NL1027828C2 - Basic lubricating oil with a high content of monocycloparaffins and a low content of multicycloparaffins. - Google Patents

Description

Basic lubricating oil with a high content of monocycloparafins and a low content of multicycloparaffins

Field of the invention 5

The invention relates to: a) a base lubricating oil with a low content of aromatics, a high weight percentage of all molecules with at least a cycloparaffme function and a high ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage of molecules containing multicyclopa Contain raffins; and b) a method for preparing the base lubricating oil of this invention.

Background of the Invention Ready lubricants and greases used for various applications, including automobiles, diesel engines, natural gas engines, shafts, transmissions and industrial applications, consist of two general components, a base lubricating oil and additives. Base lubricating oil is the most important component in these finished lubricants and contributes significantly to the properties of the finished lubricant. In general, some basic lubricating oils are used to prepare a wide variety of finished lubricants by varying the blends of the individual basic lubricating oils and individual additives.

Highly saturated basic lubricating oils of the prior art had or very low levels of cycloparaffins; or if cycloparaffins were present, a significant amount of the cycloparaffins was multicycloparaffins. A certain amount of cycloparaffins is desired in base lubricating oils to provide additive solubility and elastomer compatibility. Multicycloparaffins are less desirable than monocycloparaffins, because they lower the viscosity index, lower the oxidation stability and increase the Noack volatility.

Examples of highly saturated base lubricating oils with very low levels of cycloparaffins are poly-alpha olefins and base oils prepared via Fischer-Tropsch processes, as described in EP-A-1114124, EP-A-1114127, EP-A A-1114131, EP-A-776959, EP-A-668342 and EP-A-1029029. Basic lubricating oils according to 1027828 ..... · - '' '·· · - ♦ · "· - · ** · β # ** - * ·· 2 state of the art with a high content of cycloparaffins prepared from Fischer Tropsch wax are described in WO 02/064710 The examples of the base oils in WO 02/064710 had very low pour points and the ratio of monocycloparaffins to multicycloparaffins was lower than 15. The viscosity indices of the base 5 lubricating oils in WO 02/064710 were lower than 140. The Noack volatilities were between 6 and 14% by weight The base lubricating oils in WO 02/064710 were largely dewaxed to achieve low pour points, which gives lower yields compared to oils not in those to a large extent.

The washing feed used to prepare the base oils in WO 02/064710 had a weight ratio of compounds with at least 60 or more carbon atoms and compounds with at least 30 carbon atoms greater than 0.20.

These washing feeds are not as abundant as feeds with lower weight ratios of compounds with at least 60 or more carbon atoms and compounds with at least 30 carbon atoms. The method in WO 02/064710 required an initial hydrocracking / hydroisomerization of the washing feed followed by a step of a substantial reduction in the pour point. A loss of yield of the basic lubricating oil occurred at each of these two steps. To demonstrate this, in Example 1 of WO 02/064710, the conversion of compounds boiling at a temperature above 370 ° C to compounds boiling at a temperature below 370 ° C was 55% by weight in the hydrocracking / hydroisomerization step only . The subsequent step of lowering the pour point further reduces the yield of products boiling at a temperature higher than 370 ° C. Compounds boiling at a temperature below 370 ° C (700 ° F) are usually not recovered as base lubricating oils because of their low viscosity. Because of the loss of yield due to high conversions, the process requires feeds with a high ratio of compounds with at least 60 or more carbon atoms and compounds with at least 30 carbon atoms. j i

Due to their high content of saturated compounds and low levels of cycloparaffins, base lubricating oils prepared by most Fischer-Tropsch processes or poly-alpha olefins exhibit poor additive solubility. Additives used to prepare finished lubricants usually have polar functionality; therefore, they may be insoluble or only slightly soluble in the base lubricating oils. In order to address the problem of poor additive-solubility in highly saturated base lubricating oils with low levels of cycloparafin, various co-solvents, such as synthetic esters, are currently being used. However, these synthetic esters are very expensive and thus the blends of the base lubricating oils containing synthetic esters and having acceptable additive solubility are also expensive. The high price of these blends limits the current use of highly saturated basic lubricating oils with low levels of cycloparaffins to specialized and small markets.

US patent application 20030088133 describes that mixtures of base lubricating oils consisting of 1) alkylated cycloparaffins with 2) highly paraffinic base lubricating oils obtained via Fischer-Tropsch the additive solubility of the highly paraffinic base lubricating oils obtained from Fischer-Tropsch improve. The base lubricating oils consisting of alkylated cycloparaffins used in the blends of this application most likely also contain high levels of aromatics (more than 30 weight percent), so that the resulting blends with 15 Fischer-Tropsch base lubricating oils have a weight percentage of all molecules with at least contain at least one aromatic function of more than 0.30. The high content of aromatics causes a reduced viscosity index and oxidation stability.

What is desired are base lubricating oils with very low levels of aromatics, large amounts of monocycloparaffins and few or no multicycloparaffins, which have a moderate low pour point so that they can be produced in high yield and provide good additive solubility and elastomer compatibility. Base oils with these properties, which also have good oxidation stability, high viscosity index, low Noack volatility, and good properties at low temperature are also desired. The present invention provides these basic lubricating oils.

What is desired is a process for preparing base lubricating oils with the desired properties outlined above, which is not limited to washing feeds with a weight ratio of compounds with at least 60 or more carbon atoms and compounds with at least 30 carbon atoms of at least 30 0 , 2. What is also desired is a process for preparing base lubricating oils with the desired properties that can be carried out with a single hydroisomerization dewaxing step that involves a lower conversion of products boiling at a temperature of more than 370 ° C (700 ° F +) in products that boil at a temperature lower than 370 ° C (700 ° F-), and thus give higher yields of base lubricating oil.

Summary of the invention 5

The present invention relates to a composition of a basic lubricating oil that has a weight percentage of all molecules with at least an aromatic function lower than 0.30, a weight percentage of all molecules with at least a cycloparaffin function higher than 10 and a ratio of the weight percentage 10 molecules containing monocycloparaffins up to the weight percentage of molecules containing multicycloparaffins higher than 15.

The present invention also relates to a composition of a | base lubricating oil comprising a weight percentage of all molecules with at least an aromatic function lower than 0.30, a weight percentage of all molecules with mono-15 cycloparafins higher than 10 and a weight percentage of all molecules with multi-cycloparaffins lower than 0.1.

The present invention also relates to a composition of base lubricating oils which has a weight percentage of all molecules with at least one aromatic function lower than 0.30, a weight percentage of all molecules with at least one cycloparaffin function higher than the kinematic viscosity at 100 ° C in cSt multiplied by three and comprises a ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage of molecules containing multicycloparaffins higher than 15.

The very low content of aromatics provides excellent oxidation stability and a high viscosity index to the base lubricating oil. The high content of all molecules with at least one cycloparaffin function provides improved additive-solubility and compatibility with elastomers for the base lubricating oil. The very high ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage of molecules containing multicycloparaffins (or the high percentage by weight of molecules containing monocycloparaffins and little to no weight percentage of molecules containing multicycloparaffins) optimizes the composition of the cycloparafins. Molecules containing multicycloparaffins are less desirable as they dramatically reduce the viscosity index, oxidation stability and Noack volatility of base lubricating oils.

The present invention also relates to a method for preparing a base lubricating oil comprising the steps of: a) performing a Fischer-Tropsch synthesis with syngas to provide a product stream; b) isolating from the product stream a substantially paraffinic feedstock with less than about 30 ppm total combined nitrogen and sulfur and less than about 1 weight percent oxygen; c) dewaxing the essentially paraffinic washing feed by hydroisomerization dewaxing using a shape-selective, medium-pore molecular sieve with a noble metal hydrogenation component, the hydroisomerization temperature being between about 315 ° C (600 ° F) and about 399 ° C (750 ° F), producing an isomerized oil; and d) hydrofinishing the isomerized oil, wherein a base lubricating oil is produced with: a low weight percentage of all molecules with at least one aromatic function, a high weight percentage of all molecules with at least one cycloparaffin function and a high ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage of molecules containing multicycloparaffins.

Using the process according to the invention, high yields of base lubricating oils with good additive solubility, good elastomer compatibility, excellent oxidation stability and low volatility are prepared. In addition, the viscosity indices are high. The basic lubricating oils of the present invention can be used to prepare high quality finished lubricants, including automatic transmission fluids and multigrade motor oils, preferably without the addition of an ester co-solvent or viscosity index improving agent.

This invention overcomes the shortcomings of the prior art that have been directed to lowering the pour point and increasing the total content of cycloparaffs in base lubricating oils prepared from Fischer-Tropsch wax. Producing base oils with very low pour points using hydroisomerization dewaxing can result in oils with high weight percentages of all molecules with at least a cycloparaffin function, but at the expense of producing high weight percentages of molecules that also contain multicycloparaffins . High 10278 ^ 8 6 weight percentages of molecules containing multicycloparaffins reduce oxidation stability and viscosity index. The yields of base lubricating oil are also significantly reduced as the severity of the hydroisomerization dewaxing is increased to obtain lower pour points. The production of base oils with very low pour points from Fischer-Tropsch wax using solvent dewaxing results in oils with lower weight percentages of all molecules with at least one cycloparaffin function. A certain high level of cycloparaffins is desired for improving the additive solubility and compatibility with the base lubricating oil elastomers.

This invention overcomes the shortcomings of the prior art directed to methods for increasing the viscosity index of base lubricating oils prepared from a substantially paraffinic wash feed, the substantially paraffinic wash feed being less than about 30 ppm total combined nitrogen and sulfur and has an oxygen content of less than about 1 weight percent. A high viscosity index in basic lubricating oils according to the prior art has been obtained by carrying out a considerable degree of solvent dewaxing, whereby smaller amounts of total cycloparafins are produced in comparison with hydroisomerization dewaxing. In the prior art, a high viscosity index was also obtained according to a method in which a Fischer-Tropsch feed with a relatively narrow boiling range, with a T90-T10 between 40 to 150 ° C, is used. This invention provides basic lubricating oils with high viscosity indices using Fischer-Tropsch feeds with both narrow and wide boiling point distributions.

The very low content of aromatics in the basic lubricating oil provides an excellent oxidation stability and high viscosity index. The high content of all molecules with at least one cycloparaffin function provides improved additive solubility and compatibility with elastomers for the base lubricating oil. The very high ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage of molecules containing multicycloparaffins (or the high percentage by weight of molecules containing monocycloparaffins and little to no weight percentage of molecules containing multicycloparaffins) optimizes the composition of the cycloparaffins . Molecules containing multicycloparaffins 10278 ^ 0 7 become less desirable as they dramatically reduce the viscosity index, oxidation stability and Noack volatility of base lubricating oils.

The present invention also relates to an installation for preparing a basic lubricating oil, comprising: a) a device for producing a substantially paraffinic washing feed with less than about 30 ppm total combined nitrogen and sulfur, less than about 1 weight percent oxygen , more than about 75 weight percent of normal paraffin, less than 10 weight percent oil, a weight ratio of compounds with at least 60 or more carbon atoms and compounds with at least 30 carbon atoms below 0.18 and a T90-10 boiling point between 660 ° F and 1200 ° F; b) an apparatus for hydroisomerization dewaxing the substantially paraffinic wash feed using a medium pore size selective molecular sieve comprising a noble metal hydrogation component, the hydroisomerization temperature being between about 315 ° C (600 ° F) ) and about 399 ° C (750 ° C), for producing an isolated oil; and c) an apparatus for hydrofinishing the isomerized oil to produce base lubricating oils with low weight percentages of all molecules with at least one aromatic function, high weight percentages of all molecules with at least one cycloparaffin function and high ratios of the weight percent of molecules that contain monocycloparaffins to the weight percent of molecules that contain multicycloparaffins.

Brief description of the drawings

Figure 1 illustrates the kinematic viscosity graph at 100 ° C in cSt versus the pour point in degrees Celsius, the kinematic viscosity at 100 ° C in cSt providing the equation for calculating the flow factor of the base oil:

Flow factor of the base oil = 7.35 x ln (kinematic viscosity at 100 ° C) -18, where ln (kinematic viscosity at 100 ° C) is the natural logarithm with basis "e" of the kinematic viscosity at 100 ° C in cSt .

Figure 2 illustrates the kinematic viscosity graph at 100 ° C in cSt versus the aniline point in ° F, providing the comparison for calculating the preferred upper limits of the aniline point based on the kinematic viscosity: 1027828 8 ........

Aniline point, in ° F = 36 x ln (kinematic viscosity at 100 ° C) + 200, where ln (kinematic viscosity at 100 ° C) is the natural logarithm with basis "e" of the kinematic viscosity at 100 ° C in cSt.

Figure 3 illustrates the kinematic viscosity graph at 100 ° C in cSt 5 versus TGA Noack in weight percent, providing comparisons for calculating the preferred Noack volatility upper limits based on the kinematic viscosity:

Noack volatility, wt% = 1000 x (kinematic viscosity at 100 ° C in cSt) 2.7, the kinematic viscosity at 100 ° C being raised to the power -2.7; 10 and

Noack volatility, wt% = 900 x (kinematic viscosity at 100 ° C in cSt) 2'8, the kinematic viscosity at 100 ° C being raised to the power -2.8.

Figure 4 illustrates the kinematic viscosity graph at 100 ° C in cSt versus CCS viscosity at -35 ° C, in cP, providing the comparisons for calculating the upper limits of the CCS VIS (-35 ° C) preferred based on the kinematic viscosity: CCS VIS (-35 ° C), cP = 38 x (kinematic viscosity at 100 ° C) 3, with the kinematic viscosity at 100 ° C in cSt raised to power 3 ; and CCS VIS (-35 ° C), cP = 38 x (kinematic viscosity at 100 ° C) 2.8, raising the kinematic viscosity at 10 ° C in cSt to the power 2.8.

DETAILED DESCRIPTION OF THE INVENTION

Basic lubricating oils with a very low aromatic content prepared prior to this invention had either a very low cycloparaffin content or a high cycloparaffin content with a substantial content of multicycloparaffins and / or very low pour points. The highest known ratio of monocycloparaffins to multicyclo paraffins in base lubricating oils containing more than 10 weight percent cycloparaffins and a low aromatics content was 13: 1. The base lubricating oil with this high ratio was the base oil of Example 3 of WO 02/064710. The pour point of this example of the base oil was extremely low, -45 ° C, indicating that it had been largely dewaxed. High dewaxing of base oils to low pour points 1027828 9 takes place with a significant yield disadvantage compared to base lubricant oils that have been dewaxed to more moderate pour points.

Basic lubricating oils containing cycloparaffins are desired as cycloparaffins confer additive solubility and elastomer compatibility to these oils. Basic lubricating oils that have very high ratios of monocycloparaffins to multicycloparaffins (or a high content of monocycloparaffins and few to no multicycloparaffins) are also desirable as the multicycloparaffins reduce oxidation stability, lower viscosity index and increase Noack volatility. Models of the effects of multicycloparaffins are given in V.J.

10 Gatto et al., "The Influence of Chemical Structure on the Physical Properties and Antioxidant Response of Hydrocracked Base Stocks and Polyalphaolefins," J. Synthetic Lubrication 19-1, April 2002, pp. 3-18.

According to the present invention, base lubricating oils are prepared which have very low weight percentages of all molecules with at least one aromatic function, high weight percentages of all molecules with at least one cycloparaffin function and high ratios of the weight percent of molecules containing monocycloparaffins to the weight percent of molecules containing multicycloparaffins (or have a high weight percentage of molecules containing monocycloparaffins and very low weight percent of molecules containing multicycloparaffins). In preferred embodiments, these also have moderate pour points. Moderate pour points are achieved by producing oils with a ratio of pour point to kinematic viscosity at 100 ° C higher than a flow factor of the base oil, as defined herein. High yields of these base oils can be obtained using a method comprising the steps of: a) performing a Fischer-Tropsch synthesis to provide a product stream; b) isolating from the product stream a substantially paraffinic wash feed with less than about 30 ppm total combined nitrogen and sulfur and less than about 1 weight percent oxygen; c) dewaxing the substantially paraffinic wash feed by hydroisomerization dewaxing using a medium-pore size selective molecular sieve comprising a noble metal hydrogenation component to produce an isomerized oil; and d) hydrofinishing the isomerized oil, wherein a base lubricating oil is produced with a weight percentage of all molecules with at least one aromatic function lower than 1027828 10, a weight percentage of all molecules with at least one cycloparafine function higher than 10 and a high ratio of the weight percentage of molecules containing monocycloparafins to the weight percentage of molecules containing multi-cycloparafins (higher than 15).

In addition, step d) of the above process can be changed to: d) hydrofinishing the isomerized oil, producing a base lubricating oil with a weight percentage of all molecules with at least an aromatic function of less than 0.30, a weight percentage of all molecules with at least a cycloparaffin function higher than the kinematic viscosity at 100 ° C in cSt 10 multiplied by three and a ratio of the weight percentage of molecules containing monocycloparafins to the weight percentage of molecules containing multicycloparaffins higher than 15.

As a second alternative, step d) of the foregoing method can be changed to: c) hydrofinishing the isomerized oil to produce a base lubricating oil with a weight percentage of all molecules with at least an aromatic function of less than 0.30, a weight percentage of molecules containing monocycloparaffins higher than 10, a weight percentage of molecules containing multicycloparaffins lower than 0.1.

The kinematic viscosity is a measure of the resistance to flowing of a liquid under the influence of gravity. Many basic lubricating oils, ready lubricants prepared therefrom and the correct operation of equipment depend on the correct viscosity of the liquid being used. The kinematic viscosity is determined according to ASTM D 445-01. The results are reported in centistokes (cSt). The kinematic viscosities of the base lubricating oils of this invention are between about 2 cSt and about 20 cSt, preferably between about 2 cSt and about 12 cSt.

The pour point is a measure of the temperature at which the sample begins to flow under carefully controlled conditions. The pour point can be determined as described in ASTM D 5950-02. The results are stated in 30 degrees Celsius. Many commercially available basic lubricating oils have specifications for the pour point. If base lubricating oils have low pour points, they probably also have other good properties at low temperature, such as a low cloud point, a low clogging point of a cold filter, and a gas mixing viscosity at low temperature. The cloud point is a measure that is complementary to the pour point and is expressed as a temperature at which a sample of the base lubricating oil begins to develop a haze under carefully specified conditions. The cloud point can be determined, for example, in accordance with ASTM D 5773-5 95. Basic lubricating oils with spreads cloud point lower than about 35 ° C are also desired. Greater spreads of the flow cloud point require processing of the base lubricating oil into very low flow points to meet the cloud point specifications. The flow cloud point spreads of the base lubricating oils of this invention are generally lower than about 35 ° C, preferably lower than about 25 ° C, more preferably lower than about 10 ° C. The cloud points are generally in the range of +30 to -30 ° C.

The Noack volatility of engine oil, as measured by TGA Noack and corresponding methods, was found to correlate with the oil consumption in engines of 15 passenger cars. Strict low volatility requirements are important aspects of several recent engine oil specifications such as, for example, ACEA A-3 and B-3 in Europe and SAE J300-01 and ILSAC GF-3 in North America. Every new basic lubricating oil that is developed for use in motor vehicle oil should have a Noack volatility that is no higher than the current usual light neutral oils from group I or group II. The Noack volatility of the base lubricating oils of this invention is very low, generally lower than an amount calculated by the comparison:

Noack volatility, wt% = 1000 x (kinematic viscosity at 100 ° C) 2.7. In preferred embodiments, the Noack volatility is lower than an amount calculated by the comparison:

Noack volatility, wt% = 900 x (kinematic viscosity at 100 ° C) 2.8.

The Noack volatility is defined as the amount of oil, expressed as a percentage by weight, that is lost when the oil is heated to 250 ° C and 20 mmHg (2.67 kPa; 26.7 mbar) under atmospheric pressure, in a test crucible through which A constant stream of air is fed for 60 minutes (ASTM D 5800). A simpler method for calculating the Noack volatility and one that corresponds well with ASTM D-5800 is to use a thermogravimetric analysis test (TGA) 1027828 12 according to ASTM D-6375-99. In this description, unless otherwise stated, the TGA Noack volatility is used.

The base lubricating oils of this invention can be blended with other base oils to improve or change their properties (e.g., viscosity index, oxidation stability, pour point, sulfur content, traction coefficient or Noack volatility). Examples of base oils that can be mixed with the base lubricating oils of this invention are conventional Group I base oils, Group II base oils, Group III base oils, other GTL base oils, isomerized petroleum wax, poly-alpha olefins, polyolefin internal olefins, oligomerized olefins from a feed obtained via Fischer-Tropsch, di-esters, polyolesters, phosphate esters, alkylated aromatics, alkylated cycloparaffs and mixtures thereof.

Washing food: 15

The washing feed used to prepare the base lubricating oil of this invention is essentially paraffinic with less than about 30 ppm total combined nitrogen and sulfur. The oxygen content is less than about 1 weight percent, preferably less than 0.6 weight percent, more preferably, less than 0.2 weight percent. In most cases, the oxygen content in the essentially paraffinic washing feed is between 0.01 and 0.90 weight percent. The oil content of the feed is less than 10 weight percent, as determined according to ASTM D 721. Substantially paraffinic for the purpose of this invention is defined as having more than about 75 weight percent normal paraffin, according to gas chromatographic analysis according to ASTM D 5442 .

Nitrogen determination: Nitrogen is measured by melting the substantially paraffinic wax before oxidative combustion and chemiluminescence detection according to ASTM D 4629-96. The testing method is further described in U.S. Patent No. 6503956, which is to be incorporated by reference in its entirety. Sulfur determination: Sulfur is measured by melting the substantially paraffinic wax before ultraviolet fluorescence according to ASTM 5453-00. The testing method is further described in U.S. Patent No. 6503956.

Oxygen determination: Oxygen is measured by neutron activation analysis.

1027828 13

The washing feed useful in this invention contains a significant fraction with a boiling point higher than 343 ° C (650 ° F). The T90 boiling points of the washing feed according to ASTM D 6352 are preferably between 349 ° C (660 ° F) and 649 ° C (1200 ° F), more preferably between 482 ° C (900 ° F) and 649 ° C ( 1200 ° F), most preferably between 538 ° C (1000 ° F) and 649 ° C (1200 ° F). T90 refers to the temperature at which 90 weight percent of the feed has a lower boiling point.

The washing feed preferably has a weight ratio of molecules with at least 60 carbon atoms to molecules with at least 30 carbon atoms below 0.18. The weight ratio of molecules with at least 60 carbon atoms to 10 molecules with at least 30 carbon atoms is determined by: 1) measuring the boiling point distribution of the Fischer-Tropsch wax by simulated distillation using ASTM D 6352; 2) converting the boiling points to percentage weight distribution by carbon number, using the boiling points of n-paraffins reported in Table 1 of ASTM D 6352-98; 3) adding the 15 percent by weight of the feed with a carbon number of 30 or higher; 4) summing the weight percentage of the feed with a carbon number of 60 or higher; 5) dividing the sum of the weight percentage of the feed with a carbon number of 60 or higher by the sum of the weight percentage of the feed with a carbon number of 30 or higher. In other preferred embodiments of this invention, Fischer-Tropsch wax with a weight ratio of molecules with at least 60 carbon atoms to molecules with at least 30 carbon atoms lower than 0.15 or lower than 0.10 is used.

The boiling range distribution of the wash feed useful in the process of this invention can vary considerably. For example, the difference between the T90 and T10 boiling points, determined according to ASTM D 6352, may be greater than 95 ° C, greater than 160 ° C, greater than 200 ° C or even greater than 225 ° C.

Fischer-Tropsch synthesis and Fischer-Tropsch wax A preferred washing feed for this process is Fischer-Tropsch wax. Fischer-Tropsch wax is a product of a Fischer-Tropsch synthesis. During a Fischer-Tropsch synthesis, liquid and gaseous hydrocarbons are formed by contacting a synthesis gas (syngas) comprising a mixture of hydrogen and carbon monoxide with a Fischer-Tropsch under suitable reaction conditions of temperature and pressure. catalyst. The Fischer-Tropsch reaction is usually conducted at temperatures of about 150 ° C to about 370 ° C (about 300 ° F to about 700 ° F), preferably about 205 ° C to about 230 ° C (about 400 ° F up to about 550 ° F); pressures of about 0.7 to 41 bar (about 10 to about 600 psia), preferably 2 to 21 bar (30 to 300 psia) and catalyst space rates of about 100 to about 10,000 cm 3 / g / hour, preferably 300 to 3000 cm 3 / g / hour.

The products of the Fischer-Tropsch synthesis can range from C 1 to C 200 + 10 hydrocarbons, with the majority in the range of C 5 -C 100 +. The Fischer-Tropsch synthesis can be considered as a polymerization reaction. Using polymerization kinetics, the complete product distribution can be described with a simple, parameterized equation, referred to as the Ander-son-Schultz-Flory (ASF) distribution: 15 W "= (1-a) 2 xnxa" '1 where Wn the weight fraction of the product with carbon number is n and α is the ASF chain growth probability The higher the value of a, the longer the average chain length The ASF chain growth probability of the C20 + fraction of the Fischer-Tropsch wax according to the present invention is between about 0.85 and about 0.915.

The Fischer-Tropsch reaction can be conducted in a variety of reactor types, such as, for example, fixed-bed reactors containing one or more catalyst beds, suspension reactors, fluidized-bed reactors, or a combination of different types of reactors. Such reaction processes and reactors are known and documented in the literature. In the Fischer-Tropsch suspension process, which is preferred in the practice of the invention, use is made of superior heat (and mass) transfer characteristics for the highly exothermic synthesis reaction and paraffinic hydrocarbons having a relatively high molecular weight can be produced if a cobalt catalyst is used. In the slurry process, a syngas comprising a mixture of hydrogen and carbon monoxide is bubbled upwards as a third phase through a slurry comprising a particulate hydrocarbon synthesis catalyst of the Fischer-Tropsch type which is 1027828 '- ·· - · ..... .....

Dispersed and suspended in a suspending liquid comprising hydrocarbon products of the synthesis reaction which are liquid under the reaction conditions. The molar ratio of hydrogen to carbon monoxide can vary roughly from about 0.5 to about 4, but more usually is in the range of about 0.7 to about 2.75, and preferably from about 0.7 to about 2.5. A particularly preferred Fischer-Tropsch process is described in EP 0609079, which should also be considered as fully incorporated herein for all purposes.

Suitable Fischer-Tropsch catalysts include one or more Group VIII catalytic metals, such as Fe, Ni, Co, Ru, and Re, with cobalt being preferred. In addition, a suitable catalyst may contain a promoter. Thus, a preferred Fischer-Tropsch catalyst comprises effective amounts of cobalt and one or more of the metals Re, Ru, Pt, Fe, Ni, Th, Zr, Hf, U, Mg and La on a suitable inorganic carrier material, preferably a support material comprising one or more refractory metal oxides. In general, the amount of cobalt present in the catalyst is between about 1 and about 50 percent by weight of the total catalyst composition. The catalysts may also include basic oxide promoters such as ThC> 2, La 2 O 3, MgO and T 10 2, promoters such as ZrC> 2, noble metals (Pt, Pd, Ru, Rh, Os, Ir), coin metals (Cu, Ag, Au) and others contain transition metals such as Fe, Mn, Ni and Re. Suitable support materials include aluminum oxide, silicon dioxide, magnesium oxide, and titanium oxide or mixtures thereof. Preferred supports for cobalt-containing catalysts include titanium oxide. Useful catalysts and their preparation are known and are illustrated in U.S. Patent No. 4,566,863, which is intended as illustrative but non-limiting with regard to the choice of the catalyst.

25

Hydro-isomerization dewaxing

According to the present invention, a substantially paraffinic washing feed is dewaxed by hydroisomerization dewaxing under conditions sufficient to produce base lubricating oil with a desired composition of cycloparaffins and a moderate pour point. In general, the conditions for hydroisomerization dewaxing in the present invention are controlled such that the conversion of the compounds that boil at a temperature higher than about 1027828 16 700 ° F to the washing feed into compounds that boil at a temperature lower than about 700 ° F is kept between about 10% by weight and 50% by weight, preferably between 15% by weight and 45% by weight. Hydroisomerization dewaxing is intended to improve the cold flow properties of a base lubricating oil by selectively adding branching to the molecular structure. With hydroisomerization dewaxing, high conversion levels of waxy feed to non-waxy isoparaffins are ideally achieved while, at the same time, cracking conversion is minimized.

Hydroisomerization is carried out using a shape-selective molecular sieve with an average pore size. Hydroisomerization catalysts useful in the present invention include a shape selective molecular sieve with an average pore size and a hydrogenation component of a catalytically active metal on a refractory oxide support. The term "average pore size," as used herein, means a crystallographic free diameter in the range of about 3.9 to about 7.1 Angstroms when the porous inorganic oxide has a calcined form. The shape-selective molecular sieves with an average pore size used in the practice of the present invention are generally molecular sieves with a 1-D 10, 11 or 12 ring. The most preferred molecular sieves according to the invention are of the 1-20 D 10 ring variety, with molecular sieves having a 10 (or 11 or 12) ring 10 (or 11 or 12) tetrahedral coordinated atoms (T atoms) that are connected by oxygen atoms. In the 1-D molecular sieve, the 10-ring (or larger) pores are parallel to each other and do not form a mutual connection. It is noted, however, that 1-D 10-ring molecular sieves that meet the broader definition of the average pore size molecular sieve, but include intersecting pores with 8-membered rings, may also be encompassed by the definition of the molecular sieve according to the present invention. The classification of intrazeolite channels as 1-D, 2-D and 3-D is represented by R.M. Barrer in Zeo-lites, Science and Technology, published by F.R. Rodrigues, L.D. Rollman and C. 30 Naccache, NATO ASI Series, 1984, which classification in its entirety is to be regarded as inserted herein (see in particular page 75).

Preferred shape-selective molecular sieves with a medium pore size and used for hydroisomerization dewaxing are based on aluminum phosphates such as SAPO-11, SAPO-31 and SAPO-41. SAP0-11 and SAPO-31 are more preferred, with SAPO-11 being the most preferred. SM-3 is a particularly preferred shape-pore medium pore size SAPO and has a crystal structure that falls within that of the SAPO-11 molecular sieves. The preparation of SM-3 and its unique properties are described in U.S. Pat. Nos. 4,943,424 and 5,115,865. Preferred shape-selective molecular sieves with an average pore size and used for hydroisomerization dewaxing are zeolites such as ZSM. 22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, or fetite and ferrierite. SSZ-32 and ZSM-23 are more preferred. A preferred average pore size molecular sieve is characterized by selected crystallographic free diameters of the channels, selected crystal size (corresponding to a selected channel length) and selected acidity. Desired crystallographic free diameters of the channels of the molecular sieves are in the range of about 3.9 to about 7.1 Angstroms, with a maximum crystallographic free diameter of no more than 7.1 and a minimum crystallographic free diameter of no less then 3.9 Angstroms. Preferably, the maximum crystallographic free diameter is not greater than 7.1 and the minimum crystallographic free diameter is not less than 4.0 Angstroms. Most preferably, the maximum crystallographic free diameter is not greater than 6.5 and the minimum crystallographic free diameter is not less than 4.0 Angstroms. The crystallographic free diameters of the channels of the molecular sieves are published in the "Atlas of Zeolite Frame-work Types", fifth revised edition, 2001, of Ch. Baerlocher, W.M. Meier and D.H. Olson, Elsevier, pp. 10-15, which is incorporated herein by reference.

If the crystallographic free diameters of the channels of a molecular sieve are unknown, the effective pore size of the molecular sieve can be measured using standard adsorption techniques and hydrocarbonaceous compounds with known minimum kinetic diameters. See Breek, Zeolite Molecular Sieves, 1974 (in particular Chapter 8); Anderson et al., J. Catalysis 58, 114 (1979); and U.S. Patent No. 4,440,871, the relevant parts of which are incorporated herein by reference. Standard techniques are applied when conducting adsorption measurements to determine the pore size. It is appropriate to consider a particular molecule as excluded if it does not reach at least 95% of its equilibrium adsorption value on the molecular sieve in less than about 10 minutes (p / p0 = 0.5; 25 ° C). Molecular sieves with a medium pore size usually allow molecules with a kinetic diameter of 5.3 to 6.5 angstrom with little hindrance.

Preferred hydroisomerization dewaxing catalysts useful in the present invention have a sufficient acidity, so that 0.5 grams thereof, when placed in a tubular reactor, at 370 ° C, a pressure of 1200 psig, hydrogen flow rate of 160 ml / min and a feed rate of 1 ml / hour converts at least 50% hexadecane. The catalyst also exhibits an isomerization selectivity of 40 percent or higher (the isomerization selectivity is determined as follows: 100 x 10 (wt% branched C16 in product) / (wt% branched C16 in product + wt% C13. in product) when used under conditions leading to a conversion of 96% normal hexadecane (n-C10) to other species.

Hydroisomerization dewaxing catalysts useful in the present invention include a catalytically active hydrogenation noble metal. The presence of a catalytically active hydrogenation metal leads to product improvement, in particular viscosity index and stability. The noble metal platinum and palladium are particularly preferred, with platinum being very particularly preferred. When platinum and / or palladium is used, the total amount of the active hydrogenation metal is usually in the range of 0.1 to 5 weight percent of the total catalyst, usually 0.1 to 2 weight percent, and no more than 10 weight percent.

The carrier of a refractory oxide can be selected from those oxide supports that are commonly used for catalysts, including silica, aluminum oxide, silicon dioxide aluminum oxide, magnesium oxide, titanium oxide, and combinations thereof.

The conditions for hydroisomerization dewaxing depend on the feed that is used, the catalyst that is used, whether or not the catalyst is sulfurized, the desired yield and the desired properties of the basic lubricating oil. Conditions under which the hydroisomerization process of the present invention can be conducted include temperatures from about 315 ° C to about 399 ° C (about 600 ° F to about 750 ° F), preferably about 315 ° C to about 371 ° C (about 600 ° F to about 700 ° F); and pressures of about 15 to 3000 psig, preferably 100 to 2500 psig. The hydroisomerization dewaxing pressures in this context relate to the hydrogen partial pressure in the hydroisomerization reactor, although the hydrogen partial pressure is substantially the same (or substantially the same) as the total pressure. The fluid space velocity per hour during contacting is generally about 0.1 to 20 hours, preferably about 0.1 to about 5 hours. The ratio of hydrogen to hydrocarbon is in the range of about 1.0 to about 50 moles of ½ per mole of hydrocarbon, more preferably about 10 to about 20 moles of H 2 per mole of hydrocarbon. Suitable conditions for carrying out hydroisomerization are described in U.S. Patent Nos. 5,282,958 and 5,156,638, the contents of which are incorporated by reference in their entirety.

Hydrogen is present in the reaction zone during the hydroisomerization dewaxing process, usually in a hydrogen to feed ratio of about 0.5 to 30 MSCF / bbl (thousand standard cubic feet per vessel), preferably about 1 to about 10 MSCF / bbl. In general, hydrogen is separated from the product and returned to the reaction zone.

15

DVD treatment and DVD finishing

Hydrotreating refers to a catalytic process, usually carried out in the presence of free hydrogen, the primary purpose of which is the removal of various metal contaminants, such as arsenic, aluminum and cobalt; hetero atoms, such as sulfur and nitrogen; oxygen compounds; or aromatics from the diet. In general, in hydrotreating operations, cracking of the hydrocarbon molecules, i.e., degrading the larger hydrocarbon molecules into smaller hydrocarbon molecules, is minimized and the unsaturated hydrocarbons are either fully or partially hydrogenated. Waxy feed for the process of this invention is preferably hydrotreated for the hydroisomerization dewaxing.

Catalysts used in performing hydrotreating operations are known in the art. See, for example, U.S. Pat. Nos. 4,347,121 and 4,810,357, the contents of which are incorporated by reference in their entirety, for general descriptions of hydrotreating, hydrocracking, and of conventional catalysts used in each of the processes. Suitable catalysts include noble metals from group VIIIA

1027828 20 (according to the 1975 rules of the International Union of Pure and Applied Chemistry), such as platinum or palladium on an aluminum oxide or silicon containing matrix, and Group VIII and Group VIB metals, such as nickel-molybdenum or nickel-tin on a aluminum oxide or silicon-containing matrix. U.S. Pat. No. 3,852,207 describes a suitable noble metal catalyst and mild conditions. Other suitable catalysts are described, for example, in U.S. Pat. Nos. 4157294 and 3904513. The non-noble metal hydrogenation metals, such as nickel-molybdenum, are usually present as oxides in the final catalyst composition, but are usually used in the reduced or sulfurized forms thereof when such sulfide compounds are simply formed from the respective metal. Preferred non-noble metal catalyst compositions contain more than about 5 weight percent, preferably about 5 to about 40 weight percent molybdenum and / or tungsten, and at least about 0.5 and generally about 1 to about 15 weight percent nickel and / or cobalt, determined as the corresponding oxides. Catalysts containing noble metals, such as platinum, contain more than 0.01 percent metal, preferably between 0.1 and 1.0 percent metal. Combinations of noble metals can also be used, such as mixtures of platinum and palladium.

Conventional hydrotreating conditions vary over a wide range. In general, the total LHSV is about 0.25 to 2.0, preferably about 0.5 to 1.5. The hydrogen partial pressure is higher than 200 psia and preferably ranges from about 500 to 2000 psia. Hydrogen recycle amounts are usually higher than 50 SCF / Bbl and are preferably between 1000 and 5000 SCF / Bbl. Temperatures range from about 150 ° C to about 400 ° C (about 300 ° F to about 750 ° F) and preferably range from 230 ° C to 385 ° C (450 ° F to 725 ° F).

Hydrotreating is used as a step after hydroisomerization dewaxing in the preparation process of the base lubricating oil of this invention. This step, referred to herein as hydrofinishes, is intended to improve oxidation stability, UV stability and the appearance of the product by removing trace amounts of aromatics, olefins, color bodies and solvents. As used herein, the term UV stability refers to the stability of the base lubricating oil or finished lubricant upon exposure to UV light and oxygen. Instability is indicated when a visible precipitate is formed, which is usually observed as flakes or turbidity, or a darker color develops upon exposure to ultraviolet light and air. A general description of hydrofinishes can be found in U.S. Pat. Nos. 3,852,207 and 46,73487. Treating with clay to remove these contaminants is an alternative final process step.

Fractionation:

Optionally, the process of this invention may include fractionation of the substantially paraffinic wash feed for hydroisomerization dewaxing or fractionation of the base lubricating oil. The fractionation of the essentially paraffinic washing feed or base lubricating oil into distillate fractions usually takes place by either atmospheric or vacuum distillation, or by a combination of atmospheric and vacuum distillation. Atmospheric distillation is usually used to separate the lighter distillate fractions, such as naphtha and middle distillates, from a bottom fraction with an initial boiling point higher than about 315 ° C to about 399 ° C (about 600 ° F to about 750 ° F). At higher temperatures, thermal cracking of the hydrocarbons can occur, which leads to contamination of the equipment and to lower yields of the heavier fractions. Vacutime distillation is usually used to separate the higher boiling material, such as the base lubricating oil fractions, into fractions with a different boiling range. By fractionating the basic lubricating oil into fractions with a different boiling range, the production plant for basic lubricating oil can produce basic lubricating oils of more than one quality, or viscosity.

25

Solvent dewaxing:

Solvent dewaxing may optionally be used to remove small amounts of residual wax-like molecules from the base lubricating oil after hydroisomerization dewaxing. Solvent dewaxing takes place by dissolving the base lubricating oil in a solvent such as methyl ethyl ketone, methyl isobutyl ketone or toluene, or precipitating the wash molecules as discussed in Chemical Technology of Petroleum, third edition, William Gruse and Donald Stevens, McGraw-Hill 1027828 22

Book Company, Ine., New York, 1960, pages 566 to 570. See also U.S. Patent Nos. 4,477,333, 3773650, and 3775288.

Hydrocarbon composition of the basic lubricating oil: 5

The base lubricating oils of this invention contain more than 95 percent by weight of saturated compounds, as determined by elution column chromatography, ASTM D 2549-02. Alkenes are present in amounts smaller than can be detected by long-term C13 nuclear magnetic resonance spectroscopy (NMR). Molecules with at least one aromatic function are present in amounts less than 0.3 weight percent by HPLC-UV, and confirmed by ASTM D 5292-99 which has been modified to measure small amounts of aromatics. In preferred embodiments, molecules with at least one aromatic function are present in amounts less than 0.10 weight percent, preferably less than 0.05 weight percent, more preferably less than 0.01 weight percent. Sulfur is present in an amount of less than 25 ppm, more preferably less than 1 ppm, as determined by ultraviolet fluorescence according to ASTM D 5453-00.

Measurement of the aromatic content according to HPLC-UV: 20

In the method used to measure small amounts of molecules with at least one aromatic function in the base lubricating oils of this invention, a Hewlett Packard 1050 Series Quatemary Gradient High Performance Liquid Chromatography (HPLC) system is coupled to an HP 1500 Diode -Array UV-VIS detector, which is coupled to an HP Chem station, used. Identification of the individual aromatic classes in the highly saturated base lubricating oils was based on the pattern in its UV spectrum and its elution time. The amino column used for this analysis largely distinguishes between aromatic molecules based on their ring number (or rather the number of double bonds). Thus, the molecules containing a single ring aromatic elute the former, followed by the polycyclic aromatics in order of the increasing number of double bonds per molecule. For aromatics 1027828 23 with a similar character of the double bond, those with only an alkyl substitution on the ring elute rather than those with a naphthene substitution.

Non-equivocal identification of the various aromatic hydrocarbons of the base oil via its UV absorption spectra was made somewhat more complicated by the fact that the maximum electronic transitions thereof had all undergone a redshift compared to the pure analogs of the model compound to an extent dependent on the amount of alkyl and naphthenic substitution on the ring system. It is known that these bathochromic shifts are caused by the delocalization by the alkyl groups of the π electrons in the aromatic ring. Because few unsubstituted aromatic compounds boil in the lubricant range, some degree of redshift was expected and observed for all major aromatic groups identified.

Quantifying the elution of aromatic compounds was accomplished by integrating 1S chromatograms made of wavelengths optimized for each general class of the compounds over the respective retention time window for that aromatic compound. The limits of the retention time window for each aromatic class were determined by manually evaluating the individual absorption spectra of eluting compounds at different times and assigning them to the respective aromatic class based on their qualitative similarity with absorption spectra of model connections. With a few exceptions, only five classes of aromatic compounds were observed in highly saturated API group II and III base lubricating oils.

HPLC UV calibration: HPLC UV is used to identify these classes of aromatic compounds even at very small amounts. Multicyclic aromatics usually absorb 10 to 200 times stronger than monocyclic aromatics. Alkyl substitution also affected absorption by approximately 20%. Therefore, it is important to use HPLC to separate and identify the different aromatic species and to know how efficiently they absorb.

10278 ^ 8 24

Five classes of aromatic compounds were identified. With the exception of a slight overlap between the highest-retained alkyl 1-ring aromatic naphthenes and the least-retained alkyl naphthalenes, all classes of the aromatic compounds had baseline resolution. Integration limits for the co-eluting 1-ring and 2-ring aromatics at 272 nm took place according to the perpendicular drop method. Wavelength-dependent response factors for each general class of aromatics were first determined by constructing graphs of the Beer van Beer from mixtures of pure model compounds based on the closest spectral peep absorptions for the substituted aromatic analogs.

For example, alkylcyclohexylbenzene molecules in base oils exhibit a clear peak absorption at 272 nm corresponding to the same (forbidden) transition that unsubstituted tetraline model compounds have at 268 nm. The concentration of alkyl 1-ring aromatic naphthenes in base oil samples was calculated by assuming that the molar absorption response factor at 272 nm thereof was approximately equal to the molar absorption of tetralin at 268 nm, calculated from graphs of the Beer van Beer . Weight percent concentrations of aromatics were calculated by assuming that the average molecular weight for each class of aromatics was approximately equal to the average molecular weight for the entire base oil sample.

This calibration method was further improved by directly isolating the 1-20 ring aromatics from the base lubricating oils via extensive HPLC chromatography. Direct calibration with these aromatics eliminated the assumptions and uncertainties associated with the model compounds. As expected, the isolated aromatic sample had a lower response factor than the model compound because it was substituted to a greater extent.

More specifically, to accurately calibrate the HPLC UV method, the substituted benzene aromatics were separated from most of the basic lubricating oil using a semi-preparative HPLC unit from Waters. 10 grams of sample was diluted 1: 1 in n-hexane and injected into an amino-bonded silica column, a 5 cm x 22.4 mm ID protection followed by two 25 cm x 22.4 mm ID columns of 8- 12 microns of amino-bonded silica particles produced by Rainin Instruments, Emeryville, California, with n-hexane as the mobile phase at a flow rate of 18 ml / min. The column eluent was fractionated based on the detector response of a UV wavelength detector with 1027828 double wavelength set at 265 nm and 295 nm. Saturated fractions were collected until the absorbance at 265 nm showed a change of 0.01 absorption units, which signaled the start of the elution of monocyclic aromatics. A monocyclic aromatic fraction was collected until the absorption ratio between 265 nm and 295 nm decreased to 2.0, indicating the beginning of the elution of the bicyclic aromatics. Purification and separation of the monocyclic aromatic fraction was accomplished by rechromatographing the monoaromatic fraction of the "lagging" fraction with saturated compounds resulting from the HPLC column overloading.

This purified aromatic "standard" showed that alkyl substitution reduced the molar absorption response factor by about 20% relative to the unsubstituted tetralin.

Confirmation of aromatics by NMR: 15

The weight percentage of all molecules with at least an aromatic functional level in the purified monoaromatic standard was confirmed by long-term carbon 13 NMR analysis. NMR was easier to calibrate than HPLC-UV because it simply measured aromatic carbon and therefore the response was not dependent on the class of aromatics being analyzed. The NMR results were translated from% aromatic carbon to% aromatic molecules (so that this corresponds to HPLC-UV and D 2007) by knowing that 95-99% of the aromatics in the highly saturated base lubricating oils were monocyclic aromatics.

A high power, a long duration and a good baseline analysis were necessary for the accurate measurement of aromatics to as few as 0.2% aromatic molecules.

More specifically, for accurately measuring small amounts of all molecules with at least one aromatic function by NMR, the standard method D 5292-99 was modified to give a minimum carbon sensitivity of 500: 1 (according to ASTM standard method E 386). A test with a duration of 15 hours was used on a 400-500 MHz NMR with a Nalorac probe of 10-12 mm. Acom PC integration software was used to define the shape of the baseline and consistent integration. The carrier frequency was changed once during the test to prevent artifacts from forming an image of the aliphatic peak in the aromatic region. By taking spectra on both sides of the carrier spectra, the resolution was significantly improved.

5 Cycloparaffin distribution according to FIMS:

Paraffins are considered more stable than cycloparaffins with respect to oxidation and are therefore more desirable. Monocycloparaffins are considered more stable than multicycloparafins with regard to oxidation. However, if the weight percentage of all molecules with at least one cycloparaffin function is very low in a base lubricating oil, the additive solubility is low and the elastomer compatibility is poor. Examples of base oils with these properties are poly-alpha olefins and Fischer-Tropsch base oils (GTL base oils) with less than about 5% cycloparaffins. In order to improve these properties with ready lubricants, expensive co-solvents such as esters often have to be added. According to this invention, basic lubricating oils with a high weight percentage of molecules containing monocycloparaffins and a low weight percentage of molecules containing multicycloparaffins are achieved, so that they have a high oxidation stability and a high viscosity index in addition to good additive solubility and compatibility with elastomers.

The distribution of the saturated compounds (n-paraffin, isoparaffin and cycloparaffins) in base lubricating oils of this invention is determined by field ionization mass spectroscopy (FIMS). FIMS spectra were obtained with a VG 70VSE mass spectrometer. The samples were introduced via a fixed probe, which was heated at a rate of 50 ° C per minute from 40 ° C to 500 ° C. The mass spectrometer was scanned at a speed of 5 seconds per decade from m / z 40 to m / z 1000. The mass spectra obtained were added to generate an "average" spectrum. Each spectrum was corrected for C13 using a software package from PC-MassSpec. The FIMS ionization efficiency was evaluated using mixtures of substantially pure branched paraffins and highly naphthenic, aromatic-free base fractions. The ionization efficiencies of isoparaffins and cycloparaffins in these base oils were almost the same. Isoparaffins and 1027828 - ·· «** .....

27 cycloparafins comprise more than 99.9% of the saturated compounds in the base lubricating oils of this invention.

The basic lubricating oils of this invention are characterized by FIMS to paraffmen and cycloparafins containing a different number of rings. Monocy-cloparaffins contain one ring, dicycloparaffins contain two rings, tricycloparafins contain three rings, tetracycloparaffins contain four rings, pentacycloparaffins contain five rings and hexacycloparaffins contain six rings. Cycloparafifines with more than one ring are referred to in this invention as multicycloparaffins.

In one embodiment, the base lubricating oils of this invention have a weight percentage of all molecules with at least a cycloparafin function higher than 10, preferably higher than 15, more preferably higher than 20. They have a ratio of weight percentage of molecules containing monocycloparafins to weight percentage of molecules containing multicycloparaffins higher than 15, preferably higher than 50, more preferably higher than 100. The most preferred base lubricating oils of this invention have a weight percentage of molecules containing monocycloparaffins higher than 10 and a weight percentage of molecules containing multicycloparaffins contain less than 0.1 or even no molecules that contain multicycloparaffins. In this embodiment, the base lubricating oils can have a kinematic viscosity at 100®C between about 2 cSt and about 20 cSt, preferably between about 2 cSt and about 12 cSt, most preferably between about 3.5 cSt and about 12 cSt to have.

In another embodiment of this invention, there is a relationship between the weight percent of all molecules with at least one cycloparafin function and the kinematic viscosity of the base lubricating oils of this invention. That is, the higher the kinematic viscosity at 100 ° C in cSt, the higher the amount of all molecules with at least one cycloparaffin function that are obtained. In a preferred embodiment, the base lubricating oils have a weight percentage of all molecules with at least one cycloparaffin function higher than the kinematic viscosity in cSt multiplied by three, preferably higher than 15, more preferably higher than 20; and a ratio of weight percentage of molecules containing monocycloparaffins to weight percentage of molecules containing multicycloparaffins higher than 15, preferably higher than 50, more preferably higher than 100. The base lubricating oils have a kinematic viscosity at 100 ° C between approximately 1027828 28 spring 2 cSt and about 20 cSt, preferably between about 2 cSt and about 12 cSt. Examples of these base oils may have a kinematic viscosity at 100 ° C between about 2 cSt and about 3.3 cSt and have a weight percentage of all molecules with at least a cycloparaffin function that is very high but less than 5 weight percent.

The modified ASTM D 5292-99 and HPLC-UV test methods used to measure small amounts of aromatics and the FIMS test method used to characterize saturated compounds are described in DC Kramer et al., "Influence of Group II & III Base Oil Composition on 10 VI and Oxidation Stability ", presented at the 1999 AlChE Spring National Meeting in Houston, March 16, 1999, the contents of which are incorporated herein in their entirety.

Although the washing feeds of this invention are essentially free of olefins, basic oil processing techniques can introduce olefins, particularly at high temperatures, due to "cracking" reactions. In the presence of heat or UV light, olefins can polymerize and form products with a higher molecular weight that can color the base oil or cause settling. Generally, olefins can be removed during the process of this invention by hydrofinishing or by treatment with clay.

20

Basic oil flow factor

In preferred embodiments, the base lubricating oils of this invention have a ratio of pour point in degrees Celsius to kinematic viscosity at 100 ° C in cSt higher than the base oil flow factor of the base lubricating oil. The base oil flow factor is a function of the kinematic viscosity at 100 ° C and is calculated from the following equation: Base oil flow factor = 7.35 x ln (kinematic viscosity at 100 ° C) - 18, where ln (kinematic viscosity) is the natural logarithm with basis "e" of the kinematic viscosity at 100 ° C, measured in centistokes (cSt). The test method used to measure the pour point is ASTM D 5950-02. The pour point is determined in increments of one degree. The test method used to measure the kinematic viscosity is ASTM D 445-01. A graph of this comparison is shown in Figure 1.

VO 27828 29

This relationship between the pour point and the kinematic viscosity in preferred embodiments of this invention also defines the preferred lower limit of the pour point in degrees Celsius for each viscosity of the oil.

For preferred examples of the base lubricating oils of this invention, the lower limit of the pour point is at a given kinematic viscosity at 100 ° C = base oil flow factor x kinematic viscosity at 100 ° C. Thus, the lower limit of the pour point for a preferred 2.5 cSt base lubricating oil is -28 ° C, for a preferred 4.5 cSt base lubricating oil, -31 ° C for a 6.5 cSt base lubricating oil that is -28 ° C is preferred and for a 10 cSt base lubricating oil preferred is -11 ° C. By choosing moderately low pour points, we have oils that are not over-dewaxed and that can be produced in high yields. In most cases, the pour points of the base lubricating oils of this invention are between -35 ° C and + 10 ° C.

In preferred embodiments, the high ratio of pour point to kinetic viscosity at 100 ° C controls the pour point in a range that is moderately low, thus requiring no heavy dewaxing. Due to the vigorous dewaxing required to produce basic lubricating oils with a high content of cycloparaffins and very low pour points according to the prior art, the ratio of monocyclopa-raffins to multicycloparaffins was lowered, and what is perhaps most important was the total yield base lubricating oil and finished lubricant produced.

There is not necessarily a relationship between the base oil flow factor and the desired cycloparaffin composition between the base oils prepared by different production processes. Each desired property of the base lubricating oil of this invention should be independently selected until a relationship can be determined for a specific production process.

The base oils of this invention respond favorably to the addition of; conventional pour point lowering agents. Because of this favorable interaction, it is not necessary to over-dewash them to very low pour points, which is advantageous for the yield. By adding a pour point lowering agent, they can be mixed into products that meet the strict requirements for good low temperature properties, such as motor oil for cars.

10278 * 8 30

Other properties of the basic lubricating oil Viscosity index: The viscosity indices of the basic lubricating oils according to this invention are high.

In a preferred embodiment, they have viscosity indices higher than 28 x ln (kinematic viscosity at 100 ° C) + 95. For example, an oil of 4.5 cSt has a viscosity index higher than 137, and an oil of 6.5 cSt has a viscosity index higher than 147. In another preferred embodiment, the viscosity indices are higher than 28 x ln (kinematic viscosity at 100 ° C) + 110. The test method used for measuring the viscosity index is ASTM D 2270-93 (1998).

Aniline point: The aniline point of a basic lubricating oil is the temperature at which a mixture of aniline and oil separates. ASTM D 611-01b is the method used to measure the aniline point. This provides a rough indication of the solubility of the oil for materials in contact with the oil, such as additives and elastomers. The lower the aniline point, the greater the dissolving power of the oil. Basic lubricating oils according to the state of the art with a weight percentage of all molecules with at least an aromatic function lower than 0.30, prepared from a substantially paraffinic washing feed with less than about 30 ppm total combined nitrogen and sulfur and hydroisomerization dewaxes have high aniline points and therefore poor additive solubility and elastomer compatibility. The larger amounts of all molecules with at least one cycloparaffmeal function in the base lubricating oils of this invention lower the aniline point and thus improve additive solubility and elastomer compatibility. The aniline point of the base lubricating oils of this invention varies depending on the kinematic viscosity of the base lubricating oil at 100 ° C in cSt.

In a preferred embodiment, the aniline point of the base lubricating oils of this invention is lower than a function of the kinematic viscosity at 100 ° C. The function for the aniline point is preferably represented as follows: Aniline 1027828 31 point <36 x ln (kinematic viscosity at 100 ° C) + 200, in ° F. A graph of this comparison is shown in Figure 2.

Oxidation stability: 5

Due to the extremely low content of aromatics and multicycloparaffins in the base lubricating oils of this invention, their oxidation stability exceeds that of most base lubricating oils.

A simple way to measure the stability of base lubricating oils is by applying the Oxidator BN Test, as described by Stangeland et al. In U.S. Patent No. 3,852,207. The Oxidator BN test measures the resistance to oxidation by means of an oxygen Domte type absorption device. See R.W. Domte, "Oxidation of White Oils," Industrial and Engineering Chemistry, Vol. 28, page 26, 1936. Normally, the conditions are an atmosphere of pure oxygen at 340 ° F. The results are reported in hours for absorbing 1000 ml of O2 by 100 g of oil. In the Oxidator BN test, 0.8 ml of catalyst is used per 100 grams of oil and an additive package is included in the oil. The catalyst is a mixture of soluble metal naphlenates in kerosene. The mixture of soluble metal naphthenates stimulates the average metal analysis of used crankshaft oil. The metal content in the catalyst is as follows: copper = 6.927 ppm; iron = 4,083 ppm; lead = 80,208 ppm; manganese = 350 ppm; tin = 3565 ppm. The additive package is 80 millimoles of zinc bispolypropylene phenyldithiophosphate per 100 grams of oil, or about 1.1 grams of OLOA 260. The Oxidator BN test measures the response of a base lubricating oil in a simulated application. High values, or long times for absorbing 25 liters of oxygen, indicate good oxidation stability. Traditionally the Oxidator BN should be higher than 7 hours. For the present invention, the Oxidator BN value of the base lubricating oil is higher than about 30 hours, preferably higher than about 40 hours.

OLOA is an acronym for Oronite Lubricating Oil Additive®, which is a registered trademark of Chevron Oronite.

1-0278 * 8 32

Noack volatility:

Another important property of the basic lubricating oils of this invention is low Noack volatility. Noack volatility is defined as the amount of oil, expressed as a percentage by weight, that is lost when the oil is heated at 20 mmHg (2.67 kPa; 26.7 mbar) under atmospheric pressure at 250 ° C in a test crucible allowing 60 a constant airflow is fed for minutes (ASTM D 5800). A more common method for calculating the Noack volatility and one that corresponds well with ASTM D-5800 is to use a thermogravimetric analysis test (TGA) according to ASTM D 6375-99a. Unless otherwise stated, TGA Noack volatility is used in this description.

In preferred embodiments, the base lubricating oils of this invention have a Noack volatility that is lower than the amount calculated from the equation: Noack volatility, wt% = 1000 x (kinematic viscosity at 100 ° C), 2.7, at preferably lower than the amount calculated with the comparison: Noack volatility, wt% = 900 x (kinematic viscosity at 100 ° C) 2.8. Graphs of these comparisons are shown in Figure 3.

CCS viscosity: 20

The basic lubricating oils of this invention also have excellent low temperature and high shear viscometric properties, making them extremely suitable for use in multigrade engine oils. The cold ventilation simulator apparent viscosity (CCS VIS) is a test that is used to measure the viscometric properties of base lubricating oils under low temperature and high shear. The test method for determining CCS VIS is ASTM D 5293-02. The results are reported in centipoise, cP. CCS VIS was found to correspond to the venting of an engine at low temperature. Specifications for the maximum CCS VIS are defined for engine oils by SAE J300, revised in June 2001. The 30 CCS VIS of the basic lubricating oils of this invention measured at -,

35 ° C are low, preferably lower than an amount calculated from the equation: CCS VIS (-35 ° C), cP = 38 x (kinematic viscosity at 100 ° C) 3, more preferably lower than an amount that is calculated with the comparison: CCS VIS

1 02782.8 33 (-35 ° C), cP = 38 x (kinematic viscosity at 100 ° C) 2.8. Graphs of these comparisons are shown in Figure 4.

Compatibility with elastomers: 5

Basic lubricating oils come into direct contact with seals »gaskets and other equipment components during use. The producers of original equipment and standard-determining organizations determine the specifications for compatibility with elastomers for different types of finished lubricants. Examples of tests for compatibility with elastomers are CEC L-39-T-96 and ASTM D 4289-03. An ASTM standard with the title "Standard Test Method and Suggested Limits of Determining the Compatibility or Elastomer Seals for Industrial Hydraulic Fluid Applications" is currently being developed. Test methods for compatibility with elastomers include suspending a rubber sample of known volume under fixed conditions of temperature and duration of the test in the base lubricating oil or the finished lubricant. This is followed at the end of the test by a second measurement of the volume to determine the percentage of swelling that has taken place. Additional measurements of the changes in elongation at break and the tensile strength can be made. Depending on the type of rubber and the application, the test temperature can vary significantly. The base lubricating oils of this invention are compatible with a large number of elastomers, including, but not limited to, the following: neoprene, nitrile (acrylonitrile butadiene), hydrogenated nitrile, polyacrylate, ethylene-acrylic, polysiloxane, chlorosulfonated polyethylene, ethylene propylene copolymers, epichlorohydrin, fluorocarbon, perfluoroether and PTFE. All publications, patents, and patent applications cited in this application are to be incorporated by reference in their entirety to the same extent as if the description of each individual publication, patent application, or patent in particular and in its entirety is incorporated herein in its entirety. .

1027828 34

Examples

The following examples are provided to further illustrate the invention, but are not to be construed as limitations on the scope of the invention.

Fischer-Troosch wax

Two commercially available samples of hydrotreated Fischer-Tropsch wax prepared using a Fe-based Fischer-Tropsch synthesis catalyst (WOW8684 and NGQ9989) and three sample of hydrotreated Fischer-Tropsch wax prepared under use of a Co-based Fischer-Tropsch synthesis catalyst (WOW8782, WOW9107 and WOW9237) were analyzed and found to have the properties shown in Table I.

Table I

F ischer-T ropsch wax

Fischer-Tropsch-kataly- On Fe On Fe On Co On Co On Co sator based based based based based based CVX Sample ID WOW8684 NGQ9989 WOW8782 WOW9107 WOW9237

Sulfur, ppm 7, <2 <6 2

Nitrogen, ppm 2,4,4,1,4,7 12, 19 6, 5, 13

Oxygen according to 0.15 0.69 Ö39 ÖJ1 NA, wt% GC N-Paraffin analysis Total N-paraffin, wt% 92.15 83.72 84.47

Avg carbon number 41.6 30.7 27.3

Avg molecular weight 585.4 432.5 384.9

D 6352 SIMDIST TBP (% by weight), ° F

TÖ3 784 FÖ29 29-545Ö T5 853 Ï3Ï 568 597 571 TÖÖ 875 Ï8Ï 625 639 62I 1027828 35

Fischer-Tropsch-cataly- On Fe On Fe On Co On Co On Coator based based based based based based T2Ö 914 251 674 689 683 T3Ö 941 3Ö9 717 7I4 713 T4Ö 968 377 756 75I 752 T5Ö 995 437 792 774 788 T6Ö ÏÖÏ3 497 827 807823 T7Ö ÏÖ3Ï 553 873 839 868 T80 ÏÖ5Ï 6Ï1 9Ï4 870 ~ 9ÏÏ T9Ö ÏÖ8Ï 9ÏÏ 674 965 970 T95 ÏTÖ7 7Ö7 ÏÖ05 935 ÏÖÖ3 T993 ÏÏ33 744 ÏÖ9Ö 978 ÏÖ67 T90-T10, ° C 97 256 Ï7Ï Ï3Ï I76

% By weight of C30 + 96%, 4p6 34 ^ 9 39 ^ 78

% By weight C60 + Öi55 <MK) 0 ^ 00 Ö ^ ÖÖ Ö ^ ÖÖ C60 + / C30 + ö ^ öi öw m pö m

The Fischer-Tropsch wash feeds were hydroisomerized over a Pt / SSZ-32 catalyst or Pt / SAPO-11 catalyst on an alumina binder. The conditions of the test were a temperature between 344 and 368 ° C (652 and 5 695 ° F), LHSV 0.6 to 1.0, a reactor pressure of 300 psig or 1000 psig and a hydrogen flow rate during a single throughput between 6 and 7 MSCF / bbl. For the majority of the samples, the reactor fluids went directly to a second reactor, also at 1000 psig, which contained a Pt / Pd-on-silica-alumina hydrofinish catalyst. Conditions in that reactor were a temperature of 450 ° F and an LHSV of 1.0. Those samples that were not subjected to hydrofinishes are shown in the tables of the properties that follow.

The products boiling at a temperature higher than 650 ° F were fractionated by atmospheric or vacuum distillation to produce distillate fractions with different viscosities. Test data of specific distillate fractions useful as base lubricating oils of this invention, and comparison samples, are shown in the following examples.

1027828 36

Basic lubricating oils

Example 1, example 2 and comparative example 3:

5 Three basic lubricating oils with kinematic viscosities lower than 3.0 cSt at 100 ° C

were prepared by hydroisomerization dewaxing of Fischer-Tropsch wax and fractionation of the isomerized oil in different distillate fractions. The properties of these samples are shown in Table II.

Table II

Properties Example 1 Example 2 Comparative example 3 CVX Sample ID PGQ0118 PGQ1117 NGQ9637

Washing food NGQ9989 NGQ9989 WOW9107

Hydroisomerization temp. ° F 681 681 671

Hydroisomerization dewaxing catalyst Pt / SAPO-11 Pt / SAPO-11 Pt / SAPO-11

Reactor pressure, psig 1000 1000 1000

Viscosity at 100 ° C, cSt 2,981 2,598 2,297

Viscosity index 127 124 124

Aromatics,% 0.0128 0.0107 FIMS,% by weight of the molecules

Parafins 89.2 91.1 91.3

Monocycloparaffins 10.8 8.9 8.0

Multicycloparaffins 0.0 0.0 0.7

Total 100.0 100.0 100.0 API specific gravity 43.4 44.1 44.69

Pour point, ° C 47 -32 Ö3

Cloud point, ° C -18 -22 -7

Ratio of> 100> 100 11.4 mono / multicycloparafins

Ratio of pour point / Vis 100 -9.1 -12.3 -14.4

Basic oil flow factor -9.97 -10.98 -11.89

Aniline point, D 611, F 236.5 226.3

Noack volatility,% by weight 32.48 49.18 CCS viscosity @ -35 ° C, cP <900 <900 <900 1027828 37

Example 1 and Example 2 have low weight percentages of all molecules with at least one aromatic function, high weight percentages of all molecules with at least one cycloparaffin function and a very high ratio of the weight percent of molecules containing monocycloparaffins and the weight percent molecules that contain multicycloparaffins. Note that Example 1 contains no more than 10 weight percent of all molecules with at least one cycloparaffin function, but it has a weight percentage of all molecules with at least one cycloparaffin function higher than the kinematic viscosity at 100 ° C multiplied by three. Example 1 also has a high ratio of pour point to kinetic viscosity at 100 ° C, thereby satisfying the properties of a preferred base lubricating oil according to this invention. In addition, the ani-line points of Examples 1 and 2 fall below the line given by: 36 x ln (kinematic viscosity at 100 ° C) + 200. Comparative Example 3 has a slightly lower percentage by weight of all molecules with at least a cycloparaffin function.

Comparative example 3 also has a less desirable ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage of molecules containing multicycloparaffins and a lower ratio of pour point to kinematic viscosity which is less preferred. These examples demonstrate that a low viscosity base lubricating oil of this invention, with a kinematic viscosity at 100 ° C between 2 and about 3.3 cSt, can contain less than 10 weight percent of all molecules with at least a cycloparaffin function, but has a weight percentage of all molecules with at least one cycloparaffin function higher than 3 times the kinematic viscosity at 100 ° C.

Example 4, example 5, example 6 and example 7:

Four base lubricating oils with kinematic viscosities between 4.0 and 5.0 cSt at 100 ° C were prepared by hydroisomerization dewaxing of Fischer-Tropsch wax and fractionation of the isomerized oil in different distillate fractions. The properties of these samples are shown in Table III.

1027828 38

Table ΠΙ

Properties Example 4 Example 5 Example 6 Example 7 CVX Sample ID NGQ9712 PGQ1118 NGQ9608 NGQ9939

Washing food WOW9107 WOW9237 WOW8782 WOW8684

Hydroisomerization temp. ° F 673 652 700 682

Hydroisomerization dewaxing Pt / SAPO-11 Pt / SAPO-11 Pt / SAPO-11 Pt / SAPO-11 talysator

Reactor pressure, psig 1000 300 1000 1000 V iscosity at 100 ° C, cSt 4,104 4,397 4,415 4,524

Viscosity index 145 158 147 149

Aromatics,% 0.0086 0.0109 FIMS,% by weight of the molecules

Parafims 88.4 79> g 89.1 89.4

Monocycloparaffins H6 2, 12> 9 I04

Multicycloparaffmen "" 0> 0 "" 0> 2

Total 100.0 100.0 100.0 100.0 API specific gravity 41.78 41.6

Pour point, ° C 3Ö 31 Λ2 -17

Cloud point, ° C 3 +3 3 3Ö

Ratio of mono / multi-> 100> 100> 100 52 cycloparaffins

Ratio of pour point / Vis -4.87 -7.05 -2.72 -3.76 100

Base oil flow factor -7.62 -7.12 -7.09 -6.91

Oxidator BN, hour 40.78 26.0 41.35 34.92

Aniline point, D611, ° F 249.6 253.2

Noack volatility, wt% 14.43 10.89 12.53 CCS Viscosity @ -35C, cP 66662 2Ö79 2Ö9Ö

Examples 4, 5, 6 and 7 all had the desired properties of the basic lubricating oils of this invention. Examples 4 and 7 had exceptionally high oxidation stabilities, more than 40 hours. Examples 4 and 7 also had low aniline points, which provides a desired additive solubility and elastomer compatibility.

Example 8, comparative example 9, example 10 and example 11: 5

Four base lubricating oils with kinematic viscosities between 6.0 and 7.0 cSt at 100 ° C were prepared by hydroisomerization dewaxing of Fischer-Tropsch wax and fractionating the isomerized oil in different distillate fractions. The properties of these samples are shown in Table IV.

10

Table VI

Properties Example 8 Comparative Example 10 Example 11 Example 9 * CVX Sample ID NGQ9994 NGQ9289 NGQ9941 NGQ9988

Washing food WOW8684 WOW8684 WOW8684 WOW8684

Hydroisomerization temperature, ° F 676 685 690 681

Hydroisomerization dewaxing Pt / SAPO-11 Pt / SSZ-32 * Pt / SAPO-11 Pt / SAPO-11 catalyst

Reactor pressure, psig 1000 1000 1000 1000

Viscosity at 100 ° C, cSt 6.26 6.972 6.297 6.295

Viscosity index 158 153 153 154

Aromatics,% 0.0898 0.0141 FIMS,% by weight of the molecules

Paraffins 77.0 71.4 82.5 76.8

Monocycloparaffins 22.6 26.4 17.5 22.1

Multicycloparaffins 0.4 2.2 0.0 1.1

Total 100.0 100.0 100.0 100.0 API specific gravity 40.3 40.2 40.2

Pour point, ° C -12 -41 -23 -14

Cloud point, ° C -1 -2 -6 -6

Ratio of mono / mullet 56.5 12.0> 100 20.1 ticycloparaffins, i

Flow pipe ratio / -1.92; -5.89 -3.65 -2.22

Fish 100 1 0278 ^ 8 40

Properties Example 8 Comparative Example 10 Example 11 Example 9 *

Basic oil flow factor -4.52 -3.73 -4.48 -4.48

Aniline tip, D611, ° F 263

Noack volatility,% by weight 2.3 5.5 2.8 3.19 CCS Vis® -35C, cP 577Ö 5993 4868 5ÖÖ2 * no hydrophinishes

Examples 8, 10 and 11 are examples of basic lubricating oils of this invention. Comparative Example 9 has a low ratio of molecules containing monocycloparaffins to molecules containing multicycloparaffins. In this comparative example, the hydroisomerization washing to produce a very low pour point base oil takes place with a yield disadvantage, and this probably had an adverse effect on the ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage molecules that contain multicycloparaffins. Comparative example 9 also had a higher Noack-10 volatility than the other oils with a corresponding viscosity. Examples 8, 10 and 11 all had very low CCS VIS at -35 ° C, much lower than the amount calculated with 38 x ln (kinematic viscosity at 100 ° C) 2.8.

Example 12, comparative example 13, example 14 and example 15: 15

Four base lubricating oils with kinematic viscosities between 7.0 and 8.0 cSt at 100 ° C were prepared by hydroisomerization dewaxing of Fischer-Tropsch wax and fractionation of the isomerized oil in different distillate fractions. The properties of these samples are shown in Table V.

20

Table V

Properties Example 12 Comparative Example 14 Example 15 Example 13 CVX Sample ID NGQ9287 NGQ9288 NGQ9284 NGQ9535

Washing food WOW8684 WOW8684 WOW8684 WOW8782

Hydroisomerization temp. ° F 679 685 674 694 1027828 41

Hydroisomerization dewaxing Pt / SSZ-32 Pt / SSZ-32 Pt / SSZ-32 Pt / SAPO-11 catalyst

Reactor pressure, psig 1000 1000 1000 1000

Viscosity at 100 ° C, cSt in 7 ^ 023 7,468 7 ^ 953

Viscosity index 159 155 170 165

Aromatics,% by weight 0.0056 0.0037 0.0093 FIMS,% by weight of the molecules

Paraffins 71.3 69.0 81.4 87.2

Monocycloparaffins 27.1 28.4 18.6 12.6

Multicycloparaffins 1.6 2.6 0.0 0.2

Total 100.0 100.0 100.0 100.0 API specific gravity 39.62

Pour point, ° C ^ 27 Ö3 ^ 9 Λ2

Cloud point, ° C +6 -4 +10 +13

Ratio of mono / 16.9 10.9> 100 61 multicycloparaffins

Ratio of pour point / -3.76 -4.70 -1.21 -1.51

Fish 100

Base oil flow factor -3.51 -3.67 -3.22 -2.76

Noack volatility 4.9 5.4 4.3 2.72 CCS Vis @ -35C, cP 5873 5966 73793636

Example 14 is a base lubricating oil according to this invention with a particularly high viscosity index, higher than 28 * (Vis 100) + 110, and a particularly low CCS VIS at -35 ° C. Examples 12 and 15 also met the properties of this invention, although Example 15 did not meet the more preferred range of CCS viscosity at -35 ° C (lower than an amount calculated from the equation: CCS VIS ( -35 ° C) = 38 x (kinematic viscosity at 100 ° C) 3). Comparative Example 13 did not meet the characteristics of this invention because of a low ratio of the weight percent of molecules containing monocyclopa-raffins and the weight percent of molecules containing multicycloparaffins. This may be due to hydroisomerization dewaxing to a lower pour point in this example, which resulted in the formation of more multicycloparaffins.

1027828

Example 16: 42

A base lubricating oil with a kinematic viscosity between 9.5 and 10.0 cSt at 100 ° C was prepared by hydroisomerization dewaxing of Fischer-Tropsch wax and fractionation of the isomerized oil in different distillate fractions. The properties of this sample are shown in Table VI.

Table VI

Properties Example 16 CVX Sample Π) "PGQ0144

Washing food WOW8684

Hydroisomerization temp., ° F 669

Hydroisomerization dewaxing catalyst Pt / SAPO-11

Reactor pressure, psig 1000

Viscosity at 100 ° C, cSt 9.699

Viscosity index 168 FIMS,% by weight of the molecules Paraffins 84.4

Monocycloparaffins 14.7

Multicycloparaifmen 0.9

Total 100.0

Pour point, ° C +1

Cloud point, ° C +26

Ratio of mono / multicycloparaffins 16.3

Ratio of pour point / Fish 100 0.10

Basic oil flow factor -1.32

Oxidator BN, hour 34.64

Aniline point, D611, ° F 280.3

Noack volatility 0.9 Example 16 met the properties of the base lubricating oil of this invention, including high oxidation stability, low aniline point, and low Noack volatility. The Noack volatility is lower than the amount calculated with the comparison:

Noack volatility, wt% = 900 x (kinematic viscosity at 100 ° C) * 2.8.

1 027 8 2 8 43

Comparative example 17 (test 951-15):

A hydrotreated Fischer-Tropsch wax (Table VII) was isomerized over a Pt / SSZ-32 catalyst containing 0.3% Pt and 35% Catapal alumina binder. The conditions of the test were a hydroisomerization temperature of 560 ° F, LHSV 1.0, a reactor pressure of 300 psig and a hydrogen flow rate during a single throughput of 6 MSCF / bbl. The reactor effluent went directly to a second reactor, also at 300 psig, which contained a Pt / Pd-on-silica-alumina-hydrofinish catalyst. Conditions in that reactor were a temperature of 450 ° F and an LHSV of 1.0. Conversion and yields, as well as the properties of the hydroisomerized bottoms product of the stripper are given in Table VIII.

Table VII

Hydro-treated Fischer-Tropsch wax inspections Specific gravity, API 40.3

Nitrogen, ppm 1.6

Sulfur, ppm 2

Sim. Dist., Wt.%, F IBP / 5 512/591 10/30 637/708 50 764 70/90 827/911 95 / FBP 941/1047

Table VIII

Isomerization of FT wax over Pt / SSZ-32 at 560 ° F, 1 LHSV, 300 psig and 6 MSCF / bbl H2

Conversion <650 ° F, weight% 15.9

Conversion <700 ° F, weight% 14.1

Yields,% by weight of C1-C2 0.11 C3-C4 1.44 1027828 44 C5-180 ° F 1.89 180-290 ° F 2.13 290-650 ° F 21.62 650 ° F + 73.19

Soil product from the stripper:

Yield, weight% of feed 75.9

Sim. Dist., LV%, ° F

IBP / 5 588/662 30/50 779/838 95/99 1070/1142

Pour point, ° C +25

The bottom product of the stripper was subjected to solvent dewaxing at -15 ° C using MEK / toluene. The wax content was 33.9% by weight and the oil yield was 65.7% by weight. The yield of 650 ° F + oil subjected to solvent dewaxing was 49.9% by weight based on feed to the process. Inspections of this basic lubricating oil are given in Table IX below.

Table IX

Hydroisomerized FT wash inspections after solvent dewaxing

Comparative example 17

Identification 951-15 (455-479) CVX Sample ID PGQ1108

Viscosity index 175

Viscosity at 100 ° C, cSt 3,776

Pour point, ° C -18

Cloud point, ° C -5

Sim. Dist., LV%, ° F

IBP / 5 608/652 1027828 • -v * -. * - - · - 45 /0 / 30 670/718 50 775 70/90 890/953 95 / FBP 1004/1116 FIMS,% by weight of the molecules Paraffins 96

Monocycloparaffins 4

Multicycloparaffins 0

Total 100

Oxidator BN, hour 31.87

Ratio of mono> 100 multicycloparaffins

Ratio of pour point / Fish 100 -4.77

Comparative Example 17 shows that moderate hydroisomerization dewaxing and subsequent solvent dewaxing gave a very low weight percentage of all molecules with at least one cycloparaffin function. The hydroisomerization temperature 5 was much lower than the desired range from about 600 ° F to about 750 ° F. Although the Oxidator BN and the viscosity index of this oil were very high, it does not have the preferred additive solubility and elastomer compatibility properties associated with the base lubricating oils of this invention with higher weight percentages of all molecules having at least one cycloparaffin function. This example also indicates that the base oil flow factor, although often associated with oils that meet the properties of the base lubricating oils of this invention, is not independent of the other criteria (weight percentage of all molecules with at least a cycloparaffin function and ratio of the weight percentage of molecules containing monocycloparaffins up to the weight percentage of molecules containing multicycloparaffins, or a high weight percentage of molecules containing monocycloparaffins and a low weight percentage of molecules containing multicycloparaffins) can be used to characterize the basic lubricating oils of this invention.

1027828

Comparative example 18 (test 952-12): 46

An n-C36 feed (purchased from Aldrich) was isomerized over a Pt / SSZ-32 catalyst containing 0.3% Pt and 35% Catapal alumina binder. The conditions of the test were a hydroisomerization temperature of 580 ° F, LHSV

1.0, a reactor pressure of 1000 psig and a hydrogen flow rate during a single throughput of 7 MSCF / bbl. The reactor fouling went directly to a second reactor, also at 1000 psig, which contained a Pt / Pd-on-silica-alumina-hydrofinish catalyst. Conditions in that reactor were a temperature of 450 ° F and an LHSV of 1.0. Conversion and yields were given as shown in Table X:

Table X.

Conversion <650 ° F, wt% 32.2

Pm setting <700 ° F, wt% 34.4

Yields,% by weight of C1-C2 0.45 C3-C4 5 ^ 16 C5-180 ° F 6 ^ 22 180-350 ° F 7V4Ö 350-650 ° F 13 ^ 23 650 ° F + 6M9

The hydroisomerized bottom product of the stripper of test 952-12 had a pour point of + 20 ° C. The bottom product of the stripper was subjected to solvent dewaxing at -15 ° C using MEK / toluene. The wax content was 31.5% by weight and the oil yield was 68.2% by weight. The yield of the 650 ° C + oil dewaxed with a solvent, based on the feed to the process, was 45.5% by weight. Inspections of this oil are summarized in Table XI.

Comparative example 19 (Test FSL9497):

Test FSL9497 gave a base lubricating oil that is bound by a Pt / SSZ-32 catalyst (0.3 wt% Pt) bound with 35 wt% Catapal alumina from an n-C28 feed (purchased from Aldrich) prepared. The test took place at 1000 psig, 1027828 47 LHSV 0.8 and a one-time throughput of H2 from 7 MSCF / bbl. The hydroisomerization temperature of the reactor was 575 ° F. The effluent from the reactor was then passed over a Pt-Pd / SiO 2 -Al 2 O 3 hydrofinish catalyst at 450 ° F and, in addition to the temperature, the same conditions were applied as in the isomerization reactor.

The yield of 600 ° F + product was 71.5% by weight. The conversion of the wax to material boiling in the 600 ° F range was 28.5% by weight. The conversion at a temperature below 700 ° F was 33.6% by weight. The bottom fraction of the test (75.2 wt%) was fractionated at 743 ° F, whereby 89.2 wt% of bottom product (67.1 wt% with respect to the entire feed) was obtained.

The hydroisomerized bottom product of the stripper had a pour point of + 3 ° C. This bottoms product was subjected to solvent dewaxing at -15 ° C, with 84.2% by weight solvent-dewaxed oil (56.5% by weight with respect to the entire feed) and 15.7% by weight were obtained.

Oil inspections are shown in Table XI.

15

Table XI

Features Comparative Comparative example! δ Example 19 CVX Sample ID PGQ1110 PGQ1112

Washing food n-C36 n-C28

Viscosity at 100 ° C, cSt 5,488 3,447

Viscosity index 182 165 FIMS,% by weight of the molecules

Paraffmen 98.3 100

Monocycloparaflins 1.7 0.0

Multicycloparaffins 0.0 0.0

Total 100.0 100.0

Pour point, ° C 3-15

Aniline point, D11, F 261.9 245.1

Neither Comparative Example 18 nor Comparative Example 19 met the characteristics of this invention since they had very low weight percentages of all molecules with at least one cycloparaffin function. None of these base oils with a low cycloparaffin content had aniline points as low as the base oils 1027828 ----------- 'I. 48 according to this invention. In particular, both were higher than 36 x ln (kinematic viscosity at 100 ° C) + 200, in ° F. These oils are expected to have a lower additive solubility and a less desirable elastomer compatibility than the base oils of the invention. The hydroisomerization temperature was lower than the preferred range from about 600 ° F to 750 ° F, which probably contributed to the lower amounts of cycloparaffins in both comparative examples.

Comparative Example 20 and Comparative Example 21: Two commercially available Group III base lubricants were prepared using a wax-like petroleum feed. The wax-like petroleum feed contained more than about 30 ppm total combined nitrogen and sulfur and had a weight percent oxygen of less than about 0.1. The feed was dewaxed by hydroisomerization dewaxing using Pt / SSZ-32 at a hydroisomerization dewaxing temperature between about 343 ° C (650 ° F) and about 385 ° C (725 ° F). They were both subjected to hydrofinishes. The properties of these two samples are shown in Table XII.

Table XII

Features Comparative Comparative example 20 example 21

Description CVXÜCBÖ4R CVX UCBO 7R

CVX Monster ID WOW8047 WOW8062

Hydroisomerization temperature, ° F 600-750 ° F 600-750 ° F

Hydroisomerization dewaxing catalyst Pt / SSZ-32 Pt / SSZ-32

Viscosity at 100 ° C, cSt 4.18 6.97

Viscosity index 130 137

Aromatics,% 0.022 0.035 FIMS,% by weight of the molecules

Paraffins 24.6 24.8

Monocycloparafins 43.6 51.2

Multicycloparaffins 31.8 24.0

Total 100.0 100.0 API specific gravity 39.1 37.0 1027828 49

Features Comparative Comparative example 20 example 21

Pour point, ° C -18 -18

Cloud point, ° C -14 5

Ratio of mono / multicycloparaffins 1.4 2.1

Aniline point, D611, ° F 242.1 260.2

These two comparative examples demonstrate how base lubricating oils prepared with conventional wax-like petroleum feeds, wherein the feeds contain high levels of sulfur and nitrogen, have high weight percentages of all 5 molecules with at least one cycloparaffin function. They also have low weight percentages of all molecules with at least one aromatic function. However, they both have less desirable very low ratios of the weight percent of molecules containing monocycloparaffs to the weight percent of molecules containing multicycloparaffs, much lower than the desired ratio higher than the base lubricating oils of this invention. As a result, although having aniline points corresponding to the base lubricating oils of this invention, they have lower viscosity indices, lower than the desired level defined by the equation: VI = 28 x ln (kinematic viscosity at 100 ° C) + 95.

1027828

Claims (5)

A base lubricating oil prepared from Fischer-Tropsch wax, comprising: a. A weight percentage of all molecules with at least one aromatic function lower than 0.30; b. a weight percentage of all molecules with at least one cycloparaffin function higher than 10; and c. a ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage of molecules containing multicycloparaffins higher than 15. A base lubricating oil according to claim 1, further comprising a ratio of pour point in degrees Celsius to kinematic viscosity at 100 ° C in cSt higher than the base oil flow factor, as calculated with the following equation: Base oil flow factor = 7.35 x ln (kinematic viscosity at 100 ° C) -18. The base lubricating oil according to claim 1, wherein the weight percentage of all molecules with at least one aromatic function is less than 0.10. 20 A base lubricating oil according to claim 3, wherein the weight percentage of all molecules with at least one aromatic function is less than 0.05. 5. Basic lubricating oil according to claim 1, wherein the weight percentage of all 25 molecules with at least one cycloparaffin function is higher than 15. A base lubricating oil according to claim 5, wherein the weight percentage of all molecules with at least one cycloparaffin function is higher than 20. The basic lubricating oil according to claim 1, wherein the ratio is higher than 50. The base lubricating oil according to claim 7, wherein the ratio is higher than 100. 1027828 ----- ...... · The base lubricating oil of claim 1, further comprising a viscosity index greater than 28 x ln (kinematic viscosity at 100 ° C) +95. The basic lubricating oil according to claim 9, wherein the viscosity index is greater than 28 x ln (kinematic viscosity at 100 ° C) + 110. The base lubricating oil of claim 1, further comprising an aniline point lower than or equal to an amount calculated by the following equation: Aniline point, ° F = 36 x ln (kinematic viscosity at 100 ° C) + 200. 10 The base lubricating oil according to claim 1, further comprising a Noack volatility lower than an amount calculated from the equation: Noack volatility, wt% = 1000 x (kinematic viscosity at 100 ° C) 2.7. The base lubricating oil according to claim 12, wherein the Noack volatility is lower than the amount calculated from the equation: Noack volatility, wt% = 900 x (kinematic viscosity at 100 ° C) * 2.8. The base lubricating oil of claim 1, further comprising a CCS viscosity at -35 ° C about -20 lower than an amount calculated from the equation: CCS VIS (-35 ° C) - 38 x (kinematic viscosity at 100 ° C) 3, in centipoise. The base lubricating oil of claim 14, wherein the CCS viscosity at -35 ° C is lower than the amount calculated from the comparison: CCS VIS (-35 ° C) = 38 x (kinematic viscosity at 100 ° C) 2 to 8, in centipoise. The base lubricating oil of claim 1, wherein the kinematic viscosity at 100 ° C is between about 2 cSt and about 20 cSt. The base lubricating oil of claim 17, wherein the kinematic viscosity at 100 ° C is between about 3.5 cSt and about 12 cSt. 1027828 The base lubricating oil of claim 1, further comprising an additional base oil selected from the group consisting of conventional group I base oils, conventional group II base oils, customary group III base oils, other GTL base oils, isomerized petroleum wax, poly-alpha-olefins, poly-internal-olefins, oligomerized olefins from a Fischer-Tropsch-obtained feed, diesters, polyolesters, phosphate esters, alkylated aromatics, alkylated cycloparaffins and mixtures thereof. The base lubricating oil of claim 1, further comprising a CCS viscosity at -35 ° C to -10 that is lower than an amount calculated from the equation: CCS VIS (-35 ° C), cP = 38 x (kinematic viscosity at 100 ° C) 3. The base lubricating oil of claim 19, wherein the CCS viscosity at -35 ° C is lower than the amount calculated from the comparison: CCS VIS (-35 ° C), cP - 38 x (kinematic viscosity at 100 ° C) 2.8. A process for preparing a base lubricating oil comprising the steps of: a. Performing a Fischer-Tropsch synthesis with syngas to provide a product stream; B. isolating from the product stream a substantially paraffinic wash feed with less than about 30 ppm total combined nitrogen and sulfur and less than about 1 weight percent oxygen; c. dewaxing the substantially paraffinic washing feed by hydroisomerization dewaxing using a shape-selective molecular sieve with an average pore size comprising a noble metal hydrogenation component, wherein the hydroisomerization temperature is between about 315 ° C (600 ° F) and about 399 ° C (750 ° F), thereby producing an isomerized oil; and d. hydrofinishing the isomerized oil, producing a base lubricating oil with: i. a percentage by weight of all molecules with at least one aromatic function lower than 0.30; ii. a percentage by weight of all molecules with at least one cycloparaffin function higher than 10; and 1027828 iii. a ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage of molecules containing multicycloparaffins higher than 15. The method of claim 21, wherein the substantially paraffinic washing feed is a weight ratio of molecules with at least 60 or more carbon atoms and molecules with at least 30 carbon atoms below 0.10 and a T90 boiling point between 349 ° C (660 ° F) and 649 ° C (1200 ° F). The method of claim 22, wherein the T90 boiling point is between 482 ° C (900 ° F) and 649 ° C (1200 ° F). The method of claim 21, wherein the substantially paraffinic wash feed has a weight percent oxygen of between 0.01 and 0.90 weight percent. 15 The method of claim 21, wherein the substantially paraffinic washing feed has a difference between the T90 and T10 boiling points greater than 160 ° C. 26. A method according to claim 21, wherein the shape-selective molecular sieve with an average pore size is selected from the group consisting of SAPO-11, SAPO-31, SAPO-41, SM-3, ZSM-22, ZSM-23, ZSM -35, ZSM-48, ZSM-57, SSZ-32, offretite, ferrierite and combinations thereof. 27. The method according to claim 26, wherein the shape-selective molecular sieve with an average pore size is selected from the group consisting of SAPO-11, SSZ-32 and combinations thereof. The method of claim 21, wherein the noble metal hydrogenation component consists of platinum, palladium or mixtures thereof. 30 The method of claim 21, wherein the conversion of the compounds boiling at a temperature higher than about 370 ° C (700 ° F) to the washing feed into compounds boiling at a temperature lower than about 370 ° C ( 700 ° F) is maintained between about 15% and 45% by weight during hydroisomerization dewaxing. 30. The method of claim 21, further comprising hydrotreating the substantially paraffinic wash feed for hydroisomerization dewaxing. The method of claim 21, further comprising fractionating the base lubricating oil. The method of claim 21, wherein the base lubricating oil has a ratio of monocycloparaffins to multicycloparaffins higher than 50. 33. The method of claim 21, wherein the base lubricating oil has a pour point to kinematic viscosity ratio at 100 ° C that is higher than the base oil flow factor, as calculated by the following equation: Base oil flow factor = 7.35 x ln (kinematic viscosity of the desired fraction at 100 ° C) -18. The method of claim 21, further mixing the base lubricating oil with an additional base oil selected from the group consisting of conventional Group I base oils, conventional Group II base oils, common Group III base oils, other GTL base oils , isomerized petroleum wax, poly-alpha-olefins, poly-intem-olefins, oligomerized olefins from a feed obtained through Fischer-Tropsch, diesters, polyol esters, phosphate esters, alkylated aromatics, alkylated cycloparafins and mixtures thereof. A production plant for a basic lubricating oil, comprising: a. A device for producing a substantially paraffinic washing feed with 30 i. less than about 30 ppm total combined nitrogen and sulfur, ii. less than about 1 weight percent oxygen, iii. more than about 75 percent by weight normal paraffins, iv. less than 10 weight percent oil, 10278 ^ 8 v. a weight ratio of compounds with at least 60 or more carbon atoms and compounds with at least 30 carbon atoms lower than 0.18 and vi. a T90 boiling point between 660 ° F and 1200 ° F; 5 b. a hydroisomerization dewaxing of the substantially paraffinic wash feed using a shape-selective molecular sieve with an average pore size comprising a noble metal hydrogenation component, the hydroisomerization temperature being between about 315 ° C (600 ° F) and about 399 ° C (750 ° F), for producing an isomerized oil and 10 c. a device for hydrofinishing the isomerized oil to produce base lubricating oils with: i. a weight percentage of aromatics lower than 0.30; ii. a percentage by weight of total cycloparaffins higher than 10; and iii. a ratio of the weight percentage of molecules containing monocycloparaffins to the weight percentage of molecules containing multicycloparaffins higher than 15. 1027828