JP2008531834A - Polyalphaolefin and Fischer-Tropsch derived lubricating base oil lubricant blends - Google Patents

Abstract

  ≦ 70 wt% Fischer-Tropsch derived lubricating base oil comprising ≧ 6 wt% molecules with monocycloparaffin functionality and less than 0.05 wt% molecules with aromatic functionality; greater than about 30 cSt at 100 ° C. Blended lubricant base oils and blended lubricant products comprising at least one polyalphaolefin lubricant base oil having a dynamic viscosity of less than 150 cSt are provided. These blended lubricant base oils and blended lubricant products exhibit excellent friction and wear properties in addition to other highly desirable properties. Also provided are methods for producing these blended lubricant base oils and blended lubricant products.

Description

  The present invention relates to blended lubricating oils and blended lubricating oil products comprising a Fischer-Tropsch derived lubricating base oil and at least one polyalphaolefin lubricating base oil and a method for making the same. Blend lubricant products are surprisingly more effective to achieve acceptable wear performance than is required for Fischer-Tropsch derived lubricant base oils that are free of at least one poly alpha olefin (PAO) lubricant base oil. Requires less wear-resistant additives.

  There is a need for high performance automotive and industrial lubricants. Therefore, lubricant manufacturers must provide lubricant products that exhibit high performance. In order to produce these lubricant products, lubricant manufacturers are looking for high quality lubricant base stock blend stock. Prominent performance characteristics include additive solubility, deposit control, and lubricity.

  The growth base for these high-quality lubricant base stocks is synthetic lubricants. Synthetic lubricating oils include Fischer-Tropsch derived lubricating base oils and polyalphaolefins. Polyalphaolefins are synthetic lubricating base oils produced by chemical polymerization methods. However, these lubricating base oils are expensive to produce. The search for high performance lubricants has recently focused on Fischer-Tropsch derived lubricants. While Fischer-Tropsch derived lubricating base oils are desirable because of their biodegradability and low amounts of undesirable impurities such as sulfur, Fischer-Tropsch derived lubricating oils generally have desirable wear performance, lubricity, and deposits. Does not show performance. Although it is well known in the art that these performance characteristics are improved by the use of additives, these additives are generally expensive and therefore significantly increase the price of lubricating base oils. In addition, engine manufacturers are paying attention to the low sulfur and phosphorus limits of engine oils and additives globally, which are a safe margin for the operation of aftertreatment machinery. This is because it is considered to be provided. Antiwear additives often contain significant amounts of both sulfur and phosphorus. Accordingly, it is desirable to produce lubricating base oils with high performance characteristics without significant use of expensive additives or with reduced amounts of additives including sulfur and phosphorus.

  The production of synthetic lubricants is well known in the art, and there are numerous development attempts in producing synthetic lubricants having high performance characteristics. For example, U.S. Pat. No. 6,0081,643; U.S. Pat. No. 6,080,301; U.S. Pat. No. 6,165,949; WO00 / 14188; WO02 / 064710A2; WO02 / 066471A1; WO02 / 070629A1; The present invention relates to a manufacturing method of stock.

  The properties of hydrocracking basestocks and polyalphaolefins have also been investigated. “The Influence of Chemical Structure and the Physical Properties and Antioxidant Response of Hydrocracked Bases and Polyalphaolefin Oxidant Responses” J. et al. Gatto et al. Synthetic Lubrication 19-1, April 2002 (19), 3-18, discloses the effect of the chemical composition of hydrocracking base stocks on lubricating oil properties, oxidation performance, and oxidant addition response. . In this study, 15 hydrocracking basestocks and polyalphaolefins were analyzed.

  Despite the above investigation of synthetic lubricants, Fischer-Tropsch exhibits high performance, including improved friction and wear, without requiring the addition of large amounts of additives to achieve this high performance. There is a need for synthetic lubricating oils including derived lubricating base oils.

  The blended lubricant base oils and blended lubricant products of the present invention comprising Fischer-Tropsch derived lubricant base oils and polyalphaolefins have been found to exhibit improved friction and wear properties with reduced amounts of antiwear additives. It was.

  In one embodiment, the present invention relates to a blended lubricating base oil. The blended lubricating base oil of the present invention comprises ≧ 70 wt% Fischer-Tropsch derived lubrication comprising ≧ 6 wt% molecules with monocycloparaffinic functionality and less than 0.05 wt% molecules with aromatic functionality A base oil; and at least one polyalphaolefin lubricating base oil having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C.

  In other embodiments, the present invention relates to blended lubricant products. The blended lubricant product comprises ≧ 70 wt% Fischer-Tropsch derived lubricating base oil comprising ≧ 6 wt% molecules having monocycloparaffinic functionality and less than 0.05 wt% molecules having aromatic functionality; At least one polyalphaolefin lubricating base oil having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C .; and an effective amount of at least one antiwear additive.

  In another embodiment, the invention relates to a method of operating an internal combustion engine that includes a valve train. The method comprises operating the engine using fuel and ≧ 70% by weight comprising ≧ 6% by weight molecules having monocycloparaffinic functionality and less than 0.05% by weight molecules having aromatic functionality A Fischer-Tropsch derived lubricating base oil; at least one polyalphaolefin lubricating base oil having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C .; and a blend lubrication comprising an effective amount of at least one antiwear additive Using an oil product to lubricate the engine.

  In yet another embodiment, the present invention relates to a method for reducing wear in a ferroalloy device. The method comprises ≧ 70 wt% Fischer-Tropsch derived lubricating base oil comprising ≧ 6 wt% molecules with monocycloparaffinic functionality and less than 0.05 wt% molecules with aromatic functionality; Lubricating the device with a blended lubricant product comprising an effective amount of at least one polyalphaolefin lubricant base oil having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt; and at least one antiwear additive; and Including the step of operating the device after lubrication.

(Detailed description of the invention)
The lubricant product includes at least one lubricant base oil and at least one additive. Lubricating base oils are the most important component of lubricating oil products and are generally present in more than 70% of lubricating oil products. Lubricating oil products may be used in automobiles, diesel engines, accelerators, transmissions, and industrial applications. Lubricating oil products must meet the specifications for their intended use as determined by the relevant government organization.

  A Fischer-Tropsch derived lubricating base oil is a base oil derived at least in part from a Fischer-Tropsch process. The blended lubricating oil according to the invention comprises at least one Fischer-Tropsch derived lubricating base oil comprising ≧ 6% by weight of molecules having monocycloparaffinic functionality and less than 0.05% by weight of molecules having aromatic functionality, and At least one polyalphaolefin lubricating base oil having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C. The blended lubricating oil product of the present invention comprises at least one Fischer-Tropsch derived lubricating base oil comprising ≧ 6% by weight molecules having monocycloparaffinic functionality and less than 0.05% by weight molecules having aromatic functionality; An effective amount of at least one polyalphaolefin lubricating base oil having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C., and at least one anti-wear additive. The blended lubricant products of the present invention exhibit special friction and wear properties. Preferably, the blended lubricating base oil comprises ≧ 70 wt% Fischer-Tropsch derived lubricating base oil.

  In general, the effective amount of anti-wear additive required in lubricating oil products containing Fischer-Tropsch derived lubricating base oils is the same in lubricating oil products containing ordinary petroleum lubricating base oils or polyalphaolefin lubricating base oils. Less than required. In accordance with the present invention, surprisingly, significantly less wear-resistant additives provide monocycloparaffinic functionality than lubricating oil products containing Fischer-Tropsch derived lubricating base oils in the absence of polyalphaolefin lubricating base oils. One Fischer-Tropsch derived lubricating base oil comprising ≧ 6% by weight molecules and less than 0.05% by weight molecules having aromatic functionality, and a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C. It has been found necessary for lubricating oil products blended with polyalphaolefin lubricating base oils. Accordingly, a reduced amount of antiwear additive is required in the blended lubricant product of the present invention. Thus, the blended lubricants of the present invention can be used to make high quality engine oils and other lubricant products that meet the most stringent modern engine oil specifications.

The effective amount of at least one antiwear additive, up to at least 1,000 microns ³ compared the plane when the additive is not present and the wear volume below, below the plane in HFRR test of the present invention wear It means the amount of anti-wear additive that reduces the capacity ("the wear volume bellow the plane"). Preferably, the effective amount of the at least one anti-wear additive is a plane with 1000 g applied load of the anti-wear additive amount in the additive package or less than 460,000 μ ³ , preferably less than 350,000 μ ^3. Means the amount individually added to the blended lubricant base oil to prepare a lubricant product with lower High Frequency Reciprocating Rig (HFRR) wear capacity. According to the present invention, preferably the effective amount of at least one anti-wear additive is 0.001 to 5% by weight of the blended lubricant product. An effective amount of anti-wear additive in the blended lubricant product of the present invention is the preferred composition of the present invention when no polyalphaolefin lubricating base oil having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C. is present. Less than the effective amount of anti-wear additive required in lubricating oils, including Fischer-Tropsch derived lubricating base oils. An effective amount of anti-wear additive in the blended lubricant product of the present invention is a poly having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C. in the absence of the Fischer-Tropsch derived lubricant base oil of the present invention. Less than the effective amount of antiwear additive required in lubricating oils including alpha olefin lubricating base oils.

  Many blended lubricant specifications include limitations on wear. Examples of specifications including test limits for wear include API passenger car engine test classifications SJ and SL; ACEA 2002 European oil standards for gasoline, light diesel, and heavy diesel engines; ASTM D4950 grease classification; Cincinnati-Miraclon P-68 Hydraulic oil specification; and General Motors C-4 automatic transmission fluid specification.

  Blend lubricants and blend lubricant products according to the present invention comprise a polyalphaolefin lubricant base oil having a dynamic viscosity of greater than about 30 cSt at 100 ° C. and less than 150 cSt at 100 ° C. Poly alpha olefin lubricating base oils are available as commercial products and are also available from Shubkin, Ronald L. et al. (1993) “Polyalphaolefins in Synthetic Lubricants and High-Performance Functional Fluids” in Synthetic Lubricants and High Performance Functional Fluids, and Pernik, Mark G. (2002) “Polyalphaolefins”, STLE Annual Meeting, Houston TX, “Synthetic Lubricants Course”. Polyalphaolefin lubricating base oils having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C. are commercially available from a number of manufacturers including Chevron Phillips, British Petroleum, and ExxonMobil.

  Blend lubricant base oils and blend lubricant products according to the present invention have ≧ 6 wt% molecules with monocycloparaffin functionality, preferably ≧ 8 wt% molecules with monocycloparaffin functionality, even more preferably, A Fischer-Tropsch derived lubricating base oil containing ≧ 10% by weight of molecules with monocycloparaffinic functionality.

  Blended lubricating oils and blended lubricating oil products according to the present invention are described in US patent application Ser. No. 10 / 744,389 (filed Dec. 23, 2003), US patent application Ser. No. 10 / 744,870, which is hereby incorporated by reference in its entirety. (Filed on Dec. 23, 2003), and US patent application Ser. No. 10 / 743,932 (filed on Dec. 23, 2003), a very low weight percent of molecules with aromatic functionality, cyclo A high ratio of high weight percent of molecules with paraffin functionality and high weight percent of molecules with monocycloparaffin functionality to high weight percent of molecules with multicycloparaffin functionality (or high proportion of molecules with monocycloparaffin functionality) % And very low weight% of molecules with multicycloparaffinic functionality).

  In a preferred embodiment, the blended lubricating base oil and blended lubricating oil product according to the present invention comprises less than 0.05% by weight of molecules with aromatic functionality, greater than 10, weight of molecules with cycloparaffinic functionality. And a Fischer-Tropsch derived lubricating base oil containing a high ratio of the weight percent of molecules with monocycloparaffin functionality to the weight percent of molecules with multicycloparaffin functionality, preferably greater than 15. In another preferred embodiment, the blended lubricating base oil and blended lubricating oil product according to the present invention comprises less than 0.01, more preferably less than 0.008 weight percent of molecules having aromatic functionality. Contains Tropsch derived lubricating base oil.

  Fischer-Tropsch derived lubricating base oils containing ≧ 6% by weight of molecules with monocycloparaffinic functionality are prepared from the Fischer-Tropsch synthetic crude wax fraction by a process involving hydroisomerization. Fischer-Tropsch derived lubricating base oil used in blended lubricants and blended lubricant products is a process of preparing a product stream by performing Fischer-Tropsch synthesis, isolating a substantially paraffinic wax feed from the product stream A process comprising hydroisomerizing a substantially paraffinic wax feed, isolating the isomerized oil, and optionally hydrorefining the isomerized oil. From this process, a Fischer-Tropsch derived lubricating base oil is isolated that contains ≧ 6% by weight molecules with monocycloparaffinic functionality and less than 0.05% by weight molecules with aromatic functionality. The above-described preferred embodiments of the Fischer-Tropsch derived lubricating base oil may be isolated from this method. Preferably, the substantially paraffinic wax feed is hydroisomerized using a shape selective intermediate pore size molecular sieve comprising a noble metal hydrogenation component under conditions of about 600 ° F. to 750 ° F. . Preferred methods for making Fischer-Tropsch derived lubricating base oils are described in US patent application Ser. No. 10 / 744,389 (filed Dec. 23, 2003) and US patent application Ser. No. 10/10, herein incorporated by reference in their entirety. No. 744870 (filed on Dec. 23, 2003).

  In accordance with the present invention, blended lubricating base oils and blended lubricating oil products are Fischer-Tropsch derived lubricating groups that contain a high weight percent of molecules having cycloparaffinic functionality since cycloparaffins provide additive solubility and elastomer compatibility. It is desirable to include oil. Also, a very high ratio of the weight percent of molecules with monocycloparaffin functionality to the weight percent of molecules containing multicycloparaffin functionality (or the high weight percent of molecules with monocycloparaffin functionality and multicycloparaffin functionality Blend lubricant base oils and blend lubricant products containing Fischer-Tropsch derived lubricant base oils with extremely low weight percentages of molecules having low molecular weight with reduced oxidative stability and low viscosity This is desirable because it increases the exponent and the Noack volatility. A model of the effect of molecules with multicycloparaffinic functionality is J. et al. Gatto et al., "The Influence of Chemical Structure and the Physical Properties and Antioxidant Response of Hydrocracking Basestocks and Polyalphaolefins". Synthetic Lubrication 19-1, April 2002, pages 3-18.

  The blended lubricating oils of the present invention comprise 70 to about 99% by weight Fischer-Tropsch derived lubricating base oil and less than about 1 to 30% by weight polyalphaolefin lubricating base oil. The blended lubricating oil product of the present invention comprises 70 to about 99% by weight Fischer-Tropsch derived lubricating base oil, about 1 to 30% by weight polyalphaolefin lubricating base oil, and 0.001 to 5% by weight wear resistance. Contains additives. Preferably, the blended lubricant contains 0.001 to 4% by weight of an antiwear additive.

Definitions The following terms are used throughout the specification and have the following meanings unless otherwise indicated.

  The term “derived from a Fischer-Tropsch process” or “Fischer-Tropsch induction” means that a product, fraction, or feed is generated or produced in several stages by a Fischer-Tropsch process. Means.

  An aromatic group is a sequence of delocalized electrons whose number of delocalized electrons in a group of atoms corresponds to a solution to the Huckel rule of 4n + 2 (eg, 1 for n = 6 electrons, etc.). Means any hydrocarbon compound or group that contains at least one group of atoms sharing a cloud. Common examples include, but are not limited to, benzene, biphenyl, naphthalene, and the like.

  By molecule having aromatic functionality is meant any molecule that is or contains one or more substituents, ie aromatic groups.

  By molecule having cycloparaffinic functionality is meant any molecule that is or contains one or more substituents, ie, monocyclic or bonded polycyclic saturated hydrocarbon groups. The cycloparaffin group may be optionally substituted with one or more, preferably 1 to 3 substituents. Common examples include cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl, decahydronaphthalene, octahydropentalene, (pentadecan-6-yl) cyclohexane, 3,7,10-tricyclohexylpentadecane, decahydro-1 Although-(pentadecan-6-yl) naphthalene etc. are mentioned, it is not limited to these.

  A molecule having monocycloparaffinic functionality is any molecule that is a monocyclic saturated hydrocarbon group of 3-7 ring carbons or a single monocyclic saturated hydrocarbon group of 3-7 ring carbons. By any substituted molecule is meant. The cycloparaffin group may be optionally substituted with one or more, preferably 1 to 3 substituents. General examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl, (pentadecan-6-yl) cyclohexane, and the like.

  A molecule having multicycloparaffinic functionality is any molecule that is a bonded polycyclic saturated hydrocarbon ring group of two or more bonded rings, one or more bonded polycyclic saturated groups of two or more bonded rings It means any molecule substituted with a hydrocarbon ring group, or any molecule substituted with 2 or more monocyclic saturated hydrocarbon groups of 3 to 7 ring carbons. The bonded polycyclic saturated hydrocarbon ring group is preferably of two bonded rings. The cycloparaffin group may be optionally substituted with one or more, preferably 1 to 3 substituents. Common examples include, but are not limited to, decahydronaphthalene, octahydropentalene, 3,7,10-tricyclohexylpentadecane, decahydro-1- (pentadecan-6-yl) naphthalene, and the like.

  “Compression ignition internal combustion engine” means a diesel engine.

  An “internal combustion engine” is an engine such as an automobile gasoline piston engine or diesel engine in which fuel is burned in the engine itself, not in an external combustion heating furnace like a steam engine. These engines include natural gas engines, diesel engines, and gasoline engines. These may be two strokes or four strokes.

“Multigrade internal combustion engine crankcase oil” is a lubricant that meets the specifications of SAE J300, June 2001. The API classifies engine oils by these SAE viscosity grades. Table I below summarizes this classification.
Table I: API engine oil classification

  Engine oil with a viscosity rating of 0 W has a maximum cold crank viscosity of 6,200 cP at −35 ° C., a maximum cold pumping viscosity without yield point stress of −60,000 cP at −40 ° C., and at 100 ° C. It has a minimum low shear rate dynamic viscosity of 3.8 cSt. An engine oil with a viscosity rating of 5 W has a maximum cold crank viscosity of −6,600 cP at −30 ° C., a maximum cold pumping viscosity without yield point stress of −60,000 cP at −35 ° C., and It has a minimum low shear rate dynamic viscosity of 3.8 cSt. Engine oil with a viscosity rating of 10 W has a maximum low temperature crank viscosity of 7,000 cP at -25 ° C, a maximum low temperature pumping viscosity without yield point stress of 30,000 cP at -30 ° C, and at 100 ° C. It has a minimum low shear rate dynamic viscosity of 4.1 cSt. Engine oil with a viscosity rating of 15 W has a maximum low temperature crank viscosity of 7,000 cP at -20 ° C, a maximum low temperature pumping viscosity without yield point stress of -60 ° C at -25 ° C, and at 100 ° C. It has a minimum low shear rate dynamic viscosity of 5.6 cSt.

  “Spark ignition internal combustion engine” means a gasoline engine.

  A “valve train” in an internal combustion engine consists of a valve and a camshaft. Currently, there are two types of designs used in automotive engines for valve and camshaft arrangements. If the camshaft is placed in the cylinder head, the engine is called an overhead cam design. If the camshaft is placed in the engine block, the engine is called an overhead valve design. Both designs have these valves installed above the cylinder in the cylinder head. The difference between the two designs is the arrangement of the camshaft that operates the valve. A double overhead cam (DOHC) engine has two camshafts on each cylinder head, one camshaft moving the intake valve and the other moving the exhaust valve.

  A “low sulfur diesel engine fuel” has a sulfur content of up to about 0.05% by weight as determined by the test method specified in ASTM D2622-87.

  “Low sulfur gasoline” has a sulfur content below about 300 ppm, or 0.03%.

  Blended lubricant base oils and blended lubricant products according to the present invention exhibit desirable properties including high viscosity index, low Noack volatility, excellent oxidative stability, and low pour point in addition to special friction and wear properties. Additional benefits gained from the use of the lubricating oil product of the present invention include improved fuel economy, reduced wear of engine parts, long oil change intervals, less waste oil for disposal, and reduced high temperature deposits. Things.

Oxygen Stability Test
Oxidation stability test was determined using two different test methods, Oxidator BN with L-4 catalyst and Oxidator B. Oxidator BN was used to determine the oxygen stability of a Fischer-Tropsch derived lubricating base oil without any additives. A convenient method for measuring the stability of lubricating base oils is by use of the Oxidator BN test described by Stangeland et al. In US Pat. No. 3,852,207. Oxidator BN test measures oxidation resistance with a Dornte oxygen absorber. R. W. Dorte “Oxidation of White Oils”, Industrial and Engineering Chemistry, Vol. 28, 26, 1936. Typically, the conditions are 340 ° F. and 1 atmosphere of pure oxygen. Results are reported in the time required for 100 g of oil to absorb 1000 ml of O ₂ . In the Oxidator BN test, 0.8 ml of catalyst is used per 100 g of oil and the additive package is included in the oil. The catalyst is a mixture of soluble metal naphthenates in kerosene. The mixture of soluble metal naphthenates simulates the average metal analysis of the crankcase oil used. The metal levels in the catalyst are as follows: copper = 6,927 ppm; iron = 4,083 ppm; lead = 80,208 ppm; manganese = 350 ppm; tin = 3,565 ppm. The additive package is 80 millimoles zinc bispolypropylenephenyldithio-phosphate or about 1.1 g OLOA 260 per 100 g oil. The Oxidator BN test measures the response of the lubricating base oil in the simulated application. High values for absorbing 1 liter of oxygen, i.e. long times, indicate good oxidative stability. Originally, Oxydata BN is considered to be more than 7 hours. In the present invention, the oxydata BN value is greater than about 30 hours, preferably greater than about 40 hours.

Oxidator B was used to determine the oxygen stability of blended lubricant products that already contained oxidation resistant additives. The Oxidator B test with L-4 catalyst is a Dornte type oxygen absorber (R.W.Dornte "Oxidation of White Oils", Industrial and Engineering Chemistry, Vol. 28, 26, 1936). ) To measure oxidation resistance. Typically, the conditions are 340 ° F. and 1 atmosphere of pure oxygen, and the time required for 100 g of oil to absorb 1000 ml of O ₂ is reported. In the Oxidator B test with L-4 catalyst, 0.8 ml of catalyst is used per 100 g of oil. The catalyst is a mixture of soluble metal naphthenates in kerosene. The mixture of soluble metal naphthenates simulates the average metal analysis of the crankcase oil used. The metal levels in the catalyst are as follows: copper = 6,927 ppm; iron = 4,083 ppm; lead = 80,208 ppm; manganese = 350 ppm; tin = 3,565 ppm. The Oxidator B test with L-4 catalyst measures the response of the lubricant product in the simulated application. A high value for absorbing 1 liter of oxygen, ie a long time, indicates good stability. In general, it is considered that the Oxidator B test results with L-4 catalyst should exceed about 7 hours. Preferably, the value of Oxidator B with L-4 is greater than about 10 hours. The blended product blends of the present invention have results exceeding 10 hours. Preferably, the blended lubricant product of the present invention has an Oxidator B test result with L-4 catalyst for more than 22 hours, and even more preferably more than 30 hours.

HFRR wear test The wear test is scaled to a Rockwell altitude "C" of Vickers hardness "HV30" according to specification E92, rotated to lapped surface of RA less than 0.02 microns, polished and polished, specification E92. On a polished SAE-AISI E-52100 10 mm flat disk with SAE-AISI E-52100 6.00 mm diameter through-hardened balls (grade 24 per ANSI B3.12, 58-66 Rockwell by ASTM E18 test method) Performed on a 1 ml oil sample using a high frequency reciprocating rig (HFRR) (PCS Instruments HFR2) using a hardness “C” scale number and an RA surface finish of less than 0.05 microns. AISI E-52100 is a ferroalloy having a common elemental composition of 1.00% carbon; 0.35% manganese; 0.25% silicon; and 1.50% chromium. Test conditions are as follows: frequency 20 Hz; applied load 1,000 g; stroke length 1 mm; liquid temperature 120 ° C., relative humidity> 30%, and test duration 200 minutes. This test is a modification of the test described in ASTM D6079.

Due to the extreme hardness differences between the ball and disk, most material wear occurred on the disk in the form of a 1 mm long hemispherical wear track. Therefore, wear resistance performance was based solely on the amount of material removed from the disk, not the ball. Disc wear capacity was measured by first removing fine wear debris from the surface of the disc with a cotton swab soaked in hexane, and then wearing it with a MicroXAM-100 3D surface profiler (ADE phase shift). A rectangular area of 1/24 mm × 1.64 mm was drawn on the surface in the vicinity of the scar. Identification uses the MicroXAM software leveling procedure to first level the surface profile of the disc based on the planar area immediately adjacent to the wear scar, and then to identify the metal protruding above the plane of the surface. The volume of material removed by adhesion (lubricant release wear) from the material replaced by wear (streaks) by subtracting the volume (wear) from the void volume (adhesion) extending below the plane of the surface Was made between. The HFRR wear capacity and the HFRR net wear scar volume from the void volume extending below the surface plane were reported as HFRR wear capacity and HFRR net wear capacity below the plane, respectively, in cubic microns. Accuracy measurement of capacitance by this method is estimated to be ± 10 [mu] ^3. All lubricants were tested twice and the results averaged.

Preferably, the lubricating oil product of the present invention has an applied load of 1,000 g, less than 300,000 μ ³ , more preferably about 170,000 μ ³ or less, even more preferably less than 150,000 μ ³ , even more preferably. 110,000μ shows the HFRR wear volume below ³ below plane. Moreover, the finished lubricants of the present invention is less than 100,000Myu ^3, preferably less than 50,000Myu ^3, more preferably it shows the HFRR Net Wear Volume less than 25,000μ ^3.

Other Lubricant Tests Dynamic viscosity is a measure of the flow resistance of a fluid under gravity. The correct operation of many lubricant base oils, lubricant products made from them, and equipment depends on the proper viscosity of the fluid used. Dynamic viscosity is determined according to ASTM D445-01. Results are reported in centistokes (cSt). The blended lubricant products of the present invention have a dynamic viscosity of from about 2.0 cSt to about 20 cSt at 100 ° C.

  Viscosity index (VI) is an empirical unitless number that indicates the effect of temperature change on the dynamic viscosity of the oil. Liquid changes in viscosity with temperature and loses viscosity when heated. The higher the VI of the oil, the less the tendency of the viscosity change with temperature. High VI lubricants are required when relatively constant viscosities are required over a wide range of temperatures. VI may be determined as described in ASTM D2270-93. Preferably, the blended lubricant product of the present invention has a viscosity index greater than 140, more preferably greater than 165.

  The pour point is a measurement of the temperature at which a lubricant base oil sample begins to flow under carefully controlled conditions. The pour point may be determined as described in ASTM D5950-02. Results are reported in degrees Celsius. Many commercial lube base oils have specifications for pour points. If the lubricating base oils have a low pour point, they will probably also have other good low temperature characteristics such as low cloud point, low cold filter clogging point, and low temperature crank viscosity. The cloud point is a complementary measurement to the pour point and is expressed as the temperature at which the lubricant base oil sample begins to generate cloud under carefully specified conditions. The cloud point may be determined, for example, according to ASTM D 5773-95.

  Noack volatility is measured according to ASTM D5800 when oil is heated at 20 mm Hg (2.67 kPa; 26.7 mbar) below atmospheric pressure at 250 ° C. in a test crucible where a constant air flow is drawn for 60 minutes. Defined as the mass of oil lost in weight percent. A more convenient method for calculating Noack volatility and volatility that correlates well with ASTM D5800 is to use the thermogravimetric analyzer test (TGA) according to ASTM D6375. TGA Noack volatility is used throughout this specification unless otherwise stated. Engine oil Noack volatility, as measured by TGA Noack and similar methods, has been found to correlate with oil consumption in passenger car engines. The stringent requirements for low volatility are important aspects such as some modern engine oil specifications such as European ACEA A-3 and B-3 and North American ILSAC GF-3. Preferably, the blended lubricant product of the present invention has a Noack volatility of less than 12% by weight.

  Cold-crank simulator apparent viscosity (CCS VIS) is a test used to measure the viscosity of lubricating base oils at low temperatures and high shear. CCS VIS may also be referred to as low temperature crank viscosity. The test method for determining CCS VIS is ASTM D 5293-02 at a set temperature of -5 to -35 ° C. Results are reported in centipoise, cP. CCS VIS has been found to correlate with cold engine cranks. The specification for the maximum CCS VIS is defined for automotive engine oil by SAE J300, revised in June 2001.

  High temperature high shear rate viscosity (HTHS) measures fluid flow resistance at 1 million / second, typically at 150 ° C. under conditions resembling high load journal bearings in a burning internal combustion engine. HTHS is a good indicator of how to operate an engine with a specific lubricant at a temperature higher than the dynamic low shear rate viscosity at 100 ° C. HTHS is directly correlated to the oil film thickness at the bearing. SAE J300 (June 2001) contains the latest specifications for HTHS as measured by ASTM D4683, ASTM D4741 or ASTM D5481.

  Mini rotational viscometer (MRV) is related to the mechanism of pump capacity and is a low shear rate measurement. MRV is measured according to ASTM D4684 and may also be referred to as cold pumping viscosity. The slow sample cooling rate is an important feature of this method. Samples are pretreated to have a specified thermal history including warming, slow cooling, and soaking cycles. MRV measures the apparent yield point stress indicating a potential air-coupled pumping failure problem when the threshold is exceeded. Above a certain viscosity, currently defined as 60,000 cP by SAE J300 (June 2001), oils may face pump capacity failure through a mechanism called “flow limit” behavior. For example, SAE 10W oil is required to have a maximum viscosity of 60,000 cP at −30 ° C. without yield point stress. This method also measures the apparent viscosity under a shear rate of 1-50 / sec.

TEOST MHT is a test that determines the amount of deposits formed by automobile engine oil in mg using a heat-oxidation engine oil simulation test (TEOST) under moderately high temperature conditions. This test method is designed to predict the tendency of engine oil hot deposit formation at temperatures found in the piston-ring belt region (approximately 300 ° C.). TEOST MHT can be performed on TEOST 33C bench test equipment already in the field for ASTM D6335 with improved hardware and modified test conditions. The main hardware differences are: 1) a glass depositor rod case instead of steel, where the oxidation / deposition process can be observed, and 2) a deposit wrapped with a wire that allows thin film oil to flow over the heated rod. And 3) collection of volatiles generated in the depositor rod case during the test. TEOST MHT has a maximum specification of 45 mg total deposit in the latest engine oil inspection classification for automotive gasoline engines. In this test, API SL / ILSAC GF-3 oil, which provides improved high temperature deposit control, has increased oil drain capability, less wear, improved piston ring cleanliness, longer engine life, and improved turbo It is expected to provide charger performance. A turbocharger is an exhaust drive pump that compresses intake air and sends it to a combustion chamber above atmospheric pressure. Increased air pressure allows combustion of large amounts of fuel, resulting in increased horsepower production. Table II summarizes the TEOST MHT protocol.
Table II: TEOST MHT Protocol

  The blended lubricant product according to the present invention preferably has a TEOST-MHT total deposit weight of about 45 mg or less.

Fischer-Tropsch synthesis A Fischer-Tropsch derived lubricant base oil comprising ≧ 6% by weight of molecules with monocycloparaffinic functionality and less than 0.05% by weight of molecules with aromatic functionality is provided by Made by hydroisomerization of the wax fraction of the subsequent Fischer-Tropsch synthetic crude oil.

  In Fischer-Tropsch chemistry, synthesis gas is converted to liquid hydrocarbons by contact with a Fischer-Tropsch catalyst under reaction conditions. In general, methane and possibly heavier hydrocarbons (ethane and heavier) can be sent through a conventional syngas generator to prepare the syngas. Generally, the synthesis gas contains hydrogen and carbon monoxide and may contain small amounts of carbon dioxide and / or water. The presence of sulfur, nitrogen, halogen, selenium, phosphorus and arsenic contaminants in the synthesis gas is undesirable. For this reason and due to the quality of the synthesis gas, it is preferred to remove sulfur and other contaminants from the feed prior to performing the Fischer-Tropsch chemistry. Means for removing these contaminants are well known to those skilled in the art. For example, a protective bed of ZnO is preferred for removing sulfur impurities. Means for removing other contaminants are well known to those skilled in the art. It may also be desirable to purify the synthesis gas prior to the Fischer-Tropsch reactor to remove carbon dioxide produced during the synthesis gas reaction and further sulfur compounds that have not been previously removed. This can be accomplished, for example, by contacting the synthesis gas with a thin alkaline solution (eg, aqueous potassium carbonate) in a packed column.

Fischer - In Tropsch process, a synthesis gas comprising a mixture of H ₂ and CO Fischer under reactive conditions of suitable temperature and pressure - by Tropsch catalyst, to form a liquid and gas hydrocarbons. Fischer-Tropsch reactions are generally performed at temperatures of about 300-700 ° F. (149-371 ° C.), preferably about 400-550 ° F. (204-228 ° C.); about 10-600 psia (0.7-41 bar). ), Preferably about 30 to 300 psia (2 to 21 bar); and a catalyst space velocity of about 100 to 10,000 cc / g / hour, preferably about 300 to 3,000 cc / g / hour. Examples of conditions for conducting Fischer-Tropsch type reactions are well known to those skilled in the art.

Fischer - product Tropsch synthesis process may range of _C 1 _{-C 200+} with the scope of small quantities of _C 5 _{-C 100+.} The reaction can be carried out in various reactor types, such as a fixed bed reactor containing one or more catalyst beds, a slurry reactor, a fluidized bed reactor, or a combination of different types of reactors. Such reaction methods and reactors are well known and documented in the literature.

  The preferred slurry Fischer-Tropsch process for practicing the present invention utilizes excellent heat (and mass) transfer characteristics for a powerful exothermic synthesis reaction and, when using a relatively high molecular weight, cobalt catalyst, paraffinic carbonization. Hydrogen can be produced. In the slurry process, the synthesis gas containing hydrogen and carbon monoxide is synthesized in a granular Fischer-Tropsch type hydrocarbon synthesis dispersed and suspended in a slurry liquid containing the hydrocarbon product of the synthesis reaction that is liquid under the reaction conditions. Aerated as a third phase through the slurry containing the catalyst. The molar ratio of hydrogen to carbon monoxide may range from about 0.5 to about 4, but more generally from about 0.7 to about 2.75, preferably from about 0.7 to about Within the range of 2.5. A particularly preferred Fischer-Tropsch process is taught in EP0609079, which is fully incorporated herein by reference for all purposes.

In general, Fischer-Tropsch catalysts comprise a Group VIII transition metal on a metal oxide support. The catalyst may also contain a noble metal promoter and / or a crystalline molecular sieve. Suitable Fischer-Tropsch catalysts include one or more of Fe, Ni, Co, Ru and Re, with cobalt being preferred. Preferred Fischer-Tropsch catalysts are cobalt and Re, Ru, Pt, Fe, Ni, Th, Zr, Hf, U on a suitable inorganic support material, preferably a material comprising one or more refractory metal oxides. , One or more effective amounts of Mg and La. Generally, the amount of cobalt present in the catalyst is from about 1 to about 50% by weight of the total catalyst composition. The catalyst may be a basic oxide promoter, for example, a promoter such as ThO ₂ , La ₂ O ₃ , MgO, and TiO ₂ , ZrO ₂ , noble metals (Pt, Pd, Ru, Rh, Os, Ir). , Money metals (Cu, Ag, Au), and other transition metals such as Fe, Mn, Ni, Re, and the like. Suitable support materials include alumina, silica, magnesia and titania or mixtures thereof. A preferred support for the cobalt-containing catalyst comprises titania. Useful catalysts and their preparation are known and illustrated in US Pat. No. 4,568,663 for purposes of illustration and not limitation with respect to catalyst selection.

Certain catalysts are known to provide the possibility of relatively low to intermediate chain growth, and the reaction product contains a relatively high proportion of low molecular weight (C _2-8 ) olefins and relative _{Contains a} low proportion of high molecular weight (C ₃₀₊ ) wax. Certain other catalysts are known to provide the potential for relatively high chain growth, and the reaction product is a relatively low proportion of low molecular weight (C _2-8 ) olefins and relatively high A proportion of high molecular weight (C ₃₀₊ ) wax is included. Such catalysts are well known to those skilled in the art and can be easily obtained and / or prepared.

The product from the Fischer-Tropsch process contains mainly paraffin. The products from the Fischer-Tropsch reaction generally include light reaction products and waxy reaction products. The light reaction product (i.e., the concentrate fraction) is reduced the amount up to about C _30, mainly C ₅ -C hydrocarbons boiling below about 700 ° F in the range of ₂₀ (e.g., middle distillates Including tail gas via fuel). The waxy reaction product (ie wax fraction) is reduced to C ₁₀ in hydrocarbons boiling above about 600 ° F., mainly in the range of C ₂₀₊ (eg, vacuum via heavy paraffin). Gas oil). Both the light reaction product and the waxy product are substantially paraffinic. Waxy products generally contain more than 70% by weight linear paraffins and often more than 80% by weight linear paraffins. Light reaction products include paraffinic products with a significant proportion of alcohols and olefins. In some cases, the light reaction product may contain 50 wt% or more alcohol and olefin. It is the waxy reaction product (ie, wax fraction) that is used as feedback to the process for preparing the Fischer-Tropsch derived lubricant base oil used in the blended lubricants and blended lubricant products of the present invention. .

  Fischer-Tropsch derived lubricating base oils containing ≧ 6% by weight molecules with monocycloparaffinic functionality and less than 0.05% by weight molecules with aromatic functionality are synthesized by a Fischer-Tropsch synthesis by a process involving hydroisomerization. Prepared from a waxy fraction of crude oil. Preferably, the Fischer-Tropsch derived lubricating base oil is US patent application Ser. No. 10 / 744,389 (filed Dec. 23, 2003), which is incorporated herein by reference in its entirety, and US Patent Application No. 10 / 744,870. (Filed on Dec. 23, 2003). The Fischer-Tropsch derived lubricant base oil used in the blended lubricants and blended lubricant products of the present invention may be manufactured at a location different from where the components of the blended lubricant are received and blended.

Hydroisomerization
Hydroisomerization is intended to improve the cold flow properties of lubricating base oils by the selective addition of branches into the molecular structure. Hydroisomerization ideally minimizes conversion by pyrolysis while achieving a high level of conversion of Fischer-Tropsch wax to non-waxy iso-paraffins. Preferably, the conditions for hydroisomerization in the present invention are such that the conversion of compounds boiling above about 700 ° F. to compounds boiling below about 700 ° F. in the wax feed is from about 10 wt% to It is adjusted to be maintained at 50% by weight, preferably 15% to 45% by weight.

  According to the present invention, hydroisomerization is performed using a shape selective intermediate pore size molecular sieve. The hydroisomerization catalyst useful in the present invention comprises a shape selective intermediate pore size molecular sieve and optionally a catalytically active metal hydrogenation component on a refractory oxide support. As used herein, the term “intermediate pore size” means an effective pore size in the range of about 3.9 to about 7.1% when the porous inorganic oxide is in the calcined form. The shape selective intermediate pore size molecular sieves used in the practice of the present invention are generally 1-D 10-, 11- or 12-ring molecular sieves. Preferred molecular sieves of the present invention are of the 1-D 10-ring type, and 10- (or 11- or 12-) ring molecular sieves are 10 (or 11 or 12) tetrahedrally bonded to oxygen. It has a coordination atom (T-atom). In 1-D molecular sieves, 10-ring (or more) pores are parallel to each other and do not interconnect. However, 1-D 10-ring molecular sieves that meet the broad definition of intermediate pore size molecular sieves but contain cross pores with 8-membered rings may also be included within the definition of molecular sieves of the present invention. . The classification of internal zeolite channels, such as 1-D, 2-D and 3-D, is R.I. M.M. Barrer in Zeolites, Science and Technology, F.M. R. Rodrigues, L. D. Rollman and C.I. Naccache, edited by NATO ASI Series, 1984 (see especially page 75), the classification of which is incorporated by reference in its entirety.

  Preferred shape selective intermediate pore size molecular sieves used for hydroisomerization are based on aluminum phosphates such as SAPO-11, SAPO-31, and SAPO-41, where SAPO-11 and SAPO-31 are More preferred is SAPO-11. SM-3 is a particularly preferred shape selective intermediate pore size SAPO and has a crystalline structure that fits within the crystal structure of the SAPO-11 molecular sieve. The preparation of SM-3 and its unique features are described in US Pat. Nos. 4,943,424 and 5,158,665. Also preferred shape selective intermediate pore size molecular sieves used for hydroisomerization are ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite. And zeolites such as ferrierite, with SSZ-32 and ZSM-23 being more preferred.

  Preferred intermediate pore size molecular sieves are characterized by the selected crystal free diameter of the channel, the selected crystallite size (corresponding to the length of the selected channel), and the selected acidity. The desired crystal free diameter of the molecular sieve channel is in the range of about 3.9 to about 7.1 mm, with a maximum crystal free diameter of 7.1 or less and a minimum crystal free diameter of 3.9 mm or more. Preferably, the maximum crystal free diameter is 7.1 or less and the minimum crystal free diameter is 4.0 mm or more. Most preferably, the maximum crystal free diameter is 6.5 or less and the minimum crystal free diameter is 4.0 mm or more. The crystal free diameter of the channels of molecular sieves is described in “Atlas of Zeolite Framework Types”, revised 5th edition, 2001, Ch. Baerlocher, W.M. M.M. Meier, and D.C. H. Olson, Elsevier, pages 10-15.

Particularly preferred intermediate pore size molecular sieves useful in the method of the present invention are described, for example, in US Pat. Nos. 5,135,638 and 5,282,958, the contents of which are hereby incorporated by reference in their entirety. In US Pat. No. 5,282,958, such intermediate pore size molecular sieves have pores having a crystallite size of about 0.5 microns or less and a minimum diameter of at least about 4.8 mm and a maximum diameter of about 7.1 mm. The catalyst converts at least 50% hexadecane at 370 ° C. with a pressure of 1200 psig, a hydrogen flow rate of 160 ml / min, and a feed rate of 1 ml / hr when 0.5 g of catalyst is charged to the tube reactor. Have sufficient acidity. The catalyst also exhibits an isomerization selectivity of 40% or more when used under conditions that result in 96% conversion of linear hexadecane (n-C ₁₆ ) to other species (isomerization selectivity). It is determined as follows: 100 × (weight% branched _{C 16} in product) / (weight of _{C 13-%} in percent by weight + product branched _{C 16} in product).

If the crystal free diameter of the molecular sieve channel is not known, the effective pore size of the molecular sieve can be measured using standard adsorption methods and known minimum dynamic diameter hydrocarbon compounds. Breck, Zeolite Molecular Sieves, 1974 (especially Chapter 8); Anderson et al., J. MoI. See Catalysis 58, 114 (1979); and US Pat. No. 4,440,871, the relevant part of which is incorporated herein by reference. Standard methods are used in performing adsorption measurements to determine pore size. It is convenient to consider certain molecules to be excluded if they do not achieve at least 95% of their equilibrium adsorption value (at 25 ° C., p / p ₀ = 0.5) for molecular sieves in less than about 10 minutes. Intermediate pore size molecular sieves generally contain molecules with a dynamic diameter of 5.3 to 6.5 mm with little hindrance.

  The hydroisomerization catalyst useful in the present invention comprises a catalytically active metal hydride. The presence of a catalytically active metal hydride is particularly responsible for producing improved VI and stability. Common catalytically active metal hydrides include chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum, and palladium. Platinum and palladium metal are particularly preferred, with platinum being most preferred. When platinum and / or palladium is used, the total amount of active hydrogenation metal is generally in the range of 0.1-5% by weight of the total catalyst, usually 0.1-2% by weight. Not exceeding 10% by weight.

  The refractory oxide support may be selected from oxide supports commonly used for catalysts, including silica, alumina, silica-alumina, magnesia, titania, and combinations thereof.

The hydroisomerization conditions are tailored to achieve a Fischer-Tropsch derived lubricating base oil containing ≧ 6 wt% molecules with monocycloparaffinic functionality and less than 0.05 wt% molecules with aromatic functionality. The The hydroisomerization conditions depend on the feed used, the catalyst used, whether the catalyst is sulfurized, the desired yield, and the desired properties of the lubricating base oil. Conditions under which the hydroisomerization process of the present invention may be carried out are from about 600 ° F. to about 750 ° F. (315 ° C. to about 399 ° C.), preferably from about 600 ° F. to about 700 ° F. (315 ° C. to And a pressure of about 15 to 3000 psig, preferably 100 to 2500 psig. Hydroisomerization dewaxing pressure in this context means the hydrogen partial pressure in the hydroisomerization reactor even though the hydrogen partial pressure is substantially the same (or nearly the same) as the total pressure. The liquid space velocity during contact is generally from about 0.1 to 20 / hour, preferably from about 0.1 to about 5 / hour. The ratio of hydrogen to hydrocarbon is from about 1.0 to about 50 moles _H 2/1 mole of hydrocarbon, more preferably falls within the range of from about 10 to about 20 moles _H 2/1 mole of hydrocarbon. Suitable conditions for carrying out the hydroisomerization are described in US Pat. Nos. 5,282,958 and 5,135,638, the contents of which are incorporated by reference in their entirety.

  Hydrogen is generally in the hydroisomerization process at a ratio of hydrogen to feed of about 0.5 to 30 MSCF / bbl (1000 standard cubic feet per barrel), preferably about 1 to about 10 MSCF / bbl. Present in the reaction zone. Hydrogen may be separated from the product and recycled to the reaction zone.

Hydrotreating
The waxy feed to the hydroisomerization process may be hydrotreated before hydroisomerization dewaxing. The hydrotreatment is referred to as catalytic treatment and is usually performed in the presence of free hydrogen, the main purpose of which is various metal contaminants such as arsenic, aluminum and cobalt; heteroatoms such as sulfur and nitrogen; Oxygenates; or removal of aromatics and the like from the feedstock. In general, hydrocracking operations minimize the thermal cracking of hydrocarbon molecules, i.e., the destruction of large hydrocarbon molecules into smaller hydrocarbon molecules, and unsaturated hydrocarbons are fully or partially hydrogenated. The

  Catalysts used in performing hydrotreating operations are well known in the art. For example, U.S. Pat. No. 4,347,121, the contents of which are hereby incorporated by reference in their entirety for a general description of the hydrotreating, hydrocracking, and common catalysts used in each method. No. 4,810,357. Suitable catalysts include Group VIIIA noble metals (according to International Union of Pure and Applied Chemistry 1975), such as platinum or palladium on alumina or siliceous matrices, and Group VIII and VIB, such as alumina or Examples include nickel-molybdenum or nickel-tin on a silicon matrix. U.S. Pat. No. 3,852,207 describes suitable noble metal catalysts and mild conditions. Other suitable catalysts are described, for example, in U.S. Pat. Nos. 4,157,294 and 3,904,513. Non-noble metal hydrides, such as nickel-molybdenum, are usually present in the final catalyst composition as oxides, but usually these reduced forms or sulfide compounds are easily derived from the specific metals involved. Is used in the sulfide form. Preferred non-noble metal catalyst compositions comprise at least about 5 wt.%, Preferably about 5 to about 40 wt.% Molybdenum and / or tungsten, and at least about 0.5, generally in terms of the corresponding oxide. Contains about 1 to about 15 weight percent nickel and / or cobalt. A catalyst containing a noble metal, such as platinum, contains 0.01% or more metal, preferably 0.1 to 1.0% metal. Combinations of noble metals such as a mixture of platinum and palladium may be used.

  General hydrotreatment conditions vary over a wide range. Generally, the overall LHSV is about 0.25 to 2.0, preferably about 0.5 to 1.5. The hydrogen partial pressure exceeds 200 psia, preferably in the range of about 500 psia to about 2000 psia. The hydrogen recycle rate is generally greater than 50 SCF / Bbl, preferably 1000 to 5000 SCF / Bbl. The temperature in the reactor is about 300 ° F to about 750 ° F (about 150 ° C to about 400 ° C), preferably 450 ° F to about 725 ° F (about 230 ° C to about 385 ° C).

Hydrorefining
Hydrorefining is a hydroprocessing method that may be used as a step following hydroisomerization to prepare a Fischer-Tropsch derived lubricating base oil. Hydrorefining is intended to improve the oxidation stabilizer, UV stability, and appearance of Fischer-Tropsch derived lubricating base oils produced by removing traces of aromatics, olefins, color bodies, and solvents. Is. The term UV stability as used in this disclosure refers to the stability of a lubricating base oil or lubricating oil product when exposed to UV light and oxygen. Instability is indicated when a visible precipitate form, usually visible as floc or turbidity, or when a dark color occurs upon exposure to ultraviolet light and air. A general description of hydrorefining may be found in US Pat. Nos. 3,852,207 and 4,673,487.

  The Fischer-Tropsch derived lubricating base oil of the present invention may be hydrorefined to improve product quality and stability. During hydrorefining, the total liquid hourly space velocity (LHSV) is about 0.25 to 2.0 / hour, preferably about 0.5 to 1.0 / hour. The hydrogen partial pressure exceeds 200 psia, preferably in the range of about 500 psia to about 2000 psia. The hydrogen recycle rate is generally greater than 50 SCF / Bbl, preferably 1000 to 5000 SCF / Bbl. The temperature ranges from about 300 ° F. to about 750 ° F., preferably 450 ° F. to 600 ° F.

  Suitable hydrorefining catalysts include Group VIIIA noble metals (according to International Union of Pure and Applied Chemistry 1975), such as platinum or palladium on alumina or siliceous matrices, and non-sulfided Group VIIIA and Group VIB, for example, nickel-molybdenum or nickel-tin on alumina or a silicon matrix. U.S. Pat. No. 3,852,207 describes suitable noble metal catalysts and mild conditions. Other suitable catalysts are described, for example, in U.S. Pat. Nos. 4,157,294 and 3,904,513. Non-noble metals (such as nickel-molybdenum and / or tungsten) and at least about 0.5, and generally about 1 to about 15 weight percent nickel and / or cobalt, converted to the corresponding oxides . The noble metal (for example, platinum) catalyst contains 0.01% or more metal, preferably 0.1 to 1.0% metal. Combinations of noble metals such as a mixture of platinum and palladium may be used.

  Clay treatment to remove impurities is a selective final treatment step for preparing a Fischer-Tropsch derived lubricating base oil.

Fractionation
Optionally, a method for preparing a Fischer-Tropsch derived lubricating base oil may include a step of fractionating a substantially paraffinic wax feed prior to hydroisomerization, or a lubricant base oil obtained from a hydroisomerization step. A separation step may be included. Fractionation of the Fischer-Tropsch substantially paraffinic wax feed into distillate fractions is generally accomplished by atmospheric or vacuum distillation, or a combination of atmospheric and vacuum distillation. Atmospheric distillation is generally performed from a bottom distillate fraction having an initial boiling point above about 600 ° F. to about 750 ° F. (about 315 ° C. to about 399 ° C.), such as naphtha and intermediate distillation. Used to separate things. At high temperatures, thermal decomposition of hydrocarbons can occur, causing equipment fouling and reducing the yield of heavy matter. Vacuum distillation is commonly used to separate high boiling materials, such as lubricating base oil fractions, into different boiling range fractions. Separating the lubricating base oil into different boiling range fractions allows the lubricating base oil production plant to produce more than one grade or viscosity of the lubricating base oil.

Solvent Dewaxing
The process for making a Fischer-Tropsch derived lubricating base oil may also include a solvent dewaxing step following the hydroisomerization process. Solvent dewaxing may optionally be used to remove small amounts of residual waxy molecules from the lubricating base oil after hydroisomerization dewaxing. Solvent dewaxing involves dissolving the lubricating base oil in a solvent such as methyl ethyl ketone, methyl iso-butyl ketone, or toluene, or Chemical Technology of Petroleum, 3rd edition, William Gruse and Donald Stevens, McGraw-Hill Co., Ltd. New York, 1960, pages 566-570, by precipitating wax molecules. Solvent dewaxing is also described in U.S. Pat. Nos. 4,477,333, 3,773,650, and 3,775,288.

Fischer-Tropsch derived lubricating base oil The Fischer-Tropsch derived lubricating base oil used to prepare the blended lubricating oils and blended lubricating oil products of the present invention preferably has a viscosity of about 2-20 cSt at 100 ° C.

  Fischer-Tropsch derived lubricating base oil has ≧ 6 wt% molecules with monocycloparaffin functionality, preferably ≧ 8 wt% molecules with monocycloparaffin functionality, and even more preferably monocycloparaffin functionality ≧ 10% by weight of molecules. In a preferred embodiment, the Fischer-Tropsch derived lubricating base oil has a monocyclohexane to very low weight percent aromatics, molecules with high weight percent cycloparaffinic functionality, and weight percent molecules with multicycloparaffinic functionality. A high percentage of weight percent of molecules with paraffin functionality (or high weight percent of molecules with monocycloparaffin functionality and very low weight percent of molecules with multicycloparaffin functionality). The Fischer-Tropsch derived lubricating base oil contains less than 0.05% by weight of molecules with aromatic functionality, preferably less than 0.02% by weight. In a preferred embodiment, the Fischer-Tropsch derived lubricating base oil is a molecule having a monocycloparaffinic functionality relative to the weight percent of molecules having a cycloparaffinic functionality greater than 10 and the weight percent of molecules having a multicycloparaffinic functionality. High proportions, preferably greater than 15. In still other preferred embodiments, the Fischer-Tropsch derived lubricating base oil is less than 0.05 wt% of molecules with aromatic functionality, wt% of molecules with monocycloparaffin functionality greater than 10, And% by weight of molecules having a multicycloparaffinic functionality of less than 0.1.

Fischer-Tropsch derived lubricating base oils used in blended lubricants and blended lubricant products contain greater than 95% by weight of saturates as determined by elution column chromatography, ASTM D2549-02. Olefin is present in an amount less than the amount that can be detected by long term C ¹³ nuclear magnetic resonance spectroscopy (NMR). Molecules with aromatic functionality were present by HPLC-UV in an amount of less than 0.05% by weight and were confirmed by ASTM D 5292-99 modified to measure low level aromatics. In a preferred embodiment, the molecule with aromatic functionality is present in an amount of less than 0.02% by weight, preferably less than 0.01% by weight.

  Sulfur is present in an amount less than 25 ppm, more preferably less than 1 pp as determined by ultraviolet fluorescence according to ASTM D5453-00.

Aromatic Measurement by HPLC-UV The method used to measure low levels of molecules with aromatic functionality in a Fischer-Tropsch derived lubricant base oil is the HP 1050 Diode-Array UV connected to HP Chem-station. Use a Hewlett Packard 1050 Series Gradient High Performance Liquid Chromatography (HPLC) system coupled to a Vis detector. The identification of individual aromatic classes in highly saturated Fischer-Tropsch derived lubricating base oils was based on these UV spectral patterns and their elution times. The amino column used for this analysis distinguishes mainly aromatic molecules based on their number of rings (or more precisely, the number of double bonds). Accordingly, molecules containing monocyclic aromatics elute first, followed by polycyclic aromatics in order of increasing number of double bonds per molecule. In aromatics with the same double bond characteristics, aromatics with only alkyl substitution on the ring elute faster than aromatics with cycloparaffin substitution.

  The unambiguous identification of various base oil aromatic hydrocarbons from these UV absorption spectra indicates that the model transitions are pure to the extent that the electronic transitions of these peaks depend on the amount of alkyl and cycloparaffin substitution on the ring system. It was somewhat complicated by the fact that everything was red-shifted with respect to the body. It is well known that these deep-color shifts are caused by delocalization of π-electron alkyl groups in the aromatic ring. Since a small number of unsubstituted aromatic compounds boil in the lube range, some red-shift was expected and observed for all of the major aromatic groups identified.

  Quantification of the eluted aromatic compound was performed by integrating chromatograms made from wavelengths optimized for the general class of each compound over the appropriate retention time frame for that aromatic. Retention time frame limits for each aromatic class are determined manually by assessing the individual absorption spectra of compounds eluting at different times and based on their qualitative similarity to the model compound absorption spectra. Determined by assigning. With few exceptions, only five classes of aromatics were observed with highly saturated API Group II and III lubricant base oils.

HPLC-UV calibration HPLC-UV is used to identify these classes of aromatic compounds even at very low levels. Polycyclic aromatics generally absorb 10 to 200 times more strongly than monocyclic aromatics. Alkyl substitution also affected absorption at about 20%. Therefore, it is important to use HPLC to separate and identify the various aromatic species and know how effectively they absorb.

  Five classes of aromatic compounds have been identified. All aromatic classes were resolved to baseline, with the exception of slight overlap between the most highly retained alkyl-1-ring aromatic naphthenes and the least highly retained alkylnaphthalenes . Integration limits for co-eluting 1-ring and 2-ring aromatics at 272 nm were performed by the vertical drop method. The wavelength-dependent response factor for each common aromatic class is first determined by plotting a Beer's law plot from a pure model compound mixture based on the spectral peak absorbance closest to the substituted aromatic analog It was done.

  For example, an alkyl-cyclohexylbenzene molecule in a base oil exhibits a distinct peak absorbance at 272 nm that corresponds to the same (forbidden) transition that an unsubstituted tetralin model compound does at 268 nm. The concentration of the alkyl-1-ring aromatic naphthene in the base oil sample assumes that its molecular absorptive response factor at 272 nm was approximately equal to the molecular absorptivity of tetralin at 268 nm calculated from Beer's law plot. calculated. The aromatic weight percent concentration was calculated assuming that the average molecular weight of each aromatic class was approximately equal to the average molecular weight of the entire base oil sample.

  This calculation method was further improved by isolating the 1-ring aromatics directly from the lubricating base oil by elaborate HPLC chromatography. Direct calibration with these aromatics eliminated the assumptions and uncertainties associated with model compounds. As expected, the isolated aromatic sample had a lower response factor than the model compound because it was more substituted.

  More specifically, in order to accurately calibrate the HPLC-UV method, substituted benzene aromatics were separated from a large amount of lubricating base oil using a Water semi-separated HPLC system. A 10 g sample was diluted 1: 1 with n-hexane and injected at a flow rate of 18 ml / min onto a 5 cm × 22.4 mm ID guard amino-bonded silica column with n-hexane as the mobile phase followed by Rainin. It was injected into two 25 cm x 22.4 mm ID columns of 8-12 micron amino-bonded silica particles manufactured by Instruments, Emeryville, California. The column eluent was fractionated based on the detector response from a dual wavelength UV detector set at 265 nm and 295 nm. Saturate fractions were collected until the absorbance at 265 nm showed a change of 0.01 absorbance units that signaled the onset of monocyclic aromatic elution. The monocyclic aromatic fraction was collected until the absorbance ratio between 265 nm and 295 nm decreased to 2.0 indicating the onset of bicyclic aromatic elution. Purification and separation of the monocyclic aromatic fraction was accomplished by rechromatographically separating the monoaromatic fraction away from the “adjoint” saturate fraction produced by overloading the HPLC column.

  This purified aromatic “standard” showed that alkyl substitution reduced the molecular absorptive response factor to about 20% for unsubstituted tetralin.

Confirmation of aromatics by NMR The weight percent of molecules with aromatic functionality in the purified monoaromatic standard was confirmed by long-term carbon-13 NMR analysis. NMR is easier to calibrate than HPLC-UV because it easily measures aromatic carbon, and the response did not depend on the class of aromatic being analyzed. NMR results show that from 95% aromatics to% aromatic molecules (HPLC-UV and D2007) by knowing that 95-99% of the aromatics in the highly saturated lubricating base oil were monocyclic aromatics. To be consistent).

  High power, long duration, and good baseline analysis were necessary to accurately measure aromatics down to 0.2% aromatic molecules.

  More specifically, in order to accurately measure all molecules having a low level of at least one aromatic function by NMR, the standard D5292-99 method was modified to give a minimum carbon sensitivity of 500: 1. (According to ASTM standard procedure E386). 15 hour measurements were used with 400-500 MHz NMR with a 10-12 mm Nalorac probe. Acorn PC integration software was used to define the baseline shape and consistently integrate. The carrier frequency was changed once during the measurement to avoid the artifacts of imaging the aliphatic peak in the aromatic region. By taking the spectrum on either side of the carrier spectrum, the resolution was significantly improved.

Cycloparaffin distribution by FIMS Paraffin is considered more stable to oxidation than cycloparaffin and is therefore more desirable. Monocycloparaffins are believed to be more stable to oxidation than multicycloparaffins. However, if the weight percent of all molecules having at least one cycloparaffinic function in the lubricating base oil is very low, the additive solubility is low and the elastomer compatibility is poor. An example of a base oil having these properties is a Fischer-Tropsch base oil (GTL base oil) having a polyalphaolefin and less than about 5% cycloparaffins. To improve these properties in lubricating oil products, expensive cosolvents such as esters often must be added. Preferably, the Fischer-Tropsch derived lubricating base oil used in the blended lubricants and blended lubricant products of the present invention has a high weight percent of molecules with monocycloparaffinic functionality and a low weight percent of multicycloparaffinic functionality. Fischer-Tropsch derived lubricating base oils, and therefore blended lubricating oils and blended lubricating oil products, have high oxidative stability and high viscosity index in addition to good additive solubility and elastomer compatibility. Have

  The composition of molecules with cycloparaffin and multicycloparaffin functionality is determined using field ionization mass spectrometry (FIMS). FIMS spectra were obtained on a VG70 VSE mass spectrometer. Samples were introduced at a rate of 50 ° C./min through a solid probe heated to about 40 ° C. to 500 ° C. The mass spectrometer was scanned from m / z 40 to m / z 1000 at a rate of 5 seconds / 10 years. The acquired mass spectra were summed to generate one “averaged” spectrum. Each spectrum was C13 corrected using the PC-MassSpec software package. FIMS ionization efficiency was evaluated using a blend of nearly pure branched paraffin and a highly naphthenic non-aromatic base stock. The ionization efficiency of iso-paraffin and cycloparaffin in these base oils was essentially the same. Iso-paraffins and cycloparaffins contain more than 99.9% saturates in the lubricating base oils of the present invention. Assuming a response factor of 1.0 for all types of compounds, weight percent was given directly from area percent.

  The lubricating base oils of the present invention are characterized by paraffin and molecules with different numbers of unsaturation by FIMS. Molecules with different numbers of unsaturations may include cycloparaffins, olefins, and aromatics. Since the lubricating base oils of the present invention have very low levels of aromatics and olefins, molecules having different numbers of unsaturations may be interpreted as cyclic olefins having different numbers of rings. Therefore, in the lubricating base oil of the present invention, 1-unsaturation is monocycloparaffin, 2-unsaturation is dicycloparaffin, 3-unsaturation is tricycloparaffin, 4-unsaturation is tetracycloparaffin. Paraffin, 5-unsaturation is pentacycloparaffin, and 6-unsaturation is hexacycloparaffin. If aromatics are present in significant amounts in the lubricating base oil, they are identified as 4-unsaturated by FMIS analysis. The sum of 2-unsaturated, 3-unsaturated, 4-unsaturated, 5-unsaturated and 6-unsaturated in the white oil of the present invention is the weight percent of molecules having multicycloparaffinic functionality. The sum of 1-unsaturation in the lubricating base oils of the present invention is the weight percent of molecules having monocycloparaffinic functionality.

  In one embodiment, the Fischer-Tropsch derived lubricating base oil has a weight percent of molecules with cycloparaffinic functionality greater than 10, preferably greater than 15, and more preferably greater than 20. These have a ratio of the weight percent of molecules with monocycloparaffinic functionality to the weight percent of molecules with multicycloparaffinic functionality greater than 15, preferably greater than 50, more preferably greater than 100. In a preferred embodiment, the Fischer-Tropsch derived lubricating base oil is greater than 10% by weight of molecules with monocycloparaffinic functionality and less than 0.1 molecules with multicycloparaffinic functionality or multicycloparaffins. It has a weight percent without functional molecules. In this embodiment, the Fischer-Tropsch derived lubricating base oil has a dynamic viscosity at 100 ° C. of about 2 cSt to about 20 cSt, preferably about 2 cSt to about 12 cSt, and most preferably about 3.5 cSt to about 12 cSt.

  In other embodiments of the Fischer-Tropsch derived lubricating base oil, there is a relationship between the weight percent and dynamic viscosity of all molecules having at least one cycloparaffinic functionality of the lubricating base oil of the present invention. . That is, the higher the dynamic viscosity in cSt at 100 ° C., the higher the amount of molecules with cycloparaffinic functionality obtained. In a preferred embodiment, the Fischer-Tropsch derived lubricating base oil is a weight percent of molecules having cycloparaffinic functionality that exceeds the dynamic viscosity at cSt in a multiple of 3, preferably greater than 15, and more preferably greater than 20. Having a ratio of the weight percent of molecules with monocycloparaffinic functionality to the weight percent of molecules with multicycloparaffinic functionality of greater than 15, preferably greater than 50, more preferably greater than 100. The Fischer-Tropsch derived lubricating base oil has a dynamic viscosity at 100 ° C. of about 2 cSt to about 20 cSt, preferably about 2 cSt to about 12 cSt. Examples of these base oils may have a dynamic viscosity of from about 2 cSt to about 3.3 cSt at 100 ° C., and have a weight percent of molecules with a high but less than 10 weight percent cycloparaffinic functionality. May be.

  The modified ASTM D5292-99 and HPLC-UV test methods used to measure low levels of aromatics, and the FIMS test method used to characterize saturates, are generally incorporated herein by reference. 1999 AIChE Spring National Meeting in Houston, D.A., filed Mar. 16, 1999. C. Kramer et al., “Influence of Group II & III Base Oil Composition on VI and Oxidation Stability”.

  Although the Fischer-Tropsch wax feed is essentially free of olefins, the base oil treatment process introduces olefins, particularly at elevated temperatures, by a “cracking” reaction. In the presence of heat or UV light, the olefin polymerizes to form a high molecular weight product that causes the base oil to become colored and produce deposits. In general, olefins are removed by hydrorefining or clay treatment during the process of the present invention.

The properties of the Fischer-Tropsch derived lubricating base oil used in the examples are summarized in Table III below.
Table III: Properties of FTBO

  Originally paraffins of the different saturated hydrocarbons found in lubricating base oils are believed to be more stable to oxidation than cycloparaffins (naphthenes) and are therefore more desirable. However, when the amount of aromatics in the base oil is less than 1% by weight, the most effective way to further improve oxidative stability is to increase the viscosity index of the base oil. Fischer-Tropsch derived lubricating base oils generally contain less than 1% by weight aromatics. Due to these extremely low amounts of aromatic and multicycloparaffins in the Fischer-Tropsch derived lubricating base oils of the present invention, their high oxidative stability far exceeds that of conventional lubricating base oils. In addition, Fischer-Tropsch derived lubricating base oils are generally classified as API Group III base oils, with low sulfur content below 5 ppm, saturates content above 95%, high viscosity index, and excellent cold flow properties. Have

  Fischer-Tropsch derived lubricating base oils useful in the present invention have a high viscosity index. The viscosity index is measured according to ASTM D2270-93 (98). In general, these are greater than 120, preferably the amount calculated by the formula: Viscosity index = 28 × Ln (dynamic viscosity at 100 ° C.) + 95, more preferably the formula: Viscosity index = 28 × Ln (Dynamic viscosity at 100 ° C.) having a viscosity index exceeding the amount calculated by +105.

Blend Lubricating Base Oil The blend lubricating base oil of the present invention comprises ≧ 70 wt% Fischer-Tropsch derived lubricating base oil and at least one polyalphaolefin lubricating base oil having a dynamic viscosity at 100 ° C. of greater than about 30 cSt and less than 150 cSt. including. The blended lubricating base oil preferably comprises at least one Fischer-Tropsch derived lubricating base oil in an amount of 70 to about 99% by weight and at least one polyalphaolefin in an amount of about 1 to 30% by weight. Blended lubricating base oils may be made by blending a Fischer-Tropsch derived lubricating base oil and a polyalphaolefin lubricating base oil by methods known to those skilled in the art.

  The Fischer-Tropsch derived lubricating base oil has a dynamic viscosity at 100 ° C. of about 2 cSt to about 20 cSt, preferably about 2 cSt to about 12 cSt. Preferably, the difference in dynamic viscosity at 100 ° C. between the Fischer-Tropsch derived lubricating base oil and the polyalphaolefin lubricating base oil is greater than 40 cSt, more preferably greater than 70 cSt.

  To provide a blended lubricant product, the blended lubricant base oil is mixed with at least one antiwear additive. Blended lubricant products may be made by blending blended lubricating base oils and antiwear additives by methods known to those skilled in the art. The blended lube product components are simply a single starting from the individual components (ie, Fischer-Tropsch derived lubricating base oil, poly alpha olefin lubricating base oil, and anti-wear additive) to prepare the blended lube product. It may be blended in one step. Alternatively, the Fischer-Tropsch derived lubricating base oil and the polyalphaolefin lubricating base oil may be first blended to provide a blended base oil and then the blended base oil may be directly mixed with the antiwear additive. Good. The blend base oil may be isolated as is, or the addition of antiwear additives may be performed immediately.

  The Fischer-Tropsch derived lubricating base oil used in the blended lubricating base oils and blended lubricating oil products of the present invention may be manufactured at a location different from where the components of the blended lubricating oil are received and blended. Further, the blended lubricant product may be manufactured at a location different from where the components of the blended lubricant base oil are received and blended. Preferably, the blended lubricant base oil and blended lubricant product are made at the same location that is different from where the Fischer-Tropsch derived lubricant base oil was originally made. Thus, the Fischer-Tropsch derived lubricating base oil is manufactured at a first location and shipped to a second remote location. A second remote location receives the Fischer-Tropsch derived lubricant base oil, polyalphaolefin, and additives, and a blended lubricant product is produced at this second location.

Blended Lubricant Product The lubricating oil product comprises at least one lubricating base oil and at least one additive. Lubricating base oils are the most important components of lubricating oil products and generally comprise ≧ 70% of lubricating oil products. The lubricating oil products of the present invention may be used in automobiles, diesel engines, accelerators, transmissions, and industrial applications.

  The blended lubricating oil product of the present invention comprises at least one Fischer-Tropsch derived lubricating base oil comprising ≧ 6% by weight molecules having monocycloparaffinic functionality and less than 0.05% by weight molecules having aromatic functionality; An effective amount of at least one polyalphaolefin lubricating base oil having a dynamic viscosity greater than about 30 cSt and less than 150 cSt, and at least one anti-wear additive. The blended lubricant products of the present invention exhibit special friction and wear properties.

  In general, the effective amount of anti-wear additive required in lubricating oil products including Fischer-Tropsch derived lubricating base oils is the same in lubricating oil products containing conventional petroleum lubricating base oils or polyalphaolefin lubricating base oils. Less than the effective amount required. In accordance with the present invention, surprisingly, significantly less antiwear additives are present at about 100 ° C. than in lubricating oil products comprising Fischer-Tropsch derived lubricating base oil in the absence of polyalphaolefin lubricating base oil. ≧ 6 wt% molecules with monocycloparaffinic functionality and less than 0.05 wt% molecules with aromatic functionality blended with a polyalphaolefin lubricating base oil having a dynamic viscosity of greater than 30 cSt and less than 150 cSt It has been found that there is a need for lubricating oil products containing Fischer-Tropsch derived lubricating base oils. Accordingly, a reduced amount of anti-wear additive is required in the blended lubricant product of the present invention. Thus, the blended lubricants of the present invention can be used to make high performance engine oils and other lubricant products that meet the most stringent modern engine oil specifications.

The effective amount of at least one antiwear additive, 300,000Myu less than ³ at application load amount or 1000g antiwear additive in the additive package, preferably less than 170,000Myu ^3, more preferably 150, It means an amount that is added individually to the blended lubricant base oil to prepare the blended finished lubricants having HFRR wear volume less than 000μ ^3. Even more preferably, the blended finished lubricant has an HFRR wear volume of less than 110,000Myu ³ at application load 1000 g. In accordance with the present invention, preferably the effective amount of at least one anti-wear additive is about 0.001 to 5% by weight of the blended lubricant product. Effective amounts of anti-wear additives in the blended lubricant products of the present invention include Fischer-Tropsch derived lubricant base oil that is free of polyalphaolefin lubricant base oil and polyalphaolefin lubricant base that is free of Fischer-Tropsch derived lubricant base oil. Less than the effective amount of anti-wear additive required in lubricating oils.

  The antiwear additive chemically reacts with the metal surface in the device being lubricated to form a layer that reduces wear at low media temperatures and loads or at high temperatures and loads. Generally, the metal surface includes floor roy. The antiwear additive includes one or more metal phosphates, metal dithiophosphates, metal dialkyldithiophosphates, metal thiocarbamates, metal dithiocarbamates, metal dialkyldithiocarbamates, ethoxylated amine dialkyldithiophosphates, ethoxylate amine dithiobenzoates, It may be a neutral organic phosphate, an organic molybdenum compound, an organic sulfur compound, a sulfur compound, a chlorine compound, or a mixture thereof. Preferably the antiwear additive is a metal dialkyldithiophosphate, and even more preferably the metal is zinc. A summary of the different types of antiwear additives is given in McDonald, R .; A. and Phillips, W.M. D. , “Lubricant Additives Chemistry and Applications”, Chapters 2 and 3, 2003.

  The blended lubricating oil products of the present invention are further additives such as EP agents, surfactants, dispersants, antioxidants, pour point depressants, viscosity index improvers, ester cosolvents, viscosity modifiers, friction modifiers. Agent, demulsifier, defoamer, corrosion inhibitor, rust inhibitor, seal swelling agent, emulsifier, wetting agent, lubricity improver, metal deactivator, gelling agent, thickener, bactericidal agent, fluid Loss additives, colorants, and combinations thereof may be further included.

  When viscosity index improvers are added, preferably they are present in an amount of less than 8% by weight, and when an ester cosolvent is added, they are preferably present in an amount of less than 3% by weight. Even more preferably, the lubricating oil product according to the present invention does not comprise a viscosity index improver or ester cosolvent. Preferably, the blended lubricant product of the present invention has a viscosity index greater than 140, more preferably greater than 165, without any viscosity index improver.

  The lubricant product of the present invention may be formulated as a multi-grade internal combustion engine crankcase oil, transmission oil, powertrain liquid, turbine oil, compressor oil, hydraulic oil, or grease. In one embodiment, the blended lubricant product is a multi-grade internal combustion engine crankcase oil that meets the specifications of SAE J300, June 2001. In one embodiment, the blended lubricant product has a viscosity rating of 0W-20, 5W-XX, 10W-XX, or 15W-XX, where XX is 20, 30, 40, 50, or 60. A multi-grade internal combustion engine crankcase oil that meets the specifications for engine oils with In other embodiments, the blended lubricant product is an internal combustion engine crankcase oil that meets the specifications for at least one ACEA 2002 European oil standard for gasoline, light diesel engines, or heavy diesel engines.

  The multigrade internal combustion engine crankcase oil according to the present invention preferably exhibits a TEOST-MHT total deposit weight of about 45 mg or less.

  Surprisingly, the blended lubricant products of the present invention require a reduced amount of antiwear additive while exhibiting special friction and wear properties. The blended lubricant product of the present invention reduces wear in equipment made from ferroalloys. Ferroalloy is an alloy of iron containing various amounts of carbon, manganese, and one or more other elements, such as sulfur, nickel, silicon, phosphorus, chromium, molybdenum, and vanadium. These elements, when combined with iron, form different types of steel that vary in properties. Abrasion resistant additives are designed to react with a metal surface, usually a ferroalloy surface, to reduce wear when bumps on the surface come into contact with each other.

  When a blended lubricant product is formulated as a multi-grade internal combustion engine crankcase oil, an internal combustion engine that includes a valve train uses the fuel to operate the engine and lubricates the engine using the blended lubricant product of the present invention. May be operated. The engine may be a compression ignition engine, or more specifically, a compression ignition engine with exhaust gas after the processing unit. The engine may be a spark ignition engine, or more specifically, a spark ignition engine with exhaust gas after the processing unit. The engine may further comprise a turbocharger. The fuel may be diesel fuel, low sulfur diesel fuel, gasoline fuel, unleaded gasoline, or natural gas.

  The invention is further illustrated by the following illustrative examples, which should not be limited.

^＊１つを超える値を有する結果は２度のテスト結果である。 Example 1
Preparation of Fischer-Tropsch Wax and Fischer-Tropsch Derived Lubricating Base Oil Two samples of hydrotreated Fischer-Tropsch wax, FT wax A and FT wax B were made using a co-supported Fischer-Tropsch catalyst. did. Both samples were analyzed and found to have the properties shown in Table V.
Table V: Fischer-Tropsch wax

^* Results with more than one value are two test results.

Fischer-Tropsch synthetic crude oil has a weight ratio of a compound having at least 60 carbon atoms to a compound having at least 30 carbon atoms of less than 0.18 and a boiling point T ₉₀ of 900 ° F. to 1000 ° F. Three samples of Fischer-Tropsch wax (one sample of FT wax A and two samples of FT wax B) were hydroisomerized with Pt / SSZ-32 or Pt / SAPO-11 catalyst on an alumina binder. Operating conditions were a temperature of 652 ° F. to 695 ° F., an LHSV of 0.6 to 1.0 / hour, a reaction pressure of 1000 psig, and a flow-through hydrogen amount of 6 to 7 MSCF / bbl. The reactor effluent directly passed to the second reactor containing the Pt / Pd hydrorefining catalyst on silica-alumina was also operated at 1000 psig. The conditions of the second reactor were a temperature of 450 ° F. and LHSV of 1.0 / hour.

Products boiling above 650 ° F. were fractionated by atmospheric or vacuum distillation to produce distillate fractions of different viscosity grades. Three Fischer-Tropsch derived lubricating base oils were obtained: FT-4A (from FT wax A), and FT-4B and FT-8B (both from FT wax B). Test data for a particular distillate fraction useful as a Fischer-Tropsch derived lubricating base oil is shown in Table VI below.
Table VI: Properties of Fischer-Tropsch derived lubricating base oil

The ratio of pour point and dynamic viscosity at 100 ° C. is simply the pour point at ° C. divided by the dynamic viscosity at 100 ° C. Base oil flow factor is:
Base oil flow factor = 7.35 × Ln (dynamic viscosity at 100 ° C.) − 18
(Where Ln (dynamic viscosity at 100 ° C.) is an empirical number calculated by the natural logarithm with the base “e” of the dynamic viscosity at 100 ° C. in cSt).

(Example 2)
Preparation of Blended Lubricant Products Fischer-Tropsch derived lubricating base oils prepared above (FT-4A, FT-4B, and FT-8B) were used to make blended lubricant products.

  Several PAOs with dynamic viscosities varying at 100 ° C. were also used to make blended lubricant products. The PAOs used were as follows: Chevron Phillips PAO-4, PAO-8, and PAO-25; Durasyn (R) 174 PAO-40 (Durasyn (R) is a registered trademark of Amoco Chemical Company. ); And Mobil SHF-1003 PAO-100. The number in the PAO identification (ie PAO-100) represents the dynamic viscosity of PAO at 100 ° C. in cSt.

ＹＳは、ＭＲＶテストにおける降伏点応力の存在を意味する。 A blend comprising both a Fischer-Tropsch derived lubricant base oil and a high viscosity PAO (PAO-40 or PAO-100) is standard along with a detergent-inhibitor (DI) additive package and pour point depressant (PPD). It was formulated into engine oil for use in passenger cars. The viscosity index improver was not added to this blend because the viscosity index was already very high and therefore no viscosity index improver had to be added. Friction and wear measurements were performed on test oils using HFRR with a low HFRR coefficient of friction that generally correlates with good fuel economy. The test results for these blends are shown in Table VII.
Table VII: Extremely low wear blends of FTBO and high viscosity PAO

YS means the presence of yield point stress in the MRV test.

  The above data show that ≧ 70 wt% Fischer-Tropsch derived lubricant base oil (FT-4A and FT-8B) and high viscosity PAO (PAO-40 and PAO) with ≧ 6 wt% molecules having monocycloparaffinic functionality -100) blends showed low wear as well as excellent oxidative stability (Oxidator B with L-4 catalyst). Blends with the lowest HFRR coefficient of friction and the lowest HFRR wear capacity below the plane are ≧ 70 wt% Fischer-Tropsch derived lubricant base oil with ≧ 6 wt% molecules with monocycloparaffin functionality and high viscosity The difference in dynamic viscosity at 100 ° C between the Fischer-Tropsch derived lubricant base oil and PAO was over 70 cSt.

By comparison, as can be seen in Table VIII, ≦ 70 wt% Fischer-Tropsch derived lubricant base oil (FT-4A or FT-4B) with ≧ 6 wt% molecules with monocycloparaffin functionality and low viscosity PAO ( Blends with PAO-8 and PAO-25) or high viscosity PAO (PAO-100) showed excellent friction and wear, but ≧ 70 wt% Fischer-Tropsch derived lubricating base oil and about 100 ° C. The increased friction and wear benefits seen with blends of the present invention comprising PAO (PAO-40 and PAO-100) with dynamic viscosities greater than 30 cSt and less than 150 cSt have not been demonstrated.
Table VIII: FT and PAO blend comparison

Two 0W-20 blends were made, one with all FTBO compositions and one with all PAO compositions. HFRR wear tests were performed on these blends for comparison. The test results for these samples are shown in Table IX.
Table IX: Blend comparison of all FTBO and all PAO

  These comparative results demonstrated that a blend of all Fischer-Tropsch derived lubricant base oils gave better friction and lower wear than a blend of all PAO, but ≧ 70 wt% Fischer-Tropsch derived lubricant base It was found that blends of the same viscosity grade, 0W-20, including a mixture of oil and high viscosity PAO (PAO-100) all had significantly lower wear than the Fischer-Tropsch derived lubricant base oil blend. A mixture of Fischer-Tropsch derived lubricant base oil and high viscosity PAO of ≧ 70 wt% has a reduction in HFRR wear capacity below the plane of 12.7% (0W-20) and 35.6% (10W-30). It is amazing to give.

  While this invention has been described with reference to specific embodiments, this application is intended to cover various changes and substitutions that can be made by those skilled in the art without departing from the spirit and scope of the appended claims. To do.

Claims (29)

a. ≧ 70 wt% Fischer-Tropsch derived lubricating base oil comprising ≧ 6 wt% molecules with monocycloparaffinic functionality and less than 0.05 wt% molecules with aromatic functionality, and b. A blended lubricating base oil comprising at least one polyalphaolefin lubricating base oil having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C.   Molecules with monocycloparaffinic functionality relative to the weight percent of molecules with cycloparaffinic functionality greater than 10 and the weight percent of molecules with multicycloparaffinic functionality greater than 15 wherein the Fischer-Tropsch derived lubricating base oil The blended lubricating base oil of claim 1 comprising a weight percent ratio of:   The blend lubricating base oil of claim 1, wherein the Fischer-Tropsch derived lubricating base oil comprises a weight percent of molecules having aromatic functionality, less than 0.01.   The blended lubricating base oil of claim 1, wherein the Fischer-Tropsch derived lubricating base oil comprises ≧ 10 wt% molecules having monocycloparaffinic functionality.   The blend lubricating base oil of claim 1, wherein the difference in dynamic viscosity at 100 ° C between the Fischer-Tropsch derived lubricating base oil and the polyalphaolefin lubricating base oil is greater than 40 cSt.   The blended lubricating base oil of claim 5, wherein the difference in dynamic viscosity at 100 ° C between the Fischer-Tropsch derived lubricating base oil and the polyalphaolefin lubricating base oil is greater than 70 cSt. a. ≧ 70 wt% Fischer-Tropsch derived lubricating base oil comprising ≧ 6 wt% molecules having monocycloparaffinic functionality and less than 0.05 wt% molecules having aromatic functionality,
b. At least one polyalphaolefin lubricating base oil having a dynamic viscosity of greater than about 30 cSt and less than 150 cSt at 100 ° C., and c. A blended lubricant product comprising an effective amount of at least one antiwear additive.   The Fischer-Tropsch derived lubricant base oil is less than 0.05,% by weight of molecules with aromatic functionality, more than 10,% by weight of molecules with cycloparaffinic functionality, and more than 15, multicycloparaffins 8. The blended lubricating oil product of claim 7, comprising a ratio of weight percent of molecules with monocycloparaffin functionality to weight percent of molecules with functionality.   The blended lubricating oil product of claim 7, wherein the Fischer-Tropsch derived lubricating base oil comprises a weight percent of molecules having aromatic functionality, less than 0.01.   8. The blended lubricating oil product of claim 7, wherein the Fischer-Tropsch derived lubricating base oil comprises ≧ 8% by weight of molecules having monocycloparaffinic functionality.   11. The blended lubricating oil product of claim 10, wherein the Fischer-Tropsch derived lubricating base oil comprises ≧ 10% by weight molecules having monocycloparaffinic functionality.   The blended lubricating oil product of claim 7, wherein an effective amount of the at least one anti-wear additive is 0.001 to 5 wt%.   The blended lubricant product of claim 7, wherein the blended lubricant product has a dynamic viscosity of about 2.0 to 20 cSt at 100 ° C.   8. The blended lubricant product of claim 7, wherein the blended lubricant product has a Noack volatility of less than 12% by weight.   8. The blended lube product of claim 7, wherein the blended lube product has an Oxidator B test result with L-4 catalyst for more than 22 hours.   The blended lubricant product of claim 7, wherein the blended lubricant product has a TEOST-MHT total deposit weight of about 45 mg or less.   The blended lubricant product of claim 7, wherein the blended lubricant product has a viscosity index greater than 165. The blended finished lubricants is the 300,000Myu ³ below shows the HFRR wear volume below the plane, the blended finished lubricant of Claim 7.   The at least one anti-wear additive is a metal phosphate, a metal dithiophosphate, a metal dialkyldithiophosphate, a metal thiocarbamate, a metal dithiocarbamate, a metal dialkyldithiocarbamate, an ethoxylated amine dialkyldithiophosphate, an ethoxylated amine dithiobenzoate, medium The blended lubricating oil product of claim 7, selected from the group consisting of a functional organic phosphite, an organic molybdenum compound, an organic sulfur compound, a sulfur compound, a chlorine compound, and mixtures thereof.   EP agent, surfactant, dispersant, oxidation-resistant agent, pour point depressant, viscosity index improver, ester cosolvent, viscosity modifier, friction modifier, emulsion breaker, antifoaming agent, corrosion inhibitor, rust inhibitor Selected from the group consisting of agents, seal swelling agents, emulsifiers, wetting agents, lubricity improvers, metal deactivators, gelling agents, thickeners, bactericides, fluid loss additives, colorants, and mixtures thereof. The blended lubricating oil product of claim 7, further comprising at least one additional lubricating additive.   21. The blended lubricant product of claim 20, wherein the lubricant product is a multi-grade internal combustion engine crankcase oil, transmission oil, powertrain liquid, turbine oil, compressor oil, hydraulic oil, or grease.   The blended lubricant product of claim 21, wherein the blended lubricant product is a multigrade internal combustion engine crankcase oil that meets SAE J300 (June 2001) specifications.   For engine oils having a viscosity rating of 0W-20, 5W-XX, 10W-XX, or 15W-XX, where XX is 20, 30, 40, 50 or 60 23. A blended lubricant product according to claim 22 that meets specifications.   23. The blended lubricant product of claim 22, wherein the internal combustion engine crankcase oil meets the specifications for at least one ACEA 2002 European oil standard for gasoline engines, light diesel engines, or heavy diesel engines.   The effective amount of the at least one anti-wear additive is less than the effective amount of anti-wear additive in a lubricating oil product comprising a Fischer-Tropsch derived lubricating base oil in the absence of a polyalphaolefin lubricating base oil. 8. The blended lubricant product according to 7.   The effective amount of said at least one anti-wear additive is less than the effective amount of anti-wear additive in a lubricating oil product comprising a polyalphaolefin lubricating base oil in the absence of a Fischer-Tropsch derived lubricating base oil. 8. The blended lubricant product according to 7. a. Lubricating the engine using the blended lubricant product of claim 7; and b. A method of operating an internal combustion engine having a valve train comprising operating the engine using fuel.   28. The method of claim 27, wherein the engine is a compression ignition engine or a spark ignition engine and the fuel is diesel fuel, low sulfur diesel fuel, gasoline fuel, unleaded gasoline, or natural gas. a. Lubricating the equipment using the blended lube product of claim 7; and b. A method of reducing wear in a ferroalloy device, comprising operating the device after lubrication.