WO2009083714A2 - A method for producing a lube oil from a fischer-tropsch wax - Google Patents
A method for producing a lube oil from a fischer-tropsch wax Download PDFInfo
- Publication number
- WO2009083714A2 WO2009083714A2 PCT/GB2008/004270 GB2008004270W WO2009083714A2 WO 2009083714 A2 WO2009083714 A2 WO 2009083714A2 GB 2008004270 W GB2008004270 W GB 2008004270W WO 2009083714 A2 WO2009083714 A2 WO 2009083714A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydroisomerisation
- dewaxing
- catalyst
- fraction
- wax
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title description 7
- 239000010687 lubricating oil Substances 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- 239000002199 base oil Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 50
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- 238000005194 fractionation Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000003350 kerosene Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 241000269350 Anura Species 0.000 claims 2
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000001993 wax Substances 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000000047 product Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 22
- 238000009835 boiling Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008901 benefit Effects 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
- 238000001816 cooling Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- VZUGBLTVBZJZOE-KRWDZBQOSA-N n-[3-[(4s)-2-amino-1,4-dimethyl-6-oxo-5h-pyrimidin-4-yl]phenyl]-5-chloropyrimidine-2-carboxamide Chemical compound N1=C(N)N(C)C(=O)C[C@@]1(C)C1=CC=CC(NC(=O)C=2N=CC(Cl)=CN=2)=C1 VZUGBLTVBZJZOE-KRWDZBQOSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/08—Jet fuel
-
- 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
- waxes produced by Fischer-Tropsch processes may be hydroisomerised and dewaxed in order to obtain desirable and useful products.
- the products may include bases for formulations of lubricating oil ("base oil”), and other hydrocarbon fractions such as diesel fractions, kerosene fractions, gas fractions, naphtha fractions, and so on.
- a waxy hydrocarbon feed may be subjected to a hydroisomerisation step and a subsequent dewaxing step, under different reaction conditions. It has been suggested that this process can be carried out in one step, in which the feed is hydroisomerised and also sufficiently dewaxed so that a base oil having desirable properties can be separated from the product.
- Standard conditions for carrying out a hydroisomerisation step are a pressure of from 5 to 7 MPa, a temparature T from 300 0 C to 400 0 C and a liquid
- LHSV -i hourly space velocity
- each fraction vary depending on factors such as the nature of the feed wax which is processed and the conditions at which each process step is carried out. It is desirable to maximise the yield of base oil, since this is a high value product. The characteristics of the base oil should also be tailored to be as favourable as possible.
- Base oil can be characterised by various properties like viscosity index (VI), viscosity at 100 0 C or pour point.
- VIP viscosity index
- a hydrocarbon fraction boiling over 360 0 C, and/or comprising mainly C25 - C40 molecules can be utilised as a base oil, which can be combined with various additives before use as a lubricating oil.
- the pour point of a base oil should be ⁇ -10 0 C.
- the viscosity index of a base oil can be calculated by standard methods using the viscosity of the base oil at 40 0 C and 100 °C, and should be > 80. It is desirable for a base oil to have a pour point as low as possible, for example -20 0 C, and a high viscosity index, for example 130.
- a base oil with a low pour point and a high viscosity index can be used in the formulation of a lube oil which can operate well over a large temperature range.
- US Patent 5,362,378 discloses production of a base oil from a Fischer-Tropsch wax using hydroisomerisation without a separate dewaxing step.
- the method is catalyzed by beta zeolites having a high silica to alumina ratio, in combination with a hydrogenation/dehydrogenation component (for example a "Group VIIIA" metal, for example Pt).
- a hydrogenation/dehydrogenation component for example a "Group VIIIA" metal, for example Pt.
- the patent discloses in column 2, lines 40 - 53 that a base oil with acceptable characteristics can be produced by subjecting a Fischer-Tropsch wax to a severe hydroisomerisation step, with no dewaxing step necessary.
- European patent EP 1114127 discloses the production of a base oil from a Fischer-Tropsch wax without a separate dewaxing step.
- the catalyst disclosed comprises a catalytic metal and acidic oxide components. Olefins and oxygenates are hydrogenated during the hydroisomerisation step (page 3 line 47;
- the aim of the present invention is to provide a method for processing hydrocarbons which reduces the complexity and cost of obtaining a base oil having a low pour point, preferably below -10 0 C and a high VI, preferably above 120, more preferably above 130.
- the method provides a high yield of base oil.
- the preferred feedstock is hydrocarbon wax obtained by the Fischer-Tropsch process.
- a method of upgrading wax feedstock product from a Fischer-Tropsch synthesis reaction comprising C5+ hydrocarbons, which comprises treating the wax feedstock by subjecting the wax feedstock and a source of hydrogen to a temperature in the range 200 to 400 0 C and a pressure in the range 20 to 100 bar (2 MPa to 10 MPa) at a hydrogen to hydrocarbon liquid volumetric flow rate of 100 to 1000 Nl H 2 per 1 liquid hydrocarbon feed, over at least one bifunctional hydrogenation active catalyst, and subsequently fractionating the treated product to produce a base oil fraction; and in which the feedstock comprises the entire C5+ fraction from an FT synthesis containing at least 0.2 wt% oxygen as oxygenates and having a C5 - C9/C10+ weight ratio of at least 0.05.
- the hydroisomerisation step and the dewaxing step are carried out with a LHSV of 0.1 - 10 hr - 1, a pressure of 15 - 75 barg, a hydrogen feed of 50 - 1000 N litres of hydrogen to 1 litre of wax and a temperature of 210 - 400 ° C.
- the diesel fraction produced has: pour point ⁇ -15 0 C, cetane number > 65.
- the feed is an FT wax with high content of C20+, and a low content of olefins and oxygenates.
- the hydroisomerisation step is carried out at a temperature in the range 300 - 360 ° C and the dewaxing step is carried out at a temperature in the range 210 - 400° C.
- the reactor configuration may be according to any of the following three cases.
- the second case is one reactor containing two beds of catalyst, a first bed consisting of a catalyst effective for hydroisomerisation, and a second bed containing a catalyst effective for dewaxing.
- the third case is two reactors in series, with or without separation between, the first reactor containing a hydroisomerisation catalyst and the second reactor containing a dewaxing catalyst. In the first two cases, there is only one fractionation step, which separates the effluent from the reactor into good quality naphtha, kerosene, diesel and base oil.
- the hydroisomerisation reactor may separate naphtha, kerosene, diesel and a base oil precursor fraction (360+).
- the base oil precursor fraction is then dewaxed in the dewaxing reactor, and the effluent from the dewaxing reactor is fractionated into naphtha, kerosene, diesel and base oil.
- the base oil fraction may be fractionated into different viscosity ranges of base oil.
- a fractionation step in front of the hydroisomerisation only subjecting a certain fraction of the Fischer-Tropsch product to hydroisomerisation and dewaxing.
- there may be one or more fractionation steps between the hydroisomerisation and dewaxing either subjecting only the 360+ fraction to dewaxing, or also to separate the 360+ fraction into two or more base oil precursor fractions to be individually dewaxed.
- Fractionation before a separate dewaxing step has the advantage that the size of the dewaxing reactor can be reduced, since only the base oil precursor fraction, and not the whole process stream, will be dewaxed.
- the invention therefore extends to a method of optimising the production of base oil which comprises subjecting an F-T wax feed to a hydroisomerisation reaction and dewaxing reaction, using a common catalyst in a common reactor, and adjusting the reaction parameters of the two reactions in different zones of the reactor, the reaction parameters including temperature, pressure, LHSV.
- waxy feed having a suitable certain content of paraffinic hydrocarbon can be used, though it should be essentially sulphur and nitrogen free.
- the waxy feed can be a synthetic wax as from the FT process, a slack wax or a deoiled wax.
- the feedstock is a Fischer-Tropsch wax.
- a Fischer-Tropsch feedstock contains mainly pure paraffins, which have a high viscosity index, thus it is possible to obtain base oils having high viscosity index.
- the feedstock contains no sulphur, nitrogen or aromatics, which is highly beneficial for the production of synthetic base oils, and allows the use of a noble metal catalyst having very high hydrogenation activity. It is desirable that the feedstock containes high amounts of C20+ paraffins, in order to maximize the yield of base oil.
- the feedstock has an initial boiling point below 343 0 C, taking the entire C5+ fraction produced by the Fischer-Tropsch reaction.
- Existing processes for the production of base oil use a narrower fraction. This process is therefore novel in that the feedstock has a lower initial boiling point and wider carbon distribution than previously known.
- the IBP of the feedstock is lowered, the amount of olefins and oxygenates will also be higher, since most of the olefins are contained in the lower boiling fractions.
- the feed may be subjected to hydrotreating to saturate olefins and remove oxygenates, and removal of water before hydroisomerisation.
- the entire C5+ fraction enters the hydroisomerisation reactor without hydrotreating first. It has been found that the presence of alcohols and olefins increases the hydrogen consumption of the hydroisomerisation process. In addition, the catalyst activity is decreased, so that a higher reactor temperature is required. However, it has been realised by the present inventors that the catalyst stability is not unduly affected, and consequently it is not necessary to remove the olefins and oxygenates before the process stream goes through hydroisomerisation.
- dewaxing catalysts are known in the art. In principle any bifunctional catalyst consisting of an acidic support and a hydrogenation metal function can be used. The pores of the support should be selective with respect to iso-paraffins and n-paraffins.
- the hydrogenation metal may be at least one of a Group VIB metal and/or a Group VIII metal. If present, Group VIB metal components include tungsten, molybdenum and/or chromium as sulphide, oxide or in its elemental form, and typically in the range 5-30 wt%.
- a Group VIII metal component is present, both noble and non-noble metals, especially palladium, platinum, nickel and/or cobalt in sulphidic, oxidic and/or elemental form.
- a Group VIII metal is present, more preferably from 0.2 - 5 wt%.
- the support may be a molecular sieve, and more suitably intermediate pore size zeolites.
- the intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 ran.
- Suitable zeolites are mordenite, ferrierite, zeolite Beta, zeolite X, zeolite Y, ZSM5, ZSM-11, ZSM-12, ZSM-20, ZSM-22, ZSM-23, ZSM-25, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, ZSM-57, SSZ-32 and SSZ-48.
- Another preferred group of molecular sieves are the silicaaluminaphosphate (SAPO) materials, such as SAPO-I l, SAPO-31 and SAPO-41.
- Hydroisomerisation catalysts are also known and may be based on the same metals and supports as those listed above. In addition amorphous alumina, silica-alumina, zirconia, titania etc. may be used as supports.
- the invention also extends to products, particularly the base oil, produced in accordance with the method of the invention.
- the following examples illustrate the method as carried out on a hydrocarbon wax derived from the Fischer-Tropsch process.
- Three examples are disclosed for a combined hydroisomerisation and catalytic dewaxing process using a paraffinic C20+ wax feed.
- a further example is disclosed using the entire C5+ feed from the FT synthesis as feed to the hydroisomerisation reactor.
- the total liquid effluent from the second reactor was distilled using the ASTM D-2892 method, into naphtha (IBP ⁇ 15O 0 C), gas oil (IBP between 15O 0 C and 36O 0 C) and baseoil (IBP >360°C).
- Example 1 used a Pt/zeolite catalyst in the second reactor
- Example 2 used a Ni/zeolite catalyst in the second reactor
- Example 3 used a Pt/S APO-11 catalyst in the second reactor.
- Example I 5 a 0.35 wt% Pt/ZSM-5 catalyst was used in the dewaxing step.
- the Pt/ZSM-5 catalyst is a modification of the commercially available Ni/HYDEX-L catalysts, where the Ni metal is replaced with Pt.
- the process was carried out at a range of temperatures, between 234 0 C and 251 0 C.
- the results are shown in Table II, which lists the yield of yield in the total product (after hydroisomerisation followed by catalytic dewaxing) in terms of the wt percentage of four hydrocarbon fractions, the pour point, viscosity, viscosity index and density of the fraction having a boiling point equal or greater than 360 0 C, referred to as "360+".
- the 360+ fraction can be used as a base oil.
- a Ni/ZSM- 5 catalyst was used in the dewaxing step.
- a commercially available catalyst known as Ni/HYDEX-L was used.
- the process was carried out at a range of temperatures, between 229 0 C and 246 0 C.
- the results are shown in Table III, which lists the yield in the total product (after hydroisomerisation followed by catalytic dewaxing) in terms of the wt percentage of four hydrocarbon fractions, the pour point, viscosity, viscosity index and density of the fraction having a boiling point equal or greater than 360 0 C, referred to as "360+".
- the 360+ fraction can be used as a base oil.
- Example 3 a 0.35 wt% Pt/SAPO-11 catalyst was used in the dewaxing step.
- the process was carried out at a range of temperatures, between 328 0 C and 403 0 C.
- the results are shown in Table IV, which lists the yield in the total product (after hydroisomerisation followed by catalytic dewaxing) in terms of the wt percentage of four hydrocarbon fractions, the pour point, viscosity, viscosity index and density of the fraction having a boiling point equal or greater than 360 0 C, referred to as "360+".
- the 360+ fraction can be used as a base oil.
- Example 4 a raw Fischer-Tropsch wax, containing the entire C5+ fraction from the Fischer-Tropsch reactor including olefins, alcohols and other trace components besides paraffins, is hydroisomerised in a trickle-bed reactor over a commercial Pt/Silica-alumina catalyst. Run conditions for for the hydroisomerisation reactor were, 1.0 LHSV, 50 barg reactor pressure, and a once through hydrogen rate of 600 Nl H2/1 wax.
- the raw Fischer-Tropsch wax was produced in a slurry reactor, and contained less than lwppm sulphur and less than 1 wppm nitrogen.
- the boiling point distribution of the wax feed as determined according to the method IP/PM 98 is given in Table V.
- Example 4 the synthesized waxy feed was formed from a synthesis gas feed comprising H 2 and CO having a mole ratio of about 2.0:1 or less.
- the synthesis gas feed was reacted in a slurry reactor containing a dispersed catalyst in hydrocarbon liquid slurry (hydrocarbon products from the synthesis reaction), the catalyst comprising cobalt supported on alumina.
- the liquid product from the Fischer-Tropsch synthesis was collected as light oil, heavy oil and wax, and the three fractions were mixed in order to obtain a C5+ Fischer-Tropsch product having the boiling point distribution given in Table V.
- This C5+ fraction containing raw Fischer-Tropsch products including olefins, alcohols and other trace components from the synthesis, was hydroisomerised over a commercial available Pt/SiAl catalyst without prior prefractionation.
- the 360 °C+ content in the feed was 44 wt%.
- the catalyst Prior to the introduction of waxy C5+ Fischer-Tropsch feed to the hydroisomerisation catalyst, the catalyst was stabilized with a refined Fischer-Tropsch wax having the composition as set forth in Table I. The catalyst deactivation during the period with waxy C5+ Fischer-Tropsch feed was checked in the end by introducing to the hydroisomerisation catalyst the same refined Fischer-Tropsch wax as in the beginning.
- the conditions during the hydroisomerisation reaction were, 1.0 LHSV, 50 barg reactor pressure, and a once through hydrogen rate of 600 Nl H2/1 wax.
- the reactor bed temperature was selected in order to obtain conversion of 360°C+ from 35% to 96%. The conversion is defined as:
- 360 ⁇ C ⁇ Conv Wt%m ⁇ C " feed - Wt%360 ° C+ P r ⁇ duCt , l00% wt%360° C + feed
- Example 1 - 3 show that the selectivity of the ZSM-5 based catalysts and the S APO-11 catalyst are quite different.
- the SAPO-11 catalyst has much higher isomerisation selectivity and a lower cracking selectivity than the ZSM-5 based catalysts.
- the SAPO- 11 catalyst gives significantly higher yields of diesel and lower yields of gas and naphtha than the ZSM-5 based catalyst, which is beneficial.
- the yields of base oil, the pour point of the base oils and the viscosity index of the base oils are comparable for the three catalysts.
- Pt as the hydrogenation component is beneficial over Ni as the hydrogenation metal, due to lower gas make, and also lower naphtha make.
- Example 3 The yield of lighter fractions is lower in Example 3 than in the two comparative examples, which is beneficial.
- the hydroisomerisation and dewaxing the SAPO-11 catalyst is quite different.
- the SAPO-11 catalyst has much higher isomerisation selectivity and a lower cracking selectivity than the ZSM-5 based catalysts.
- the SAPO-11 catalyst give significantly higher yields of diesel and lower yields of base oil, the pour point of the base oils and the viscosity index of the base oils are comparable for the three catalysts.
- Pt as the hydrogenation component is beneficial over Ni as the hydrogenation metal, due to lower gas make, and also lower naptha make.
- Example 3 The yield of lighter fractions is lower in Example 3 than in the two comparative examples, where is beneficial to overall value of the products of the process.
- the low cracking selectivity in combination with high isomerisation selectivity makes the SAPO-11 catalyst suitable for a one step process, with one reactor and one catalyst (Figure 1), for combined hydroisomerisation and catalytic dewaxing.
- Figure 1 high yields of base oil with good cold flow properties and a high viscosity index can be produced by a one step process using the SAPO-11 catalyst.
- the high cracking selectivity for ZSM-5 based dewaxing catalysts makes them no good candidates for such a one step process.
- These catalysts are most suitable for two step processes (Figure 3), or alternatively, a one reactor process ( Figure 2) with two different catalyst layers, with interstage cooling between the catalyst layers. Table VII
- a wax feed 11 and a hydrogen feed 12 are mixed and fed to the top of hydroisomerisation reactor 13.
- the reactor includes a bed 14 of a hydroisomerisation catalyst.
- the hydroisomerised wax product leaves the bottom of the reactor 13 via an outlet line 15 and this is fed to a fractionation column 16.
- the product is split into gas fraction 17, a naptha fraction 18, a kerosene fraction 19, a diesel fraction 21 and a base oil 22.
- the arrangement in Figure 2 is similar to that in Figure 1 in that a mixed feed of wax 11 and hydrogen 12 is fed to the top of a reactor 23.
- the reactor 23 is a combined hydroisomerisation and dewaxing reactor, and to this end, it includes a bed 24 of a hydroisomerisation catalyst and beneath this, a bed 25 of a dewaxing catalyst.
- the mixed feed passes through the two catalyst beds 24, 25 sequentially and the hydroisomerised and dewaxed product 26 is fed to a fractionation column 16, as before. Similar product fractions 17 to 22 are removed.
- a part of the fresh hydrogen 12 is added in between the two catalyst layers 24 and 25 in a separate line 27.
- the hydrogen added in between the catalyst beds 24 and 25 is either superheated to increase the bed 25 temperature compared to the bed 24 temperature or quenched to decrease the bed 25 temperature compared to the bed 24 temperature.
- the base oil fraction 22 is mixed with hydrogen, or at least make-up hydrogen 32, and the mixture is fed to the top of the dewaxing reactor 31. It then passes through a dewaxing catalyst bed 34.
- the dewaxed product 35 is fed to a second fractionation column 36 where it is split into a gas fraction 37, a naphtha fraction 38, a kerosene fraction 39, a diesel fraction 41 and a gas oil fraction 42.
- the first fractionation column 16 is dispensed with and the base oil fraction 15 from the hydroisomerisation reactor 13 is fed directly to the dewaxing reactor 31, after mixing with the make-up hydrogen 32.
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Abstract
A method of upgrading wax feedstock product from a Fischer-Tropsch synthesis reaction comprising C5+ hydrocarbons, which comprises treating the wax feedstock by subjecting the wax feedstock and a source of hydrogen to a temperature in the range 200 to 400° C and a pressure in the range 20 to 100 bar (2 MPa to 10 MPa) at a hydrogen to hydrocarbon liquid volumetric flow rate of 100 to 1000 N1 H2 per 1 liquid hydrocarbon feed, over at least one bifunctional hydrogenation active catalyst, and subsequently fractionating the treated product to produce a base oil fraction. The feedstock comprises the entire C 5+ fraction from an FT synthesis containing at least 0.2 wt% oxygen as oxygenates and having a C5 - C9/C10+ weight ratio of at least 0.05.
Description
A method for producing a lube oil from a Fischer-Tropsch wax
It is known that waxes produced by Fischer-Tropsch processes may be hydroisomerised and dewaxed in order to obtain desirable and useful products. The products may include bases for formulations of lubricating oil ("base oil"), and other hydrocarbon fractions such as diesel fractions, kerosene fractions, gas fractions, naphtha fractions, and so on.
A waxy hydrocarbon feed may be subjected to a hydroisomerisation step and a subsequent dewaxing step, under different reaction conditions. It has been suggested that this process can be carried out in one step, in which the feed is hydroisomerised and also sufficiently dewaxed so that a base oil having desirable properties can be separated from the product.
Standard conditions for carrying out a hydroisomerisation step are a pressure of from 5 to 7 MPa, a temparature T from 300 0C to 400 0C and a liquid
-i hourly space velocity (LHSV) of 1 to 2 h . The process stream may then be subjected to a dewaxing step, for example, catalytic dewaxing or solvent dewaxing. The process stream is fractionated and hydrocarbon fractions, for example, naphtha, kerosene, diesel and base oil fractions, may be obtained.
The yield and properties of each fraction vary depending on factors such as the nature of the feed wax which is processed and the conditions at which each process step is carried out. It is desirable to maximise the yield of base oil, since this is a high value product. The characteristics of the base oil should also be tailored to be as favourable as possible.
Base oil can be characterised by various properties like viscosity index (VI), viscosity at 100 0C or pour point. A hydrocarbon fraction boiling over 360 0C,
and/or comprising mainly C25 - C40 molecules can be utilised as a base oil, which can be combined with various additives before use as a lubricating oil. The pour point of a base oil should be < -10 0C. The viscosity index of a base oil can be calculated by standard methods using the viscosity of the base oil at 40 0C and 100 °C, and should be > 80. It is desirable for a base oil to have a pour point as low as possible, for example -20 0C, and a high viscosity index, for example 130. A base oil with a low pour point and a high viscosity index can be used in the formulation of a lube oil which can operate well over a large temperature range.
US Patent 5,362,378 discloses production of a base oil from a Fischer-Tropsch wax using hydroisomerisation without a separate dewaxing step. The method is catalyzed by beta zeolites having a high silica to alumina ratio, in combination with a hydrogenation/dehydrogenation component (for example a "Group VIIIA" metal, for example Pt). The patent discloses in column 2, lines 40 - 53 that a base oil with acceptable characteristics can be produced by subjecting a Fischer-Tropsch wax to a severe hydroisomerisation step, with no dewaxing step necessary.
European patent EP 1114127 discloses the production of a base oil from a Fischer-Tropsch wax without a separate dewaxing step. The catalyst disclosed comprises a catalytic metal and acidic oxide components. Olefins and oxygenates are hydrogenated during the hydroisomerisation step (page 3 line 47;
The aim of the present invention is to provide a method for processing hydrocarbons which reduces the complexity and cost of obtaining a base oil having a low pour point, preferably below -100C and a high VI, preferably above 120, more preferably above 130. The method provides a high yield of
base oil. The preferred feedstock is hydrocarbon wax obtained by the Fischer-Tropsch process.
According to one aspect of the invention, there is provided a method of upgrading wax feedstock product from a Fischer-Tropsch synthesis reaction comprising C5+ hydrocarbons, which comprises treating the wax feedstock by subjecting the wax feedstock and a source of hydrogen to a temperature in the range 200 to 4000C and a pressure in the range 20 to 100 bar (2 MPa to 10 MPa) at a hydrogen to hydrocarbon liquid volumetric flow rate of 100 to 1000 Nl H2 per 1 liquid hydrocarbon feed, over at least one bifunctional hydrogenation active catalyst, and subsequently fractionating the treated product to produce a base oil fraction; and in which the feedstock comprises the entire C5+ fraction from an FT synthesis containing at least 0.2 wt% oxygen as oxygenates and having a C5 - C9/C10+ weight ratio of at least 0.05.
Conveniently, the hydroisomerisation step and the dewaxing step are carried out with a LHSV of 0.1 - 10 hr - 1, a pressure of 15 - 75 barg, a hydrogen feed of 50 - 1000 N litres of hydrogen to 1 litre of wax and a temperature of 210 - 400°C.
The preferred reaction conditions may be: Pressure 40 -70 barg, LHSV = 0.5 - 2
-1 h , reaction temperature: 230 - 400 0C, H2/oil ratio 200 - 800 Nl/1. Preferably, the diesel fraction produced has: pour point < -150C, cetane number > 65. Preferably, the feed is an FT wax with high content of C20+, and a low content of olefins and oxygenates. In a preferred regime, the hydroisomerisation step is carried out at a temperature in the range 300 - 360°C and the dewaxing step is carried out at a temperature in the range 210 - 400° C.
Thus, the reactor configuration may be according to any of the following three cases. Preferably there is one reactor containing one catalyst (preferably Pt/S APO-11), which effectively converts the FT product into good quality diesel and base oil using no separate dewaxing. The second case is one reactor containing two beds of catalyst, a first bed consisting of a catalyst effective for hydroisomerisation, and a second bed containing a catalyst effective for dewaxing. The third case is two reactors in series, with or without separation between, the first reactor containing a hydroisomerisation catalyst and the second reactor containing a dewaxing catalyst. In the first two cases, there is only one fractionation step, which separates the effluent from the reactor into good quality naphtha, kerosene, diesel and base oil.
In the third case there may be a fractionation step between the hydroisomerisation reactor and the dewaxing reactor, which separates into naphtha, kerosene, diesel and a base oil precursor fraction (360+). The base oil precursor fraction is then dewaxed in the dewaxing reactor, and the effluent from the dewaxing reactor is fractionated into naphtha, kerosene, diesel and base oil.
In addition, for all three cases, the base oil fraction may be fractionated into different viscosity ranges of base oil. Optionally there could be a fractionation step in front of the hydroisomerisation, only subjecting a certain fraction of the Fischer-Tropsch product to hydroisomerisation and dewaxing. In addition there may be one or more fractionation steps between the hydroisomerisation and dewaxing, either subjecting only the 360+ fraction to dewaxing, or also to separate the 360+ fraction into two or more base oil precursor fractions to be individually dewaxed. Fractionation before a separate dewaxing step has the advantage that the size of the dewaxing reactor can be reduced, since only the base oil precursor fraction, and not the whole process stream, will be dewaxed.
The invention therefore extends to a method of optimising the production of base oil which comprises subjecting an F-T wax feed to a hydroisomerisation reaction and dewaxing reaction, using a common catalyst in a common reactor, and adjusting the reaction parameters of the two reactions in different zones of the reactor, the reaction parameters including temperature, pressure, LHSV.
Any waxy feed having a suitable certain content of paraffinic hydrocarbon can be used, though it should be essentially sulphur and nitrogen free. The waxy feed can be a synthetic wax as from the FT process, a slack wax or a deoiled wax.
The feedstock is a Fischer-Tropsch wax. A Fischer-Tropsch feedstock contains mainly pure paraffins, which have a high viscosity index, thus it is possible to obtain base oils having high viscosity index. In addition the feedstock contains no sulphur, nitrogen or aromatics, which is highly beneficial for the production of synthetic base oils, and allows the use of a noble metal catalyst having very high hydrogenation activity. It is desirable that the feedstock containes high amounts of C20+ paraffins, in order to maximize the yield of base oil.
Preferably, the feedstock has an initial boiling point below 343 0C, taking the entire C5+ fraction produced by the Fischer-Tropsch reaction. Existing processes for the production of base oil use a narrower fraction. This process is therefore novel in that the feedstock has a lower initial boiling point and wider carbon distribution than previously known. When the IBP of the feedstock is lowered, the amount of olefins and oxygenates will also be higher, since most of the olefins are contained in the lower boiling fractions.
The feed may be subjected to hydrotreating to saturate olefins and remove
oxygenates, and removal of water before hydroisomerisation. Preferably, the entire C5+ fraction enters the hydroisomerisation reactor without hydrotreating first. It has been found that the presence of alcohols and olefins increases the hydrogen consumption of the hydroisomerisation process. In addition, the catalyst activity is decreased, so that a higher reactor temperature is required. However, it has been realised by the present inventors that the catalyst stability is not unduly affected, and consequently it is not necessary to remove the olefins and oxygenates before the process stream goes through hydroisomerisation.
Several dewaxing catalysts are known in the art. In principle any bifunctional catalyst consisting of an acidic support and a hydrogenation metal function can be used. The pores of the support should be selective with respect to iso-paraffins and n-paraffins. The hydrogenation metal may be at least one of a Group VIB metal and/or a Group VIII metal. If present, Group VIB metal components include tungsten, molybdenum and/or chromium as sulphide, oxide or in its elemental form, and typically in the range 5-30 wt%. More preferably only a Group VIII metal component is present, both noble and non-noble metals, especially palladium, platinum, nickel and/or cobalt in sulphidic, oxidic and/or elemental form. Typically less than 10 wt% of a Group VIII metal is present, more preferably from 0.2 - 5 wt%. The support may be a molecular sieve, and more suitably intermediate pore size zeolites. Preferably the intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 ran. Suitable zeolites are mordenite, ferrierite, zeolite Beta, zeolite X, zeolite Y, ZSM5, ZSM-11, ZSM-12, ZSM-20, ZSM-22, ZSM-23, ZSM-25, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, ZSM-57, SSZ-32 and SSZ-48. Another preferred group of molecular sieves are the silicaaluminaphosphate (SAPO) materials, such as SAPO-I l, SAPO-31 and SAPO-41.
Hydroisomerisation catalysts are also known and may be based on the same metals and supports as those listed above. In addition amorphous alumina, silica-alumina, zirconia, titania etc. may be used as supports.
The invention also extends to products, particularly the base oil, produced in accordance with the method of the invention.
The following examples illustrate the method as carried out on a hydrocarbon wax derived from the Fischer-Tropsch process. Three examples are disclosed for a combined hydroisomerisation and catalytic dewaxing process using a paraffinic C20+ wax feed. A further example is disclosed using the entire C5+ feed from the FT synthesis as feed to the hydroisomerisation reactor.
In Examples 1 to 3, a refined Fischer-Tropsch wax was hydroisomerised in a first trickle-bed reactor over a commercial Pt/Silica-alumina catalyst. Properties for the paraffinic wax feed are given in Table 1. The total effluent from the first reactor was passed over a dewaxing catalyst in a second trickle-bed reactor. Run conditions for both reactors in all examples were, LHSV = 1 h"1, 50 barg reactor pressure, and a once through hydrogen rate of 600 Nl H2/1 wax. The total liquid effluent from the second reactor was distilled using the ASTM D-2892 method, into naphtha (IBP < 15O0C), gas oil (IBP between 15O0C and 36O0C) and baseoil (IBP >360°C). Example 1 used a Pt/zeolite catalyst in the second reactor, Example 2 used a Ni/zeolite catalyst in the second reactor and Example 3 used a Pt/S APO-11 catalyst in the second reactor.
In Example I5 a 0.35 wt% Pt/ZSM-5 catalyst was used in the dewaxing step. The Pt/ZSM-5 catalyst is a modification of the commercially available
Ni/HYDEX-L catalysts, where the Ni metal is replaced with Pt. The process was carried out at a range of temperatures, between 234 0C and 251 0C. The results are shown in Table II, which lists the yield of yield in the total product (after hydroisomerisation followed by catalytic dewaxing) in terms of the wt percentage of four hydrocarbon fractions, the pour point, viscosity, viscosity index and density of the fraction having a boiling point equal or greater than 360 0C, referred to as "360+". The 360+ fraction can be used as a base oil.
In Comparative Example 2, a Ni/ZSM- 5 catalyst was used in the dewaxing step. A commercially available catalyst known as Ni/HYDEX-L was used. The process was carried out at a range of temperatures, between 229 0C and 246 0C. The results are shown in Table III, which lists the yield in the total product (after hydroisomerisation followed by catalytic dewaxing) in terms of the wt percentage of four hydrocarbon fractions, the pour point, viscosity, viscosity index and density of the fraction having a boiling point equal or greater than 360 0C, referred to as "360+". The 360+ fraction can be used as a base oil.
In the example according to the invention, Example 3, a 0.35 wt% Pt/SAPO-11 catalyst was used in the dewaxing step. The process was carried out at a range of temperatures, between 328 0C and 403 0C. The results are shown in Table IV, which lists the yield in the total product (after hydroisomerisation followed by catalytic dewaxing) in terms of the wt percentage of four hydrocarbon fractions, the pour point, viscosity, viscosity index and density of the fraction having a boiling point equal or greater than 360 0C, referred to as "360+". The 360+ fraction can be used as a base oil.
Conversion and yields, as well as the properties of the obtained base oils are given in Table II - Table IV. The conversion is calculated as the conversion of
components boiling above 360 °C into components boiling below 360 0C.
Table 1 : Properties for the wax feed
Table II
Pt/ZSM-5
R1 temperature [°C]
325 325 321 321 316 316 (hydroisomerisation) 316 311 311 306 R2 temperature [°C]
Reactor 238 243 243 249 249 254 260 260 254 (dewaxing) 254 conditions
360+ conversion R1 [%] 65,6 66,5 43,6 44,6 22,1 21 ,5 19,6 10,0 10,0 5,7
360+ conversion R1 + R2
69,7 75,8 52,4 56,9 46,6 48,8 56,4 47,5 57,5 52,0 [%]
Gas (C1-C4) 6,7 7,5 6,7 10,0 9,7 15,6 20,5 15,8 22,4 17,6
Yields in total C5-150 0C 21,4 25,7 19,2 21 ,3 19,4 21 ,1 24,8 24,4 30,8 27,9 effluent from R2 (after dewaxing) 150 °C - 360°C 44,3 45,3 29,5 28,0 19,8 15,0 14,1 10,5 8,3 10,5
360°C + (base oil) 30,3 24,2 47,6 43,1 53,4 51,2 43,6 52,5 42,5 48,0
Pour point [°C] -30 <-39 -21 <-39 -18 -30 <-39 -12 -33 -3
Viscosity at 40 °C [cSt] 18,8 18,8 21,2 20,8 22,8 21,7 22,6 22,4 21,6 22,3
Properties of 360 Viscosity at 100 °C [cSt] 4,2 4,1 4,6 4,5 4,9 4,7 4,7 4,9 4,7 4,9 °C + fraction
Viscosity Index 126 125 134 133 141 136 130 145 137 153
Density at 15 °C 817 817 819 819 820 819 820 819 819 819
Table III
Ni/HYDEX-L
R1 temperature [°C]
330 330 330 327 327 327 (hydroisomerisation)
R2 temperature [°C]
230 235 240 235 240 245
Reactor conditions (dewaxing)
360+ conversion R1 [%] 65,3 65,9 67,0 46,7 44,6 43,4
360+ conversion R1 + R2 [%] 69,5 73,6 78,0 57,4 59,3 64,9
Gas (C1-C4) 6,5 9,0 15,2 7,5 11 ,8 18,3
Yields in total C5-150 "C 21,3 24,9 29,9 18,6 22,0 26,7 effluent from R2
(after dewaxing) 150 °C - 360°C 43,9 38,5 33,1 33,7 28,3 24,7
360°C + (base oil) 30,5 26,4 22,0 42,6 40,7 35,1
Pour point [°C] -24 -30 <-39 -21 -27 <-39
Viscosity at 40 0C [cSt] 19,2 18,9 19,1 20,1 20,1 21,3
Properties of 360
Viscosity at 100 °C [cSt] 4,3 4,2 4,2 4,5 4,5 4,5 °C + fraction
Viscosity Index 133 129 128 139 140 127
Density at 15 °C 778 778 111 792 794 795
Table IV
Pt/SAPO-11
R1 temperature [*C] 330 330 326 326 326 326 321 321 321 321 316 316 316 197 197
R2 temperature [°C]
Reactor 328 333 338 348 358 368 368 373 378 385 385 390 395 398 403 conditions 360+ conversion R1 [%1 61 63 45 40 44 44 24 23 24 21 8 8 8 0 0
360+ conversion R1
+ R2 [%] 70 75 51 54 63 68 44 48 51 57 47 56 59 46 53
Gas (C1-C4) 3,5 3,8 2,5 2,9 3,6 4,1 2,9 3,3 3,5 4,3 4,2 4,9 4,9 5,5 5,5
Yields in total C5-150 °C 17,3 19,3 11,2 11,6 14,5 16,5 10,1 10,6 12,0 13,7 11,1 13,2 14,9 11,4 13,5
150 °C - 360°C 50,7 52,6 37,1 40,4 44,7 47,0 32,8 33,9 36,5 41 ,1 35,2 37,9 40,8 31,5 34,8
360°C + (base oil) 28,5 24,5 48,6 45,1 36,4 32,2 55,8 52,5 48,0 41,7 50,2 44,4 39,8 52,3 47,2
Pour point [°C] -18 -27 * -18 -30 -30 -18 -24 -24 -33 -24 -30 -33 -21 -21
Viscosity at 40 °C * 18,1 * 20,2 19,8 19,4 * * 21,4 19,5 19,1 20,7 20,0
Properties [cSt] of 360 °C + Viscosity at 10O 0C * 4,1 * 4,5 4,4 4,3 4,7 4,6 4,5 4,4 4,8 4,3 4,4 4,7 4,5 fraction [cSt]
Viscosity Index 133 * 145 138 133 * * * * 148 141 137 153 144
Density at 15 °C *
In Example 4, a raw Fischer-Tropsch wax, containing the entire C5+ fraction from the Fischer-Tropsch reactor including olefins, alcohols and other trace components besides paraffins, is hydroisomerised in a trickle-bed reactor over a commercial Pt/Silica-alumina catalyst. Run conditions for for the hydroisomerisation reactor were, 1.0 LHSV, 50 barg reactor pressure, and a once through hydrogen rate of 600 Nl H2/1 wax. The raw Fischer-Tropsch wax was produced in a slurry reactor, and contained less than lwppm sulphur and less than 1 wppm nitrogen. The boiling point distribution of the wax feed as determined according to the method IP/PM 98 is given in Table V.
Table V
In Example 4, the synthesized waxy feed was formed from a synthesis gas feed comprising H2 and CO having a mole ratio of about 2.0:1 or less. The synthesis gas feed was reacted in a slurry reactor containing a dispersed catalyst in hydrocarbon liquid slurry (hydrocarbon products from the synthesis reaction), the catalyst comprising cobalt supported on alumina. The liquid product from the Fischer-Tropsch synthesis was collected as light oil, heavy oil and wax, and the three fractions were mixed in order to obtain a C5+ Fischer-Tropsch product having the boiling point distribution given in Table V. This C5+ fraction, containing raw Fischer-Tropsch products including olefins, alcohols and other trace components from the synthesis, was hydroisomerised over a commercial available Pt/SiAl catalyst without prior prefractionation. The 360 °C+ content in the feed was 44 wt%. Prior to the introduction of waxy C5+ Fischer-Tropsch feed to the hydroisomerisation catalyst, the catalyst was stabilized with a refined Fischer-Tropsch wax having the composition as set forth in Table I. The catalyst deactivation during the period with waxy C5+ Fischer-Tropsch feed was checked in the end by introducing to the hydroisomerisation catalyst the same refined Fischer-Tropsch wax as in the beginning. The conditions during the hydroisomerisation reaction were, 1.0 LHSV, 50 barg reactor pressure, and a once through hydrogen rate of 600 Nl H2/1 wax. The reactor bed temperature was selected in order to obtain conversion of 360°C+ from 35% to 96%. The conversion is defined as:
360^C^Conv = Wt%mθ C"feed - Wt%360°C+PrθduCt , l00% wt%360° C+feed
The results are given in Table VI, showing the 360°C+ conversion and the reactor temperature at increasing time on stream and with change in feed composition.
Table VI
After 8 days on stream with the refined Fischer-Tropsch wax, stable activity was obtained at a temperature of 322.5°C and a 360°C+ conversion slightly above 80%. Then introducing the raw Fischer-Tropsch wax at day 9, the reactor bed temperature had to be increased in order to sustain a high conversion level. About 12 days after introducing the C5+ Fischer-Tropsch wax, the activity started to stabilize again, and the catalyst activity, expressed as the required temperature increase needed to achieve the same level of yield, was about 18.5 °C less than that for the refined Fischer-Tropsch wax.
However, a slow deactivation was observed for some days, and first 5 days later the catalyst activity seemed to be stable at a reactor temperature of 336°C and 47 % 360°C+ conversion. The reactor bed temperature was than adjusted to collect information about the yields and product qualities obtainable at six different conversion levels over a period of about 30 days (day 26 to day 55). The yields at different 360°C+ conversion levels are given in Table VII along with the cold flow properties of the 150-360 fractions.
Then the same reactor conditions as at day 36 were repeated, in order to check the deactivation during a period of almost four weeks. A decrease in 360°C+ conversion of about 3% was observed, corresponding to about 0.9 0C. At day 64, after 55 days on stream with raw Fischer-Tropsch wax, the feed was changed back to refined Fischer-Tropsch wax. The immediate catalyst activity was then approximately the same for the two feeds. After a few days on stream with the refined Fischer-Tropsch wax, some reactivation of the catalyst activity was observed, but the catalyst reactivation was rather slow.
After 20 days on stream, the 360°C+ conversion increased by 14 %, corresponding to about 2.3 0C. The next 10 days the catalyst activity was stable,
and a 360°C+ conversion of 92% was reached at about 344 0C. The total irreversible deactivation during the period with C5+ raw Fischer-Tropsch wax was 19 °C, occurring all in the first three weeks of operation with this raw wax feed.
These results indicate that the total liquid product from the Fischer-Tropsch reactor can be hydroisomerised in one reactor, without removal of oxygenates, olefins and other trace components in the feed in a hydrotreating step prior to the hydroisomerisation unit. No measurable levels of oxygenates were found in the product, thus, oxygenates in the feed are hydrogenated over the hydroisomerisation catalyst. The only catalytic effect of hydroisomerisation of the total C5+ Fischer-Tropsch product without hydrotreating the feed first, is a reactor bed temperature of about 20 0C above that for refined Fischer-Tropsch wax.
The results in Example 1 - 3 show that the selectivity of the ZSM-5 based catalysts and the S APO-11 catalyst are quite different. The SAPO-11 catalyst has much higher isomerisation selectivity and a lower cracking selectivity than the ZSM-5 based catalysts. The SAPO- 11 catalyst gives significantly higher yields of diesel and lower yields of gas and naphtha than the ZSM-5 based catalyst, which is beneficial. The yields of base oil, the pour point of the base oils and the viscosity index of the base oils are comparable for the three catalysts. For the two ZSM-5 based catalyst, Pt as the hydrogenation component is beneficial over Ni as the hydrogenation metal, due to lower gas make, and also lower naphtha make.
- The yield of lighter fractions is lower in Example 3 than in the two comparative examples, which is beneficial.
The hydroisomerisation and dewaxing the SAPO-11 catalyst is quite different. The SAPO-11 catalyst has much higher isomerisation selectivity and a lower cracking selectivity than the ZSM-5 based catalysts. The SAPO-11 catalyst give significantly higher yields of diesel and lower yields of base oil, the pour point of the base oils and the viscosity index of the base oils are comparable for the three catalysts. For the two ZSM-5 based catalyst, Pt as the hydrogenation component is beneficial over Ni as the hydrogenation metal, due to lower gas make, and also lower naptha make.
- The yield of lighter fractions is lower in Example 3 than in the two comparative examples, where is beneficial to overall value of the products of the process.
- The hydroisomerisation and dewaxing temperatures can be very similar with the dewaxing catalyst of Example 3, which is an advantage when using two catalysts in one reactor, because additional cooling or heating between the different catalyst layers is not required.
- The low cracking selectivity in combination with high isomerisation selectivity makes the SAPO-11 catalyst suitable for a one step process, with one reactor and one catalyst (Figure 1), for combined hydroisomerisation and catalytic dewaxing. As shown in Example 3, high yields of base oil with good cold flow properties and a high viscosity index can be produced by a one step process using the SAPO-11 catalyst. The high cracking selectivity for ZSM-5 based dewaxing catalysts makes them no good candidates for such a one step process. These catalysts are most suitable for two step processes (Figure 3), or alternatively, a one reactor process (Figure 2) with two different catalyst layers, with interstage cooling between the catalyst layers.
Table VII
Reactor R1 temperature [°C] 334.4 336.0 338.4 341.9 345.8 347.7 conditions 360+ conversion R1 [%] 36% 47% 52% 62% 86% 95%
Gas (C1-C4) 0,3% 0,6% 0,5% 0,8% 1,2% 1,5%
C5-15CTC 9,3% 11,5% 12,1% 13,6% 18,5% 22,0%
Yields in total effluent from R2 150-3600C 62,6% 64,9% 67,1% 69,7% 75,3% 75,0%
Unconverted wax
28,0% 23,2% 20,8% 16,1% 5,1% 2,0% (360°C+)
The three preferred reactor configurations will now be described by way of example in the reference to the accompanying drawings, in which the three Figures are schematic representations of the three configurations.
In Figure 1, a wax feed 11 and a hydrogen feed 12 are mixed and fed to the top of hydroisomerisation reactor 13. The reactor includes a bed 14 of a hydroisomerisation catalyst. The hydroisomerised wax product leaves the bottom of the reactor 13 via an outlet line 15 and this is fed to a fractionation column 16. In the fractionation column 16, the product is split into gas fraction 17, a naptha fraction 18, a kerosene fraction 19, a diesel fraction 21 and a base oil 22.
The arrangement in Figure 2 is similar to that in Figure 1 in that a mixed feed of wax 11 and hydrogen 12 is fed to the top of a reactor 23. However, the reactor 23 is a combined hydroisomerisation and dewaxing reactor, and to this end, it includes a bed 24 of a hydroisomerisation catalyst and beneath this, a bed 25 of a dewaxing catalyst.
The mixed feed passes through the two catalyst beds 24, 25 sequentially and the hydroisomerised and dewaxed product 26 is fed to a fractionation column 16, as before. Similar product fractions 17 to 22 are removed.
In order to be able to control the temperature in catalyst bed 24 and 25 individually a part of the fresh hydrogen 12 is added in between the two catalyst layers 24 and 25 in a separate line 27. The hydrogen added in between the catalyst beds 24 and 25 is either superheated to increase the bed 25 temperature compared to the bed 24 temperature or quenched to decrease the bed 25
temperature compared to the bed 24 temperature.
In the arrangement shown in Figure 3, there is a hydroisomerisation reactor 13 and a separate dewaxing reactor 31. In this case, the mixed feed of wax 11 and hydrogen 12 is fed to the hydroisomerisation reactor 13, in the same way as in the arrangement of Figure 1, and the hydroisomerised wax product leaves the bottom of the reactor via the outlet line 15 and is fed to the fractionation column 16. Again as in Figure 1, the product from the reactor is split into the five fractions 17 to 22.
However, the base oil fraction 22 is mixed with hydrogen, or at least make-up hydrogen 32, and the mixture is fed to the top of the dewaxing reactor 31. It then passes through a dewaxing catalyst bed 34. The dewaxed product 35 is fed to a second fractionation column 36 where it is split into a gas fraction 37, a naphtha fraction 38, a kerosene fraction 39, a diesel fraction 41 and a gas oil fraction 42.
In a possible variant, the first fractionation column 16 is dispensed with and the base oil fraction 15 from the hydroisomerisation reactor 13 is fed directly to the dewaxing reactor 31, after mixing with the make-up hydrogen 32.
Claims
1. A method of upgrading wax feedstock product from a Fischer-Tropsch synthesis reaction comprising C5+ hydrocarbons, which comprises treating the wax feedstock by subjecting the wax feedstock and a source of hydrogen to a temperature in the range 200 to 400° C and a pressure in the range 20 to 100 bar (2 MPa to 10 MPa) at a hydrogen to hydrocarbon liquid volumetric flow rate of 100 to 1000 Nl H2 per 1 liquid hydrocarbon feed, over at least one bifunctional hydrogenation active catalyst, and subsequently fractionating the treated product to produce a base oil fraction; and in which the feedstock comprises the entire C5+ fraction from an FT synthesis containing at least 0.2 wt% oxygen as oxygenates and having a C5 - C9/C10+ weight ratio of at least 0.05.
2. A method as claimed in Claim 1, in which the proportion of the feedstock having a melting point <20°C is at least 10 wt%.
3. A method as claimed in any preceding claim, in which the treatment of the wax feedstock comprises hydroisomerisation and dewaxing.
4. A method as claimed in Claim 3, in which the hydroisomerisation and dewaxing are carried out simultaneously over a common bifunctional catalyst.
5. A method as claimed in Claim 4, in which the catalyst comprises a Group VIII metal on a SAPO support.
6. A method as claimed in Claim 5, in which the catalyst comprises platinum on a SAPO-11 molecular sieve support.
7. A method as claimed in Claim 3, in which the feedstock is first subjected to hydroisomerisation and then dewaxing.
8. A method as claimed in Claim 7, in which the hydroisomerisation is catalysed by a catalyst comprising a Group VIII metal and optionally a promoter on a silica-alumina support.
9. A method as claimed in Claim 7 or Claim 8, in which the dewaxing is catalysed by a catalyst comprising a Group VIII metal on a silicoaluminophosphate molecular sieve support.
10. A method as claimed in Claim 7 or Claim 8, in which the dewaxing is catalysed by a catalyst comprising platinum on a support comprising SAPO 11 and/or ZSM-5.
11. A method as claimed in any of Claims 3 to 10, in which the hydroisomerisation step and the dewaxing step are carried out with a LHSV of 0.1 - 10 hr - l5 a pressure of 15 - 75 barg, a hydrogen feed of 50 - 1000 N litres of hydrogen to 1 litre of wax and a temperature of 210-400°C.
12. A method as claimed in Claim any of Claims 3 to 10, in which the hydroisomerisation step is carried out at temperature in the range 300 - 360°C and the dewaxing step is carried out at a temperature in the range 210 - 400°C.
13. A method as claimed in any of Claims 7 to 12, in which the hydroisomerisation step is carried out in a hydroisomerisation zone and the dewaxing step is then carried out in a dewaxing zone, in one single reactor.
14. A method as claimed in any of Claims 7 to 12, in which first the hydroisomerisation and then the dewaxing steps are carried out sequentially in separate reactors, prior to fractionation.
15. A method as calimed in any of Claims 7 to 12, in which the feedstock is first subjected to hydroisomerisation, then to a first fractionation, then a base oil fraction from the first fractionation is subjected to dewaxing and the dewaxed product is subjected to a second fractionation.
16. A method as claimed in any preceding claim, in which the fractionation products comprise a gas fraction, a naphthe fraction, a kerosene fraction, a diesel fraction and a base oil fraction.
17. A method as claimed in any preceding claim, in which the wax feedstock is not subjected to a hydrotreating step prior to the hydroisomerisation step.
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GB0725271.1A GB2455995B (en) | 2007-12-27 | 2007-12-27 | A method of producing a lube oil from a Fischer-Tropsch wax |
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US9492818B2 (en) | 2009-06-12 | 2016-11-15 | Albemarle Europe Sprl | SAPO molecular sieve catalysts and their preparation and uses |
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US5362378A (en) * | 1992-12-17 | 1994-11-08 | Mobil Oil Corporation | Conversion of Fischer-Tropsch heavy end products with platinum/boron-zeolite beta catalyst having a low alpha value |
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GB0725271D0 (en) | 2008-02-06 |
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GB2455995A (en) | 2009-07-01 |
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