US20080045614A1 - Process to Make a Base Oil - Google Patents
Process to Make a Base Oil Download PDFInfo
- Publication number
- US20080045614A1 US20080045614A1 US11/628,691 US62869105A US2008045614A1 US 20080045614 A1 US20080045614 A1 US 20080045614A1 US 62869105 A US62869105 A US 62869105A US 2008045614 A1 US2008045614 A1 US 2008045614A1
- Authority
- US
- United States
- Prior art keywords
- fischer
- wax
- tropsch
- feed
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002199 base oil Substances 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- 239000003921 oil Substances 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 3
- 239000001993 wax Substances 0.000 description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- 239000002808 molecular sieve Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000011959 amorphous silica alumina Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- -1 e.g. Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004150 EU approved colour Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 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
- 238000001035 drying Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229940104869 fluorosilicate Drugs 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C10M109/00—Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
- C10M109/02—Reaction products
-
- 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
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/02—Specified values of viscosity or viscosity index
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products 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
- C10N2020/02—Viscosity; 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
- C10N2030/02—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
Definitions
- the invention is related to a process to prepare a base oil having a kinematic viscosity at 100° C. of greater than 7 cSt from a Fischer-Tropsch derived wax by performing first a hydro-isomerisation followed by a dewaxing step.
- a base oil having a kinematic viscosity at 100° C. of about 5 cSt can be obtained by subjecting a Fischer-Tropsch derived wax having a congealing point of about 70° C. and a T10 wt % recovery point of about 430° C. to a hydro-isomerisation step followed by a solvent or catalytic dewaxing step.
- the yield of base oil was reported to be about 40 wt % when performing the process by means of solvent dewaxing.
- a disadvantage of the process as disclosed in EP-A-776959 is that when base oils having a higher viscosity are desired significantly lower yields are found.
- the object of the present invention is thus to improve the yield of base oils having a kinematic viscosity of greater than 7, especially greater than 8 cSt at 100° C.
- the Fischer-Tropsch wax used as the feed for the present process is obtained via the well-known Fischer-Tropsch hydrocarbon synthesis process.
- Fischer-Tropsch hydrocarbon synthesis involves the preparation of hydrocarbons from a mixture of carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a suitable catalyst.
- the Fischer-Tropsch catalyst normally is selective for preparing paraffinic molecules, mostly straight-chain paraffins, and the product from a Fischer-Tropsch synthesis reaction therefore usually is a mixture of a large variety of paraffinic molecules.
- Those hydrocarbons that are gaseous or liquid at room temperature are recovered separately, for instance as fuel gas (C 5 —), solvent feedstocks and detergent feedstocks (up to C 17 ).
- the more heavy paraffins (C 18 +) are recovered as one or more wax fractions, commonly referred to as Fischer-Tropsch wax(es) or synthetic wax(es).
- Fischer-Tropsch wax(es) or synthetic wax(es) are useful as the feed, which meet the aforementioned requirements with respect to its T10wt % recovery boiling point.
- the Fischer-Tropsch wax may comprise iso-paraffins.
- the presence of iso-paraffins will however be relatively low.
- a measure of the amount of iso-paraffins is the oil content of the wax.
- the wax content as used in the description is measured according to the following procedure. 1 weight part of the to be measured oil fraction is diluted with 4 parts of a (50/50 vol/vol) mixture of methyl ethyl ketone and toluene, which is subsequently cooled to ⁇ 27° C. in a refrigerator. The mixture is subsequently filtered at ⁇ 27° C. The wax is removed from the filter and weighed. If reference is made to oil content a wt % value is meant which is 100% minus the wax content in wt %.
- the wax content is preferably above 50 wt %, more preferably above 60 wt % and even more preferably between 60 and 100 wt % as measured according to the above method.
- preferred Fischer-Tropsch wax feeds are those having a congealing point in the range of above 80° C. and more preferably between 90 and 150° C.
- Those Fischer-Tropsch waxes melting above 90° C. suitably have a kinematic viscosity at a temperature T, which is 10 to 20° C. higher than their melting point, in the range of from 8 to 15 mm 2 /s, preferably from 9 to 14 mm 2 /s.
- the hydrocarbon diluent used in step (a) may in principle be any hydrocarbon mixture having a T90 recovery point of below 400° C.
- the diluent is a paraffin fraction as obtained in the above referred to Fischer-Tropsch synthesis. More preferably it is a fraction boiling for more than 80 wt % between 250 and 400° C.
- the paraffin diluent may be a heavy Fischer-Tropsch derived gas oil or a substantially waxy product having a wax content of above 80 wt %, preferably above 90 wt %. Mixtures of such products may also be used.
- the feed to step (a) is prepared by performing a Fischer-Tropsch synthesis to prepare a Fischer-Tropsch synthesis product. Isolating, by means of distillation, from said Fischer-Tropsch synthesis product the Fischer-Tropsch wax as defined above, an intermediate wax product boiling for more than 80 wt % between 300 and 500° C. and a lower boiling fraction which is used as diluent as defined above. The heavy wax fraction and diluent fraction are combined to form the feed to step (a).
- the intermediate wax product is a paraffin wax product having a congealing point of between 45 and 80 or even as high as 90° C. and more preferably between 50 and 85° C.
- This wax product is preferably kept separate from the feed to step (a) and is suitably marketed as paraffin wax.
- the intermediate wax product may be further separated in two or more fractions resulting in wax products having a narrow carbon distribution.
- the Fischer-Tropsch wax may be subjected to a hydrogenation step prior to the above separation. Hydrogenation, or optionally a mild hydroisomerisation, may suitably be performed on the intermediate wax product after it has been isolated to obtain a marketable wax product.
- the non-hydrogenated blend can be used directly in step (a).
- the hydroconversion catalyst used in step (a) may in principle be any catalyst known in the art to be suitable for isomerising paraffinic molecules.
- suitable hydroconversion catalysts are those comprising a hydrogenation component supported on a refractory oxide carrier, such as amorphous silica-alumina, alumina, fluorided alumina, molecular sieves (zeolites) or mixtures of two or more of these.
- Suitable catalysts have been found to be those comprising a Group VIII metal, especially nickel, platinum or palladium and a silica-alumina carrier as will be described in more detail below.
- hydroconversion catalysts comprising platinum and/or palladium as the hydrogenation component.
- a very much preferred hydroconversion catalyst comprises platinum and palladium supported on an amorphous silica-alumina (ASA) carrier.
- ASA amorphous silica-alumina
- the platinum and/or palladium is suitably present in an amount of from 0.1 to 5.0% by weight, more suitably from 0.2 to 2.0% by weight, calculated as element and based on total weight of carrier. If both present, the weight ratio of platinum to palladium (calculated as element) may vary within wide limits, but suitably is in the range of from 0.05 to 10, more suitably 0.1 to 5.
- Suitable noble metal on ASA catalysts are, for instance, disclosed in WO-A-94/10264 and EP-A-0,582,347.
- Other suitable noble metal-based catalysts such as platinum on a fluorided alumina carrier, are disclosed in e.g. U.S. Pat. No. 5,059,299 and WO-A-92/20759.
- a second type of suitable hydroconversion catalysts are those comprising at least one Group VIB metal, preferably tungsten and/or molybdenum, and at least one non-noble Group VIII metal, preferably nickel and/or cobalt, as the hydrogenation component.
- both metals are present as oxides, sulphides or a combination thereof.
- the Group VIB metal is suitably present in an amount of from 1 to 35% by weight, more suitably from 5 to 30% by weight, calculated as element and based on total weight of catalyst.
- the non-noble Group VIII metal is suitably present in an amount of from 1 to 25% wt, preferably 2 to 15% wt, calculated as element and based on total weight of carrier.
- a hydroconversion catalyst of this type which has been found particularly suitable is a catalyst comprising nickel and tungsten supported on fluorided alumina.
- a preferred catalyst which can be used in a non-sulphided form comprises a non-noble Group VIII metal, e.g., iron, nickel, in conjunction with a Group IB metal, e.g., copper, supported on an acidic support.
- the catalyst has a surface area in the range of 200-500 m 2 /gm, preferably 0.35 to 0.80 ml/gm, as determined by water adsorption, and a bulk density of about 0.5-1.0 g/ml.
- the catalyst support is preferably an amorphous silica-alumina where the alumina is present in amounts of less than about 30 wt %, preferably 5-30 wt %, more preferably 10-20 wt %.
- the support may contain small amounts, e.g., 20-30 wt %, of a binder, e.g., alumina, silica, Group IVA metal oxides, and various types of clays, magnesia, etc., preferably alumina.
- a binder e.g., alumina, silica, Group IVA metal oxides, and various types of clays, magnesia, etc., preferably alumina.
- the catalyst is prepared by co-impregnating the metals from solutions onto the support, drying at 100-150° C., and calcining in air at 200-550° C.
- the Group VIII metal is present in amounts of about 15 wt % or less, preferably 1-12 wt %, while the Group IB metal is usually present in lesser amounts, e.g., 1:2 to about 1:20 ratio respecting the Group VIII metal.
- a typical catalyst is shown below: Ni, wt % 2.5-3.5 Cu, wt % 0.25-0.35 Al 2 O 3 —SiO 2 wt % 65-75 Al 2 O 3 (binder) wt % 25-30 Surface Area 290-325 m 2 /gm Pore Volume (Hg) 0.35-0.45 ml/gm Bulk Density 0.58-0.68 g/ml
- Suitable hydroconversion catalysts are those based on zeolitic materials, suitably comprising at least one Group VIII metal component, preferably Pt and/or Pd, as the hydrogenation component.
- Suitable zeolitic materials include Zeolite beta, Zeolite Y, Ultra Stable Y, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-35, SSZ-32, ferrierite, zeolite beta, mordenite and silica-aluminophosphates, such as SAPO-11 and SAPO-31 or said list and ZSM-48.
- suitable hydroisomerisation catalysts are, for instance, described in WO-A-92/01657.
- the hydroconversion conditions applied in step (a) are those known to be suitable in hydro-isomerisation operations. Suitable conditions, then, involve operating temperatures in the range of from 275 to 450° C., preferably 300 to 425° C., a hydrogen partial pressure in the range of from 10 to 250 bar, suitably 25 to 200 bar, a weight hourly space velocity (WHSV) in the range of from 0.1 to 10 kg/l/h, preferably 0.2 to 5 kg/l/h, and a gas rate in the range of from 100 to 5,000 Nl/kg, preferably 500 to 3,000 Nl/kg.
- WHSV weight hourly space velocity
- step (a) the conditions in step (a) are so chosen that the wax conversion is preferably between 40 and 90 wt % and more preferably between 60 and 90 wt %.
- the effluent of step (a) may be directly used as feed to a dewaxing step. Especially if catalytic dewaxing is applied in step (b) it has been found advantageous to perform step (a) and (b) in a series flow configuration, thus without any intermediate separation of lower boiling compounds. Alternatively one may separate from the effluent of step (a) a lighter fraction such to reduce the volume of feed to step (a).
- the effective cutpoint of such a separation or said otherwise of the heavy remaining fraction is suitably in the range of from 400 to 550° C.
- the effective cutpoint of the heavy fraction is the temperature above which at least at least 85% by weight and preferably at least 90% by weight, of the hydrocarbons present in this heavy fraction has its boiling point.
- This separation or fractionation can be achieved by techniques known in the art, such as atmospheric and vacuum distillation or vacuum flashing.
- step (b) the base oil precursor fraction obtained in step (a) is subjected to a pour point reducing treatment.
- a pour point reducing treatment is understood every process wherein the pour point of the base oil is reduced by more than 10° C., preferably more than 20° C., more preferably more than 25° C.
- the pour point reducing treatment can be performed by means of a so-called solvent dewaxing process or by means of a catalytic dewaxing process.
- Solvent dewaxing is well known to those skilled in the art and involves admixture of one or more solvents and/or wax precipitating agents with the base oil precursor fraction and cooling the mixture to a temperature in the range of from ⁇ 10° C. to ⁇ 40° C., preferably in the range of from ⁇ 20° C. to ⁇ 35° C., to separate the wax from the oil.
- the oil containing the wax is usually filtered through a filter cloth which can be made of textile fibres, such as cotton; porous metal cloth; or cloth made of synthetic materials.
- Dichloromethane and mixtures of methyl ethyl ketone and toluene or methyl ethyl ketone and methyl isobutyl ketone are generally preferred. Examples of these and other suitable solvent dewaxing processes are described in Lubricant Base Oil and Wax Processing, Avilino Sequeira, Jr, Marcel Dekker Inc., New York, 1994, Chapter 7.
- the slack wax obtained in the solvent dewaxing treatment of step (b) is suitably recycled, i.e. all or part of this slack wax is routed back to the hydroconversion step (a), most conveniently by blending it with the fresh Fisher-Tropsch wax feed, provided the feed characterisation is still within the definition according to the present invention. In this way the final yield of lubricating base oil can be maximised.
- step (b) is performed by means of a catalytic dewaxing process.
- a catalytic dewaxing process it has been found that base oils having a pour point of even below ⁇ 40° C. can be prepared when starting from a base oil precursor fraction as obtained in step (a) of the present process.
- the catalytic dewaxing process can be performed by any process wherein in the presence of a catalyst and hydrogen the pour point of the base oil precursor fraction is reduced as specified above.
- Suitable dewaxing catalysts are heterogeneous catalysts comprising a molecular sieve and optionally in combination with a metal having a hydrogenation function, such as the Group VIII metals.
- Molecular sieves, and more suitably intermediate pore size zeolites have shown a good catalytic ability to reduce the pour point of the base oil precursor fraction under catalytic dewaxing conditions.
- the intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 nm.
- Suitable intermediate pore size zeolites are mordenite, ZSM-5, ZSM-12, ZSM-22, ZSM-23, SSZ-32, ZSM-35 and ZSM-48.
- Another preferred group of molecular sieves are the silica-aluminaphosphate (SAPO) materials of which SAPO-11 is most preferred as for example described in U.S. Pat. No. 4,859,311.
- SAPO silica-aluminaphosphate
- ZSM-5 may optionally be used in its HZSM-5 form in the absence of any Group VIII metal.
- the other molecular sieves are preferably used in combination with an added Group VIII metal.
- Suitable Group VIII metals are nickel, cobalt, platinum and palladium.
- the dewaxing catalyst suitably also comprises a binder.
- the binder can be a synthetic or naturally occurring (inorganic) substance, for example clay, silica and/or metal oxides. Natural occurring clays are for example of the montmorillonite and kaolin families.
- the binder is preferably a porous binder material, for example a refractory oxide of which examples are: alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions for example silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. More preferably a low acidity refractory oxide binder material, which is essentially free of alumina, is used. Examples of these binder materials are silica, zirconia, titanium dioxide, germanium dioxide and mixtures of two or more of these of which examples are listed above. The most preferred binder is silica.
- a refractory oxide of which examples are: alumina, silica-alumina, silica-magnesia, si
- a preferred class of dewaxing catalysts comprise intermediate zeolite crystallites as described above and a low acidity refractory oxide binder material which is essentially free of alumina as described above, wherein the surface of the aluminosilicate zeolite crystallites has been modified by subjecting the aluminosilicate zeolite crystallites to a surface dealumination treatment.
- a preferred dealumination treatment is by contacting an extrudate of the binder and the zeolite with an aqueous solution of a fluorosilicate salt as described in for example U.S. Pat. No. 5,157,191 or WO-A-0029511.
- dewaxing catalysts as described above are silica bound and dealuminated Pt/ZSM-5, silica bound and dealuminated Pt/ZSM-23, silica bound and dealuminated Pt/ZSM-12, silica bound and dealuminated Pt/ZSM-22, as for example described in WO-A-0029511 and EP-B-832171.
- Catalytic dewaxing conditions are known in the art and typically involve operating temperatures in the range of from 200 to 500° C., suitably from 250 to 400° C., hydrogen pressures in the range of from 10 to 200 bar, preferably from 40 to 70 bar, weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per litre of catalyst per hour (kg/l/hr), suitably from 0.2 to 5 kg/l/hr, more suitably from 0.5 to 3 kg/l/hr and hydrogen to oil ratios in the range of from 100 to 2,000 litres of hydrogen per litre of oil.
- WHSV weight hourly space velocities
- steps (a) and (b) may be performed in one step using the same catalyst comprising a molecular sieve.
- steps (a) and (b) can be performed using a molecular sieve comprising catalyst in both steps wherein the pore opening of the molecular sieve in step (a) is larger than the molecular sieve used in step (b) suitably making use of the catalysts as exemplified at steps (a) and (b) above.
- wax feedstocks A and D were prepared by hydrogenation of a Fischer-Tropsch synthesis product followed by distillate separation using wiped film evaporators.
- Products B and C are the intermediate wax products as discussed also above. These wax products B and C having a narrow carbon distribution may find application in for example hot melt adhesives, printing inks, cable filling, match sticks, corrugated board, fibre board and PVC lubricants.
- the unique white colour of these waxes make them ideal for application requiring colour additive, e.g. crayons, candles, graphic arts and other decorative items.
- the opaque appearance produces true colour brilliance with minimum colouring agents.
- a Fischer-Tropsch wax feed B having the properties as listed in Table I was contacted with a fluorided NiW/alumina catalyst (5.0% wt Ni, 23.1% wt W, 4.6% wt F, all based on total weight of carrier) at a temperature ranging from 370 to 400° C., a hydrogen partial pressure of 140 bar, a WHSV of 1 kg/l/h and a gas rate of 1,500 Nl/kg.
- the effluent was fractionated and the 390° C.+ fraction (obtained at a yield of 87.8% by weight based on total effluent) was subsequently solvent dewaxed using MEK/toluene at ⁇ 20° C. It was found that the final base oil yield had a maximum at 388° C. reactor temperature.
- Table 2 the results are presented.
- Example 2 The Fischer-Tropsch feed as used in Example 1 was contacted with a PtPd/ASA (0.3% wt Pt, 1% wt Pd, ASA: silica/alumina molar ratio is 55/45) catalyst at a different temperatures, whilst the other conditions were the same as applied in Example 1.
- the effluent was fractionated and the 390° C.+ fraction and the residue was subsequently solvent dewaxed using MEK/toluene at ⁇ 20° C.
- the results are presented in FIG. 1 .
- the oil obtained at the highest yield had a VI of 150, a pour point of ⁇ 24° C., a kinematic viscosity at 100° C. (Vk100) of 9.161 mm 2 /s and a Noack volatility of 5.8% by weight.
- Example 2 but at a hydrogen partial pressure of 90 bar. See FIG. 1 for results.
- the oil obtained at the highest yield had a VI of 146, a pour point of ⁇ 27° C., a kinematic viscosity at 100° C. (Vk100) of 8.13 mm 2 /s and a Noack volatility of 7.2% by weight.
- Example 2 but at a hydrogen partial pressure of 40 bar. See FIG. 1 for results.
- the oil obtained at the highest yield had a VI of 151, a pour point of ⁇ 24° C., a kinematic viscosity at 100° C. (Vk100) of 8.317 mm 2 /s and a Noack volatility of 6.7% by weight.
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Abstract
Process to prepare a base oil having a kinematic viscosity at 100° C. of greater than 6 cSt from a Fischer-Tropsch derived wax having a T10wt % recovery boiling point of above 500° C. by performing the following steps, (a) contacting a feed comprising the Fischer-Tropsch wax and between 5 and 40 wt % of a hydrocarbon diluent having a T90wt % recovery point of below 400° C. with a hydro-isomerisation catalyst under hydro-isomerisation, and (b) dewaxing the isomerised product of step (a) and isolating the base oil from the dewaxed oil obtained in step (b).
Description
- The invention is related to a process to prepare a base oil having a kinematic viscosity at 100° C. of greater than 7 cSt from a Fischer-Tropsch derived wax by performing first a hydro-isomerisation followed by a dewaxing step.
- Such a process is described in EP-A-776959. This publication discloses that a base oil having a kinematic viscosity at 100° C. of about 5 cSt can be obtained by subjecting a Fischer-Tropsch derived wax having a congealing point of about 70° C. and a T10 wt % recovery point of about 430° C. to a hydro-isomerisation step followed by a solvent or catalytic dewaxing step. The yield of base oil was reported to be about 40 wt % when performing the process by means of solvent dewaxing.
- A disadvantage of the process as disclosed in EP-A-776959 is that when base oils having a higher viscosity are desired significantly lower yields are found.
- The object of the present invention is thus to improve the yield of base oils having a kinematic viscosity of greater than 7, especially greater than 8 cSt at 100° C.
- This object is achieved with the following process. Process to prepare a base oil having a kinematic viscosity at 100° C. of greater than 6 cSt from a Fischer-Tropsch derived wax having a T10wt % recovery boiling point of above 500° C. by performing the following steps,
-
- (a) contacting a feed comprising the Fischer-Tropsch wax and between 5 and 40 wt % of a hydrocarbon diluent having a T90 wt % recovery point of below 400° C. with a hydro-isomerisation catalyst under hydro-isomerisation conditions,
- (b) dewaxing the isomerised product of step (a) and isolating the base oil from the dewaxed oil.
Applicants found that not only the yield to the high viscosity base oil can be improved also the viscosity of the end base oil is higher when processing a feed also containing a diluent.
- The Fischer-Tropsch wax used as the feed for the present process, is obtained via the well-known Fischer-Tropsch hydrocarbon synthesis process. In general, such Fischer-Tropsch hydrocarbon synthesis involves the preparation of hydrocarbons from a mixture of carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a suitable catalyst. The Fischer-Tropsch catalyst normally is selective for preparing paraffinic molecules, mostly straight-chain paraffins, and the product from a Fischer-Tropsch synthesis reaction therefore usually is a mixture of a large variety of paraffinic molecules. Those hydrocarbons that are gaseous or liquid at room temperature are recovered separately, for instance as fuel gas (C5—), solvent feedstocks and detergent feedstocks (up to C17). The more heavy paraffins (C18+) are recovered as one or more wax fractions, commonly referred to as Fischer-Tropsch wax(es) or synthetic wax(es). For the purpose of the present invention only those Fischer-Tropsch waxes are useful as the feed, which meet the aforementioned requirements with respect to its T10wt % recovery boiling point.
- The Fischer-Tropsch wax may comprise iso-paraffins. The presence of iso-paraffins will however be relatively low. A measure of the amount of iso-paraffins is the oil content of the wax. The wax content as used in the description is measured according to the following procedure. 1 weight part of the to be measured oil fraction is diluted with 4 parts of a (50/50 vol/vol) mixture of methyl ethyl ketone and toluene, which is subsequently cooled to −27° C. in a refrigerator. The mixture is subsequently filtered at −27° C. The wax is removed from the filter and weighed. If reference is made to oil content a wt % value is meant which is 100% minus the wax content in wt %. The wax content is preferably above 50 wt %, more preferably above 60 wt % and even more preferably between 60 and 100 wt % as measured according to the above method.
- Within the limits defined hereinbefore, preferred Fischer-Tropsch wax feeds are those having a congealing point in the range of above 80° C. and more preferably between 90 and 150° C. Those Fischer-Tropsch waxes melting above 90° C. suitably have a kinematic viscosity at a temperature T, which is 10 to 20° C. higher than their melting point, in the range of from 8 to 15 mm2/s, preferably from 9 to 14 mm2/s.
- The hydrocarbon diluent used in step (a) may in principle be any hydrocarbon mixture having a T90 recovery point of below 400° C. Preferably the diluent is a paraffin fraction as obtained in the above referred to Fischer-Tropsch synthesis. More preferably it is a fraction boiling for more than 80 wt % between 250 and 400° C. The paraffin diluent may be a heavy Fischer-Tropsch derived gas oil or a substantially waxy product having a wax content of above 80 wt %, preferably above 90 wt %. Mixtures of such products may also be used.
- In a preferred embodiment the feed to step (a) is prepared by performing a Fischer-Tropsch synthesis to prepare a Fischer-Tropsch synthesis product. Isolating, by means of distillation, from said Fischer-Tropsch synthesis product the Fischer-Tropsch wax as defined above, an intermediate wax product boiling for more than 80 wt % between 300 and 500° C. and a lower boiling fraction which is used as diluent as defined above. The heavy wax fraction and diluent fraction are combined to form the feed to step (a). The intermediate wax product is a paraffin wax product having a congealing point of between 45 and 80 or even as high as 90° C. and more preferably between 50 and 85° C. This wax product is preferably kept separate from the feed to step (a) and is suitably marketed as paraffin wax. The intermediate wax product may be further separated in two or more fractions resulting in wax products having a narrow carbon distribution. The Fischer-Tropsch wax may be subjected to a hydrogenation step prior to the above separation. Hydrogenation, or optionally a mild hydroisomerisation, may suitably be performed on the intermediate wax product after it has been isolated to obtain a marketable wax product. The non-hydrogenated blend can be used directly in step (a).
- The hydroconversion catalyst used in step (a) may in principle be any catalyst known in the art to be suitable for isomerising paraffinic molecules. In general, suitable hydroconversion catalysts are those comprising a hydrogenation component supported on a refractory oxide carrier, such as amorphous silica-alumina, alumina, fluorided alumina, molecular sieves (zeolites) or mixtures of two or more of these. Suitable catalysts have been found to be those comprising a Group VIII metal, especially nickel, platinum or palladium and a silica-alumina carrier as will be described in more detail below.
- One type of preferred catalysts to be applied in the hydroconversion step in accordance with the present invention are hydroconversion catalysts comprising platinum and/or palladium as the hydrogenation component. A very much preferred hydroconversion catalyst comprises platinum and palladium supported on an amorphous silica-alumina (ASA) carrier. The platinum and/or palladium is suitably present in an amount of from 0.1 to 5.0% by weight, more suitably from 0.2 to 2.0% by weight, calculated as element and based on total weight of carrier. If both present, the weight ratio of platinum to palladium (calculated as element) may vary within wide limits, but suitably is in the range of from 0.05 to 10, more suitably 0.1 to 5. Examples of suitable noble metal on ASA catalysts are, for instance, disclosed in WO-A-94/10264 and EP-A-0,582,347. Other suitable noble metal-based catalysts, such as platinum on a fluorided alumina carrier, are disclosed in e.g. U.S. Pat. No. 5,059,299 and WO-A-92/20759.
- A second type of suitable hydroconversion catalysts are those comprising at least one Group VIB metal, preferably tungsten and/or molybdenum, and at least one non-noble Group VIII metal, preferably nickel and/or cobalt, as the hydrogenation component. Usually both metals are present as oxides, sulphides or a combination thereof. The Group VIB metal is suitably present in an amount of from 1 to 35% by weight, more suitably from 5 to 30% by weight, calculated as element and based on total weight of catalyst. The non-noble Group VIII metal is suitably present in an amount of from 1 to 25% wt, preferably 2 to 15% wt, calculated as element and based on total weight of carrier. A hydroconversion catalyst of this type which has been found particularly suitable is a catalyst comprising nickel and tungsten supported on fluorided alumina.
- A preferred catalyst which can be used in a non-sulphided form comprises a non-noble Group VIII metal, e.g., iron, nickel, in conjunction with a Group IB metal, e.g., copper, supported on an acidic support. The catalyst has a surface area in the range of 200-500 m2/gm, preferably 0.35 to 0.80 ml/gm, as determined by water adsorption, and a bulk density of about 0.5-1.0 g/ml. The catalyst support is preferably an amorphous silica-alumina where the alumina is present in amounts of less than about 30 wt %, preferably 5-30 wt %, more preferably 10-20 wt %. Also, the support may contain small amounts, e.g., 20-30 wt %, of a binder, e.g., alumina, silica, Group IVA metal oxides, and various types of clays, magnesia, etc., preferably alumina.
- The preparation of amorphous silica-alumina microspheres has been described in Ryland, Lloyd B., Tamele, M. W., and Wilson, J. N., Cracking Catalysts, Catalysis: volume VII, Ed. Paul H. Emmett, Reinhold Publishing Corporation, New York, 1960, pp. 5-9.
- The catalyst is prepared by co-impregnating the metals from solutions onto the support, drying at 100-150° C., and calcining in air at 200-550° C. The Group VIII metal is present in amounts of about 15 wt % or less, preferably 1-12 wt %, while the Group IB metal is usually present in lesser amounts, e.g., 1:2 to about 1:20 ratio respecting the Group VIII metal.
- A typical catalyst is shown below:
Ni, wt % 2.5-3.5 Cu, wt % 0.25-0.35 Al2O3—SiO2 wt % 65-75 Al2O3 (binder) wt % 25-30 Surface Area 290-325 m2/gm Pore Volume (Hg) 0.35-0.45 ml/gm Bulk Density 0.58-0.68 g/ml - Another class of suitable hydroconversion catalysts are those based on zeolitic materials, suitably comprising at least one Group VIII metal component, preferably Pt and/or Pd, as the hydrogenation component. Suitable zeolitic materials, then, include Zeolite beta, Zeolite Y, Ultra Stable Y, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-35, SSZ-32, ferrierite, zeolite beta, mordenite and silica-aluminophosphates, such as SAPO-11 and SAPO-31 or said list and ZSM-48. Examples of suitable hydroisomerisation catalysts are, for instance, described in WO-A-92/01657.
- The hydroconversion conditions applied in step (a) are those known to be suitable in hydro-isomerisation operations. Suitable conditions, then, involve operating temperatures in the range of from 275 to 450° C., preferably 300 to 425° C., a hydrogen partial pressure in the range of from 10 to 250 bar, suitably 25 to 200 bar, a weight hourly space velocity (WHSV) in the range of from 0.1 to 10 kg/l/h, preferably 0.2 to 5 kg/l/h, and a gas rate in the range of from 100 to 5,000 Nl/kg, preferably 500 to 3,000 Nl/kg.
- Suitably the conditions in step (a) are so chosen that the wax conversion is preferably between 40 and 90 wt % and more preferably between 60 and 90 wt %.
- The effluent of step (a) may be directly used as feed to a dewaxing step. Especially if catalytic dewaxing is applied in step (b) it has been found advantageous to perform step (a) and (b) in a series flow configuration, thus without any intermediate separation of lower boiling compounds. Alternatively one may separate from the effluent of step (a) a lighter fraction such to reduce the volume of feed to step (a). The effective cutpoint of such a separation or said otherwise of the heavy remaining fraction is suitably in the range of from 400 to 550° C. The effective cutpoint of the heavy fraction is the temperature above which at least at least 85% by weight and preferably at least 90% by weight, of the hydrocarbons present in this heavy fraction has its boiling point. This separation or fractionation can be achieved by techniques known in the art, such as atmospheric and vacuum distillation or vacuum flashing.
- In step (b) the base oil precursor fraction obtained in step (a) is subjected to a pour point reducing treatment. With a pour point reducing treatment is understood every process wherein the pour point of the base oil is reduced by more than 10° C., preferably more than 20° C., more preferably more than 25° C.
- The pour point reducing treatment can be performed by means of a so-called solvent dewaxing process or by means of a catalytic dewaxing process. Solvent dewaxing is well known to those skilled in the art and involves admixture of one or more solvents and/or wax precipitating agents with the base oil precursor fraction and cooling the mixture to a temperature in the range of from −10° C. to −40° C., preferably in the range of from −20° C. to −35° C., to separate the wax from the oil. The oil containing the wax is usually filtered through a filter cloth which can be made of textile fibres, such as cotton; porous metal cloth; or cloth made of synthetic materials. Examples of solvents which may be employed in the solvent dewaxing process are C3-C6 ketones (e.g. methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof), C6-C10 aromatic hydrocarbons (e.g. toluene), mixtures of ketones and aromatics (e.g. methyl ethyl ketone and toluene), autorefrigerative solvents such as liquefied, normally gaseous C2-C4 hydrocarbons such as propane, propylene, butane, butylene and mixtures thereof. Dichloromethane and mixtures of methyl ethyl ketone and toluene or methyl ethyl ketone and methyl isobutyl ketone are generally preferred. Examples of these and other suitable solvent dewaxing processes are described in Lubricant Base Oil and Wax Processing, Avilino Sequeira, Jr, Marcel Dekker Inc., New York, 1994, Chapter 7.
- The slack wax obtained in the solvent dewaxing treatment of step (b) is suitably recycled, i.e. all or part of this slack wax is routed back to the hydroconversion step (a), most conveniently by blending it with the fresh Fisher-Tropsch wax feed, provided the feed characterisation is still within the definition according to the present invention. In this way the final yield of lubricating base oil can be maximised.
- Preferably step (b) is performed by means of a catalytic dewaxing process. With such a process it has been found that base oils having a pour point of even below −40° C. can be prepared when starting from a base oil precursor fraction as obtained in step (a) of the present process.
- The catalytic dewaxing process can be performed by any process wherein in the presence of a catalyst and hydrogen the pour point of the base oil precursor fraction is reduced as specified above. Suitable dewaxing catalysts are heterogeneous catalysts comprising a molecular sieve and optionally in combination with a metal having a hydrogenation function, such as the Group VIII metals. Molecular sieves, and more suitably intermediate pore size zeolites, have shown a good catalytic ability to reduce the pour point of the base oil precursor fraction under catalytic dewaxing conditions. Preferably the intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 nm. Suitable intermediate pore size zeolites are mordenite, ZSM-5, ZSM-12, ZSM-22, ZSM-23, SSZ-32, ZSM-35 and ZSM-48. Another preferred group of molecular sieves are the silica-aluminaphosphate (SAPO) materials of which SAPO-11 is most preferred as for example described in U.S. Pat. No. 4,859,311. ZSM-5 may optionally be used in its HZSM-5 form in the absence of any Group VIII metal. The other molecular sieves are preferably used in combination with an added Group VIII metal. Suitable Group VIII metals are nickel, cobalt, platinum and palladium. Examples of possible combinations are Pt/ZSM-35, Ni/ZSM-5, Pt/ZSM-23, Pd/ZSM-23, Pt/ZSM-48 and Pt/SAPO-11. Further details and examples of suitable molecular sieves and dewaxing conditions are for example described in WO-A-9718278, U.S. Pat. No. 4,343,692, U.S. Pat. No. 5,053,373, U.S. Pat. No. 5,252,527 and U.S. Pat. No. 4,574,043.
- The dewaxing catalyst suitably also comprises a binder. The binder can be a synthetic or naturally occurring (inorganic) substance, for example clay, silica and/or metal oxides. Natural occurring clays are for example of the montmorillonite and kaolin families. The binder is preferably a porous binder material, for example a refractory oxide of which examples are: alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions for example silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. More preferably a low acidity refractory oxide binder material, which is essentially free of alumina, is used. Examples of these binder materials are silica, zirconia, titanium dioxide, germanium dioxide and mixtures of two or more of these of which examples are listed above. The most preferred binder is silica.
- A preferred class of dewaxing catalysts comprise intermediate zeolite crystallites as described above and a low acidity refractory oxide binder material which is essentially free of alumina as described above, wherein the surface of the aluminosilicate zeolite crystallites has been modified by subjecting the aluminosilicate zeolite crystallites to a surface dealumination treatment. A preferred dealumination treatment is by contacting an extrudate of the binder and the zeolite with an aqueous solution of a fluorosilicate salt as described in for example U.S. Pat. No. 5,157,191 or WO-A-0029511. Examples of suitable dewaxing catalysts as described above are silica bound and dealuminated Pt/ZSM-5, silica bound and dealuminated Pt/ZSM-23, silica bound and dealuminated Pt/ZSM-12, silica bound and dealuminated Pt/ZSM-22, as for example described in WO-A-0029511 and EP-B-832171.
- Catalytic dewaxing conditions are known in the art and typically involve operating temperatures in the range of from 200 to 500° C., suitably from 250 to 400° C., hydrogen pressures in the range of from 10 to 200 bar, preferably from 40 to 70 bar, weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per litre of catalyst per hour (kg/l/hr), suitably from 0.2 to 5 kg/l/hr, more suitably from 0.5 to 3 kg/l/hr and hydrogen to oil ratios in the range of from 100 to 2,000 litres of hydrogen per litre of oil. By varying the temperature between 275, suitably between 315 and 375° C. at between 40-70 bars, in the catalytic dewaxing step it is possible to prepare base oils having different pour point specifications varying from suitably −10 to −60° C.
- Optionally steps (a) and (b) may be performed in one step using the same catalyst comprising a molecular sieve. Optionally steps (a) and (b) can be performed using a molecular sieve comprising catalyst in both steps wherein the pore opening of the molecular sieve in step (a) is larger than the molecular sieve used in step (b) suitably making use of the catalysts as exemplified at steps (a) and (b) above.
- The invention is now further illustrated by the following examples without restricting the scope of the invention to these specific embodiments.
- In the experiments use was made of wax feedstocks A and D. These wax feedstocks were prepared by hydrogenation of a Fischer-Tropsch synthesis product followed by distillate separation using wiped film evaporators. Products B and C are the intermediate wax products as discussed also above. These wax products B and C having a narrow carbon distribution may find application in for example hot melt adhesives, printing inks, cable filling, match sticks, corrugated board, fibre board and PVC lubricants. The unique white colour of these waxes make them ideal for application requiring colour additive, e.g. crayons, candles, graphic arts and other decorative items. The opaque appearance produces true colour brilliance with minimum colouring agents.
TABLE 1 feedstock A B C D Kinematic 4.663 n.a. n.a. n.a. viscosity at 40° C. (cSt) Kinematic n.a. 2.929 5.520 n.a. viscosity at 100° C.(cSt) Kinematic n.a. n.a. n.a. 12.97 viscosity at 120° C.(cSt) Congealing 30 50 70 100 point (° C.) Initial boiling 287 316 337 492 point (° C.) T 10 wt %305 362 432 530 recovery point (° C.) T 50 wt %337 405 483 591 recovery point (° C.) T 90 wt % 362 437 529 655 recovery point (° C.) Final boiling 389 460 575 685 point
n.a. = not analysed
Comparative Experiment A - A Fischer-Tropsch wax feed B having the properties as listed in Table I was contacted with a fluorided NiW/alumina catalyst (5.0% wt Ni, 23.1% wt W, 4.6% wt F, all based on total weight of carrier) at a temperature ranging from 370 to 400° C., a hydrogen partial pressure of 140 bar, a WHSV of 1 kg/l/h and a gas rate of 1,500 Nl/kg. The effluent was fractionated and the 390° C.+ fraction (obtained at a yield of 87.8% by weight based on total effluent) was subsequently solvent dewaxed using MEK/toluene at −20° C. It was found that the final base oil yield had a maximum at 388° C. reactor temperature. In table 2 the results are presented.
- Comparative Experiment B
- Experiment A was repeated for feed C at various reactor temperatures ranging from 383 to 399° C. It was seen that the final base oil yield had a maximum at 389° C. reactor temperature. In table 2 the results are presented.
- Comparative Experiment C
- Experiment A was repeated for feed D at a reactor temperature of 409 and 420° C. At 409 a maximum base oil yield was observed. In table 2 the results are presented.
- Experiment A was repeated except that the feed consisted of 20 wt % of feed A and 80 wt % of feed D. The reactor temperature ranged from 403 to 420° C. The results are presented in Table 2.
TABLE 2 Ex. A B C C 1 1 1 Feed Feed B Feed C Feed D Feed D 20% 20% 20% Feed Feed Feed A/80% A/80% A/80% feed D feed D feed D Reactor 388 389 409 420 395 405 420 temperature Base oil 27.3 47.5 27.4 18.2 31.7 40.6 <3.7 yield (wt % on feed) Pour point −18 −15 −18 −18 −21 −18 n.a. (° C.) Kinematic 3.147 4.712 7.240 7.240 8.986 8.495 n.a. viscosity at 100° C. (cSt) Viscosity 145 148 148 148 154 157 n.a. Index Noack 23.1 9.0 7.2 7.2 4.4 5.9 n.a. volatility (wt %) - The Fischer-Tropsch feed as used in Example 1 was contacted with a PtPd/ASA (0.3% wt Pt, 1% wt Pd, ASA: silica/alumina molar ratio is 55/45) catalyst at a different temperatures, whilst the other conditions were the same as applied in Example 1. The effluent was fractionated and the 390° C.+ fraction and the residue was subsequently solvent dewaxed using MEK/toluene at −20° C.
- The results are presented in
FIG. 1 . In this FIGURE also some results of Examples according to Example 1 are presented for comparison reasons. The oil obtained at the highest yield had a VI of 150, a pour point of −24° C., a kinematic viscosity at 100° C. (Vk100) of 9.161 mm2/s and a Noack volatility of 5.8% by weight. - As Example 2 but at a hydrogen partial pressure of 90 bar. See
FIG. 1 for results. The oil obtained at the highest yield had a VI of 146, a pour point of −27° C., a kinematic viscosity at 100° C. (Vk100) of 8.13 mm2/s and a Noack volatility of 7.2% by weight. - As Example 2 but at a hydrogen partial pressure of 40 bar. See
FIG. 1 for results. The oil obtained at the highest yield had a VI of 151, a pour point of −24° C., a kinematic viscosity at 100° C. (Vk100) of 8.317 mm2/s and a Noack volatility of 6.7% by weight.
Claims (8)
1. A process to prepare a base oil having a kinematic viscosity at 100° C. of greater than 6 cSt from a Fischer-Tropsch derived wax having a T10wt % recovery boiling point of above 500° C. comprising:
(a1) performing a Fischer-Tropsch synthesis to prepare a Fischer-Tropsch synthesis product;
(a2) isolating, by means of distillation, from said Fischer-Tropsch synthesis product a Fischer-Tropsch wax, an intermediate wax product boiling for more than 80 wt % between 300 and 500° C., and a hydrocarbon diluent having a T90 wt % recovery point of below 400° C.; and
(a3) combining the Fischer-Tropsch wax and the diluent to form a feed to step (a);
(a) contacting the feed comprising the Fischer-Tropsch wax and between 5 and 40 wt % of a hydrocarbon diluent having a T90 wt % recovery point of below 400° C. with a hydro-isomerisation catalyst under hydro-isomerisation conditions,
(b) dewaxing isomerised product of step (a) and isolating a base oil from the dewaxed oil.
2. The process according to claim 1 , wherein the content of the Fischer-Tropsch wax in the feed to step (a) is greater than 70 wt %.
3. The process according to claim 1 , wherein the diluent is Fischer-Tropsch derived product.
4. The process according to claim 1 , wherein the T10wt % recovery point of the diluent is between 250 and 370° C.
5. The process according to claim 1 , wherein the isomerisation catalyst used in step (b) comprises nickel, platinum or palladium.
6. The process according to claim 5 , wherein in step (a) a catalyst is used comprising a silica-alumina carrier and in step (b) a dewaxing catalyst is used comprising platinum or palladium and ZSM-48 and wherein steps (a) and (b) are performed in series flow.
7. The process according to claim 1 , wherein the base oil obtained by the process has a kinematic viscosity at 100° C. of greater than 8 cSt, a viscosity index of greater than 140 and a Noack volatility of below 7 wt %.
8. The process according to claim 1 , wherein the feed to step (a) is prepared by performing a Fischer-Tropsch synthesis to prepare a Fischer-Tropsch synthesis product, isolating, by means of distillation, from said Fischer-Tropsch synthesis product a Fischer-Tropsch wax, an intermediate wax product boiling for more than 80 wt % between 300 and 500° C. and a diluent, combining the Fischer-Tropsch wax and the diluent to form a feed to step (a) and keeping separate from the feed to step (a) the intermediate wax product.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04291433.3 | 2004-06-08 | ||
| EP04291433 | 2004-06-08 | ||
| PCT/EP2005/052620 WO2005121280A1 (en) | 2004-06-08 | 2005-06-07 | Process to make a base oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20080045614A1 true US20080045614A1 (en) | 2008-02-21 |
Family
ID=34931155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/628,691 Abandoned US20080045614A1 (en) | 2004-06-08 | 2005-06-07 | Process to Make a Base Oil |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20080045614A1 (en) |
| EP (1) | EP1758969A1 (en) |
| JP (1) | JP2008501838A (en) |
| CN (1) | CN101006163A (en) |
| RU (1) | RU2006146997A (en) |
| WO (1) | WO2005121280A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110042267A1 (en) * | 2008-02-08 | 2011-02-24 | Jx Nippon Oil & Energy Corporation | Hydroisomerization catalyst, process for producing the same, method of dewaxing hydrocarbon oil, and process for producing lube base oil |
| CN105647575A (en) * | 2016-02-18 | 2016-06-08 | 惠生工程(中国)有限公司 | Natural gasoline upgrading and utilizing technology |
| US10189975B2 (en) | 2012-08-01 | 2019-01-29 | Shell Oil Company | Cable fill composition |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007011462A1 (en) | 2005-07-19 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Lubricants from mixed alpha-olefin feeds |
| GB2455995B (en) * | 2007-12-27 | 2012-09-26 | Statoilhydro Asa | A method of producing a lube oil from a Fischer-Tropsch wax |
| DE102010044319A1 (en) * | 2010-09-03 | 2012-03-08 | Sasol Wax Gmbh | Wax blends comprising long-chain hydrocarbons and alcohols, printing ink compositions and thermal transfer ribbons containing such wax blends and use of wax blends |
| RU2621685C2 (en) * | 2011-11-01 | 2017-06-07 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Paraffin wax |
| EP3337880A1 (en) | 2015-08-21 | 2018-06-27 | ExxonMobil Chemical Patents Inc. | Lubricant base stock blends |
| US10059898B2 (en) | 2015-08-21 | 2018-08-28 | Exxonmobil Chemical Patents Inc. | High-viscosity metallocene polyalpha-olefins with high electrohydrodynamic performance |
| US10611980B2 (en) | 2015-10-15 | 2020-04-07 | Exxonmobil Chemical Patents Inc. | Lubricant containing high-viscosity metallocene polyalpha-olefins |
| US10144894B2 (en) | 2016-07-20 | 2018-12-04 | Exxonmobil Chemical Patents Inc. | Shear-stable oil compositions and processes for making the same |
| WO2018026406A1 (en) | 2016-08-02 | 2018-02-08 | Exxonmobil Chemical Patents Inc. | Unsaturated polyalpha-olefin materials |
| US10351488B2 (en) | 2016-08-02 | 2019-07-16 | Exxonmobil Chemical Patents Inc. | Unsaturated polyalpha-olefin materials |
| WO2018182982A2 (en) | 2017-03-28 | 2018-10-04 | Exxonmobil Chemical Patents Inc. | Metallocene-catalyzed polyalpha-olefins |
| WO2018182984A1 (en) | 2017-03-28 | 2018-10-04 | Exxonmobil Chemical Patents Inc. | Metallocene compounds |
| WO2019160630A1 (en) | 2018-02-19 | 2019-08-22 | Exxonmobil Chemical Patents Inc. | Functional fluids comprising low-viscosity polyalpha-olefin base stock |
| CN109517626A (en) * | 2018-12-29 | 2019-03-26 | 大连隆星新材料有限公司 | A kind of preparation method of high-quality Fischer-Tropsch wax |
| CN109486524A (en) * | 2018-12-29 | 2019-03-19 | 大连隆星新材料有限公司 | A kind of device producing high-quality Fischer-Tropsch wax |
| CN109486528A (en) * | 2018-12-29 | 2019-03-19 | 大连隆星新材料有限公司 | A kind of device producing Fischer-Tropsch wax crude product |
| EP4010385B1 (en) | 2019-08-09 | 2025-01-22 | ExxonMobil Chemical Patents Inc. | Process to produce low viscosity polyalphaolefins using non-aromatic-hydrocarbon soluble activators |
| EP4051656A1 (en) | 2019-10-28 | 2022-09-07 | ExxonMobil Chemical Patents Inc. | Dimer selective metallocene catalysts, non-aromatic hydrocarbon soluble activators, and processes to produce poly alpha-olefin oligmers therewith |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997018278A1 (en) * | 1995-11-14 | 1997-05-22 | Mobil Oil Corporation | Integrated lubricant upgrading process |
| US5766274A (en) * | 1997-02-07 | 1998-06-16 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
| ZA989528B (en) * | 1997-12-03 | 2000-04-19 | Schuemann Sasol S A Pty Ltd | "Production of lubricant base oils". |
| US6179994B1 (en) * | 1998-09-04 | 2001-01-30 | Exxon Research And Engineering Company | Isoparaffinic base stocks by dewaxing fischer-tropsch wax hydroisomerate over Pt/H-mordenite |
| US6332974B1 (en) * | 1998-09-11 | 2001-12-25 | Exxon Research And Engineering Co. | Wide-cut synthetic isoparaffinic lubricating oils |
| US7704379B2 (en) * | 2002-10-08 | 2010-04-27 | Exxonmobil Research And Engineering Company | Dual catalyst system for hydroisomerization of Fischer-Tropsch wax and waxy raffinate |
-
2005
- 2005-06-07 CN CNA2005800188630A patent/CN101006163A/en active Pending
- 2005-06-07 JP JP2007526423A patent/JP2008501838A/en not_active Abandoned
- 2005-06-07 RU RU2006146997/04A patent/RU2006146997A/en not_active Application Discontinuation
- 2005-06-07 US US11/628,691 patent/US20080045614A1/en not_active Abandoned
- 2005-06-07 EP EP05754524A patent/EP1758969A1/en not_active Withdrawn
- 2005-06-07 WO PCT/EP2005/052620 patent/WO2005121280A1/en not_active Ceased
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110042267A1 (en) * | 2008-02-08 | 2011-02-24 | Jx Nippon Oil & Energy Corporation | Hydroisomerization catalyst, process for producing the same, method of dewaxing hydrocarbon oil, and process for producing lube base oil |
| US9518232B2 (en) | 2008-02-08 | 2016-12-13 | Jx Nippon Oil & Energy Corporation | Hydroisomerization catalyst, process for producing the same, method of dewaxing hydrocarbon oil, and process for producing lube base oil |
| US10189975B2 (en) | 2012-08-01 | 2019-01-29 | Shell Oil Company | Cable fill composition |
| CN105647575A (en) * | 2016-02-18 | 2016-06-08 | 惠生工程(中国)有限公司 | Natural gasoline upgrading and utilizing technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101006163A (en) | 2007-07-25 |
| WO2005121280A1 (en) | 2005-12-22 |
| EP1758969A1 (en) | 2007-03-07 |
| JP2008501838A (en) | 2008-01-24 |
| RU2006146997A (en) | 2008-07-20 |
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