EP1212390B1 - Nouvelle huile de base hydrocarbonee pour lubrifiants a indice de viscosite tres eleve - Google Patents
Nouvelle huile de base hydrocarbonee pour lubrifiants a indice de viscosite tres eleve Download PDFInfo
- Publication number
- EP1212390B1 EP1212390B1 EP00960815A EP00960815A EP1212390B1 EP 1212390 B1 EP1212390 B1 EP 1212390B1 EP 00960815 A EP00960815 A EP 00960815A EP 00960815 A EP00960815 A EP 00960815A EP 1212390 B1 EP1212390 B1 EP 1212390B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- base oil
- oil according
- viscosity index
- carbon atoms
- equal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Revoked
Links
- 239000002199 base oil Substances 0.000 title claims abstract description 58
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 13
- 239000000314 lubricant Substances 0.000 title claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 11
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000009472 formulation Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010705 motor oil Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 33
- 239000002585 base Substances 0.000 description 18
- 238000006467 substitution reaction Methods 0.000 description 15
- 229920013639 polyalphaolefin Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241001080024 Telles Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
Definitions
- the invention relates to a hydrocarbon base oil for high-end lubricants, obtained from hydrocarbon cuts from various sources. More specifically, the invention relates to an oil of this type, having a viscosity index VI, calculated according to standard NF T 60-136, greater than 130, for a kinematic viscosity measured at 100 ° C (Vk @ 100 ° C) , measured according to standard NF T 60-100, between 3.5 and 4.5 mm 2 / s (or cSt).
- This base oil finds a preferential application in the formulations of lubricants for engines, in particular in the automobile industry, as well as for industrial uses.
- Base oils are currently classified according to the API classification into five groups, according to characteristics defined in Table 1 below: Table 1 Saturated compounds (% by weight) Sulfur content (% by weight) Viscosity index VI Group 1 ⁇ 90 > 0.03 80 ⁇ VI ⁇ 120 Group II > 90 ⁇ 0.03 80 ⁇ VI ⁇ 120 Group III > 90 ⁇ 0.03 > 120 Group IV PAO (Poly- ⁇ -olefins) Group V Others (esters)
- viscosity index or VI of petroleum products is calculated from their kinematic viscosities at 40 ° C and 100 ° C, according to standard NF T 60-136.
- Such bases obtained from hydrocracking residues subjected to a dewaxing with solvent and forming part of group III according to the API classification described above, are currently produced, in particular by the Applicant, under the name NHC5 (“Neutral HydroCracked ”), with a Vk @ 100 ° C of 4.5 to 5 mm 2 / s (4.5 to 5 cSt).
- Patent application FR 2 194 767 A describes, in particular, a process for preparing a high VI lubricating oil, comprising a catalytic hydrocracking treatment of a mineral fraction with high boiling point, a effluent fractionation, dewaxing of the boiling residue above 350 ° C. and catalytic hydroisomerization of the paraffin obtained.
- EP-A-0 323 092 describes a process for producing high VI oil, comprising steps of hydrotreatment, catalytic hydroisomerization and dewaxing
- WO 97/21788 A describes a process for producing a biodegradable lubricating base oil, comprising a step of hydroisomerization and catalytic hydrocracking of a fraction of boiling point above 370 ° C.
- the object of the present invention is therefore to obtain a new base oil for high-end lubricants, obtained from hydrocarbon cuts from various sources, having a high viscosity index and improved cold properties, in particular a pour point below -18 ° C, ensuring satisfactory rheological properties to the finished lubricating oils formulated from this base oil, in a wide range of temperatures (from -30 to + 100 ° C), thanks to a particular branching structure of the paraffinic molecules composing it.
- the base oil according to the invention is much better in performance than bases currently available on the market, derived from hydrocracked products and having undergone solvent dewaxing (oils of the NHC5 type), or dewaxing catalytic, and which belong to group III according to the API classification described above.
- it can also replace known synthetic bases such as poly- ⁇ -olefins (PAO), belonging to group IV, whose performances are well known for increasing the VI, but which have the major drawback of have a cost much higher than the bases of mineral origin.
- PAO poly- ⁇ -olefins
- the subject of the invention is a hydrocarbon base oil for lubricants, having a viscosity index VI greater than or equal to 130, comprising mainly long, isoparaffinic hydrocarbon chains, comprising a number of carbon atoms greater than 25 and branched on several carbon atoms, characterized in that the hydrocarbon chains have a ratio of the number of substituents composed of at least two carbon atoms to the number of methyl substituents greater than or equal to 0.9, and in that these chains have a ratio of the number of substituents composed of at least two carbon atoms, to the number of CH 2 long chain groups, greater than or equal to 0.23.
- the base oil according to the invention has a ratio of the viscosity index when cold (VIF) to the viscosity index (VI) (measured according to standard NF T 60-136) greater than or equal at 1.
- the base oil has a content of naphthenic molecules less than or equal to 0.1.
- the base oil has a Noack volatility value of less than 13% by weight (calculated according to standard CEC-L-40-A 95), as well as a pour point (calculated according to standard NFT 60- 105) below -18 ° C.
- it has a Saybolt color value of + 30 (measured according to the ASTM D 156 method).
- the base oil has a cold viscosity index (VIF) greater than 125.
- the base oil has a dynamic CCS viscosity at -30 ° C of less than 1200 mPa.s (calculated according to standard ASTM D 5293), for a kinematic viscosity Vk at 100 ° C of 4 mm 2 / s.
- the base oil according to the invention has a viscosity index VI greater than 130 and less than or equal to 135, for a kinematic viscosity Vk at 100 ° C of between 3.5 and 4.5 mm 2 / s or cSt.
- this base oil has a viscosity index VI greater than 135 for a kinematic viscosity Vk at 100 ° C of between 4.5 and 5 mm 2 / s.
- a second object of the invention relates to the use of the base oil defined above, in the formulation of lubricants for engines, in particular for automobiles, with a view in particular to formulating an OW30 grade.
- a third subject of the invention relates to a process for the preparation of the base oil of the invention successively comprising the stages of hydrotreatment, hydrodewaxing, fractionation and hydrofinishing of residue cuts from hydrocracking.
- the new base oil exhibits advantageous properties when cold, characterized, on the one hand, by a pour point of less than - 18 ° C and, on the other hand , by a new so-called cold viscosity index (VIF) such that the oil has a cold viscosity index (VIF) / viscosity index (VI) ratio, greater than or equal to 1.
- the cold viscosity index VIF is calculated in using the usual formula for calculating the VI (according to standard NF T 60-136), which integrates the values of kinematic viscosity at 100 ° C and 40 ° C of the product to be measured, but by replacing the value of kinematic viscosity with 40 ° C, the kinematic viscosity value at -30 ° C. The latter is obtained by dividing the dynamic viscosity at - 30 ° C (which is measurable) by the density at - 30 ° C of the product, calculated from the density at 15 ° C, by temperature correction.
- All these oils have a kinematic viscosity Vk @ 100 ° C of between 4 and 5 mm 2 / s (4 and 5 cSt).
- Mass spectrometry made it possible to evaluate the content of naphthenic molecules in the various base oils: there are approximately 10% for oil A, as well as for oil B, against 30% for oil C, 40% for oil D and 60% for oil E.
- fillers can advantageously be used, in mixture with the previous fillers, for doping them, in particular paraffins or Fischer-Tropsch synthetic waxes, waxes or slack waxes, and distillates for atmospheric or vacuum distillation.
- the lubricating base oil according to the invention by oligomerization of olefins, in particular of light alpha-olefins present in particular in the heavy petrol of visbreaking units or in l essence of FCC (cracker catalytic).
- This oligomerization is carried out in the presence of a catalyst of the phosphoric acid or aluminum chloride type, at temperatures between approximately 190 ° C. and 340 ° C. and it leads to hydrocarbon products with very branched long chains.
- the base oils thus obtained having a VI greater than 130 and a VIF greater than 125, can replace synthetic lubricating bases of the PAO type, with an advantageous economic advantage, in formulations for oils for automobile engines and in particular in grades such as OW30, for which the requirements of cold properties are the most severe: kinematic viscosity Vk @ 100 ° C between 9.3 and 12.5 mm 2 / s and dynamic viscosity CCS at -30 ° C less than 3250 mPa.s.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9911219 | 1999-09-08 | ||
FR9911219A FR2798136B1 (fr) | 1999-09-08 | 1999-09-08 | Nouvelle huile de base hydrocarbonee pour lubrifiants a indice de viscosite tres eleve |
PCT/FR2000/002463 WO2001018156A1 (fr) | 1999-09-08 | 2000-09-07 | Nouvelle huile de base hydrocarbonee pour lubrifiants a indice de viscosite tres eleve |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1212390A1 EP1212390A1 (fr) | 2002-06-12 |
EP1212390B1 true EP1212390B1 (fr) | 2003-01-29 |
Family
ID=9549629
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00960815A Revoked EP1212390B1 (fr) | 1999-09-08 | 2000-09-07 | Nouvelle huile de base hydrocarbonee pour lubrifiants a indice de viscosite tres eleve |
Country Status (14)
Country | Link |
---|---|
US (1) | US6599864B1 (ja) |
EP (1) | EP1212390B1 (ja) |
JP (1) | JP2003520867A (ja) |
KR (1) | KR100711294B1 (ja) |
AT (1) | ATE231908T1 (ja) |
AU (1) | AU769075B2 (ja) |
CA (1) | CA2382893A1 (ja) |
DE (1) | DE60001331T2 (ja) |
DK (1) | DK1212390T3 (ja) |
ES (1) | ES2190986T3 (ja) |
FR (1) | FR2798136B1 (ja) |
PT (1) | PT1212390E (ja) |
WO (1) | WO2001018156A1 (ja) |
ZA (1) | ZA200201564B (ja) |
Families Citing this family (154)
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US7282137B2 (en) * | 2002-10-08 | 2007-10-16 | Exxonmobil Research And Engineering Company | Process for preparing basestocks having high VI |
US20040129603A1 (en) * | 2002-10-08 | 2004-07-08 | Fyfe Kim Elizabeth | High viscosity-index base stocks, base oils and lubricant compositions and methods for their production and use |
US7704379B2 (en) | 2002-10-08 | 2010-04-27 | Exxonmobil Research And Engineering Company | Dual catalyst system for hydroisomerization of Fischer-Tropsch wax and waxy raffinate |
US20040154957A1 (en) * | 2002-12-11 | 2004-08-12 | Keeney Angela J. | High viscosity index wide-temperature functional fluid compositions and methods for their making and use |
US20080029431A1 (en) * | 2002-12-11 | 2008-02-07 | Alexander Albert G | Functional fluids having low brookfield viscosity using high viscosity-index base stocks, base oils and lubricant compositions, and methods for their production and use |
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BRPI0714243A2 (pt) * | 2006-07-12 | 2013-03-12 | Shell Int Research | embalagem combinada para composiÇço de lubrificante e combustÍvel para operar um motor a diesel, disposiÇço de motor para a geraÇço de energia cinemÁtica e tÉrmica, veÍculo de transporte, bomba d'Água ou gerador de energia estacionÁrio, processo para a geraÇço de energia com emissço de gÁs àxido de nitrogÊnio de exaustço reduzida,e, uso da embalagem combinada de lubrificante e combustÍvel |
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1999
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2000
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- 2000-09-07 AT AT00960815T patent/ATE231908T1/de not_active IP Right Cessation
- 2000-09-07 PT PT00960815T patent/PT1212390E/pt unknown
- 2000-09-07 DE DE60001331T patent/DE60001331T2/de not_active Revoked
- 2000-09-07 CA CA002382893A patent/CA2382893A1/fr not_active Abandoned
- 2000-09-07 KR KR1020027003055A patent/KR100711294B1/ko not_active IP Right Cessation
- 2000-09-07 US US10/070,380 patent/US6599864B1/en not_active Expired - Fee Related
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- 2000-09-07 ES ES00960815T patent/ES2190986T3/es not_active Expired - Lifetime
- 2000-09-07 EP EP00960815A patent/EP1212390B1/fr not_active Revoked
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WO2001018156A1 (fr) | 2001-03-15 |
AU7299300A (en) | 2001-04-10 |
DE60001331D1 (de) | 2003-03-06 |
KR100711294B1 (ko) | 2007-04-25 |
ATE231908T1 (de) | 2003-02-15 |
FR2798136A1 (fr) | 2001-03-09 |
AU769075B2 (en) | 2004-01-15 |
US6599864B1 (en) | 2003-07-29 |
ZA200201564B (en) | 2003-07-30 |
DK1212390T3 (da) | 2003-05-19 |
JP2003520867A (ja) | 2003-07-08 |
FR2798136B1 (fr) | 2001-11-16 |
PT1212390E (pt) | 2003-06-30 |
KR20020052180A (ko) | 2002-07-02 |
CA2382893A1 (fr) | 2001-03-15 |
ES2190986T3 (es) | 2003-09-01 |
EP1212390A1 (fr) | 2002-06-12 |
DE60001331T2 (de) | 2004-01-15 |
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