Patent Grant
11473028
Aspects of the present disclosure generally relate to isoparaffin oligomers derived from C14 through C18 olefins, such as one or more of linear internal, branched internal and alpha-olefins. According to certain aspects, the isoparaffinic oligomers may be used as lubricant base oils.
Poly alpha-olefins (PAOs) and Poly internal-olefins (PIOs) make up an important class of hydrocarbon lubricating oils. They are typically produced by the polymerization of alpha-olefins or internal-olefins in the presence of a Friedel Craft catalyst such as AlCl3, BF3, or BF3 complexes. For example, 1-octene, 1-decene, 1-dodecene, and 1-tetradecene have been used to manufacture PAOs. Similarly, C8-18 internal olefins have been used to manufacture PIOs. Oligomerization of these olefins is typically followed by fractionation and hydrogenation to remove any remaining unreacted hydrocarbons and unsaturated moieties. Disclosures of processes for making PIOs can be found, for example, in EP 1,104,747, EP 0,776,960, and U.S. Pat. No. 4,910,355.
Hydrocarbon lubricating oils are commonly categorized by kinematic viscosity (KV) in centistokes (cSt), measured at 100° C. according to ASTM D445. For example, 2 cSt, 2.5 cSt, 4 cSt, 5 cSt, 6 cSt, 7 cSt, 8 cSt, and 9 cSt PAOs and PIOs have been prepared comprising various combinations of oligomers and homopolymers of C8-C18 linear mono-olefins. PAOs and PIOs were developed as high-performance functional lubricating oils that have improved performance, e.g., over a wide operational temperature range.
The automotive industry is placing greater demands on engine oils, operating at higher temperatures for longer times and requiring lower viscosity engine oil formulations such as 0W-30 and 0W-20 engine oils which improve vehicle fuel economy by lowering friction losses. This is driving a demand for low viscosity PAOs and PIOs, such as around 4 cSt kinematic viscosity, while maintaining low Noack volatility and good low-temperature performance properties. Thus, a need exists for low viscosity base oils which exhibit advantageous properties which may include a low Noack volatility, calculated according to ASTM D 5800 Standard Test Method for Evaporation Loss of Lubricating Oils by the Noack Method, and that may also include a low cold-crank viscosity (i.e. dynamic viscosity according to ASTM D 5293), and can include the ability to pass a stricter 0W engine oils viscometric requirement.
Prior efforts to prepare various PAOs that can meet the increasingly stringent performance requirements of modern lubricants and automotive engine oil particularly have favored low viscosity polyalphaolefin base oils derived from 1-decene alpha-olefins, alone or in some blend with other mineral or Fischer-Tropsch derived base oils. However, the polyalphaolefin derived from 1-decene can be prohibitively expensive, due the high cost of 1-decene as a result of its significantly limited availability. Furthermore, there is generally a need for new base oils with improved properties, and methods of manufacture thereof, including base oils comprising PAOs and/or PIOs derived from materials other than 1-decene.
Commercially, some C28 to C36 oligomers of alpha olefins are made from a mixed feed of C8, C10 and C12 alpha olefins, with 1-decene being incorporated for the purpose of imparting the most desirable properties. In contrast, 4 cSt PAOs and PIOs made without decene have yielded base oils lacking in one or more important physical properties. Thus, PAOs made from mixed alpha-olefin feeds such as the C28 to C36 oligomers described above may have the advantage that they lower the amount of decene that is needed to impart predetermined properties. However, they still do not completely remove the requirement for providing decene as a significant proportion of the oligomer. Furthermore, the process to make these PAOs may also result in the production of significant quantities of cross-oligomers that do not have the desired properties for a 4 cSt base oil. Accordingly, narrow distillation cuts must typically be taken to select only the oligomers having the desired properties, resulting in undesirably low yields of functional product.
Accordingly, there remains a need for a base oil composition having properties within commercially acceptable ranges, such as properties including the viscosity, Noack volatility, and low temperature cold-cranking viscosity, for use in automotive and other applications, as well as a method of manufacturing such base oil compositions. Furthermore, there remains a need for base oil compositions having improved properties and methods of manufacture thereof, where the base oil compositions have reduced amounts of 1-decene incorporated therein, and may even eliminate the use of 1-decene in the manufacture thereof.
Also, the demand for low viscosity (e.g., 4 to 10 cSt at 100° C.) PAOs outpace the supply. Specifically, it is highly desirable to produce a lubricant base oil that has similar or equivalent properties to the C10 trimer based PAO (often referred to as 4 cSt PAO). There is also a continuing need for improved base oils, e.g. base oils that have a wide operational temperature range, and a continuing need for base oils derived from renewable feedstock.
PIOs are not used commercially today, although they have been sold in the market historically. Their properties are inferior to PAOs, and not useful for lower viscosity engine oil formulations such as 0W-30 and 0W-20 engine oils. For example, a 4 cSt PIO made from internal olefins having a branching ratio of CH3/CH2 (as determined by 1H NMR) of 0.2083, a viscosity of 4.33 cSt at 100° C., a VI of 122 and a pour point of −54 C has the flaw that its Noack volatility is too high, at 15.3 (Reference: Synthetic Lubricants And High-Performance Functional Fluids, Revised And Expanded. Edited by Leslie R. Rudnick and Ronald L. Shubkin; CRC Press 1999, Table 1, page 55).
Oligomerization catalysts and processes for making base oils materials from alpha olefins and internal olefins are described, for example, in U.S. Pat. No. 4,910,355. According to this disclosure, and olefin oligomer functional fluid is prepared using internal olefins. Specifically, olefin oligomers are obtained by a mixture of C8-18 olefins containing 50-90 weight percent α-olefins and 10-50 weight percent internal olefins and oligomerizing this mixture using a Friedel Crafts catalyst (e.g. BF3) and a promoter (e.g. n-butanol), to form trimers. The mixture of olefins can be formed from α-olefins (e.g. 1-decene) by subjecting the α-olefins to isomerization until 10-50 weight percent of the olefins are internal olefins. In this disclosure, the pour points of the exemplified C10 trimer are very good, but the Viscosity Index (VI) is less than 110 for a mixture of 50:50 1-decene: internal decenes; which is below the acceptable VI for 0W-20 motor oils.
EP 0,136,377 discloses the oligomerization of at least 99 wt. % of internal mono olefins to make PIOs having 9 to 24 carbon atoms, with a catalyst comprising boron trifluoride; the product made here have either too high viscosity, >4.3 cSt at 100° C. or the VI is 124 or less. The Noack volatility is also >16%. Conversion to the 4 cSt fraction are not disclosed. U.S. Pat. No. 5,453,556 discloses the oligomerization of alpha and internal olefins using a tungstate modified zirconia; in one example, the reaction of an aloha and internal C14 olefin produce products with higher viscosities (>4.72 cSt at 100° C.) than what is desired; the pour points are relatively high (−25 and −28° C.). In U.S. Pat. No. 7,456,329 a feedstock of unsaturated olefins is oligomerized to form an unsaturated polyolefin; the saturated dimer requires isomerization over a zeolite catalyst to lower the pour point from −17° C. (which remains excessively high). The other deficiency of this patent is the viscosities at 100° C. are greater than 4.5 cSt. U.S. Pat. No. 8,124,820 discloses oligomerizing alpha olefins to produce dimers and oligomers over a solid catalyst in a continuous flow reactor. In one example, dimers of 1-hexadecene were made with pour points that are excessively high, at higher than −25° C., VI >140 and vis >4.2 cSt at 100° C.; however, the conversion to products is less than 60% and the selectivity to dimer is about 90%. U.S. Pat. No. 8,501,675 High viscosity novel base oil lubricant viscosity blends; —viscosity of at least 135 cSt, KV 100° C. and a CH3/CH2 branch ratio less than 0.19 (or 19%). In US 20100298616 a feed comprising olefins having at least 10 carbons are simultaneously hydrogenated and isomerized in the presence of hydrogen at a temperature and a hydrogenation/isomerization catalyst.
U.S. Pat. No. 5,264,642 discloses that the molecular structure of alpha olefins oligomers correlates very well with improved lubricant properties in commercial synthetic lubricants. Specifically, the reference discloses that one characteristic of the molecular structure of saturated olefin oligomers that has been found to correlate very well with improved lubricant properties in commercial synthetic lubricants is the ratio of methyl to methylene groups in the oligomer (e.g., as measured by 1H NMR, also referred to as the branch ratio). U.S. Pat. No. 5,264,642 discloses that the Viscosity Index for the PAOs disclosed therein increases with lower branch ratios. According to this reference, PAOs prepared from 1-decene by cationic polymerization, and having branch ratios of greater than 0.20 (with branching occurring by rearrangement, isomerization, or other mechanism), yield synthetic lubricants with excessive branching, which constrains the lubricant properties, particularly with respect to viscosity index. That is, U.S. Pat. No. 5,264,642 discloses that a branching ratio greater than 0.20 results in a base oil with poor lubricant properties, and especially a poor viscosity index.
Furthermore, PAOs existing in the market today are derived from fossil fuels, and hence are not renewable. Therefore, it is also desirable to produce base oils and PAOs from renewable sources.
In U.S. Pat. No. 8,449,760 a Fischer-Tropsch derived base oil lubricant is described with properties including −19° C. Pour Point, a viscosity at 40° C. of 17.55 cSt, and a viscosity at 100° C. of 4.303 cSt, with a VI of 161. Accordingly, while the viscosity properties are excellent, this lubricant is deficient as the pour point is only −19° C. (i.e., too high). Other low temperature properties such as CCS are not disclosed but it can be surmised by the pour point that they have a −35° C. CCS of the disclosed lubricant is not optimum for 0W engine applications (i.e., too high). A low CCS at −35° C. is required for 0W engine oil applications.
Other processes using F-T wax feeds for making base oils are described in U.S. Pat. No. 7,795,484, US 20130317263, U.S. Pat. No. 9,464,238, US 20110054230, US 20110132803, U.S. Pat. Nos. 5,608,122, 7,795,484, US 20090014354, and US 20120238788.
Provided herein are novel compositions and methods for preparation of a novel base oil having improved properties, such as including at least one of an excellent Viscosity index (VI), Cold Crank Simulation viscosity (ASTM D 5293), and Noack Volatility. According to one aspect, the composition includes a mixture of olefin feedstocks having a carbon chain length in a range of from C14 to C18, where at least one of the olefin feeds has an average double bond position between 1.5 and 5.0 (e.g., as measured by gas chromatography). Additional olefin feedstocks, may optionally be provided, such as with greater than 90% alpha olefin.
In certain advantageous embodiments, the base oils are derived from one or more alpha-olefin feedstocks where a portion of at least one alpha-olefin feedstock has been isomerized to yield an internal olefin having a defined average double-bond position. According to this embodiment, the isomerized alpha olefin portion of the feedstock and the un-isomerized alpha-olefin form an olefin feed mixture. The olefin feed mixture may comprise by wt % at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or even at least about 100% internal olefin, where the average double bond position of the internal olefin is controlled to be in a range between 1.5 and 5.0. According to one embodiment, the oligomer products have performance comparable to API Group III base oils or Group IV PAOs. Additionally, aspects of the present disclosure may provide, in certain embodiments, suitable sources of feedstocks for base oils and lubricant compositions that exhibit good properties over relatively wide temperature ranges, as described further herein.
In this embodiment, a low amount of isomerization takes place during oligomerization yielding a well-defined sharp singlet on the end of the initial peak grouping (trimer) which characterizes the singularly branched isomers.
According to aspects of the disclosure, olefin oligomers are obtained by providing at least one C14-C18 olefin monomer, or a mixture of two or more of said olefins monomer, where at least one of the olefin monomer is an internal olefin monomer that has an average double bond position in the range of 1.5 to 5.0 (e.g., as shown in box 1 of
Other non-limiting examples of suitable Lewis acids that may be used for oligomerization and/or isomerization include metalloid halides and metal halides typically used as Friedel-Crafts catalysts, e.g. AlCl3, BF3, BCl3, AlBr3, TiCl3, TiCl4, SnCl4, or SbCl5. Any of the metalloid halide or metal halide catalysts can be used with or without a co-catalyst protic promoter (e.g. water, alcohol, acid, or ester). BF3 catalyst with a protic co-catalyst promoter can be used in any suitable amount.
For engine oil applications, in certain embodiments it may be important that the base oil have excellent viscometrics (e.g., high VI, >125) with a low enough pour point to allow the material to pass SAE 0W low temperature viscosity requirements in a formulated engine oil.
Feedstocks
According to one aspect, the feedstocks useful for making a dimer that has desirable viscosity for an engine oil are C14-C18 olefin monomers. Furthermore, aspects of the disclosure may require that at least one of the olefin monomers provided as the feedstock has an average double bond that is controlled to be at an average position in the range of from 1.5-5.0. The average double bond position can be measured by any conventional method, such as for example via a gas chromatography method. Furthermore, the internal olefin monomer having the defined average double bond position can be prepared, for example, through the isomerization of an alpha olefin, such as one that is derived from ethylene, see for example, U.S. Pat. No. 7,393,991 or from dehydrated alcohols, see for example U.S. Pat. No. 7,795,484. U.S. Pat. No. 7,393,991 details to the selective isomerization of alpha olefins to internal olefins by passing the olefin through a catalyst bed containing zeolite catalyst and/or montmorillonite catalyst at elevated temperatures. As disclosed herein, the average double bond position of the olefin monomer can be controlled to define the amount and length of branching present in the oligomer product.
In one embodiment, a first feedstock comprises a C14 to C18 internal olefin monomer. A second feedstock may also optionally be provided, which comprises at least one of a C14 to C18 alpha olefin monomer, and/or a C14 to C18 internal olefin monomer. For example, the first feedstock may be prepared by isomerizing at least a portion of C14 to C18 alpha olefin monomers under isomerization conditions suitable to generate an isomerized C14 to C18 alpha olefin product having an average double bond position in the range of from 1.5 to 5.0.
In another embodiment, the first feedstock is prepared by isomerization of C14 to C18 alpha olefin monomers selected from the group consisting of tetradecene, pentadecene, hexadecane, heptadecene and octadecene. In another embodiment, C14 to C18 alpha olefin monomers used to prepare the first feed stock (via isomerization thereof) are prepared by dehydration of C14 to C18 primary alcohols selected from the group consisting of 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol and 1-octadecanol. In yet another embodiment, C14 to C18 primary alcohols are converted to the C14 to C18 alpha olefin monomers, and isomerized to form the isomerized C14 to C18 olefin monomer of the first feed-stock product by exposure to a di-functional catalyst (e.g., a catalyst capable of both dehydrating the primary alcohols to form alpha olefin monomers, and isomerizing the alpha-olefin monomers to internal olefins.
In another embodiment, the feedstock used to form the C14 to C18 internal olefin monomers comprises less than 20% by weight of branched olefin monomers. In yet another embodiment, the feedstock used to form the C14 to C18 internal olefin monomers comprises less than 10% by weight of branched olefin monomers. In yet another embodiment, the feedstock used to form the C14 to C18 internal olefin monomers comprises less than 5% by weight of branched olefin monomers.
Furthermore, in another embodiment, an amount of decene in any of the first and/or second feedstocks is less than 10% by weight. In yet another embodiment, an amount of decene in any of the first and/or second feedstocks is less than 5% by weight.
In yet another embodiment, the isomerization conditions used to form the internal olefin monomers of the first feedstock comprise heating C14 to C18 alpha olefin monomers in the presence of an isomerization catalyst to a temperature in a range of from 100 to 400° C. In yet another embodiment, isomerization conditions comprise heating C14 to C18 alpha olefin monomers in the presence of an isomerization catalyst in a fixed bed reactor with a liquid hourly space velocity (LHSV) of 0.5-2 h−1 In yet another embodiment, isomerization of at least a portion of the C14 to C18 alpha olefin monomers comprises heating the monomers in the presence of an isomerization catalyst selected from the group consisting of activated alumina, gamma-alumina, zirconium oxide on gamma alumina, theta-alumina with or without the presence of alkali metal.
In another embodiment, the isomerization conditions result in greater than 30% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers. In another embodiment, the isomerization conditions result in greater than 50% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers. In yet another embodiment, the isomerization conditions result in greater than 60% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers. In yet a further embodiment, the isomerization conditions result in greater than 70% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers. In a further embodiment, the isomerization conditions result in greater than 80% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers. In yet another embodiment the isomerization conditions result in greater than 90% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers.
In yet another embodiment, the average double bond position of the isomerized C14 to C18 olefin monomer product is in the range of from 1.5 to 5.0. In yet another embodiment, the average double bond position of the isomerized C14 to C18 olefin monomer product is in the range of from 1.5 to 4.5. In yet another embodiment, the average double bond position of the isomerized C14 to C18 olefin monomer product is in the range of from 2.0 to 4.4. In yet another embodiment, the average double bond position of the isomerized C14 to C18 olefin monomer product is in the range of from 2.5 to 4.2. In yet another embodiment, the average double bond position of the isomerized C14 to C18 olefin monomer product is in the range of from 3.0 to 4.0. In yet another embodiment, the average double bond position of the isomerized C14 to C18 olefin monomer product is in the range of from 3.5 to 3.9.
Renewable Feedstocks
In some variations, about 100% of the carbon atoms in the olefin feedstocks described herein may originate from renewable carbon sources. In some variations, about 100% of the carbon atoms in the olefin co-monomer (e.g., the second feedstock) originate from renewable carbon sources. For example, an alpha-olefin co-monomer may be produced by oligomerization of ethylene derived from dehydration of ethanol produced from a renewable carbon source. In some variations, an alpha-olefin co-monomer may be produced by dehydration of a primary alcohol other than ethanol that is produced from a renewable carbon source. Said renewable alcohols can be dehydrated into alpha olefins, or isomerized simultaneously to a desired average double bond position using gamma alumina as a di-functional catalyst. In some embodiments, hydrocarbon terpene feedstocks derived from renewable resources are coupled with one or more olefins that are derived from renewable resources.
In one embodiment, at least one of the first and second feedstocks comprises at least 1% by weight of a terpene. In yet another embodiment, at least one of the first and second feedstocks comprises at least 5% by weight of a terpene. In yet another embodiment, at least one of the first and second feedstocks comprises at least 10% by weight of a terpene. In yet another embodiment, at least one of the first and second feedstocks comprises at least 20% by weight of a terpene. In yet another embodiment, at least one of the first and second feedstocks comprises at least 30% by weight of a terpene. In yet another embodiment, at least one of the first and second feedstocks comprises at least 40% by weight of a terpene. In yet another embodiment, at least one of the first and second feedstocks comprises at least 50% by weight of a terpene.
Oligomerization Conditions
The present disclosure relates to a method for making saturated C28-C36 hydrocarbon dimers, suitable for use as lubricant base oils.
According to one embodiment of a process of forming the dimer composition, a first feed stock comprising an isomerized C14 to C18 olefin monomer is oligomerized, either by oligomerization with itself or optionally with a second feedstock comprising at least one of C14 to C18 alpha olefin monomers and/or C14 to C18 internal olefin monomers, to produce an oligomer product comprising dimers, trimers, and higher oligomers. In one embodiment, the second feedstock comprises internal olefin monomers prepared by a manner that is the same as and/or similar to the isomerization methods used to prepare the isomerized olefin product of the first feedstock, and/or may be provided by a different method. The second feedstock may have the same or a different chain length than the first feedstock, and/or may have internal olefin monomers with the same or different average double bond position (or may be alpha olefin monomers). In one embodiment, when the second feedstock is a C14 alpha olefin, the first feedstock comprises olefin monomers having at least one more carbon for the carbon chain length, such as C15 to C18 olefin monomers.
In another embodiment of a method of preparing the base oil, in an oligomerization process, an alpha olefin (e.g., 1-tetradecene) is mixed with an alpha or internal olefin (e.g., hexadecene internal olefin having the defined average bond position) polymerized either by semi-batch or continuous mode in a single stirred tank reactor or by continuous mode in a series of stirred tank reactors using for example BF3 and/or BF3 promoted with a mixture of linear alcohol and an alkyl acetate ester under reaction conditions which impart a controlled amount of isomerization during the oligomerization process to produce a branched unsaturated oligomer.
In another embodiment, the internal olefin monomer C14 to C18 isomerized product is oligomerized with a second feedstock, the second feedstock comprising C14 to C18 internal olefin monomers. In yet another embodiment the internal olefin monomer C14 to C18 isomerized product is oligomerized with a second feedstock, the second feedstock comprising C14 to C18 alpha olefin monomers including one or more of linear and branched alpha olefins. In yet another embodiment, the internal olefin monomer C14 to C18 isomerized product is oligomerized with a second feedstock comprising C14 to C18 alpha olefins including branched olefins in a content by weight of up to 36% by weight of the C14 to C18 alpha olefins. In yet another embodiment, the internal olefin monomer C14 to C18 isomerized product is oligomerized with a second feedstock comprising C14 to C18 alpha olefins including branched olefins in a content by weight of up to 25% by weight of the C14 to C18 alpha olefins. In yet another embodiment, the internal olefin monomer C14 to C18 isomerized product is oligomerized with a second feedstock comprising C14 to C18 alpha olefins including branched olefins in a content by weight of up to 15% by weight of the C14 to C18 alpha olefins. In yet another embodiment, the internal olefin monomer C14 to C18 isomerized product is oligomerized with a second feedstock comprising C14 to C18 alpha olefins including branched olefins in a content by weight of up to 5% by weight of the C14 to C18 alpha olefins.
In another embodiment, the internal monomer olefin C14 to C18 isomerized product is isomerized with a second feedstock comprising C14 to C18 alpha olefin monomers in a ratio by weight of the internal monomer olefin C14 to C18 product to the C14 to C18 alpha olefin monomers in a range of from 80:20 to 20:80. In yet another embodiment, the internal monomer olefin C14 to C18 isomerized product is oligomerized with a second feedstock comprising C14 to C18 alpha olefin monomers in a ratio by weight of the internal monomer C14 to C18 product to the C14 to C18 alpha olefin monomers in a range of from 70:30 to 50:50.
In another embodiment, the internal monomer olefin C14 to C18 isomerized product is oligomerized with a second feedstock comprising C14 to C18 olefin monomers having a different chain length than the internal monomer olefin C14 to C18 isomerized olefin monomer product. In yet another embodiment, the internal monomer olefin C14 to C18 isomerized monomer product comprises C16 to C18 internal olefin monomers, and is oligomerized with a second feedstock comprising C14 alpha olefin monomers. In another embodiment, the internal monomer olefin C14 to C18 isomerized product comprises C16 internal olefin monomers, and is oligomerized with a second feedstock comprising C14 alpha olefins to form the oligomer product. In yet another embodiment, the internal monomer olefin C14 to C18 isomerized product comprises C16 internal olefin monomers, and the C16 internal olefin monomers are oligomerized with each other or a second feedstock comprising C16 olefin monomers to form the oligomer product.
In yet another embodiment, oligomerization is performed using a boron trifluoride oligomerization catalyst, an alcohol promoter, and an ester promoter in at least one continuously stirred reactor under oligomerization conditions. In yet another embodiment, the oligomerization reaction is performed at a temperature in the range of from 15° C. to 110° C. In yet another embodiment, the oligomerization reaction is performed at a temperature in the range of from 20° C. to 110° C. In a further embodiment, the oligomerization reaction is performed at a temperature in the range of from 40° C. to 110° C. In yet a further embodiment, the oligomerization reaction is performed at a temperature in the range of from 60° C. to 110° C. In yet a further embodiment, the oligomerization reaction is performed at a temperature in the range of from 80° C. to 110° C. In another embodiment, the oligomerization reaction is performed at a temperature in the range of from 90° C. to 110° C. In yet another embodiment, the oligomerization reaction is performed at a temperature in the range of from 90° C. to 100° C. In one embodiment, the oligomerization is performed using a continuously stirred tank reactor. In yet another embodiment, the average residence time of oligomers in a continuously stirred tank reactor is in the range from 60 to 400 minutes. In another embodiment, the average residence time of oligomers in a continuously stirred tank reactor is in the range from 90 to 300 minutes. In a further embodiment, the average residence time of oligomers in a continuously stirred tank reactor is in the range of from 120 to 240 minutes. In another embodiment, an average residence time of oligomers in a continuously stirred tank reactor is in the range from 150 to 240 minutes. In yet another embodiment, the average residence time of oligomers in a continuously stirred tank reactor is in the range from 180 to 240 minutes.
In yet another embodiment invention, the reaction mixture is distilled to remove the unreacted monomer. For example, the unreacted monomer may be separated from the oligomer product, such as via distillation, and can be recycled back into the mixture of the first and/or second feedstocks for oligomerization thereof.
In a further embodiment, the oligomer product is hydrogenated to form a saturated oligomer product comprising a mixture of branched saturated hydrocarbons including hydrogenated dimer, trimer, and higher oligomers. According to one aspect, the mixture of branched saturated hydrocarbons is hydrogenated to the extent that the Bromine Index is below 1000 mg Br2/100 g, as measured by ASTM D2710-09.
The hydrogenated dimer can be separated from the saturated oligomer product, such as via distillation or other separation method. In one embodiment, the saturated oligomer product is fractionated by distillation to produce two or more base oil lubricant fractions. The one or more fractions comprising the hydrogenated dimer may be used as a base oil having advantageous properties as described herein. Furthermore, controlling the different parameters of said oligomerization can have large effect on the physical properties of the resulting oligomers. For example, in one embodiment, the oligomerization process may be performed under conditions to further at least partially isomerize olefin monomers in one or more of the first and second feedstock. For example, the oligomerization process may be performed in the presence of a catalyst, and under oligomerization conditions, that further promote one or more of isomerization of the double-bond in an olefin monomer and/or a skeletal isomerization of the oligomer product and/or olefin monomer. In yet another embodiment, parameters of the oligomerization process are controlled to promote the thermal and oxidative stability of the base oil. For example, in one embodiment, the parameters of the oligomerization process may be controlled such that the oligomerization product comprises less than 0.5 wt. % of benzylic groups formed as oligomerization by-products, and may even be substantially free of such benzylic groups.
Base Oil
According to embodiments of the disclosure, a base oil comprising dimers of C14-C18 olefin monomers is provided, which base oil can exhibit improved properties such as reduced Noack Volatility and cold temperature properties that may be suitable for automotive engine oil applications as well as other uses. In particular, as described herein, the dimers of the C14-C18 olefin monomers are prepared by oligomerizing at least one feedstock comprising internal olefin monomers, where the internal olefin monomers have a defined average double bond position. For example, olefin monomers such as alpha olefins may be subjected to a controlled isomerization process that results in isomerization of the position of the olefin double bond to the defined average position, and the resulting oligomer product obtained via oligomerization of the isomerized olefin monomers provides a branched hydrocarbon product including branched dimers, trimers, and higher oligomers. The branched dimers can be used to form the base oil having the improved properties.
Accordingly, in one embodiment, the saturated hydrocarbon base oil comprises dimers of C14-C18 olefin monomers, with the dimers having an average carbon number in the range of from 29 to 36 For example, in one embodiment the saturated hydrocarbon base oil may comprise a dimer of a C14 and a C16 olefin monomer. In yet another embodiment, the saturated hydrocarbon base oil may comprise a dimer of a C16 olefin monomer with another C16 olefin monomer. Other combinations of any of C14, C15, C16, C17 and C18 olefin monomers may also be provided. At least one of the olefin monomers forming the dimers is an olefin monomer that is an internal olefin monomer having the defined average double bond position, such as an olefin monomer that has been subjected to isomerization to provide internal olefin monomers with an average double bond position that is within a defined range. In one embodiment, the dimer is formed from the oligomerization of an internal olefin monomer having the defined average double bond position with an alpha olefin. In yet another embodiment, the dimer is formed from oligomerization of an internal olefin monomer having the defined average double bond position with itself. In yet another embodiment, the dimer is formed from oligomerization of an internal olefin monomer having the defined average double bond position with a second internal olefin monomer having the same or a different average double bond position.
The dimers further comprise an average carbon number corresponding to the total number of carbon atoms in the dimer resulting from the combination of olefin monomers, with the average carbon number being in the range of from 29 to 36. For example, a dimer product of C14 and C16 olefin monomers would result in an average carbon number of least 30 (14+16). Similarly, a dimer product of C16 and C16 olefin monomers would result in an average carbon number of at least 32 (16+16). A dimer product of C14 and C18 olefin monomers would similarly result in an average carbon number of 32 (14+18). Accordingly, the olefin monomers that are selected to prepare the dimer product are chosen such that the final dimer product has an average total number of carbon atoms that within the range of from 29 to 36.
The base oil having the improved properties according to aspects of the disclosure further comprises the dimers as a significant percent by weight of the base oil composition. For example, the dimers may make up at least 50% by weight and even at least 80% by weight, such as 90% by weight and even 95% by weight of the composition of the base oil, and may even make up at least 98% by weight and even at least 99% by weight of the composition of the base oil.
According to one embodiment, an extent and type of branching that occurs in the dimers can be characterized according to one or more of a Branching Index, Branching Ratio, and Paraffin Branching Proximity of the dimer product, as these terms are defined herein. Generally speaking, the Branching Index and the Branching Ratio are related to the relative number of branch termination points in the dimer, whereas the Paraffin Branching Proximity is related to the average number of repeat carbon atoms in the resulting branched chains of the branched dimers. As defined further herein, the Branching Index and Branching Ratio for the dimer can be determined by 1H NMR techniques (BI and BR) or IR techniques (BR), where the Branching Index is calculated by taking the ratio of the total number of methyl hydrogens to the total number of hydrogens in the dimer (CH3/(CH3+CH2+CH)), where the hydrogens that are being counted are also non-benzylic hydrogens and the Branching Ratio is calculated by taking the ratio of methyl groups to methylene groups by 1H NMR or IR. That is, the Branching Index of the dimer may be defined according to formula (1) below:
Branching Index (BI)=(number of methyl group hydrogens/total number of hydrogens)*100, (1)
and the Branching Ratio (BR) may be defined according to formula (2) below:
Branching Ratio (BR)=(methyl groups)/(methylene groups). (2)
According to one embodiment, the average branching index (BI) of the dimer product is at least 22, such as in the range of from 22 to 26.
Referring to
Similarly, referring to
As yet another measure of the extent and/or type of branching that occurs in the dimer product of the base oil, the paraffin branching proximity (BP) can be understood as a measure of the % equivalent recurring methylene carbons that are five or more removed from an end group or a branch of the dimer product (e.g., c carbon groups), and thus is related to the average length of carbon chains in the dimer product. The Branching Proximity can be determined according to a 13C NMR technique, and may be calculated according to the following formula:
paraffin Branching Proximity (BP)=(number of ε carbon groups/total number of carbon groups)*100,
An ε carbon group in the formula is defined as a carbon group that is separated from any terminal carbon atom groups or branching carbon groups by at least 4 carbon groups. In one embodiment, the branching proximity for the dimer product may be in the range of from 18 to 26, such as in the range of from 20 to 24. For Example, referring to
In one embodiment, the average paraffin branching proximity (BP) for the dimer product, as determined by 13C NMR, is no more than 26, and may also be at least 18, such as in a range of from 18 to 26. Referring to the dimer product in
According to one embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits improved properties, such as volatility and cold temperatures properties suitable for use in automotive engine oil formulations. In one embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility as measured by ASTM D5800 that is less than 14%. In yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility as measured by ASTM D5800 that is less than 13%. In yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility as measured by ASTM D5800 that is less than 12%. In yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility as measured by ASTM D5800 that is less than 11%. In yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility as measured by ASTM D5800 that is less than 10%. In yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility as measured by ASTM D5800 that is less than 9%. In yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility as measured by ASTM D5800 that is less than 8%. In yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility as measured by ASTM D5800 that is less than 7%. Generally, the Noack Volatility will be at least 6%.
According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Pour Point as measured by ASTM D97 of no greater than −27° C. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Pour Point as measured by ASTM D97 of no greater than −30° C. According to one embodiment, the Pour Point as measured by ASTM D97 will be no greater than −33° C. as measured by ASTM D97. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Pour Point as measured by ASTM D97 of no greater than −36° C. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Pour Point as measured by ASTM D97 of no greater than −39° C. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Pour Point as measured by ASTM D97 of no greater than −42° C.
According to one embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Cold Crank Simulated (CCS) dynamic viscosity as measured by ASTM D5293 at −35° C. of 1800 cP or less. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Cold Crank Simulated (CCS) dynamic viscosity as measured by ASTM D5293 at −35° C. of 1700 cP or less. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Cold Crank Simulated (CCS) dynamic viscosity as measured by ASTM D5293 at −35° C. of 1600 cP or less. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Cold Crank Simulated (CCS) dynamic viscosity as measured by ASTM D5293 at −35° C. of 1500 cP or less. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Cold Crank Simulated (CCS) dynamic viscosity as measured by ASTM D5293 at −35° C. of 1400 cP or less. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Cold Crank Simulated (CCS) dynamic viscosity as measured by ASTM D5293 at −35° C. of 1300 cP or less. According to yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Cold Crank Simulated (CCS) dynamic viscosity as measured by ASTM D5293 at −35° C. of 1200 cP or less. In general, the Cold Crank Simulated (CCS) dynamic viscosity as measured by ASTM D5293 at −35° C. will be a least 1100 cP.
According to one embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a kinematic viscosity (KV100) as measured by ASTM D445 in the range of from 3.7 to 4.8. According to another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a kinematic viscosity (KV100) as measured by ASTM D445 in the range of from 3.7 to 4.5. According to another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a kinematic viscosity (KV100) as measured by ASTM455 in the range of from 3.8 to 4.4. According to another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a kinematic viscosity (KV100) as measured by ASTM D445 in the range of from 3.9 to 4.3. According to another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a kinematic viscosity (KV100) as measured by ASTM D445 in the range of from 4.0 to 4.2.
According to one embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Viscosity Index (VI) as measured by ASTM D445 that is greater than 125. According to another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Viscosity Index (VI) as measured by ASTM D445 that is greater than 130. According to another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Viscosity Index (VI) as measured by ASTM D445 that is greater than 135. According to another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Viscosity Index (VI) as measured by ASTM D445 that is greater than 140. Generally, the Viscosity Index (VI) as measured by ASTM D445 will be less than 150.
As another example, in one embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility of less than 14%, a Pour Point no greater than −27° C., and a CCS at −35° C. that is less than 1900 cP. Furthermore, in one embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Viscosity Index that is greater than 125, and a KV(100) that is in the range of from 3.7 to 4.8, such as in the range of from 3.7 to 4.5.
In yet another embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Cold Crank Simulated (CCS) dynamic viscosity at −35° C. that is related to the value of the KV(100) for the saturated hydrocarbon base oil. Specifically, the CCS dynamic viscosity may be a value which is less than or equal to the value of the following equation:
−14.167(KV100){circumflex over ( )}2+107.42(KV100)−190
The relationship between the CCS dynamic viscosity values and KV(100) is discussed in more detail below.
In yet further embodiment, the saturated hydrocarbon base oil comprising the dimer product exhibits a Noack Volatility that is related to the value of the KV(100) for the saturated hydrocarbon base oil. Specifically, the Noack Volatility may be a value which is less than or equal to the value of the following equation:
−1583.3(KV100){circumflex over ( )}2+13858(KV100)−28500
The relationship between the Noack Volatility values and KV(100) is discussed in more detail below.
In one embodiment, the saturated hydrocarbon base oil comprises less than 10% of dimers containing singularly branched isomers, according to the simulated distillation test ASTM D2887. According to another embodiment, the saturated hydrocarbon base oil comprises less than 5% of dimers containing singularly branched isomers, according to the simulated distillation test ASTM D2887. The saturated hydrocarbon base oil comprises less than 1% of dimers containing singularly branched isomers, according to the simulated distillation test ASTM D2887 is discussed in more detail below.
Temperature Isomerization Effect
Temperature variation tables (1 and 2 below) illustrate the effect of oligomerization temperature on dimer products, according to one aspect of the disclosure. Generally, increasing the oligomerization temperature increases the amount of isomerization that occurs during BF3 catalyzed oligomerization. Comparative example A is a sample of C14 dimers made at relatively low oligomerization temperature, with little isomerization taking place during oligomerization. Comparative examples B and C show the physical property changes of the product when C14 is dimerized at the relatively higher temperatures of 60 and 80° C. respectively. As shown in these Comparative Example, larger amounts of branched isomers reduce an oligomer's pour point, while simultaneously decreasing the VI and increasing the CCS@ −35° C. Accordingly, proper balance of the isomerization, including isomerization pre-oligomerization as well as any isomerization occurring during oligomerization, may be controlled to obtain optimal engine oil properties for dimers derived from long chain olefins (C14-C18)
C14 Only Dimers with Changes in Oligomerization Temperature
The C28 molecules from C14-only dimers seen in table (1) have significantly lower viscosity and boiling point distribution than the traditional C30 chain length molecules used for engine oils. This results in a Noack volatility that is too high to be desirable as an 0W engine oil alone. Surprisingly, it has been discovered that, according to one aspect, combining C14 olefin monomers with a longer chain olefin can provide a base oil having desirable properties, as is shown in more detail below (see, e.g., table 3). According to one aspect, the C14 olefin monomers are reacted in a predetermined ratio with C16 olefin monomers. For example, the reaction mixture can comprise C14 olefin in less than or equal to 50% of the olefin mixture. In another embodiment, the reaction mixture can comprise of less than 40% of C14 olefin monomers. In another embodiment, the reaction mixture can comprise of less than 35% of C14 olefin monomers. Isomerization of one or more olefin monomers can be performed prior to oligomerization, and/or the olefin feed can be reacted under specified reaction conditions to induce oligomer isomerization, as discussed in more detail below. According to one embodiment, using an oligomerization temperature greater than 18° C. In another embodiment, using an oligomerization temperature greater than 50° C. In another embodiment, using an oligomerization temperature greater than 80° C. In another embodiment, using an oligomerization temperature greater than 90° C. and even greater than 100° C., enables the oligomers to obtain desirable engine oil properties as seen in Examples 1 through 6 in table 3 below.
Furthermore, the C32 molecules from C16 LAO seen in table (2) have a higher viscosity and boiling point distribution than the traditional C30 chain length molecules used for engine oils. Comparative Example D is a dimer of C16 alpha olefin that was oligomerized at 30° C. with little isomerization occurring during oligomerization. This results in pour point and CCS @ −35° C. that are too high to be desirable as an 0 w engine oil alone. However, the higher boiling point of the C32 does advantageously reduce the Noack volatility. Comparative Example E is a dimer of C16 alpha olefins oligomerized at a relatively high temperature, such that significant isomerization occurred during the oligomerization. While isomerization during oligomerization improved cold temperature properties of C16 alpha olefin dimers, in this instance it did not provide the correct branching necessary to yield the cold temperature viscometrics desirable for engine oils.
Double Bond Isomerization
Accordingly, while proper balancing of the ratios of 1-tetradecene (C14) and longer chain length alpha olefins can solve the volatility issue of the tetradecene dimer, it did not produce dimers with superior low temperature properties. The linearity of the long chain LAO dimers tends to produce dimers with a higher pour point, as shown in comparative example F in table 3 below. Accordingly, it has been discovered that additional branching is needed to achieve desired cold flow properties. Specifically, according to one aspect, it has been discovered that one way of controlling branching, such as by introducing appropriate length of the branches in the product, is by controlling the average double bond position in the olefin monomer(s) used as the olefin feed for a given oligomerization. Increasing the average double bond position will increase the size of the branches present within the oligomer. A further unexpected finding is that olefin feeds having an average double bond position of about 2.5-3.5 are more susceptible and may experience excess isomerization as shown in example 2 and 3 in table 3, at elevated oligomerization temperatures, than those olefins with higher or lower average double bond positions. Olefins with an even higher average double bond position, such as about 3.6 or greater, can also yield desirable branching when oligomerization occurs at an elevated temperature, to promote the desired degree of further isomerization. For example, the base oil resulting from oligomerization at about 100° C. of, olefins having a double bond position of about 3.6, exhibit excellent cold temperature viscometrics, reduced CCS @ −35° C. and a sufficiently low pour point. Furthermore, according to one aspect, good base oil properties can also be obtained with olefin feeds having average double bond position lower than about 3.6, by making adjustments to the oligomerization temperature. For example, using an olefin feed with a 2.5-3.5 average double bond position, an oligomerization temperature less than 100° C. will reduce the isomerization of the oligomers, and yield base oils with a CCS @ −35° C. below 1800 cP, seen in table 3 as example 6. As shown in table 3 below C16 olefins between 2.5-3.5 average double bond position yield preferable results when oligomerized at temperatures below 100° C., and olefins with an average double bond position above 3.6 yield preferred properties when oligomerized at 100° C. or greater.
Description of Average Double Bond Analysis
As seen in table 3, the average double bond position of the isomerized olefin allows for control of the properties of the resulting oligomers, to advantageous effect. That is, simply controlling the ratio of alpha- to internal-olefins in the olefin feed is not sufficient to obtain the optimal base oil properties (see, e.g., U.S. Pat. No. 4,910,355).
In one embodiment, the average double bond position can be measured using Gas Chromatography with a flame ionization method. Using a column with a stationary phase which is 50% phenyl and 50% methylpolysiloxane, allows for the separation of the alpha and beta isomers at each olefin double bond position along a linear hydrocarbon of at least C8 to C20. An example of the analysis of an isomerized olefin using the Gas Chromatography method disclosed is seen in
Table (4) Shows isomer of Hexadecene in descending order of the left to right peaks seen in
Furthermore, according to one aspect, the isomerization that can occur during oligomerization at high temperatures can create a large number of branched isomers, in addition to any branches introduced by the isomerization of olefin feed pre-oligomerization. Referring to
According to one aspect of the disclosure, the fraction of highest boiling point singularly branched dimers as compared to the total dimer is characterized to be less than 0.1% by area, preferably less than 0.05% by area, or even preferably less than 0.01% by area (not present or detectable) as shown in
Branching Index Requirements
By increasing the isomerization in the olefin monomers and/or oligomers, such as by changing the average double bond position in the olefin monomers to provide a defined average double bond position, and/or by controlling oligomerization conditions to increase isomerization (skeletal isomerization or otherwise), the resulting oligomer product may exhibit increased branching, as reflected in an increased branching index. As discussed above, the branching index is calculated by determining the number of methyl hydrogens in the product, divided by the total number of hydrogens (non-benzylic) measured by 1H NMR. Surprisingly, by using selective olefin isomerization pre-oligomerization, or optionally in combination with isomerization during oligomerization, and/or even post-oligomerization isomerization of the oligomer, the dimer fraction comprised of C28-C36 saturated hydrocarbons is found to have excellent physical properties for 0W engine oils, when branching index is maintained between 22 and 26 per 100 carbons (or 0.22 and 0.26).
The table 5 below shows the comparison of a conventional 4 cSt base oil made from 1-decene trimer, and example 4 according to the present disclosure, which is a C14 and C16 dimer. The table shows that the Branching index of Example 4 is greater than 22, and the physico-chemical properties of the hydrogenated product in example 4 are improved over the 1-decene trimer product, and has better Noack and VI properties, while the CCS is comparable.
Conversely prior PAOs made with C8-C12 olefins have been understood to have better properties when they have a branching ratio below 0.19 as described in U.S. Pat. Nos. 8,501,675 and 4,827,064. In the table below, the properties of PIO dimer made with C13 through C16 internal olefins, PAO trimer made with decene alpha olefins, and Example 4 of the present disclosure show that even though example 4 has a higher 1H NMR CH3/CH2 ratio (branching ratio) than the conventional PAO and PIO, it nonetheless has superior Noack and VI.
The calculated Branching Index (BI) and paraffin Branching Proximity (BP) for a representative example of a 1-tetradecene and 1-hexadecene dimer 4 cSt PAO lubricant oil made according to aspects of the disclosure is shown in
For purposes of comparison, the calculated Branching Index (BI) and paraffin Branch Proximity (BP) for a representative example of a 1-decene trimer 4 cSt PAO lubricant oil is shown in
The calculated Branching Index (BI) and paraffin Branching Proximity (BP) for a representative example of a 4 cSt isomerized-GTL lubricant oil is shown in
Another aspect of the disclosure is that the base oils also have excellent viscometric properties under low temperature and high shear, making them very useful in multigrade engine oils. The cold-cranking simulator apparent viscosity (CCS Viscosity) is a standard test used to measure the viscometric properties of lubricating base oils under low temperature and high shear. The test method to determine CCS Viscosity is ASTM D 5293-15. Results are reported in centipoise, cP. CCS Viscosity has been found to correlate with low temperature engine cranking. The CCS Viscosity measured at −35° C. of the lubricating base oils of this invention are relatively low. The combination of kinematic viscosity at 100° C. and CCS (dynamic viscosity) at −35° C. is represented by the following formula:
CCS viscosity at −35° C.<−1333.3(KV100){circumflex over ( )}2+11933(KV100)−24900
This formula is represented in the plot of CCS Viscosity vs. Kinematic viscosity at 100° C. shown in
Noack volatility of engine oil, as measured by ASTM D5800-15, has been found to correlate with oil consumption in passenger car engines. Strict requirements for low volatility are important aspects of several recent engine oil specifications, such as, for example, ACEA A-3 and B-3 in Europe, and SAE J300-01, ILSAC GF-5, and future ILSAC GF-6, in North America. Any new lubricating base oil developed for use in 0W automotive engine oils should have a Noack volatility no greater than 14%. The Noack volatility of the lubricating base oils of this disclosure are relatively low. In preferred embodiments, the combination of kinematic viscosity at 100° C. and Noack volatility are represented by the following formula:
Noack volatility<−16.583(KV100){circumflex over ( )}2+125.36(KV100)+223.8
This Noack formula is represented in the plot of Noack Volatility vs. Kinematic viscosity at 100° C. shown in
The following Examples are provided to illustrate aspects of the disclosure, but are not intended in any way to limit the scope of the disclosure provided herein.
Obtained 1-Hexadecene with less than 8% branched and internal olefins. Isomerized 1-hexadecene using a Pd on alumina catalyst in a batch slurry reaction at 200° C. for 4 hours to obtain linear internal olefin (LIO) with an average double bond position of 1.76. An olefin mixture comprised of 70% of said isomerized hexadecene and 30% of 1-tetradecene was oligomerized. The oligomerization reaction used between 1 and 10 PSI of BF3 with a co-catalyst composition of BuOH and BuAc. The reaction was held at 100° C. during semi continuous addition of olefins and co-catalyst. The unreacted monomer was then distilled off and the residue was hydrogenated to a Br index (ASTM D2710) of less than 1000 mg Br/100 g. A following distillation was used to remove the dimer from the residue to obtain a base oil with a KV100 of 4.21 cSt, with a viscosity index of 128, with a −33° C. pour point (ASTM D97), a dynamic viscosity at −35° C. of 1889 cP (ASTM D5923), and a Noack volatility (ASTM D5800) of 11.8%.
Obtained 1-Hexadecene with less than 8% branched and internal olefins. Isomerized 1-hexadecene using a Pd on alumina catalyst in a batch slurry reaction at 260° C. for 4 hours to obtain linear internal olefin (LIO) with an average double bond position of 2.54. An olefin mixture comprised of 70% of said isomerized hexadecene and 30% of 1-tetradecene was oligomerized. The oligomerization reaction used between 1 and 10 psi of BF3 with a co-catalyst composition of BuOH and BuAc. The reaction was held at 100° C. during semi continuous addition of olefins and co-catalyst. The unreacted monomer was then distilled off and the residue was hydrogenated to a Br index (ASTM D2710) of less than 200 mg Br/100 g. A following distillation was used to remove the dimer from the residue to obtain a base oil with a KV100 of 4.24 cSt, with a viscosity index of 120, with a −45° C. pour point (ASTM D97), a dynamic viscosity at −35° C. of 2005.5 cP (ASTM D5923), and a Noack volatility (ASTM D5800) of 12.1%.
Obtained 1-Hexadecene with less than 8% branched and internal olefins. Isomerized 1-hexadecene using a Pd on alumina catalyst in a batch slurry reaction at 260° C. for 4 hours to obtain linear internal olefin (LIO) with an average double bond position of 3.15. An olefin mixture comprised of 70% of said isomerized hexadecene and 30% of 1-tetradecene was oligomerized. The oligomerization reaction used between 1 and 10 psi of BF3 with a co-catalyst composition of BuOH and BuAc. The reaction was held at 100° C. during semi continuous addition of olefins and co-catalyst. The unreacted monomer was then distilled off and the residue was hydrogenated to a Br index (ASTM D2710) of less than 200 mg Br/100 g. A following distillation was used to remove the dimer from the residue to obtain a base oil with a KV100 of 4.24 cSt, with a viscosity index of 120, with a −45° C. pour point (ASTM D97), a dynamic viscosity at −35° C. of 2005.5 cP (ASTM D5923), and a Noack volatility (ASTM D5800) of 12.1%.
Obtained 1-Hexadecene with less than 8% branched and internal olefins. Isomerized 1-hexadecene using a Pd on alumina catalyst in a batch slurry reaction at 270° C. for 4 hours to obtain linear internal olefin (LIO) with an average double bond position of 3.85. An olefin mixture comprised of 70% of said isomerized hexadecene and 30% of 1-tetradecene was oligomerized. The oligomerization reaction used in 6 psi of BF3 with a co-catalyst composition of BuOH and BuAc. The reaction was held at 100° C. during semi continuous addition of olefins and co-catalyst. The unreacted monomer was then distilled off and the residue was hydrogenated to a Br index (ASTM D2710) of less than 200 mg Br/100 g. A following distillation was used to remove the dimer from the residue to obtain a base oil with a KV100 of 3.85 cSt, with a viscosity index of 132, with a −33° C. pour point, a dynamic viscosity at −35° C. of 1469 (ASTM D5923), and a Noack volatility (ASTM D5800) of 12.5%.
Obtained 1-hexadecene with less than 8% branched and internal olefins. Isomerized 1-hexadecene using a Pd on alumina catalyst in a batch slurry reaction at 270° C. for 4 hours to obtain linear internal olefin (LIO) with an average double bond position of 4.21. An olefin mixture comprised of 70% of said isomerized hexadecene and 30% of 1-tetradecene was oligomerized. The oligomerization reaction used between 1 and 10 psi of BF3 with a co-catalyst composition of BuOH and BuAc. The reaction was held at 100° C. during semi continuous addition of olefins and co-catalyst. The unreacted monomer was then distilled off and the residue was hydrogenated to a Br index (ASTM D2710) of less than 200 mg Br/100 g. A following distillation was used to remove the dimer from the residue to obtain a base oil with a KV100 of 4.21 cSt, with a viscosity index of 127, with a −33° C. pour point, a dynamic viscosity at −35° C. of 1642 (ASTM D5923), and a Noack volatility (ASTM D5800) of 11.6%.
Obtained 1-hexadecene with less than 8% branched and internal olefins. Isomerized 1-hexadecene using a Pd on alumina catalyst in a batch slurry reaction at 270° C. for 4 hours to obtain linear internal olefin (LIO) with an average double bond position of 2.7. An olefin mixture comprised of 70% of said isomerized hexadecene and 30% of 1-tetradecene was oligomerized. The oligomerization reaction used between 1 and 10 psi of BF3 with a co-catalyst composition of BuOH and BuAc. The reaction was held at 100° C. during semi continuous addition of olefins and co-catalyst. The unreacted monomer was then distilled off and the residue was hydrogenated to a Br index (ASTM D2710) of less than 200 mg Br/100 g. A following distillation was used to remove the dimer from the residue to obtain a base oil with a KV100 of 4.04 cSt, with a viscosity index of 132, with a −36° C. pour point, a dynamic viscosity at −35° C. of 1593 (ASTM D5923), and a Noack volatility (ASTM D5800) of 12.2%.
Obtained 1-hexadecene with less than 8% branched and internal olefins. Isomerized 1-hexadecene using a Pd on alumina catalyst in a batch slurry reaction at 260° C. for 4 hours to obtain linear internal olefin (LIO) with an average double bond position of 3.85. An olefin mixture comprised of 50% of said isomerized hexadecene and 50% of 1-tetradecene was oligomerized. The oligomerization reaction used between 1 and 10 psi of BF3 with a co-catalyst composition of BuOH and BuAc. The reaction was held at 100° C. during semi continuous addition of olefins and co-catalyst. The unreacted monomer was then distilled off and the residue was hydrogenated to a Br index (ASTM D2710) of less than 1000 mg Br/100 g. A following distillation was used to remove the dimer from the residue to obtain a base oil with a KV100 of 3.7 cSt, with a viscosity index of 136, with a −27° C. pour point (ASTM D97), a dynamic viscosity at −35° C. of 1030 cP (ASTM D5923), and a Noack volatility (ASTM D5800) of 12.3%.
Average Double Bond Position:
The term “Average Double Bond Position” as used herein refers to the average of the double bond positions for all olefins in the feed and/or olefin mixture, where a double bond position of ‘1’ is assigned for a double bond located between a terminal end carbon and the adjacent carbon (terminal end carbon+1), a double bond position of ‘2’ is assigned for a double bond located between this adjacent carbon (terminal end carbon+1) and the next adjacent carbon (terminal end carbon+2), etc. In one embodiment, the Average Double Bond Position of an olefin can be determined by using a Gas Chromatographic Method. According to one aspect, a suitable Gas Chromatographic method uses a column with a stationary phase which is 50% phenyl and 50% methylpolysiloxane, to allow for the separation of the alpha and beta isomers at each double bond position along a hydrocarbon chain, such as a hydrocarbon chain having a chain length in the range of C8 to C20. The isomers with the double bond between the terminal end carbon and adjacent carbon are labeled as the alpha isomers. The cis and trans isomers of the internal olefins are separated for each of the given double bond positions by the isomer's polarity and boiling point (e.g. 2-hexadecene, 3-hexadecene, etc.). The peak area of the Gas Chromatograph corresponding to each isomer integrated, and the area percent multiplied by the double bond position of each the isomer. The products are summed and normalized to give an average double bond position for an isomerized olefin monomer feedstock.
Olefin
The term “Olefin” as used herein refers a hydrocarbon containing at least one carbon-carbon double bond. For example, according to aspects of the disclosure herein, an olefin may comprise a hydrocarbon chain length of from C14 to C18, and may have a double bond at an end (primary position) of the hydrocarbon chain (alpha-olefin) or at an internal position (internal-olefin). In one embodiment, the olefin is a mono-olefin, meaning that the olefin contains only a single double-bond group.
Alpha Olefins
The term “Alpha Olefin” as used herein refers an olefin that has α carbon-carbon double bond at an end of the olefin hydrocarbon chain (terminal position). For example, according to aspects of the disclosure herein, alpha olefins may comprise a hydrocarbon chain length of from C14 to C18, such as compounds having a chemical formula of C14H28, C16H32 and C18H36. In one embodiment, the alpha olefin is a mono-alpha-olefin, meaning that the alpha olefin contains only a single double-bond group.
Linear Alpha Olefin (LAO)
The term “Linear Alpha Olefin” as used herein refers an olefin that is linear (i.e., unbranched), and has a double bond at an end of the olefin hydrocarbon chain (terminal position). For example, according to aspects of the disclosure herein, alpha olefins may comprise a hydrocarbon chain length of from C14 to C18, such as compounds having a chemical formula of C14H28, C16H32 and C18H36. In one embodiment, the linear alpha olefin is a mono-alpha-olefin, meaning that the alpha olefin contains only a single double-bond group.
Internal Olefins
The term “Internal Olefin” as used herein refers an olefin that has an internal carbon-carbon double bond that is interior to the terminal end of the olefin hydrocarbon chain (e.g., at a position other than the alpha-position), and does not contain α carbon-carbon double bond at the terminal position. For example, according to aspects of the disclosure herein, internal olefins may comprise a hydrocarbon chain length of from C14 to C18, such as compounds having a chemical formula of the olefin has no more carbons than the specified carbon number, e.g. C14H28, C16H32 and C18H36. In one embodiment, the internal olefin is a mono-internal-olefin, meaning that the internal olefin contains only a single double-bond group.
Linear Internal Olefins
The term “Linear Internal Olefin” as used herein refers an olefin that is linear (i.e., unbranched), and that has α carbon-carbon double bond that is interior to the terminal end of the olefin hydrocarbon chain (e.g., at a position other than the alpha-position), and does not contain α carbon-carbon double bond at the terminal position. For example, according to aspects of the disclosure herein, linear internal olefins may comprise a hydrocarbon chain length of from C14 to C18, such as compounds having a chemical formula of the olefin has no more carbons than the specified carbon number, e.g. C14H28, C16H32 and C18H36. In one embodiment, the linear internal olefin is a mono-internal-olefin, meaning that the linear internal olefin contains only a single double-bond group.
Linear Mono-Olefins
Mixture of olefins or alkenes distinguished from other olefins with a similar molecular formula by linearity of the hydrocarbon chain length and a distribution of double bond positions in the molecule, from alpha to internal position. For example, according to aspects of the disclosure herein, linear mono-olefins may comprise a hydrocarbon chain length of from C14 to C18 with a chemical formula C14H28, C16H32, and/or C18H36.
Isomerized Olefin
The term “Isomerized Olefin” is used herein to refer to an olefin feed and/or mixture that has been subjected to an isomerization process, such that an average double-bond position in the olefin and/or olefins feed has been shifted from a position close to or at the terminal double position (alpha position), to a distribution of cis/trans double bond positions more interior along the chain length. For example, in one embodiment, isomerized olefins can be formed by isomerization of linear alpha olefins (LAO), which have their double bond at the terminal end of the hydrocarbon chain, to linear internal olefins having an average double bond position more interior along the chain.
Branched Alpha-Olefins
The term “Branched Alpha-Olefin” is used herein to refer to an olefin that has alkyl (such as methyl or ethyl) branch groups along the hydrocarbon chain length of the olefin, and has a double bond at an end of the olefin hydrocarbon chain (primary position). For example, according to aspects of the disclosure herein, branched alpha olefins may comprise C14 to C18 olefins. In one embodiment, the branched alpha olefin is a mono-alpha-olefin, meaning that the branched alpha olefin contains only a single double-bond group.
Branched Internal Olefins
The term “Branched Internal-Olefin” is used herein to refer to an olefin that has alkyl (such as methyl or ethyl, or even longer) branch groups along the hydrocarbon chain length of the olefin, and has a double bond that is interior to the terminal end of the olefin hydrocarbon chain (e.g., at a position other than the alpha-position), and does not contain α carbon-carbon double bond at the terminal position. For example, according to aspects of the disclosure herein, branched internal olefins may comprise C14 to C18 olefins. In one embodiment, the branched internal olefin is a mono-alpha-olefin, meaning that the branched alpha olefin contains only a single double-bond group.
Dimer
The term “Dimer” as used herein refers to molecules formed by the combination of two monomers via a chemical process, where in monomers may be the same or different type of monomer unit. The dimer may be formed by chemical reaction and/or other type of bonding between the monomers. In one embodiment, a dimer is the product of oligomerization between two olefin monomers.
Oligomer
The term “oligomer” as used herein refers to a molecule having 2-100 monomeric units, and encompasses dimers, trimers, tetramers, pentamers, and hexamers. An oligomer may comprise one type of monomer unit or more than one type of monomer unit, for example, two types of monomer units, or three types of monomer units. “Oligomerization” as used herein refers to the formation of a molecule having 2-100 monomeric units from one or more monomers, and encompasses dimerization, trimerization, etc. of one type or different types of monomer, and also encompasses the formation of adducts and/or complexes between the same or more than one type of monomer.
Dimer Total Average Carbon Number
The term “Dimer Total Average Carbon Number” is used herein to refer to a total number of carbons in the dimer. Accordingly, a “C29-C36” dimer as referred to herein is a dimer having a total average number of carbon atoms in a range of from 29 to 36.
Terpenes
The term “Terpenes” as used herein refers to compounds having multiples of units of isoprene, which has the molecular formula C5H8. The basic molecular formula of terpenes are multiples of that, (C5H8)n where n is the number of linked isoprene units, and terpenes can be derived biosynthetically from such units of isoprene. Monoterpenes consist of two isoprene units and have the molecular formula C10H16. Sesquiterpenes consist of three isoprene units.
Renewable
The term “Renewable” as used herein means any biologically derived composition, including fatty alcohols, olefins, or oligomers. Such compositions may be made, for nonlimiting example, from biological organisms designed to manufacture specific oils, as discussed in WO 2012/141784, but do not include petroleum distilled or processed oils such as, for non-limiting example, mineral oils. A suitable method to assess materials derived from renewable resources is through “Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis” (ASTM D6866-12 or ASTM D6866-11). Counts from 14C in a sample can be compared directly or through secondary standards to SRM 4990C. A measurement of 0% 14C relative to the appropriate standard indicates carbon originating entirely from fossils (e.g., petroleum based). A measurement of 100% 14C indicates carbon originating entirely from modern sources (See, e.g., WO 2012/141784, incorporated herein by reference).
Base Oil
The term “Base Oil” as used herein refers an oil used to manufacture products including dielectric fluids, hydraulic fluids, compressor fluids, engine oils, lubricating greases, and metal processing fluids.
Viscosity Index
The term “Viscosity index” as used herein refers to viscosity index as measured according to “Standard Practice for Calculating Viscosity Index From Kinematic Viscosity at 40 and 100° C.” (ASTM D2270) published by ASTM International, which is incorporated herein by reference in its entirety.
Kinematic Viscosity
The term “Kinematic Viscosity” as used herein refers to viscosities at 40° C. and at 100° C. measured according to “Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)” (ASTM D445) published by ASTM International, which is incorporated herein by reference in its entirety.
Cold-Cranking Simulator Viscosity
The term “Cold-Cranking Simulator Viscosity” (abbreviated CCS) refers to cold cranking simulator viscosity as measured according to “Standard Test Method for Apparent Viscosity of Engine Oils Between −5 and −35° C. Using the Cold-Cranking Simulator” (ASTM D5293) published by ASTM International, which is incorporated herein by reference in its entirety.
Pour Point
The term “Pour Point” refers to temperature at which a lubricant becomes semi solid and at least partially loses its flow characteristics, and is measured according to “Standard Test Method for Pour Point of Petroleum Products” (ASTM D97) published by ASTM International, which is incorporated herein by reference in its entirety.
Noack Volatility
The term “Noack Volatility” is used herein to a measure of evaporative weight loss as_carried out according to “Standard Test Method for Evaporation Loss of Lubricating Oils by the Noack Method” (ASTM D5800), or “Standard Test Method for Evaporation Loss of Lubricating Oils by Thermogravimetric Analyzer (TGA) Noack Method” (ASTM D6375, TGA-Noack method), each published by ASTM International, and each of which is incorporated herein by reference in its entirety.
Bromine Index
The term “Bromine Index” is used herein to refer to a test for determining the degree of unsaturation of a product, such as a hydrogenated oligomer and/or dimer product, and can be determined in accordance with ASTM D2710-09, which is incorporated by reference herein in its entirety.
Branching Ratio (BR)
The “Branching Ratio” as used herein refers to a measure of the number of methyl groups (CH3) to the number of methylene groups (CH2) in a sample by 1H NMR, such as sample comprising dimer or other oligomer. The Branching Ratio can be defined according to the following formula:
Branching Ratio (BR)=(methyl groups)/(methylene groups).
The number of methyl and methylene groups can be determined via Infrared Spectroscopy or other accepted method. Methods for determining the Branching Ratio are further described in U.S. Pat. Nos. 4,827,064; 5,264,642; 8,501,675, which are hereby incorporated by reference herein in their entireties.
Branching Index (BI)
The term “Branching Index” is referred to herein as a measure of the percentage of methyl protons divided by the total number of protons (non-benzylic) in a sample, such as a sample comprising a dimer or oligomer. According to one embodiment, the Branching Index can be calculated using 1H NMR, by determining the percent of the non-benzylic methyl hydrogen content in the range of 0.5 to 1.05 ppm, per the total non-benzylic aliphatic hydrogen content in the range of 0.5 to 2.1 ppm. The formula for calculating the Branching Index is as follows:
branching index (BI)=(total content of methyl group hydrogens/total content of hydrogens)*100.
Measurement of the Branching Index is further described in U.S. Pat. Nos. 6,090,989 and 7,018,525, both of which are hereby incorporated by reference herein in their entirety.
Branch Proximity (BP)
The term “Branching Proximity” is used herein is used to refer to the % equivalent recurring methylene carbons, which are four or more removed from a carbon end group or branching carbon group (e.g., the epsilon carbons as shown in
paraffin branching proximity (BP)=(number of εcarbon groups/total number of carbon groups)*100,
where an ε carbon group is defined as a carbon group that is separated from any terminal carbon atom groups or branching carbon groups by at least 4 carbon groups. Further description of the measurement of the Branching Proximity is described in U.S. Pat. No. 6,090,989, and further description of epsilon carbons is provided in U.S. 2008/0171675, both of which are hereby incorporated by reference herein in their entireties.
Aspects of the invention may further be described with respect to the following embodiments:
A saturated hydrocarbon base oil comprising:
dimers of C14-C18 olefin monomers, the dimers having an average carbon number in a range of from 29 to 36, the dimers being present in an amount of at least 95 wt % of the saturated hydrocarbon base oil, wherein the saturated hydrocarbon base oil is characterized in that:
an average branching index (BI) of the oil as determined by 1H NMR is in a range of from 22 to 26, wherein the branching index (BI) is equivalent to the following equation (1):
branching index (BI)=(number of methyl group hydrogens/total number of hydrogens)*100, and (1)
an average paraffin branching proximity (BP) as determined by 13C NMR in a range of from 18 to 26, wherein the paraffin branching proximity (BP) is equivalent to the following equation (2):
paraffin branching proximity (BP)=(number of ε carbon groups/total number of carbon groups)*100, (2)
where an ε carbon group is defined as α carbon group that is separated from any terminal carbon atom groups or branching carbon groups by at least 4 carbon groups,
wherein the saturated hydrocarbon base oil comprises a Noack Volatility that is less than 14%, a Pour Point no greater than −27° C., and a CCS at −35° C. of less than 1800 cP.
The saturated hydrocarbon base oil prepared according to embodiment 1 wherein the saturated hydrocarbon base oil has a branching proximity (BP) as determine by 13C NMR in a range from 20 to 24.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a KV(100) that is in the range of 3.7 to 4.8, a viscosity index that is greater than 125.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a KV(100) that is in the range of 3.7 to 4.5, a viscosity index that is greater than 125.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil has a viscosity index that is greater than 130.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil has a viscosity index that is greater than 135.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil has a viscosity index that less than 140.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Cold Crank Simulated (CSS) dynamic viscosity at −35° C. of 1800 cP or less.
The saturated hydrocarbon base oil according any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Cold Crank Simulated (CSS) dynamic viscosity at −35° C. of 1700 cP or less.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Cold Crank Simulated (CSS) dynamic viscosity at −35° C. of 1600 cP or less.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Cold Crank Simulated (CSS) dynamic viscosity at −35° C. of 1500 cP or less.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Cold Crank Simulated (CSS) dynamic viscosity at −35° C. of 1400 cP or less.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Cold Crank Simulated (CSS) dynamic viscosity at −35° C. of 1300 cP or less.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Cold Crank Simulated (CSS) dynamic viscosity at −35° C. of 1200 cP or less.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Cold Crank Simulated (CSS) dynamic viscosity at −35° C. which is less than the value of the following equation:
Dynamic viscosity by CCS at −35° C.≤−14.167(KV100){circumflex over ( )}2+107.42(KV100)−190.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Noack Volatility which is less than 14% loss by ASTM D5800.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Noack Volatility which is less than 13% loss by ASTM D5800.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Noack Volatility which is less than 12% loss by ASTM D5800.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Noack Volatility which is less than 11% loss by ASTM D5800.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Noack Volatility which is less than 10% loss by ASTM D5800.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Noack Volatility which is less than 9% loss by ASTM D5800.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Noack Volatility which is less than 8% loss by ASTM D5800.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Noack Volatility which is less than 7% loss by ASTM D5800.
The saturated hydrocarbon base oil according to any preceding embodiment, wherein the saturated hydrocarbon base oil comprises a Noack Volatility by ASTM D5800 which is less than the value of the following equation:
Noack Volatility≤−1583.3(KV100){circumflex over ( )}2+13858(KV100)−28500.
A saturated hydrocarbon base oil with less than 10% of the dimers containing singularly branched isomers according to simulated distillation (ASTM D2887).
A saturated hydrocarbon base oil with less than 5% of the dimers containing singularly branched isomers according to simulated distillation (ASTM D2887).
A saturated hydrocarbon base oil with less than 1% of the dimers containing singularly branched isomers according to simulated distillation (ASTM D2887).
A method of preparing a saturated hydrocarbon base oil, comprising:
The method of embodiment 28, wherein the first feedstock comprises C14 to C18 alpha olefin monomers selected from the group consisting of tetradecene, pentadecene, hexadecane, heptadecene and octadecene.
The method of any preceding embodiment, further comprising preparing the C14 to C18 alpha olefin monomers of the first feed stock by dehydration of C14 to C18 primary alcohols selected from the group consisting of tetradecanol, pentadecanol, hexadecanol, heptadecanol and octadecanol.
The method of any preceding embodiment, wherein C14 to C18 primary alcohols are converted to the C14 to C18 alpha olefin monomers of the first feedstock and isomerized to form the isomerized C14 to C18 olefin monomer product by exposure to a di-functional catalyst.
The method of any preceding embodiment, wherein the first feedstock comprises less than 20% by weight of branched olefin monomers.
The method of any preceding embodiment, wherein the first feedstock comprises less than 5% by weight of branched olefin monomers.
The method of any preceding embodiment, wherein an amount of decene in any of the first and/or second feedstocks is less than 10% by weight.
The method of any preceding embodiment, wherein an amount of decene in any of the first and/or second feedstocks is less than 5% by weight.
The method of any preceding embodiment, wherein the isomerization conditions comprise heating the C14 to C18 alpha olefin monomers in the presence of an isomerization catalyst to a temperature in a range of from 100 to 400° C.
The method of any of preceding embodiment, wherein the isomerization conditions comprise heating the C14 to C18 alpha olefin monomers in the presence of an isomerization catalyst in a fixed bed reactor with a liquid hourly space velocity (LHSV) of 0.5-2 h-1.
The method of any preceding embodiment, wherein isomerization of at least a portion of the C14 to C18 alpha olefin monomers comprises heating the monomers in the presence of an isomerization catalyst selected from the group consisting of activated alumina, gamma-alumina, zirconium oxide on gamma alumina, theta-alumina with or without the presence of alkali metal.
The method of any preceding embodiment, wherein the isomerization conditions result in greater than 50% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers.
The method of any preceding embodiment, wherein the isomerization conditions result in greater than 60% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers.
The method of any preceding embodiment, wherein the isomerization conditions result in greater than 70% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers.
The method of any preceding embodiment, wherein the isomerization conditions result in greater than 80% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers.
The method of any preceding embodiment, wherein the isomerization conditions result in greater than 90% conversion of the C14 to C18 olefin alpha olefin monomers to C14-C18 internal olefin monomers.
The method of any preceding embodiment, wherein the internal olefin monomer C14 to C18 is oligomerized with a second feedstock, the second feedstock comprising C14 to C18 internal olefin monomers.
The method of any preceding embodiment, wherein the internal olefin monomer C14 to C18 product is oligomerized with a second feedstock, the second feedstock comprising C14 to C18 alpha olefin monomers including one or more of linear and branched alpha olefins.
The method of any preceding embodiment, wherein the internal olefin monomer C14 to C18 product is oligomerized with a second feedstock comprising C14 to C18 alpha olefins including branched olefins in a content by weight of up to 36% by weight of the C14 to C18 alpha olefins.
The method of any preceding embodiment, wherein the internal olefin monomer C14 to C18 product is oligomerized with a second feedstock comprising C14 to C18 alpha olefins including branched olefins in a content by weight of up to 25% by weight of the C14 to C18 alpha olefins.
The method of any preceding embodiment, wherein the internal olefin monomer C14 to C18 product is oligomerized with a second feedstock comprising C14 to C18 alpha olefins including branched olefins in a content by weight of up to 15% by weight of the C14 to C18 alpha olefins.
The method of any preceding embodiment, wherein the internal olefin monomer C14 to C18 product is oligomerized with a second feedstock comprising C14 to C18 alpha olefins including branched olefins in a content by weight of up to 5% by weight of the C14 to C18 alpha olefins.
The method of any preceding embodiment, comprising oligomerizing the internal monomer olefin C14 to C18-product with a second feedstock comprising C14 to C18 alpha olefin monomers in a ratio by weight of the internal monomer olefin C14 to C18 product to the C14 to C18 alpha olefin monomers in a range of from 80:20 to 20:80.
The method of any preceding embodiment, comprising oligomerizing the internal monomer olefin C14 to C18 product with a second feedstock comprising C14 to C18 alpha olefin monomers in a ratio by weight of the internal monomer C14 to C18 product to the C14 to C18 alpha olefin monomers in a range of from 70:30 to 50:50.
The method of any preceding embodiment, wherein the internal monomer olefin C14 to C18 product is oligomerized with a second feedstock comprising C14 to C18 olefin monomers having a different chain length than the internal monomer olefin C14 to C18 olefin monomer product.
The method of any preceding embodiment, wherein the internal monomer olefin C14 to C18 monomer product comprises C16 to C18 internal olefin monomers, and is oligomerized with a second feedstock comprising C14 alpha olefin monomers.
The method of any preceding embodiment, wherein the internal monomer olefin C14 to C18 product comprises C16 internal olefin monomers, and is oligomerized with a second feedstock comprising C14 alpha olefins to form the oligomer product.
The method of any preceding embodiment, wherein the internal monomer olefin C14 to C18 product comprises C16 internal olefin monomers, and wherein the C16 internal olefin monomers are oligomerized with each other or a second feedstock comprising C16 olefin monomers to form the oligomer product.
The method of any preceding embodiment, wherein oligomerization is performed using a boron trifluoride oligomerization catalyst, an alcohol promoter, and an ester promoter in at least one continuously stirred reactor under oligomerization conditions;
The method of any preceding embodiment, wherein the oligomerization reaction is performed at a temperature in the range of from 15° C. to 110° C.
The method of any preceding embodiment, wherein the oligomerization reaction is performed at a temperature in the range of from 40° C. to 110° C.
The method of any preceding embodiment, wherein the oligomerization reaction is performed at a temperature in the range of from 60° C. to 110° C.
The method of any preceding embodiment, wherein the oligomerization reaction is performed at a temperature in the range of from 80° C. to 110° C.
The method of any preceding embodiment, wherein the oligomerization reaction is performed at a temperature in the range of from 90° C. to 110° C.
The method of any preceding embodiment, wherein the oligomerization is performed using a continuously stirred tank reactor.
The method of any preceding embodiment, wherein the average residence time of oligomers in a continuously stirred tank reactor is in the range from 60 to 400 minutes.
The method of any preceding embodiment, wherein the average residence time of oligomers in a continuously stirred tank reactor is in the range from 90 to 300 minutes.
The method of any preceding embodiment, wherein the average residence time of oligomers in a continuously stirred tank reactor is in the range from 120 to 240 minutes.
The method of any preceding embodiment, wherein the average residence time of oligomers in a continuously stirred tank reactor is in the range from 150 to 240 minutes.
The method of any of preceding embodiment, wherein the average residence time of oligomers in a continuously stirred tank reactor is in the range from 180 to 240 minutes.
The method of any preceding embodiment, wherein at least one of the first or second feedstocks comprises at least 50 wt % of a terpene.
The method of any preceding embodiment, wherein at least one of the first or second feedstocks comprises at least 40 wt % of a terpene.
The method of any preceding embodiment, wherein at least one of the first or second feedstocks comprises at least 30 wt % of a terpene.
The method of any preceding embodiment, wherein at least one of the first or second feedstocks comprises at least 20 wt % of a terpene.
The method of any preceding embodiment, wherein at least one of the first or second feedstocks comprises at least 10 wt % of a terpene.
The method of any preceding embodiment, wherein at least one of the first or second feedstocks comprises at least 5 wt % of a terpene.
The method of any preceding embodiment, wherein at least one of the first or second feedstocks comprises at least 1 wt % of a terpene.
The method of any preceding embodiment, wherein unreacted monomer is separated from the oligomer product and recycled for oligomerization thereof.
The method of any preceding embodiment, wherein the hydrogenated dimer is separated from the saturated oligomer product by a distillation process.
The method of any preceding embodiment, wherein the average double bond position of linear olefins in the isomerized C14 to C18 olefin monomer product is in the range of from 1.5 to 5.0.
The method of any preceding embodiment, wherein the average double bond position of linear olefins in the isomerized C14 to C18 olefin monomer product is in the range of from 1.5 to 4.5.
The method of any preceding embodiment, wherein the average double bond position of linear olefins the isomerized C14 to C18 olefin monomer product is in the range of from 2.0 to 4.4.
The method of any preceding embodiment, wherein the average double bond position of linear olefins the isomerized C14 to C18 olefin monomer product is in the range of from 2.5 to 4.2.
The method of any preceding embodiment, wherein the average double bond position of linear olefins the isomerized C14 to C18 olefin monomer product is in the range of from 3.0 to 4.0.
The method of any preceding embodiment, wherein the average double bond position of linear olefins the isomerized C14 to C18 olefin monomer product is in the range of from 3.5 to 3.9.
The method of any preceding embodiment, wherein oligomerization is performed under conditions to further at least partially isomerize the olefin monomers.
The method of any of preceding embodiment, wherein oligomerization product contains less than 0.5% benzylic groups.
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| PCT/US2018/041981 | 7/13/2018 | WO |
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| WO2019/014533 | 1/17/2019 | WO | A |
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