133A1 (en) * | 2015-04-24 | 2016-10-27 | Uop Llc | Process for the production of jet-range hydrocarbons |
WO2019011582A1 (en) | 2017-07-13 | 2019-01-17 | Exxonmobil Chemical Patents Inc. | Process for the removal of nitrogen-containing compounds from a hydrocarbon feed |
US20210355048A1 (en) * | 2018-10-17 | 2021-11-18 | Exxonmobil Chemical Patents Inc. | Oligomerization of Olefins |
US11905227B2 (en) * | 2018-10-17 | 2024-02-20 | Exxonmobil Chemical Patents Inc. | Oligomerization of olefins |
Also Published As
Publication number | Publication date |
---|---|
US20160221891A1 (en) | 2016-08-04 |
US10138175B2 (en) | 2018-11-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10138175B2 (en) | Particles including zeolite catalysts and their use in oligomerization processes | |
EP2072484B1 (en) | Olefin oligomerization process | |
EP1751079B1 (en) | Olefin oligomerization process | |
US9573861B2 (en) | Olefin oligomerization process | |
EP2917168B1 (en) | Fluid catalytic cracking process | |
KR20130086342A (en) | Process for co-oligomerization of olefins | |
US9505685B2 (en) | Olefin oligomerization process | |
US9550705B2 (en) | Olefin oligomerization process | |
JP2007514702A (en) | Improvement of catalytic reaction | |
US20110306812A1 (en) | Process for the cooligomerization of olefins | |
US10508063B2 (en) | Olefin oligomerization in the presence of cyclopentene | |
WO2012033562A1 (en) | Extrudates including zeolite catalysts and their use in oligomerization processes | |
US9428427B2 (en) | Process for nitrile removal from hydrocarbon feeds | |
US9505674B2 (en) | Processes for treating olefin feedstreams and related oligomerization processes | |
CN104718024B (en) | Method for dimerizing olefins | |
US8426663B2 (en) | Catalytic conversion of alkylaromatic compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: EXXONMOBIL CHEMICAL PATENTS INC., TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TOSIN, GERALDINE;JANSSEN, MARCEL J.G.;HAMILTON, PAUL;AND OTHERS;SIGNING DATES FROM 20110705 TO 20110707;REEL/FRAME:026626/0393 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |