ES2348041T3 - METHOD OF ANALYSIS OF BASE MATERIALS FOR LOW TEMPERATURE PROPERTIES. - Google Patents

Abstract

- A process to predict the properties of the Mini Rotary Viscometer (MRV) of formulated oils based on the distribution of paraffins, comprising: (a) injecting a sample of base material into a first column of a two-dimensional gas chromatograph, said first column being coated with a non-polar material to separate the sample of base material into a series of components of the first dimension sample having a first series of retention times; (b) injecting the separated components of the sample of the first dimension of step (a) into a second column coated with a semi-polar material to further separate the separated components of the sample from the first dimension in components of the sample of the second dimension that have a second series of retention times; (c) subject the first and second series of retention times to qualitative analysis to identify all paraffinic components in the range of carbon numbers from 16 to 50; (d) select a lower carbon number n and a higher carbon number m in the range of 16 to 50; (e) for each individual carbon number L in the range of n to m, group the isoparaffinic components of said carbon number into 3 groups A, B and C; (f) subject the first and second series of retention times to quantitative analysis to identify, for each of said groups of said carbon number L, the respective amounts (IPA) L, (IPB) L, (IPC) L of isoparaffins in% by weight of the total sample; and, (g) calculate an Isoparaffin Index by the formula: Isoparaffin Index = ES 2 348 041 T3 (h) compare the calculated Isoparaffin Index with the calculated Isoparaffin Index for standard samples of known MRV where the Index Isoparaffins of the standard samples is a value of approximately 0.8 or less.

Description

FIELD OF THE INVENTION

 This invention relates to a method for analyzing a lubricating oil for low temperature properties. The method uses gas chromatography in two dimensions (2D GC) to determine the amounts of paraffins and isoparaffins in the oil. In particular, the method analyzes a particular fraction of isoparaffins that correlates with the low temperature behavior. The composition information thus obtained is correlated with the properties of the Mini-Rotary Viscometer (MRV) of the formulated oil.

BACKGROUND OF THE INVENTION

 Modern industry standards are imposing increasing demands on the behavior of low-temperature engine oils. The low temperature behavior of formulated motor oils can be improved by improving the base oil, by improving the additives used in the formulation of the oil, or both. The low temperature properties of the base oils can also be improved using a synthetic base oil such as a poly-alpha-olefin (PAO). twenty

 The low temperature properties of any oil are influenced by the presence of waxes such as long chain paraffins. It is believed that these materials form wax crystals at low temperatures. These wax materials in turn adversely affect the fluidity of the oil thus causing a deterioration of the low temperature properties. It is common practice to remove at least partially the waxy materials 25 from the base oils by dewaxing. Dewaxing can be carried out with solvents or by catalytic means. Dewaxing with solvent is a physical method in which waxy molecules are separated based on their solubility properties in selected solvents. Catalytic dewaxing chemically converts waxy molecules into other molecules that have better low temperature properties. The catalytic dewaxing can be performed by cracking of waxy molecules or by isomerization of waxy molecules.

 Another approach typically used in association with dewaxing is the addition of additives such as critical pour point depressants as part of an additive package added to the base material of the lubricating oil to form a formulated oil. The depressants of the critical pour point are as a rule polymeric materials that improve the fluidity of an oil, that is, reduce the critical pour point. However, which-

Any given depressant of the critical pour point will have a different influence on the critical pour point depending on the nature of the oil in question. While a given critical pour point depressant may be effective in one oil, it may be ineffective in another. Therefore, it is necessary to test the low temperature properties of an oil to know the influence of any additive package given that it contains a depressor of the critical pour point.

 One method for determining the low temperature pumpability of an engine oil is based on the Mini Rotary Viscometer (MRV). Other means of measuring the low temperature properties of a formulated oil include Brookfield Viscosity, Brookfield Viscosity scanning, the Cold Start Simulator test (CCS) and Point 10 of Critical Fluidity. Although these test methods can provide information about the low temperature properties of any given oil, they do not necessarily provide information as to the compositional characteristics of said oil.

 Various physical techniques have been developed to investigate the composition of crude oils and their fractions, including Fourier transform infrared spectroscopy (FTIR), liquid chromatography, gas chromatography (GC), nuclear magnetic resonance (NMR ), and mass spectrometry (MS). Due to the complexity of petroleum mixtures such as crude oils, no technique is able to provide precise details of the composition of all the individual molecules that constitute the petroleum mixture. twenty

 The GC / MS methods use GC to at least partially separate a mixture into its components, and the MS is then used to identify the components. Petroleum mixtures are very difficult to solve in individual components due to the complexity of the mixtures and similar retention times of many individual molecules under given GC conditions. 25

 Two-dimensional gas chromatography (2D GC) is a recent technique that has been developed as a high resolution alternative to conventional GC / MS techniques. In 2D GC, a sample is subjected to two sequential chromatographic separations. The first separation is a partial separation by a first or primary separation column. The partially separated components are then injected into a second or secondary column, in which they undergo further separation. The two columns usually have different selectivities to achieve the desired degree of separation. An example of 2D GC can be found in U.S. Pat. No. 5,196,039.

 Vendeuvre et al., J. of Chromatography A, 1086, (2005), pp. 21-28 describes the 2D GC analysis of middle distillates, in which the distribution of hydrocarbons is determined by chemical class and by number of carbon atoms, and suggests a further characterization of

the sample by assignment to each group of isomers of a macroscopic property such as mass, viscosity or cetane number.

 It would be desirable that the chromatographic separation information regarding distribution of the paraffins in a base material available from 2D GC could be correlated with the low temperature properties of the formulated oils. 5

SUMMARY OF THE INVENTION

 This invention relates to a process for predicting the properties of the Mini Rotary Viscometer (MRV) of an extensive range of formulated oils, preferably for use in internal combustion engines of passenger vehicles, based on the distribution of paraffins, which comprises: 10

 (a) injecting a sample of base material into a first column of a two-dimensional gas chromatograph, said first column being coated with a non-polar material to separate the sample of base material into a series of components of the sample of the first dimension that have a first series of retention times;

 (b) inject the separated components of the sample of the first dimension of step 15 (a) into a second column covered with a semi-polar material to further separate the separated components of the sample from the first dimension in components of the second dimension sample that have a second series of retention times;

 (c) subject the first and second retention time series to qualitative analysis to identify all paraffinic components in the range of carbon numbers from 16 to 50;

 (d) select a lower number of carbons n and a higher number of carbons m in the range of 16 to 50;

 (e) for each individual carbon number L in the range of n to m, group the 25 isoparaffinic components for said carbon number into 3 groups A, B, and C;

 (f) subject the first and second retention time series to quantitative analysis to identify, for each of said groups corresponding to said carbon number L, the respective amounts (IPA) L, (IPB) L, (IP ) C) L of isoparaffins in% by weight of the total sample; 30

 (g) calculate an Isoparaffin Index by the formula:

   Isoparaffin Index =

Y,

 (h) compare the calculated Isoparaffin Index with the calculated Isoparaffin Index for standard MRV samples known where the Paraffin Index of the standard samples is a value of approximately 0.8 or less.

BRIEF DESCRIPTION OF THE DRAWINGS

 Figure 1 shows a 2D GC of a typical 130 N lubricant refining sample. 5

 Figure 2 is a graph showing a representation of the measured MRV of the formulated base oil against the Isoparaffin Index for a series of samples having different calculated Paraparaffin Indices.

 Figure 3 shows a typical 2D GC chromatogram (GC x GC) of a commercial base material used as a feedstock. 10

 Figure 4 are GC chromatograms illustrating compositional changes in the n-paraffin, IPA, IPB and IPC regions for an SDW → HDW sample.

 Figure 5 is a graph of GC chromatograms showing the GC retention time derived from isomerization products of a commercial feed, the hexadecane (nC16) and octaeicosan (nC28) model compounds, all on the 15 Pt catalyst / ZSM-48.

 Figure 6 shows GC chromatograms illustrating compositional changes in the n-paraffin, IPA, IPB and IPC regions for an HDW → SDW sample.

DETAILED DESCRIPTION OF THE INVENTION

 The base materials used to formulate motor oils are typically derived from petroleum distillates having a distillation point of 10% greater than 270ºC (518ºF) and a distillation point of 95% less than 621ºC (1150ºF) measured by ASTM D86 or D2887. Since these distillates frequently contain undesirable amounts of pollutants that contain sulfur and / or nitrogen, they can be extracted with solvents, hydrotreated, or both before further processing. The terms "base oil" and "base material" are used interchangeably herein.

 The solvent extraction process selectively dissolves the aromatic components in an extract phase while leaving the most paraffinic components in a refining phase. Naphthenes are distributed between the extract and refined phases. Typical solvents for solvent extraction include phenol, furfural and N-methyl-30 pyrrolidone. By controlling the ratio of solvent to oil, the extraction temperature and the method of contacting the distillate to be extracted with the solvent, the degree of separation between the extract and refining phases can be controlled. Pollutants that contain sulfur and nitrogen are concentrated in the extract phase.

 For hydrotreatment, the catalysts are those effective for hydrotreatment 35 such as catalysts containing Group 6 metals (based on the format of the IUPAC Periodic Table having Groups of 1 to 18), metals of Groups 8-10, and mixtures

thereof. Preferred metals are nickel, tungsten, molybdenum, cobalt and mixtures thereof. These metals or mixtures of metals are typically present as oxides or sulfides on supports of refractory metal oxides. The metal mixture may also be present as mass metal catalysts in which the amount of metal is 30% by weight or greater, based on catalyst. Suitable metal oxide supports include oxides such as silica, alumina, silica alumina or titanium oxide, preferably alumina. Preferred aluminas are porous aluminas such as gamma or eta. The amount of metals, either individually or in mixtures, is between approximately 0.5 and 35% by weight, based on the catalyst. In the case of preferred mixtures of Group 9-10 metals with Group 6 metals, Group 10 9-10 metals are present in amounts of 0.5 to 5% by weight, based on the catalyst, and Group 6 metals are present in amounts of 5 to 30% by weight. Metal quantities can be measured by atomic absorption spectroscopy, inductively coupled plasma atomic emission spectrometry or other methods specified by the ASTM for individual metals. fifteen

 The acidity of the metal oxide supports can be controlled by the addition of promoters and / or impurifiers, or by control of the nature of the metal oxide support, e.g., by control of the amount of silica incorporated into a silica-alumina support. Examples of promoters and / or impurifiers include halogen, especially fluorine, phosphorus, bo-ro, yttrium oxide, rare earth oxides and magnesia. Promoters such as the 20 halogens generally increase the acidity of the metal oxide supports, while moderately basic impurifiers, such as yttrium oxide or magnesia, tend to reduce the acidity of said supports.

 Especially preferred metal catalysts include cobalt / molybdenum (1-5% Co as oxide, 10-25% Mo as oxide), nickel / molybdenum (1-5% p Ni as oxide, 10-25% 25 p. Co as oxide) , or nickel / tungsten (1-5% p Ni as oxide, 10-30% W as oxide) on alumina.

 Hydrotreatment conditions include temperatures of 150 ° C to 400 ° C, preferably 200 ° C to 350 ° C, a hydrogen partial pressure of 1480 to 20,786 kPa (200 to 3000 psig), preferably 2859 to 13,891 kPa (400 to 2000 psig), a spatial velocity from 0.1 to 10 LHSV, preferably 0.1 to 5 LHSV, and a hydrogen to feed ratio of 89 to 1780 m3 / m3 (500 to 10,000 scf / B), preferably 178 to 890 m3 / m3.

 The hydrotreated base material can be passed directly to a dewaxing step or, preferably, released from volatile materials to remove gaseous contaminants such as hydrogen sulfide and ammonia before dewaxing. The release of volatile materials can be done by conventional means such as flash tanks or fractionators.

Dewaxed

 Dewaxing is a method used to control the low temperature properties of base materials. It is generally accepted that waxy molecules such as long chain paraffins crystallize at low temperatures thereby adversely impacting cold flow properties. Therefore, the removal of waxy molecules from the base material is considered to improve the low temperature properties of the base materials. Two commonly used methods of removing waxy molecules from the base materials are solvent dewaxing, catalytic dewaxing, or a combination of solvent and catalytic dewaxing. The offset dewaxing is dewaxed with solvent followed by catalytic dewaxing. 10

 For dewaxing with solvent, the dewaxing solvent used may include C3-C6 ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of MEK and MIBK, aromatic hydrocarbons such as toluene, mixtures of ketones and aromatics such as MEK / toluene, ethers such as methyl-t-butyl ethers and mixtures thereof with ketones or aromatics. Similarly, normally gaseous liquefied hydrocarbons such as propane, propylene, butane, butylene, and combinations thereof can be used as the solvent. Preferably, the solvent employed will be a mixture of methyl ethyl ketone and methyl isobutyl ketone.

 The solvent dewaxing process typically involves mixing the feedstock of the boiling range of the lubricating oils with a solvent dewaxed at atmospheric pressure, separating the precipitated wax and recovering the solvent for recycling. The feed material of the boiling range of the lubricating oils is mixed with cooled solvent to form an oil-solvent solution and the pre-precipitated wax is thereafter separated, for example, by filtration. The temperature and the solvent are selected so that the oil dissolves in the cooled solvent, while the wax precipitates.

 A particularly suitable solvent dewaxing process involves the use of a cooling tower in which the solvent is previously cooled and gradually added at several points along the height of the cooling tower. The feed stream mixture of the boiling range of the lubricating solvent oils is stirred during the cooling step to allow a substantially instantaneous mixing of the precooled solvent with the feed stream of the boiling range of the lubricating oils. The precooled solvent is gradually added along the length of the cooling tower to maintain an average cooling rate of or less than 10ºF / minute (approximately -12ºC / minute), usually between approximately -35 1ºF and approximately 5ºF / minute (approximately -17ºC to approximately -15ºC / minute). The final temperature of the feed stream mixture in the range of

Boiling of the lubricating oil-solvent / wax precipitated in the cooling tower will usually be between 0ºF and 50ºF (-17.8ºC and 10ºC). The mixture can then be sent to a scraped surface cooler to separate the precipitated wax from the mixture.

 As indicated above, solvent dewaxing of the feed stream of the boiling range of the lubricating oils takes place under effective solvent dewaxing conditions. As effective solvent dewaxing conditions, those solvent dewaxing conditions that are capable of removing at least a portion of the wax contained in the feed stream of the boiling range of the lubricating oils should be considered. Generally, effective solvent dewaxing conditions will include an amount of solvent such that, when added to the feed stream of the boiling range of the lubricating oils is sufficient to provide a liquid / solid weight ratio of about 5/1 to approximately 20/1 at the dewaxing temperature and a solvent / oil volume ratio between 1.5 / 1 and 5/1. Solvent dewaxing of the feed stream of the boiling range of the lubricating oils typically results in a partially dewaxed fraction having a critical pour point of about + 30 ° C to about -20 ° C.

 Catalytic dewaxing usually involves one or both of the following mechanisms: catalytic dewaxing by cracking of waxy molecules or catalytic dewaxing by isomerization of waxy molecules. Catalytic dewaxing by cracking implies reduction of molecular weight, since the wax crystals are cracked to molecules of lower molecular weight. Catalytic dewaxing by isomerization involves isomerizing waxy molecules (linear chain paraffins) to branched chain paraffins. It should be noted that very few, if any, dewaxing catalysts operate exclusively by a single mechanism. 25

 Catalysts for catalytic cracking dewaxing include ZSM-5, ZSM-11, ZSM-22, ZSM-35, mordenite and beta. Since this form of dewaxing involves cracking of waxy molecules, some loss of performance may occur. Dewaxing catalysts can be characterized by their alpha values. The alpha value of a catalyst is an approximate indication of the catalytic cracking activity of the catalyst compared to a standard catalyst, and provides the relative rate constant (conversion rate of normal hexane per catalyst volume and per unit of time). It is based on the activity of the amorphous silica-alumina cracking catalyst taken as an alpha value of 1 (Rate Constant = 0.016 s-1). The alpha test is described in U.S. Pat. No. 3,354,078 and in the Journal of Catalysis, 4, 522-529 (1965); 6, 278 (1966); and 35 61, 395 (1980). The catalysts used for dewaxing by catalytic cracking can have an alpha value greater than 100, preferably 100 to 180. The alpha value of a

Catalyst can be increased by initially treating the catalyst with nitric acid or by gentle steam treatment as set forth in U.S. Pat. No. 4,326,994. Steam treatment is a means of adjusting the silica: alumina ratio of the catalyst and therefore its alpha value.

 The catalysts for dewaxing by isomerization are those that isomerize at least a portion of the waxy molecules of n-paraffin to isoparaffins. Waxy molecules may be of mineral origin, synthetic origin or a mixture of both, e.g. a Fischer-Tropsch wax. Said isomerization catalysts minimize the amount of dewaxing by cracking mechanisms. Because there is a small reduction in molecular weight associated with isomerization catalysts, there is less performance loss compared to cracking dewaxing. Isomerization dewaxing catalysts typically contain metal filler with Group 6 metals, Group 8-10 metals and mixtures thereof (based on the IUPAC format). Especially preferred metals are noble metals of Groups 8-10, especially Pt, Pd or mixtures thereof. These metals are charged at the rate of 0.1 to 15% by weight based on catalyst.

 Hydrodeparaffinate catalysts suitable for use in this invention may be crystalline or amorphous. Amorphous hydrodeparaffinized catalysts include alumina, fluorinated alumina, silica-alumina, and fluorinated silica-alumina. Such catalysts are well known. The crystalline materials with molecular sieves that contain at least 20 a channel of 10 or 12 rings and can be based on aluminosilicates (zeolites) or on alumino minophosphates such as silicoaluminophosphates (SAPOs) and magnealuminophosphates (MAPOs). Molecular sieves suitable for use in this invention contain at least one channel of 10 or 12 rings. Examples of such zeolites include ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrite, ITQ-13, MCM-68 and MCM-71. Examples of aluminophosphates containing at least one 10-ring channel include ECR-42, SAPO-11, SAPO-31 and SAPO-41. Examples of molecular sieves containing 12 ring channels include zeolite beta and MCM-68.

 Molecular sieves are typically composed of binder materials that are resistant to high temperatures and that can be used under hydrodeparaffinized conditions to form a finished hydrodeparaffinized catalyst or may lack binder (self agglomerates). The binder materials are usually inorganic oxides such as silica, alumina, silica-aluminas, binary combinations of silica with other metal oxides such as titanium oxide, magnesia, thorium oxide, zirconium oxide and the like, and tertiary combinations of these oxides such as silica-35 alumina-thorium oxide and silica-alumina-magnesia. The preferred binder is alumina. The amount of molecular sieve in the finished hydrodewax catalyst is 10 to

100%, preferably 35 to 100% by weight, based on the catalyst. Such catalysts are produced by methods such as spray drying, extrusion and the like. The hydrodeparaffinizing catalyst can be used in the sulphurated or non-sulfurized form, and is preferably in the sulphurated form.

 The effective hydrodewaxing conditions used herein include temperatures between about 200 ° C and about 400 ° C, preferably about 225 ° C to about 350 ° C, more preferably 250 ° C to 310 ° C, pressures between about 2860 and about 20786 kPa (about 400 to about 3000 psig), preferably about 4238 to about 17338 kPa (about 600 to 10 about 2500 psig), more preferably about 4238 to about 10443 kPa (about 600 to about 1500 psig) , hydrogen gas treatment rates of about 89 to about 890 m3 / m3 (about 500 to about 5,000 standard cubic feet H2 / barrel), preferably about 107 to about 445 m3 / m3 15 (about 600 to about 2,500 standard cubic feet H2 / barrel), and vel hourly spatial ocitudes of the liquid ("LHSV") of about 0.1 to about 10 V / V / h, preferably about 0.1 to about 5 V / V / h, more preferably about 0.5 to about 2 V / V / h.

Formulated Oils 20

 The properties of the formulated oils, particularly the low temperature properties, are a function of the base material and the additive package used to prepare the formulated oil. As indicated above, the low temperature properties, eg, the critical pour point, Brookfield viscosity, MRV, cold start simulator test (CCS) and gel index, of a base material are seen adversely affected 25 by waxes. Therefore, it is advantageous to remove at least part of the waxy components of the base material by dewaxing. The viscosity index (VI) of the oil is similarly affected by the components of the base materials. The VI is unfavorably impacted by components such as aromatics that have a low VI. The low temperature properties are also affected depending on whether the base material itself is synthetic such as PAO or of mineral origin.

 The MRV of a formulated base oil is an indicator of low temperature properties. MRV is measured by standard tests such as ASTM D3829 and D4684. The MRV test measures the pumping efficiency of a base oil formulated at a low temperature. Lower MRV values are correlated with better low temperature properties. 35

 Another factor that influences the properties of the formulated oil is the additive package (adpak) used to formulate the oil. Additive packages contain at least

a selected component of dispersants, detergents, wear inhibitors, antioxidants, rust inhibitors, demulsifiers, extreme pressure agents, friction modifiers, multifunctional additives, viscosity index improvers, critical pour point depressants, and foam inhibitors .

 Many different additive packages are commercially available. Accurate formulations vary depending on the manufacturer and the proposed use of the engine oil. For example, engine oils for diesel engines may contain different additive components compared to engine oils for diesel-powered engines. Formulations for hot climates will vary from those for cold climates.

Two-dimensional Gas Chromatography 10

 2D GC is an alternative to gas chromatography / mass spectrometry. In the 2D GC, a sample is injected into a first column and the separated components are injected into a second column in series with the first.

 A sample is injected into an input device connected to the input of a first column to produce a first dimension chromatogram. Injection of the sample can be performed by any known sample injection device, such as a syringe. The input device may retain a single sample or may have multiple samples for injection in the first column. The column contains a stationary phase that is usually the column covering material.

 The first column may be coated with a non-polar material. When the column coating material is a methyl silicone polymer, the polarity can be measured by the percentage of methyl groups substituted by the phenyl group. The polarity of the coating materials is measured on a percentage substitution scale per phenyl group from 0 to 100, 0 being non-polar and considering 80 (80% substitution with phenyl) as polar. These methyl silicone polymers are considered non-polar and have 25 polarity values in the range of 0 to 20. Phenyl substituted methyl silicone polymers are considered semi-polar and have polarity values of 21 to 50. Materials Overlays of phenyl substituted methyl silicone polymers have been designated as polar materials when more than 50% substitution with phenyl group is included in the polymers. Other polar coating polymers, such as the so-called Carbowax, have also been used in chromatographic applications. Carbowax materials are high molecular weight polyethi-glycols. Additionally, a series of carboran-silicone polymers sold under the trade name Dexsil have been specially designed for high temperature applications.

 The first column coated with a non-polar material provides a first separation of the sample. The first separation, also known as the first dimension, generates a series of bands over a given period of time. These chromatograms

First dimension are not different from the chromatogram that could be obtained in a conventional cro-matography. The bands represent the individual components or groups of components of the injected sample, and are separated or partially superimposed with adjacent bands.

 When the complex mixture is separated in the column of the first dimension, it still undergoes many co-elutions that cannot be separated by the column of the first dimension. The bands of materials separated in the first dimension were then sent in their entirety to the second column for further separation, especially of the co-eluted components. This further separation is known as a second dimension. The second dimension is a second column coated with a semi-polar or polar material, preferably a semi-polar coating material.

 In order to make data acquisition as well as the detector signal significant, a modulator is required to manage the flow between the end of the first column and the beginning of the second column. The modulators can be thermal modulators that use a trap / release mechanism. In this mechanism, cold gas nitro-15 is used to trap the sample separated from the first dimension followed by a periodic pulse of hot nitrogen to release the trapped sample to a second dimension. Each pulse is analogous to a sample injection in the second dimension.

 The role of the modulator is (1) to collect the continuous flow of eluent that leaves the end of the first column with a fixed period of time (modulated period), and (2) inject the eluent collected at the beginning of the second column for release of the eluent collected at the end of the modulated period. The function of the modulator is (1) define the start time of a specific separation in the column of the second dimension and (2) define the length of the second dimensional separation (modulation period).

 The separate bands from the second dimension are coupled with the 25 bands from the first dimension to form a complete 2D chromatogram. The bands are arranged in a retention plane in which the retention times of the first dimension and the retention times of the second dimension form the axes of the 2D chromatogram.

 For example, a conventional GC experiment requires 80 minutes to separate a mixture (a chromatogram with 80 minutes of retention time, X axis). When the same experiment is performed in 2D GC conditions with a modulation period of 10 seconds, it will become 480 chromatograms (60 seconds x 80 minutes divided by 10 seconds) where each 10-second chromatogram (Y axis) is aligned one by one along the axis of retention times (X axis). In the 2D GC, the x-axis is the retention time of the first dimension (the same as in conventional GC), the y-axis is the retention time of the second dimension, and the peak intensity should stand out in the z axis of the third

dimension. In order to express this 3D image on two-dimensional paper, the intensity has been converted based on a pre-defined gray scale table to express its relative peak intensity by the gray scale.

 Figure 1 shows a 2D GC chromatogram of a typical 130N lubricant refining sample. In this 2D GC / FID (flame ionization detector) operation, the 5-point data of the experiment dimension is 480x1000. The dimension of the display is: 2880x2000. The adjustment of the separation columns used is: first column, SGE BPX-5 (BPX is a phenyl-siloxane polymer), 30 meters, 0.25 mm ID, 1.0 µm film; and second column, SGE BPX 50, 9.0 meters, 0.25 mm ID, 0.25 µm film. The oven temperature program was set at 210 ° C for 0 minutes and increased to 1.5 ° C for a minute to 315 ° C for 10 minutes. The flow program is 1.5 ml per minute for 0 minutes and increased from 0.05 ml / minute per minute to 5.0 ml per minute for 0 minutes. The inlet temperature was set at 300 ° C with a division / no division ratio of 75: 1. The injection volume of the sample is 0.2 µl.

 To determine the Isoparaffin Index, the total paraffinic components in the base oil are identified in the carbon number range of 16 to 50. The Isoparaffin Index is calculated for a given carbon range limited by a number of carbon bonds. lower, n, and a higher number of carbons, m. For example, the lower carbon value can be selected as n = 23 and a higher carbon value as m = 31 for the 130 N lubricant refining mixture. Since the resolution is not sufficient to identify individual isoparaffins, Isoparaffins are distributed in groups. For a given number of carbons L, the isoparaffins for said number of carbons are assembled into discrete groups, preferably three groups designated as (IPA) L, (IPB) L and (IPC) L. The process is repeated for each number of carbons over the total number of carbons range from n to m in the 2D GC spectrum. The peak volume of each group of components of 25 normal paraffins and isoparaffins is integrated to obtain the percentage by weight of a specific component referred to the total sample. In the 2D GC chromatogram of the refined lubricant 130N, shown in Figure 1, the calculation is made from the number of carbons 23 to 31 (C23 to C31). The composition of individual components is summarized in Table 1 below. 30

TABLE 1

Composition of the 130N Lubricant Refining Based on the GC 2D Chromatogram

 Carbon Number

 23 24 25 26 27 28 29 30 31

 N

 0.98 2.10 3.58 3.66 3.36 2.60 1.89 1.11 0.57

 IPA

 0.16 0.47 1.33 1.70 1.86 1.52 1.18 0.88 0.57

 IPB

 0.31 0.85 1.61 1.82 1.70 1.50 1.18 0.75 0.35

 CPI

 0.08 0.16 0.38 0.44 0.35 0.40 0.27 0.16 0.06

 N is the amount of normal paraffin for each individual carbon number, but this is not necessary to calculate the Isoparaffin Index. For any given sample, the Isoparaffin Index is calculated as the ratio of the sum of Isoparaffins A referred to the range of carbon numbers from n to m to the sum of isoparaffins B plus C in the range of carbon numbers from n to m. This is represented by the following equation 1:

  10

 (one)

   Isoparaffin Index =

 In the above equation, n is a lower number of carbons in the range of 16 to 50, m is the higher number of carbons in the range of 16 to 50, (IP) L is the amount of iso-paraffins in% by weight for each individual number of carbons L. The subscripts A, 15 B, and C represent the different groups of iso-paraffins in Table 1 above.

For the data in Table 1, n = 23 and m = 31, it is 9.67,

is 10.07 and 20 is 2.30. The Isoparaffin Index is calculated as

9.67 / (10.03 + 2.30), or 0.78.

 The data collection process shown in Figure 1 and Table 1 above is repeated for a series of standard samples not formulated. For the purposes of calculating the Isoparaffin Index, the sample can be formulated or not formulated, since

The Isoparaffin Index is independent of the additive package used to formulate the samples. In contrast, the MRV for each sample is measured on a formulated sample, since the MRV is influenced by the additive package used to formulate the sample, and the Isoparaffin Index is calculated on the basis of 2D GC analysis. The same additive package is used to formulate each sample. A commercial additive package 5 for GF3 engine oils was used to make the formulated oil. This package contains a detergent / inhibitor package, a viscosity modifier, and a critical pour point depressant. The results for a series of samples that had different calculated Isopara-fine Indices and corresponding MRVs are represented in Figure 2, which is a graph in which the MRV measured is the Y axis and the Isoparaffin Index is the X axis for The 10 series of samples.

 As can be seen from Figure 2, if the desired MRV of the formulated base oil is 40,000 cP, then the target Isoparaffin Index is 0.8. For any given sample of formulated oil, if the Isoparaffin Index s for the base oil is less than 0.8, it can be formulated in an oil that has an MRV of 40,000 cP or less. fifteen

 The traditional MRV measurement requires a large amount of finished lubricating oil, such as, but not limited to, a sample of motor oil (150 to 200 ml) and also needs long test periods (> 45 hours) at temperature low between -10ºC and -40ºC. In many cases, the viscosimetric properties of the base oil cannot be translated into the low temperature flow property of the formulated engine oil. It is very desirable to develop an analytical tool that can accurately predict the low temperature behavior of a PCMO formulated from the base material in a rapid test. Accurate MRV prediction using the advanced 2D GC technique can dramatically reduce the time and cost associated with the conventional MRV test.

 This invention can be more fully understood by reference to the following non-limiting examples.

EXAMPLES

 The following examples are aimed at demonstrating the impact of the evaluation of the Isoparaffin Index on the base materials produced using various process schemes. The Isoparaffin Index is correlated with the MRV measured for these 30 base materials. First, solvent dewaxing ("SDW") was applied followed by catalytic dewaxing ("HDW") to a commercially available base material to improve the low temperature behavior. A deeper dewaxing evaluation on a light base ("LBS") refined 130N of light base material ("LBS") was then completed to focus the impact on the low temperature behavior of the formulation of motor oils with materials base produced from various dewaxing process schemes. The base materials were produced by dewaxing

according to two different dewaxing schemes, which combined HDW and SDW in different proportions. One case focused on partial dewaxing with solvents to an intermediate critical pour point followed by HDW to the final target critical pour point, in order to preserve wax production. Another focused on partial HDW to an intermediate critical flow point followed by SDW to the final day-5 critical flow point. The Isoparaffin Index allowed the evaluation of the base materials to predict which would behave better from the MRV point of view of the formulated oil.

Example 1

 A commercial dewaxing base material with solvents such as feed was used in compensated dewaxing experiments (SDW followed by HDW). Commercial base material 10 is a mixture of approximately 81% by weight of light base material and approximately 19% by weight of medium base material. A refined 130 N lubricant was used as the feed in the two combined dewaxing systems. The properties of the base material are summarized in Table 2.

 Table 2 15

 Properties of Commercial Base Material and Refining 130N

 Food Description

 Commercial Base Material Refined Lubricant 130N

 Sample Used in Operation in Pilot Plant

 Compensated HDW SDW → HDW HDW → SDW

 Cloud Point (ºC)

 - 35.6

 Critical pour point (ºC)

 -18 31

 Density at 15 ° C (g / cc)

 0.844 0.8332

 Sulfur (ppmp)

 <10 <1

 Nitrogen (ppmp)

 <1 <0.3

 Color (Lovibond Saybolt)

 > +30> +30

 Refractive Index at 75 ° C

 - 1,4401

 Kinematic Viscosity at 40 ° C (cSt)

 23.3 16,910

 Kinematic Viscosity at 100 ° C (cSt)

 4.6 3,972

 Viscosity Index

 114 135.1

 Wax Content (%)

 - 25.3

 MRV (cP)

 36211 -

Example 2

 All HDW work on three process methods used as the commercially available Pt / ZSM-48 dewaxing catalyst. 1/16 "(1.59 mm) commercial quadrilobular extrudates contain 65% ZSM-48 crystals combined with 35% alumina. Platinum was impregnated in the extrudates using tetraamine-platinum nitrate.

HDW procedure

 The HDW studies were carried out using a continuous catalyst test unit, which consists of a liquid feeding system with an ISCO jerin-guilla pump, a fixed bed tubular reactor with a three-zone furnace, collected from 10 liquid product, and an online MTI GC for gas analysis. Typically, 5-10 cc of catalyst was sieved to 14/20 meshes and loaded into a 3/8 "(9.53 mm) upstream stainless steel reactor containing a 1/8" thermometric diver ( 3.18 mm). After testing the unit under pressure, the catalyst was dried at 300 ° C for 2 hours with 250 cc / min of N2 at room pressure. If catalyst presulfurization was required, 2% H2S in hydrogen was flowed through the catalyst bed at 100 sccm for 1 hour. Once the catalyst treatment was completed, the reactor was cooled to 150 ° C, the unit pressure was adjusted to 1000 psig (70.3kg / cm2) by adjusting the Mity-Mite back pressure regulator and the gas flow was changed from N2 to H2. The liquid feed material was introduced into the reactor at the desired liquid hourly space velocity (LHSV). Once the liquid feed reached the downstream precipitation boiler, the reactor temperature was increased to the target value. A material balance (MB) was initiated until the unit remained on the line for 6 hours. The total liquid product (TLP) was collected in the MB drip boiler. Gas samples were analyzed with an online HP MTI gas chromatograph (GC) equipped with both TCD and FID detectors. A series of operations were carried out to know the activity properties of the catalyst / product based on the process variables, such as LHSV and process temperature. The TLP product of each balance was cut at 370 ° C by batch distillation. The properties of 370 ° C dewaxed oil + were analyzed.

Laboratory SDW Procedure 30

 Dewaxed with solvents in the laboratory were conducted using a single stage batch filtration with the large Buchner funnel apparatus. This device uses a 24 cm filtration area and has a capacity of up to 1.5 gallons (5.67 liters) of oil / wax / solvent suspension. The solvent was a mixture of methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK). 35

 As the filtration proceeds, the predominantly waxy component is retained on the surface of the filtration medium, passing the filtrate (oil and solvent).

te) through the filter to a collection flask. These products are then released from their respective solvents using a vacuum volatile rotary separator to complete the filtration process. DWO and wax were further analyzed to determine their individual physical properties.

 The feed and base material produced as described above was then mixed-5 rum to then manufacture a motor oil for passenger vehicles (PCMO) 5W-30. The previous base material had a lighter viscosity than that required for the finished 5W-30 oil and therefore a second base material that was somewhat heavier was added to all mixtures in order to match the desired viscosity target of the oil. base. A commercial additive package for GF-3 engine oils was then added in order to make the formulated oil. This package consists of a detergent / inhibitor package, a viscosity modifier, and a critical pour point depressant. The package used and the second base material were kept constant in all mixtures, only the light base material being varied. The formulated oils were tested for cold flow properties with a Mini-Rotary Viscometer (MRV), in accordance with ASTM 15 D4684.

Example 3

2D GC Measurement of Base Oil Composition

 The 2D GC system (GCxGC) consists of an Agilent 6890 gas chromatograph (Agilent Technology, Wilmington, DE), configured with input, columns, and detectors. An input system with split / no split with an automatic 8-vial tray sample taker was used. The two-dimensional capillary column system uses a first non-polar column (BPX-5, 30 meters, 0.25 mm ID, 1.0 µm film), and a second polar column (BPX-50, 9 meters, 0 , 25 mm ID, 0.25 µm film). Both capillary columns are products of SGE Inc. Austin, TX. A dual-jet thermal modulation assembly based on Zoex technology (Zoex Corp. Lincoln, NE) which is a dual-jet "jet-release" thermal modulator cooled by liquid nitrogen is installed between these two columns. A flame ionization detector (FID) is used for signal detection. A 0.2 microliter sample with 75: 1 division was injected at 300 ° C from the inlet. The carrier gas is programmed from 1.5 ml / minute with 0 minutes of retention and an in-30 growth of 0.05 ml / minute per minute to 5.0 ml / minute with 0 minutes of retention. The oven was programmed from 210 ° C with 0 minutes of retention and 1.5 ° C per minute of increase to 315 ° C with 0 minutes of retention. The total run time of the GC was 70 minutes. The modulation period was 10 seconds. The sampling rate for the detector was 100 Hz. After data acquisition, they were processed for qualitative and quantitative analysis. The qualitative analysis converted the data into a two-dimensional image that was processed by a commercial program, "Transform" (Research Systems Inc.,

Boulder, CO). The two-dimensional image was further processed by the "PhotoS-hop" program (Adobe System Inc., San José, CA) to generate images ready for publication. An internal program was used to quantify peak volumes.

 Figure 3 shows a 2D GC chromatogram (GCxGC) of the solvent dewaxed commercial feed material described in Example 1. Using C27 as an example, the chromatogram demonstrates the detailed identifications of n-paraffins (N) and iso-paraffins (IP) and the integration volumes selected from the identified components. Since all iso-paraffins are not completely resolved in the two-dimensional space, the iso-paraffins have been grouped into three regions, IPA, IPB and IPC, for each associated carbon number of the base oil components. While the peaks identified over the total retention time of the 2D GC chromatogram (in the range of C23 to C31) are integrated, the weight percentage of n-paraffins and iso-paraffins can be quantitatively obtained for each number associated carbon. Table 3 shows a typical weight percentage of n-paraffins and iso-paraffins for each of the associated carbon numbers in the commercial feed. fifteen

TABLE 3

 COMMERCIAL FEEDING MATERIAL Critical Fluidity Point = -18ºC MRV = 36211 cP

 Carbon Number

 23 24 25 26 27 28 29 30 31

 N

 0.27 0.66 0.95 0.84 1.00 0.79 0.51 0.41 0.28

 IPA

 0.14 0.66 1.34 1.76 1.88 1.62 1.30 1.04 0.68

 IPB

 0.42 0.89 1.46 1.52 1.71 1.52 1.16 0.79 0.54

 CPI

 0.09 0.26 0.65 1.02 0.62 0.58 0.42 0.32 0.22

Example 4

 This example defines a base oil composition (base material) with superior LTP. A comparison was made between base materials produced from the combinations of commercial processes SDW and HDW (using Pt / ZSM-48). The upstream dewaxing process (SDW or HDW) dewaxed the feed to a critical flow point in the range of about -16 to about -20 ° C. The downstream process (HDW or SDW) completed the dewaxing to the point of target critical fluidity. For formulated engine oils containing base materials manufactured in this way (SDW followed by HDW), a significant improvement in the low temperature behavior of the formulated engine oil was achieved, as measured by the MRV for the formulated engine. In contrast, if the base oil was manufactured by HDW to an intermediate critical pour point followed by SDW to the target point, the oils from

formulated engines containing said base material did not exhibit an improvement in low temperature behavior as measured by MRV.

 SDW commercial base material with a critical pour point of -18 ° C, when formulated for engine in a 5W-30 engine oil, reached an MRV measurement of ~ 36,211 cP. The structural molecular composition was calculated on the basis of 2D GC analysis and re-summed in Table 3.

 The compensated HDW produced base materials which, when formulated in a 5W-30 motor oil, demonstrated the maximum improvement in cold flow behavior as measured by the reduction of MRV for a given critical pour point. For example, compensated catalytic hydrodeparaffin up to approximately -19 ° C of 10 critical pour point is effective in decreasing MRV from 36,211 cP to an average value of 19,536 cP, a 46% reduction in MRV apparent viscosity. When compared to commercial feed, it is clearly seen that the concentration of IPA for each carbon number decreased (Table 4).

TABLE 4 15

 Compensated HDW, ZSM-48 Pto. Critical fluidity = -19 ° C MRV = 19536 cP Temp. Rxn 290 ° C

 Carbon Number

 23 24 25 26 27 28 29 30 31

 N

 0.31 0.71 0.98 0.86 1.01 0.79 0.50 0.40 0.28

 IPA

 0.14 0.61 1.16 1.46 1.60 1.35 1.07 0.88 0.57

 IPB

 0.49 1.03 1.63 1.68 1.89 1.63 1.24 0.83 0.56

 CPI

 0.12 0.28 0.69 1.08 0.66 0.60 0.44 0.32 0.22

 Motor oils formulated with the SDW → HDW base materials also exhibited a significant improvement in MRV compared to the total SDW base material. The 2D GC composition analysis presented the different molecular structures of the intermediate dewaxed products and the way in which the final dewaxing stage 20 eliminates the remaining wax of the intermediate products. SDW first typically eliminates high molecular weight waxy paraffins based on physical separation. In contrast, the HDW process converts the waxy hydrocarbon molecules into isomerized using bifunctional catalysts. In the case of SDW → HDW, the feed was subjected to SDW in the first step to a point of intermediate critical fluidity by reduction of the waxy molecules of the heavy tails. As shown by gas chromatography, the initial SDW process selectively removes the highest molecular weight n-paraffin. The following HDW process effectively isomerizes the n-paraffins and isoparaffin until the desired lubricating properties are achieved. The detailed molecular compositions

at each process stage they are presented in Figure 4 and Tables 5-7. Figure 4 are GC chromatograms illustrating the compositional changes in the n-paraffin, IPA, IPB and IPC regions for the SDW → HDW sample. Table 5 shows a refining feed and the distribution of n-paraffins and isoparaffins based on the number of carbons identified in each case in the feed of the lubricant refining. Tables 6 and 7 show the intermediate compound SDW and the product SDW-HDW: The distribution of n-paraffins and iso-paraffins based on the number of carbons identified in each case.

 TABLE 5

 Refined Lubricant 130N Critical Pour Point = 30 ° C MRV = N / A

 Carbon Number

 23 24 25 26 27 28 29 30 31

 N

 0.98 2.10 3.58 3.66 3.36 2.60 1.89 1.11 0.57

 IPA

 0.16 0.47 1.33 1.70 1.86 1.52 1.18 0.88 0.57

 IPB

 0.31 0.85 1.61 1.82 1.70 1.50 1.18 0.75 0.35

 CPI

 0.08 0.16 0.38 0.44 0.35 0.40 0.27 0.16 0.06

 Total: 41.88

 TABLE 6 10

 SDW Critical Pour Point = 10 ° C MRV = N / A

 Carbon Number

 23 24 25 26 27 28 29 30 31

 N

 1.02 1.82 2.63 2.02 1.69 1.08 0.70 0.38 0.18

 IPA

 0.18 0.59 1.61 2.00 2.18 1.77 1.36 0.94 0.61

 IPB

 0.35 1.01 1.89 2.05 1.89 1.56 1.11 0.65 0.29

 CPI

 0.07 0.14 0.45 0.50 0.42 0.47 0.29 0.17 0.07

 Total: 36.13

TABLE 7

 SDW → HDW Critical Pour Point = -16 ° C MRV = 37257 cP Rxn Temp = 310 ° C

 Carbon Number

 23 24 25 26 27 28 29 30 31

 N

 0.66 1.20 1.46 1.19 1.29 0.91 0.48 0.34 0.19

 IPA

 0.58 1.14 1.71 1.94 2.01 1.58 1.18 0.82 0.46

 IPB

 1.13 1.93 2.57 2.39 2.47 1.99 1.38 0.80 0.43

 CPI

 0.34 0.49 1.06 1.48 0.87 0.72 0.46 0.30 0.16

 Total: 40.13

 Figure 5 shows GC chromatograms illustrating the identifications of the n-paraffin, IPA, IPB and IPC regions using the nC16 and 5 nC28 model paraffin compounds. The lower chromatogram corresponds to the isomerization products of the model compound nC28, the intermediate chromatogram corresponds to a commercial base material, and the upper chromatogram corresponds to a refined 130 N lubricant. The chromatogram inserted in the right corner corresponds to the isomerization products of compound nC16. 10

 Based on the GC retention time derived from the isomerization products using the hexadecane (nC16) and octaeicosan (nC28) model compound on a Pt / ZSM-48 catalyst (represented in Figure 5), it was identified that the components Major in the IPA region were identified as mono-methyl isomers of the corresponding carbon number species. The IPB region contained the mixture of n-methyl mo-15 derivatives of the corresponding carbon number species and dimethyl isomers of a carbon number greater than the corresponding carbon number species. The IPC region consisted of dimethyl isomers of a carbon number greater than the corresponding carbon number species.

 Figure 6 shows GC chromatograms illustrating compositional changes in the n-paraffin, IPA, IPB and IPC regions for the HDW → SDW sample. Tables 8-10 summarize the detailed molecular composition of the feed and the product at each stage of the process. Table 8 shows the refined lubricant 130 N: n-paraffin and isoparaffin distribution based on the number of carbons. Table 9 shows the intermediate HDW compound: distribution of paraffins and isoparaffins based on the number of carbons. Table 10 shows the product HDW → SDW: distribution of n-paraffins and isoparaffins based on the number of carbons.

 Significantly poor MRV behavior was observed for motor oils formulated with base materials dewaxed by HDW → SDW versus SDW → HDW. In this product HDW → SDW, the refined lubricant 130 N was subjected to HDW up to -7 ° C followed by SDW up to -20 ° C, which is a critical pour point very similar to the case of compensated HDW. The MRV viscosity of the 5W-30 was 92,649 cP, much greater than 5 that of the compensated HDW base oil. Therefore this formulated oil does not meet MRV specifications.

 The first step HDW homogenously isomerized the waxy n-paraffins to preferably produce isomers with methyl monosubstitution. The subsequent SDW step effectively eliminated n-paraffins. A very significant amount of molecules with 10 monomethyl isomers (concentrated in the IPA region) that remained in the intermediate critical pour point product was not effectively removed in the second SDW step due to a lower crystallization temperature (see Figure 6) .

 These partially HDW molecules could impose greater difficulties for the SDW process to effectively reduce the MRV in equivalent critical pour point products. Consequently, the significant remaining amount of monomethylic species was detrimental to MRV. The HDW → SDW sample had a slightly higher content of paraffins (42.68% by weight) than that of the SDW → HDW sample (40.13% by weight).

TABLE 8 20

 Refined Lubricant 130N Critical Pour Point = 30 ° C MRV = N / A

 Carbon Number

 23 24 25 26 27 28 29 30 31

 N

 0.98 2.10 3.58 3.66 3.36 2.60 1.89 1.11 0.57

 IPA

 0.16 0.47 1.33 1.70 1.86 1.52 1.18 0.88 0.57

 IPB

 0.31 0.85 1.61 1.82 1.70 1.50 1.18 0.75 0.35

 CPI

 0.08 0.16 0.38 0.44 0.35 0.40 0.27 0.16 0.06

 Total: 41.88

TABLE 9

 HDW Critical Pour Point = -7 ° C MRV = N / A Rxn Temp: 300 ° C

 Carbon Number

 23 24 25 26 27 28 29 30 31

 N

 0.54 1.14 1.54 1.34 1.42 1.06 0.63 0.43 0.23

 IPA

 0.68 1.61 2.71 3.26 3.07 2.48 1.80 1.29 0.67

 IPB

 0.76 1.58 2.45 2.59 2.74 2.33 1.66 1.00 0.56

 CPI

 0.21 0.48 0.95 1.39 0.88 0.77 0.53 0.35 0.20

 Total: 47.30

 TABLE 10

 HDW → SDW Critical Pour Point = 20 ° C MRV = 92649 cP

 Carbon Number

 23 24 25 26 27 28 29 30 31

 N

 0.46 0.98 1.33 1.13 1.26 0.91 0.50 0.35 0.19

 IPA

 0.77 1.73 2.81 3.16 2.92 2.23 1.57 0.99 0.54

 IPB

 0.76 1.45 2.14 2.09 2.23 1.85 1.31 0.76 0.43

 CPI

 0.23 0.46 1.00 1.47 0.91 0.77 0.50 0.33 0.18

 Total: 42.68

 5

 If a comparison is made between the base material products illustrated in Table 4, Table 7 and Table 10, the calculated Isoparaffin Index (based on Equation 1) for the compensated HDW base material product in Table 4 is 8.84 / (10.99 + 4.41) = 0.57 (MRV = 19,536 cP). The Isoparaffin Index calculated for the product of the SDW → HDW base material in Table 7 is 11.43 / (15.09 + 5.88) = 0.55 (MRV = 37257 cP), while 10 is the Isoparaffin Index for the base product HDW → SDW in Table 10 it is 16.72 / (13.02 + 5.84) = 0.89 (MRV = 92649 cP). Based on these results, it can be seen that the MRV for the compensated HDW base material in Table 4 would produce a lower value than for the product of the SDW → HDW base material in Table 7 and for the product of the HDW → SDW base material in Table 10. 15

Claims (18)

 1.- A process to predict the properties of the Mini Rotary Viscometer (MRV) of formulated oils based on the distribution of paraffins, comprising:  (a) injecting a sample of base material into a first column of a two-dimensional gas chromato-graph, said first column being coated with a non-polar material to separate the sample of base material into a series of components of the first sample dimension that have a first series of retention times;  (b) inject the separated components of the sample of the first dimension of step (a) into a second column covered with a semi-polar material to further separate the separated components of the sample from the first dimension in components of the sample of the second dimension that have a second series of retention times;  (c) subject the first and second series of retention times to qualitative analysis to identify all paraffinic components in the range of carbo-15 numbers from 16 to 50;  (d) select a lower carbon number n and a higher carbon number m in the range of 16 to 50;  (e) for each individual carbon number L in the range of n to m, group the isoparaffinic components of said carbon number into 3 groups A, B and C; twenty  (f) subject the first and second series of retention times to quantitative analysis to identify, for each of said groups of said carbon number L, the respective amounts (IPA) L, (IPB) L, (IPC) L of isoparaffins in% by weight of the total sample;  (g) calculate an Isoparaffin Index by the formula:   25    Isoparaffin Index = Y,  (h) compare the calculated Isoparaffin Index with the calculated Isoparaffin Index for standard MRV samples known where the Isoparaffin Index of the standard samples is a value of approximately 0.8 or less.  2. The process of claim 1, wherein the base material has been extracted with solvents, hydrotreated or extracted and hydrotreated.  3. The process of claim 1, wherein the base material has been dewaxed by at least one of dewaxing with solvents or catalytic dewaxing.  4. The process of claim 3, wherein the base material is dewaxed by catalytic dewaxing, the catalytic dewaxing having conditions including temperatures between approximately 200 ° C and 400 ° C, pressures between approximately 2860 and 20786 kPa, hydrogen treatment rates gas of approximately 89 to 890 m3 / m3, and hourly space velocities of the liquid of approximately 0.1 to 10 V / V / h. 5  5. The process of claim 1 wherein the non-polar material has a polarity between 0 and 20.  6. The process of claim 5 wherein the non-polar material is a methyl silicone polymer.  7. The process of claim 1 wherein the semipolar material has a polarity between 20 and 50.  8. The process of claim 7 wherein the semipolar material is a methyl silicone polymer in which at least some of the methyl groups have been substituted by phenyl.  9. The process of claim 1 wherein the separate components of the sample of the first dimension are sent to a modulator.  10. The process of claim 1 wherein the retention times for the separate components of the second dimension are coupled with the retention times for the components of the sample of the components of the sample of the first dimension to form a complete 2D chromatogram. twenty  11. The process of claim 1 wherein n is 23 and m is 31.  12. The process of claim 3 wherein the base material is dewaxed by catalytic dewaxing using a Pt / ZSM-48 dewaxing catalyst.  13. The process of claim 1 wherein the sample of the base material may be formulated or not formulated. 25  14. The process of claim 13 wherein the formulated sample contains a package of additives.  15. The process of claim 14 wherein the additive package contains at least one component selected from dispersants, detergents, wear inhibitors, antioxidants, rust inhibitors, demulsifiers, extreme pressure agents, friction modifiers, multifunctional additives , viscosity index improvers, critical pour point depressants, and foam inhibitors.  16. The process of claim 1 wherein the MRV of the oils formulated for an Isoparaffin Index of 0.8 or less is 40,000 cP or less.  17. The process of claim 1 wherein the formulated oils are for use in internal combustion engines of passenger vehicles.