CA2009830A1 - Lubricating base oils - Google Patents
Lubricating base oilsInfo
- Publication number
- CA2009830A1 CA2009830A1 CA 2009830 CA2009830A CA2009830A1 CA 2009830 A1 CA2009830 A1 CA 2009830A1 CA 2009830 CA2009830 CA 2009830 CA 2009830 A CA2009830 A CA 2009830A CA 2009830 A1 CA2009830 A1 CA 2009830A1
- Authority
- CA
- Canada
- Prior art keywords
- lubricating base
- base oil
- viscosity index
- catalyst
- aromaticity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002199 base oil Substances 0.000 title claims abstract description 37
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 102100027708 Astrotactin-1 Human genes 0.000 description 1
- 101000936741 Homo sapiens Astrotactin-1 Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G45/68—Aromatisation of hydrocarbon oil 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Lubricants (AREA)
- Catalysts (AREA)
Abstract
A B S T R A C T
IMPROVEMENTS RELATING TO LUBRICATING BASE OILS
Lubricating base oils of enhanced aromaticity and high viscosity index are manufactured by dehydrogenation of a high viscosity index base oil over a suitable catalyst and, optionally, subsequent hydrotreating of the dehydrogenated product.
IMPROVEMENTS RELATING TO LUBRICATING BASE OILS
Lubricating base oils of enhanced aromaticity and high viscosity index are manufactured by dehydrogenation of a high viscosity index base oil over a suitable catalyst and, optionally, subsequent hydrotreating of the dehydrogenated product.
Description
IMPROVEMENTS RELATING TO LUBRICATING BASE OILS
This invention relates to lubricat$ng base oils and is particularly concerned with a process for the manufacture of such base oils with a high viscosity index and to lubricating base oils which can be obtained by that process.
Lubricating base oils are derived from various mineral crude oils by a variety of refining processes, generally directed to obtaining a lubricating base oil with a suitable viscosity index for the intended end use.
The preparation of high viscosity index lubricating base oils can be carried out as follows. A crude oil is separated by distillation at atmospheric pressure into a number of distillate fractions and a residue, known as long residue. The long residue is than separated by distillation at reduced pressure into a number of vacuum distillates and a vacuum residue known as short residue.
From the vacuum distillate fractions lubricating base oils are prepared by refining processes which include wax removal from the vacuum distillate fractions. From the short residue asphalt can be removed by known deasphalting processes to give a deasphalted oil from which wax can subsequently be removed to yield a residual lubricating base oil, known as bright stock. The wax obtained during refining of the various lubricating base oil fractions is designated as slack wax.
Such slack waxes can be catalytically hydrotreated to yield high viscosity index lubricating base oils uslng processes such as those described in GB 1j429,494 and European patent applicaeion No. 324 528.
The high viscosity index base oils obtained by such processes have excellent characteristics in many respects, especially as they ~ obviate the need for the addition of polymeric viscosity index !~ 30 improvers. However, as a result of the processing involved in their , manufacture, they have a low aromaticity when compared with .~
.
` ' `
200~
This invention relates to lubricat$ng base oils and is particularly concerned with a process for the manufacture of such base oils with a high viscosity index and to lubricating base oils which can be obtained by that process.
Lubricating base oils are derived from various mineral crude oils by a variety of refining processes, generally directed to obtaining a lubricating base oil with a suitable viscosity index for the intended end use.
The preparation of high viscosity index lubricating base oils can be carried out as follows. A crude oil is separated by distillation at atmospheric pressure into a number of distillate fractions and a residue, known as long residue. The long residue is than separated by distillation at reduced pressure into a number of vacuum distillates and a vacuum residue known as short residue.
From the vacuum distillate fractions lubricating base oils are prepared by refining processes which include wax removal from the vacuum distillate fractions. From the short residue asphalt can be removed by known deasphalting processes to give a deasphalted oil from which wax can subsequently be removed to yield a residual lubricating base oil, known as bright stock. The wax obtained during refining of the various lubricating base oil fractions is designated as slack wax.
Such slack waxes can be catalytically hydrotreated to yield high viscosity index lubricating base oils uslng processes such as those described in GB 1j429,494 and European patent applicaeion No. 324 528.
The high viscosity index base oils obtained by such processes have excellent characteristics in many respects, especially as they ~ obviate the need for the addition of polymeric viscosity index !~ 30 improvers. However, as a result of the processing involved in their , manufacture, they have a low aromaticity when compared with .~
.
` ' `
200~
lubricating base olls of lower viscosity index. Thus they have a reduced ability to solubilize other materials, for example materials resulting from oxidation reactions which occur in the commercial lubricants prepared therefrom.
The present invention is directed to the preparation of novel lubricating base oils having a high viscosity index together with comparatively high aromaticity. Surprisingly it has been found that such aromatics-containing base oils can be obtained by dehydrogenating and selectively rehydrogenating a high viscosity index lubricating base oil while still maintaining the desired high viscosity index.
Accordingly, one aspect of the present invention provides a novel process for introducing aromaticity to a lubricating base oil comprising contacting a lubricating base oil feedstock having a high viscosity index with a dehydrogenating catalyst and recovering a product having enhanced aromaticity therefrom. By high viscosity index is understood a viscosity index of at least 125 as determined by ASTM D-567. The feedstock preferably has an extra high viscosity index of at least 135.
At least a portion of the product having enhanced aromaticity may be subjected, in accordance with a further aspect of the present invention, immediately downstream of the dehydrogenation or after further processing and/or transportation, to hydrotreating in the presence of hydrogen and a suitable catalyst and recavering a hydrotreated product therefrom.
It has also surprisingly been found that the hydrotreating does not substantially decrease the aromaticity, so that there is obtained a product of increased aromaticity from which olefinic unsaturation has substantially been removed by the hydrotreatment.
Furthermore, the product has been found to maintaln a high viscosity index, together with an increased aromatic content.
Suitably, the aromatic content i9 increased by contact with the dehydrogenating catalyst by an amount of at least 3 mmol/100 g.
Therefore, in accordance with a still further aspect of the invention, there are provided, as novel products, lubricating base 200983~) oils having an extra high viscosity index of at least 135 and an aromatic content of at least 3 mmol/100 g. These base oils may be the direct products of the dehydrogenation, containing some olefinic unsaturation, or the products of the subsequent hydrotreatment to give base oils from which the olefinic unsaturation has substantially been re~oved.
The lubricating base oil feedstock having a high viscosity index may be obtained for example by the processes described in GB 1,429,494 and EP 324 528. The viscosity index as determined by ASTM D-567 is at least 125 and is preferably at least 135, more preferably above 140. The base oils suitably also have a low pour point below -10 C (as determined by ASTM D-27).
The dehydrogenating catalyst employed to introduce aromaticity to the lubricating base oil is preferably a cGmposite catalyst comprising a Group VIII noble metal component, a Group IVA metal component and a refractory oxide support. The Group VIII noble metal component is preferably platinum and is preferably present in an amount of 0.1 to 1 ~wt, preferably 0.3 to 0.5 ~wt. The Group IVA
metal component is preferably tin and is preferably present in an amount of 0.1 to 1 ~wt, preferably 0.3 to 0.5 ~wt. The refractory oxide support is preferably alumina but may also be materials such as silica, silica-alumina, magnesia, zirconia, titania or mixtures thereof.
It is possible, though not essential, to neutralize the catalyst support, for example with an alkali metal or alkaline earth metal component, preferably lithium, or, alternatively potassium. Suitable catalysts are described, for example, in US
Patent No. 4,672,146.
The dehydrogenation reaction is normally carried out at a relatively high temperature and moderate pressure. Suitable temperatures are in the range of 300 C to 600 C, preferably from 400 to 500 C, with a hydrogen partial pressure of l to 30 bar, preferably from 5 to 15 bar. Suitable sp~ce velocities range from 0.2 to 20, preferably from 2 to 10 kg/l catalyst.h. A suitable 2~983n gas/feedstock ratio ranges from 200 to 2500 Nl/kg, preferably from 500 to 1200 Nl/kg.
The product having increased aromaticity may be subjected to subsequent hydrotreating immediately downstream of the dehydrogenation and with or without removal of, for example, gaseous products. Alternatively the product may be sub~ected to further processing, such as deep dewaxing, solvent extraction and/or transportation to a separate station for subsequent hydrotreatment.
The catalyst used in the hydrotreatment contains at least one hydrogenating metal component. The metal component is suitably selected from the Groups VIB and/or VIII of the Periodic Tab}e of the Elements. These Groups include the noble metals platinum and palladium. It is however preferred to use nickel and/or cobalt, and molybdenum and/or tungsten compounds.
The amount of nickel and/or cobalt present in the catalyst can sultably vary between 1 and 20a by weight, calculated as metal on total catalyst, preference being given to amounts in the range of 1.5 to 12% by weight. The amounts of molybdenum and/or tungsten may advantageously vary between 5 and 40~ by weight, calculated as metal on total catalyst, preference being given to amounts in the range of 8 to 30~ by weight.
The metal components may be incorporated on a support by any conventional technique, such as impregnation, dry-impregnation, precipitation or a combination thereof. Any suitable support material may be used, such as the refractory oxides silica, alumina, silica-alumina, magnesia, zirconia, titania or mixtures thereof. Silica, silica-alumina and alumina are preferred support materials, in particular alumina. Natural and synthetic crystalline aluminosilicates can also be used, such as fau~asite-type zeolites, in particular zeolite Y, mordenite-type zeolites and ZSN-5 type zeolites, or mixtures containing such a zeolite.
The catalysts are normally sulphided and may be fluorided by techniques known in the art. The catalyst preferably further comprises phosphorus, advantageously in an amount of from 0.5 to 2~ 83~) ~
The present invention is directed to the preparation of novel lubricating base oils having a high viscosity index together with comparatively high aromaticity. Surprisingly it has been found that such aromatics-containing base oils can be obtained by dehydrogenating and selectively rehydrogenating a high viscosity index lubricating base oil while still maintaining the desired high viscosity index.
Accordingly, one aspect of the present invention provides a novel process for introducing aromaticity to a lubricating base oil comprising contacting a lubricating base oil feedstock having a high viscosity index with a dehydrogenating catalyst and recovering a product having enhanced aromaticity therefrom. By high viscosity index is understood a viscosity index of at least 125 as determined by ASTM D-567. The feedstock preferably has an extra high viscosity index of at least 135.
At least a portion of the product having enhanced aromaticity may be subjected, in accordance with a further aspect of the present invention, immediately downstream of the dehydrogenation or after further processing and/or transportation, to hydrotreating in the presence of hydrogen and a suitable catalyst and recavering a hydrotreated product therefrom.
It has also surprisingly been found that the hydrotreating does not substantially decrease the aromaticity, so that there is obtained a product of increased aromaticity from which olefinic unsaturation has substantially been removed by the hydrotreatment.
Furthermore, the product has been found to maintaln a high viscosity index, together with an increased aromatic content.
Suitably, the aromatic content i9 increased by contact with the dehydrogenating catalyst by an amount of at least 3 mmol/100 g.
Therefore, in accordance with a still further aspect of the invention, there are provided, as novel products, lubricating base 200983~) oils having an extra high viscosity index of at least 135 and an aromatic content of at least 3 mmol/100 g. These base oils may be the direct products of the dehydrogenation, containing some olefinic unsaturation, or the products of the subsequent hydrotreatment to give base oils from which the olefinic unsaturation has substantially been re~oved.
The lubricating base oil feedstock having a high viscosity index may be obtained for example by the processes described in GB 1,429,494 and EP 324 528. The viscosity index as determined by ASTM D-567 is at least 125 and is preferably at least 135, more preferably above 140. The base oils suitably also have a low pour point below -10 C (as determined by ASTM D-27).
The dehydrogenating catalyst employed to introduce aromaticity to the lubricating base oil is preferably a cGmposite catalyst comprising a Group VIII noble metal component, a Group IVA metal component and a refractory oxide support. The Group VIII noble metal component is preferably platinum and is preferably present in an amount of 0.1 to 1 ~wt, preferably 0.3 to 0.5 ~wt. The Group IVA
metal component is preferably tin and is preferably present in an amount of 0.1 to 1 ~wt, preferably 0.3 to 0.5 ~wt. The refractory oxide support is preferably alumina but may also be materials such as silica, silica-alumina, magnesia, zirconia, titania or mixtures thereof.
It is possible, though not essential, to neutralize the catalyst support, for example with an alkali metal or alkaline earth metal component, preferably lithium, or, alternatively potassium. Suitable catalysts are described, for example, in US
Patent No. 4,672,146.
The dehydrogenation reaction is normally carried out at a relatively high temperature and moderate pressure. Suitable temperatures are in the range of 300 C to 600 C, preferably from 400 to 500 C, with a hydrogen partial pressure of l to 30 bar, preferably from 5 to 15 bar. Suitable sp~ce velocities range from 0.2 to 20, preferably from 2 to 10 kg/l catalyst.h. A suitable 2~983n gas/feedstock ratio ranges from 200 to 2500 Nl/kg, preferably from 500 to 1200 Nl/kg.
The product having increased aromaticity may be subjected to subsequent hydrotreating immediately downstream of the dehydrogenation and with or without removal of, for example, gaseous products. Alternatively the product may be sub~ected to further processing, such as deep dewaxing, solvent extraction and/or transportation to a separate station for subsequent hydrotreatment.
The catalyst used in the hydrotreatment contains at least one hydrogenating metal component. The metal component is suitably selected from the Groups VIB and/or VIII of the Periodic Tab}e of the Elements. These Groups include the noble metals platinum and palladium. It is however preferred to use nickel and/or cobalt, and molybdenum and/or tungsten compounds.
The amount of nickel and/or cobalt present in the catalyst can sultably vary between 1 and 20a by weight, calculated as metal on total catalyst, preference being given to amounts in the range of 1.5 to 12% by weight. The amounts of molybdenum and/or tungsten may advantageously vary between 5 and 40~ by weight, calculated as metal on total catalyst, preference being given to amounts in the range of 8 to 30~ by weight.
The metal components may be incorporated on a support by any conventional technique, such as impregnation, dry-impregnation, precipitation or a combination thereof. Any suitable support material may be used, such as the refractory oxides silica, alumina, silica-alumina, magnesia, zirconia, titania or mixtures thereof. Silica, silica-alumina and alumina are preferred support materials, in particular alumina. Natural and synthetic crystalline aluminosilicates can also be used, such as fau~asite-type zeolites, in particular zeolite Y, mordenite-type zeolites and ZSN-5 type zeolites, or mixtures containing such a zeolite.
The catalysts are normally sulphided and may be fluorided by techniques known in the art. The catalyst preferably further comprises phosphorus, advantageously in an amount of from 0.5 to 2~ 83~) ~
12% by weight calculated as elemental phosphorus, based on total catalyst.
The hydrotreating reaction is suitably carried out under comparatively mild conditions. Suitable temperatures are in the range of 100-400 C, preferably from 200-300 C with a hydrogen partial pressure in the range of 20 to~l50 bar, preferably from 40 to 60 bar. Suitable space velocities range from 0.1 to 5 kg/l catalyst.h, preferably from 0.5 to 2 kg/l catalyst.h, while a suitable gas/feedstock ratio ranges from 200 to 2000 Nl/kg, preferably from 400 to 1000 Nl/kg.
The invention will now be illustrated by means of the following examples.
A high viscosity index lubricating base oil was used as feedstock. This oil had the following characteristics:
kinematic viscosity at 100 C (Vk 100) 5.39 mm2/s pour point -18 C
viscosity index 144.4 aromatics content (mmol/100 g) mono 0.388 di 0.010 poly 0.017 bromine index (mg/100 g) lO
The feedstock was used for a series of dehydrogenation experiments in an automated one-reactor trickle-flow unit under gas once-through mode of operation and using temperatures as given in Table 1, a hydrogen pressure of 10 bar, a gas/feedstock ratio of 700 Nl/kg, and a space velocity of 4 kg/l.h. The catalyst employed was a platinum/tin catalyst on a lithlum-neutralized alumina support and contained 0.40 ~wt platinum and 0.41 ~wt tin, with an initial pore volume of 0.93 cm3/g and an initial surface area of 131 m /g. Aromatics content was determined by W absorption.
The results of the experiments are given in Table l.
':
.
Z009~330 Experiment No. 1 2 3 4 5 6 Average Temp. 440 460 400 430 450 470 Yield, ~wt on feedstock < 370 C 9.110.1 1.4 7.1 8.2 11.8 > 370 C 90.989.9 98.692.9 91.8 88.2 Oil Properties Vk 100 mm2/s 4.724.71 5.334.93 4.82 4.68 VI 143.5 142.7145.5144.4 142.8 141.3 pour point C -15 -15 -18 Aromatics, mmol/100 g mono 27.10 31.653.0310.75 18.69 25.70 di 1.031.29 0.0670.3980.737 1.11 poly 0.605 0.8740.0730.230 0.413 0.752 It will be seen from the above results that aromaticity has been introduced to the lubricating base oil while maintaining a high viscosity index over a range of operating temperatures. The products were found to have a content of olefinic unsaturation (by determination of the bromine number in accordance with ASTM
D-1159-82) of from 1 to 6.
A high viscosity index, high aromatics lubricating base oil obtained as described in Example 1 and having the propertles given in Table 2 below was hydrotreated in a one-reactor micro-flow unit under gas once-through mode of operation. The conditions of operation were a temperature of 260 C, a hydrogen pressure of 50 bar, a gas/feedstock ratio of 500 Nl/kg and a space velocity of 1 kg/l.h. The catalyst employed was a hydrotreating catalyst comprising 2.5~ by weight of nickel, 13.5~ by weigh~ of molybdenum .' , ' - 7 - ~ ~ a 3 and 2.9~ by weight of phosphorus on alumina, the percentages being based on total catalyst. Aromatics content was determined by W
absorption.
The results are given in Table 2.
Feed Product Oil Properties Vk 100 mm /s 4.718 4.746 VI 143.5 143 pour point C -15 -12 Aromatics, mmol/100 g mono 28.4 23.3 di 1.2 poly 0.62 0.14 Bromine number (mg/100 g) 4 The yield of > 370 C, ~wt on feedstock, was 99~.
It will be seen from the above results that hydrotreatment of the aromat~zed lubricating base oil has given a product in which the aromaticity and the viscosity index have not been adversely affected. The product was found to have a low content of olefinic unsaturation by determination of the bromine index (ASTN D-1491-78 which was found to be 20 mg/100 g.
;
.' ~ ' ` ' ~, .
'
The hydrotreating reaction is suitably carried out under comparatively mild conditions. Suitable temperatures are in the range of 100-400 C, preferably from 200-300 C with a hydrogen partial pressure in the range of 20 to~l50 bar, preferably from 40 to 60 bar. Suitable space velocities range from 0.1 to 5 kg/l catalyst.h, preferably from 0.5 to 2 kg/l catalyst.h, while a suitable gas/feedstock ratio ranges from 200 to 2000 Nl/kg, preferably from 400 to 1000 Nl/kg.
The invention will now be illustrated by means of the following examples.
A high viscosity index lubricating base oil was used as feedstock. This oil had the following characteristics:
kinematic viscosity at 100 C (Vk 100) 5.39 mm2/s pour point -18 C
viscosity index 144.4 aromatics content (mmol/100 g) mono 0.388 di 0.010 poly 0.017 bromine index (mg/100 g) lO
The feedstock was used for a series of dehydrogenation experiments in an automated one-reactor trickle-flow unit under gas once-through mode of operation and using temperatures as given in Table 1, a hydrogen pressure of 10 bar, a gas/feedstock ratio of 700 Nl/kg, and a space velocity of 4 kg/l.h. The catalyst employed was a platinum/tin catalyst on a lithlum-neutralized alumina support and contained 0.40 ~wt platinum and 0.41 ~wt tin, with an initial pore volume of 0.93 cm3/g and an initial surface area of 131 m /g. Aromatics content was determined by W absorption.
The results of the experiments are given in Table l.
':
.
Z009~330 Experiment No. 1 2 3 4 5 6 Average Temp. 440 460 400 430 450 470 Yield, ~wt on feedstock < 370 C 9.110.1 1.4 7.1 8.2 11.8 > 370 C 90.989.9 98.692.9 91.8 88.2 Oil Properties Vk 100 mm2/s 4.724.71 5.334.93 4.82 4.68 VI 143.5 142.7145.5144.4 142.8 141.3 pour point C -15 -15 -18 Aromatics, mmol/100 g mono 27.10 31.653.0310.75 18.69 25.70 di 1.031.29 0.0670.3980.737 1.11 poly 0.605 0.8740.0730.230 0.413 0.752 It will be seen from the above results that aromaticity has been introduced to the lubricating base oil while maintaining a high viscosity index over a range of operating temperatures. The products were found to have a content of olefinic unsaturation (by determination of the bromine number in accordance with ASTM
D-1159-82) of from 1 to 6.
A high viscosity index, high aromatics lubricating base oil obtained as described in Example 1 and having the propertles given in Table 2 below was hydrotreated in a one-reactor micro-flow unit under gas once-through mode of operation. The conditions of operation were a temperature of 260 C, a hydrogen pressure of 50 bar, a gas/feedstock ratio of 500 Nl/kg and a space velocity of 1 kg/l.h. The catalyst employed was a hydrotreating catalyst comprising 2.5~ by weight of nickel, 13.5~ by weigh~ of molybdenum .' , ' - 7 - ~ ~ a 3 and 2.9~ by weight of phosphorus on alumina, the percentages being based on total catalyst. Aromatics content was determined by W
absorption.
The results are given in Table 2.
Feed Product Oil Properties Vk 100 mm /s 4.718 4.746 VI 143.5 143 pour point C -15 -12 Aromatics, mmol/100 g mono 28.4 23.3 di 1.2 poly 0.62 0.14 Bromine number (mg/100 g) 4 The yield of > 370 C, ~wt on feedstock, was 99~.
It will be seen from the above results that hydrotreatment of the aromat~zed lubricating base oil has given a product in which the aromaticity and the viscosity index have not been adversely affected. The product was found to have a low content of olefinic unsaturation by determination of the bromine index (ASTN D-1491-78 which was found to be 20 mg/100 g.
;
.' ~ ' ` ' ~, .
'
Claims (12)
1. A process for the manufacture of a lubricating base oil of enhanced aromaticity comprising contacting a lubricating base oil feedstock having a high viscosity index with a dehydrogenating catalyst and recovering a product having enhanced aromaticity therefrom.
2. A process according to claim 1, wherein the aromaticity is increased by an amount of at least 3 mmol/100 g.
3. A process according to claim 1 or 2, wherein the viscosity index of the feedstock is at least 135.
4. A process according to claim 1, 2 or 3, wherein the dehydrogenating catalyst comprises a Group VIII noble metal component, a Group IVA metal component and a refractory oxide support, preferably platinum, tin and an alumina support.
5. A process according to any one of the preceding claims, wherein the reaction temperature is from 300 to 600 °C and the hydrogen partial pressure is from 1 to 30 bar.
6. A process according to any one of the preceding claims, wherein at least a portion of the product of enhanced aromaticity is subjected to hydrotreating in the presence of hydrogen and a suitable catalyst and a hydrotreated product is recovered therefrom, preferably using a hydrotreating catalyst which comprises nickel and/or cobalt and molybdenum and/or tungsten, especially a hydrotreating catalyst which further comprises phosphorus.
7. A process accordlng to claim 6, wherein the hydrotreating is carried out at a temperature of 100 to 400°C and a hydrogen partial pressure of 20 to lS0 bar.
8. A lubricating base oil having a viscosity index of at least 135 and an aromatic content of at least 3 mmol/100 g.
9. A lubricating base oil according to claim 8 having an aromatic content of at least 10 mmol/100 g.
10, A lubricating base oil according to claim 8 or 9 containing olefinic unsaturation.
11. A lubricating base oil according to claim 8 or 9 from which the olefinic unsaturation has been substantially removed.
12. A lubricating base oil when prepared by the process of any one of the preceding claims 1 to 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8901874 | 1989-02-14 | ||
| FR8901874A FR2643084A1 (en) | 1989-02-14 | 1989-02-14 | IMPROVEMENTS IN BASIC LUBRICATING OILS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2009830A1 true CA2009830A1 (en) | 1990-08-14 |
Family
ID=9378748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2009830 Abandoned CA2009830A1 (en) | 1989-02-14 | 1990-02-12 | Lubricating base oils |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0383395B1 (en) |
| JP (1) | JPH02247297A (en) |
| CA (1) | CA2009830A1 (en) |
| DE (1) | DE69006371T2 (en) |
| ES (1) | ES2049909T3 (en) |
| FR (1) | FR2643084A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5427703A (en) * | 1992-07-17 | 1995-06-27 | Shell Oil Company | Process for the preparation of polar lubricating base oils |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6716503A (en) * | 1967-12-04 | 1969-06-06 | ||
| US3530061A (en) * | 1969-07-16 | 1970-09-22 | Mobil Oil Corp | Stable hydrocarbon lubricating oils and process for forming same |
| US3880747A (en) * | 1970-09-08 | 1975-04-29 | Sun Oil Co Pennsylvania | Catalytic hydrofinishing of lube oil product of solvent extraction of petroleum distillate |
| US4672146A (en) * | 1985-07-02 | 1987-06-09 | Uop Inc. | Dehydrogenation catalyst compositions and its use in dehydrogenation |
-
1989
- 1989-02-14 FR FR8901874A patent/FR2643084A1/en not_active Withdrawn
-
1990
- 1990-02-09 DE DE1990606371 patent/DE69006371T2/en not_active Expired - Fee Related
- 1990-02-09 ES ES90200321T patent/ES2049909T3/en not_active Expired - Lifetime
- 1990-02-09 EP EP19900200321 patent/EP0383395B1/en not_active Expired - Lifetime
- 1990-02-09 JP JP2862590A patent/JPH02247297A/en active Pending
- 1990-02-12 CA CA 2009830 patent/CA2009830A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| ES2049909T3 (en) | 1994-05-01 |
| EP0383395B1 (en) | 1994-02-02 |
| DE69006371T2 (en) | 1994-06-09 |
| JPH02247297A (en) | 1990-10-03 |
| EP0383395A1 (en) | 1990-08-22 |
| DE69006371D1 (en) | 1994-03-17 |
| FR2643084A1 (en) | 1990-08-17 |
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