JP2008533247A - Super light hydrocarbon liquid - Google Patents

Abstract

  The present invention relates to an ultralight hydrocarbon liquid derived from a wax with a high paraffin content. This ultralight hydrocarbon liquid is suitable for use as a lubricant additive diluent oil in oil soluble additive concentrates. This ultralight hydrocarbon liquid derived from waxes with a high paraffin content has a viscosity of about 1.0 to 3.5 cSt at 100 ° C. and a Noack volatility of less than 50 wt. It contains molecules with functional groups and less than 0.30% by weight aromatics. This ultralight hydrocarbon liquid has excellent volatility additive diluent oil because it has low volatility, low viscosity, good additive solubility, and excellent solubility in lubricating base stocks. The present invention also relates to a lubricating oil product comprising an oil-soluble additive concentrate made with an ultralight hydrocarbon liquid and a lubricating oil product comprising an oil-soluble additive concentrate. The invention further relates to a method of making these lubricating oil additive diluents, oil soluble additive concentrates, and lubricating oil products.

Description

  The present invention relates to a lubricant additive diluent derived from a high paraffin wax and an oil-soluble additive concentrate comprising the lubricant additive diluent. The present invention also relates to a lubricating oil product comprising an oil-soluble additive concentrate. The invention further relates to a method of making these lubricating oil additive diluents, oil soluble additive concentrates, and lubricating oil products.

  Lubricating oil additives, especially automotive additives, such as viscosity index improvers and detergent-inhibitor (DI) packages, require lubricating oil diluent diluents to make them usable. Accordingly, the lubricant additive diluent oil is used to dissolve the lubricant additive to provide an oil soluble additive concentrate. These oil-soluble additive concentrates make an additive that is easy to transport, handle, and ultimately blend into a lubricating base oil to provide a lubricating oil product. Oil soluble additive concentrates are not as such or can not be used as lubricating oil products. Rather, the oil-soluble additive concentrate is blended with a lubricating base oil stock to provide a lubricating oil product. It is desirable that the lubricant additive diluent oil readily dissolves the lubricant additive to provide an oil additive concentrate that is readily soluble in the lubricant base stock. In addition, lubricant additive diluents introduce any undesirable characteristics into the lubricating base stock, and ultimately into the lubricating oil product, including, for example, high volatility, high viscosity, and impurities such as heteroatoms. It is desirable not to.

  Different lubricant additive diluents require different amounts of lubricant additive diluent to provide a suitable oil-soluble additive concentrate. For example, an oil-soluble additive concentrate that includes a gear oil additive package may contain as little as 25% by weight of a lubricant additive diluent. Oil-soluble additive concentrates including DI packages generally contain about 50% by weight lubricant additive diluent oil. Oil-soluble additive concentrates containing viscosity index improvers typically contain about 90% by weight or more of the lubricant additive diluent oil.

  The lubricant additive diluents currently used with most DI packages and viscosity index improvers are highly aromatic base oils that fall into API Group I. API Group I base oils with high solubility and convenience are preferred as lubricant additive diluents. However, these Group I oils have sub-average low temperature performance, and they are more susceptible to oxidation than modern oils that are more highly saturated. Furthermore, Group I oils have a lower viscosity index (VI) and higher volatility than other base oils. In addition, Group I base oils have a high sulfur concentration. The lubricant additive diluent oil can comprise up to 5-10% by weight of the lubricant product. Thus, the nature of the lubricant additive diluent oil is important because undesirable properties in the lubricant additive diluent oil negatively impact the properties of the lubricant product. Although these properties are more desirable for lubricating oil products, normal API Group II, normal Group III, and Group IV base oils are used as lubricant additive diluents due to their poor ability to dissolve additives. Difficult to do. Therefore, these base oils are not practical as lubricating oil additive diluent oils.

  When added to a lubricating base oil stock, common oil soluble additives, concentrates, including DI packages or viscosity index improvers, tend to thicken the lubricating oil product composition and impair its low temperature performance. Low viscosity lubricant additive diluents that have been used in the past as an attempt to avoid thickening of lubricant products have high volatility or poor additive solubility, making them unsuitable for most applications Was supposed to be. When added to engine oil, common oil-soluble additive concentrates tend to adversely affect cold-crank simulator (CCS) viscosity and mini-rotary viscometer (MRV). When added to automatic transmission fluids and gear oils, common oil-soluble additive concentrates tend to adversely affect Brookfield viscosity at low temperatures.

  Accordingly, lubricating oil additive diluents having low viscosity, low volatility, and low concentrations of impurities such as sulfur-containing compounds are desired. Common lubricating base oils with low volatility also have high viscosities that make them unsuitable for most applications, and common lubricating base oils with low viscosity also give them It has low volatility and poor additive solubility that makes it unsuitable for most applications.

  Engine manufacturers have introduced chemical limits on engine oils and additives that they think globally provide a safety factor for the operations required by exhaust aftertreatment devices. These requirements directly affect what is suitable for use as an additive, lubricant base stock, and lubricant additive diluent. Low sulfur and phosphorus limits for engine oil have been proposed. With a limit of about 0.3 wt% sulfur, the zinc dithio-diphosphate antiwear additive would be partially replaced with more expensive additives, requiring a reduction in sulfur detergents, It is necessary to provide a degree of freedom. As the limit moves toward 0.2 wt% sulfur, reduced sulfur or zero sulfur lubricating base oils and diluent oils will essentially meet compositional goals. International Lubricant Standardization and Accreditation Committee (ILSAC) GF-4 passenger car engine oil, API PC-10 heavy engine oil, and other high quality lube product standards require low sulfur compositions.

  The ILSAC / Oil Committee will establish a new GF-4 standard for passenger car motor oils on January 8, 2004, with a recommendation start date for introducing GF-4 to the market on July 1, 2004. Adopted. The new bench test requirement for engine oils that meet the GF-4 standard is the maximum sulfur content according to ASTM D1552. Thus, 10 W oil can have a maximum of 0.7 wt% sulfur, while 0 W and 5 W oils can have a maximum of 0.5 wt% sulfur. In addition, oils that meet the GF-4 standard have a Noack volatility of less than 15% by weight ASTM D5800 after 1 hour at 250 ° C. and simulated distillation by ASTM D6417 with a maximum of 10% at 371 ° C. There must be. API PC-10 is a proposed standard for heavy duty diesel engine oil and is expected to be approved in 2006 or 2007. PC-10 oil is also expected to lower the limit on sulfur, similar to the amount of sulfur required for GF-4 passenger car motor oil.

  Therefore, a lubricating oil additive with low sulfur, excellent additive solubility, good elastomer compatibility, low volatility, low viscosity, high oxidation stability, good low temperature performance, and excellent solubility in lubricating base oils Dilution oil is required.

  The present invention relates to an ultralight hydrocarbon liquid derived from a wax with a high paraffin content. These ultralight hydrocarbon liquids derived from high paraffin wax may be used as lubricant additive diluent oils. Accordingly, the present invention relates to a lubricant additive diluent derived from a high paraffin wax and an oil soluble additive concentrate comprising the lubricant additive diluent. The present invention also relates to a lubricating oil product comprising an oil-soluble additive concentrate. The invention further relates to these ultralight hydrocarbon liquids derived from high paraffin waxes, lubricant additive diluents, oil soluble additive concentrates, and methods of making lubricant products.

  The lubricant product includes at least one lubricant base oil and at least one additive. Generally, the at least one additive is lubricated in the form of an oil-soluble additive concentrate comprising at least one additive and a lubricant additive diluent oil to improve the solubility of the additive in the lubricant base oil. Added to the base oil. As a lubricant additive diluent oil, it is important that the oil is strong enough so that it does not contribute to the volatility of the lubricant product and not so strong to thicken the lubricant product.

  Surprisingly, it has been found that certain lubricating base oils derived from paraffin-rich waxes make excellent lubricating additive diluents. Examples of suitable paraffin-rich waxes include Fischer-Tropsch derived wax, slack wax, deoiled slack wax, and refined foot oil, waxy lubricating raffinate, n-paraffin wax, linear alpha olefin (NAO) wax, chemical These include waxes produced in plant processes, deoiled petroleum derived waxes, microcrystalline waxes, and mixtures thereof. These high paraffin waxes are processed to provide a lubricating base oil fraction having unexpectedly low volatility and low viscosity, and also unexpectedly good additive solubility. In one preferred embodiment, the high paraffin wax is a Fischer-Tropsch derived wax and provides a Fischer-Tropsch derived lubricating base oil fraction.

Thus, surprisingly, it contains more than 3% by weight of molecules with cyclic paraffin functionality and less than 0.30% by weight of aromatics with a kinematic viscosity of about 1.0 cSt to 3.5 cSt at 100 ° C. and formula:
Noack volatility coefficient = 160-40 (kinematic viscosity at 100 ° C)
It has been found that lubricating base oils derived from high paraffin waxes having a Noack volatility below the Noak volatility coefficient calculated in can be conveniently used as a lubricant additive diluent.

  Preferably, the lubricating base oil fraction derived from the high paraffin wax has a viscosity of about 2.0 to 3.5 cSt at 100 ° C, more preferably about 2.0 to 3.0 cSt at 100 ° C. Preferably, the lubricating base oil fraction derived from the high paraffin wax has a Noack volatility of less than 50% by weight. Lubricating base oil fractions derived from high paraffin waxes according to the present invention have an unexpectedly low Noack volatility that gives these relatively low kinematic viscosities.

  The lubricating base oils of the present invention can also have a preferred alkyl branch configuration. Therefore, the lubricating base oil of the present invention can contain mainly methyl branches. Branches are 6-18 alkyl branches per 100 carbons, more than 25% branches are 5 or more carbon atoms apart, and less than 40% branches are 2 to 3 apart from each other It can be such that it is within carbon atoms.

  These lubricating base oils derived from high paraffin waxes can be used in applications that require low volatility, low viscosity, special low temperature performance, and good additive solubility. Furthermore, these lubricating base oils derived from high paraffin waxes exhibit excellent oxidation resistance and good elastomer compatibility. Conveniently, lubricating base oil fractions derived from waxes with high paraffin content should be used as additive diluent oils in applications requiring low volatility, such as ILSAC GF-4 and API PC-10 engine oils. Can do.

  The lubricating base oil fraction derived from the high paraffin wax of the present invention is prepared from the high paraffin wax by a process involving hydroisomerization. Preferably, the paraffin-rich wax is hydroisomerized using a shape selective intermediate pore size molecular sieve containing a noble metal hydrogenation component under conditions of about 600 ° F. to 750 ° F.

  In one preferred embodiment, the high paraffin wax is a Fischer-Tropsch derived wax and provides a Fischer-Tropsch derived lubricating base oil fraction. The lubricating base oil fraction is prepared from a Fischer-Tropsch synthetic crude waxy fraction. Accordingly, the Fischer-Tropsch derived lubricating base oil fraction used in the oil-soluble additive concentrate is a process of performing a Fischer-Tropsch synthesis to provide a product stream, a substantially paraffinic wax feed from the product stream. Of the substantially paraffinic wax feed, isolating the isomerized oil, and optionally hydrorefining the isomerized oil. From this method, less than 0.30 wt.% Aromatics and greater than 3 wt.% Molecules with cyclic paraffin functional groups, kinematic viscosity at 100 ° C. and less than Noack volatility coefficient of about 1.0 cSt to 3.5 cSt A Fischer-Tropsch derived lubricating base oil fraction having a Noack volatility of The preferred embodiment Fischer-Tropsch lube base oil referred to herein may also be isolated from this process. Preferably, the paraffinic wax feed is hydroisomerized using a shape selective intermediate pore size molecular sieve containing a noble metal hydrogenation component under conditions of about 600 ° F. to 750 ° F. A preferred method for making a Fischer-Tropsch derived lubricating base oil is described in US patent application Ser. No. 10 / 744,870, filed Dec. 23, 2003, which is hereby incorporated by reference in its entirety. A Fischer-Tropsch lube base oil fraction having a high monocyclic paraffin and a low polycyclic paraffin is described in US patent application Ser. No. 10/744, filed Dec. 23, 2003, which is incorporated herein by reference in its entirety. 389.

  According to the present invention, the lubricating base oil fraction derived from the high paraffin wax contains molecules having a relatively high weight percent of cyclic paraffin functional groups. In a preferred embodiment, the lubricating base oil fraction derived from the high paraffin wax contains more than 5% by weight of molecules with cyclic paraffin functional groups. In another preferred embodiment, the lubricating base oil fraction derived from the paraffin-rich wax is greater than 5% of molecules having monocyclic paraffin functional groups relative to the weight percent of molecules having polycyclic paraffin functional groups. Including the ratio by weight. High ratio of weight percent of molecules with monocyclic paraffin functional groups to weight percent of molecules with polycyclic paraffin functional groups (or high weight percent of molecules with monocyclic paraffin functional groups and polycyclic paraffin functionality Lubricating base oil fractions derived from high paraffin waxes, including low weight percent of molecules with groups) are special lubricating oil additive diluent oils, creating special oil-soluble additive concentrates.

  Although these lubricating base oil fractions derived from high paraffin waxes contain a high paraffin content, they provide VI improvers and lubricating oil additives because cyclic paraffins provide additive solubility. It shows unexpected solubility in additives including packages. These lubricating base oil fractions derived from high paraffin waxes are also desirable because molecules with polycyclic paraffinic functional groups reduce oxidative stability, lower viscosity index, and increase Noak volatility. . A model of the effect of molecules with polycyclic paraffin functional groups is J. et al. Gatto et al. , “The Influence of Chemical Structure on Physical Properties and Antioxidant Response of Hydrolytic Basestocks and Polyalphaolefins” (The Influencing of the Chemical Properties and Antioxidant Response of Hydrocracked). Synthetic Lubrication 19-1, April 2002, pages 3-18. Furthermore, the lubricating base oil fraction of the present invention exhibits unexpectedly low volatility and relatively low viscosity.

  Thus, in a preferred embodiment, a lubricating base oil fraction derived from a paraffin-rich wax used as a lubricating oil additive diluent in an oil soluble additive concentrate has a very low weight percent aromatic functionality. A high ratio (or monocyclic) of the weight percent of molecules having a monocyclic paraffin functionality to the weight percent of molecules having a high weight percent, a molecule having a high weight percent cyclic paraffin functionality, and a molecule having a polycyclic paraffin functionality. High weight percent of molecules with a paraffinic functional group and very low weight percent of molecules with a polycyclic paraffinic functional group). The lubricating base oils of the present invention can also have a preferred alkyl branch configuration.

Lubricating base oil fraction derived from high paraffin waxes used as lubricant additive diluents in oil soluble additive concentrates is greater than 95 wt% as determined by elution column chromatography of ASTM D2549-02 Contains saturates. Olefin is present in an amount less than the amount that can be detected by long term C ¹³ nuclear magnetic resonance spectroscopy (NMR). Preferably, molecules with aromatic functional groups are present by HPLC-UV in an amount of less than 0.3% by weight and confirmed by ASTM D 5292-99 modified to measure low level aromatics. In a preferred embodiment, the molecule having an aromatic functional group is present in an amount of less than 0.10 wt%, preferably less than 0.05 wt%, more preferably less than 0.01 wt%. Sulfur is present in an amount of less than 25 ppmw, preferably less than 5 ppmw, more preferably less than 1 ppmw, as determined by ultraviolet fluorescence according to ASTM D5453-00.

According to the present invention, a lubricating base oil fraction derived from a high paraffin wax is conveniently used as a lubricating additive diluent in an oil soluble additive concentrate. The oil-soluble additive concentrate according to the present invention comprises 5 to 98% by weight of a lubricating base oil fraction derived from a high paraffin wax and at least 2% by weight of one or more lubricating oil additives, The fraction is
Noak volatility with greater than 3 wt% molecules with cyclic paraffin functionality and less than 0.30 wt% aromatics, viscosity of about 1.0-3.5 cSt at 100 ° C and noak volatility coefficient Have Lubricating base oil fractions derived from high paraffin waxes readily dissolve lubricating oil additives and provide an easily soluble oil additive concentrate in the lubricating base oil stock. In addition, lubricating base oil fractions derived from high paraffin waxes may have any undesirable characteristics in the lubricating base oil stock, and hence the final, including, for example, high volatility, high viscosity, and impurities such as heteroatoms. Do not introduce into lubricant products. The lubricating oil product according to the present invention comprises an oil-soluble additive concentrate and one or more lubricating base oils. The lubricating oil product may optionally include one or more additional additives and other oil-soluble additive concentrates.

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

  “API CI-4” is a standard in the current engine oil service business field of powerful engine oil.

  “API PC-10” is a new standard for engine oil service business that has been proposed for powerful engine oil. PC-10 oil is also expected to have a reduced limit on sulfur, in the same amount as GF-4 automotive gasoline engine oil.

  “ILSAC GF-3” is a standard in the field of engine oil service for automobile gasoline engines, published on July 1, 2001.

  “ILSAC GF-4” is a new standard in the field of engine oil service for automobile gasoline engines, which was approved on January 8, 2004 and published on July 1, 2004. This business area introduces new sulfur limits according to ASTM D1552. The maximum sulfur limit for 0W and 5W oil is 0.5% by weight, while the maximum sulfur limit for 10W oil is 0.7% by weight.

  “SAE J300 multi-grade engine oil” is an engine oil defined by engine oil viscosity classification for multi-grade engine oil in SAE J300 revised in June 2001. Multigrade viscosity types are 0W-XX, 5W-XX, 15W-XX, 20W-XX, and 25W-XX (XX is 20, 30, 40, 50, or 60). Special limitations include maximum low temperature crank viscosity according to ASTM D5293, maximum low temperature pumping viscosity without yield stress according to ASTM D4684, minimum and maximum low shear rate kinematic viscosity at 100 ° C. according to ASTM D445, and according to ASTM D4683 or ASTM D5481 Defined as minimum high temperature high shear rate viscosity.

  The term “derived from a Fischer-Tropsch process” or “Fischer-Tropsch induction” means that the product, fraction, or feed is generated or produced at any stage by the Fischer-Tropsch process. Means.

  The term “derived from petroleum” or “petroleum-derived” means that the product, fraction, or feed is generated from residual fuel in the steam head upstream from the distillation of petroleum crude oil and non-vaporizable residue. means. The source of petroleum induction can be from a gas field concentrate.

  A high paraffin wax generally means a wax having a high content of n-paraffins of more than 40% by weight, preferably more than 50% by weight, more preferably more than 75% by weight. Preferably, the high paraffin waxes used in the present invention also have very low levels of nitrogen and sulfur, generally less than 25 ppm, preferably less than 20 ppm, combined with nitrogen and sulfur. Examples of waxes with high paraffin content that may be used in the present invention include slack wax, deoiled slack wax, refined foot oil, waxy lubricating raffinate, n-paraffin wax, NAO wax, wax produced by chemical plant processing. , Deoiled petroleum derived waxes, microcrystalline waxes, Fischer-Tropsch waxes, and mixtures thereof. The pour point of the high paraffin wax useful in the present invention is above 50 ° C, preferably above 60 ° C.

  The term “derived from high paraffin wax” means that the product, fraction, or feed originates from or is produced at any stage by the high paraffin wax. To do.

  An aromatic is a continuous cloud of delocalized electrons whose number of delocalized electrons in a group of atoms corresponds to a solution to the Huckel rule of 4n + 2 (for example, 6 electrons if n = 1). By any hydrocarbon compound containing at least one group of shared atoms is meant. Common examples include, but are not limited to, benzene, biphenyl, naphthalene, and the like.

  By molecule having a cyclic paraffin functional group is meant any molecule that is or contains one or more substituents, monocyclic or bonded polycyclic saturated hydrocarbon groups. The cyclic paraffin group can be optionally substituted with one or more, preferably 1-3 substituents. Representative 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.

  The molecule having a monocyclic paraffin functional group is any molecule that is a monocyclic saturated hydrocarbon group having 3 to 7 ring carbons, or a single monocyclic saturated hydrocarbon having 3 to 7 ring carbons. Means any molecule substituted with a group. The cyclic paraffin group can be optionally substituted with one or more, preferably 1-3 substituents. Representative examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl, (pentadecan-6-yl) cyclohexane, and the like.

  A molecule having a polycyclic paraffin functional group is any molecule that is a bonded polycyclic saturated hydrocarbon ring group of two or more bonded rings, one or more bonded polycyclic rings of two or more bonded rings It means any molecule substituted with a saturated hydrocarbon ring group, or any molecule substituted with two 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 cyclic paraffin group may be optionally substituted with one or more, preferably 1 to 3 substituents. Representative examples include, but are not limited to, decahydronaphthalene, octahydronaphthalene, 3,7,10-tricyclohexylpentadecane, decahydro-1- (pentadecan-6-yl) naphthalene, and the like.

  Brookfield viscosity: ASTM D2983-03 is used to determine the low shear rate viscosity of automotive liquid lubricants at low temperatures. Low temperature, low shear rate viscosities of automatic transmission fluids, gear oils, torque and tractor fluids, and industrial and automotive hydraulic fluids are often specified in Brookfield viscosities. The GM 2003 DEXRONE® III automatic transmission fluid standard requires a maximum Brookfield viscosity of 20,000 cP at −40 ° C. The Ford MERCON® V standard requires a Brookfield viscosity of 5,000 to 13,000 cP at −40 ° C. Automotive gear lubricant viscosity classification SAE J306 for 75W gear lubricant has a low temperature viscosity specification such that the maximum temperature for a viscosity of 150,000 cp is −40 ° C. When added to automatic transmission fluids and gear oils, the oil-soluble additive concentrates of the present invention do not adversely affect Brookfield viscosity at low temperatures.

  Kinematic viscosity is a measurement of the flow resistance of a liquid under gravity. The exact operation of many lubricant base oils, lubricant products made from them, and equipment depends on the appropriate viscosity of the liquid being used. Kinematic viscosity is determined according to ASTM D445-01. Results are reported in centistokes (cSt). The Fischer-Tropsch derived lubricating base oil fraction of the present invention has a kinematic viscosity at 100 ° C. of about 1.0 cSt to 3.5 cSt. Preferably, the lubricating base oil fraction derived from a high paraffin wax has a kinematic viscosity at 100 ° C. of about 2.0 cSt to 3.5 cSt, more preferably a lubricating base derived from a high paraffin wax. The oil fraction has a kinematic viscosity at 100 ° C. of about 2.0 cSt to 3.0 cSt.

  Viscosity index (VI) is an empirical unitless number that indicates the effect of temperature change on the kinematic viscosity of the oil. Liquids change viscosity with temperature and decrease in viscosity when heated; the higher the VI of an oil, the lower its tendency to change viscosity with temperature. High VI lubricants are required when relatively constant viscosities are required over a wide range of temperatures. For example, in some automobiles, engine oil must flow sufficiently freely to allow cold start, but must be sufficiently viscous after warming to provide complete lubrication. VI can be determined as described in ASTM D2270-93. Preferably, the lubricating base oil fraction derived from the high paraffin wax has a viscosity index of about 105-155.

The “viscosity index coefficient” of a lubricating base oil derived from a wax with a high paraffin content is an empirical number derived from the kinematic viscosity of the lubricating base oil fraction. The viscosity index coefficient is:
Viscosity index coefficient = 28 × ln (kinematic viscosity of lubricating base oil fraction at 100 ° C.) + 95
Calculated by

  The lubricating base oil fraction derived from the high paraffin wax may have a viscosity index that exceeds the viscosity index coefficient.

  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 lubricating base oils have specifications for pour points. If the lubricating base oils have low pour points, they will also probably have other good low temperature properties such as low cloud points, low cold filter clogging points, 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 lubricating base oil sample begins to cloud under carefully specified conditions. The cloud point can be determined, for example, according to ASTM D5773-95. Lubricating base oils having a pour point-cloud point difference below about 35 ° C are desirable. The high pour point-cloud point difference requires the lubricating base oil to be processed to a very low pour point in order to meet cloud point specifications.

  Noack volatility is measured according to ASTM D5800 when the oil is heated at a pressure below 20 mmHg (2.67 kPa; 26.7 mbar) from atmospheric pressure at 250 ° C. in a test crucible with a constant air flow for 60 minutes. Defined as the mass of oil, expressed 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 Noak volatility is used throughout this specification unless otherwise stated. Engine oil noack volatility, measured by TGA Noak and similar methods, has been found to correlate with fuel economy in passenger car engines. The stringent requirements for low volatility are important aspects such as some of the latest engine oil standards such as European ACEA A-3 and B-3 and North American ILSAC GF-3. Preferably, the lubricating base oil fraction derived from the high paraffin wax of the present invention has a Noack volatility of less than 50% by weight. More preferably, the lubricating base oil fraction derived from the high paraffin wax of the present invention has a Noack volatility of less than 35% by weight.

The “Noak volatility coefficient” of a lubricating base oil derived from a wax with a high paraffin content is an empirical number derived from the kinematic viscosity of the lubricating base oil fraction. The Noack volatility coefficient is:
Noack volatility coefficient = 160-40 (kinematic viscosity at 100 ° C)
Calculated by

  Lubricating base oil fractions derived from high paraffin wax have a Noak volatility below the Noack volatility coefficient.

The aniline point test indicates whether the oil can damage elastomers (rubber compounds) that come into contact with the oil. The aniline point is the lowest temperature (° F. or ° C.) at which equal volumes of aniline (C ₆ H ₅ NH ₂ ) and oil form a single phase and is referred to as the “aniline point temperature”. The aniline point (AP) correlates roughly with the amount and type of aromatic hydrocarbons in the oil sample. Low AP indicates high aromaticity, while high AP indicates low aromatic content. The aniline point is determined according to ASTM D611-04. Preferably, the lubricating base oil fraction derived from the high paraffin wax of the present invention has an aniline point greater than 36 × ln (the kinematic viscosity of the lubricating base oil fraction at 100 ° C.) + 200. Accordingly, lubricating base oil fractions derived from high paraffin waxes exhibit good elastomer compatibility.

Oxidator BN with L-4 catalytic test is a Dornte oxygen absorber (RW Dorte “Oxidation of White Oils”, Industrial and Engineering Chemistry, Vol. 28, page 26. , 1936) to measure oxidation resistance. Typically, the conditions are 340 ° F. and 1 atmosphere of pure oxygen, and the results are reported in the time it takes for 100 g of oil to absorb 1000 ml of O ₂ . In Oxidator BN with L-4 catalyst test, 0.8 ml of catalyst is used per 100 g of oil. The catalyst is a mixture of soluble metal naphthenates in kerosene, simulating the average metal analysis of the crankcase oil used. 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 millimole zinc bispolypropylenephenyldithio-phosphate or about 1.1 g OLOA® 260 per 100 g oil. Oxidator BN with the L-4 catalyst test 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. OLOA (registered trademark) is an acronym for Oronite Lubricating Oil Additive (registered trademark), and is a registered trademark of Chevron Texaco Oronite Company.

  In general, Oxidator BN results with the L-4 catalyst test should exceed about 7 hours. Preferably, the oxydata BN value with L-4 will exceed about 10 hours. Preferably, the lubricating base oil fraction derived from the high paraffin wax of the present invention has a result of greater than about 10 hours. The Fischer-Tropsch derived lubricating base oil fraction of the present invention has a result that significantly exceeds 10 hours. Preferably, the Fischer-Tropsch derived lubricating base oil fraction of the oil-soluble additive concentrate of the present invention has an Oxidator BN test result with an L-4 catalyst of greater than 25 hours.

High Paraffin Wax The high paraffin wax used to make the lubricating base oil of the present invention can be any wax having a high content of n-paraffins. Preferably, the paraffin-rich wax comprises more than 40% by weight, preferably more than 50% by weight, more preferably more than 75% by weight n-paraffins. Preferably, the high paraffin waxes used in the present invention also have very low levels of nitrogen and sulfur, generally less than 25 ppm total, preferably less than 20 ppm, combined with nitrogen and sulfur. . Examples of waxes with high paraffin content that may be used in the present invention include slack wax, deoiled slack wax, refined foot oil, waxy lubricating raffinate, n-paraffin wax, NAO wax, wax produced by chemical plant processing. , Deoiled petroleum derived waxes, microcrystalline waxes, Fischer-Tropsch waxes, and mixtures thereof. The pour point of the high paraffin wax useful in the present invention is above 50 ° C, preferably above 60 ° C.

  These high paraffin waxes have been found to have low volatility and low viscosity and can be processed to provide lubricating base oil fractions with unexpectedly good additive solubility. . In one preferred embodiment, the high paraffin wax is a Fischer-Tropsch derived wax and provides a Fischer-Tropsch derived lubricating base oil fraction.

Fischer-Tropsch synthesis 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 provide syngas. Generally, the synthesis gas contains hydrogen and carbon monoxide, and can 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 be desirable to purify the syngas before the Fischer-Tropsch reactor to remove the carbon dioxide produced during the syngas reaction and any additional sulfur compounds that have not yet been 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 the reaction conditions of appropriate 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 / hr, preferably about 300 to 3,000 cc / g / hr. Examples of conditions for conducting Fischer-Tropsch type reactions are well known to those skilled in the art.

The product of the Fischer-Tropsch synthesis method can be in the C ₁ -C ₂₀₀₊ range, mostly with the C ₅ -C ₁₀₀₊ range. 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 superior heat (and mass) transfer characteristics for a powerful exothermic synthesis reaction and is relatively high in molecular weight and paraffin when a cobalt catalyst is used. Series hydrocarbons 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 also 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 can include a noble metal promoter (s) and / or 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 is a basic oxide promoter, for example, ThO ₂ , La ₂ O ₃ , MgO, TiO ₂ , promoters such as 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, etc. can also be included. 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 readily 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% linear paraffins and often more than 80% 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. What is used as a feedstock for the process for providing a Fischer-Tropsch derived lubricating base oil fraction for use as a lubricant additive diluent in oil soluble concentrates and lubricant products according to the present invention is waxy. Reaction product (ie wax fraction).

  Fischer-Tropsch lube base oil fractions used as lubricant additive diluents in oil-soluble additive concentrates are prepared from a Fischer-Tropsch synthetic crude waxy fraction by a process involving hydroisomerization. Preferably, the Fischer-Tropsch lubricant base oil is made by the method described in US patent application Ser. No. 10 / 744,870 (filed Dec. 23, 2003), which is hereby incorporated by reference in its entirety. . The Fischer-Tropsch lubricant base oil fraction used in the oil-soluble additive concentrate according to the present invention is different from the location where the components of the oil-soluble additive concentrate are received and blended, and the oil-soluble additive concentrate. It can be manufactured at a location different from where the product is blended with the lubricant base stock to provide the lubricant product. The location where the oil-soluble additive concentrate is made can be the same as or different from where the lubricant product is made.

Methods for providing light lubricating base oil fractions These light lubricating base oil fractions derived from the high paraffin wax of the present invention provide lubricating base oil fractions as described herein. To this end, it is made by a method comprising providing a paraffin-rich wax and hydroisomerizing the paraffin-rich wax. Preferably, the paraffin-rich wax is hydroisomerized using a shape selective intermediate pore size molecular sieve containing a noble metal hydrogenation component under conditions of about 600 ° F. to 750 ° F.

  In one preferred embodiment, the high paraffin wax is a Fischer-Tropsch derived wax, which provides a Fischer-Tropsch derived lubricating base oil fraction. The Fischer-Tropsch derived lubricating base oil fraction used in the oil-soluble additive concentrate is made by a Fischer-Tropsch synthesis process followed by hydroisomerization of the waxy fraction of Fischer-Tropsch synthetic crude oil.

Hydroisomerization High paraffin waxes are subjected to a process involving hydroisomerization to provide a lubricating base oil fraction useful as a lubricating additive diluent in the oil soluble additive concentrate according to the present invention.

  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 achieves a high conversion level of paraffin-rich waxes to non-waxy iso-paraffins while at the same time minimizing conversion by pyrolysis. Preferably, the conditions for hydroisomerization in the present invention are such that 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 “medium pore size” means an effective pore size in the range of about 3.9 to about 7.1 liters 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 not interconnected. 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 can also be included within the definition of molecular sieves of the present invention. Please be careful. The classification of internal zeolite channels, such as 1-D, 2-D and 3-D, is described in R.D. M.M. Barrer in Zeolites, Science and Technology, edited by F.R. R. Rodrigues, L. D. Rollman and C.I. Naccache, NATO ASI Series, 1984 (see especially page 75).

  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. The 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”, 5th revised 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 entire contents of which are incorporated herein by reference. ing. In US Pat. No. 5,282,958, such an intermediate pore size molecular sieve is a fine particle 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. Has holes. 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 is as determined: 100x (weight% branched _{C 16} in product) / (weight of _{C 13-%} in percent by weight + product branched _{C 16} in product).

  Such particularly preferred molecular sieves are further characterized by pores or channels having a crystallographic free diameter in the range of about 4.0 to about 7.1 mm, preferably in the range of 4.0 to 6.5 mm. Also good. The crystallographic free diameter of the channels of molecular sieves is described in “Atlas of Zeolite Framework Types”, 5th revised edition, 2001, Ch. Baerlocher, W.M. M.M. Meier, and D.C. H. Olson, Elsevier, pages 10-15.

If the crystallographic 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 kinetic diameter hydrocarbon compounds. it can. Breck, Zeolite Molecular Sieves, 1974 (especially Chapter 8); Anderson et al. , J .; 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 kinematic 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 causes product improvements, particularly VI and stability improvements. Common catalytically active metal hydrides include chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum, and palladium. Platinum and palladium metals 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 conventionally used for catalysts, including silica, alumina, silica-alumina, magnesia, titania, and combinations thereof.

The conditions for hydroisomerization are adjusted to achieve a lubricating base oil fraction containing less than about 0.3 wt.% Aromatics and greater than 3 wt.% Molecules with cyclic paraffin functionality. Preferably, this condition is greater than 5% by weight of molecules having a cyclic paraffin functional group, and greater than 5, more preferably greater than 15, even more preferably greater than 50. A lubricating base oil fraction comprising a ratio of the weight percent of molecules with monocyclic cyclic paraffin functionality to the weight percent of molecules is provided. The conditions for the hydroisomerization depend on the nature of 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 include from about 500 ° F. to about 775 ° F. (260 ° C. to about 413 ° C.), preferably from about 600 ° F. to about 750 ° F. (315 ° C. to A temperature of about 600 ° F to about 700 ° F (315 ° C to about 371 ° C); and a pressure of about 15 to 3000 psig, preferably 100 to 2500 psig. Hydroisomerization pressure in this context refers to 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. Hydrogen ratio to hydrocarbon is from about 1.0 to about 50 moles _{H 2} / hydrocarbon 1 mole, more preferably falls within the range of from about 10 to about 20 moles _{H 2} / hydrocarbon mole. Suitable conditions for performing hydroisomerization are described in US Pat. Nos. 5,282,958 and 5,135,638, the entire contents of which are incorporated by reference.

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

Hydroprocessing The paraffin-rich wax feed to the hydroisomerization process can be hydrotreated prior to hydroisomerization. Hydroprocessing 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, in hydrotreating operations, the pyrolysis operation of hydrocarbon molecules, i.e., the destruction of large hydrocarbon molecules into small hydrocarbon molecules is minimized, and unsaturated hydrocarbons are fully or partially hydrogenated. .

  Catalysts used in performing hydrotreating operations are well known in the art. For example, U.S. Pat. No. 4,347,121, the entire contents of which are hereby incorporated by reference for a general description of the hydrotreating, hydrocracking, and common catalysts used in each process. No. and 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 are usually used in these reduced or sulfide forms, and such sulfide compounds are It is used in the sulfide form if it is easily formed from the specific metal involved. Preferred non-noble metal metal catalyst compositions are about 5% by weight or more, preferably about 5 to about 40% by weight molybdenum and / or tungsten, and at least about 0.5, generally about 1 to about 15% by weight of 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 ranges from 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 process that may be used as a step following hydroisomerization to provide a lubricating base oil fraction derived from waxes that are high in paraffin content. Hydrorefining is intended to improve the oxidative stability, UV stability, and appearance of lubricating base oil fractions by removing traces of aromatics, olefins, color bodies, and solvents. The term UV stability as used in this disclosure refers to the stability of a lubricating base oil fraction 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 can be found in US Pat. Nos. 3,852,207 and 4,673,487.

  Lubricating base oil fractions derived from the high paraffin wax of the present invention can 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 (e.g., nickel-molybdenum and / or tungsten, etc.) and at least about 0.5, generally from about 1 to about 15 weight percent nickel and / or cobalt were converted as the corresponding oxides. (Platinum etc.) The catalyst contains 0.01% or more of metal, preferably 0.1 to 1.0% of metal, and a combination of noble metals such as a mixture of platinum and palladium can also be used.

  Clay treatment to remove impurities is an alternative final processing step to provide a lubricating base oil fraction derived from high paraffin wax.

Fractionation In some cases, a method for providing a light lubricating base oil fraction derived from a paraffin-rich wax is obtained from a step of fractionating a paraffin-rich wax feed prior to hydroisomerization, or a hydroisomerization step. And a lubricating base oil fractionation step. Fractionation of the paraffin-rich wax feed or isomerized lubricating base oil into fractions is generally accomplished by atmospheric or vacuum distillation, or by 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 generally used to separate high boiling materials, such as lube 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 lubricating base oil fraction derived from a high paraffin wax may also include a solvent dewaxing step following the hydroisomerization process. Solvent dewaxing can optionally be used to remove small amounts of residual waxy molecules from the lubricating base oil after hydroisomerization. Solvent dewaxing involves dissolving a 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. . 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.

Lubricating base oil fractions derived from high paraffin waxes The light lubricating base oil fractions derived from high paraffin waxes according to the present invention are used as lubricant additive diluent oils in oil-soluble additive concentrates. Is suitable. Lubricating base oil fractions derived from high paraffin waxes are about 1.0 cSt to 3.5 cSt at 100 ° C, preferably about 2 cSt to 3.5 cSt at 100 ° C, more preferably about 2 cSt to 3.cSt at 100 ° C. It has a viscosity of 0 cSt. Given a relatively low degree viscosity, lubricating base oil fractions derived from high paraffin waxes advantageously have a high Noack volatility. The lubricating base oil fraction derived from waxes with high paraffin content has the following formula:
Noack volatility coefficient = 160-40 (kinematic viscosity at 100 ° C)
Having a Noack volatility less than the Noack volatility coefficient calculated by Preferably, the lubricating base oil fraction derived from the high paraffin wax has a Noack volatility of less than 50 wt%, preferably less than 35 wt%. Accordingly, lubricating base oil fractions derived from the high paraffin wax of the present invention advantageously have both low viscosity and low volatility.

  In certain preferred embodiments, the lubricating base oil fraction derived from the paraffin-rich wax has a VI of about 105-155.

Preferably, the viscosity index of the lubricating base oil fraction derived from the high paraffin wax is:
Viscosity index coefficient = 28 × ln (dynamic viscosity of Fischer-Tropsch derived lubricating base oil fraction at 100 ° C.) + 95
Exceeds viscosity index coefficient calculated by In other preferred embodiments, the lubricating base oil fraction derived from the high paraffin wax comprises a weight percent of molecules with cyclic paraffin functionality that is greater than 3 times the kinematic viscosity at 100 ° C.

  The lubricating base oil fraction according to the present invention has good low volatility such that it does not contribute to the volatility of the lubricating oil product, while also not being strong enough to thicken the lubricating oil product. Accordingly, these lubricating base oil fractions have low volatility and low viscosity.

  The lubricating base oil fraction according to the present invention contains extremely low levels of unsaturation. The lubricating base oil fraction contains less than 0.3 wt% aromatics and more than 3 wt% molecules with cyclic paraffin functional groups. Preferably, the lubricating base oil fraction comprises a ratio of the weight percent of molecules with monocyclic paraffin functional groups to the weight percent of molecules with polycyclic paraffin functional groups of greater than 5.

  In a preferred embodiment, the lubricating base oil fraction comprises more than 5% by weight of molecules with cyclic paraffin functional groups. In other preferred embodiments, the lubricating base oil fraction used in the oil-soluble additive concentrate has a polycyclic paraffinic functionality greater than 5, preferably greater than 15, more preferably greater than 50. It includes the ratio of the weight percent of molecules with monocyclic paraffin functional groups to the weight percent of molecules. In another preferred embodiment, the lubricating base oil fraction comprises a ratio by weight percent of molecules having cyclic paraffin functional groups that is greater than 3 times the kinematic viscosity at 100 ° C.

  In a preferred embodiment, the lubricating base oil fraction contains more than 9 branches per 100 carbons. The lubricating base oil fraction used as the lubricating oil additive diluent in the oil soluble additive concentrate can also have a preferred alkyl branch configuration. Therefore, the lubricating base oil of the present invention may contain mainly methyl branches. Branches are 6-18 alkyl branches per 100 carbons, more than 25% branches are separated from each other by a distance of 5 or more carbon atoms, and less than 40% branches are within 2-3 Can be separated from each other by a distance of carbon atoms.

  These lubricating base oil fractions containing cyclic paraffins have unexpectedly good solubility for additives, including VI improvers and lubricating oil additive packages, since cyclic paraffins provide additive solubility. Show. High ratio of weight percent of molecules with monocyclic paraffin functional groups to weight percent of molecules with polycyclic paraffin functional groups (or high weight percent of molecules with monocyclic paraffin functional groups and polycyclic paraffin functionality The lubricating base oil fraction containing low weight percent of molecules with groups) also allows molecules with polycyclic paraffin functional groups to reduce oxidative stability, lower viscosity index, and increase Noak volatility. desirable. Thus, the lubricating base oil fraction according to the present invention exhibits good oxidative stability and high Noack volatility.

  Preferably, the lubricating base oil fraction of the present invention has an aniline point of greater than 36 × ln (kinematic viscosity of the lubricating base oil fraction at 100 ° C.) + 200. Therefore, the lubricating base oil fraction according to the present invention exhibits good elastomer compatibility.

The lubricating base oil fraction of the present invention used as a diluent oil in oil soluble additive concentrates and lubricating oil products contains more than 95% by weight of saturates as determined by elution column chromatography of 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). Preferably, molecules with aromatic functional groups are present by HPLC-UV in an amount of less than 0.3% by weight and confirmed by ASTM D 5292-99 modified to measure low level aromatics. In a preferred embodiment, the molecule having at least an aromatic functional group is present in an amount of less than 0.10 wt%, preferably less than 0.05 wt%, more preferably less than 0.01 wt%. Sulfur is present in an amount of less than 25 ppm, preferably less than 5 ppm, more preferably less than 1 ppm as determined by ultraviolet fluorescence according to ASTM D5453-00.

  Lubricating base oil fractions derived from high paraffin waxes readily dissolve lubricating additives and provide an oil additive concentrate that is readily soluble in lubricating base oil stocks. Furthermore, the lubricating base oil fraction does not introduce any undesirable characteristics into the lubricating base oil stock and hence ultimately into the lubricating oil product, including, for example, high volatility, high viscosity, and impurities such as heteroatoms. .

  In a preferred embodiment, the lubricating base oil fraction according to the present invention is a Fischer-Tropsch derived lubricating base oil fraction. Fischer-Tropsch derived waxes are particularly well suited for providing Fischer-Tropsch derived lubricating base oil fractions having the properties described above.

Aromatic Measurement by HPLC-UV The method used to measure molecules with low levels of aromatic functionality in lubricating base oils is the HP 1050 Diode-Array UV-Vis detector connected to the HP Chem-station. Hewlett Packard 1050 Series Quadratic Gradient High Performance Liquid Chromatography (HPLC) system coupled to. Identification of individual aromatic classes in highly saturated lubricating base oils was based on these UV spectral patterns and their elution times. The amino column used for this analysis distinguishes aromatic molecules primarily based on their ring number (or more precisely, the number of double bonds). Therefore, 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 cyclic paraffin substitution.

  The unambiguous identification of various base oil aromatic hydrocarbons from these UV absorption spectra indicates that the model transition is pure to the extent that the electronic transitions of these peaks depend on the amount of alkyl and cyclic paraffin substitution on the ring system. It was somewhat complicated by the fact that everything was moved on the red side 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 aromatics boil in the lubricating oil range, some degree of red shift was expected and was 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 each general class of compound over the appropriate retention time frame for that aromatic. Retention time frame limits for each aromatic class manually assess individual absorption spectra of compounds eluting at different times and assign them to the appropriate aromatic class based on their qualitative similarity to 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 about 20% absorption. 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. With the exception of slight overlap between the most highly retained alkyl-cycloalkyl-1-ring aromatics and the least highly retained alkylnaphthalenes, all aromatic classes are baseline elucidated It was done. Integration limits for co-eluting 1-ring and 2-ring aromatics at 272 nm were performed by the vertical drop method. Wavelength-dependent response coefficients for each common aromatic class were 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. .

  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 alkyl-cycloalkyl-1-ring aromatics in the base oil sample is such that its molecular absorptivity response coefficient at 272 nm is approximately equal to the molecular absorptivity of tetralin at 268 nm calculated from Beer's law plot. Calculated assuming. 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 coefficient than the model compound because it was more substituted.

  More specifically, in order to accurately calibrate the HPLC-UV method, the substituted benzene aromatics were separated from a large amount of lubricating base oil using a Waters 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 x 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. 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 absorptivity response coefficient by about 20% compared to 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 was easier to calibrate than HPLC UV because it easily measured 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. In other words).

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

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

Cyclic paraffin distribution by FIMS Paraffin is considered to be more stable to oxidation than cyclic paraffin and is therefore more desirable. Monocyclic paraffins are considered to be more stable to oxidation than polycyclic paraffins. However, if the weight percent of all molecules having at least one cyclic paraffin functionality is very low in the oil, the additive solubility is low and the elastomer compatibility is poor. An example of an oil having these properties is Fischer-Tropsch oil (GTL oil) having less than about 5% cyclic paraffin. To improve these properties in lubricating oil products, expensive cosolvents such as esters often must be added. Preferably, the oil fraction derived from a paraffin-rich wax and used as a dielectric fluid comprises a high weight percent molecule with monocyclic paraffin functionality and a low weight percent molecule with polycyclic paraffin functionality. As a result, the oil fraction has high oxidative stability, low volatility, good miscibility with other oils, good additive solubility and good elastomer compatibility.

The lubricating base oils of the present invention were characterized by alkanes and molecules with different numbers of unsaturations by FIMS. The distribution of molecules in the oil fraction was determined by field ionization mass spectrometry (FIMS). FIMS spectra were obtained on a Micromass VG70VSE mass spectrometer. The sample was introduced into the spectrophotometer via a solid probe, preferably with a small amount (about 0.1 mg) of base oil to be tested in a glass capillary. The capillary was placed on the tip of a solid probe for the mass spectrometer, and the probe was heated to about 40 ° C. to 500 ° C. under a vacuum operation of about 10 ⁻⁶ Torr at a rate of 50 ° C. per minute. 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 ¹³ C corrected using the PC-MassSpec software package.

  Assuming that the response factor for all compound types was 1.0, weight percent was determined from area percent. The acquired mass spectra were summed to generate one “averaged” spectrum. The output from the FIMS analysis is the average of alkanes, 1-unsaturated, 2-unsaturated, 3-unsaturated, 4-unsaturated, 5-unsaturated, and 6-unsaturated in the test sample. % By weight.

  Molecules with different numbers of unsaturations may include cyclic paraffins, olefins, and aromatics. If aromatics are present in significant amounts in the lubricating base oil, these are most often identified by FIMS analysis as 4-unsaturated. If olefins are present in significant amounts in the lubricating base oil, these are most often identified by FIMS analysis as 1-unsaturated. 1-unsaturated, 2-unsaturated, 3-unsaturated, 4-unsaturated from FIMS analysis minus the weight percent of olefins by proton NMR and minus the weight percent of aromatics by HPLC-UV Product, 5-unsaturated, and 6-unsaturated is the total weight percent of molecules having cyclic paraffin functional groups in the lubricating base oil of the present invention. The sum of 2-unsaturated, 3-unsaturated, 4-unsaturated, 5-unsaturated, and 6-unsaturated from FIMS analysis minus the aromatic weight percent by HPLC-UV is ,% By weight of molecules having polycyclic paraffin functional groups in the oil of the present invention. Note that if the aromatic content is not measured, it is considered less than 0.1 wt% and is not included in the calculation for the total wt% of molecules with cyclic paraffin functionality.

  In one embodiment, the lubricating base oil fraction derived from a high paraffin wax has a weight percent of molecules having a cyclic paraffin functionality greater than 3, preferably greater than 5. Preferably, the lubricating base oil fraction derived from the paraffin-rich wax is also monocyclic relative to the weight percent of molecules having a polycyclic paraffinic functionality greater than 5, preferably greater than 15, more preferably greater than 50. Having a ratio by weight% of molecules having a paraffinic functional group. In a preferred embodiment, the lubricating base oil fraction contains more than 9 alkyl branches per 100 carbons.

  In another embodiment of a lubricating base oil fraction derived from a high paraffin wax, between the weight percent of all molecules having at least one cyclic paraffin functional group and the kinematic viscosity of the lubricating base oil of the present invention. There is a relationship. That is, the higher the kinematic viscosity at 100 ° C. in cSt, the greater the amount of molecules with cyclic paraffin functional groups obtained. In a preferred embodiment, the lubricating base oil fraction derived from the high paraffin wax has a weight percent of molecules with cyclic paraffin functional groups that is greater than 3 times the kinematic viscosity in cSt. Lubricating base oil fractions derived from high paraffin wax are about 1.0 cSt to about 3.5 cSt, preferably about 2.0 cSt to about 3.5 cSt, more preferably about 2.0 cSt to about 3 at 100 ° C. Has a kinematic viscosity of 0.0 cSt.

  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. D. filed on March 16, 1999 at 1999 AIChE Spring National Meeting in Houston. C. Kramer et al. , “Influence of Group II & III Base Oil Composition on VI and Oxidation Stability”, “Group II & III Base Oil Composition VI and Oxidation Stability”.

  While the paraffin-rich wax feed is essentially free of olefins, the base oil processing method can introduce olefins, particularly by “pyrolysis” reactions at high temperatures. In the presence of heat or UV light, olefins polymerize to form high molecular weight products that cause the base oil to become colored and produce deposits. In general, olefins can be removed by hydrorefining or clay treatment during the process of the present invention.

  Properties of exemplary Fischer-Tropsch lubricant base oils suitable for use as lubricant additive diluents in oil soluble additive concentrates are summarized in Table II in the Examples.

Lubricating oil additive The lubricating oil product comprises at least one lubricating base oil and at least one additive. Generally, the at least one additive is lubricated in the form of an oil-soluble additive concentrate comprising at least one additive and a lubricant additive diluent oil to improve the solubility of the additive in the lubricant base oil. Added to the base oil. The intended use for the lubricating oil product will dictate the additives required to provide a suitable lubricating oil product.

  The lubricating oil additive diluent oil of the present invention may be used with any additive or additive package suitable for use in a lubricating base oil to provide a lubricating oil product.

  Additives for use in lubricating base oils to provide lubricating oil products include viscosity index improvers, detergents, dispersants, antiwear additives, EP agents, antioxidants, pour point depressants, viscosity index Improver, viscosity modifier, friction modifier, demulsifier, defoamer, colorant, color stabilizer, corrosion inhibitor, rust inhibitor, seal swell agent, metal deactivator, biocide, and these There may be mentioned additives selected from the group consisting of mixtures.

  The viscosity index improver is selected from the group consisting of olefin copolymers, copolymers of ethylene and propylene, polyalkyl acrylates, polyalkyl methacrylates, polyisobutylene, hydrogenated styrene-isoprene copolymers, hydrogenated styrene-butadiene, and mixtures thereof. Can do.

  The additive can be in the form of a lubricant additive package that includes several additives to provide a lubricant product having the desired properties. Lubricating oil additive packages for use in lubricating base oils to provide lubricating oil products include detergent-inhibitor (DI) packages, engine oil additive packages, automatic transmission liquid additive packages, powerful transmissions A lubricant additive package selected from the group consisting of a liquid additive package, a power steering liquid additive package, a gear oil additive package, and an industrial oil additive package.

  According to the present invention, a lubricating base oil fraction derived from a high paraffin wax can be used with an engine oil additive package designed for ILSAC GF-4 or API PC-10 engine oils. it can.

  Two or more more commonly used additive categories in lubricant products are DI packages and VI improvers. The DI package helps to suspend oil contaminants and combustion by-products, and in addition to prevent oxidation of the lubricating oil product associated with the formation of the resulting varnish and sludge deposits. VI improvers modify the viscosity characteristics of lubricating oils by reducing the rate of thinning with increasing temperature and the rate of thickening at low temperatures. This allows VI improvers to provide enhanced functionality at low and high temperatures. In many applications, VI improvers are used with DI packages to provide lubricating oil products.

Oil Soluble Additive Concentrate The lubricating oil additive diluent of the present invention is one or more additives to provide an oil soluble additive concentrate that is added to a lubricating base oil stock to provide a lubricating oil product. Blended with. The oil soluble additive concentrate according to the present invention comprises a lubricating base oil fraction derived from the highly paraffinic wax described herein, and one or more additives. The oil-soluble additive concentrate according to the present invention may further comprise a conventional Group I base oil, a conventional Group II base oil, or a mixture thereof. When used as a further component in the oil-soluble additive concentrate according to the present invention, preferably the conventional Group I base oil or the conventional Group II base oil consists of 100N, 150N, 220N, and mixtures thereof. Selected from the group.

  The oil soluble additive concentrate according to the present invention is not suitable as a lubricating oil product as such and is blended with a lubricating base oil stock to provide a lubricating oil product. The additive is readily soluble in a lubricating base oil fraction derived from the high paraffin wax of the present invention, and the resulting oil-soluble additive concentrate provides a lubricating base oil stock for providing a lubricating oil product. It is easily soluble in

  Conveniently, the oil-soluble additive concentrate according to the present invention does not introduce any undesirable characteristics into the lubricating base oil stock including impurities such as, for example, high volatility, high viscosity, high turbidity, or heteroatoms. The oil-soluble additive concentrate according to the present invention has a small amount of heteroatom-containing compounds including nitrogen and sulfur-containing compounds and exhibits excellent solubility in lubricating base oil stocks. Furthermore, the oil-soluble additive concentrates according to the present invention exhibit good elastomer compatibility, low volatility, high oxidative stability, good low temperature performance, and low viscosity.

  Oil-soluble additive concentrates can be made by blending a lubricating base oil fraction derived from a high paraffin wax and one or more lubricating oil additives by methods known to those skilled in the art. . The oil soluble additive concentrate component is a single step performed from the individual components (ie, Fischer-Tropsch derived lubricant base oil fraction, DI package and VI improver) to provide the oil soluble concentrate directly. Can be blended. Alternatively, the lubricating base oil fraction derived from the paraffin-rich wax and one additive (ie, DI package) are first blended and then the resulting blend is the second additive (ie, VI improver). ). The blend of lubricating base oil fraction derived from the high paraffin wax and the first additive can be isolated as is, or the second additive can be added immediately.

  The oil-soluble additive concentrate preferably comprises a lubricating base oil fraction derived from 5 to 98% by weight paraffin-rich wax and at least 2% by weight of one or more lubricating oil additives. More preferably, the oil-soluble additive concentrate comprises a lubricating base oil fraction derived from 95-5% by weight of high paraffin wax and 5-95% by weight of one or more lubricating oil additives. The oil soluble additive concentrate will contain the amount of lubricating base oil fraction used as the lubricating oil additive diluent oil, which varies with the additive. For example, an oil-soluble additive concentrate with a DI package can include a lubricating base oil fraction derived from about 50% by weight high paraffin wax. The oil-soluble additive concentrate with VI improver preferably comprises a lubricating base oil fraction derived from 2-20% by weight VI improver and 98-80% by weight high paraffin wax. The oil-soluble additive concentrate with the gear oil additive package may include a lubricating base oil fraction derived from a wax having a high paraffin content up to 25% by weight.

Lubricating Oil Products To provide a lubricating oil product, the oil-soluble additive concentrate of the present invention is blended with one or more lubricating base oil stocks. In addition to one or more lubricating base oil stocks, the oil-soluble additive concentrates of the present invention also provide additional additives, other additive concentrates, or combinations thereof to provide a lubricating oil product. Can be blended with. Accordingly, the lubricating oil product comprises the oil soluble additive concentrate of the present invention and one or more lubricating base oil stocks. Optionally, the lubricating oil product can also include additional additives, other additive concentrates, or combinations thereof.

  The lubricating oil product is preferably 0.5-50% by weight of the oil-soluble additive concentrate of the present invention and 30-99.5% by weight of one or more lubricating base oils, preferably 0.5-50. % By weight of the oil-soluble additive concentrate of the present invention and 50-99.5% by weight of one or more lubricating base oils. The lubricating base oil can be any oil suitable for use as a lubricating base oil for the intended purpose of the lubricating oil product. Lubricating base oils include conventional Group I base oils, conventional Group II base oils, conventional Group III base oils, Fischer-Tropsch derived base oils, Group IV base oils, poly internal olefins, diesters, polyol esters, phosphate esters, It can be a lubricating base oil selected from the group consisting of alkylated aromatics (ie, alkylated naphthalene), alkylated cyclic paraffins, vegetable oils, and mixtures thereof. The lubricant base stock and additives will be selected based on the intended use of the lubricant product.

  In certain embodiments, the lubricating oil product according to the present invention meets the standards for SAE J300 multigrade engine oil. The lubricating oil product according to the present invention may also meet a standard selected from the group consisting of ILSAC GF-3, ILSAC GF-4, API CI-4, API PC-10, and combinations thereof. Preferably, the lubricating oil product according to the present invention comprises less than 0.7 wt.% Total sulfur as measured by ASTM D1552, more preferably less than 0.5 wt.% Total sulfur as measured by ASTM D1552.

  Lubricating oil products are known to those skilled in the art of oil-soluble additive concentrates according to the present invention and one or more lubricating base oil stocks, optionally further additives, other additive concentrates, or combinations thereof. It can be made by blending by a known method. Lubricating oil products may be blended in a single step performed from individual components (ie, oil soluble concentrate and one or more lubricating base oil stocks) to provide the lubricating oil product directly. Alternatively, the oil soluble additive concentrate and one lubricating base oil stock are first blended to provide a lubricating oil blend, and the lubricating oil blend is then blended with one or more additional lubricating base oil stocks and Optionally, it can be mixed with further additives, other additive concentrates, or combinations thereof. Lubricating oil blends can be isolated as is, or additional lubricating base oil stock, additional additives, or other additive concentrates can be added immediately.

  Lubricating base oil fractions derived from high paraffin waxes used as lubricating additive diluents can be made at a location different from where the components of the oil soluble concentrate are received and blended. Further, the lubricating oil product can be manufactured at a location different from where the components of the oil soluble concentrate are received and blended.

  In a preferred embodiment, the lubricating base oil fraction is derived from a Fischer-Tropsch process and the oil soluble concentrate and the lubricating oil product are the same as where the Fischer-Tropsch derived lubricating base oil fraction was originally made. Made in place. Further, the components of the lubricating oil product (ie, Fischer-Tropsch derived lubricating base oil fraction, lubricating base oil stock, and additives) may all be made at different locations. Preferably, the Fischer-Tropsch derived lubricating base oil fraction is made at a remote location (ie, a location away from the refinery or market that may have a higher construction cost than the refinery or market. Under quantitative conditions, the transport distance between the remote location and the refinery or market is manufactured at least 100 miles, preferably more than 500 miles, most preferably more than 1000 miles).

  Preferably, the Fischer-Tropsch derived lubricating base oil is manufactured at a first remote location and shipped to a second location. The lubricating base oil stock to be included in the lubricating oil product can be manufactured at the same location as the first remote location or at a third remote location. The second location accepts a Fischer-Tropsch derived lubricating base oil fraction, lubricating base oil stock, and additives. Oil-soluble concentrates and lube oil products are produced at this second location.

Other uses In addition to the use as a lubricant additive diluent oil, the ultralight hydrocarbon liquids of the present invention are also used in mineral seal oils, rolling mill oils, agricultural spray oils, drill fluids, high flash cleaning solvents, spindle oils. , Ink diluents, dielectric fluids, and food applications.

  Drill fluid: Any number of liquid and gaseous fluids and fluid and solid mixtures (as solid suspensions, liquid, gas and solid mixtures and emulsions) used in operations for drilling boreholes in the ground ). Drill fluid classification has been attempted in a number of ways, often creating unconventional confusion. One classification scheme given herein selects components that clearly define the function and performance of fluids: (1) water-based, (2) non-water-based and (3) gaseous (air). Only based on mud composition. Each category is a fluid used in hydrocarbon drilling operations with various sub-categories that overlap considerably with each other, particularly fluids that contain significant amounts of suspended solids, emulsified water or oil. Mud includes all types of drill fluids: water-based, oil-based and synthetic-based. Although fluids that are essentially free of solids are not strictly considered mud, fluids that are completed and completed during drilling are sometimes referred to as mud.

  Rolling mill oil: A lubricant used in machines for rolling metal into sheets, bars, or other shapes. Common metals to be rolled include steel and aluminum. The lubricant must provide a low coefficient of friction, acceptable bearing capacity, and produce a smooth product surface.

  Mineral seal oil: General terms for light lubricants with the following properties: low viscosity, slight color, low odor, high aniline point, low pour point, good color stability, and low volatility.

  Agricultural spray oil: A light-viscosity oil sprayed on growing grains or harvested agricultural products to improve product quality and yield. They are used to reduce insect damage, control fungi and other diseases, reduce dust, and reduce evapotranspiration. Oils should have low phytotoxicity and volatility, plus odorless, non-toxic and biodegradable.

  Spindle oil: Light viscosity oil used in high-speed light load bearings used in, for example, fiber spinning frames and automatic machine tools. These low viscosity oils lower operating temperatures and increase mechanical efficiency. These are generally formulated with additives including antioxidants, dust suppressants, and antiwear agents. Desirable properties of spindle oil are high oxidative stability, low volatility, low fouling, low pour point, and high viscosity index.

  Dielectric fluid: A dielectric fluid is a fluid that can maintain a stable electric field and act as an electrical insulator. Thus, the dielectric fluid helps dissipate the heat generated by the energizing components and insulate these components from the device enclosure and other internal components and devices.

The invention is further illustrated by the following illustrative examples that are non-limiting.
Example 1
Preparation of Fischer-Tropsch Wax and Fischer-Tropsch Lubricating Base Oil Samples of commercially available hydrotreated Fischer-Tropsch wax and Co-based Fischer-Tropsch catalyst made using an Fe-based Fischer-Tropsch synthetic catalyst. Samples of hydrotreated Fischer-Tropsch wax made using were analyzed and found to have the properties shown in Table I.

  The Fischer-Tropsch wax feed was hydroisomerized with Pt / SAPO-11 catalyst on alumina binder. Operating conditions were: temperature of 652-695 ° F. (344-368 ° C.), liquid hourly space velocity (LHSV) of 0.6-1.0 / hour, reactor pressure of 1000 psig, and 6-7 MSCF / The bbl flow-through hydrogen rate. The reactor effluent was passed directly at 1000 psig to a second reactor containing Pt / Pd on a silica-alumina hydrorefining catalyst. The conditions for the second reactor were 425-700 ° F. (218-372 ° C.) and 1.0 / hr LHSV.

  The product boiling above about 600 ° F. was fractionated by atmospheric or vacuum distillation to produce five fractions having a viscosity of about 2.0-3.5 cSt at 100 ° C. The properties of the five fractions are shown in Table II.

(Example 2)
Preparation of Oil Soluble Additive Concentrate The five Fischer-Tropsch derived lubricant base oil fractions of the above examples can be used as a lubricant additive diluent and added to provide an oil soluble additive concentrate. Agents can be blended.

  Thus, 98-80 wt% Fischer-Tropsch derived lube base oil fraction is blended with 20-2 wt% olefin copolymer VI improver to provide an oil soluble additive concentrate. For example, the Fischer-Tropsch derived lubricating base oil fraction of Example 3 was blended with about 6 wt% olefin copolymer VI improver. There were no signs of polymer coming out of solution or any other overall insolubles.

(Example 3)
(Comparative example)
Of four commercially available conventional petroleum derived oils (Penzoil 75HC, Petro Canada VHVI2, Nexbase 3020, and Ergon Hygold 60) and a commercially available poly alpha olefin (Chevon Synfluid 2) having a viscosity of less than 3.0 cSt at 100 ° C. Properties are shown in Table III.

  The conventional petroleum derived oils and polyalphaolefins exemplified above having viscosities of 2.0-3.5 cSt at 100 ° C. are all greater than 50% by weight, and more particularly greater than 59% by weight volatility. Have In comparison, the Noack volatility of the Fischer-Tropsch lubricant base oil fractions of Examples 1-5 were all significantly less than 50% by weight. Accordingly, the Fischer-Tropsch lubricating base oil fraction of the present invention has low volatility and low viscosity.

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

Claims (59)

  Lubricant having a viscosity of about 1.0 to 3.5 cSt at 100 ° C. and a Noack volatility less than the Noak volatility coefficient calculated by the following formula: A lubricant additive diluent comprising an oil fraction, wherein the lubricant base oil fraction comprises more than 3% by weight of molecules having cyclic paraffin functional groups and less than 0.30% by weight of aromatics.   The lubricating oil additive diluent oil according to claim 1, wherein the lubricating base oil fraction is a Fischer-Tropsch derived lubricating base oil fraction.   The lubricating oil additive diluent according to claim 1, wherein the lubricating base oil fraction comprises more than 5% by weight of molecules having cyclic paraffin functional groups.   The lubricating oil of claim 1, wherein the lubricating base oil fraction comprises a ratio of weight percent of molecules having monocyclic paraffin functional groups to weight percent of molecules having polycyclic paraffin functional groups, greater than 5. Additive diluent oil.   The lubricating oil additive diluent according to claim 1, wherein the lubricating base oil fraction comprises a weight percent of molecules having cyclic paraffin functional groups that exceeds 3 times its kinematic viscosity at 100 ° C.   The lubricating oil additive diluent according to claim 1, wherein the lubricating base oil fraction comprises more than 9 alkyl branches per 100 carbons.   The lubricant additive diluent oil according to claim 1, wherein the lubricant base oil fraction has a Noack volatility of less than 50 wt%.   The lubricating oil additive diluent according to claim 1, further comprising a conventional Group I base oil or a conventional Group II base oil. Having a viscosity of about 1.0-3.5 cSt at 100 ° C. and a Noak volatility of less than a Noak volatility coefficient calculated by the following formula: Noak volatility coefficient = 160-40 (kinematic viscosity at 100 ° C.), 5 to 98% by weight of a lubricating base oil fraction comprising more than 3% by weight of molecules having cyclic paraffin functional groups and less than 0.30% by weight of aromatics;
An oil-soluble additive concentrate comprising at least 2% by weight of one or more lubricating oil additives.   The oil-soluble additive concentrate of claim 9, wherein the lubricating base oil fraction is a Fischer-Tropsch derived lubricating base oil fraction.   The oil-soluble additive concentrate of claim 9, wherein the lubricating base oil fraction has a viscosity of about 2.0 to 3.5 cSt at 100 ° C.   The oil-soluble additive concentrate of claim 11, wherein the lubricating base oil fraction has a viscosity index of about 105-155. The lubricating base oil fraction has the following formula:
Viscosity index coefficient = 28 × ln (dynamic viscosity of Fischer-Tropsch derived lubricating base oil fraction at 100 ° C.) + 95
The oil-soluble additive concentrate according to claim 9, having a viscosity index that exceeds the viscosity index coefficient calculated by:   The oil-soluble additive concentrate according to claim 9, wherein the lubricating base oil fraction comprises a weight percent of molecules having cyclic paraffin functional groups that exceeds 3 times the kinematic viscosity at 100 ° C.   The oil-soluble additive concentrate of claim 9, wherein the lubricating base oil fraction comprises more than 9 alkyl branches per 100 carbons.   The oil-soluble additive concentrate of claim 9, wherein the lubricating base oil fraction has a Noack volatility of less than 50 wt%.   The oil-soluble additive concentrate of claim 9, wherein the oil-soluble additive concentrate further comprises a conventional Group I base oil or a conventional Group II base oil.   The oil-soluble additive concentrate of claim 9, wherein the lubricating base oil fraction has an aniline point of greater than 36 × ln (kinematic viscosity of the lubricating base oil fraction at 100 ° C.) + 200.   The oil-soluble additive concentrate according to claim 9, wherein the lubricating base oil fraction comprises more than 5% by weight of molecules having cyclic paraffin functional groups.   10. The oil solubility of claim 9, wherein the lubricating base oil fraction comprises a ratio of weight percent of molecules with monocyclic paraffin functional groups to weight percent of molecules with polycyclic paraffin functional groups greater than 5. Additive concentrate.   The oil-soluble additive concentrate of claim 9, wherein the lubricating base oil fraction has a sulfur content of less than 5 ppmw.   The one or more lubricating oil additives are a viscosity index improver, detergent, dispersant, antiwear additive, EP agent, antioxidant, pour point depressant, viscosity index improver, viscosity modifier, friction modifier Selected from the group consisting of agents, demulsifiers, defoamers, colorants, color stabilizers, corrosion inhibitors, rust inhibitors, seal swell agents, metal deactivators, biocides, and mixtures thereof. The oil-soluble additive concentrate according to claim 9.   The oil-soluble additive concentrate of claim 9, wherein the one or more lubricating oil additives comprise a lubricating oil additive package.   The lubricant additive package is a detergent-inhibitor package, an engine oil additive package, an automatic transmission liquid additive package, a powerful transmission liquid additive package, a power steering liquid additive package, a gear oil additive package, and an industry. 24. The oil soluble additive concentrate of claim 23, selected from the group consisting of oil additive packages.   23. The oil-soluble additive concentrate according to claim 22, wherein the oil-soluble additive concentrate comprises 2 to 20 wt% viscosity index improver.   The viscosity index improver is selected from the group consisting of olefin copolymers, copolymers of ethylene and propylene, polyalkyl acrylates, polyalkyl methacrylates, polyisobutylene, hydrogenated styrene-isoprene copolymers, hydrogenated styrene-butadiene, and mixtures thereof. 26. The oil-soluble additive concentrate according to claim 25. a. i. Having a viscosity of about 1.0-3.5 cSt at 100 ° C. and a Noak volatility of less than a Noak volatility coefficient calculated by the following formula: Noak volatility coefficient = 160-40 (kinematic viscosity at 100 ° C.), From 5 to 98% by weight of a lubricating base oil fraction comprising more than 3% by weight of molecules having cyclic paraffin functional groups and less than 0.30% by weight of aromatics, and ii. At least 2% by weight of one or more lubricant additives
An oil-soluble additive concentrate comprising:
b. A lubricating oil product comprising one or more lubricating base oils.   28. The lubricating oil product of claim 27, comprising 0.5 to 50% by weight of an oil soluble additive concentrate and 30 to 99.5% by weight of one or more lubricating base oils.   28. A lubricating oil product according to claim 27, wherein the lubricating base oil fraction comprises more than 5% by weight of molecules having cyclic paraffin functional groups.   28. The lubricating oil of claim 27, wherein the lubricating base oil fraction comprises a ratio of weight percent of molecules having monocyclic paraffin functional groups to weight percent of molecules having polycyclic paraffin functional groups greater than 5. Product.   28. A lubricating oil product according to claim 27, wherein the lubricating base oil fraction comprises more than 9 alkyl branches per 100 carbons.   28. A lubricating oil product according to claim 27, wherein the lubricating base oil fraction has a Noack volatility of less than 50% by weight.   28. The lubricating oil product of claim 27, wherein the oil soluble additive concentrate further comprises a conventional Group I base oil or a conventional Group II base oil.   The one or more lubricating oil additives are a viscosity index improver, detergent, dispersant, antiwear additive, EP agent, antioxidant, pour point depressant, viscosity index improver, viscosity modifier, friction modifier Selected from the group consisting of agents, demulsifiers, defoamers, colorants, color stabilizers, corrosion inhibitors, rust inhibitors, seal swell agents, metal deactivators, biocides, and mixtures thereof. The lubricating oil product according to claim 27.   28. A lubricant product according to claim 27, wherein the one or more lubricant additives comprise a lubricant additive package.   The lubricant additive package is a detergent-inhibitor package, an engine oil additive package, an automatic transmission liquid additive package, a powerful transmission liquid additive package, a power steering liquid additive package, a gear oil additive package, and an industry. 36. The lubricating oil product of claim 35, selected from the group consisting of an oil additive package.   The one or more lubricating base oils are a conventional Group I base oil, a conventional Group II base oil, a conventional Group III base oil, a Fischer-Tropsch derived base oil, a Group IV base oil, a poly internal olefin, a diester, 28. The lubricating oil product of claim 27, selected from the group consisting of polyol esters, phosphate esters, alkylated aromatics, alkylated cyclic paraffins, alkylated naphthalenes, vegetable oils, and mixtures thereof.   28. The lubricant product of claim 27, wherein the lubricant product meets SAE J300 multi-grate engine oil specifications.   40. The lubrication of claim 38, wherein the lubricant product further meets a standard selected from the group consisting of ILSAC GF-3, ILSAC GF-4, API CI-4, API PC-10, and combinations thereof. Oil products.   28. The lubricating oil product of claim 27, wherein the lubricating oil product comprises less than 0.7 wt% total sulfur as measured by ASTM D1552. a. Having a viscosity of about 1.0-3.5 cSt at 100 ° C. and a Noak volatility of less than a Noak volatility coefficient calculated by the following formula: Noak volatility coefficient = 160-40 (kinematic viscosity at 100 ° C.), Providing a lubricating base oil fraction comprising greater than 3% by weight of molecules having cyclic paraffin functional groups and less than 0.30% by weight of aromatics;
b. Blending the lubricating base oil fraction with at least 2% by weight of one or more lubricating oil additives;
c. Isolating the oil-soluble additive concentrate. A method for producing the oil-soluble additive concentrate. a. Performing a Fischer-Tropsch synthesis to provide a product stream;
b. Isolating a substantially paraffinic wax feed from the product stream;
c. Hydroisomerizing the substantially paraffinic wax feed using a shape selective intermediate pore size molecular sieve comprising a noble metal hydrogenation component under conditions of about 600 ° F. to about 750 ° F .;
d. Isolating the isomerized oil;
e. The isomerized oil is hydrorefined to obtain a viscosity of about 1.0 to 3.5 cSt at 100 ° C. and Noak volatilization calculated by the following formula: Noak volatility coefficient = 160-40 (kinematic viscosity at 100 ° C.) Providing a Fischer-Tropsch derived lubricating base oil fraction having a Noack volatility of less than a degree factor, greater than 3 wt%, having molecules with cyclic paraffin functionality, and less than 0.30 wt% aromatics. When,
f. Blending the Fischer-Tropsch derived lubricating base oil fraction with at least 2% by weight of one or more lubricating oil additives;
g. Isolating the oil soluble additive concentrate;
A method for producing an oil-soluble additive concentrate.   43. The method of claim 42, further comprising distilling the isomerized oil to provide the Fischer-Tropsch derived lubricating base oil fraction.   43. The method of claim 42, wherein the noble metal hydrogenation component is platinum, palladium, or a combination thereof.   The shape selective intermediate pore size molecular sieves are SAPO-11, SAPO-31, SAPO-41, SM-3, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32. 43. The method of claim 42, selected from the group consisting of:, offretite, ferrierite, and combinations thereof.   43. The lubricating base oil fraction comprising a ratio of weight percent of molecules with monocyclic paraffin functional groups to weight percent of molecules with polycyclic paraffin functional groups of greater than 5, 43%. Method.   43. The method of claim 41 or 42, further comprising blending the lubricating base oil fraction with a conventional Group I base oil or a conventional Group II base oil.   48. The method of claim 47, wherein the conventional Group I base oil or conventional Group II base oil is selected from the group consisting of 100N, 150N, 220N, and mixtures thereof. a. Having a viscosity of about 1.0-3.5 cSt at 100 ° C. and a Noak volatility of less than a Noak volatility coefficient calculated by the following formula: Noak volatility coefficient = 160-40 (kinematic viscosity at 100 ° C.), Providing a lubricating base oil fraction comprising greater than 3% by weight of molecules having cyclic paraffin functional groups and less than 0.30% by weight of aromatics;
b. Blending the lubricating base oil fraction with one or more lubricating oil additives to provide an oil soluble additive concentrate comprising at least 2% by weight of the one or more lubricating oil additives;
c. Blending the oil-soluble additive concentrate with one or more lubricating base oils.   50. The method of claim 49, wherein the lubricating oil product comprises 0.5-50% by weight of an oil soluble additive concentrate and 30-99.5% by weight of one or more lubricating base oils.   50. A process according to claim 41 or 49, wherein the lubricating base oil fraction is derived from a Fischer-Tropsch process.   50. The method of claim 41, 42, or 49, wherein the lubricating base oil fraction comprises more than 5% by weight of molecules having cyclic paraffin functional groups.   52. The lubricating base oil fraction comprises a ratio of weight percent of molecules with monocyclic paraffin functional groups to weight percent of molecules with polycyclic paraffin functional groups of greater than 15; The method described in 1.   The one or more lubricating oil additives are a viscosity index improver, detergent, dispersant, antiwear additive, EP agent, antioxidant, pour point depressant, viscosity index improver, viscosity modifier, friction modifier. Selected from the group consisting of agents, demulsifiers, defoamers, colorants, color stabilizers, corrosion inhibitors, rust inhibitors, seal swell agents, metal deactivators, biocides, and mixtures thereof. 50. A method according to claim 41, 42 or 49.   50. The method of claim 41, 42, or 49, wherein the one or more lubricant additives comprise a lubricant additive package.   The lubricant additive package includes a detergent-inhibitor package, an engine oil additive package, an automatic transmission liquid additive package, a powerful transmission liquid additive package, a power steering liquid additive package, a gear oil additive package, and an industrial 56. The method of claim 55, selected from the group consisting of an oil additive package.   The one or more lubricating base oils are a conventional Group I base oil, a conventional Group II base oil, a conventional Group III base oil, a Fischer-Tropsch derived base oil, a Group IV base oil, a poly internal olefin, a diester, 50. The method of claim 49, selected from the group consisting of polyol esters, phosphate esters, alkylated aromatics, alkylated cyclic paraffins, alkylated naphthalenes, vegetable oils, and mixtures thereof.   50. The method of claim 49, wherein the lubricant product meets SAE J300 multi-grate engine oil specifications.   59. The method of claim 58, wherein the lubricant product further conforms to a standard selected from the group consisting of ILSAC GF-3, ILSAC GF-4, API CI-4, API PC-10, and combinations thereof. .