DE112011102541T5 - APPLICATION-SPECIFIC MANUFACTURED LUBRICANT COMPOSITIONS COMPRISING A BIOLOGICAL ESTER COMPONENT, AND METHOD FOR MANUFACTURING THE SAME - Google Patents

Abstract

The present invention relates generally to methods for making custom finished lubricant compositions comprising biodegraded diester types. In some embodiments, biologically derived fatty acid groups are reacted with Fischer-Tropsch gas-to-liquid reaction products and / or degradation products (eg, gas-to-liquid-produced α-olefins) to obtain a biologically derived diester species then selectively mixed with base oil and one or more types of additives to obtain an application-specific finished lubricant product having a biomass-derived component.

Description

FIELD OF THE INVENTION

This invention relates to finished lubricating compositions and their preparation, and more particularly to application specific finished lubricating compositions comprising a diester component, in particular wherein the diester constituent is at least partially derived from biomass.

BACKGROUND

Esters have been used as lubricating oils for more than 50 years. They are used in various applications from jet engines to cooling. Esters were even the first synthetic crankcase engine oils in automotive applications. However, esters were almost completely displaced by polyalphaolefins (PAOs) because the cost of PAOs is lower and their formulation has similarities to mineral oils. However, in fully synthetic engine oils, esters are almost always used in combination with PAOs to offset the effect on gaskets, solubility of additives, reducing volatility, and improving energy efficiency through improved lubricity.

Ester-based lubricants generally have excellent lubricating properties due to the polarity of the ester molecules that make them up. Due to the polarity of the ester functionality, esters have a greater affinity for metal surfaces than PAOs and mineral oils. Therefore, they very effectively produce protective films on metal surfaces, these protective films serving to attenuate wear of the metals. Such lubricants are less volatile than traditional lubricants and often have a much higher flash point and vapor pressure. Ester lubricants are excellent solvents and dispersants and can easily dissolve and disperse the waste products of oils, i. h., they reduce the accumulation of oil residues. Although ester lubricants are relatively stable to heat and oxidation processes, the ester functionalities provide microbes with a point of action for their biodegradation activity more efficiently and effectively than their mineral oil-based analogs, and thus are more environmentally friendly. However, as previously mentioned, the preparation of esters is more expensive and expensive than that of their PAO counterparts.

More recently, Miller et al., U.S. Patent Application No. 20080194444 A1, published Aug. 14, 2008, and Miller et al., U.S. Patent Application No. 20090198075 A1, published Aug. 6, 2009 , novel diester based lubricant compositions and their corresponding preparation are described. The diester synthesis described in these patent applications makes the diester lubricant formulations economically more economical.

In light of the foregoing, and despite the advantages described, further integration of such synthesis of diester-based lubricants in one or more other processes, particularly those which further involve converting low value waste products into custom finished lubricant compositions, may render the economics of ester-based production Influencing lubricants in a favorable manner.

BRIEF SUMMARY OF THE INVENTION

The present invention relates generally to methods for making custom finished lubricant compositions comprising biodegraded diester types. In some embodiments, biologically derived fatty acid groups are reacted with Fischer-Tropsch (FT) gas-to-liquid (GtL) reaction products and / or degradation products (ie, α-olefins) to obtain a biologically derived diester species which is then selectively may be mixed with base material (oil) and one or more types of additives to obtain an application-specific finished lubricant product having a biomass-derived component.

In some embodiments, the present invention relates to processes for making such finished lubricant compositions, which processes generally include the steps of: (a) preparing an amount of epoxidized olefins, wherein the step of preparing comprises the following substeps: (i) isolating alpha olefins ( α-olefins) prepared in a gas-to-liquid process to obtain isolated α-olefins; (ii) isomerizing at least a major portion of the isolated alpha olefins to obtain an amount of internalized olefins; and (iii) epoxidizing at least the major portion of the internalized olefins to obtain an amount of epoxidized olefins containing a Include epoxide ring; and (b) obtaining an amount of esterifying agent, wherein the esterifying agent is derived from triglyceride-bonded fatty acid groups, whereby the recovery results in esterifying agents selected from the group consisting of carboxylic acids, acyl halides, acylanhydrides, and combinations thereof, wherein the step of obtaining comprises the following substeps : (i ') selecting a biomass source comprising triglycerides, said triglycerides comprising fatty acid groups of suitable length; (ii ') releasing a major portion of the fatty acid groups from the triglyceride molecules of which they are an ingredient to give esterifying agents; (c) esterifying at least a major portion of the epoxidized olefins with the esterifying agent to give an amount of a diester species; and (d) combining the amount of diester species with an amount of base oil and an adjunct containing at least one additive selected from the group consisting of antioxidants, cleaners, antiwear agents, metal deactivators, corrosion inhibitors, rust inhibitors, friction modifiers, antifoams, viscosity index improvers, demulsifiers, emulsifiers , Tackifiers, complexing agents, extreme pressure additives, pour point depressants and combinations thereof; wherein the selecting of the at least one additive is substantially determined by the end use of the produced lubricant composition, wherein the type of lubricant composition may be selected from the group consisting of turbine oils, metalworking fluids, hydraulic fluids, compressor oils, chain oils, agricultural engine oils, tractor hydraulic fluids, marine oils, paper machine oils , Spindle and textile oils, trailer wheel bearing greases and combinations thereof.

wobei R₁, R₂, R₃ und R₄ gleich oder unabhängig ausgewählt sind aus C₂- bis C₁₇-Kohlenwasserstoffgruppen (vide infra).Typically, the finished lubricant compositions made by the above processes, together with a base oil and one or more types of additives, comprise at least one diester species, the diester species generally having the following structure:

wherein R ₁ , R ₂ , R ₃ and R _{4 are the} same or independently selected from C ₂ to C ₁₇ hydrocarbon groups (vide infra).

The foregoing has outlined broadly the features of the present invention in order to facilitate the understanding of the following detailed description. In the following, further features and advantages of the invention will be described, which form the subject of the claims of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention and its advantages, reference should now be made to the following description taken in conjunction with the accompanying drawings, in which:

1 shows an exemplary diester species that may be used to form at least a portion of the diester component of at least some of the lubricant compositions described herein, wherein the lubricant compositions are prepared in accordance with some embodiments of the present invention;

2 FIG. 10 is a flowchart illustrating an exemplary method of making a lubricant composition according to some embodiments of the present invention; FIG.

3 (Scheme 1) illustrates how at least some diesters of the diester component of finished lubricant compositions can be made from an epoxy type by going through a diol (dihydroxy) intermediate species, according to some embodiments of the present invention;

4 (Scheme 2) illustrates how at least some diesters of the diester constituent of finished lubricant compositions can be produced by direct esterification of an epoxide species, according to some embodiments of the present invention;

5 (Scheme 3) illustrates how at least some diesters of the diester component of finished lubricant compositions can be generated via an enzyme-assisted path, according to some embodiments of the present invention;

6 (Scheme 4) illustrates how fractional crystallization can be used to tailor the diester component of the finished lubricant composition according to some modified embodiments of the present invention; and

7 (Scheme 5) illustrates how fractional crystallization can be used to tailor the diester component of the finished lubricant composition according to other modified embodiments of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

1 Introduction

As mentioned in a previous section, the present invention relates to methods of making application-specific lubricant compositions having a biomass-derived component. In some embodiments, biologically derived fatty acid groups (ie, derived from a renewable biomass source) are reacted with Fischer-Tropsch (FT) gas-to-liquid (GtL) reaction products and / or degradation products (ie, α-olefins) to produce a biological obtained diester species, which can then be selectively mixed with base material (oil) and one or more types of additives to obtain an application-specific finished lubricant product with a biomass-derived component.

As bioliquids and biofuels are increasingly gaining public attention and become a major topic for many oil industry stakeholders, the use of biomass in the production of finished lubricants of this type may be attractive from a variety of perspectives (eg, renewable, legislative, economical) , Since biomass is used in preparing the diester component of the finished lubricants described herein, such lubricants are considered to be biolubricants or at least lubricants comprising a biologically derived constituent.

2. Definitions

"Lubricants" as defined herein are substances (usually a fluid under operating conditions) introduced between two moving surfaces to reduce friction and wear therebetween. This definition also includes fats whose viscosity drops sharply when shear is applied.

As used herein, "base oil" means the largest single component (by weight) of a lubricant composition. Base oils are divided into five groups (I-V) by the American Petroleum Institute (API). See API Publication Number 1509. The API base oil category from the following table (Table 1) is used to define the type of composition and / or origin of the base oil. Table 1. Base oil category Sulfur (%) Saturation (%) viscosity Index Group I > 0.03 and or <90 80 to 120 Group II <0.03 and > 90 80 to 120 Group III <0.03 and > 90 > 120 Group IV All polyalphaolefins (PAOs) Group V All base oils not included in Groups I, II, III or IV (eg esters)

"Mineral base oils" as defined herein are base oils made by refining a crude oil.

The "pour point" as defined here represents the lowest temperature at which a fluid flows or flows. See, for example, B. ASTM International Standard Test Method D 5950-02 (R 2007) ,

The "cloud point" as defined herein represents the temperature at which a fluid begins phase separation due to the formation of crystals. See, for example, B. ASTM International Standard Test Method D 5771-05 ,

"Centistoke", abbreviated "cSt", is a unit of kinematic viscosity of a fluid (eg a lubricant), where 1 Centistoke 1 equals one square millimeter per second (1 cSt = 1 mm ² / s). See, for example, B. ASTM International Standard Test Method D 2270-04 , The units cSt and mm ² / s are used interchangeably here.

With respect to the description of molecules and / or molecular fragments, "R _m ", where "m" is an index, denotes a hydrocarbon group, which molecules and / or molecular fragments may be linear and / or branched.

As defined herein, "C _n ", where "n" is an integer, describes a hydrocarbon molecule or moiety (eg, an alkyl group), where "n" indicates the number of carbon atoms in the fragment or molecule.

The term "carbon number" is used here analogously to "C _n ". One difference, however, is that the carbon number denotes the total number of carbon atoms in a molecule (or molecular fragment), whether or not it is pure carbon. For example, linoleic acid has a carbon number of 18.

The term "internal olefin" as used herein refers to an olefin (i.e., an alkene) having a non-terminal carbon-carbon double bond (C = C). This is in contrast to "α-olefins" which have a terminal carbon-carbon double bond.

The term "adjacent" as used herein refers to the attachment of two functional groups (substituents) to adjacent carbons in a hydrocarbon-based molecule, e.g. B. adjacent diesters.

The term "fatty acid group" as used herein refers to any molecular species and / or any molecular fragment comprising the acyl moiety of a fatty (carboxylic) acid.

The prefix "bio / bio" as used herein refers to a renewable source of biological origin, such that the source typically excludes fossil fuels. Such a relationship is typically recovery, i. H. a bioester is obtained from a biomass precursor material.

"Fischer-Tropsch products", as defined herein, refers to molecular species derived from a catalytically-driven reaction between CO and H ₂ (ie, "syngas"). See, for example, B. Dry "The Fischer-Tropsch process: 1950-2000" Vol. 71 (3-4), pp. 227-241, 2002 ; Schulz, "Short history and present trends of Fischer-Tropsch synthesis" Applied Catalysis A, Vol. 186, pp. 3-12, 1999 ; Claeys and Van Steen, "Fischer-Tropsch Technology" chapter 8, pp. 623-665, 2004 ,

"Gas-to-liquid" as used herein refers to Fischer-Tropsch processes for producing liquid hydrocarbons and hydrocarbon-based species (eg, oxygenates).

As used herein, "application-specific finished lubricant compositions" refer to lubricant compositions that have been formulated for a particular end-use application.

3. Finished lubricant compositions

wobei R₁, R₂, R₃ und R₄ gleich oder unabhängig ausgewählt sind aus einem C₂- bis C₁₇-Kohlenwasserstofffragment. Abhängig von der Ausführungsform können solche resultierenden Diesterarten ein Molekulargewicht zwischen 340 atomaren Masseeinheiten (AMU) und 780 AMU aufweisen.Methods of the present invention (vide infra) generally contemplate application specific finished lubricant compositions comprising a biologically derived diester component wherein the diester component comprises a set of (adjacent) diester species having the following chemical structure:

wherein R ₁ , R ₂ , R ₃ and R _{4 are the} same or independently selected from a C ₂ to C ₁₇ hydrocarbon fragment. Depending on the embodiment, such resulting diester species may have a molecular weight between 340 atomic mass units (AMU) and 780 AMU.

In some embodiments, the diester component of the above-described lubricant compositions is substantially homogeneous. In some or other embodiments, the diester component of these compositions comprises a variety (ie, a mixture) of diester species. In some embodiments, the diester component of the finished lubricant compositions comprises an amount of at least one diester species derived from a C ₈ to C ₁₄ olefin and a C ₆ to C ₁₄ carboxylic acid.

In some embodiments, the finished lubricant composition comprises an amount of at least one diester species selected from the group consisting of decanoic acid 2-decanoyloxy-1-hexyl-octyl ester and its isomers, tetradecanoic acid 1-hexyl-2-tetradecanoyloxy-octyl esters and their isomers, Dodecanoic acid 2-dodecanoyloxy-1-hexyl octyl ester and its isomers, hexanoic acid 2-hexanoyloxy-1-hexyl octyl ester and its isomers, octanoic acid 2-octanoyloxy-1-hexyl octyl ester and its isomers, hexanoic acid 2-hexanoyloxy 1-pentyl heptyl ester and isomers, octanoic acid 2-octanoyloxy-1-pentyl heptyl ester and isomers, decanoic acid 2-decanoyloxy-1-pentyl heptyl ester and its isomers, decanoic acid 2-decanoyloxy-1-pentyl heptyl ester and Isomeres, dodecanoic acid 2-dodecanoyloxy-1-pentyl heptyl ester and isomers, tetradecanoic acid 1-pentyl-2-tetradecanoyloxyheptyl ester and isomers, tetradecanoic acid 1-butyl-2-tetradecanoyloxyhexyl ester and isomers, D odecanoic acid-1-butyl-2-dodecanoyloxy-hexyl ester and isomers, decanoic acid-1-butyl-2-decanoyloxy-hexyl ester and isomers, octanoic acid 1-butyl-2-octanoyloxy-hexyl ester and isomers, hexanoic acid-1-butyl-2-hexanoyloxy hexyl esters and isomers, tetradecanoic acid 1-propyl-2-tetradecanoyloxy-pentyl ester and isomers, dodecanoic acid 2-dodecanoyloxy-1-propyl-pentyl ester and isomers, decanoic acid 2-decanoyloxy-1-propyl-pentyl ester and isomers, octanoic acid-2 octanoyloxy-1-propyl-pentyl ester and isomers, hexanoic acid-2-hexanoyloxy-1-propyl-pentyl ester and isomers, and mixtures thereof.

Referring to 1 become exemplary diester compositions 1 - 7 which are produced by steps / substeps of the processes described below, all of which compositions can be formed from a 1-tetradecene-α-olefin and a dodecanoic acid (C ₁₂ -fatty acid), and wherein structural diversity results therefrom how far the 1-tetradecene was "internalized". composition 1 For example, results from the direct epoxidation of the 1-tetradecene. Any or all compositions 1 - 7 may be present in the diester component of the application-specific finished lubricant compositions of the present invention.

4. Process for producing finished lubricant compositions

As mentioned in the preceding paragraphs, the present invention generally relates to methods of making application specific lubricant compositions comprising a biomass-derived component as described above.

Referring to the flowchart 2 in at least one embodiment, the present invention relates to at least one process for preparing lubricant compositions, the process comprising the steps of: ( 201 ) Preparing an amount of epoxidized olefins, wherein the steps of preparing comprises the following substeps: ( 201 ) Isolating alpha-olefins (α-olefins) prepared in a gas-to-liquid (GtL) process to obtain isolated α-olefins; ( 201b ) Isomerizing at least a major portion of the isolated α-olefins to obtain an amount of internalized olefins; and ( 201c ) Epoxidizing at least the majority of the internalized olefins to obtain an amount of epoxidized olefins comprising an epoxide ring; and ( 202 Obtaining an amount of esterifying agent wherein the esterifying agent is derived from triglyceride-bonded fatty acid groups whereby the recovery yields esterifying agents selected from the group consisting of carboxylic acids, acyl halides, acylanhydrides and combinations thereof, the step of obtaining comprising the substeps of: 202a ) Selecting a biomass source comprising triglycerides, said triglycerides comprising fatty acid groups of suitable length; ( 202b ) Releasing a major portion of the fatty acid groups from the triglyceride molecules of which they are an integral part to form esterifying agents; ( 203 ) Esterifying at least a major portion of the epoxidized olefins with the esterifying agent to give an amount of a diester species; and ( 204 ) Combining the amount of the diester species with an amount of base oil and an additive component comprising at least one additive selected from the group consisting of antioxidants, cleaners, antiwear agents, metal deactivators, corrosion inhibitors, rust inhibitors, friction modifiers, anti-foaming agents, viscosity index improvers, demulsifiers, emulsifiers, tackifiers, Complexing agents, extreme pressure additives, pour point depressants and combinations thereof; wherein the selecting of the at least one additive is substantially determined by the end use of the produced lubricant composition, wherein the type of lubricant composition may be selected from the group consisting of turbine oils, metalworking fluids, hydraulic fluids, compressor oils, chain oils, agricultural engine oils, tractor hydraulic fluids, marine oils, paper machine oils , Spindle and textile oils, trailer wheel bearing greases and combinations thereof.

The GtL process, in which the α-olefins are prepared, can be a low temperature (200-300 ° C) Fischer-Tropsch (NTFT) process, a high-temperature Fischer-Tropsch (HTFT) (> 300 ° C) or a combination of the two. In addition, in some such embodiments, the GtL process may include one or more additional processes after the initial Fischer-Tropsch synthesis.

In some of the processes described above, the sub-step of isolating the α-olefins comprises their separation from a substantially paraffinic GtL product. Such separation may be accomplished by various methods including, but not limited to, distillation, fractionation, membrane separation, phase separation, and combinations thereof.

In some of the processes described above, the substep of isomerization includes using an olefin isomerization catalyst such as, but not limited to, crystalline aluminosilicate and similar materials and aluminophosphates. See, for example, Schaad, U.S. Patent No. 2,537,283 , issued Jan. 9, 1951; Holm et al. U.S. Patent No. 3,211,801 , issued on Oct. 12, 1965; Noddings et al. U.S. Patent No. 3,270,085 issued on 30 Aug 1966; Noddings, U.S. Patent No. 3,327,014 issued on June 20, 1967; Mitsutani et al. U.S. Patent No. 3,304,343 , issued on Feb. 14, 1967; Holm et al. U.S. Patent No. 3,448,164 issued on 3 June 1969; Johnson et al. U.S. Patent No. 4,593,146 issued on 3 June 1986; Tidwell et al. U.S. Patent No. 3,723,564 issued on March 27, 1973; and Miller, U.S. Patent No. 6,281,404 issued on Aug. 28, 2001; the latter claiming a crystalline aluminophosphate based catalyst having 1-dimensional pores of a size between 3.8 Å and 5 Å.

With respect to the above-mentioned epoxidation step (ie, the epoxidation step), the above-described olefin (which has been internalized from an α-olefin) may be reacted with a peroxide (e.g., H ₂ O ₂ ) or a peroxide acid (e.g., peracetic acid ) to produce an epoxide. See, for example, B. Swern et al., "Epoxidation of Oleic Acid, Methyl Oleate and Oleyl Alcohol with Perbenzoic Acid" J. Am. Chem. Soc., Vol. 66 (11), pp. 1925-1927, 1944 ,

In some of the processes described above, the sub-step of releasing triglyceride-bonded fatty acid groups includes hydrolyzing the triglycerides to yield glycerol and carboxylic acid, the latter being effective for use as an esterification agent (see, e.g. Huber et al., "Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering" Chem. Rev., Vol. 106, pp. 4044-4098, 2006 ). In some such embodiments, a substep is further provided wherein the carboxylic acids are separated substantially on the basis of their degree of unsaturation, such that the esterifying agents used in the subsequent step of esterification are substantially homogeneous in their degree of unsaturation. See Miller, US Patent Application Publication No. 20090285728 A1, published Nov. 19, 2009.

In some of the processes described above, the step of esterifying the epoxidized olefins is through a diol intermediate (see Miller et al., U.S. Patent Application Publication No. 20080194444 A1, published Aug. 14, 2008). Such a diol intermediate can be generated by epoxide ring opening to obtain the corresponding diol, which ring opening is achieved via acid catalyzed or base catalyzed hydrolysis. Exemplary acid catalysts include, but are not limited to, Bronsted acids (eg, HCl, H ₂ SO ₄ , H ₃ PO ₄ , perhalates, etc.), Lewis acids (eg, TiCl ₄ and AlCl ₃ ). , Solid acids such as acidic aluminas and silicas or their mixtures and the like. See, for example, B. Parker et al., "Mechanisms of Epoxide Reactions" Chem. Rev., Vol. 59 (4), pp. 737-799, 1959 ; and Paterson et al., "Meso Epoxides in Asymmetric Synthesis: Enantioselective Opening by Nucleophiles in the Presence of Chiral Lewis Acids" Angew. Chem. Int. Ed., Vol. 31 (9), pp. 1179-1180, 1992 , Base-catalyzed hydrolysis typically involves the use of bases such as aqueous solutions of sodium or potassium hydroxide.

In some such embodiments, the diol intermediate is reacted with the esterification agent in the presence of an acid catalyst. Scheme 1 ( 3 ) shows such an exemplary route that leads to a diester type through a diol type, wherein the diester species in some such embodiments may subsequently be included as the diester component or a portion thereof in a finished lubricant composition.

In some of the processes described above, the step of esterifying the epoxidized olefins is directly by a reaction between the epoxidized olefin and the esterification agent (see Miller et al., U.S. Patent Application Publication No. 20090198075 A1, published Aug. 6, 2009). In some such embodiments, the step of esterifying the epoxidized olefins is carried out in the presence of an acid catalyst, which acid catalyst can be selected from the group consisting of H ₃ PO ₄ , H ₂ SO ₄ , sulfonic acid, Lewis acids, silica and alumina. based solid acids, Amberlyst, tungsten oxide and combinations thereof. In some embodiments, during the step of direct esterification, one attempts to remove water generated as a result of the esterification process. Such experiments can have a positive effect on the diester yield. Scheme 2 ( 4 ) shows such an exemplary route that leads to a diester species via direct esterification of the epoxide species.

In some of the processes described above, the sub-step of epoxidizing enzymes is supported (see Miller et al., U.S. Patent Application Publication No. 12 / 270,235, filed Nov. 13, 2008). Scheme 3 ( 5 ) exemplifies such an exemplary approach whereby the epoxidation of the internalized olefin is promoted or mediated by enzymes. While Scheme 3 shows an exemplary route involving the direct esterification of the epoxide species (to a diester species), such epoxidation may alternatively be via a diol species.

In some of the processes described above, the diester species formed is selected from the group consisting of decanoic acid 2-decanoyloxy-1-hexyl octyl ester and its isomers, tetradecanoic acid 1-hexyl-2-tetradecanoyloxy-octyl esters and their isomers, dodecanoic acid-2 dodecanoyloxy-1-hexyl octyl ester and its isomers, hexanoic acid 2-hexanoyloxy-1-hexyl octyl ester and its isomers, octanoic acid 2-octanoyloxy-1-hexyl octyl ester and its isomers, hexanoic acid 2-hexanoyloxy-1-pentyl -heptyl esters and isomers, octanoic acid 2-octanoyloxy-1-pentyl heptyl ester and isomers, decanoic acid 2-decanoyloxy-1-pentyl heptyl ester and its isomers, decanoic acid 2-decanoyloxy-1-pentyl heptyl ester and isomers, dodecanoic acid 2-dodecanoyloxy-1-pentyl heptyl ester and isomers, tetradecanoic acid 1-pentyl-2-tetradecanoyloxyheptyl ester and isomers, tetradecanoic acid 1-butyl-2-tetradecanoyloxyhexyl ester and isomers, dodecanoic acid 1-butyl-2-dodecanoyloxy hexyl and isomers, decanoic acid 1-butyl 2-decanoyloxyhexyl ester and isomers, octanoic acid 1-butyl-2-octanoyloxyhexyl ester and isomers, hexanoic acid 1-butyl-2-hexanoyloxyhexyl ester and isomers, tetradecanoic acid 1-propyl-2 - tetradecanoyloxy pentyl ester and isomers, dodecanoic acid 2-dodecanoyloxy-1-propyl pentyl ester and isomers, decanoic acid 2-decanoyloxy-1-propyl pentyl ester and isomers, octanoic acid 2-octanoyloxy-1-propyl pentyl ester and isomers, hexanoic acid- 2-hexanoyloxy-1-propyl-pentyl ester and isomers, and mixtures thereof.

In some of the processes described above, in the combining step, the base oil is selected from the group consisting of GtL base oils, mineral base oils, diester-based base oils, and mixtures thereof. In some such embodiments, the base fluid is a GtL base oil or a diester-based base oil.

In some embodiments, all or part of the additive ingredient is provided as an additive package. In some or other embodiments, all or part of the diester ingredient is combined with all or part of the additive ingredient to collectively form an additive package. In some embodiments, the amount of the diester component or portion thereof serves to aid dispersion of all or part of the additive ingredient in the base oil. For further information on existing variants of lubricant additives and the properties they impart, see e.g. B. Rudnick, LR Lubricant Additives: Chemistry and Applications, 2nd Edition, CRC Press, Boca Raton, 2009 ,

In some of the processes described above, the substep of selecting a biomass source comprising triglycerides is based on the identification and sufficient content of triglyceride molecules carrying fatty acid groups of a length more desirably suitable for use as a particular lubricant composition. For example, in its hydrolyzed form, palm oil comprises about 44 percent palmic acid, a saturated fatty acid having a carbon number of 16.

In some of the processes described above, the lubricant composition is a hydraulic fluid having a pour point of about -80 ° C to about 0 ° C.

In some of the processes described above, the lubricant composition is a turbine oil having a viscosity index (VI) of at least 90 to at most 130 and having a RPVOT oxidation stability of at least 250 minutes. up to a maximum of 2300 min. Please refer ASTM Standard Guide and Test Method D 2272-02

In some of the processes described above, the lubricant composition is a metal processing fluid having a pour point of about -20 ° C to about 0 ° C. Such metal processing fluids typically have a viscosity in the range of about 32 centistokes (cSt) to about 220 cSt, measured at 40 ° C.

In some of the processes described above, the lubricant composition is a compressor oil having a VI of at least 90 to at most 130 and a pour point of at least -60 ° C to at most 0 ° C. Such a compressor oil typically has a viscosity of from about 32 cSt to about 220 cSt, measured at 40 ° C.

In some of the processes described above, the lubricant composition is a chain oil having a VI in the range of at least 50 to at most 130 and an aniline point in the range of at least 0 ° C to at most 130 ° C.

5. Modifications

Variations (ie, alternative embodiments) of the above-described methods of making application specific lubricant compositions include, but are not limited to, incorporating the methods into one or more other processes to produce one or more related or different products and / or the manufactured products by one or more of the method embodiments described above.

As an example of such a modified embodiment described, Scheme 4 ( 6 ) an exemplary process embodiment of the present invention wherein the diester synthesis proceeds via a direct esterification of one type of epoxide. In this scheme, a fractional crystallization process is used to separate saturated fatty acids from unsaturated fatty acids using the saturated fatty acids in direct esterification (see Miller, US Patent Application Publication No. 20090285728 A1, published Nov. 19, 2009). In some such provided In modified embodiments, the unsaturated fatty acids may be hydrorefined to obtain saturated fatty acids, which are subsequently recycled to the direct esterification sub-process. Additionally or alternatively, the unsaturated fatty acids can be reacted to form triester and / or diester species used in other compositions or in the finished lubricating compositions described herein (see, e.g., Elomari et al., U.S.A. Patent Application Serial No. 12 / 480,032, filed June 8, 2009, and Elomari et al., U.S. Patent Application Serial No. 12 / 498,663, filed July 7, 2009).

Of course, the modified embodiment described above can be modified such that the esterification proceeds via a diol species, as shown in Scheme 5 (FIG. 7 ) is shown. In addition, each of the alternate embodiments of Schemes 4 and 5 may use enzymes to aid in the epoxidation of the internalized olefins.

Additionally or alternatively, in some alternative embodiments, the FT / GtL process may be tuned or otherwise adapted to produce α-olefins as the primary product stream and / or with a high yield of particular chain length / carbon number α-olefins. Separation subprocesses may be employed to further refine the alpha-olefin type which is ultimately epoxidized on the way to diester formation, according to some embodiments of the present invention.

6. Examples

The following examples serve to demonstrate and / or more specifically illustrate certain embodiments of the present invention. Those skilled in the art will understand that the methods disclosed in the following examples are only exemplary embodiments of the present invention. However, in light of the present disclosure, those skilled in the art will understand that many changes may be made to the specific embodiments described and still obtain a like or similar result without departing from the spirit and scope of the present invention.

EXAMPLE 1

This example is intended to illustrate how various aspects of the methods described above can be adapted to obtain a hydraulic fluid (oil), according to some embodiments of the present invention.

In some of the foregoing embodiments, hydraulic oils can be prepared by blending a quantity of the biologically derived diester type (vide supra) with base oil and the following: zinc-based or ashless metal-free antiwear additives, antioxidants, and anti-rust additives. Hydraulic fluids of this type can be designed to minimize metal-to-metal contact, as required by all anti-wear hydraulic fluids, thereby contributing to equipment life extension. Furthermore, these hydraulic oils can be designed for use in vane, piston and gear pumps. Such hydraulic oils typically have a viscosity of from about 5 cSt to about 360 cSt, measured at 40 ° C, and have a viscosity index (VIs) between about 95 and 350, a flash point between about 120 ° C and about 400 ° C and a pour point between about -80 ° C and about 0 ° C.

EXAMPLE 2

This example is intended to illustrate how various aspects of the methods described above can be adapted to obtain turbine oil, in accordance with some embodiments of the present invention.

Turbine oils may be prepared by mixing one or more biologically derived diester species (as described in Section 3) with base oil and ashless additives, which typically include one or more corrosion inhibitors, antioxidants, antifoaming agents, demulsifiers, and wear inhibitors. These turbine oils can be designed to have high oxidation and thermal stability, resulting in longer lubricant life and less equipment downtime. In addition, to avoid contamination of water, rapid separation from the oil allows quick setting of the water so that it can be drained from the system. Such turbine oils described herein can be used in steam and gas turbines with and without Reduction gears are used, as well as in centrifugal, rotary and reciprocating compressors that need rust and oxidation protection.

EXAMPLE 3

This example is intended to illustrate how various aspects of the methods described above can be adapted to obtain a metal processing oil, in accordance with some embodiments of the present invention.

Metalworking fluids may be prepared by mixing the biologically derived diester species (i.e., one or more of the types described in Section 3) with or without base oil and ashless and / or ash-containing additives. Typically, the additives include one or more antioxidants, metal deactivators, wear inhibitors, rust inhibitor additives and anti-foaming agents. In accordance with some embodiments of the present invention, the metalworking fluids may be configured to have high thermal and oxidative stability, thus providing longer lubricant life, less oil change, less deposition on the processed or mobile equipment, more ester lubricity, increased solubility and increased Operating time. In addition, their low volatility results in reduced oil composition and the generation of less oil vapor or mist during work. This provides a healthier work environment for businesses and reduces the extent to which oil settles on finished parts and equipment. In addition, the reduced tendency of sludge and deposit formation results in less filter clogging, less maintenance and increased uptime.

EXAMPLE 4

This example is intended to illustrate how various aspects of the methods described above can be adapted to obtain a compressor oil, in accordance with some embodiments of the present invention.

Air compressor oils may be prepared by mixing the biologically derived diester species (i.e., one or more of the species described in Section 3) with base oil and ashless and / or ash-containing additives. Typically, the additives include one or more antioxidants, metal deactivators, wear inhibitors, rust inhibitor additives and anti-foaming agents. According to some embodiments of the present invention, the compressor oils may be designed to have high thermal and oxidative stability, providing for longer lubricant life, less oil change, and longer operating times. In addition, their low volatility results in a reduced oil composition and less oil downstream from the compressor. In addition, the reduced tendency for sludge and deposit formation results in less filter clogging, less maintenance and increased operating time of compressors. It is envisaged that such compressor oils can be used in reciprocating, rotary and / or vane compressors.

EXAMPLE 5

This example is intended to illustrate how various aspects of the methods described above can be adapted to obtain a chain oil, in accordance with some embodiments of the present invention.

The chain oils can be prepared by blending the above-described diester type with base oil, zinc-based or ashless metal-free antiwear agents, tackifiers, antioxidants, metal deactivators, antifoams, and anti-rust additives. Such chain oils may be designed to lubricate chain and link parts associated with chain saws and other chain-containing equipment. Oils of this type are intended to have excellent solubility in order to dissolve resin in forestry applications. Metal-to-metal contact is kept to a minimum to help extend chain life. These chain oils typically have a viscosity of 5 cSt to 360 cSt, measured at 40 ° C, a viscosity index of 50 to 250, a flash point of 120 ° C to 400 ° C and a pour point of 0 ° C to -80 ° C.

7th final

In summary, the present invention relates generally to methods of making custom lubricant formulations comprising biologically derived diester species. In some embodiments, biologically derived fatty acid groups are reacted with Fischer-Tropsch gas-to-liquid reaction products / degradation products (ie, α-olefins) to yield a biologically derived diester species which is then selectively mixed with base material (oil) and one or more additive species can be mixed to obtain an application-specific finished lubricant product with a component derived from biomass.

All patents and publications cited herein are hereby incorporated into the present subject matter as far as they do not contradict the present subject matter. It is understood that some of the structures, functions, and operations described above of the embodiments described above are not necessary to practice the present invention and have been included only to complete one or more embodiments. It is also to be understood that certain structures, functions, and operations discussed in the cited patents and publications cited above may be practiced in conjunction with the present invention, but are not critical to its practice. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the spirit and scope of the present invention as defined in the appended claims.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 2537283 [0044]
• US 3211801 [0044]
• US 3270085 [0044]
• US 3327014 [0044]
• US 3304343 [0044]
• US 3448164 [0044]
• US 4593146 [0044]
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• US 6281404 [0044]

Cited non-patent literature

• ASTM International Standard Test Method D 5950-02 (R 2007) [0023]
• ASTM International Standard Test Method D 5771-05 [0024]
• ASTM International Standard Test Method D 2270-04 [0025]
• Dry "The Fischer-Tropsch Process: 1950-2000" Vol. 71 (3-4), pp. 227-241, 2002 [0033]
• Schulz, "Short history and present trends of Fischer-Tropsch synthesis" Applied Catalysis A, Vol. 186, pp. 3-12, 1999 [0033]
• Claeys and Van Steen, "Fischer-Tropsch Technology" chapter 8, p. 623-665, 2004 [0033]
• Swern et al., "Epoxidation of Oleic Acid, Methyl Oleate and Oleyl Alcohol with Perbenzoic Acid" J. Am. Chem. Soc., Vol. 66 (11), pp. 1925-1927, 1944 [0045]
• Huber et al., "Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering" Chem. Rev., Vol. 106, pp. 4044-4098, 2006 [0046]
• Parker et al., "Mechanisms of Epoxy Reactions" Chem. Rev., Vol. 59 (4), pp. 737-799, 1959 [0047]
• Paterson et al., "Meso Epoxides in Asymmetric Synthesis: Enantioselective Opening by Nucleophiles in the Presence of Chiral Lewis Acids" Angew. Chem. Int. Ed., Vol. 31 (9), pp. 1179-1180, 1992 [0047]
• Rudnick, LR Lubricant Additives: Chemistry and Applications, 2nd Edition, CRC Press, Boca Raton, 2009 [0053]
• ASTM Standard Guide and Test Method D 2272-02 [0056]

Claims (20)

A process for preparing lubricant compositions, the process comprising the steps of: a) preparing an amount of epoxidized olefins, wherein the steps of preparing comprises the following substeps: i) isolating α-olefins prepared in a gas-to-liquid process to obtain isolated α-olefins; ii) isomerizing at least a major portion of the isolated α-olefins to obtain an amount of internalized olefins; and iii) epoxidizing at least the majority of the internalized olefins to obtain an amount of epoxidized olefins comprising an epoxide ring; and b) obtaining an amount of esterifying agent wherein the esterifying agents are derived from triglyceride-bonded fatty acid groups, whereby the recovery yields esterifying agents selected from the group consisting of carboxylic acids, acyl halides, acylanhydrides, and combinations thereof, wherein the step of obtaining comprises the following substeps: i ') selecting a biomass source comprising triglycerides, the triglycerides comprising fatty acid groups of suitable length; ii ') releasing a major portion of the fatty acid groups from the triglyceride molecules of which they are an ingredient to give esterifying agents; c) esterifying at least a major portion of the epoxidized olefins with the esterifying agent to give an amount of a diester species; and d) combining the amount of diester species with an amount of base oil and an adjunct component comprising at least one additive selected from the group consisting of antioxidants, cleaners, antiwear agents, metal deactivators, corrosion inhibitors, rust inhibitors, friction modifiers, antifoams, viscosity index improvers, demulsifiers, emulsifiers, tackifiers Complexing agents, extreme pressure additives, pour point depressants and combinations thereof; wherein the selecting of the at least one additive is substantially determined by the end use of the produced lubricant composition, wherein the type of lubricant composition may be selected from the group consisting of turbine oils, metalworking fluids, hydraulic fluids, compressor oils, chain oils, agricultural engine oils, tractor hydraulic fluids, marine oils, paper machine oils , Spindle and textile oils, trailer wheel bearing greases and combinations thereof. The process of claim 1, wherein the sub-step of isolating the α-olefins comprises separating them from a substantially paraffinic GtL product. The process of claim 1, wherein the substep of isomerization includes using an olefin isomerization catalyst. The process of claim 1, wherein the sub-step of epoxidizing enzymes is promoted. The process of claim 1, wherein the sub-step of releasing triglyceride-bonded fatty acid groups comprises hydrolyzing the triglycerides to obtain carboxylic acids as the esterifying agent. The process of claim 5 further comprising a substep of separating the carboxylic acids substantially based on their degree of unsaturation such that the esterifying agents used in the subsequent step of esterification are substantially homogeneous in their degree of unsaturation. The process of claim 1, wherein the step of esterifying the epoxidized olefins proceeds via a dihydroxide intermediate. The process of claim 7, wherein the dihydroxide intermediate is reacted with the esterifying agent in the presence of an acid catalyst. The process of claim 1 wherein the step of esterifying the epoxidized olefins is directly via reaction between the epoxidized olefin and the esterification agent. The process of claim 9, wherein the step of esterifying the epoxidized olefins is in the presence of an acid catalyst. The process of claim 10, wherein the acid catalyst is selected from the group consisting of H ₃ PO ₄ , H ₂ SO ₄ , sulfonic acid, Lewis acids, silica and alumina-based solid acids, Amberlyst, tungsten oxide, and combinations thereof. The process of claim 1, wherein in the step of combining, the base oil is selected from the group consisting of GtL base oils, mineral base oils, diester based base oils, and mixtures thereof. The process of claim 1, wherein the diester species formed is selected from the group consisting of decanoic acid 2-decanoyloxy-1-hexyl octyl ester and its isomers, tetradecanoic acid 1-hexyl-2-tetradecanoyloxy-octyl esters and their isomers, dodecanoic acid-2 dodecanoyloxy-1-hexyl octyl ester and its isomers, hexanoic acid 2-hexanoyloxy-1-hexyl octyl ester and its isomers, octanoic acid 2-octanoyloxy-1-hexyl octyl ester and its isomers, hexanoic acid 2-hexanoyloxy-1-pentyl -heptyl esters and isomers, octanoic acid 2-octanoyloxy-1-pentyl heptyl ester and isomers, decanoic acid 2-decanoyloxy-1-pentyl heptyl ester and its isomers, decanoic acid 2-decanoyloxy-1-pentyl heptyl ester and isomers, dodecanoic acid 2-dodecanoyloxy-1-pentyl heptyl ester and isomers, tetradecanoic acid 1-pentyl-2-tetradecanoyloxyheptyl ester and isomers, tetradecanoic acid 1-butyl-2-tetradecanoyloxyhexyl ester and isomers, dodecanoic acid 1-butyl-2-dodecanoyloxy hexyl esters and isomers Decanoic acid 1-butyl-2-decanoyloxyhexyl ester and isomers, octanoic acid 1-butyl-2-octanoyloxyhexyl ester and isomers, hexanoic acid 1-butyl-2-hexanoyloxyhexyl ester and isomers, tetradecanoic acid 1-propyl-2-tetradecanoyloxy -pentyl esters and isomers, dodecanoic acid 2-dodecanoyloxy-1-propyl-pentyl ester and isomers, decanoic acid 2-decanoyloxy-1-propyl-pentyl ester and isomers, octanoic acid 2-octanoyloxy-1-propyl-pentyl ester and isomers, hexanoic acid-2 hexanoyloxy-1-propyl pentyl ester and isomers, and mixtures thereof. The process of claim 12, wherein the base oil is a GtL base oil, and wherein the amount of diester ingredient serves to aid dispersion of the additive ingredient in the base oil. The process of claim 1, wherein the substep of selecting a biomass source comprising triglycerides is based on the identification and sufficient content of triglyceride molecules carrying fatty acid groups of a length more desirably suitable for use as a particular lubricant composition. The process of claim 1, wherein the lubricant composition is a hydraulic fluid having a pour point of about -80 ° C to about 0 ° C. The process of claim 1, wherein the lubricant composition is a turbine oil having a VI of at least 90 to at most 130 and having a RPVOT oxidation stability of at least 250 minutes to at most 2300 minutes. The process of claim 1, wherein the lubricant composition is a metal processing fluid having a pour point of about -20 ° C to about 0 ° C. The process of claim 1, wherein the lubricant composition is a compressor oil having a VI of at least 90 to at most 130 and a pour point of at least -60 ° C to at most 0 ° C. The process of claim 1, wherein the lubricant composition is a chain oil having a VI in the range of at least 50 to at most 130 and an aniline point in the range of at least 0 ° C to at most 130 ° C.

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