EP0155822A2 - Verfahren zur katalytischen Entwachsung unter Verwendung von ZSM-11 Zeolith - Google Patents
Verfahren zur katalytischen Entwachsung unter Verwendung von ZSM-11 Zeolith Download PDFInfo
- Publication number
- EP0155822A2 EP0155822A2 EP85301771A EP85301771A EP0155822A2 EP 0155822 A2 EP0155822 A2 EP 0155822A2 EP 85301771 A EP85301771 A EP 85301771A EP 85301771 A EP85301771 A EP 85301771A EP 0155822 A2 EP0155822 A2 EP 0155822A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- zsm
- dewaxing
- oil
- stock
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 35
- 239000010457 zeolite Substances 0.000 title claims description 32
- 230000003197 catalytic effect Effects 0.000 title claims description 31
- 230000008569 process Effects 0.000 title claims description 29
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 19
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 18
- 239000003921 oil Substances 0.000 claims abstract description 37
- 239000010687 lubricating oil Substances 0.000 claims abstract description 29
- 239000000295 fuel oil Substances 0.000 claims abstract description 12
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract 10
- 239000003054 catalyst Substances 0.000 claims description 121
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- 230000000694 effects Effects 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 239000001993 wax Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000010779 crude oil Substances 0.000 claims description 7
- -1 platinum group metals Chemical class 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 29
- 238000005984 hydrogenation reaction Methods 0.000 claims 18
- 229910052759 nickel Inorganic materials 0.000 claims 15
- 239000000047 product Substances 0.000 claims 13
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims 12
- 229910052593 corundum Inorganic materials 0.000 claims 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 11
- 239000000203 mixture Substances 0.000 claims 10
- 239000000314 lubricant Substances 0.000 claims 9
- 230000008901 benefit Effects 0.000 claims 8
- 238000005470 impregnation Methods 0.000 claims 7
- 230000007935 neutral effect Effects 0.000 claims 7
- 150000001875 compounds Chemical class 0.000 claims 6
- 229910052750 molybdenum Inorganic materials 0.000 claims 6
- 229910052681 coesite Inorganic materials 0.000 claims 5
- 229910052906 cristobalite Inorganic materials 0.000 claims 5
- 229910052682 stishovite Inorganic materials 0.000 claims 5
- 229910052905 tridymite Inorganic materials 0.000 claims 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 4
- 238000009835 boiling Methods 0.000 claims 4
- 238000005342 ion exchange Methods 0.000 claims 4
- 239000000463 material Substances 0.000 claims 4
- 239000011733 molybdenum Substances 0.000 claims 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 3
- 239000000654 additive Substances 0.000 claims 3
- 239000010953 base metal Substances 0.000 claims 3
- 239000001307 helium Substances 0.000 claims 3
- 229910052734 helium Inorganic materials 0.000 claims 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 3
- 238000010348 incorporation Methods 0.000 claims 3
- 150000002739 metals Chemical class 0.000 claims 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 3
- 238000012545 processing Methods 0.000 claims 3
- 239000000243 solution Substances 0.000 claims 3
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 2
- 229910003296 Ni-Mo Inorganic materials 0.000 claims 2
- 229910003294 NiMo Inorganic materials 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- 230000009286 beneficial effect Effects 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 2
- 150000007942 carboxylates Chemical class 0.000 claims 2
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 239000011651 chromium Substances 0.000 claims 2
- 239000004927 clay Substances 0.000 claims 2
- 239000010941 cobalt Substances 0.000 claims 2
- 229910017052 cobalt Inorganic materials 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 2
- 239000000446 fuel Substances 0.000 claims 2
- WUHYYTYYHCHUID-UHFFFAOYSA-K iridium(3+);triiodide Chemical compound [I-].[I-].[I-].[Ir+3] WUHYYTYYHCHUID-UHFFFAOYSA-K 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 2
- 239000012263 liquid product Substances 0.000 claims 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims 2
- 229910052763 palladium Inorganic materials 0.000 claims 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims 2
- 230000000737 periodic effect Effects 0.000 claims 2
- 238000012216 screening Methods 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 239000010936 titanium Substances 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 2
- 229910052721 tungsten Inorganic materials 0.000 claims 2
- 239000010937 tungsten Substances 0.000 claims 2
- 238000010977 unit operation Methods 0.000 claims 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims 1
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims 1
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 claims 1
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims 1
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- OTOBABIFUHCBCF-UHFFFAOYSA-P C=1C=CC=CC=1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Ir](C(=O)Cl)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Ir](C(=O)Cl)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 OTOBABIFUHCBCF-UHFFFAOYSA-P 0.000 claims 1
- PLZNEAAEBKBGCC-UHFFFAOYSA-O C=1C=CC=CC=1P(C=1C=CC=CC=1)([Pt])C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)([Pt])C1=CC=CC=C1 PLZNEAAEBKBGCC-UHFFFAOYSA-O 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000005069 Extreme pressure additive Substances 0.000 claims 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- DKBAQFAPARKJMS-UHFFFAOYSA-I [Re](Cl)(Cl)(Cl)(Cl)Cl.C(CN)N Chemical compound [Re](Cl)(Cl)(Cl)(Cl)Cl.C(CN)N DKBAQFAPARKJMS-UHFFFAOYSA-I 0.000 claims 1
- XRJHOHOZMIECRE-UHFFFAOYSA-N [Rh].C1(C=CC=C1)C=C Chemical compound [Rh].C1(C=CC=C1)C=C XRJHOHOZMIECRE-UHFFFAOYSA-N 0.000 claims 1
- 230000002411 adverse Effects 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229910000323 aluminium silicate Inorganic materials 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 238000003556 assay Methods 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 claims 1
- 238000010960 commercial process Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 125000004989 dicarbonyl group Chemical group 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims 1
- 238000002474 experimental method Methods 0.000 claims 1
- 238000011010 flushing procedure Methods 0.000 claims 1
- 238000004817 gas chromatography Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 229910001507 metal halide Inorganic materials 0.000 claims 1
- 150000005309 metal halides Chemical class 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 1
- 150000002830 nitrogen compounds Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- IHUHXSNGMLUYES-UHFFFAOYSA-J osmium(iv) chloride Chemical compound Cl[Os](Cl)(Cl)Cl IHUHXSNGMLUYES-UHFFFAOYSA-J 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- 235000019809 paraffin wax Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 238000005325 percolation Methods 0.000 claims 1
- 235000019271 petrolatum Nutrition 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 239000002574 poison Substances 0.000 claims 1
- 231100000614 poison Toxicity 0.000 claims 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 238000010998 test method Methods 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- WJYMPXJVHNDZHD-UHFFFAOYSA-N 1,3,5-triethylbenzene Chemical compound CCC1=CC(CC)=CC(CC)=C1 WJYMPXJVHNDZHD-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Definitions
- porous inorganic solids that were originally found useful for catalytic processes included certain clays, aluminas, silica-aluminas and other silicas coprecipitated with magnesia, for example, and such solids are still extensively used in the industry. In general, all of these solids had pores that were not of uniform size, and most of the pore volume was in pores having diameters larger than about 30 Angstroms, with some of the pores as large or larger than 100 Angstroms.
- Zeolite molecular sieves have been found to be highly effective as hydrocarbon conversion catalysts.
- the conversion of gas oil to gasoline and distillate by catalytic cracking, the alkylation of benzene to ethylbenzene, the isomerization of xylenes and the disproportionation of toluene all involve molecules which are smaller in critical diameter than 1,3,5-triethylbenzene, and such molecules are occluded and acted upon by zeolite molecular sieves having an effective pore diameter of about 10 Angstroms.
- a particularly interesting catalytic transformation which requires a molecular sieve catalyst is the reduction of the pour point of waxy distillates and residual hydrocarbon fractions.
- Effective pour point reduction depends on the selective conversion of normal, high melting point paraffin molecules that have an effective critical diameter of about 5 Angstroms to substances of lower molecular weight that are easily separated from the low-pour product.
- Effective catalytic dewaxing depends at least in part on the regularity of the pore size of the crystalline zeolites, which allows selective conversion of unwanted constituents.
- Crystalline zeolite ZSM-11 is disclosed in U.S. Patent 3,709,979.
- Example 9 of this patent taught fluid catalytic cracking at 875°F of a gas oil having a pour point of 100°F. High yields of olefins were obtained. The pour point of the product was reduced.
- U.S. 4,332,670 taught catalytic dewaxing of middle distillates to produce a low pour fuel oil by using an intermediate pore size zeolite. There are no examples showing use of ZSM-11.
- ZSM-11 which has been ignored experimentally by all prior workers in the lube oil and fuel oil area, is better for catalytic dewaxing than ZSM-5.
- the present invention provides a process for catalytically dewaxing a wax containing hydrocarbon feedstock to produce a dewaxed oil which comprises contacting said stock at a temperature of 230 to 450°C, at a pressure of atmospheric to 14,000 kPa, and in the presence of hydrogen in a reaction zone with a catalyst comprising ZSM-11.
- the present invention provides a process for producing lubricating oil base stock with high viscosity index comprising contacting a lubricating oil base feedstock containing waxy components with a dewaxing catalyst comprising 10 to 95 wt % ZSM-11 catalyst and 90 to 5 wt % refractory inorganic oxide binder in a catalytic dewaxing zone operated at 230 to 400°C, a pressure of atmospheric to 14,000 kPa, liquid hourly space velocity of 0.1 to 20 and wherein hydrogen is present and the ratio of hydrogen to hydrocarbon is 50 to 1,000 volumes of Ha at standard conditions per volume of liquid oil at standard conditions to produce a lubricating oil base stock with reduced wax content.
- a dewaxing catalyst comprising 10 to 95 wt % ZSM-11 catalyst and 90 to 5 wt % refractory inorganic oxide binder in a catalytic dewaxing zone operated at 230 to 400°C, a pressure of atmospheric to 14,000 kPa, liquid
- the present invention provides a process for catalytic dewaxing of a wax containing oil comprising contacting said oii in the presence of hydrogen at a temperature of 23D to 450°C, a hydrogen partial pressure of atmospheric to 14,000 kPa with a fixed bed of catalyst comprising ZSM-11 and a platinum group metal component to produce a catalytically dewaxed oil.
- the silica to alumina mole ratio of ZSM-11, and other zeolites may be determined by conventional analysis. This ratio is meant to represent, as closely as possible, the ratio in the rigid anionic framework of the zeolite crystal and to exclude aluminum in the binder or in cationic or other form within the channels. Although zeolites with silica to alumina mole ratios of at least 10 are useful, it is preferred to use zeolites having higher ratios than about 12, preferably about 15 to 200. In addition, zeolites as otherwise characterized herein but which are substantially free of aluminum, that is zeolites having silica to alumina mole ratios of up to infinity, are found to be useful and even preferable in some instances.
- Such "high silica” or “highly siliceous” zeolites tend to be hydrophobic and are intended to be included within this description. Also included within this definition are substantially pure silica analogues of the useful zeolites described herein, that is to say those zeolites having no measurable amount of aluminum (silica to alumina mole ratio of infinity) but which otherwise embody the characteristics disclosed.
- the acid activity may be adjusted by crystallizing the ZSM-11 with only a little, or a lot, of aluminum, steaming the ZSM-11, acid extracting, or any other means conventionally used to adjust acid activity.
- One method of measuring acid activity is to measure the cracking activity of a catalyst to obtain an alpha value or alpha activity.
- a method of determining alpha activity is described in U.S. Patent 4,016,218.
- the alpha test is a good measure of cracking activity, but not a measure of hydroisomerization activity.
- 0ur ZSM-11 dewaxing process is believed to proceed by both cracking and hydroisomerization, so alpha activity provides some information about only one of the several reactions believed to occur during dewaxing.
- An activated large pore zeolite, e.g., RENaX might have an alpha activity of over 10,000 and be a good FCC catalyst but do little or no dewaxing.
- a good dewaxing catalyst e.g., Ni-ZSM-5, partially deactivated by coking, might have a low alpha activity and still do a good dewaxing job, so long as reactor temperatures were raised somewhat to adjust for the low alpha activity.
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59109484A | 1984-03-19 | 1984-03-19 | |
| US59109384A | 1984-03-19 | 1984-03-19 | |
| US59092684A | 1984-03-19 | 1984-03-19 | |
| US591094 | 1984-03-19 | ||
| US590926 | 1984-03-19 | ||
| US591093 | 1984-03-19 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0155822A2 true EP0155822A2 (de) | 1985-09-25 |
| EP0155822A3 EP0155822A3 (en) | 1988-01-13 |
| EP0155822B1 EP0155822B1 (de) | 1990-12-19 |
Family
ID=27416588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85301771A Expired - Lifetime EP0155822B1 (de) | 1984-03-19 | 1985-03-14 | Verfahren zur katalytischen Entwachsung unter Verwendung von ZSM-11 Zeolith |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0155822B1 (de) |
| AU (1) | AU578930B2 (de) |
| BR (1) | BR8501129A (de) |
| DE (1) | DE3580928D1 (de) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0404666A1 (de) * | 1989-06-21 | 1990-12-27 | Institut Français du Pétrole | Verfahren zur katalytischen Entparaffinierung |
| WO1994022981A1 (en) * | 1993-04-05 | 1994-10-13 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | A process for producing heavy lubricating oil having a low pour point |
| US6399845B1 (en) | 1997-05-29 | 2002-06-04 | Fortum Oil & Gas Oy | Process for producing high grade diesel fuel |
| WO2017112647A1 (en) * | 2015-12-21 | 2017-06-29 | Exxonmobil Research And Engineering Company | Trim dewaxing of distillate fuel |
| WO2017112558A1 (en) * | 2015-12-21 | 2017-06-29 | Exxonmobil Research And Engineering Company | Trim dewaxing of distillate fuel |
| WO2017112377A1 (en) * | 2015-12-21 | 2017-06-29 | Exxonmobil Research And Engineering Company | Base metal dewaxing catalyst |
| WO2018160424A1 (en) * | 2017-03-03 | 2018-09-07 | Exxonmobil Research And Engineering Company | Trimetallic base metal hdn+hds+dewaxing catalysts, their preparation and use |
| EP3397382A1 (de) * | 2015-12-28 | 2018-11-07 | ExxonMobil Research and Engineering Company | Sequenzielle imprägnierung eines porösen trägers zur bildung einer edelmetalllegierung |
| WO2018204155A1 (en) * | 2017-05-05 | 2018-11-08 | Exxonmobil Research And Engineering Company | Noble metal and base metal dewaxing catalyst |
| WO2025000895A1 (zh) * | 2023-06-30 | 2025-01-02 | 中国石油天然气股份有限公司 | 一种正构烷烃加氢异构催化剂及其制备方法、包含其的组合物和应用 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2131227A1 (de) * | 1971-06-18 | 1972-12-21 | Atlantic Richfield Co | Verfahren zur Herstellung von Weissoel |
| US3709979A (en) * | 1970-04-23 | 1973-01-09 | Mobil Oil Corp | Crystalline zeolite zsm-11 |
| US3956102A (en) * | 1974-06-05 | 1976-05-11 | Mobil Oil Corporation | Hydrodewaxing |
| CA1108084A (en) * | 1976-12-20 | 1981-09-01 | Philip D. Caesar | Gas oil processing |
| US4181598A (en) * | 1977-07-20 | 1980-01-01 | Mobil Oil Corporation | Manufacture of lube base stock oil |
| US4428819A (en) * | 1982-07-22 | 1984-01-31 | Mobil Oil Corporation | Hydroisomerization of catalytically dewaxed lubricating oils |
-
1985
- 1985-02-27 AU AU39207/85A patent/AU578930B2/en not_active Ceased
- 1985-03-14 EP EP85301771A patent/EP0155822B1/de not_active Expired - Lifetime
- 1985-03-14 BR BR8501129A patent/BR8501129A/pt unknown
- 1985-03-14 DE DE8585301771T patent/DE3580928D1/de not_active Expired - Lifetime
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0404666A1 (de) * | 1989-06-21 | 1990-12-27 | Institut Français du Pétrole | Verfahren zur katalytischen Entparaffinierung |
| FR2648823A1 (fr) * | 1989-06-21 | 1990-12-28 | Inst Francais Du Petrole | Procede de deparaffinage catalytique |
| WO1994022981A1 (en) * | 1993-04-05 | 1994-10-13 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | A process for producing heavy lubricating oil having a low pour point |
| CN1042948C (zh) * | 1993-04-05 | 1999-04-14 | 切夫里昂美国公司 | 生产低倾点的重质润滑油的方法 |
| US6399845B1 (en) | 1997-05-29 | 2002-06-04 | Fortum Oil & Gas Oy | Process for producing high grade diesel fuel |
| CN108472637A (zh) * | 2015-12-21 | 2018-08-31 | 埃克森美孚研究工程公司 | 馏出物燃料的修整脱蜡 |
| US20180362860A1 (en) * | 2015-12-21 | 2018-12-20 | Exxonmobil Research And Engineering Company | Trim dewaxing of distillate fuel |
| WO2017112377A1 (en) * | 2015-12-21 | 2017-06-29 | Exxonmobil Research And Engineering Company | Base metal dewaxing catalyst |
| US10035962B2 (en) | 2015-12-21 | 2018-07-31 | Exxonmobil Research And Engineering Company | Trim dewaxing of distillate fuel |
| CN108367280A (zh) * | 2015-12-21 | 2018-08-03 | 埃克森美孚研究工程公司 | 馏出物燃料的修整脱蜡 |
| WO2017112647A1 (en) * | 2015-12-21 | 2017-06-29 | Exxonmobil Research And Engineering Company | Trim dewaxing of distillate fuel |
| US10669491B2 (en) | 2015-12-21 | 2020-06-02 | Exxonmobil Research And Engineering Company | Base metal dewaxing catalyst |
| WO2017112558A1 (en) * | 2015-12-21 | 2017-06-29 | Exxonmobil Research And Engineering Company | Trim dewaxing of distillate fuel |
| EP3397382A1 (de) * | 2015-12-28 | 2018-11-07 | ExxonMobil Research and Engineering Company | Sequenzielle imprägnierung eines porösen trägers zur bildung einer edelmetalllegierung |
| US10632453B2 (en) | 2017-03-03 | 2020-04-28 | Exxonmobil Research And Engineering Company | Trimetallic base metal dewaxing catalyst |
| WO2018160424A1 (en) * | 2017-03-03 | 2018-09-07 | Exxonmobil Research And Engineering Company | Trimetallic base metal hdn+hds+dewaxing catalysts, their preparation and use |
| WO2018204155A1 (en) * | 2017-05-05 | 2018-11-08 | Exxonmobil Research And Engineering Company | Noble metal and base metal dewaxing catalyst |
| US10888850B2 (en) | 2017-05-05 | 2021-01-12 | Exxonmobil Research And Engineering Company | Noble metal and base metal dewaxing catalyst |
| WO2025000895A1 (zh) * | 2023-06-30 | 2025-01-02 | 中国石油天然气股份有限公司 | 一种正构烷烃加氢异构催化剂及其制备方法、包含其的组合物和应用 |
| CN119259109A (zh) * | 2023-06-30 | 2025-01-07 | 中国石油天然气股份有限公司 | 一种正构烷烃加氢异构催化剂及其制备方法、包含其的组合物和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU578930B2 (en) | 1988-11-10 |
| AU3920785A (en) | 1985-10-03 |
| BR8501129A (pt) | 1985-11-05 |
| EP0155822A3 (en) | 1988-01-13 |
| EP0155822B1 (de) | 1990-12-19 |
| DE3580928D1 (de) | 1991-01-31 |
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