TWI488959B - Manufacture of lubricating base oil - Google Patents
Manufacture of lubricating base oil Download PDFInfo
- Publication number
- TWI488959B TWI488959B TW099127331A TW99127331A TWI488959B TW I488959 B TWI488959 B TW I488959B TW 099127331 A TW099127331 A TW 099127331A TW 99127331 A TW99127331 A TW 99127331A TW I488959 B TWI488959 B TW I488959B
- Authority
- TW
- Taiwan
- Prior art keywords
- oil
- lubricating base
- base oil
- mass
- catalyst
- Prior art date
Links
- 239000002199 base oil Substances 0.000 title claims description 100
- 230000001050 lubricating effect Effects 0.000 title claims description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 46
- 239000003921 oil Substances 0.000 claims description 116
- 239000003054 catalyst Substances 0.000 claims description 79
- 239000012188 paraffin wax Substances 0.000 claims description 76
- 229910052751 metal Inorganic materials 0.000 claims description 68
- 239000002184 metal Substances 0.000 claims description 68
- 238000005984 hydrogenation reaction Methods 0.000 claims description 50
- 239000011148 porous material Substances 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 239000011593 sulfur Substances 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 24
- 238000000354 decomposition reaction Methods 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 235000019271 petrolatum Nutrition 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000746 purification Methods 0.000 claims description 17
- 238000003795 desorption Methods 0.000 claims description 16
- 239000010687 lubricating oil Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000001993 wax Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 4
- 235000011613 Pinus brutia Nutrition 0.000 claims description 4
- 241000018646 Pinus brutia Species 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 239000004264 Petrolatum Substances 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000004200 microcrystalline wax Substances 0.000 claims description 3
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 3
- 235000019198 oils Nutrition 0.000 claims description 3
- 235000019809 paraffin wax Nutrition 0.000 claims description 3
- 229940066842 petrolatum Drugs 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 238000006317 isomerization reaction Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005194 fractionation Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000003209 petroleum derivative Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 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
- 238000011156 evaluation Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YFVXLROHJBSEDW-UHFFFAOYSA-N 4-[(4-nitrophenyl)diazenyl]-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1N=NC(C=C1)=CC=C1NC1=CC=CC=C1 YFVXLROHJBSEDW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-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
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 239000010725 compressor oil Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- -1 polycyclic aromatic compound Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- 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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
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Description
本發明係關於一種潤滑油基油之製造方法。
石油製品中，噴射機燃料、輕油、潤滑油等為重視其於低溫下之流動性之製品。為此較理想的是，於該等製品中所使用之基油將成為使低溫流動性下降之原因的正構石蠟等蠟成分完全或者部分去除，或者將其轉化為蠟成分以外者。又，近年來，因藉由費托(Fischer-Tropsch)合成(以下記為「FT合成」)所得之烴油中硫等環境負荷物質之含量較少，因而作為燃料油、潤滑油製造用之原料而受到注目，但該烴油中亦含有大量的蠟成分。
作為自烴油中去除蠟成分之脫蠟技術，例如已知有藉由液化丙烷或甲基乙基酮等溶劑萃取蠟成分之方法。但是，該方法有如下問題：裝置規模變大、運轉成本較高、可適用之原料油種類受限、製品產率因原料油種類而受限。
另一方面，作為將烴油中之蠟成分轉化為非蠟成分之脫蠟技術，例如已知有接觸脫蠟技術，其係於分子狀氫氣之存在下，使烴油與具有氫化-脫氫化功能及異構化功能之兩者之氫化異構化脫蠟觸媒接觸，將烴油中之正構石蠟異構化為異構石蠟。
接觸脫蠟作為改善烴油之低溫流動性之方法較為有效，為獲得適用於潤滑油用基油之餾分，必須充分提高正構石蠟之轉化率。但是，接觸脫蠟所使用之氫化異構化觸媒於具有異構化功能之同時亦具有烴分解功能，故隨著正構石蠟之轉化率上升，亦在進行烴油之分解、輕質化，而難以產率佳地獲得所需之餾分。特別是於製造要求高黏度指數及低流動點之高品質潤滑油用基油時，經濟性佳地獲得目標餾分會非常困難，因此，於該領域中多使用聚α-烯烴等合成系基油。
根據上述情況，於潤滑油基油之製造領域中，業界要求一種由含有蠟成分之烴油產率佳地獲得所需之異構石蠟餾分之脫蠟技術。
在此以前，亦有提高用於接觸脫蠟之氫化異構化觸媒之異構化選擇性之嘗試。例如下述專利文獻1中所揭示：使直鏈狀或有極少分枝之碳數10以上之烴原料於異構化條件下與觸媒接觸，而製造經脫蠟之潤滑油之製程，上述觸媒係由含有週期表第8~10族等之金屬之ZSM-22(Zeolite Sieve of Molecular，沸石分子篩)、ZSM-23、ZSM-48等具有中等程度大小的一維狀細孔，且微晶之大小不超過約0.5 μm之分子篩構成(專利文獻1)。
專利文獻1：美國專利第5,282,958號說明書
但是，即便是上述專利文獻1所記載之潤滑油基油製造製程，觸媒之異構化選擇性亦說不上充分，並且難以由含有正構石蠟成分之烴油高產率地獲得所需之適於潤滑油基油之異構石蠟餾分。特別是於製造高品質之潤滑油基油時，必須將其轉化率提高至實質上不含正構石蠟之程度，此種情形下，正構石蠟及/或作為異構化生成物之異構石蠟之分解反應變得旺盛，難於以具有經濟性之產率獲得目標潤滑油基油。
本發明係鑒於上述課題而完成者，其目的在於提供一種可由含有正構石蠟之原料油，穩定且高產率地獲得高品質之潤滑油基油的潤滑油基油之製造方法。
即，本發明提供一種潤滑油基油之製造方法，其包括：第一步驟，其係於分子狀氫氣之存在下，使含有碳數20以上之正構石蠟之原料油與第一觸媒接觸而獲得第一生成油；及第二步驟，其係於分子狀氫氣之存在下，使上述第一生成油與第二觸媒接觸而獲得第二生成油；上述第一觸媒含有：於氨脫附溫度依賴性評價中於300~800℃時NH3
之脫附量相對於NH3
之總脫附量之分率為80~90%的第一載體，承載於該第一載體之選自屬於週期表第6族之金屬之至少一種的第一金屬，及承載於上述第一載體之選自屬於週期表第8~10族之金屬之至少一種的第二金屬；上述第一觸媒中之按上述第一金屬之氧化物換算之含有比例C1
(質量%)，與按上述第二金屬之氧化物換算之含有比例C2
(質量%)之和C1
+C2
為22~36質量%；上述第一觸媒中之上述第二金屬之含量D2
(莫耳)相對於上述第一金屬之含量D1
(莫耳)之比D1
/D2
為1.07~7.78。
藉由本發明之潤滑油基油之製造方法，可由含有碳數20以上之正構石蠟之原料油穩定且高產率地獲得潤滑油基油。更詳細而言，先前之潤滑油基油之製造方法中，存在以下問題：若欲充分提高正構石蠟之轉化率，則會因同時引起之正構石蠟之氫化分解反應，而導致產率下降。又，若欲抑制氫化分解反應，則會導致正構石蠟之轉化率下降。若正構石蠟之轉化率下降，則需要在後續之脫蠟步驟中去除過量之正構石蠟，其結果會導致產率下降。相對於此，根據本發明之潤滑油基油之製造方法，對於含有碳數20以上之正構石蠟之原料油，可一面抑制氫化分解反應，一面有效地進行氫化脫硫、氫化脫氮及氫化異構化。如此而獲得之生成油中，碳數20以上之各石蠟之總含量為與原料油相同程度，硫及氮之含量充分降低，碳數20以上之正構石蠟之大部分被轉化為碳數20以上之異構化石蠟。
本發明之潤滑油基油之製造方法中，較佳為以如下方式進行上述第一步驟：碳數未達20之輕質石蠟之含有比例為0~10質量%，碳數20以上之異構化石蠟之含有比例為70質量%以上，硫之含有比例為10質量ppm以下，氮之含有比例為3質量ppm以下。根據此種製造方法，可使上述效果更加顯著。
較佳為上述第一觸媒中含有鉬及/或鎢作為上述第一金屬，較佳為含有鈷及/或鎳作為上述第二金屬。根據此種觸媒，可進一步抑制氫化異構化所伴隨之氫化分解反應。
又，較佳為上述第一觸媒中進而含有承載於上述第一載體之磷，且上述第一觸媒中之按該磷之氧化物換算之含有比例為0.1~8質量%。此種觸媒有進一步提高觸媒活性之傾向。
又，較佳為上述第一觸媒之平均細孔半徑為40~200，細孔半徑未達40之細孔之總細孔容積為總細孔容積之0.1~5%，細孔半徑較200大之細孔之總細孔容積為總細孔容積之0.1~5%。根據此種觸媒，可更有效地進行氫化脫硫、氫化脫氮及氫化異構化。
較佳為上述第一載體係含有氧化鋁、二氧化矽及氧化鋯之複合氧化物之載體。藉由含有此種載體，上述第一觸媒可進一步抑制氫化異構化所伴隨之氫化分解反應，且確實地具有可承受商業使用之機械強度。
上述第一步驟中，將上述碳數20以上之正構石蠟之一部分或全部異構化為異構石蠟。
較佳為上述原料油係選自由松蠟、脫蠟油、石蠟、微晶蠟、凡士林、費托蠟、減壓輕油、減壓輕油氫化分解油、常壓殘油氫化分解油及減壓殘油氫化分解油所組成群中之至少一種。此等原料油可經濟性較佳且穩定地獲得。
本發明之潤滑油基油之製造方法中，較佳為以下述式(3)所表示之正構石蠟之轉化率為70%以上之方式進行上述第一步驟。根據於此種轉化率下所獲得之第一生成油，能以更高產率獲得高品質之潤滑油基油。
正構石蠟之轉化率(%)=[1-(上述第一生成油中之碳數20以上之正構石蠟之總質量)/(上述原料油中之碳數20以上之正構石蠟之總質量)]×100 (3)本發明之潤滑油基油之製造方法中，較佳為以上述第二生成油中之碳數20以上之正構石蠟的含有比例為5質量%以下之方式進行上述第二步驟。根據此種製造方法，能以更高產率獲得高品質之潤滑油基油。
較佳為：上述第二觸媒係含有第二載體與承載於該第二載體之活性金屬之氫化異構化觸媒；上述第二載體含有一維10員環中細孔徑沸石，與選自氧化鋁、二氧化矽、氧化鋯、二氧化鈦、氧化鎂及氧化硼之至少一種之多孔質無機氧化物；上述活性金屬為鉑及/或鈀。根據此種觸媒，可更有效地進行氫化異構化，故能以更高產率獲得高品質之潤滑油基油。
本發明之潤滑油基油之製造方法中，較佳為以下述式(4)所表示之正構石蠟之轉化率為95%以上之方式進行上述第二步驟。根據此種製造方法，能以更高產率獲得高品質之潤滑油基油。
正構石蠟之轉化率(%)=[1-(上述第二生成油中之碳數20以上之正構石蠟之總質量)/(上述第一生成油中之碳數20以上之正構石蠟之總質量)]×100 (4)
本發明之潤滑油基油之製造方法中，亦可對上述第二生成油進一步進行氫化純化。上述第二生成油一面抑制氫化分解反應一面進行氫化異構化。因此，上述氫化純化可為較先前進行之氫化純化條件更溫和之條件，並可抑制氫化處理所伴隨之氫化分解反應所導致之產率下降。
本發明之潤滑油基油之製造方法中，較佳為經上述第一步驟及上述第二步驟，而獲得選自由以下潤滑油基油所組成群中之至少1種潤滑油基油：沸點為340~410℃，黏度指數為105以上，流動點為-25℃以下，硫為5質量ppm以下之70Pale潤滑油基油；沸點為390~470℃，黏度指數為130以上，流動點為-12.5℃以下，硫為5質量ppm以下之SAE10潤滑油基油；沸點為450~520℃，黏度指數為130以上，流動點為-12.5℃以下，硫為5質量ppm以下之SAE20潤滑油基油；及沸點為510~550℃，黏度指數為130以上，流動點為-10℃以下，硫為5質量ppm以下之SAE30潤滑油基油。該等潤滑油基油於實用上具有充分之性能，根據本發明之製造方法，亦能以高產率獲得此等高品質之潤滑油基油。
根據本發明，可提供一種潤滑油基油之製造方法，其由含有正構石蠟之原料油穩定且高產率地獲得高品質之潤滑油基油。
以下，對本發明之較佳實施形態進行詳細說明。
(第一步驟)
於本實施形態之潤滑油基油之第一步驟中，於分子狀氫氣之存在下，使含有碳數20以上之正構石蠟之原料油與第一觸媒接觸而獲得第一生成油。第一觸媒含有：於氨脫附溫度依賴性評價中於300~800℃時NH3
之脫附量相對於NH3
之總脫附量之分率為80~90%的第一載體；承載於第一載體之選自屬於週期表第6族之金屬之至少一種的第一金屬；承載於第一載體之選自屬於週期表第8~10族之金屬之至少一種的第二金屬。又，第一觸媒中之按第一金屬之氧化物換算之含有比例C1
(質量%)與按第二金屬之氧化物換算之含有比例C2
(質量%)之和C1
+C2
為22~36質量%，第一觸媒中之第二金屬之含量D2
(莫耳)相對於第一金屬之含量D1
(莫耳)之比D1
/D2
為1.07~7.78。
於第一步驟中，將原料油中之硫及氮去除，且將碳數20以上之正構石蠟之一部分異構化為異構石蠟。於第一步驟中，可一面抑制正構石蠟之氫化分解，一面效率佳地進行氫化脫硫、氫化脫氮及氫化異構化。即，根據第一步驟，可獲得碳數20以上之各石蠟之總含量為與原料油相同程度，硫及氮之含量充分降低，且碳數20以上之正構石蠟中大部分轉化為碳數20以上之異構化石蠟之生成油，並能由此種生成油高產率地獲得高品質之潤滑油基油。再者，所謂「高品質」，係指因硫之含量較少而環境負荷較少，且由於優異之低溫性能而可達成優異之低耗油性能。
於本實施形態之潤滑油基油製造方法中，經第一步驟與進行氫化脫蠟之第二步驟後，可根據需要進一步包括氫化純化、分餾等步驟。該等步驟中，可一面抑制第一生成油之氫化分解反應一面充分地進行正構石蠟之異構化，因此與先前之氫化脫蠟、氫化純化、分餾等之條件相比較，可於溫和的條件下充分獲得高品質之潤滑油基油。因此，可高產率地獲得高品質之潤滑油基油。
作為原料油，可較佳地使用選自由松蠟、脫蠟油、石蠟、微晶蠟、凡士林、費托蠟、減壓輕油、減壓輕油氫化分解油、常壓殘油氫化分解油及減壓殘油氫化分解油所組成群中之至少一種。此等原料油可經濟性佳且穩定地獲得。
第一步驟中所使用之第一觸媒含有：第一載體，承載於第一載體之選自屬於週期表第6族之金屬之至少一種的第一金屬，及承載於第一載體之選自屬於週期表第8~10族之金屬之至少一種的二金屬，來作為活性金屬。第一觸媒中除第一金屬及第二金屬以外，還可進一步含有金屬。再者，第一金屬及第二金屬較佳為以氧化物之形式承載於第一載體。
作為第一載體，較佳為含有固體酸性質；較佳為於氨脫附溫度依賴性評價中300~800℃下NH3
之脫附量相對於NH3
之總脫附量之分率為80~90%者；就可使潤滑油基油之產率進一步提高之觀點而言，更佳為81%~89.5%者。
此處，所謂「NH3
脫附溫度依賴性評價」，為文獻(Sawa M.,Niwa M.,Murakami Y.,Zeolites 1990,10,532;Karge H. G.,Dondur V.,J. Phys. Chem. 1990,94,765等)中所介紹之方法，並以如下方式進行。首先，將載體於氮氣流下於400℃以上之溫度下預處理30分鐘以上，去除吸附分子後，使其於100℃下吸附NH3
直至飽和。其次，將該載體以10℃/分鐘以下之升溫速度自100℃升溫至800℃而使NH3
脫附，於每特定溫度下監控因脫附而分離之NH3
。然後，求得於300℃~800℃時NH3
之脫附量相對於NH3
之總脫附量(於100~800℃時之脫附量)之分率。
作為第一載體，較佳為含有氧化鋁、二氧化矽及氧化鋯之複合氧化物之非晶載體。含有此種載體之觸媒，可進一步抑制氫化異構化所伴隨之氫化分解反應，且具有承受商業性使用之機械強度。
第一觸媒中，將相對於第一觸媒總量的按第一金屬之氧化物換算之含有比例設為C1
(質量%)，將相對於第一觸媒總量的按第二金屬之氧化物換算之含有比例為C2
(質量%)時，C1
+C2
為22~36質量%，就可進一步抑制氫化分解反應之觀點而言，較佳為24~33質量%，更佳為25~30質量%。
再者，C1
(質量%)係由下述式(1)所求得之值，C2
(質量%)係由下述式(2)所求得之值。
[數1]
此處，所謂「第一觸媒中之按第一金屬之氧化物換算之含有質量」，係表示與第一觸媒中之第一金屬之含量(莫耳)相同莫耳量之第一金屬之氧化物的質量。即表示，於第一金屬之含量為X莫耳之情形下，相當於第一金屬之氧化物X莫耳之質量。又，所謂「第一觸媒中之按第二金屬氧化物換算之含有質量」，係表示與第一觸媒中之第二金屬之含量(莫耳)相同莫耳量之第二金屬之氧化物的質量。
又，於第一觸媒中，第二金屬之含量D2
(莫耳)相對於第一金屬之含量D1
(莫耳)之比D1
/D2
為1.07~7.78，就可進一步抑制氫化分解反應之觀點而言，較佳為2.08以上，更佳為2.25以上，又，較佳為6.75以下，更佳為5.71以下。
於第一觸媒中，較佳為含有鉬及/或鎢作為第一金屬，較佳為含有鈷及/或鎳作為第二金屬。根據此種觸媒，可進一步抑制氫化異構化所伴隨之氫化分解反應。
第一觸媒中，藉由氮吸附法之BET法(Brunauer-Emmett-Teller method)所求得之觸媒之平均細孔半徑為40~200，更佳為60~150。於平均細孔半徑小於40之情形下，有反應分子(例如，碳數20以上之正構石蠟、硫、氮等)於細孔內擴散不會充分進行，而使觸媒活性下降之情形。又，若平均細孔半徑大於200，則因觸媒之表面積變小而有觸媒活性下降之傾向。
於第一觸媒中，細孔半徑未達40之細孔之總細孔容積較佳為總細孔容積之0.1~5%，更佳為0.1~3%。至於細孔半徑未達40之細孔中反應分子之擴散的容易性，雖然比大於其之細孔差，但仍不可忽視對脫硫反應之幫助，於小於0.1%之情形下存在有效之觸媒表面積減少，而使活性下降之擔憂。另一方面，於大於5%之情形下存在由於擴散之影響，活性反而下降之擔憂。
於第一觸媒中，細孔半徑大於200之細孔之總細孔容積較佳為總細孔容積之0.1~5%，更佳為0.1~4%。該區域內之細孔可認為係左右反應分子到達反應活性點之到達程度的重要細孔。若其小於0.1%，則有反應分子之擴散不充分而使活性下降之情形，若其大於5%，則可認為觸媒之表面積本身會減少而使活性下降。根據此種觸媒，可更有效地進行氫化脫硫、氫化脫氮及氫化異構化。
使第一金屬及第二金屬承載於載體之方法並無特別限定，可使用於製造觸媒時所通常應用之公知方法。作為此種方法，較佳為採用將含有第一金屬及第二金屬之鹽的溶液含浸於載體中之方法。又，亦較佳為採用平衡吸附法、孔隙充填法(Pore-filling method)，初濕含浸法(Incipient-wetness method)等。例如，孔隙充填法係預先測定載體細孔容積，並含浸與其相同容積之金屬鹽溶液中之方法，含浸方法並無特別限定，可根據金屬承載量或載體之物性而用適當之方法含浸。
第一步驟較佳為以如下方式進行：於第一生成油中，碳數未達20之輕質石蠟之含量為0~10質量%，碳數20以上之異構化石蠟之含量為70質量%以上，硫之含量為10質量ppm以下，氮之含量為3質量ppm以下。根據此種生成油，能以更高產率獲得潤滑油基油。又，下述之第二步驟(氫化脫蠟步驟)中，因使第一生成油之硫及氮充分降低，故可不損及第二觸媒(氫化脫蠟觸媒)之活性，而有效地進行氫化脫蠟。
又，於第一步驟中，下述式(3)所表示之正構石蠟之轉化率較佳為70%以上。
正構石蠟之轉化率(%)=[1-(第一生成油中之碳數20以上之正構石蠟之總質量)/(原料油中之碳數20以上之正構石蠟之總質量)]×100 (3)
至於第一步驟中原料油與第一觸媒之接觸條件，例如較佳為氫氣分壓為3~20 MPa，觸媒層平均反應溫度為250~450℃，LHSV(liquid hourly space velocity，液體時空流速)為0.5~5.0 h-1
，氫氣/油比為1000~8000 scf/b。根據此等條件，可容易地獲得上述較佳之第一生成油。又，上述接觸條件特佳為原料油含有碳數20以上之正構石蠟、硫500質量ppm以上、氮10質量ppm以上之情形。
本實施形態之潤滑油基油之製造方法中，可根據需要進而經氫化脫蠟、溶劑脫蠟、氫化純化、分餾等步驟而獲得潤滑油基油。
先前之潤滑油基油之製造方法中，若進行純化至實質上不含正構石蠟之程度，則會因伴隨純化操作之石蠟成分之損失，而無法獲得充分之產率。相對於此，於本發明之製造方法中，由於在第一步驟中可產率佳地獲得異構化石蠟，因此伴隨純化操作之石蠟成分之損失較少，而可高產率地獲得高品質之潤滑油基油。
本實施形態之潤滑油基油之製造方法中，就獲得更高品質之潤滑油基油之觀點而言，亦可對第一生成油進一步進行氫化處理。第一生成油一面抑制氫化分解反應一面進行氫化異構化。因此，上述氫化處理可為較先前進行之氫化處理之條件更溫和之條件，可抑制因氫化處理所伴隨之氫化分解反應引起的產率之下降。
上述氫化處理可為一階段亦可為多階段。作為氫化處理，可舉出氫化脫蠟、氫化純化等，根據需要可將其組合，而獲得具有所需性狀之潤滑油基油。
以下，作為較佳之製造方法之一例，係對如下製造方法進行說明：將第一生成油氫化脫蠟(第二步驟(氫化脫蠟步驟))，繼而進行氫化純化(氫化純化步驟)，將所得之基油分餾而獲得所需之潤滑油基油(分餾步驟)。
(第二步驟)
於第二步驟中，於分子狀氫氣之存在下，使第一生成油與第二觸媒接觸而獲得第二生成油。此處獲得之第二生成油較佳為進行氫化脫蠟，即實質上不含碳數20以上之正構石蠟(即，碳數20以上之正構石蠟之含有比例為5質量%以下)。第二步驟即所謂之氫化脫蠟步驟。
作為第二觸媒，可使用公知之氫化異構化觸媒，例如較佳為含有載體(以下稱為「第二載體」)及承載於第二載體之活性金屬(以下稱為「第三金屬」)之觸媒，更佳為第二載體具有固體酸性質之雙功能觸媒。作為第二載體，可舉出一維10員環中細孔徑沸石與選自氧化鋁、二氧化矽、氧化鋯、二氧化鈦、氧化鎂、氧化硼之至少一種之多孔質無機氧化物之混合物等。該等中，一維10員環中細孔徑沸石較佳為選自ZSM-22、ZSM-23及ZSM-48之至少一種沸石。又，作為承載於第二載體之第三金屬，較佳為鉑及/或鈀。
於第二步驟中，下述式(4)所表示之正構石蠟之轉化率較佳為95%以上。
正構石蠟之轉化率(%)=[1-(第二生成油中之碳數20以上之正構石蠟之總質量)/(第一生成油中之碳數20以上之正構石蠟之總質量)]×100 (4)
於第二步驟中，例如較佳為於氫氣分壓為0.5~20 Mpa，觸媒層平均反應溫度為250~400℃，LHSV為0.5~10.0 h-1
，氫氣/油比為1000~10000 scf/b下進行氫化脫蠟。
(氫化純化(氫化精加工)步驟)
於氫化純化步驟中，於分子狀氫氣之存在下，使第二生成油與第三觸媒接觸，而獲得第三生成油。於氫化純化步驟中，藉由將第二生成油中之烯烴成分或多環芳香族化合物氫化，而可提高色相及/或氧化穩定性。
作為第三觸媒，可使用公知之氫化純化觸媒，較佳為含有載體與承載於該載體之金屬。作為載體，可舉出氧化鋁、二氧化矽、氧化鋯、氧化鈦、氧化硼等。又，作為承載於載體之金屬，可舉出鎳、鉬、鈷、鎢、鈀、鉑等。可將複數種金屬承載於載體，較佳為鉑-鈀，鎳-鉬，鈷-鉬，鎳-鎢等組合。
於氫化純化步驟中，例如較佳為於氫氣分壓為1~20 Mpa，觸媒層平均反應溫度為200~350℃，LHSV為0.1~10.0 h-1
，氫氣/油比為1000~10000 scf/b下進行氫化純化。
(分餾步驟)
於分餾步驟中，自第三生成油蒸餾分離潤滑油餾分。此時，有時亦獲得作為輕質分之燃料油餾分。
於分餾步驟中，藉由將第三生成油減壓蒸餾，而可較佳地獲得被稱為70Pale、SAE10、SAE20、SAE30之潤滑油基油。更具體而言，於分餾步驟中，可獲得分別具有以下所示之性狀之潤滑油基油，作為相當於70Pale、SAE10、SAE20、SAE30之潤滑油基油。再者，所謂NOACK蒸發量，係表示依據ASTM D5800而測定之蒸發損失量。
70Pale：沸點為340~410℃，100℃下運動黏度為2.2~3.8mm2
/s，黏度指數為105以上，流動點為-25℃以下，且硫為5質量ppm以下。
SAE10：沸點為390~470℃，100℃下運動黏度為3.5~5.6mm2
/s，黏度指數為130以上，-30℃下CCS(Cold Cranking Simulator，低溫模擬驅動設備)黏度為2800以下，NOACK蒸發量為16質量%以下，流動點為-12.5℃以下，且硫為5質量ppm以下。
SAE20：沸點為450~520℃，100℃下運動黏度為5.6~9.3mm2
/s，黏度指數為130以上，流動點為-12.5℃以下，且硫為5質量ppm以下。
SAE30：沸點為510~550℃，100℃下運動黏度為9.3~12.5 mm2
/s，黏度指數為130以上，流動點為-10℃以下，且硫為5質量ppm以下。
藉由本實施形態之潤滑油基油之製造方法所獲得之潤滑油基油，其本身具有優秀之熱、氧化穩定性，進而，於該潤滑油基油中調配添加劑之情形下，能使該添加劑於潤滑油基油中充分穩定地溶解保持，並以更高水準表現出該添加劑之功能。因此，於該潤滑油基油中調配了抗氧化劑之潤滑油組合物中，可達成高水準之熱、氧化穩定性。例如所得之潤滑油基油相當於70Pale之情形時，其RBOT(Rotating Bomb Oxidation Test，旋轉氧彈試驗)壽命可為290 min以上。又，所得之潤滑油基油相當於SAE10之情形時，其RBOT壽命可為350 min以上。又，所得之潤滑油基油相當於SAE20之情形時，其RBOT壽命可為400 min以上。再者，本發明中所謂之RBOT壽命，係指對於在潤滑油基油中添加0.2質量%之酚系抗氧化劑(2,6-二第三丁基-對甲酚；DPBC)之組合物，依據JIS K 2514而測定之RBOT值。
進而，根據由本實施形態之製造方法所得之潤滑油基油，因潤滑油基油本身之黏度-溫度特性及摩擦特性優異，因此可提高摩擦降低效果，進而達成節能性之提高。進而，因該潤滑油基油於添加劑之效果方面亦優異，於該潤滑油基油中調配摩擦降低劑之情形時，可達成高水準之摩擦降低效果及節能性。
藉由本實施形態之製造方法所得之潤滑油基油具有如上所述般優異之特性，因此可較佳地用作各種潤滑油之基油。作為潤滑油基油之用途，具體可舉出：客車用汽油引擎、摩托車用汽油引擎、柴油引擎、燃氣引擎、燃氣熱泵用引擎、船舶用引擎、發電引擎等內燃機中所用之潤滑油(內燃機用潤滑油)；自動變速機、手動變速機、無段變速機、最後減速機等驅動傳遞裝置中所用之潤滑油(驅動傳遞裝置用油)；緩衝器、建築機械等之油壓裝置中所用之油壓液壓油；壓縮機油；渦輪油；齒輪油；冷凍機油；金屬加工用油劑等；藉由在該等用途中使用本發明之潤滑油基油，而能以高水準達成各潤滑油之黏度-溫度特性，熱、氧化穩定性，節能性，省油耗性等特性之提高，並且能以高水準達成各潤滑油之長壽命化及降低環境負荷物質。
(實施例1~12，比較例1~9)
實施例1所記載之非晶氧化鋁二氧化矽氧化鋯複合氧化物係依據下述方法調製而成。首先，分別準備溶液A、溶液B、溶液C。溶液A：於90 ml離子交換水中溶解20 g硫酸鋁16水合物試劑所得之溶液。溶液B：於50 ml離子交換水中溶解11.4 g水玻璃3號所得之溶液。溶液C：於50 ml離子交換水中溶解2.3g硫酸鋯4水合物試劑所得之溶液。
其次，於以pH14使溶液B凝膠化後，以pH7熟化2小時所得之漿料中，加入溶液C，進而將該漿料調整為pH7，而生成二氧化矽氧化鋯複合氫氧化物。於其中加入溶液A使之為pH7，並生成二氧化矽氧化鋯氧化鋁複合氫氧化物。過濾、清洗所得之漿料，藉由加熱濃縮調整水分後，經擠壓成型、乾燥、煅燒，而獲得直徑約1.5 mm，長度約10 mm之擠壓成型體(載體)。對所獲得之載體實施氨脫附溫度依賴性評價，將於300~800℃時NH3
之脫附量相對於NH3
之總脫附量之分率示於表1。於該載體上以成為表1所記載之含量之方式，以孔隙充填法承載金屬，並進行硫化而獲得第一觸媒。
再者，對於實施例1以外之觸媒，亦以滿足表1之載體組成之方式，調整溶液A、溶液B、溶液C之濃度而製作載體，於所得之載體上以成為表1所記載之含量之方式，以孔隙充填法承載金屬，並進行硫化而獲得第一觸媒。
繼而，於表3所示之條件下使上述表1所示之觸媒與具有下述表2所示之性狀之松蠟接觸，獲得具有表3所示之性狀之生成油(第一生成油)。再者，表中分解率係根據藉由氣相層析法(Gas Chromatography)分析之生成油中碳數為19以下之成分的產率而求得之值，異構化率係表示根據藉由氣相層析法分析求得之碳數為20以上之成分中的異構物比例而求得之值。又，硫係表示基於JIS K2541「原油及石油製品-硫試驗方法」而測定之值，氮係表示基於JIS K2609「原油及石油製品-氮試驗方法」而測定之值。
繼而，對實施例1~12、比較例1~8中所得之第一生成油，分別於下述表4所示之條件下進行氫化處理(氫化脫蠟步驟)，而獲得第二生成油。再者，表中碳數20以上之正構石蠟含量係表示藉由氣相層析法分析求得之值。對比較例9中所得之第一生成油進行溶劑脫蠟，即相對於第一生成油而加入3.5倍量之甲基乙基酮/甲苯混合溶劑(混合比例50體積%/50體積%)，於-32℃下過濾，並將溶劑脫蠟後之生成油作為第二生成油。
進而，對於第二生成油，於活性金屬為鉑、載體為氧化鋁之觸媒存在下，於反應溫度為220℃，LHSV為2 h-1
，氫氣分壓為5 Mpa，氫氣/油比為3000 scf/b之條件下進行氫化處理(氫化純化步驟)，而獲得第三生成油。將所得之第三生成油藉由減壓蒸餾而分餾，而獲得按常壓換算為340~410℃之餾分的70Pale基油、按常壓換算為390~470℃之餾分的SAE10基油、按常壓換算為450~520℃之餾分的SAE20基油、按常壓換算為510~550℃之餾分的SAE30基油。所得之基油之產率及各性狀如表5所示。再者，運動黏度(100℃)及黏度指數(VI，Viscosity Index)係基於JIS K2283「原油及石油製品-運動黏度試驗方法及黏度指數計算方法」而測定，流動點係基於JIS K2269「原油及石油製品之流動點及石油製品濁點試驗方法」而測定。實施例中均可高產率地獲得高品質之潤滑油基油。
Claims (15)
- 一種潤滑油基油之製造方法，其包括：第一步驟，其係於分子狀氫氣之存在下，使含有碳數20以上之正構石蠟之原料油與第一觸媒接觸而獲得第一生成油；及第二步驟，其係於分子狀氫氣之存在下，使上述第一生成油與第二觸媒接觸而獲得第二生成油；上述第一觸媒包含：於氨脫附溫度依賴性評價中300~800℃下NH3 之脫附量相對於NH3 之總脫附量之分率為80~90%的第一載體，承載於該第一載體之選自屬於週期表第6族之金屬之至少一種的第一金屬，及承載於上述第一載體之選自屬於週期表第8~10族之金屬之至少一種的第二金屬；上述第一觸媒中之按上述第一金屬之氧化物換算之含有比例C1 (質量%)、與按上述第二金屬之氧化物換算之含有比例C2 (質量%)之和C1 +C2 為22~36質量%；上述第一觸媒中之上述第二金屬之含量D2 (莫耳)相對於上述第一金屬之含量D1 (莫耳)之比D2 /D1 為1.07~7.78。
- 如請求項1之潤滑油基油之製造方法，其中上述第一生成油中碳數未達20之輕質石蠟之含有比例為0~10質量%，碳數20以上之異構化石蠟之含有比例為70質量%以上，硫之含有比例為10質量ppm以下，氮之含有比例為3質量ppm以下。
- 如請求項1或2之潤滑油基油之製造方法，其中上述第一觸媒含有鉬及/或鎢作為上述第一金屬。
- 如請求項1或2之潤滑油基油之製造方法，其中上述第一觸媒含有鈷及/或鎳作為上述第二金屬。
- 如請求項1或2之潤滑油基油之製造方法，其中上述第一觸媒進而含有承載於上述第一載體之磷，上述第一觸媒中之按該磷的氧化物換算之含有比例為0.1~8質量%。
- 如請求項1或2之潤滑油基油之製造方法，其中上述第一觸媒之平均細孔半徑為40~200Å，細孔半徑未達40Å之細孔之總細孔容積為總細孔容積之0.1~5%，細孔半徑大於200Å之細孔之總細孔容積為總細孔容積之0.1~5%。
- 如請求項1或2之潤滑油基油之製造方法，其中上述第一載體係含有氧化鋁、二氧化矽及氧化鋯之複合氧化物之載體。
- 如請求項1或2之潤滑油基油之製造方法，其中上述第一步驟中將上述碳數20以上之正構石蠟之一部分異構化為異構石蠟。
- 如請求項1或2之潤滑油基油之製造方法，其中上述原料油係選自由松蠟、脫蠟油、石蠟、微晶蠟、凡士林、費托蠟、減壓輕油、減壓輕油氫化分解油、常壓殘油氫化分解油及減壓殘油氫化分解油所組成群中之至少一種。
- 如請求項1或2之潤滑油基油之製造方法，其中於上述第一步驟中，下述式(3)所表示之正構石蠟之轉化率為70%以上：正構石蠟之轉化率(%)=[1-(上述第一生成油中之碳數20以上之正構石蠟之總質量)/(上述原料油中之碳數20以 上之正構石蠟之總質量)]×100 (3)。
- 如請求項1或2之潤滑油基油之製造方法，其中於上述第二生成油中，碳數20以上之正構石蠟之含有比例為5質量%以下。
- 如請求項1或2之潤滑油基油之製造方法，其中上述第二觸媒係含有第二載體與承載於該第二載體之活性金屬之氫化異構化觸媒；上述第二載體含有一維10員環中細孔徑沸石，及選自氧化鋁、二氧化矽、氧化鋯、二氧化鈦、氧化鎂及氧化硼之至少一種之多孔質無機氧化物；上述活性金屬為鉑及/或鈀。
- 如請求項1或2之潤滑油基油之製造方法，其中於上述第二步驟中，下述式(4)所表示之正構石蠟之轉化率為95%以上：正構石蠟之轉化率(%)=[1-(上述第二生成油中之碳數20以上之正構石蠟之總質量)/(上述第一生成油中之碳數20以上之正構石蠟之總質量)]×100 (4)。
- 如請求項1或2之潤滑油基油之製造方法，其中對上述第二生成油進一步進行氫化純化。
- 如請求項1或2之潤滑油基油之製造方法，其中經上述第一步驟及上述第二步驟，而獲得選自由以下潤滑油基油所組成群中之至少一種潤滑油基油：沸點為340~410℃，黏度指數為105以上，流動點為-25℃以下，硫為5質量ppm以下之70Pale潤滑油基油； 沸點為390~470℃，黏度指數為130以上，流動點為-12.5℃以下，硫為5質量ppm以下之SAE10潤滑油基油；沸點為450~520℃，黏度指數為130以上，流動點為-12.5℃以下，硫為5質量ppm以下之SAE20潤滑油基油；及沸點為510~550℃，黏度指數為130以上，流動點為-10℃以下，硫為5質量ppm以下之SAE30潤滑油基油。
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| US9284500B2 (en) * | 2013-03-14 | 2016-03-15 | Exxonmobil Research And Engineering Company | Production of base oils from petrolatum |
| CN105154136B (zh) * | 2015-07-14 | 2017-09-05 | 马春磊 | 一种氯化石蜡的生产工艺和设备 |
| US11312917B2 (en) | 2015-12-25 | 2022-04-26 | Idemitsu Kosan Co., Ltd. | Mineral base oil, lubricant composition, internal combustion engine, lubricating method of internal combustion engine |
| US20170283711A1 (en) * | 2016-03-31 | 2017-10-05 | Exxonmobil Research And Engineering Company | Methods for fractionation of lubricant feeds |
| CN108559595A (zh) * | 2018-05-24 | 2018-09-21 | 佛山途胜汽车科技有限公司 | 一种汽车引擎养护液 |
| CN109722304A (zh) * | 2019-01-28 | 2019-05-07 | 海南汉地阳光石油化工有限公司 | 一种液压油的生产方法 |
| CN113677778A (zh) * | 2019-03-28 | 2021-11-19 | 引能仕株式会社 | 润滑油基础油的制造方法 |
| CN114806635B (zh) * | 2022-03-31 | 2024-04-12 | 海南汉地阳光石油化工有限公司 | 一种铜板轧制专用基础油的制备方法 |
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| TW200900145A (en) * | 2007-06-27 | 2009-01-01 | Nippon Oil Corp | Hydroisomerization catalyst, method of dew axing hydrocarbon oil, process for producing base oil, and process for producing lube base oil |
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| EP2468840A1 (en) | 2012-06-27 |
| RU2528977C2 (ru) | 2014-09-20 |
| KR101811200B1 (ko) | 2017-12-22 |
| AU2010285834A1 (en) | 2012-03-08 |
| MY156322A (en) | 2016-02-15 |
| US9057026B2 (en) | 2015-06-16 |
| KR20120064674A (ko) | 2012-06-19 |
| US20120217186A1 (en) | 2012-08-30 |
| JP5290912B2 (ja) | 2013-09-18 |
| WO2011021513A1 (ja) | 2011-02-24 |
| AU2010285834B2 (en) | 2016-03-31 |
| TW201113364A (en) | 2011-04-16 |
| EP2468840A4 (en) | 2016-02-10 |
| JP2011038059A (ja) | 2011-02-24 |
| RU2012110229A (ru) | 2013-09-27 |
| CN102471704A (zh) | 2012-05-23 |
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