EP2970806A1 - High viscosity high quality group ii lube base stocks - Google Patents
High viscosity high quality group ii lube base stocksInfo
- Publication number
- EP2970806A1 EP2970806A1 EP14714434.9A EP14714434A EP2970806A1 EP 2970806 A1 EP2970806 A1 EP 2970806A1 EP 14714434 A EP14714434 A EP 14714434A EP 2970806 A1 EP2970806 A1 EP 2970806A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- dewaxing
- stage
- group
- hydrocracking
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 claims abstract description 154
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 134
- 239000000314 lubricant Substances 0.000 claims abstract description 93
- 125000003118 aryl group Chemical group 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims description 298
- 229910052751 metal Inorganic materials 0.000 claims description 91
- 239000002184 metal Substances 0.000 claims description 91
- 229910052739 hydrogen Inorganic materials 0.000 claims description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 56
- 239000001257 hydrogen Substances 0.000 claims description 54
- 239000010457 zeolite Substances 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 45
- 229910021536 Zeolite Inorganic materials 0.000 claims description 43
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 42
- 230000003197 catalytic effect Effects 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 27
- 239000002283 diesel fuel Substances 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 13
- 239000010687 lubricating oil Substances 0.000 claims description 12
- -1 demulsifiers Substances 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000003879 lubricant additive Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
- 239000007866 anti-wear additive Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 239000005069 Extreme pressure additive Substances 0.000 claims 1
- 239000006078 metal deactivator Substances 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 90
- 239000000203 mixture Substances 0.000 abstract description 59
- 238000009472 formulation Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 151
- 239000000047 product Substances 0.000 description 145
- 239000002585 base Substances 0.000 description 131
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 112
- 239000000463 material Substances 0.000 description 63
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 56
- 229910052717 sulfur Inorganic materials 0.000 description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 47
- 239000011593 sulfur Substances 0.000 description 47
- 239000011230 binding agent Substances 0.000 description 44
- 239000000377 silicon dioxide Substances 0.000 description 41
- 239000013078 crystal Substances 0.000 description 39
- 238000000926 separation method Methods 0.000 description 38
- 239000003921 oil Substances 0.000 description 36
- 239000002199 base oil Substances 0.000 description 31
- 238000005194 fractionation Methods 0.000 description 29
- 239000000446 fuel Substances 0.000 description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 229910044991 metal oxide Inorganic materials 0.000 description 21
- 150000004706 metal oxides Chemical class 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 238000009835 boiling Methods 0.000 description 20
- 238000012545 processing Methods 0.000 description 19
- 230000001590 oxidative effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 150000002739 metals Chemical class 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 230000008901 benefit Effects 0.000 description 16
- 238000005984 hydrogenation reaction Methods 0.000 description 15
- 229910000510 noble metal Inorganic materials 0.000 description 15
- 229910052750 molybdenum Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 229910052697 platinum Inorganic materials 0.000 description 12
- 229910052721 tungsten Inorganic materials 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000002808 molecular sieve Substances 0.000 description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 238000004088 simulation Methods 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- AEFBNJXWRHSZGO-UHFFFAOYSA-N 1,2,3,3a,4,5-hexahydropyrene Chemical compound C1=C2CCCC(CC3)C2=C2C3=CC=CC2=C1 AEFBNJXWRHSZGO-UHFFFAOYSA-N 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000010723 turbine oil Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 238000004018 waxing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- PYIHTIJNCRKDBV-UHFFFAOYSA-L trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;dichloride Chemical class [Cl-].[Cl-].C[N+](C)(C)CCCCCC[N+](C)(C)C PYIHTIJNCRKDBV-UHFFFAOYSA-L 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
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- 238000010348 incorporation Methods 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
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- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
-
- 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
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
-
- 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
- C10G2400/04—Diesel oil
-
- 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
- C10G2400/10—Lubricating oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/74—Noack Volatility
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/135—Steam engines or turbines
Definitions
- This disclosure provides high viscosity high quality Group II lube base stocks with improved properties produced by an integrated hydrocrackmg and de waxing process.
- Hydrocrackmg of hydrocarbon feedstocks is often used to convert lower value hydrocarbon fractions into higher value products, such as conversion of vacuum gas oil (VGO) feedstocks to diesel fuel and lubricants.
- Typical hydrocrackmg reaction schemes can include an initial hydrotreatment step, a hydrocra.cki.ng step, and a post hydrotreatment step. After these steps, the effluent can be fractionated to separate out a desired diesel fuel and/or lubricant oil basestock.
- API Group II basestocks have a saturates content of 90 wt % or greater, a sulfur content of not more than 0,03 wt% and a VI greater than 80 but less than 120.
- API Group III basestocks are the same as Group II basestocks except that the VI is at least. 120.
- a process scheme such as the one detailed above is typically suitable for production of Group II and Group III basestocks from an appropriate feed.
- U.S. Patent 6,884,339 describes a. method for processing a feed to produce a lubricant base oil and optionally distillate products.
- a feed is hydrotreated and then hydrocracked without intermediate separation.
- An example of the catalyst for hydrocracking can be a supported Y or beta zeolite.
- the catalyst also includes a hydro-dehydrogenating metal, such as a combination of Ni and Mo,
- the hydrotreated, hydrocracked effluent is then atmospherically distilled.
- the portion boiling above 340°C is catalytically dewaxed in the presence of a bound molecular sieve that includes a hydro-dehydrogenating element.
- the molecular sieve can be ZSM-48, EU-2, EU- 1 1, or ZBM-30.
- the hydro-dehydrogenating element can be a noble Group VIII metal, such as Pt or Pd.
- U.S. Patent 7,371,315 describes a method for producing a lubricant base oil and optionally distillate products.
- a feed is provided with a sulfur content of less than 1000 wppm.
- the feed can be a hydrotreated feed.
- the feed can be a hydrocracked feed, such as a feed hydrocracked in the presence of a zeolite Y-containing catalyst.
- the feed is converted on a noble metal on an acidic support. This entire converted feed can be dewaxed in the presence of a dewaxing catalyst.
- U.S. Patent 7,300,900 describes a catalyst and a method for using the catalyst to perform conversion on a hydrocarbon feed.
- the catalyst includes both a Y zeolite and a zeolite selected from ZBM-30, ZSM-48, EU-2, and EU-1 1. Examples are provided of a two stage process, with a first stage hydrotreatment of a feed to reduce the sulfur content of the feed to 15 wppm, followed by hydroprocessing using the catalyst containing the two zeolites. An option is also described where it appears that the effluent from a hydrotreatment stage is cascaded without separation to the dual-zeolite catalyst, but no example is provided of the sulfur level of the initial feed for such a process.
- Base stocks are commonly used for the production of lubricants, such as lubricating oils for autom.oti.ves, industrial lubricants and lubricating greases.
- a base oil is defined as a combination of two or more base stocks used to make a lubricant composition. They are also used as process oils, white oils, metal working oils and heat transfer fluids.
- Finished lubricants consist of two general components, lubricating base stock and additives.
- Lubricating base stock is the major constituent in these finished lubricants and contributes significantly to the properties of the finished lubricant. In general, a few lubricating base stocks are used to manufacture a wide variety of finished lubricants by varying the mixtures of individual lubricating base stocks and individual additives.
- base stocks are categorized in five groups based on their saturated hydrocarbon content, sulfur level, and viscosity index (Table 1 ).
- Lube base stocks are typically produced in large scale from non-renewable petroleum sources.
- Group I, II, and III base stocks are all derived from crude oil via extensive processing, such as solvent extraction, solvent or catalytic dewaxing, and hydroisomerization.
- Group III base stocks can also be produced from synthetic hydrocarbon liquids obtained from natural gas, coal or other fossil resources.
- Group IV base stocks, the polyalphaoletins (PAO) are produced by oligome ization of alpha olefins, such as 1-decene.
- Group V base stocks include everything that does not belong to Groups I-IV, such as naphthenics, poiya!kylene glycols (PAG), and esters.
- lubricating base stocks are base stocks having kinematic viscosity of about 3 cSt or greater at 100°C (KvlOO); pour point (PP) of about - 12°C or less; and viscosity index (VI) about 90 or greater.
- KvlOO kinematic viscosity of about 3 cSt or greater at 100°C
- PP pour point
- VI viscosity index
- high performance lubricating base stocks should have a Noack volatility no greater than current conventional Group I or Group II light neutral oils.
- Group II lube base stocks have limitations in terms of the lubricant applications that they may be used in because of limitations in their viscosity.
- Group II lube base stocks are produced by catalytic processing to a kinematic viscosity at 100°C of less than or equal to 17 cSt. This viscosity limitation necessitates the use of Group I base stocks or Group IV synthetic base stocks in certain lubricant applications.
- solvent extracted Group I base stocks allow for high viscosity, but at lower quality, Chemically produced Group IV synthetic base stocks (PAOs) address the viscosity and quality gap regime described above, but are significantly more expensive and compositionally narrower (i.e. paraffmic structures of specific design) than Group II base stocks.
- PAOs Chemically produced Group IV synthetic base stocks
- an advantageous Group II lube base stock comprises from greater than or equal to 90 wt.% saturates, and less than 10 wt.% aromatics, and having an aromatic performance ratio between 1.0 and 5.0.
- a further aspect of the present disclosure relates to an advantageous lubricating oil including a Group II lube base stock and an effective amount of one or more one or more lubricant additives, wherein the lube base stock comprises from greater than or equal to 90 wt.% saturates, and less than 10 wt.% aromatics, and has an aromatic performance ratio between 1 ,0 and 5.0.
- a still further aspect of the present disclosure relates to an advantageous method for producing a diesel fuel and a Group II base stock, comprising: contacting a feedstock with a hydrotreating catalyst under first effective hydrotreating conditions to produce a liydrotreated effluent; fractionating the liydrotreated effluent to produce at least a first diesel product fraction and a bottoms fraction; dew axing the bottoms fraction under effective catalytic dewaxing conditions, the dew axing catalyst including at least one non- dealuminated, unidimensional, 10-member ring pore zeolite, and at least one Group VI metal.
- Group VIII metal or combination thereof hydrocracking the bottoms fraction under effective hydrocracking conditions; and fractionating the hydrocracked, dewaxed bottoms fraction to form at least a second diesel product fraction and a Group II lubricant base oil product fraction, wherein the Group II lubricant base oil product fraction includes greater than or equal to 90 wt.% saturates, and less than 10 wt.% aromatics, and has an aromatic performance ratio between 1.0 and 5.0.
- Figure 1 schematically shows an example of a multi-stage reaction system according to an embodiment of the invention.
- Figure 2 schematically shows examples of catalyst configurations for a first reaction stage.
- Figure 3 schematically shows examples of catalyst configurations for a second reaction stage.
- Figure 4 shows predicted diesel fuel product yields for various processing configurations.
- Figures 5 and 6 show measured feed conversion and diesel fuel product yields for various processing configurations.
- Figure 7 schematically shows an example of a three-stage reaction system according to an alternative embodiment of the invention.
- Figure 9 schematically shows an example of a still yet another three-stage reaction system according to an alternative embodiment of the invention.
- Figure 1 0 is UV spectrograph of the inventive Group II base stocks disclosed herein and a comparative prior art Group II base stock.
- One option for processing a heavier feed is to use hydrocracking to convert a portion of the feed. Portions of the feed that are converted below a specified boiling point, such as a 70Q°F (371 °C) portion that can be used for naphtha and diesel fuel products, while the remaining unconverted portions can be used as lubricant oil basestocks.
- Improvements in diesel and/or lube basestock yield can be based in part on alternative configurations that are made possible by use of a dewaxing catalyst.
- zeolite Y based hydrocracking catalysts are selective for cracking of cyclic and/or branched hvdrocarbons. Paraffmic molecules with little or no branching may require severe hydrocrackiiig conditions in order to achieve desired levels of conversion. This can result in overcraeking of the cyclic and/or more heavily branched molecules in a feed.
- a catalytic dewaxing process can increase the branching of paraffmic molecules. This can increase the ability of a subsequent hydrocrackiiig stage to convert the paraffmic molecules with increased numbers of branches to lower boiling point species.
- a dewaxing catalyst can be selected that is suitable for use in a sweet or sour environment while minimizing conversion of higher boiling molecules to naphtha and other less valuable species.
- the dewaxing catalyst can be used as part of an integrated process in a first stage that includes an initial liydrotreatment of the feed, hydrocracking of the hydrotreated feed, and dewaxing of the effluent from the hydrocracking, and an optional final liydrotreatment.
- the dewaxing stage can be performed on the hydrotreated feed prior to hydrocracking.
- the hydrocracking stage can be omitted.
- any catalytic dewaxing and/or hydroisomerization is performed in a separate reactor. This is due to the fact conventional catalysts are poisoned by the heteroatom contaminants (such as H 2 S NI1 3 , organic sulfur and/or organic nitrogen) typically present in the hydrocracker effluent.
- a separation step is used to first decrease the amount of the heteroatom contaminants. Because a distillation also needs to be performed to separate various cuts from the hydrocracker effluent, the separation may be performed at the same time as distillation, and therefore prior to dewaxing. This means that some valuable hydrocarbon molecules that could be used in a diesel or lube basestock cut are left out.
- the Applicants have also discovered that the process configurations of the instant disclosure produce high viscosity, high quality Group II base stocks that have novel compositional characteristics with respect to prior art Group II base stocks.
- the compositional advantage may be derived from the saturates and the naphtheno-aromatic portions of the composition. Additionally, the Applicants have observed lower than expected Noack volatilities for the high viscosity materials as compared to applicable references, particularly at relatively lower pour point.
- Typical feeds would include, for example, vacuum gas oils boiling up to about 593°C (about 1 100°F) and usually in the range of about 350°C to about 500°C (about 660°F to about 935°F) and, in this case, the proportion of diesel fuel produced is correspondingly greater.
- the sulfur content of the feed can be at least 100 ppm by weight of sulfur, or at least 1000 ppm by weight of sulfur, or at least 2000 ppm. by weight of sulfur, or at least 4000 ppm by weight of sulfur, or at least 40,000 ppm by weight of sulfur.
- Light cycle oils are particularly preferable as a feed component to the process.
- a suitable feedstock 1 15 is introduced into first reaction stage 1 10 along with a hydrogen-containing stream 1 17.
- the feedstock is hydro processed in the presence of one or more catalyst beds under effective conditions.
- the effluent 1 19 from first reaction stage 1 10 is passed into separation stage 120.
- the separation stage 120 can produce at least a diesel product fraction 124, a bottoms fraction 126, and gas phase fraction 128.
- the gas phase fraction can include both contaminants such as H 2 S or NH 3 as well as low boiling point species such as Ci -C-4 hydrocarbons.
- the separation stage 120 can also produce a naphtha fraction 122 and/or a kerosene fraction (not shown).
- the bottoms fraction 126 from the separation stage is used as input to the second hydroprocessing stage 130, along with a second hydrogen stream 137.
- the bottoms fraction is hydroprocessed in second stage 130.
- At least a portion of the effluent from second stage 130 can be sent to a fractionator 140 for production of one or more products, such as a second naphtha product 142, a second diesel product 144, or a lubricant base oil product 146, Another portion of the bottoms from the fractionator 140 can optionally be recycled back 147 to second stage 130.
- At least a portion of the effluent 259 from third reaction stage 250 can then be sent to a fractionator (not shown) for production of one or more products, such as a naphtha product 242, a fuel/diesel product 244, or a lubricant base oil product 246.
- a fractionator not shown
- Another portion of the bottoms 261 from the third reaction stage 250 can optionally be recycled back to either the second reaction stage 230 via recycle stream 263 or the second fractionation stage 240 via recycle stream 265 or a combination thereof.
- Recycle stream 263 is utilized when the product from third reaction stage 250 does not meet cold flow property specifications of the diesel product 244 or lubricant base oil product 246 and further dewaxing is necessary to meet the specifications.
- the first reaction stage 410 may be a conventional hydrotreating reactor operating at effective hydrotreating conditions.
- the first reaction stage effluent 419 is fed to a first fractionator 420.
- the first fractionator 420 is a stage capable of removing a first fuel/diesel range material 428 and a first lube range material 426.
- the first lube range material 426 from the fractionator is used as input to the second reaction stage/hydroprocessing stage 430 along with a second hydrogen stream 427,
- the first lube range material 426 is hydroprocessed in the second reaction stage 430.
- the second reaction stage 430 may be a hydrocracking reactor loaded with a hydrocracking catalyst.
- the second fractionator 450 may produce one or more products, such as a naphtha and LPG product 442, a fuel/diesel product 444, or a lubricant base oil product 446.
- a portion of the first fuel/diesel range material 428 from the first fractionator 420 may be recycled to the third reaction stage 440 via flow line 438 where an improvement in cold flow properties of the fuel/diesel product is desired.
- a portion or all of the first fuel/diesel range material 428 from first fractionator 420 may be recycled to the third reaction stage (see flow line 439).
- the first and second fuel/diesel range materials 439 and 444 may then be combined to form a combined fuel/diesel product 448.
- the reaction system of Figure 9 is particularly suitable for coproducing diesel and lube oil with good low- temperature properties while producing limited amounts of naphtha and LPG .
- Configuration B includes a liydrotreatment catalyst and a dewaxing catalyst.
- a sour reaction stage based on Configurat on B can be useful for producing an effluent with improved cold flow properties relative to Configuration A.
- a diesel fuel produced from processing in Configuration B can have a improved cloud point.
- the yield of diesel fuel will also be improved while reducing the amount of bottoms.
- the bottoms from Configuration B can also have an improved pour point. After fractionation to separate out products such as a diesel fuel product, as well as contaminant gases such as H 2 S and NH 3 , the bottoms can be further processed in a second stage.
- a final bed of hydro finishing catalyst could be added to any of Configurations E, F, or G.
- Configuration H shows this type of configuration, with beds of hydrocracking, dewaxing, and hydrofinishing catalyst.
- each stage can include one or more reactors, so one option can be to house the hydrofinishing catalyst in a separate reactor from the catalysts shown for Configurations E, F, or G. This separate reactor is schematically represented in Configuration H.
- the hydrofinishing beds can be included either before or after fractionation of the effluent from the second (or non-sour) reaction stage. As a result, hydrofinishing can be performed on a portion of the effluent from the second stage if desired.
- Configurations E, F, and G can be used to make both a fuel product and a lubricant base oil product from the bottoms of the first sour stage.
- the yield of diesel fuel product can be higher for Configuration F relative to Configuration E, and higher still for Configuration G.
- the relative diesel yield of the configurations can be modified, such as by recycling a portion of the bottoms for further conversion.
- Configurations E, F, G, or H can optionally be expanded to include still more catalyst beds.
- one or more additional dewaxing and/or hydrocracking catalyst beds can be included after the final dewaxing or catalyst bed shown in a Configuration. Additional beds can be included in any convenient order.
- one possible extension for Configuration E would be to have a series of alternating beds of dewaxing catalyst and hydrocracking catalyst. For a series of four beds, this could result in a series of dewaxing - hydrocracking - dewaxing - hydrocracking.
- Configuration F A similar extension of Configuration F could be used to make a series of hydrocracking - ⁇ dewaxing - ⁇ hydrocracking dewaxing. A hydrofinishing catalyst bed could then be added after the final additional hydrocracking or dewaxing catalyst bed.
- One example of a combination of configurations can be a combination of Configuration B with any of Configurations E, F, G, or H, or in particular a combination with Configuration F or H.
- Configuration B does not include a hydrocracking stage, so any diesel boiling range molecules present in a feed after only hydrotreatment and dewaxing are removed prior to hydrocracking.
- the second stage can then be operated to generate a desired level of conversion to diesel boiling range molecules without overcracking of any diesel molecules present in the initial feed.
- FIG. 1 Another example of a combination of configurations can be a combination of Configuration D with any of Configurations E, F, G, or H, or in particular a combination with Configuration E or G.
- Configuration D the initial dewaxing catalyst bed can be used to make longer chain paraffins in a feedstock more accessible to the following hydrocracking catalyst. This can allow for the higher amounts of conversion under milder conditions, as the dewaxing catalyst is used to facilitate the hydrocracking instead of using increased temperature or hydrogen partial pressure.
- the conversion process can be continued in the second stage. Note that this type of configuration can include a recycl e loop on the second stage to further increase diesel production. This could include an extinction recycle if no lube product is desired.
- Hydrotreating catalysts are typically those containing Group VTB metals (based on the Periodic Table published by Fisher Scientific), and non-noble Group VIII metals, i.e., iron, cobalt and nickel and mixtures thereof. These metals or mixtures of metals are typically present as oxides or sulfides on refractory metal oxide supports. Suitable metal oxide supports include low acidic oxides such as silica, alumina or titania, preferably alumina.
- Preferred metal catalysts include cobalt/molybdenum (1 -10% Co as oxide, 10-40% Mo as oxide), nickel/molybdenum (1-10% Ni as oxide, 10-40% Co as oxide), or nickel/tungsten (1- 10% Ni as oxide, 10-40% W as oxide) on alumina.
- suitable nickel/molybdenum catalysts include KF-840, KF-848, or a stacked bed of KF-848 or KF-840 and Nebula-20.
- the hydrotreating catalyst can be a bulk metal catalyst, or a combination of stacked beds of supported and bulk metal catalyst.
- bulk metal it is meant that the catalysts are unsupported wherein the bulk catalyst particles comprise 30- 100 wt. % of at least one Group VIII non-noble metal and at least one Group VIB metal, based on the total weight of the bulk catalyst particles, calculated as metal oxides and wherein the bulk catalyst particles have a surface area of at least 10 rrrVg.
- the molybenum: tungsten ratio preferably lies in the range of 9: 1- 1 :9.
- the Group VIII non-noble metal comprises nickel and/or cobalt.
- the Group VIB metal comprises a combination of molybdenum and tungsten.
- combinations of nickel/niolybdenum/ tungsten and cobalt/molybdenum/tungsten and nickel/cobalt/molybdenum, ' ' ' tungsten are used. These types of precipitates appear to be sinter-resistant. Thus, the active surface area of the precipitate is maintained during use.
- the metals are preferably present as oxidic compounds of the corresponding metals, or if the catalyst composition has been sulfided, sulfidic compounds of the corresponding metals.
- the bulk metal hydrotreating catalysts can have a median diameter of not more than 5000 ⁇ , or not more than 3000 urn.
- the median particle diameter lies in the range of 0.1-50 um and most preferably in the range of 0.5-50 ⁇ .
- one or more beds of hydrotreatment catalyst can be located downstream from a hydrocracking catalyst bed and/or a dewaxing catalyst bed in the first stage.
- the hydrotreatment conditions can be selected to be similar to the conditions above, or the conditions can be selected independently.
- a hydrocracking process in the first stage can be carried out at temperatures of 200°C to 450°C, hydrogen partial pressures of from 250 psig to 5000 psig (1.8 MPa to 34.6 MPa), liquid hourly space velocities of from 0.2 h "! to 10 If 1 , and hydrogen treat gas rates of from 35.6 m 3 /m 3 to 1781 m 3 /m 3 (200 SCF/B to 10,000 SCF/B).
- the conditions will have temperatures in the range of 300°C to 450°C, hydrogen partial pressures of from 500 psig to 2000 psig (3.5 MPa- 13.9 MPa), liquid hourly space velocities of from 0.3 h '1 to 2 h " ! and hydrogen treat gas rates of from 213 m 3 /m 3 to 1068 m 3 /m 3 (1200 SCF/B to 6000 SCF/B).
- a hydrocracking process in a second stage can be performed under conditions similar to those used for a first stage hydrocracking process, or the conditions can be different.
- the conditions in a second stage can have less severe conditions than a hydrocracking process in a first (sour) stage.
- the temperature in the hydrocracking process can be 20°C less than the temperature for a hydrocracking process in the first stage, or 30°C less, or 40°C less.
- the pressure for a hydrocracking process in a second stage can be 100 psig (690 kPa) less than a hydrocracking process in the first stage, or 200 psig (1380 kPa) less, or 300 psig (2070 kPa) less.
- Hydrofinishing and/or aromatic saturation catalysts can include catalysts containing Group VI metals, Group VIII metals, and mixtures thereof.
- preferred metals include at least one metal sulfide having a strong hydrogenation function.
- the hydrofinishing catalyst can include a Group VIII noble metal, such as Pt, Pd, or a combination thereof.
- the mixture of metals may also be present as bulk metal catalysts wherein the amount of metal is about 30 wt. % or greater based on catalyst.
- Suitable metal oxide supports include low acidic oxides such as silica, alumina, silica-aluminas or titania, preferably alumina,
- the preferred hydrofinisliing catalysts for aromatic saturation will comprise at least one metal having relatively strong hydrogenation function on a porous support.
- Typical support materials include amorphous or crystalline oxide materials such as alumina, silica, and silica-alumina.
- the support materials may also be modified, such as by halogenation, or in particular fluorination.
- the metal content of the catalyst is often as high as about 20 weight percent for non-noble metals.
- a preferred hydrofinisliing catalyst can include a crystalline material belonging to the M41S class or family of catalysts.
- the M41S family of catalysts are mesoporous materials having high silica content. Examples include MCM-41, MCM-48 and MCM-50. A preferred member of this class is MCM-41 , If separate catalysts are used for aromatic saturation and hydrofinisliing, an aromatic saturation catalyst can be selected based on activity and/or selectivity for aromatic saturation, while a hydrofinisliing catalyst can be selected based on activity for improving product specifications, such as product color and polynuclear aromatic reduction.
- Hydro finishing condition s ca include temperatures from about
- catalytic dewaxing can be included as part of the hydroprocessing in a first stage (or otherwise in a sour environment.) Because a separation does not occur in the first stage, any sulfur in the feed at the beginning of the stage will still be in the effluent that is passed to the catalytic dewaxing step in some form. For example, consider a first stage that includes hydrotreatment catalyst, hydrocracking catalyst, and dewaxing catalyst. A portion of the organic sulfur in the feed to the stage will be converted to H 2 S during hydrotreating and/or hydrocracking. Similarly, organic nitrogen in the feed will be converted to ammonia.
- the total combined sulfur from the hydrotreating process in both organic liquid form and gas phase may be greater than 1 ,000 ppm by weight, or at least 2,000 ppm by weight, or at least 5,000 ppm by weight, or at least 10,000 ppm by weight, or at least 20,000 ppm by weight, or at least 40,000 ppm by weight.
- these sulfur levels are defined in terms of the total combined sulfur in liquid and gas forms fed to the dewaxing stage in parts per million (ppm) by weight on the hydrotreated feedstock basis.
- Elimination of a separation step in the first reaction stage is enabled in part by the ability of a dewaxing catalyst to maintain catalytic activity in the presence of elevated levels of nitrogen and sulfur.
- Conventional catalysts often require pre-treatment of a feedstream to reduce the sulfur content to less than a few hundred ppm.
- hydrocarbon feedstreams containing up to 4.0 wt% of sulfur or more can be effectively processed using the inventive catalysts.
- the total combined sulfur content in liquid and gas forms of the hydrogen containing gas and hydrotreated feedstock can be at least 0.1 wt%, or at least 0,2 wt%, or at least 0.4 wt%, or at least 0.5 wt%, or at least 1 wt%, or at least 2 wt%, or at least 4 wt%.
- Sulfur content may be measured by standard ASTM methods D2622.
- Hydrogen treat gas circulation loops and make-up gas can be configured and controlled in any number of ways.
- treat gas enters the hydrotreating reactor and can be once through or circulated by compressor from high pressure flash drums at the back end of the hydrocracking and/or dewaxing section of the unit.
- make-up gas can be put into the unit anywhere in the high pressure circuit preferably into the hydrocracking/dewaxing reactor zone.
- the treat gas may be scrubbed with amine, or any other suitable solution, to remove H 2 S and N3 ⁇ 4.
- the treat gas can be recycled without cleaning or scrubbing.
- the liquid effluent may be combined with any hydrogen containing gas, including but not limited to H 2 S containing gas.
- the dewaxing catalysts according to the invention are zeolites that perform dewaxing primarily by isomerizing a hydrocarbon feedstock. More preferably, the catalysts are zeolites with a unidimensional pore structure. Suitable catalysts include 10-member ring pore zeolites, such as EU-1, ZSM-35 (or ferrierite), ZSM-1 1, ZSM-57, NU-87, SAPO-l i, and ZSM-22. Preferred materials are EU-2, EU-1 1 , ZBM-30, ZSM-48, or ZSM-23. ZSM-48 is most preferred.
- the catalysts according to the invention further include a metal hydrogenation component.
- the metal hydrogenation component is typically a Group VI and/or a Group VIII metal.
- the metal hydrogenation component is a Group VIII noble metal.
- the metal liydrogenation component is Pt, Pd, or a mixture thereof.
- the metal liydrogenation component can be a combination of a non-noble Group VIIT metal with a Group VI metal. Suitable combinations can include Ni, Co, or Fe with Mo or W, preferably Ni with Mo or W.
- the amount of metal in the catalyst can be at least 0.1 wt% based on catalyst, or at least 0.15 wt%, or at least 0.2 wt%, or at least 0.25 wt%, or at least 0.3 wt%, or at least 0.5 wt% based on catalyst.
- the amount of metal in the catalyst can be 20 wt% or less based on catalyst, or 10 wt% or less, or 5 wt% or less, or 2.5 wt% or less, or 1 wt% or less.
- the amount of metal can be from 0.1 to 5 wt%, preferably from 0.1 to 2 wt%, or 0.25 to 1.8 wt%, or 0.4 to 1.5 wt%.
- the metal is a combination of a non- noble Group VIII metal with a Group VI metal
- the combined amount of metal can be from 0.5 wt% to 20 wt%, or 1 wt% to 15 wt%, or 2.5 wt% to 10 wt%.
- the dewaxing catalysts used in processes according to the invention are catalysts with a low ratio of silica to alumina.
- the ratio of silica to alumina in the zeolite can be less than 200: 1, or less than 1 10: 1, or less than 100: 1, or less than 90: 1, or less than 80: 1.
- the ratio of silica to alumina can be from 30: 1 to 200: 1 , 60: 1 to 1 10: 1, or 70: 1 to 100: 1.
- the dewaxing catalysts useful in processes according to the invention can also include a hinder.
- the dewaxing catalysts used in process according to the invention are formulated using a low- surface area binder
- a low surface area binder represents a binder with a surface area of 100 m ' 7 ' g or less, or 80 m ' 7 ' g or less, or 70 m ' 7 ' g or less.
- a bound catalyst can be produced by starting with powders of both the zeolite and binder, combining and mulling the powders with added water to form a mixture, and then extruding the mixture to produce a bound catalyst of a desired size.
- Extrusion aids can also be used to modify the extrusion flow properties of the zeolite and binder mixture.
- the amount of framework alumina in the catalyst may range from 0.1 to 3.33 wt%, or 0.1 to 2.7 wt%, or 0.2 to 2 wt%, or 0.3 to 1 wt%.
- a binder composed of two or more metal oxides can also be used.
- the weight percentage of the low surface area binder is preferably greater than the weight percentage of the higher surface area binder.
- both metal oxides used for forming a mixed metal oxide binder have a sufficiently low surface area, the proportions of each metal oxide in the binder are less important.
- the two metal oxides can be incorporated into the catalyst by any convenient method.
- one binder can be mixed with the zeolite during formation of the zeolite powder, such as during spray drying.
- the spray dried zeolite/binder powder can then be mixed with the second metal oxide binder prior to extrusion.
- Process conditions in a catalytic dewaxing zone in a sour environment can include a temperature of from 200 to 450°C, preferably 270 to 400°C, a hydrogen partial pressure of from 1.8 to 34.6 mPa (250 to 5000 psi), preferably 4.8 to 20.8 mPa, a liquid hourly space velocit of from 0.2 to 10 v/v/hr, preferably 0.5 to 3,0, and a hydrogen circulation rate of from 35,6 to 1781 m 3 /m 3 (200 to 10,000 scf/B), preferably 178 to 890.6 m 3 /m 3 (1000 to 5000 scf/B).
- the dewaxing catalyst conditions can be similar to those for a sour environment.
- the conditions in a second stage can have less severe conditions than a dewaxing process in a first (sour) stage.
- the temperature in the dewaxing process can be 20°C less than the temperature for a dewaxing process in the first stage, or 30°C less, or 40°C less.
- the pressure for a dewaxing process in a second stage can be 100 psig (690 kPa) less than a dewaxing process in the first- stage, or 200 psig (1380 kPa) less, or 300 psig (2070 kPa) less.
- the catalytic dewaxing catalyst includes from 0.1 wt% to 3.33 wt% framework alumina, 0.1 wt% to 5 wt% Pt, 200: 1 to 30: 1 Si0 2 :Al 2 0 3 ratio and at least one low surface area, refractory metal oxide binder with a surface area of 100 ni7e or less,
- ZSM-48 with a Si0 2 :Al 2 0 3 ratio of less than 1 10, preferably from about 70 to about 1 10.
- ZSM-48 crystals will be described variously in terms of "as-synthesized" crystals that still contain the (200: 1 or less Si0 2 :Al 2 0 3 ratio) organic template; calcined crystals, such as Na-form ZSM-48 crystals; or calcined and ion-exchanged crystals, such as H-form ZSM-48 crystals.
- the ZSM-48 crystals after removal of the structural directing agent have a particular morphology and a molar composition according to the general formula:
- n Si0 2 :Al 2 0 3 where n is from 70 to 1 10, preferably 80 to 100, more preferably 85 to 95. In another embodiment, n is at least 70, or at least 80, or at least 85. In yet another embodiment, n is 1 10 or less, or 100 or less, or 95 or less. In still other embodiments, Si may be replaced by Ge and Al may be replaced by Ga, B, Fe, Ti, V, and Zr.
- the as-synthesized form of ZSM-48 crystals is prepared from a mixture having silica, alumina, base and hexamethonium salt directing agent.
- the molar ratio of structural directing agent: silica in the mixture is less than 0.05, or less than 0.025, or less than 0.022.
- the molar ratio of structural directing agen silica in the mixture is at least 0.01, or at least 0.015, or at least 0.016.
- the molar ratio of stmctural directing agent:silica in the mixture is from 0.015 to 0.025, preferably 0.016 to 0.022.
- the as-synthesized form of ZSM-48 crystals has a silica:alumina molar ratio of 70 to 1 10. In still another embodiment, the as-synthesized form of ZSM-48 crystals has a silica:alumina molar ratio of at least 70, or at least 80, or at least 85. In yet another embodiment, the as-synthesized form of ZSM-48 crystals has a silica:alumina molar ratio of 1 10 or less, or 100 or less, or 95 or less.
- the molar composition will contain silica, alumina and directing agent, it should be noted that the as-synthesized form of ZSM-48 crystals may have molar ratios slightly different from the molar ratios of reactants of the reaction mixture used to prepare the as-synthesized form. This result may occur due to incomplete incorporation of 100% of the reactants of the reaction mixture into the crystals formed (from the reaction mixture).
- the ZSM-48 composition is prepared from an aqueous reaction mixture comprising silica or silicate salt, alumina or soluble aluminate salt, base and directing agent. To achieve the desired crystal morphology, the reactants in reaction mixture have the following molar ratios:
- Si0 2 :Al 2 0 3 (preferred) 70 to 1 10
- Si0 2 (preferred) 0.015 to 0.025
- the silica source is preferably precipitated silica and is commercially available from Degussa.
- Other silica sources include powdered silica including precipitated silica such as Zeosil® and silica gels, silicic acid colloidal silica such as Ludox® or dissolved silica. In the presence of a base, these other silica sources may form silicates.
- the alumina may be in the form of a soluble salt, preferably the sodium salt and is commercially available from US Aluminate.
- Other suitable aluminum sources include other aluminum salts such as the chloride, aluminum alcoholates or hydrated alumina such as gamma alumina, pseudobohemite and colloidal alumina.
- the base used to dissolve the metal oxide can be any alkali metal hydroxide, preferably sodium or potassium hydroxide, ammonium hydroxide, diquaternary hydroxide and the like.
- the directing agent is a hexamethoiiium salt such as hexamethonium dichloride or hexamethoiiium hydroxide.
- the anion (other than chloride) could be other anions such as hydroxide, nitrate, sulfate, other halide and the like.
- Hexamethonium dichloride is ⁇ , ⁇ , ⁇ , ⁇ ', ⁇ ', ⁇ '-hexamethyl-l ,6-hexanediammonium dichloride,
- the crystals obtained from the synthesis according to the invention have a morphology that is free of fibrous morphology. Fibrous morphology is not desired, as this crystal morphology inhibits the catalytic dewaxing activity of ZSM-48.
- the crystals obtained from the synthesis according to the invention have a morphology that contains a low percentage of needle-like morphology. The amount of needle-like morphology present in the ZSM-48 crystals can be 10% or less, or 5% or less, or 1% or less. In an alternative embodiment, the ZSM-48 crystals can be free of needle-like morphology.
- the as-synthesized ZSM-48 crystals should be at least partially dried prior to use or further treatment. Drying may be accomplished by heating at temperatures of from 100 to 400°C, preferably from 100 to 250°C. Pressures may be atmospheric or subatmospheric. If drying is performed under partial vacuum conditions, the temperatures may be lower than those at atmospheric pressures.
- porous matrix materials in addition to silica- aluminas include other binary materials such as silica-magnesia, silica-thoria, silica-zirconia, silica-beryllia and silica-titania as well as ternary materials such as silica-alumina-magnesia, silica-alumina-thoria and silica-alumina-zirconia.
- the matrix can be in the form of a co-gel.
- the bound ZSM-48 framework alumina will range from 0.1 wt% to 3.33 t% framework alumina.
- ZSM-48 crystals as part of a catalyst may also be used with a metal hydrogenation component.
- Metal hydrogenation components may be from Groups 6-12 of the Periodic Table based on the IUPAC system having Groups 1-18, preferably Groups 6 and 8-10, Examples of suc metals include Ni, Mo, Co, W, Mn, Cu, Zn, Ru, Pt or Pd, preferably Pt or Pd.
- Mixtures of hydrogenation metals may also be used such as Co/Mo, i/Mo, Ni/W and Pt/Pd, preferably Pt/Pd.
- the amount of hydrogenation metal or metals may range from 0.1 to 5 wt%, based on catalyst.
- the amount of metal or metals is at least 0.1 wt%, or at least 0.25 wt%, or at least 0.5 wt%, or at least 0.6 wt%, or at least 0.75 wt%, or at least 0.9 wt%. In another embodiment, the amount of metal or metals is 5 wt% or less, or 4 wt% or less, or 3 wt% or less, or 2 wt% or less, or 1 wt% or less.
- Methods of loading metal onto ZSM-48 catalyst are well known and include, for example, impregnation of ZSM-48 catalyst with a metal salt of the hydrogenation component and heating.
- the ZSM-48 catalyst containing hydrogenation metal may also be sulfided prior to use.
- High purity ZSM-48 crystals made according to the above embodiments have a relatively low silica: alumina ratio.
- the silica: alumina ratio can be 1 10 or less, or 90 or less, or 75 or less.
- This lower silica: alumina ratio means that the present catalysts are more acidic. In spite of this increased acidity, they have superior activity and selectivity as well as excellent yields. They also have environmental benefits from the standpoint of health effects from crystal form and the small crystal size is also beneficial to catalyst activity.
- any suitable method for producing ZSM-23 with a low Si0 2 :Al 2 0 3 ratio may be used.
- US 5,332,566 provides an example of a synthesis method suitable for producing ZSM-23 with a low ratio of Si0 2 :AI 2 0.3.
- a directing agent suitable for preparing ZSM-23 can be formed by methylating iminobispropylamine with an excess of iodomethane. The methylation is achieved by adding the iodomethane dropwise to iminobispropylamine which is solvated in absolute ethanoi. The mixture is heated to a reflux temperature of 77°C for 18 hours. The resulting solid product is filtered and washed with absolute ethanoi.
- the directing agent produced by the above method can then be mixed with colloidal silica sol (30% Si0 2 ), a source of alumina, a source of alkali cations (such as Na or K), and de Ionized water to form a hydrogel
- the alumina source can be any convenient source, such as alumina sulfate or sodium a!uminate.
- the solution is then heated to a crystallization temperature, such as 170°C, and the resulting ZSM-23 crystals are dried.
- the ZSM-23 crystals can then be combined with a low surface area binder to form a catalyst according to the invention.
- the Group II lube base stocks of the present disclosure are well suited as lube base stocks without blending limitations, and further, the lube base stock products are also compatible with lubricant additives for lubricant formulations.
- the Group II lube base stocks of the present disclosure can optionally be blended with other lube base stocks to form lubricants.
- Useful co-base lube stocks include Group I, III, IV and V base stocks and gas-to-liquid (GTL) oils.
- One or more of the co-base stocks may be blended into a lubricant composition including the Group II lube base stock at from 0.1 to 50 wt.%, or 0.5 to 40 wt.%, 1 to 35 wt.%, or 2 to 30 wt.%, or 5 to 25 wt.%, or 10 to 20 wt.%, based on the total lubricant composition.
- Lubricants incorporating the Group II lube base stocks of the present disclosure may optionally include lube base stock additives, such as detergents, dispersants, antioxidants, anti-wear additives, pour point depressants, viscosity index modifiers, friction modifiers, de-foaming agents, corrosion inhibitors, wetting agents, rust inhibitors, and the like.
- the additives are incorporated with the Group II base stocks of the present disclosure to make a finished lubricant that has desired viscosity and physical properties.
- Typical additives used in lubricant formulation can be found in the book "Lubricant Additives, Chemistry and Applications", Ed. L. R, Rudnick, Marcel Dekker, Inc. 270 Madison Ave.
- lubricating oil compositions contain one or more of the additives discussed above, the additive(s) are blended into the composition in an amount effective for it to perform its intended function. Typical amounts of such additives useful in the present invention are shown in Table 2 below.
- the total of the additional additives in the lubricating oil composition may range from 0.1 to 50 wt.%., or 0.5 to 40 wt.%, 1 to 35 wt.%, or 1 to 20 wt.% of the composition, or 2 to 18 wt.%, or 3 to 1 5 wt.%, or 4 to 10 wt.%, or 5 to 8 wt.%.
- the weight amounts in the table below, as well as other amounts mentioned in this patent, unless otherwise indicated are directed to the amount of active ingredient (that is the non-solvent portion of the ingredient).
- the wt.%> indicated below are based on the total weight of the lubricating oil composition.
- Lubricant compositions including the Group II base stock of the instant disclosure have improved oxidative stability than analogous lubricant compositions including prior art Group II base stocks.
- the oxidative stability as measured by the RPVOT per the 1)2272 test method yields a time to a 25.4 psi pressure drop of between 820 to 1000, or 875 to 1000, or 875 to 950 minutes.
- Anti-foam Agent 0.001-3 0.001-0.15
- the Group II lube base stocks and lubricant compositions can be employed in the present disclosure in a variety of lubricant-related end uses, such as a lubricant oil or grease for a device or apparatus requiring lubrication of moving and/or interacting mechanical parts, components, or surfaces.
- Useful apparatuses include engines and machines.
- the Group II lube base stocks of the present disclosure are most suitable for use in the formulation of automotive crank case lubricants, automotive gear oils, transmission oils, many industrial lubricants including circulation lubricant, industrial gear lubricants, grease, compressor oil, pump oils, refrigeration lubricants, hydraulic lubricants, metal working fluids.
- Group II lube base stocks of this disclosure are derived from renewable sources; it is considered a sustainable product and can meet "sustainability" standards set by different industry groups or government regulations. [00118] The following are examples of the present disclosure and are not to be construed as limiting.
- Example 1A Synthesis of ZSM-48 crystals with S A O ⁇
- a mixture was prepared from a mixture of Di water, Hexamethonium Chloride (56% solution), Ultrasil silica, Sodium Aluminate solution (45%), and 50% sodium hydroxide solution, and -0.15% (to reaction mixture) of ZSM-48 seed crystals.
- the mixture had the following molar composition:
- the mixture was reacted at 320°F (160°C) in a 5 -gal autoclave with stirring at 250 RPM for 48 hours.
- the product was filtered, washed with deionized (DI) water and dried at 250°F (120°C).
- the XRD pattern of the as-synthesized material showed the typical pure phase of ZSM-48 topology.
- the SEM of the as-synthesized material shows that the material was composed of agglomerates of small irregularly shaped crystals (wit an average crystal size of about 0.05 microns).
- the resulting ZSM-48 crystals had a Si0 2 /Al 2 0 3 molar ratio of -71.
- the as-svnthesized crystals were converted into the hydrogen form by three ion exchanges with ammonium nitrate solution at room temperature, followed by drying at 250°F ( 120°C) and calcination at 1000°F (540°C) for 4 hours.
- the resulting ZSM-48 (70: 1 Si0 2 : A1 2 0 3 ) crystals had a total surface area of -290 m 2 /g (external surface area of -130 m 2 /g), and an Alpha value of - 100, -40 % higher than current ZSM-48(90: 1 Si0 2 : A1 2 0 3 ) Alumina crystals.
- the H-form crystals were then steamed at 700°F, 750°F, 800°F, 900°F, and 1000°F for 4 hours for activity enhancement and Alpha values of these treated products are shown below:
- the sour service hydroisomerization catalyst was prepared by mixing 65 wt% ZSM-48 (-70/1 Si0 2 /Al 2 0 3 , see Example 1A) with 35 wt% P25 Ti0 2 binder and extruding into a 1/20" quadralobe. This catalyst was then precalcined in nitrogen at 1000°F, ammonium exchanged with ammonium nitrate, and calcined at 1000°F in full air. The extrudate was then steamed for 3 hours at 750°F in full steam.
- the steamed catalyst was impregnated to 0.6 wt% platinum via incipient wetness using platinum tetraamine nitrate, dried, and then calcined at 680°F for 3 hours in air.
- the ratio of micropore surface area to total surface area is about 45%.
- a dewaxing or hydroisomerization step can be included in both a first, sour reaction stage and a second, non-sour reaction stage.
- MVGO medium vacuum gas oil feed
- Example 2 Example of advantage of interstage distillate recovery
- a feedstock is represented as a one or more groups of molecules.
- the groups of molecules are based on the carbon number of the molecules and the molecular class of the molecules.
- process conditions selected for the simulation such as pressure, temperature, hydrogen treat gas rate, and/or space velocity
- each group of molecules is reacted according to a reaction order and rate appropriate for the group.
- Suitable reaction rate data for different types or groups of molecules can be obtained from the published literature, or reaction rate data can be generated experimentally.
- the products of the reaction calculations for each group of molecules are used to determine an output product in the simulation. In the reaction calculations, aromatics equilibrium can also be considered and used to modify the calculated aromatics content in the product.
- Example 3 Example of improved diesel yield followed by interstage separation
- FIG. 5 shows results from a series of runs performed on an MVGO feed using various configurations of catalysts.
- a first reactor was used that included a conventional hydrotreating catalyst.
- An MVGO feed was hydrotreated to produce a hydrotreated effluent having a sulfur content of less than 100 wppm.
- the hydrotreated effluent was then fractionated to remove all distillate and lighter hydrocarbons.
- the unconverted bottoms was hydroprocessed in a second reactor.
- the second reactor included a bed of hydrocracking catalyst, and an optional bed of dewaxing catalyst either prior to or after the hydrocracking catalyst bed.
- the hydrocracking catalyst was HSZ-390, a USY zeolite based catalyst.
- the dewaxing catalyst was selected from one of three choices.
- One type of catalyst was based on a 70:1 silica to alumina ratio ZSM-48 molecular sieve bound with a P25 (DeGussa) titania binder.
- the catalyst included a 65:35 ratio of molecular sieve to binder.
- the catalyst also included 2 wt% of Pt relative to the total weight of the catalyst.
- Another catalyst was based on a 90: 1 silica to alumina ratio ZSM-48 molecular sieve, including a DT-51D (Rhone-Poulenc) titania binder and 2 wt% of Pt.
- a third catalyst was based on a 64: 1 silica to alumina ratio ZSM-23 molecular sieve, including a Versal-300 alumina binder and 2 wt% of Pt.
- ZSM-48 and ZSM-23 catalysts may be referred to as dewaxing catalysts.
- FIG. 5 shows the yield of diesel fuel product and the 700°F+ conversion of the feed for the various runs.
- a boiling range of 400°F-700°F was selected as corresponding to a diesel fuel product.
- the data in FIG. 5 can be used to compare the diesel yield, as a function of 700°F+ conversion, for a USY catalyst alone versus stacked beds of both USY and another catalyst, in FIG.
- a configuration involving USY catalyst alone provided a comparable or better diesel yield as compared to configurations where USY catalyst was stacked above a dewaxing catalyst.
- One exception is for a stacked bed of the USY above 70: 1 ZSM-48, where an increase in diesel yield was observed at a processing temperature of 350°C.
- a stacked bed having a ZSM-48 dewaxing catalyst followed by the USY catalyst showed an improved diesel yield relative to only the USY" catalyst at a range of processing temperatures. From 330°C to 350°C, using either the 70: 1 or the 90:1 ZSM-48 above a US Y catalyst resulted in an improved diesel yield at a comparable level of conversion.
- FIG. 6 shows a plot of a portion of the data from FIG. 5 that demonstrates the increase in the maximum diesel yield.
- the run corresponding to only the USY catalyst and runs including one bed each of ZSM-48 and USY " are shown.
- an increased diesel yield can be achieved by processing a feed using a dewaxing catalyst, such as ZSM-48, followed by a hydrocracking catalyst, such as USY' ' , to produce 65% to 90% conversion.
- the amount of conversion can be selected to be 70% to 85%.
- the integrated hydrocracking and dewaxing process depicted in Figure 1 was used to make a Group IT base stock. More particularly, using the process of Figure 1, the first reactor 1 10 of Figure 1 was configured to do deep hydrotreating (as shown in configuration A of Figure 2) followed by separation (as shown in 120 of Figure 1 ). The second reactor 130 of Figure 1 was configured for doing dewaxing followed by hydrocracking in the same reactor (as shown in configuration E of Figure 3).
- the Group II lube base stock produced had a kinematic viscosity at 1 00°C of 15 cSt and a VI of 106.4.
- the pour point was -42°C.
- the aromatics content was 51 mmol/kg imhydrofinished.
- the STAR 7 method test results were a saturates content of 97.1 wt.%, an aromatic ring class 1 of 2.2 wt.%, an aromatic ring class 2 of 0.2 wt.%, an aromatic ring class 3 of 0. 1 wt.%, an aromatic ring class 4 of 0.5 wt.%, and a recovery of 92.5 wt.%.
- FIG. 10 is UV spectrograph of the inventive Group II base stock produced using the integrated hydrocracking and dewaxing process depicted in Figure 1 , but to a viscosity of 4.5 cSt. Also included in Figure 10 is a comparative prior art Group II base stock produced to a viscosity of 4.5 cSt.
- the inventive Group II base stock has a small peak at about a 305 nm wavelength, which is absent in the prior art Group II base stock, and confirms a compositional difference between the two, showing the presence of a small amount of 3 to 4+ ring aromatics and naphtheno-aromatics.
- the absorptivity differences in the UV spectroscopy test of Figure 2 between the inventive material and the prior-art Group II material confirm the compositional differences between the two and these differences are summarized in Table 4 below.
- compositional differences between the inventive material and the conventional group II base stocks was also evidenced by mass spectroscopy analysis in which the aromatic and naphtheno-aromatic species were separated using the method described in U.S. Patent No. 8,1 14,678, herein incorporated by reference, and x-class analysis or ring class analysis testing was performed.
- the compositional differences were quantified by the aromatic performance ratio, which is defined as the ratio of the total amount of species of the hydrogen deficiency ring class numbers -10, -8 and -6 to the total amount of species of the hydrogen deficiency numbers -2, 0 and 2.
- NMR test results on the inventive Group II lube base stock indicate less branching diversity on the aromatics ring structures. Typically shorter branches are due to some LCO carry-over from previous processing steps. However, the UV spectroscopy data of Figure 10 indicates that the LCO endpoint barely overlapped with the 4.5 cSt material boiling range.
- Initial NMR results confirm some unexpected differences in branching on the molecules as compared to comparative prior art Group IT base stocks. Additionally, shorter branches on the aromatics would not explain a higher viscosity / better viscosity retention that was observed for the inventive material. These differences would not be expected to lead to an overall better lubes quality, and hence these results are unexpected and surprising.
- Example 5 Improved Group II Base stock Using Different Feeds
- the HVGO was also used in a prior art catalytic process that produced 10-1 1 cSt conventional Group II base stocks.
- the comparative Group II base stocks had a viscosity of 10-1 1 cSt and the Noack volatility and pour points are shown in Table 7 below.
- Lubricant compositions for industrial turbine oils were produced with the inventive Group II base stock (5 and 1 1 cSt viscosity) along with a prior art- comparative Group II base stock to test the oxidative stability.
- the industrial turbine oils were comprised of the inventive or the prior-art reference material and trace quantities of defoaming additives and pour point depressants.
- Oxidative stability was measured using the RPVGT test (ASTM D2272 test for the time in minutes to a 25.4 psi pressure drop). The oxidative stability results are depicted in Figure 1 1.
- the oxidative stability for the industrial turbine formulation using 1 1 cSt base stock showed a strong correlation to total aromatics in the inventive material, whereas the oxidative stability for the industrial turbine oil formulation using a 5 cSt base stock did not correlate with the total aromatic content in the inventive material. It is hypothesized that this difference may be due to differences in multi-ring naphthene species between the 5 cSt inventive Group II base stock and the 1 1 cSt inventive Group II base stock. It should be noted that in both cases, the performance is improved/higher as compared to the formulation using the conventional base stock material.
- inventive Group II base stocks in finished lubricant compositions outperform the prior art Group II lube base stocks in the same lubricant compositions. Further investigation is needed for saturates and other species that may be countering some of the negative effects expected from less paraffinic branching on the aromatics for the inventive Group II base stocks.
- An MVGO feed similar to the one described above can be processed in a reaction system having two stages. In the first stage, the feed is hydrotreated under effective hydrotreating conditions. The hydrotreated effluent is then hydrocracked under effective hydrocracking conditions using a catalyst based on zeolite Y, The hydrotreated, hydrocracked effluent is then dewaxed in the presence of a dewaxing catalyst suitable for use in sour service.
- the catalyst can include a bound ZSM-48 zeolite impregnated with less than 1 wt% Pt, The above processes occur without an intermediate separation step.
- the dewaxed effluent is then fractionated.
- the fractionation produces both a naphtha product fraction and a diesel product fraction.
- the diesel product from the fractionator is suitable for use in the diesel pool.
- the diesel product has a sulfur content of 15 wppm or less, and a cloud point below ⁇ 10°C.
- the fractionator also produces a bottoms fraction.
- the bottoms fraction has a pour point below the pour point of the initial MVGO feed.
- the bottoms fraction is passed into a second reaction stage. Due to the hydrotreatment in the first stage, the sulfur content of the bottoms fraction is less than 50 wppm. In the second stage, the bottoms fraction is hydrocracked, hydro finished, and then dewaxed. The effluent from the second stage is fractionated to form a naphtha product, a diesel product, and a lubricant base oil product. Optionally, a portion of the lubricant base oil product is recycled to increase the amount of diesel produced in the second reaction stage. Additional Embodiments :
- a method for producing a naphtha fuel, a diesel fuel, and a lubricant basestock.
- the method includes contacting a hydrotreated feedstock with a hydrocracking catalyst under first effective liydrocracking conditions to produce a hydrocracked effluent, the hydrotreated feedstock being cascaded to the hydrocracking catalyst without intermediate separation; cascading the entire hydrocracked effluent, without separation, to a catalytic dewaxing stage; dewaxing the entire hydrocracked effluent under first effective catalytic dewaxing conditions in the presence of a dewaxing catalyst, the dewaxing catalyst includes at least one non-dealuminated, uni dimensional, 10-member ring pore zeolite and at least one Group VI or Group VIII metal or combination thereof; fractionating the dewaxed effluent to produce at least a naphtha product fraction, a first diesel product fraction, and a bottoms
- a method according to the first embodiment wherein the dewaxing of the bottoms fraction is performed prior to said hydrocracking of the bottoms fraction.
- a method according to any of the above embodiments is provided, wherein the bottoms fraction is dewaxed prior to said hydrocracki ng of the bottoms fraction and after sai d hydrocracking of the bottom s fraction.
- a method according to the third embodiment is provided, wherein the bottoms fraction is dewaxed after said hydrocracking of the bottoms fraction under third effective catalytic dewaxmg conditions.
- a method for producing a diesel fuel and a lubricant basestock includes contacting a hvdrotreated feedstock with a dewaxing catalyst under first effective dewaxing conditions to produce a dewaxed effluent, the dewaxing catalyst includes at least one non- dealuminated, unidimensional, 10-member ring pore zeolite and at least one Group VIII metal, the combined total sulfur in liquid and gaseous forms fed to the dewaxing stage is greater than 1000 ppm by weight of sulfur on the hvdrotreated feedstock basis, the hydrotreated feedstock being cascaded to the dewaxing catalyst without intermediate separation; fractionating the dewaxed effluent to produce at least a first diesel product fraction and a bottoms fraction; hydrocracking the bottoms fraction under second effective hydrocracking conditions; dewaxing the bottoms fraction under second effective catalytic dewaxing conditions; and fractionating the hydrocr
- a method according to the sixth embodiment wherein dewaxing the bottoms fraction occurs prior to said hydrocracking of the bottoms fraction.
- a method according to the seventh embodiment wherein the bottoms fraction is dewaxed prior to said hydrocracking of the bottoms fraction and dewaxed after said hydrocracking of the bottoms fraction.
- a method according to any of the sixth through eighth embodiments is provided, further comprising contacting the dewaxed feedstock with a hydrocracking catalyst under first effective hydrocracking conditions prior to fractionation of the dewaxed effluent.
- the second effective catalytic dewaxing conditions include a temperature that is at least about 20°C lower than a temperature of the first effective catalytic dewaxing conditions.
- a method according to any of the above embodiments wherein a hydroge gas introduced as part of first- effective hydrocracking conditions or as part of first effective dewaxing conditions is chosen from a hydrotreated gas effluent, a clean hydrogen gas, a recycle gas and combinations thereof.
- the dewaxing catalyst comprises a molecular sieve having a Si0 2 :AI 2 0 3 ratio of 200: 1 to 30: 1 and comprises from 0.1 wt% to 3.33 wt% framework A1 2 0 3 content, the dewaxing catalyst including from 0. 1 to 5 wt% platinum.
- a method according to any of the above embodiments is provided, wherein the molecular sieve is EU-1, ZSM-35, ZSM- 1 1 , ZSM-57, NU-87, ZSM-22, EU-2, EU-1 1, ZBM-30, ZSM-48, ZSM-23, or a combination thereof.
- a method according to the thirteenth embodiment wherei the molecular sieve is ZSM-48, ZSM-23, or a combination thereof, and preferably is ZSM-48.
- the dewaxing catalyst comprises at least one low surface area metal oxide, refractory binder, the binder being silica, alumina, titania, zirconia, or silica-alumina.
- the metal oxide, refractory binder further comprises a second metal oxide, refractory binder different from the first metal oxide, refractory binder.
- the dewaxing catalyst comprises a micropore surface area to total surface area ratio of greater than or equal to 25%, wherein the total surface area equals the surface area of the external zeolite plus the surface area of the binder, the surface area of the binder being 100 nrVg or less.
- the hydrocracking catalyst is a zeolite Y based catalyst.
- fractionating to form a lubricant base oil product fraction comprises forming a plurality of lubricant base oil products, including a lubricant base oil product having a viscosity of at least 2cSt, and a lubricant base oil product having a viscosity of at least 4 cSt suitable for use in engine oils made according to SAE J300 in 0W-, 5W-, or 10W- grades.
- a method according to any of the above embodiments is provided, wherein at least a portion of the lubricant base oil product fraction is recycled as an input to said hydrocracking of the bottoms fraction.
- a method according to any of the above embodiments wherein the first diese! product fraction has a higher cetane rating than the hydrotreated effluent, a lower cloud point than the hydrotreated effluent, or both a higher cetane rating and a lower cloud point than the hydrotreated effluent
- a method according to any of the above embodiments wherein the first diesel product fraction has a cloud point of less than -10°C, the second diesel product fraction has a cloud point of less than -10°C, and the hydrotreated effluent has a cloud point that is at least 5°C higher than the first diesel product fraction cloud point or the second diesel product fraction cloud point.
- the first effective hydrocracking conditions include a temperature of 200°C to 45Q°C, a hydrogen partial pressure of 250 psig to 5000 psig (1 .8 MPa to 34.(5 MPa), a liquid hourly space velocity of 0.2 h "1 to 10 h “1 , and a hydrogen treat gas rate of 35.6 m 3 /m J to 1781 m 3 /m J (200 SCF/B to 10,000 SCF/B), and preferably the first effective hydrocracking conditions include a temperature of 300°C to 450°C, a hydrogen partial pressure of 500 psig to 2000 psig (3.5 MPa- 13.9 MPa), a liquid hourly space velocity of 0.3 h " 1 to 2 h "J , and a hydrogen treat gas rate of 213 m " 7m to 1068 m ' Vm 4 (1200 SCF/B to 6000 SCF/B).
- the second effective hydrocracking conditions include a temperature of 200°C to 450°C, a hydrogen partial pressure of 250 psig to 5000 psig (1 .8 MPa to 34.(5 MPa), a liquid hourly space velocity of 0,2 h " ' to 10 l.i "J , and a hydrogen treat gas rate of 35,6 nrVm 3 to 1781 nrVm 3 (200 SCF/B to 10,000 SCF/B), and preferably the second effective hydrocracking conditions include a temperature of 300°C to 450°C, a hydrogen partial pressure of 500 psig to 2000 psig (3.5 MPa- 13.9 MPa), a liquid hourly space velocity of 0.3 If 1 to 2 If 1 , and a hydrogen treat gas rate of 213 m 3 /m 3 to 1068 m m 3 (1200 SCF/B to 6000 SCF/B).
- the first effective dewaxing conditions include a temperature of from 200°C to 450°C, preferably 270°C to 400°C, a hydrogen partial pressure of from 1.8 MPa to 34.6 MPa (250 psi to 5000 psi), preferably 4.8 mPa to 20.8 mPa (700 psi to 3000 psi), a liquid hourly space velocity of from 0.2 to 10 hr "1 , preferably 0.5 to 3.0 hr "1 , and a hydrogen circulation rate of from 35.6 to 1781 m 3 /m J (200 to 10,000 scf/B), preferably 178 to 890.6 nrvm 3 (1000 to 5000 scf/B).
- the second effective dewaxing conditions include a temperature of from 200°C to 450°C, preferably 270°C to 400°C, a hydrogen partial pressure of from 1.8 MPa to 34.6 MPa (250 psi to 5000 psi), preferably 4.8 mPa to 20.8 mPa (700 psi to 3000 psi), a liquid hourly space velocity of from 0.2 to 10 hr "1 , preferably 0.5 to 3.0 hr "1 , and a hydrogen circulation rate of from 35.6 to 1781 m7m 3 (200 to 10,000 scf/B), preferably 178 to 890.6 m 3 /m 3 (1000 to 5000 scf/B).
- a method for producing a diesel fuel and a lubricant basestock includes contacting a feedstock with a hydrotreating catalyst under first effective hydrotreating conditions to produce a hydrotreated effluent; fractionating the hydrotreated effluent to produce at least a first diesel product fraction and a bottoms fraction; dewaxing the bottoms fraction under effective catalytic dewaxing conditions, the dewaxing catalyst includes at least one non-dealuminated, imidimensional, 10-member ring pore zeolite and at least one Group VI metal. Group VIII metal or combination thereof; hydrocracking the bottoms fraction under effective hydrocracking conditions; and fractionating the hydrocracked, dewaxed bottoms fraction to form at least a second diesel product fraction and a lubricant base oil product fraction.
- a method according to the twenty-seventh embodiment wherein the effective hydrocracking conditions include a temperature of 200°C to 450°C, a hydrogen partial pressure of 250 psig to 5000 psig (1.8 MPa to 34.6 MPa), a liquid hourly space velocity of 0.2 if ' to 10 If', and a hydrogen treat gas rate of 35.6 m 3 /m 3 to 1781 m ' Vm 3 (200 SCF/B to 10,000 SCF/B).
- a method according to any of the twenty-seventh or twenty-eighth embodiments wherein the effective dewaxing conditions include a temperature of from 200°C to 45Q°C, a hydrogen partial pressure of from 1.8 MPa to 34.6 MPa (250 psi to 5000 psi), a liquid hourly space velocity of from 0.2 to 10 hr "1 , and a hydrogen circulation rate of from 35.6 to 1781 m 3 /m 3 (200 to 10,000 sef B).
- a method according to any of the twenty-seventh through twenty-ninth embodiments is provided, wherein the total conversion of the hydrocracked, dewaxed bottoms relati ve to the feedstock is 65% to 90%, preferably 70% to 85%.
- a method for producing a diesel fuel and a lubricant basestock including: contacting a feedstock with a hydrotreating catalyst under effective hydrotreating conditions to produce a hydrotreated effluent; fractionating the hydrotreated effluent to produce at least a first diesel product fraction and a bottoms fraction; hydrocracking the bottoms fraction under effective hydrocracking conditions; dewaxing the bottoms fraction under effective catalytic dewaxing conditions, the dewaxing catalyst including at least one non-dealuminated, unidimensional, 10-m.ember ring pore zeolite, and at least one Group VI metal, Group VIII metal or combination thereof; and fractionating the hydrocracked, dewaxed bottoms fraction to form at least a second diesel product fraction and a lubricant base oil product fraction.
- a method according to the thirty-first embodiment is provided, wherein at least a portion of the first diesel product fraction is fed to the dewaxing step.
- a method according to the thirty-first to thirty-second embodiments is provided further including combining the first diesel product fraction and the second diesel product fraction.
- a method according to the thirty-first to thirty-third embodiments is provided further including hydrofinishing the hydrocracked, dewaxed bottoms fraction under effective hydrofinishing conditions prior to the second fractionating step.
- a method for producing a diesel fuel and a lubricant basestock including: contacting a feedstock with a hydrotreating catalyst under effective hydrotreating conditions to produce a hydrotreated effluent; fractionating the hydrotreated effluent to produce at least a first diesel product fraction and a first bottoms fraction; dewaxing the bottoms fraction under effective catalytic dewaxing conditions, the dewaxing catalyst including at least one non-dealuminated, unidimensional, lG-member ring pore zeolite, and at least one Group VI metal, Group VIIT metal or combination thereof; fractionating the dewaxed bottoms fraction to form at least a second diesel product fraction and a second bottoms fraction, hydrocracking the second bottoms fraction under effective hydrocracking conditions to form a third bottoms fraction, and fractionating the third bottoms fraction to form at least a naphtha product fraction, a diesel product fraction and a lubricant base oil product fraction
- a method according to the thirty-fifth embodiment is provided, wherein at least a portion of the third bottoms fraction is recycled back to the dewaxing step.
- a method according to the thirty-fifth to thirty-sixth embodiments is provided, wherei at least a portion of the third bottoms fraction is recycled back to the second fractionating step.
- a method according to the thirty-fifth to thirty-seventh embodiments is provided further including hydrofinishing the third bottoms fraction under effective hydrofinishing conditions prior to the third fractionating step.
- a method for producing a diesel fuel and a lubricant basestock including: contacting a feedstock with a hydrotreating catalyst under effective hydrotreating conditions to produce a hydrotreated effluent; fractionating the hydrotreated effluent to produce at least a first diesel product fraction and a first bottoms fraction; hydrocracking the first bottoms fraction under effective hydrocracking conditions to form a second bottoms fraction; fractionating the second bottoms fraction to form at least a second diesel product fraction and a third bottoms fraction, dewaxing at least a portion of the third bottoms fraction under effective catalytic dewaxing conditions, the dewaxing catalyst including at least one non-dealuminated, unidimensional, 10-member ring pore zeolite, and at least one Group VI metal, Group VIII metal or combination thereof; and fractionating the dewaxed third bottoms fraction and the non-dewaxed third bottoms fraction to form at least a naphtha product
- a method according to the thirty-ninth embodiment is provided, further including dewaxing a portion of the first diesel product fraction, the second diesel product fraction or a combination thereof under effective catalytic dewaxing conditions.
- a method according to the thirty-ninth to fortieth embodiments is provided, further including combining the first diesel product fraction, the second diesel product fraction and the third diesel product fraction.
- a method according to the thirty-ninth to forty-first embodiments is provided, further including hydrofin shing the dewaxed third bottoms fraction under effective hydrofin shing conditions prior to the third fractionating step.
- a method for producing a naphtha fuel, a diesel fuel, and a lubricant basestock including: contacting a hvdrotreated feedstock without intermediate separation with a hydrocracking catalyst under first effective hydrocracking conditions to produce a hydrocracked effluent; catalytically dewaxing without intermediate separation the entire hydrocracked effluent under first effective catalytic dewaxing conditions in the presence of a first dewaxing catalyst including at least one non-deamminated, unidimensional, 10-member ring pore zeolite, and at least one Group VI metal or Group VIII metal or combination thereof to form a dewaxed effluent, wherein the combined total sulfur in liquid and gaseous forms fed to the catalytic dewaxing step is greater than 1000 ppm by weight of sulfur on a hvdrotreated feedstock basis; fractionating the dewaxed effluent to produce at least a naph
- a method according to the forty- third to forty-fourth embodiments wherein the catalytically dewaxing of the bottoms fraction occurs prior to the second hydrocracking step, after the second hydrocracking step, or both prior to and after the second hydrocracking step,
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Abstract
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US13/803,378 US9487723B2 (en) | 2010-06-29 | 2013-03-14 | High viscosity high quality group II lube base stocks |
PCT/US2014/017918 WO2014175952A1 (en) | 2013-03-14 | 2014-02-24 | High viscosity high quality group ii lube base stocks |
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US10647925B2 (en) | 2015-12-28 | 2020-05-12 | Exxonmobil Research And Engineering Company | Fuel components from hydroprocessed deasphalted oils |
US10590360B2 (en) | 2015-12-28 | 2020-03-17 | Exxonmobil Research And Engineering Company | Bright stock production from deasphalted oil |
US10808185B2 (en) | 2015-12-28 | 2020-10-20 | Exxonmobil Research And Engineering Company | Bright stock production from low severity resid deasphalting |
US10494579B2 (en) | 2016-04-26 | 2019-12-03 | Exxonmobil Research And Engineering Company | Naphthene-containing distillate stream compositions and uses thereof |
EP3494195A1 (en) * | 2016-08-03 | 2019-06-12 | ExxonMobil Research and Engineering Company | Raffinate hydroconversion for production of high performance base stocks |
CA3045779A1 (en) * | 2016-12-29 | 2018-07-05 | Exxonmobil Research And Engineering Company | Block processing for base stock production from deasphalted oil |
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WO2011153178A2 (en) * | 2010-06-02 | 2011-12-08 | The Lubrizol Corporation | Lubricating composition containing a carboxylic functionalised polymer |
US8992764B2 (en) * | 2010-06-29 | 2015-03-31 | Exxonmobil Research And Engineering Company | Integrated hydrocracking and dewaxing of hydrocarbons |
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