WO2005001006A2 - Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including fischer-tropsch wax - Google Patents
Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including fischer-tropsch wax Download PDFInfo
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- WO2005001006A2 WO2005001006A2 PCT/US2004/019253 US2004019253W WO2005001006A2 WO 2005001006 A2 WO2005001006 A2 WO 2005001006A2 US 2004019253 W US2004019253 W US 2004019253W WO 2005001006 A2 WO2005001006 A2 WO 2005001006A2
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- WIPO (PCT)
- Prior art keywords
- process according
- hydrocracking
- hydroisomerization
- catalyst
- viscosity
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000000314 lubricant Substances 0.000 title claims abstract description 62
- 239000000446 fuel Substances 0.000 title claims abstract description 31
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 79
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 64
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 64
- 239000002199 base oil Substances 0.000 claims abstract description 56
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 53
- 239000002808 molecular sieve Substances 0.000 claims abstract description 40
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011148 porous material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims description 105
- 230000008569 process Effects 0.000 claims description 99
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000004064 recycling Methods 0.000 claims description 5
- 210000003918 fraction a Anatomy 0.000 claims description 3
- 239000000047 product Substances 0.000 description 59
- 239000001993 wax Substances 0.000 description 35
- 238000009835 boiling Methods 0.000 description 27
- 238000005984 hydrogenation reaction Methods 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 238000005336 cracking Methods 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000006317 isomerization reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- -1 SAPO-11 and SAPO-41 Chemical compound 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000011593 sulfur Chemical group 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000012169 petroleum derived wax Substances 0.000 description 3
- 235000019381 petroleum wax Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Chemical group 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 210000002683 foot Anatomy 0.000 description 1
- 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 1
- 239000000499 gel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Definitions
- This invention relates to processes for converting waxy hydrocarbon feedstocks into salable products. More particularly, the invention relates to a process of converting a Fischer-Tropsch derived waxy feedstock to middle distillate fuels and lubricant base oils.
- a Fischer-Tropsch synthesis process may be used to convert a gas composed primarily of CO and H 2 (commonly referred to as synthesis gas or syngas) under catalytic conditions to a wide variety of gaseous, liquid and solid hydrocarbonaceous products. Many of these liquid and solid products contain waxy materials composed of high molecular weight paraffins. These paraffinic waxes can crystallize upon cooling, and products comprising these paraffinic waxes typically have unacceptably high pour points and high cloud points. Pour point is the temperature at which a sample will begin to flow under carefully controlled conditions and may be measured according to ASTM D5950-96.
- Cloud point is the temperature at which a sample begins to develop a haze under controlled conditions and may be measured according to ASTM D5773-95. It is known to catalytically convert waxy paraffins in hydrocarbon feedstocks to lower boiling hydrocarbons within the middle distillate product range. This conversion may be accomplished by hydroprocessing techniques, such as hydrocracking and hydroisomerization. Hydrocracking converts larger molecules into smaller ones and introduces some amount of branching into the cracked products. Hydroisomerization primarily introduces branching into the paraffinic molecules, thus improving properties, such as pour and cloud points. Unreacted components of the hydrocarbon feed, which have not been hydrocracked and/or hydroisomerized, may be recycled for further treatment to provide additional products in the desired boiling range.
- EP 0544766 Bl teaches a process for preparing low pour point middle distillate hydrocarbons by contacting a hydrocarbonaceous feedstock with a large pore hydrocracking catalyst and a catalyst comprising an intermediate pore size silicoaluminophosphate molecular sieve and a hydrogenation component.
- United States Patent No. 5,935,414 relates to a process for reducing the wax content of wax-containing hydrocarbon feedstocks to produce middle distillate products, which include a low freeze point jet fuel and/or a low pour point and low cloud point diesel fuel and heating oil.
- the feedstock is contacted with a hydrocracking catalyst containing a carrier, at least one hydrogenation metal component of Group VIB and Group VIII metals, and a large pore zeolite such as a Y type zeolite, in a hydrocracking zone in the presence of hydrogen at elevated temperature and pressure.
- a dewaxing catalyst containing a crystalline, intermediate pore size molecular sieve selected from metallosilicates and silicoaluminophosphates in a hydrodewaxing zone in the presence of hydrogen at elevated temperature and pressure.
- 5,139,647 relates to a process for making middle distillates from a hydrocarbonaceous feedstock by a hydrocracking and isomerization.
- the feedstock is contacted with a catalyst containing an intermediate pore size silicoaluminophosphate molecular sieve and a hydrogenation component.
- United States Patent No. 4,859,312 relates to a process for making middle distillates. The process uses a catalyst comprising a silicoaluminophosphate molecular sieve such as SAPO-11 and SAPO-41, and platinum or palladium, a hydrogenation component, to simultaneously subject heavy oils to hydrocracking and isomerization reactions.
- EP 0323092 A2 and United States Patent No. 4,943,672 relate to a process for converting Fischer Tropsch wax into a lubricating oil having a high viscosity index and a low pour point.
- the wax is hydrotreated under relatively severe conditions and thereafter the hydrotreated wax is hydroisomerized in the presence of hydrogen on a specified type of fluorided Group VIII metal-on-alumina catalyst. The hydroisomerate is then dewaxed to produce a premium lubricating oil base stock.
- United States Patent No. 4,080,397 discloses a method for upgrading a
- EP 0583836 Al discloses a process for preparing of hydrocarbon fuels.
- a substantially paraffinic hydrocarbon product is prepared, and the hydrocarbon product is contacted with hydrogen in the presence of a hydroconversion catalyst under conditions such that substantially no isomerization or hydrocracking of the hydrocarbon product occurs.
- At least a portion of the hydrocarbon product from this process is contacted with hydrogen in the presence of a hydroconversion catalyst under conditions such that hydrocracking and isomerization of the hydrocarbon feed occurs to yield a substantially paraffinic hydrocarbon fuel.
- EP 0147873 Al discloses a process for preparing middle distillates.
- Middle distillates are prepared from syngas by a two stage series-flow process.
- the process comprises a Fischer Tropsch synthesis over a special Zr, Ti, or Cr promoted Co- catalyst followed by hydroconverting the total synthesized product of a Fischer- Tropsch synthesis over a supported noble metal catalyst.
- the primary product of the process be lubricant base oil having good low temperature properties (i.e., cloud point, pour point, cold filter plugging point, etc. and high viscosities).
- the present invention relates to a process for treating a waxy hydrocarbon feedstock.
- the process comprises contacting the feedstock with a hydrocracking catalyst in a hydrocracking zone, producing a hydrocracking effluent and contacting the hydrocracking effluent with a molecular sieve hydroisomerization catalyst in a hydroisomerization zone, producing a hydroisomerization effluent.
- the hydroisomerization effluent is fractionated, providing a heavy fraction and a middle distillate fuel.
- a lubricant base oil fraction is isolated from the heavy fraction and this lubricant base oil has a viscosity index of greater than 130, a pour point of less than -15°C, and a viscosity of greater than 3 cSt at 100°C.
- the present invention further relates to a process for treating a 650°F+ waxy hydrocarbon feedstock.
- the process comprises contacting the feedstock with a hydrocracking catalyst in a hydrocracking zone, producing a hydrocracking effluent, and contacting the hydrocracking effluent with a molecular sieve hydroisomerization catalyst in a hydroisomerization zone, producing a hydroisomerization effluent.
- the hydroisomerization effluent is fractionated, providing a heavy fraction and a middle distillate fuel; and a lubricant base oil fraction is isolated from the heavy fraction.
- the lubricant base oil has a viscosity index of greater than 130, a pour point of less than -15°C, and a viscosity of greater than 3 cSt at 100°C.
- the present invention relates to a process for treating a 650°F+ waxy hydrocarbon feedstock.
- the feedstock is contacted with a hydrocracking catalyst in a hydrocracking zone, producing a hydrocracking effluent; and the hydrocracking effluent is contacted with a molecular sieve hydroisomerization catalyst in a hydroisomerization zone, producing a hydroisomerization effluent.
- the hydroisomerization effluent is fractionated, providing a heavy fraction and a middle distillate fuel; and a lubricant base oil fraction is isolated from the heavy fraction.
- the lubricant base oil produced from this process has a viscosity index of greater than 130, a pour point of less than
- the 650°F+ waxy hydrocarbon feedstock comprises greater than 20 weight % 900°F+ components.
- FIGURE illustrates a schematic representation of one embodiment of the process of the present invention.
- the present invention relates to a process for producing high yields of high quality lubricant base oils from waxy hydrocarbon feedstocks. It has been discovered that one can readily and economically convert waxy hydrocarbon feeds having high initial boiling points and containing high levels of paraffinic waxes, such as Fischer Tropsch waxes, into high quality middle distillate fuels and high quality lubricant base oils, with the lubricant base oils being the primary product. In the processes of the present invention these waxy hydrocarbon feeds are contacted with a hydrocracking catalyst followed by a hydroisomerization catalyst, separated into a middle distillate product and a heavy fraction. From the heavy fraction a lubricant base oil is isolated.
- a hydrocracking catalyst followed by a hydroisomerization catalyst
- This process converts high boiling waxy hydrocarbon feeds into high quality middle distillate fuels with low pour and cloud points and high quality lubricant base oils with high viscosity indexes, and low pour and cloud points.
- the process of the present invention results in less cracking of the high boiling end of the high boiling waxy feed (i.e., less conversion of the high boiling end of the feed to lighter products). Accordingly, high quality lubricant base oils with high viscosity indexes, and low pour and cloud points.
- Heavy fraction is the heavier fraction separated after hydrocracking and hydroisomerization of a waxy hydrocarbon feedstock.
- the heavy fraction has an initial boiling point in the range of 600 to 750°F, an end boiling point in the range of 950 to greater than 1200 °F.
- the heavy fraction comprises lubricant base oil and wax.
- the heavy fraction may have a wax content between 0.1 and 5 weight percent.
- a heavy fraction may also be fractionated such that a bottoms fraction is obtained.
- Bottoms fraction is a non- vaporized (i.e. residuum) fraction contained as a part of file heavy fraction.
- waxy hydrocarbon feedstock useful in the processes disclosed herein may be synthetic waxy feedstocks, such as Fischer Tropsch waxy hydrocarbons, or may be derived from natural sources, such as petroleum waxes.
- the waxy hydrocarbon feedstock contains greater than 50% wax, more preferably greater than about 80% wax, most preferably greater than about 90% wax.
- wax content is determined by a solvent dewaxing process. The solvent dewaxing process is a standard method, and well known in the art.
- 650°F+ waxy hydrocarbon feedstock has an initial boiling point of 650°F wherein at least 70 wt%, preferably at least 85 wt%, of the feedstock boils above
- “Middle distillate fuel” or “middle distillate fuel fraction” is the lighter fraction separated after hydrocracking and hydroisomerization of a waxy hydrocarbon feedstock. It is a material containing hydrocarbons with boiling points between approximately 300°F to 650°F.
- the term “distillate” means that traditional fuels of this type could be generated from vapor overhead streams from distilling petroleum crude.
- distillate fuels include naphtha, jet fuel, diesel fuel, kerosene, aviation gas, fuel oil, and blends thereof.
- “Lubricant base oil” means a fraction meeting specifications for a lubricant base oil.
- Lubricant base oil fractions are isolated from the heavy fractions according to the process of the present invention.
- Properties of the lubricant base oils provided according to the present invention include initial boiling points in the range of 600 to 750°F, end boiling points in the range of 900 to greater than 1200°F, viscosities in the range of 3 to 15 cSt at 100°C, viscosity indices in the range of 115 to 160, preferably in the range of 130 to 180, and more preferably in the range of 140 to 180, pour points less then -9°C, preferably in the range of -10 to -24°C, and cloud points in the range of 0 to -20°C.
- Hydrocarbon or hydrocarbonaceous means a compound or substance that contains hydrogen and carbon atoms, which may also include heteroatoms such as oxygen, sulfur or nitrogen.
- a waxy hydrocarbon feedstock is converted to a middle distillate fuel product and a lubricant base oil product by contacting the feedstock with a hydrocracking catalyst and then a hydroisomerization catalyst.
- the process according to the present invention provides a lubricant base oil product having a high viscosity index and low pour and cloud points.
- the process of the present invention results in less cracking of the high boiling end of the high boiling waxy feed (i.e., less conversion of the high boiling end of the feed to lighter products).
- the processes as described herein are able to convert this heavy waxy feed to high quality middle distillate products and high quality lubricant base oil products.
- the waxy hydrocarbon feedstock has an initial boiling point of less than 700°F+.
- the waxy hydrocarbon feedstock has an end boiling point in the range of 1000 to greater than 1200 °F.
- the waxy hydrocarbon feedstock to the processes as described herein comprises greater than 70 weight percent 650°F+ material, and even more preferably greater than 85 weight percent 650°F+ material.
- the feed preferably comprises greater than 20 weight percent 900°F+ material .
- the waxy feeds to the process of the present invention are comprised of greater than 80 weight % wax, preferably greater than 95 weight % wax.
- wax content is determined by a solvent dewaxing process.
- the solvent dewaxing process is a standard method, and well known in the art. In the process, 300 grams of a waxy product is diluted 50/50 by volume with a 4: 1 mixture of methyl ethyl ketone and toluene which had been cooled to -20° C. The mixture is cooled at a uniform slow rate in the range of about 0.5° to 4.5° C./min to -15°C, and then filtered through a Coors funnel at -15° C. using Whatman No. 3 filter paper.
- the wax is removed from the filter and placed in a tarred 2 liter flask. Solvent remaining in the wax is removed on a hot plate and the wax weighed.
- the waxy hydrocarbon feedstocks useful in the processes disclosed herein may be synthetic waxy feedstocks, such as Fischer Tropsch waxy hydrocarbons, or may be derived from natural sources, such as petroleum waxes. Accordingly, the waxy feedstocks to the processes may comprise Fischer Tropsch derived waxy feeds, petroleum waxes, waxy distillate stocks such as gas oils, lubricating oil stocks, high pour point polyalphaolefins, foots oils, normal alpha olefin waxes, slack waxes, deoiled waxes, and microcrystalline waxes, and mixtures thereof.
- the waxy feedstocks are derived from Fischer Tropsch waxy feeds.
- the waxy hydrocarbon feedstock may be hydrotreated prior to the process as described herein if desired.
- hydrotreating is typically not necessary.
- a preferred waxy feed of the present invention is a Fischer-Tropsch derived waxy feed.
- syngas is converted to liquid hydrocarbons by contact with a Fischer-Tropsch catalyst under reactive conditions.
- methane and optionally heavier hydrocarbons ethane and heavier
- synthesis gas contains hydrogen and carbon monoxide, and may include minor amounts of carbon dioxide and/or water.
- a mildly alkaline solution e.g., aqueous potassium carbonate
- contacting a synthesis gas comprising a mixture of H 2 and CO with a Fischer-Tropsch catalyst under suitable temperature and pressure reactive conditions forms liquid and gaseous hydrocarbons.
- the Fischer-Tropsch reaction is typically conducted at temperatures of about 300-700°F (149-371°C), preferably about 400-550°F (204-228°C); pressures of about 10-600 psia, (0.7-41 bars), preferably about 30-300 psia, (2-21 bars); and catalyst space velocities of about 100-10,000 cc/g/hr, preferably about 300-3,000 cc/g/hr. Examples of conditions for performing Fischer-Tropsch type reactions are well known to those of skill in the art.
- the products of the Fischer-Tropsch synthesis process may range from C ⁇ to C 2 oo + with a majority in the C 5 to Cioo + range.
- the reaction can be conducted in a variety of reactor types, such as fixed bed reactors containing one or more catalyst beds, slurry reactors, fluidized bed reactors, or a combination of different type reactors.
- Such reaction processes and reactors are well known and documented in the literature.
- Fischer-Tropsch catalysts contain a Group VIII transition metal on a metal oxide support.
- the catalysts may also contain a noble metal promoter(s) and/or crystalline molecular sieves.
- Certain catalysts are known to provide chain growth probabilities that are relatively low to moderate, and the reaction products include a relatively high proportion of low molecular (C 2 . 8 ) weight olefins and a relatively low proportion of high molecular weight (C 3 n + ) waxes.
- reaction products include a relatively low proportion of low molecular (C 2 . 8 ) weight olefins and a relatively high proportion of high molecular weight (C 3 o + ) waxes.
- the product from a Fischer-Tropsch process contains predominantly paraffins; however, it may also contain C 2+ olefins, oxygenates, and heteroatom impurities.
- the most abundant oxygenates in Fischer-Tropsch products are alcohols, and mostly primary linear alcohols. Less abundant types of oxygenates in Fischer-Tropsch products include other alcohol types such as secondary alcohols, acids, esters, aldehydes, and ketones.
- the products from Fischer-Tropsch reactions generally include a light reaction product and a waxy reaction product.
- the light reaction product i.e., the condensate fraction
- the waxy reaction product includes hydrocarbons boiling above about 600°F (e.g., vacuum gas oil through heavy paraffins), largely in the C 2(J+ range, with decreasing amounts down to do- Both the light reaction product and the waxy product are substantially paraffinic.
- the waxy product generally comprises greater than 70 weight % normal paraffins, and often greater than 80 weight % normal paraffins.
- the light reaction product comprises paraffinic products with a significant proportion of alcohols and olefins. In some cases, the light reaction product may comprise as much as 50 weight %, and even higher, alcohols and olefins.
- the waxy hydrocarbon feedstock is contacted with a hydrocracking catalyst in a hydrocracking zone, producing a hydrocracking effluent and the hydrocracking effluent is contacted with a molecular sieve hydroisomerization catalyst in a hydroisomerization zone, producing a hydroisomerization effluent.
- the hydrocracking catalyst and hydroisomerization catalyst maybe arranged in a variety of design options so long as the entire effluent from the hydrocracking zone is passed to the hydroisomerization zone. Accordingly, the hydrocracking and hydroisomerization catalysts may be layered in a single reaction zone in a single reactor, or the hydrocracking and hydroisomerization catalysts may be layered in close-coupled series reactors with no heating, product withdrawal or feed inlet between reactors.
- the preferred catalyst system is a layered catalyst system, with the hydrocracking catalyst layered above the hydroisomerization catalyst, preferably in a ratio of about 1 : 1 to 15 : 1.
- the hydrocracking zone of the process includes a hydrocracking catalyst.
- hydrocracking the high molecular weight wax molecules are cracked into a desirable boiling range. During cracking, at least some of the cracked molecules may also be isomerized. The resulting cracked product largely comprises a mixture of paraffins and isoparaffins, which boil in the desired fuel or lubricant oil product range According to the present process, it is desired to minimize the cracking of the feedstock so that a smaller amount of light products will be produced.
- Hydrocracking catalysts are well known to those of skill in the art.
- Conventional hydrocracking catalysts generally comprise a cracking component, a hydrogenation component and a binder or matrix. Such catalysts are well known in the art.
- the matrix component can be of many types including some that have acidic catalytic activity.
- the catalyst may also contain a large pore zeolitic or non-zeolitic crystalline molecular sieve, where large pore is defined as having a pore diameter of greater than 7.1 A.
- suitable molecular sieves include zeolite Y, zeolite X and the so called ultra stable zeolite Y and high structural silica: alumina ratio zeolite Y such as that described in U.S. Patent No. 4,401,556, 4,820,402 and 5,059,567.
- Small crystal size zeolite Y such as that described in U.S. Patent No. 5,073,530, can also be used.
- Non-zeolitic molecular sieves which can be used include, for example, silicoaluminophosphates (SAPO), ferroaluminophosphate, titanium aluminophosphate and the various ELAPO molecular sieves described in U.S. Patent No. 4,913,799 and the references cited therein. Details regarding the preparation of various non-zeolite molecular sieves can be found in U.S. Patent No. 5,114,563
- the molecular sieve content of the hydrocracking catalyst is less than 2 wt%.
- Suitable matrix materials may also include synthetic or natural substances as well as inorganic materials such as clay, silica and/or metal oxides such as silica- alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylia, silica-titania as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia zirconia.
- the latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
- Naturally occurring clays which can be composited with the catalyst include those of the montmorillonite and kaolin families. These clays can be used in the raw state as originally mined or initially subjected to calumniation, acid treatment or chemical modification.
- the hydrogenation component will be a Group VI, Group VII, or Group VIII metal or oxide or sulfide thereof, preferably one or more of molybdenum, tungsten, cobalt, or nickel, or the sulfides or oxides thereof. If present in the catalyst, these hydrogenation components generally make up from about 5 weight % to about 40 weight % of the catalyst.
- platinum group metals especially platinum and or palladium, may be present as the hydrogenation component, either alone or in combination with the base metal hydrogenation components such as molybdenum, tungsten, cobalt, or nickel. If present, the platinum group metals will generally make up from about 0.1 weight % to about 2 weight % of the catalyst.
- the hydrogenation component can be added to the catalyst by methods such as co- mulling, impregnation, or ion-exchange.
- Typical hydrocracking conditions include: reaction temperature of from about 400 to 950°F (204 to 510°C), preferably 600 to 750°F (316 to 399°C); reaction pressure of from about 300 to 5000 psig (2.1 to 34.5 MPa), preferably 500 - 2000 psig (5.2-13.8 MPa); liquid hourly space velocity (LHSV) of from about 0.1 to
- the effluent from the hydrocracking zone is then contacted with an intermediate pore size molecular sieve hydroisomerization catalyst in a hydroisomerization zone.
- intermediate pore size means an effective pore aperture in the range of from about 4.8 to about 7.1 A when the porous inorganic oxide is in the calcined form.
- Hydroisomerization dewaxing is intended to improve the cold flow properties of a lubricating base oil by the selective addition of branching into the molecular structure. Hydroisomerization dewaxing ideally will achieve high conversion levels of waxy feed to non-waxy iso-paraffins while at the same time minimizing the conversion by cracking.
- a hydroisomerization dewaxing catalyst useful in the present invention comprises a shape selective intermediate pore size molecular sieve and optionally a catalytically active metal hydrogenation component on a refractory oxide support.
- the shape selective intermediate pore size molecular sieves used in the practice of the present invention are generally 1-D 10-, 11- or 12-ring molecular sieves.
- the preferred molecular sieves of the invention are of the 1-D 10-ring variety, where 10- (or 11 -or 12-) ring molecular sieves have 10 (or 11 or 12) tetrahedrally-coordinated atoms (T-atoms) joined by oxygens.
- T-atoms tetrahedrally-coordinated atoms
- the 10-ring (or larger) pores are parallel with each other, and do not interconnect.
- the classification of intrazeolite channels as 1-D, 2-D and 3-D is set forth by R. M. Barrer in Zeolites, Science and Technology, edited by F. R. Rodrigues, L.D. Rollman and C. Naccache, NATO ASI Series, 1984 which classification is incorporated in its entirety by reference (see particularly page 75).
- Preferred shape selective intermediate pore size molecular sieves used for hydroisomerization dewaxing are based upon aluminum phosphates, such as SAPO- 11, SAPO-31, and SAPO-41.
- SAPO-11 and SAPO-31 are more preferred, with SAPO-11 being most preferred.
- SM-3 is a particularly preferred shape selective intermediate pore size SAPO, which has a crystalline structure falling within that of the SAPO-11 molecular sieves. The preparation of SM-3 and its unique characteristics are described in U.S. Patent Nos. 4,943,424 and 5,158,665.
- zeolites such as ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite, and ferrierite. SSZ-32 and ZSM-23 are more preferred.
- a particularly preferred intermediate pore size molecular sieve, which is useful in the present process is described, for example, in United States Patents No. 5,135,638 and 5,282,958, the contents of which are hereby incorporated by reference in their entirety.
- such an intermediate pore size molecular sieve has a crystallite size of no more than about 0.5 microns and pores with a minimum diameter of at least about 4.8 A and with a maximum diameter of about 7.1 A.
- the catalyst has sufficient acidity so that 0.5 grams thereof when positioned in a tube reactor converts at least 50% of hexadecane at 370°C, a pressure of 1200 psig, a hydrogen flow of 160 ml/min, and a feed rate of 1 ml/hr.
- the catalyst also exhibits isomerization selectivity of 40 or greater (isomerization selectivity is determined as follows: 100 x (weight % branched C16 in product) / (weight % branched C16 in product + weight % C13- in product) when used under conditions leading to 96% conversion of normal hexadecane (n-C16) to other species.
- Such a particularly preferred molecular sieve may further be characterized by pores or channels having a crystallographic free diameter in the range of from about 4.0 to about 7.1 A , and preferably in the range of 4.0 to 6.5 A.
- Hydroisomerization dewaxing catalysts useful in the present invention optionally comprise a catalytically active hydrogenation metal. The presence of a catalytically active hydrogenation metal leads to product improvement, especially VI and stability.
- Typical catalytically active hydrogenation metals include chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum, and palladium.
- the metals platinum and palladium are especially preferred, with platinum most especially preferred. If platinum and/or palladium is used, the total amount of active hydrogenation metal is typically in the range of 0.1 to 5 weight percent of the total catalyst, usually from 0.1 to 2 weight percent, and not to exceed
- the refractory oxide support may be selected from those oxide supports which are conventionally used for catalysts, including silica, alumina, silica- alumina, magnesia, titania and combinations thereof.
- the intermediate pore molecular sieve hydroisomerization catalyst is particularly suited for hydroisomerizing normal paraffins to produce a low cloud point, low pour point product.
- distillate fuel fractions recovered from the hydroisomerization step have reduced cloud points.
- the hydroisomerization step reduces the pour point of the heavy fraction, and permits at least a portion of the heavy fraction to be recovered for lubricant oils.
- the process of the present invention results in less cracking of the high boiling end of the high boiling waxy feed (i.e., less conversion of the high boiling end of the feed to lighter products). Accordingly, high quality lubricant base oils with high viscosity indexes, low pour points, and higher viscosities are produced. According to the process of the present invention, preferably less than 60 weight percent of the 650°F+ products is the feed is converted to 650°F- products. Therefore, with this process, cracking conversion is minimized while achieving low pour points in the products, hi addition, since there is less cracking, high yields of high quality lubricant base oil products are provided.
- the product of this hy ⁇ ocracking/hydroisomerization process is fractionated by conventional methods to provide at least a middle distillate fuel fraction and a heavy fraction.
- the fractionation can be accomplished by conventional methods of distillation with an appropriate cut point for isolating the middle distillate fuel fraction and heavy fraction.
- a lubricant base oil is isolated from heavy fraction.
- the heavy fraction may be fractionated by convention methods, including vacuum distillation, to provide the lubricant base oil fraction and optionally, a bottoms fraction may also be isolated.
- the bottoms fraction may be recycled to the hydrocracking reaction zone. When recycling all or a portion of the bottoms fraction, the bottoms fraction may be subjected to the hydrocracking step of the present invention alone or may be combined with another waxy hydrocarbon feedstock.
- a high quality lubricant base oil is isolated from the heavy fraction without the need for an additional dewaxing step.
- a high viscosity lubricant base oil is provided by the processes of the present invention due to less cracking of the high boiling end of the waxy feedstock. Preferably less than 60 weight percent of the 650 + in the feed is converted to 650°F- products.
- the lubricant base oil recovered from the process of the present invention has a viscosity index of greater than 130, preferably greater than 140, and more preferably greater than 150.
- the lubricant base oil provided also has a pour point of less than -15°C.
- the lubricant base oil has a viscosity of greater than 3 cSt at 100°C, preferably greater than 4 cSt at 100°C, and more preferably greater than 5 cSt at 100°C.
- the recovered lubricant oil may optionally be subjected to hydrofinishing in a mild hydrogenation process to improve its stability to heat and oxidation.
- the hydrofinishing can be conventionally carried out in the presence of a metallic hydrogenation catalyst such as, for example, platinum on alumina.
- the hydrofinishing can be carried out at a temperature of from about 190 to about 340°C, a pressure of from about 300 to about 3000 psig (2.76 to 20.7 Mpa), a LHSV between about 0.1 and 20, and hydrogen recycle rates of about 400 to about 1500 SCF/bbl.
- the lubricant base oil recovered from the processes of the present invention may be used as such as a lubricant, or it may be blended with another refined lubricant stock having different properties.
- the lubricant base oil, prior to use as a lubricant may be blended with one or more additives, for example, as antioxidants, extreme pressure additives, viscosity index improvers, and the like.
- FIGURE illustrates a schematic representation of one embodiment of the present invention.
- a waxy hydrocarbon feedstock (10) is fed into a single reactor (100) containing a hydrocracking catalyst in a hydrocracking zone (110) and a hydroisomerization catalyst in a hydroisomerization zone (120), wherein the hydrocracking zone (110) is above the hydroisomerization zone (120).
- the waxy hydrocarbon feedstock (10) is first contacted with the hydrocracking catalyst in the hydrocracking zone (110) and the effluent from the hydrocracking zone (110) is next contacted with the hydroisomerization catalyst in the hydroisomerization zone (120).
- the entire effluent (20) from the hydroisomerization zone (120) is then fractioned in a fractionator (200), providing a heavy fraction (30), a middle distillate fuel (50) and a lighter product (70).
- a lubricant base oil (60) and optionally a bottoms fraction (40) are obtained from the heavy fraction (30).
- the lubricant base oil has a viscosity index of greater than 130, a pour point of less than -15°C, and a viscosity at 100°C of greater than 3 cSt.
- the bottoms fraction (40) may be recycled to the hydrocracking zone (110) in the reactor (100).
- the fractionation also produces a middle distillate product (50).
- the lubricant base oil (60) may be optionally hydrofinished in a hychofinishing unit (300) to provide a hydro finished lube oil (70).
- Example 1 A 450°F+ Arab Heavy VGO first stage product was hydrocracked at 68% 700°F+ conversion at 1.2 hr "1 LHSV and 1800 psig over a nickel-tungsten/silica-alumina hydrocracking catalyst (Catalyst A), the 700°F+ bottoms had a +21°C pour point and 125 VI.
- Catalyst A nickel-tungsten/silica-alumina hydrocracking catalyst
- Catalyst B Pt SAPO-11 hydroisomerization catalyst at the same conditions yielded a 725°F+ product (4 cSt at 100°C) of -20°C pour point and 127 VI.
- Cloud point in the diesel cut was decreased and cetane index increased versus the case with Catalyst A alone.
- Total mid-distillate was 56.9 weight %, versus 53.1 weight % with Catalyst A alone, due in part to an extension of the diesel endpoint from 700°F to 725°F.
- Example 2 A light Fischer-Tropsch wax (Table I) was hydrocracked over a sulfided nickel-tungsten/silica-alumina catalyst followed at 1 hr "1 LHSV, 1000 psig, 685°F, and 6300 standard cubic feet (SCF)/Bbl. At these conditions, conversion below 650°F was 80.4 weight %. The liquid product was cut at about 350°F and about 675°F to give a diesel fraction. Yields and properties of the diesel cut and 675°F+ bottoms are given in Table II. The cloud point of the bottoms fraction (+29°C) was too high to be preferred for lube use.
- Example 3 The same feed as in Example 2 was hydrocracked over a sulfided 3/1 layered bed of the same catalyst as in Example 2 and then over a Pt/SAPO-11 catalyst bound with 15 weight % alumina. Conditions were the same as in Example 2, that is 1.0 hr "1 overall LHSV, 1000 psig, 685°F, and 6.3 MSCF/Bbl H 2 . Conversion below 650°F was 74.6 weigh %. The product was cut at about 350°F and about 650°F to give a diesel cut. Yields and properties of the diesel cut and 650°F+ bottoms are given in Table III. The diesel was high temperature stable by ASTM test D6468. Aromatics in the diesel were less than 0.5 weight %. The cetane index was very high (73.8) and the cloud point very low (-57°C). The 650°F+ stripper bottoms were found to be a 3 cSt (at 100°C) oil with low pour and cloud points and high VI.
- Example 4 The run of Example 3 was continued, but at a catalyst temperature of 670°F. At this temperature, conversion below 650°F was 40.1 weight %. Yields and properties of the 650°F+ stripper bottoms are given in Table IV. This is found to be a 3.4 cSt (at 100°C) oil of high VI.
- Example 5 A 700-1000°F hydrotreated Fischer-Tropsch Wax (Table V) was hydrocracked over the same layered bed catalyst system of Example 3. Conditions included a 1.0 hr "1 overall LHSV, reactor pressure of 300 psig, 680°F for the top catalyst and 690°F for the bottom catalyst, and 6.3 MSCF/Bbl H . Conversion below 650°F was 58.2 weight %. The product was cut at about 300°F and about 650°F to give a diesel cut. Yields and properties of the diesel cut and 650°F+ bottoms are given in Table VI. The diesel was high temperature stable by ASTM test D6468. Aromatics in the diesel were 6.1 weight %. The cetane index was high (67.6) and the cloud point was -44°C. The 650°F+ stripper bottoms were found to be a 5 cSt (at 100°C) oil with low pour and cloud points and very high VI.
- Example 6 A full boiling range hydrotreated Fischer-Tropsch Wax (Table VII), from which the feed of Table V was prepared, was hydrocracked over the same layered bed catalyst system of Example 3. Conditions included a 1.0 hr "1 overall LHSV, reactor pressure of 1000 psig, 680°F for the top catalyst and 691°F for the bottom catalyst, and 6.3 MSCF/Bbl H 2 . Conversion below 650°F was 45.9 weight %. Yields and properties of the 650°F+ stripper bottoms are given in Table VIII. This was found to be a 5.5 cSt (at 100°C) oil with low pour point and very high VI.
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JP2006517326A JP5481014B2 (en) | 2003-06-19 | 2004-06-16 | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds containing Fischer-Tropsch wax |
AU2004252511A AU2004252511B2 (en) | 2003-06-19 | 2004-06-16 | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including Fischer-Tropsch wax |
BRPI0411616-0A BRPI0411616A (en) | 2003-06-19 | 2004-06-16 | process for treating a waxy hydrocarbon feedstock |
GB0600805A GB2418673B (en) | 2003-06-19 | 2004-06-16 | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including fischer-tropsch wax |
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Also Published As
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GB0600805D0 (en) | 2006-02-22 |
NL1026464C2 (en) | 2005-08-09 |
JP2007520580A (en) | 2007-07-26 |
US20040256286A1 (en) | 2004-12-23 |
GB2418673B (en) | 2008-05-28 |
JP5481014B2 (en) | 2014-04-23 |
AU2004252511B2 (en) | 2010-02-25 |
CN1836028A (en) | 2006-09-20 |
AU2004252511A1 (en) | 2005-01-06 |
GB2418673A (en) | 2006-04-05 |
ZA200600303B (en) | 2007-11-28 |
CN100469858C (en) | 2009-03-18 |
NL1026464A1 (en) | 2004-12-21 |
WO2005001006A3 (en) | 2005-04-28 |
BRPI0411616A (en) | 2006-08-08 |
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