EP1212390B1 - Hydrocarbon base oil for lubricants with a very high viscosity index - Google Patents

Abstract

The invention concerns a novel hydrocarbon base oil for lubricants, having a viscosity index not less than 130, comprising mainly long isoparaffinic hydrocarbon chains, branched over several carbon atoms. The invention is characterized in that said chains comprise a number of carbon atoms greater than 25 and have a ratio of the number of substituents consisting of at least two carbon atoms over the number of methyl-type substituents, not less than 0.9.

Description

The invention relates to a hydrocarbon base oil for high-end lubricants, obtained from hydrocarbon cuts from various sources. More specifically, the invention relates to an oil of this type, having a viscosity index VI, calculated according to standard NF T 60-136, greater than 130, for a kinematic viscosity measured at 100 ° C (Vk @ 100 ° C) , measured according to standard NF T 60-100, between 3.5 and 4.5 mm ² / s (or cSt). This base oil finds a preferential application in the formulations of lubricants for engines, in particular in the automobile industry, as well as for industrial uses.

Base oils are currently classified according to the API classification into five groups, according to characteristics defined in Table 1 below: Table 1 Saturated compounds (% by weight) Sulfur content (% by weight) Viscosity index VI Group 1 <90 > 0.03 80 <VI <120 Group II > 90 <0.03 80 <VI <120 Group III > 90 <0.03 > 120 Group IV PAO (Poly-α-olefins) Group V Others (esters)

It has long been known to produce base oils for group I lubricants from certain cuts of distillates obtained by vacuum distillation of crude paraffinic oils, because it is the high isoparaffin content of these crudes which gives them good values of VI. These distillates are extracted by solvent, producing a raffinate rich in paraffins and an extract rich in aromatics; the raffinate is then dewaxed by mixing with an organic solvent (for example, methyl ethyl ketone or MEC), cooling and filtration, so as to obtain, by separation, solid or slack wax (elimination from n-paraffins) and an oil having a VI d '' at least 95 and good cold properties (point flow); this oil is finally hydrofinished to stabilize it and improve its color.

Remember that the viscosity index or VI of petroleum products is calculated from their kinematic viscosities at 40 ° C and 100 ° C, according to standard NF T 60-136.

However, for several years, the increasingly severe operating conditions of automobile engines have led to more stringent specifications for the base oils from which engine oils are formulated, in particular a reduction in their volatility and in their point flow and an increase in their VI (above 105). However, such characteristics cannot always be obtained only by solvent extraction of distillation cuts (“straight run”), hence the development of processes for producing oils from other cuts, such as those obtained from 'catalytic hydrocracking and / or catalytic hydrodewaxing. In fact, during the hydrocracking reaction of the hydrocarbon feedstocks, mainly the saturation of the aromatic compounds and the decyclization of the naphthenes occur, while the hydrodewaxing reaction causes the cracking and isomerization of the n-paraffins and improves the cold properties of the lubricant bases obtained.

Such bases, obtained from hydrocracking residues subjected to a dewaxing with solvent and forming part of group III according to the API classification described above, are currently produced, in particular by the Applicant, under the name NHC5 (“Neutral HydroCracked ”), with a Vk @ 100 ° C of 4.5 to 5 mm ² / s (4.5 to 5 cSt).

It is already known to those skilled in the art to produce lubricating base oils having a high viscosity index (VI), for example greater than 125, from hydrocarbon feedstocks originating from heavy fractions or residues of a hydrocracker. Patent application FR 2 194 767 A describes, in particular, a process for preparing a high VI lubricating oil, comprising a catalytic hydrocracking treatment of a mineral fraction with high boiling point, a effluent fractionation, dewaxing of the boiling residue above 350 ° C. and catalytic hydroisomerization of the paraffin obtained.

The association of hydrocracking and isomerization stages with specific catalysts, for the manufacture of high VI lubricants, is also described in EP 0 574 191 A and EP 0 597 935 A. This is also the case for EP 0 744 452 A, which describes a process for the production of such base oils, comprising a step of hydrocracking with a catalyst based on platinum and / or palladium of a hydrocracker background fraction, so as to convert at least 25% by weight of the hydrocarbon fraction having a boiling point of at least 370 ° C., followed by an effluent fractionation step, the heavy fraction having an VI of at least 125 and preferably greater than 135, with a kinematic viscosity at 100 ° C of at least 3.5 mm ² / s or cSt, the heavy fraction then undergoing a dewaxing step. However, these patents or published applications do not give any details on the cold properties of the lubricant bases obtained, such as their pour point, nor on their structure.

Another known route for obtaining high VI base oils consists in using highly paraffinic hydrocarbon charges, in particular composed of n-paraffins or waxes obtained by Fischer-Tropsch synthesis or slack wax. Thus, in particular, that EP-A-0 323 092 describes a process for producing high VI oil, comprising steps of hydrotreatment, catalytic hydroisomerization and dewaxing, and that WO 97/21788 A describes a process for producing a biodegradable lubricating base oil, comprising a step of hydroisomerization and catalytic hydrocracking of a fraction of boiling point above 370 ° C. of a charge of Fischer-Tropsch paraffins, a step fractionation of the effluent obtained, the heavy fraction of which contains paraffins branched by methyl radicals, and finally a dewaxing step with solvent. If the latter application describes a branching rate per molecule of between 6 and 7.5 methyl groups per 100 carbon atoms, it is specified that there are very few branches by groups with 2 carbon atoms (ethyl) or more.

However, the Applicant has established, surprisingly, that the quality of these oils is linked to the isoparaffinic nature of the hydrocarbon chains of the cuts used and, in particular, to a specific relationship between the different types of substituents carried by these chains.

The object of the present invention is therefore to obtain a new base oil for high-end lubricants, obtained from hydrocarbon cuts from various sources, having a high viscosity index and improved cold properties, in particular a pour point below -18 ° C, ensuring satisfactory rheological properties to the finished lubricating oils formulated from this base oil, in a wide range of temperatures (from -30 to + 100 ° C), thanks to a particular branching structure of the paraffinic molecules composing it.

It has been observed in particular that the base oil according to the invention is much better in performance than bases currently available on the market, derived from hydrocracked products and having undergone solvent dewaxing (oils of the NHC5 type), or dewaxing catalytic, and which belong to group III according to the API classification described above. Surprisingly, it can also replace known synthetic bases such as poly-α-olefins (PAO), belonging to group IV, whose performances are well known for increasing the VI, but which have the major drawback of have a cost much higher than the bases of mineral origin.

To this end, the subject of the invention is a hydrocarbon base oil for lubricants, having a viscosity index VI greater than or equal to 130, comprising mainly long, isoparaffinic hydrocarbon chains, comprising a number of carbon atoms greater than 25 and branched on several carbon atoms, characterized in that the hydrocarbon chains have a ratio of the number of substituents composed of at least two carbon atoms to the number of methyl substituents greater than or equal to 0.9, and in that these chains have a ratio of the number of substituents composed of at least two carbon atoms, to the number of CH ₂ long chain groups, greater than or equal to 0.23.

It has been established, in fact, that for a base oil, when the value of the two ratios which have just been defined is less than 0.9 and 0.23 respectively, the characteristics of the finished lubricating oils obtained at from this base are less efficient.

In particular, the base oil according to the invention has a ratio of the viscosity index when cold (VIF) to the viscosity index (VI) (measured according to standard NF T 60-136) greater than or equal at 1.

Advantageously, the base oil has a content of naphthenic molecules less than or equal to 0.1.

In particular, the base oil has a Noack volatility value of less than 13% by weight (calculated according to standard CEC-L-40-A 95), as well as a pour point (calculated according to standard NFT 60- 105) below -18 ° C. In addition, it has a Saybolt color value of + 30 (measured according to the ASTM D 156 method).

In addition, the base oil has a cold viscosity index (VIF) greater than 125.

More particularly, the base oil has a dynamic CCS viscosity at -30 ° C of less than 1200 mPa.s (calculated according to standard ASTM D 5293), for a kinematic viscosity Vk at 100 ° C of 4 mm ² / s.

In particular, the base oil according to the invention has a viscosity index VI greater than 130 and less than or equal to 135, for a kinematic viscosity Vk at 100 ° C of between 3.5 and 4.5 mm ² / s or cSt.

More specifically, this base oil has a viscosity index VI greater than 135 for a kinematic viscosity Vk at 100 ° C of between 4.5 and 5 mm ² / s.

A second object of the invention relates to the use of the base oil defined above, in the formulation of lubricants for engines, in particular for automobiles, with a view in particular to formulating an OW30 grade.

A third subject of the invention relates to a process for the preparation of the base oil of the invention successively comprising the stages of hydrotreatment, hydrodewaxing, fractionation and hydrofinishing of residue cuts from hydrocracking.

It turned out that the new base oil, according to the invention, exhibits advantageous properties when cold, characterized, on the one hand, by a pour point of less than - 18 ° C and, on the other hand , by a new so-called cold viscosity index (VIF) such that the oil has a cold viscosity index (VIF) / viscosity index (VI) ratio, greater than or equal to 1. The cold viscosity index VIF is calculated in using the usual formula for calculating the VI (according to standard NF T 60-136), which integrates the values of kinematic viscosity at 100 ° C and 40 ° C of the product to be measured, but by replacing the value of kinematic viscosity with 40 ° C, the kinematic viscosity value at -30 ° C. The latter is obtained by dividing the dynamic viscosity at - 30 ° C (which is measurable) by the density at - 30 ° C of the product, calculated from the density at 15 ° C, by temperature correction.

• huile de base B obtenue à partir d'une charge très paraffinique, par exemple du gatsch, hydrocraquée et hydrodéparaffinée,
• huile de base C obtenue à partir d'une charge moins paraffinique, hydrocraquée et hydrodéparaffinée,
• huile de base D du type NHC5,
• huile de base E du type 150N ( groupe I).

Different analysis methods have been used to analyze the base oil according to the invention (base oil A) and the following competitive products:

• base oil B obtained from a very paraffinic filler, for example slack wax, hydrocracked and hydrodewaxed,
• base oil C obtained from a less paraffinic, hydrocracked and hydrodewaxed filler,
• base oil D of type NHC5,
• base oil E of type 150N (group I).

All these oils have a kinematic viscosity Vk @ 100 ° C of between 4 and 5 mm ² / s (4 and 5 cSt).

Mass spectrometry made it possible to evaluate the content of naphthenic molecules in the various base oils: there are approximately 10% for oil A, as well as for oil B, against 30% for oil C, 40% for oil D and 60% for oil E.

The ¹³ C NMR spectra of these base oils were obtained by the following TOTAL method of sample preparation: 0.77 g of oil is incorporated in 1.5 ml of deuterated chloroform, to which 200 μl of dioxane have been added ( 0.23 g). The addition of dioxane (which gives a single fine peak at 67.2 ppm, outside the saturated carbon zone), in constant quantity, allows an internal normalization of each spectrum and makes it possible to compare the peak heights of different spectra between them. The values appearing in Table 2 below are peak heights expressed in cm, all normalized with respect to the dioxane peak at 100 cm, and therefore comparable with one another.

• A) carbones naphténiques : leur présence ne se traduit pas par des pics fins, mais par un fond continu dans la zone des carbones saturés (65- 5 ppm), très peu visible d'un point de vue qualitatif.
• B) carbones aromatiques : la teneur en carbones aromatiques de ces huiles est faible (inférieure à 1 %) et ceux-ci ne donnent pas de pics fins.
• C) carbones paraffiniques : le spectre de ces carbones est d'une façon générale un spectre de pics dans la zone des carbones saturés (65-5 ppm). Ces pics correspondent à des carbones paraffiniques dans des environnements particuliers. La plupart de ces pics sont identifiés et attribués à des structures connues. En particulier, on peut distinguer :
  • le pic « CH₂ de chaîne longue » caractéristique de motifs CH₂ situés à plus de trois atomes de carbone d'un bout de chaîne ou d'une substitution ; on note (voir Tableau 2 ci-après) que la hauteur de ce pic est nettement plus grande pour l'huile de base B que pour les autres huiles de base, ce qui traduit la présence de morceaux de chaînes droites sans substitution en moyenne plus longs dans cette huile que dans les autres ; l'huile D et l'huile A présentent des valeurs plus faibles ;
  • le nombre de substitutions méthyl par molécule, noté « Subst.C1 », correspond à la somme des hauteurs de quatre pics caractéristiques ; l'huile B présente la valeur la plus élevée, suivie par l'huile A et l'huile C ;
  • le nombre de substitutions plus longues par molécule, c'est-à-dire de deux atomes de carbone et plus (éthyl et plus), noté « Subst. C2+ », correspond à la somme de trois pics caractéristiques ; on constate que l'huile A, selon l'invention, est nettement plus riche que les autres en substitutions longues.

Examination of the ¹³ C NMR spectra reveals the following points:

• A) Naphthenic carbons: their presence does not result in fine peaks, but in a continuous background in the area of saturated carbons (65-5 ppm), very little visible from a qualitative point of view.
• B) aromatic carbons: the aromatic carbons content of these oils is low (less than 1%) and these do not give fine peaks.
• C) paraffinic carbons: the spectrum of these carbons is generally a spectrum of peaks in the region of saturated carbons (65-5 ppm). These peaks correspond to paraffinic carbons in particular environments. Most of these peaks are identified and attributed to known structures. In particular, we can distinguish:
  • the “long chain CH ₂ ” peak characteristic of CH _{2 units} located at more than three carbon atoms from a chain end or from a substitution; we note (see Table 2 below) that the height of this peak is significantly greater for base oil B than for other base oils, which indicates the presence of pieces of straight chains without substitution on average more long in this oil than in the others; oil D and oil A have lower values;
  • the number of methyl substitutions per molecule, noted “Subst.C1”, corresponds to the sum of the heights of four characteristic peaks; oil B has the highest value, followed by oil A and oil C;
  • the number of longer substitutions per molecule, ie two or more carbon atoms (ethyl and more), noted "Subst. C2 + ”, corresponds to the sum of three characteristic peaks; it is found that the oil A, according to the invention, is clearly richer than the others in long substitutions.

Furthermore, if we report the number of substitutions of 2 carbons and more on the number of methyl substitutions, we obtain the highest value for oil A, 0.947, close to 1, indicating a balanced substitution mode, whereas, for oils D, B and C, and a fortiori for E, the substitution ratio is more in favor of the methyl groups.

Likewise, the ratio of the number of substitutions of 2 carbons and more to the number of CH ₂ long chain units, expressed in%, gives a value greater than 23% for oil A, whereas it only reaches 21.8% for oil C and around 14% for oils B and D, oil E remaining below 3%. This characterizes, for oil A according to the invention, a structure of n-paraffinic chains shorter than those of an original base very rich in paraffins, but substituted with a larger number of longer chains. Table 2 Base oil A Base oil B Base oil C Base oil D Base oil E Analysis of ¹³ C NMR spectra (height of peaks in cm) CH2 long chain peaks 59.34 87.03 50.22 76.14 42,49 Pics Subst.C1 14.64 16.37 14.33 13.66 9.85 Pics Subst.C2 + 13.86 12.44 10.95 10.89 1.27 Subst.C2 + / Subst.C1 report 0.947 0.760 0.764 0.797 0.129 100 * Subst.C2 + / CH2 long chain ratio 23.36 14.29 21,80 14,30 2.99 % naphthenic molecules 10 10 30 40 60 VI 131.4 142 126 128 100 VIF 135.7 112 123 113 50 VIF / VI 1.03 0.79 0.98 0.88 0.5

• (1) une première étape d'hydrotraitement à température comprise entre 380 et 480 °C, à haute pression (8 MPa<PH₂<27 MPa ), et basse vitesse spatiale horaire (0,15<VVH<1 h^-1), sur catalyseur du type Ni-Mo, dopé ou non, sur support de type amorphe. Lors de cette étape se produisent la décyclisation des naphtènes, la saturation des aromatiques et du craquage, conduisant à une amélioration du VI et un abaissement de la viscosité cinématique ;
• (2) une seconde étape de déparaffinage catalytique à température élevée (T comprise entre environ 300 et 400 °C), en présence d'un catalyseur de type zéolithique dopé par des métaux nobles tels que du platine, au cours de laquelle ont lieu des réactions de craquage et d'isomérisation des n-paraffines. Cette étape permet d'améliorer les propriétés à froid de la coupe traitée, notamment d'abaisser son point d'écoulement, tout en préservant la valeur du VI ;
• (3) une troisième étape de fractionnement sous vide, pour obtenir des coupes d'environ 400-470 °C (TBP), permettant d'ajuster la viscosité cinématique Vk@100 °C à environ 4 mm²/s, et la volatilité Noack en dessous de 13% ;
• (4) une dernière étape d'hydrofinition, à T<250°C, à pression élevée, (PH₂>10 Mpa), à faible vitesse spatiale horaire (0,3<VVH<0,8 h^-1) et avec un catalyseur Pt /Pd ou Ni, permettant de saturer les composés aromatiques (teneur <1000 ppm) pour conférer à l'huile une faible coloration (valeur de couleur Saybolt +30) et une stabilité à l'oxydation.

According to a preferred, but non-limiting, embodiment to obtain the very good viscosimetric and flow properties at cold of the lubricating base oil according to the invention, the Applicant has implemented the following sequence of steps, starting from residues resulting from hydrocracking treatment having a boiling point of between 300 and 600 ° VS :

• (1) a first hydrotreatment step at a temperature between 380 and 480 ° C, at high pressure (8 MPa <PH ₂ <27 MPa), and low hourly space speed (0.15 <VVH <1 h ^-1 ) , on a Ni-Mo type catalyst, doped or not, on an amorphous type support. During this stage, the decyclization of the naphthenes occurs, the saturation of the aromatics and the cracking, leading to an improvement in the VI and a lowering of the kinematic viscosity;
• (2) a second stage of catalytic dewaxing at high temperature (T between approximately 300 and 400 ° C.), in the presence of a zeolitic type catalyst doped with noble metals such as platinum, during which cracking and isomerization reactions of n-paraffins. This step makes it possible to improve the cold properties of the treated cut, in particular to lower its pour point, while preserving the value of the VI;
• (3) a third vacuum fractionation step, to obtain sections of approximately 400-470 ° C (TBP), allowing the kinematic viscosity Vk @ 100 ° C to be adjusted to approximately 4 mm ² / s, and the volatility Noack below 13%;
• (4) a final hydrofinishing step, at T <250 ° C, at high pressure, (PH ₂ > 10 Mpa), at low hourly space speed (0.3 <VVH <0.8 h ^-1 ) and with a Pt / Pd or Ni catalyst, allowing the aromatic compounds to be saturated (content <1000 ppm) to give the oil a weak coloration (Saybolt color value +30) and oxidation stability.

However, other types of fillers can advantageously be used, in mixture with the previous fillers, for doping them, in particular paraffins or Fischer-Tropsch synthetic waxes, waxes or slack waxes, and distillates for atmospheric or vacuum distillation.

Furthermore, it can also be envisaged to obtain the lubricating base oil according to the invention, by oligomerization of olefins, in particular of light alpha-olefins present in particular in the heavy petrol of visbreaking units or in l essence of FCC (cracker catalytic). This oligomerization is carried out in the presence of a catalyst of the phosphoric acid or aluminum chloride type, at temperatures between approximately 190 ° C. and 340 ° C. and it leads to hydrocarbon products with very branched long chains.

The base oils thus obtained, having a VI greater than 130 and a VIF greater than 125, can replace synthetic lubricating bases of the PAO type, with an advantageous economic advantage, in formulations for oils for automobile engines and in particular in grades such as OW30, for which the requirements of cold properties are the most severe: kinematic viscosity Vk @ 100 ° C between 9.3 and 12.5 mm ² / s and dynamic viscosity CCS at -30 ° C less than 3250 mPa.s.

• huile de base A : 80,1
• additif de performance : 13,8
• additif améliorant le VI : 5,8
• additif diminuant le point d'écoulement : 0,3

The Applicant has thus formulated a motor oil of grade OW30 with a composition, in% by weight:

• base oil A: 80.1
• performance additive: 13.8
• VI improving additive: 5.8
• additive reducing the pour point: 0.3

• viscosité cinématique Vk@100°C :   9,65 mm²/s
• viscosité cinématique à 40°C :   50,8 mm²/s
• VI :   178
• viscosité dynamique CCS à -30°C :   3000 mPa.s,

et elle satisfait ainsi aux spécifications de ce grade, en remplacement d'une huile de base du type PAO ou mélange PAO et ester. En outre, une telle formulation satisfait en particulier aux critères du test moteur TU3MH (selon la norme CEC-L-55-T-95).This oil has the following characteristics:

• kinematic viscosity Vk @ 100 ° C: 9.65 mm ² / s
• kinematic viscosity at 40 ° C: 50.8 mm ² / s
• VI: 178
• CCS dynamic viscosity at -30 ° C: 3000 mPa.s,

and it thus meets the specifications of this grade, replacing a base oil of the PAO type or mixture of PAO and ester. In addition, such a formulation satisfies in particular the criteria of the TU3MH engine test (according to standard CEC-L-55-T-95).

These bases can also find interesting applications in formulations for industrial lubricants.

Claims (12)

1. A hydrocarbon base oil for lubricants having a viscosity index (VI) greater than or equal to 130, principally comprising long isoparaffinic hydrocarbon chains containing a number of carbon atoms higher than 25 and branched over several carbon atoms, characterised in that these hydrocarbon chains have a ratio of the number of substituents composed of at least two carbon atoms to the number of methyl substituents greater than or equal to 0.9, and in that these chains have a ratio of the number of substituents composed of at least two carbon atoms to the number of long chain CH₂ groups greater than or equal to 0.23.
2. A base oil according to claim 1, characterised in that it has a ratio of the cold viscosity index (VIF) to the viscosity index (VI) greater than or equal to 1.
3. A base oil according to either one of claims 1 and 2, characterised in that it has a content of naphthenic molecules lower than or equal to 0.1.
4. A base oil according to any one of claims 1 to 3, characterised in that it has a Noack volatility value lower than 13 % by weight.
5. A base oil according to any one of claims 1 to 3, characterised in that it has a flow point below -18°C.
6. A base oil according to any one claims 1 to 3, characterised in that has a Saybolt colour value of +30.
7. A base oil according to claim 2, characterised in that it has a cold viscosity index (VIF) greater than 125.
8. A base oil according to any one of the preceding claims, characterised in that it has a dynamic viscosity at -30°C of less than 1200 m Pa.s, for a kinematic viscosity Vk at 100°C of 4 mm²/s.
9. A base oil according to any one of claims 1 to 3, characterised in that it has a viscosity index (VI) of between 130 and 135 for a kinematic viscosity Vk at 100°C of between 3.5 and 4.5 mm²/s.
10. A base oil according to any one of claims 1 to 3, characterised in that it has a viscosity index VI greater than 135 for a kinematic viscosity Vk at 100°C of 4.5 and 5 mm²/s.
11. Use of the base oil according to any one of the preceding claims, in the formulation of engine lubricants, in particular for automobiles, especially with a view to formulating a 0W30 grade.
12. A process for preparing a base oil according to any one of claims 1 to 10, characterised in that it comprises the following successive steps:

    a) a first hydrotreatment step at a temperature of between 380°C and 480°C, at high pressure (8 MPa<PH₂<27 MPa), and low hourly spatial velocity (0.15<VVH<1 h^-1), over a catalyst of Ni-Mo type, which is doped or not, on a support of amorphous type, of residues arising from a hydrocracking treatment having a boiling point of between 350 and 600°C;

    b) a second catalytic dewaxing step at high temperature (T between about 300 and 400°C), in the presence of a catalyst of the zeolitic type doped with noble metals, such as platinum;

    c) a third vacuum fractionation step so as to obtain fractions of approximately 400-470°C (TBP);

    d) a final hydrofinishing step, at T<250°C, at high pressure, (PH₂>10 Mpa), at low hourly spatial velocity (0.3<WH<0.8 h^-1) and with a Pt/Pd or Ni catalyst.