Patent Application
20190264112
The present disclosure is generally directed to the field of lubricants, more specifically to hydrocarbon base oils obtained by the oligomerization of one or more olefin feedstocks. In one embodiment, the olefin feedstock comprises a population of olefins derived from alcohols. In another embodiment, the process comprises the preparation of an olefin feedstock including those manufactured by the dehydration of alcohols, an oligomerization step, a hydrogenation step, and a fractional distillation step.
Base oils are the major constituent in lubricants for automobiles, such as 2-stroke, 4-stroke, gear oil, and transmission oils; aviation, such as turbine; and industrial uses, such as hydraulic fluid, compressor oil, lubricating greases, and process oils. Lubricants typically consist of 60-100% base stock by weight and the remainder in additives to control their fluid properties and improve low temperature behavior, oxidative stability, corrosion protection, demulsibility and water rejection, friction coefficients, lubricities, wear protection, air release, color, and other properties.
The American Petroleum Institute (API) publication API 1509, “Engine Oil Licensing and Certification System, 17th Edition”, defines a base oil or base stock as: “ . . . a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both. Base stocks may be manufactured using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining. Rerefined stock shall be substantially free from materials introduced through manufacturing, contamination, or previous use.” Base oil is the base stock or blend of base stocks used in API-licensed oil.
Generally lubricating base oils are base oils having kinematic viscosity of about 2 mm2/s or greater at 100° C. (KV100, kinematic viscosity measured at 100° C.); a pour point (PP) of about −15° C. or less; and a viscosity index (VI) of 120 or greater.
The oils in Group III are very high viscosity index (VHVI) base oils, which are manufactured from crude oil by hydrocracking and catalytic dewaxing or solvent dewaxing. Group III base oils can also be manufactured by catalytic dewaxing of slack waxes originating from crude oil refining, or by catalytic dewaxing of waxes originating from Fischer-Tropsch synthesis from natural gas or coal based raw materials.
Group IV base oils are polyalphaolefin (PAO, or poly-α-olefin) base oils. PAOs are synthetic hydrocarbon base oils which have good flow properties at low temperatures, relatively high thermal and oxidative stability, low evaporation losses at high temperatures, higher viscosity index, good friction and wear behavior, good hydrolytic stability, and excellent thermal conductivity. PAOs are not toxic and are miscible with mineral oils and esters. Consequently, PAOs are suited for use in engine oils, compressor oils, hydraulic oils, gear oils, and greases. Typically PAO is produced by catalytic oligomerization of alpha olefins ranging from 1-octene to 1-dodecene, with 1-decene being a preferred material, most commonly used as synthetic base oils in modern engine lubricants. PAOs useful as synthetic base oils may be synthesized by homogeneous Friedel-Crafts catalyst such as boron trifluoride (BF3) or aluminum chloride (AlCl3), typically followed by hydrogenation to remove residual unsaturation and improve thermo-oxidation stability.
PAOs may be produced by the use of Friedel-Craft catalysts, such as aluminum trichloride or boron trifluoride, and a protic promoter. The alpha olefins generally used as feedstock are those in the C8 to C20 range, most preferably 1-octene, 1-nonene, 1-decene, 1-dodecene, and 1-tetradecene.
Alternatives to the Friedel-Craft process include metallocene catalyst systems. Most of the metallocene-based focus has been on high viscosity index PAOs (HVI-PAOs) and higher viscosity oils for industrial and commercial applications. Examples include U.S. Pat. No. 6,706,828, which discloses a process for producing PAOs from metallocene catalysts with methylalumoxane (MAO). Others have made various PAOs, such as polydecene, using various metallocene catalysts not typically known to produce polymers or oligomers with any specific tacticity. Examples include WO 96/23751, EP 0 613 873, U.S. Pat. Nos. 5,688,887, 6,043,401, WO 03/020856 (equivalent to US 2003/0055184), U.S. Pat. Nos. 5,087,788, 6,414,090, 6,414,091, 4,704,491, 6,133,209, and 6,713,438. Although most of the research on metallocene-based PAOs has focused on higher viscosity oils, recent research has looked at producing low viscosity PAOs for automotive applications. US 2007/0043248 discloses a process using a metallocene catalyst for the production of low viscosity (4 to 10 cSt) PAO basestocks. This technology is attractive because the metallocene-based low viscosity PAO has excellent lubricant properties.
A number of US patents have also used BF3 to oligomerize linear olefins other than alpha olefins to produce Group V synthetic hydrocarbons having properties similar to group IV PAO base oils. For example, U.S. Pat. No. 4,910,355 describes a process using a mixture of C8-18 olefins, preferably C10 olefins, containing about 50-90 weight percent α-olefins and about 10-50 weight percent internal olefins, and contacting this mixture with a catalytic amount of a Friedel-Crafts catalyst, preferably BF3, and a catalyst promoter, preferably alcohol or water, at a temperature of about 10°-80° C., washing to remove catalyst, distilling to remove monomer and optionally dimer, and hydrogenating to obtain a substantially saturated olefin oligomer. The resultant oligomer exhibits a pour point that is lower than the pour point obtained with a comparative α-olefin under the same oligomerization conditions.
Large quantities of PAOs are used in a variety of lubricating applications. However, PAOs existing in the market today are derived from fossil fuels, and hence are not renewable.
There is a continuing need for improved base oils, for example, base oils that have a wide operational temperature range, and a continuing need for base oils derived from renewable feedstock.
The present invention relates to a process for production of saturated olefin oligomers for use as a synthetic hydrocarbon base oil by:
A further object of the invention is an alternative process for the manufacture of branched, saturated hydrocarbons suitable for Group IV PAO base oils.
The process according to the invention comprises multiple steps where, in the first step, an alcohol feedstock comprising one or more alcohols is dehydrated in the presence of γ-alumina catalyst to form an olefin mixture. In a subsequent step, the olefin mixture is combined with up to two co-monomers with a catalyst system under process conditions to form an oligomer product comprising dimers, trimers, and higher oligomers. In a subsequent step, the oligomer product is hydrogenated to produce a fully saturated branched hydrocarbon. For example, in one embodiment, ethanol is dehydrated to ethylene and included in the olefin mixture.
Other objects and features will be in part apparent and in part pointed out hereinafter.
Corresponding reference characters indicate corresponding parts throughout the drawings.
“Base oil” as used herein is an oil used to manufacture products including dielectric fluids, hydraulic fluids, compressor fluids, engine oils, lubricating greases, and metal processing fluids.
“Biobased base oil” as used herein is any base oil derived from renewable compositions (e.g., a natural alcohol such as a fatty alcohol).
“Fatty acid” as used herein is a carboxylic acid with a long aliphatic tail (i.e., chain), which is either saturated or unsaturated. Most naturally occurring fatty acids have a chain with an even number of carbon atoms, for example, from 4 to 28.
“Fatty alcohol” as used herein is a high-molecular-weight, straight-chain or branched chain primary alcohol, and may range from as few as 4 carbons to as many as 28 carbons. Fatty alcohols may be derived from natural fats and oils, or fatty acids as described herein.
“Primary alcohol” as used herein means an organic compound having a hydrocarbon chain (e.g., CnH2n) terminating with a hydroxyl (—OH) functional group. Non-limiting examples of primary alcohols include n-butanol or isobutanol (C4), 1-pentanol, isoamyl alcohol, or 2-methyl-1-butanol (C5), 1-hexanol (C6), 1-heptanol (C7), 1-octanol or phenethyl alcohol (C8), 1-nonanol (C9), 1-decanol or tryptophol (C10), undecanol (C11), dodecanol (C12), tridecan-1-ol (C13), 1-tetradecanol (C14), 1-pentadecanol (C15), cetyl alcohol (C16).
“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).
“Sesquiterpene” as used herein is a class of terpenes that consist of three isoprene units and have the empirical formula C15H24. Sesquiterpenes may be acyclic or contain rings.
“Terpenes” as used herein means biosynthetic units of isoprene (e.g., (C5H8)n, where n is the number of linked isoprene units). Representative examples of terpenes (or terpenoids) include, but are not limited to, monoterpenes, partially hydrogenated monoterpenes, sesquiterpenes, and the like.
“Terpene” as used herein is a compound that is capable of being derived from isopentyl pyrophosphate (IPP) or dimethyl allyl pyrophosphate (DMAPP), and the term terpene encompasses hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, tetraterpenes, and polyterpenes. A hydrocarbon terpene contains only hydrogen and carbon atoms and no heteroatoms such as oxygen, and in some embodiments has the general formula (C5H8)n, where n is 1 or greater. A “conjugated terpene” or “conjugated hydrocarbon terpene” as used herein refers to a terpene comprising at least one conjugated diene moiety. It should be noted that the conjugated diene moiety of a conjugated terpene may have any stereochemistry (e.g., cis or trans, or E or Z)) and may be part of a longer conjugated segment of a terpene, for example, the conjugated diene moiety may be part of a conjugated triene moiety. It should be understood that hydrocarbon terpenes as used herein also encompasses monoterpenoids, sesquiterpenoids, diterpenoids, triterpenoids, tetraterpenoids and polyterpenoids that exhibit the same carbon skeleton as the corresponding terpene, but have either fewer or additional hydrogen atoms than the corresponding terpene, for example, terpenoids having 2 fewer, 4 fewer, or 6 fewer hydrogen atoms than the corresponding terpene, or terpenoids having 2 additional, 4 additional, or 6 additional hydrogen atoms than the corresponding terpene. The terms “terpene” and “isoprenoids” are used interchangeably herein, and are a large and varied class of organic molecules that can be produced by a wide variety of plants and some insects. Some terpenes or isoprenoid compounds can also be made from organic compounds such as sugars by microorganisms, including bioengineered microorganisms. Because terpenes or isoprenoid compounds can be obtained from various renewable sources, they are useful monomers for making eco-friendly and renewable base oils.
“Olefin co-monomer” refers to any olefin containing at least one carbon-carbon double bond. “Olefin co-monomer(s)” means one or more olefin co-monomers, where it is understood that two olefin co-monomers refers to two olefin co-monomers that are different from each other, etc.
“Alpha-olefin” as used herein refers to any olefin having at least one terminal, unconjugated carbon-carbon double bond. “Alpha-olefin” encompasses linear alpha-olefins (LAOs) and branched alpha-olefins. Alpha-olefins may contain one or more carbon-carbon double bonds in addition to the terminal olefinic bond, for example, alpha, omega-dienes.
“Linear internal olefins (LIOs)” as used herein refers to linear olefins containing one or more carbon-carbon double bonds, none of which are located at a terminal position. “Branched internal olefins” as used herein refers to branched olefins containing one or more carbon-carbon double bonds, none of which are located at a terminal position.
“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 of monomer, and also encompasses the formation of adducts between more than one type of monomer.
“Polymer” as used herein refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type, and having more than 100 monomeric units. The generic term “polymer” embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as “interpolymer.” The generic term “interpolymer” encompasses the term “copolymer” (which generally refers to a polymer prepared from two different monomers) as well as the term “terpolymer” (which generally refers to a polymer prepared from three different types of monomers), and polymers made by polymerizing four or more types of polymers.
“Dimer” or “dimeric species” as used herein refers to any type of adducts formed between two molecules, and encompasses 1:1 adducts of the same types of molecules or 1:1 adducts of different types of molecules, unless specifically stated otherwise. “Trimer” or “trimeric species” as used herein refers to any type of adducts formed between three molecules, and encompasses 1:1:1 of the same types of molecules or three different types of molecules, and 1:2 or 2:1 adducts of two different types of molecules. “Tetramer” or “tetrameric species” as used herein refers to any type of adducts formed between four molecules. “Pentamer” or “pentameric species” as used herein refers to any type of adducts formed between five molecules. “Hexamer” or “hexameric species” as used herein refers to any type of adducts formed between six molecules.
“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 viscosities at 40° C. and at 100° C. are 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.
“Pour point” 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.
“Cold cranking simulator viscosity” as used herein 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.
“Boiling point” refers to the natural boiling point of a substance at atmospheric pressure, unless indicated otherwise. Simulated Distillation may be carried out according to “Standard Test Method for Boiling Range Distribution of Petroleum Distillates in Boiling Range from 174° C. to 700° C. by Gas Chromatography” (ASTM D 6352—02), “Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography” (ASTM D2887), or “Standard Test Method for Estimation of Engine Oil Volatility by Capillary Gas Chromatography” (ASTM D 6417), each published by ASTM International, and each of which is incorporated herein by reference in its entirety.
Evaporative weight loss may be 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.
The degree of unsaturation of a product, such as a hydrogenated oligomer product, can be quantified according to the Bromine Index of the product, as determined in accordance with ASTM D2710-09, which is incorporated by reference herein in its entirety.
In the following description, all numbers disclosed herein are approximate values, regardless of whether the word “about” or “approximate” is used in connection therewith. Numbers may vary by 1%, 2%, 5% or sometimes 10 to 20%. Whenever a numerical range with a lower limit RL and an upper limit RU is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers Rk within the range are specifically disclosed: Rk=RL+k*(RU−RL), wherein k is a variable ranging from 1% to 100% with a 1% increment (i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . 50 percent, 51 percent, 52 percent, . . . 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent). Further, any numerical range defined by any two numbers Rk as defined above is also specifically disclosed herein.
As used herein and unless otherwise indicated, a reaction that is “substantially complete” means that the reaction contains more than about 80% desired product by percent yield, more than about 90% desired product by percent yield, more than about 95% desired product by percent yield, or more than about 97% desired product by percent yield. As used herein, a reactant that is “substantially consumed” means that more than about 85%, more than about 90%, more than about 95%, more than about 97% of the reactant has been consumed, by weight %, or by mol %. As used herein, % refers to % measured as wt. % or as area % by GC-MS or GC-FID, unless specifically indicated otherwise.
As used herein and unless otherwise indicated, a composition that is made up “predominantly” of a particular component includes at least about 60% of that component. A composition that “consists essentially of” a component refers to a composition comprising 80% or more of that component, unless indicated otherwise.
Unless otherwise stated herein, all concentration percentages shall be understood to be on a weight percent basis.
Referring now to
In certain embodiments, the process of the present disclosure may be used to form biobased base oils. For example, in one such embodiment, at least about 10% of the carbon atoms in the base oil originate from renewable carbon sources. By way of further example, in one such embodiment, at least about 20% of the carbon atoms in the base oil originate from renewable carbon sources. By way of further example, in one such embodiment, at least about 30% of the carbon atoms in the base oil originate from renewable carbon sources. By way of further example, in one such embodiment, at least about 40% of the carbon atoms in the base oil originate from renewable carbon sources. By way of further example, in one such embodiment, at least about 50% of the carbon atoms in the base oil originate from renewable carbon sources. By way of further example, in one such embodiment, at least about 60% of the carbon atoms in the base oil originate from renewable carbon sources. By way of further example, in one such embodiment, at least about 70% of the carbon atoms in the base oil originate from renewable carbon sources. By way of further example, in one such embodiment, at least about 80% of the carbon atoms in the base oil originate from renewable carbon sources. By way of further example, in one such embodiment, at least about 90% of the carbon atoms in the base oil originate from renewable carbon sources. In some variations, the carbon atoms of the base oil comprise at least about 95%, at least about 97%, at least about 99%, or about 100% of originate from renewable carbon sources. By way of further example, in one such embodiment, at least about 90% of the carbon atoms in the base oil originate from renewable carbon sources. In some variations, the carbon atoms of the base oil comprise less than 100% of originate from renewable carbon sources. In some variations, the carbon atoms of the base oil comprise less than 95%, or even less than 90%. In some variations, about 10% to about 90% of the carbon atoms of the base oil are from renewable carbon sources. The origin of carbon atoms in the reaction product adducts may be determined by any suitable method, including but not limited to reaction mechanism combined with analytical results that demonstrate the structure and/or molecular weight of adducts, or by carbon dating (e.g., according to “Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis” (ASTM D6866-12), which is incorporated herein by reference in its entirety). For example, using ASTM D6866-12 or another suitable technique, a ratio of carbon 14 to carbon 12 isotopes in the biobased base oil can be measured by liquid scintillation counting and/or isotope ratio mass spectroscopy to determine the amount of modern carbon content in the sample. A measurement of no modern carbon content indicates all carbon is derived from fossil fuels. A sample derived from renewable carbon sources will indicate a concomitant amount of modern carbon content, up to 100%
In some embodiments of this disclosure, one or more repeating units of a biobased hydrocarbon base oil is a specific species of partially hydrogenated, conjugated hydrocarbon terpenes. Such specific species of partially hydrogenated, conjugated terpenes may or may not be produced by a hydrogenation process. In certain variations, a partially hydrogenated, conjugated hydrocarbon terpene species is prepared by a method that includes one or more steps in addition to or other than catalytic hydrogenation. Non-limiting examples of specific species of partially hydrogenated, conjugated hydrocarbon terpenes include sesquiterpenes, dihydromyrcene, tetrahydromyrcene, dihydroocimene, and tetrahydroocimene.
In certain embodiments, the oligomer product may be isomerized during the hydrogenation step. Isomerizations may include the generation of E- or Z-mixtures of olefins in a biobased hydrocarbon base oil. Isomerizations may also include the generation of E- and Z-olefins within a biobased hydrocarbon base oil. For example, in one embodiment, during the hydrogenation step, the oligomer product may be isomerized into an all Z-olefin mixture. By way of further example, in one embodiment, during the hydrogenation step, the oligomer product may be isomerized into an all E-olefin mixture.
In some embodiments, the present disclosure includes a process for the generation of polyalphaolefins (PAOs) from alcohol-derived feedstocks. The process may include a feedstock composition, a first olefinic mixture, an optional second olefinic mixture, an oligomerization, a distillation, a hydrogenation, a separation, and a final base oil composition.
Referring now to
As illustrated in
In one exemplary embodiment, the olefin feedstock comprises 0-25% 1-decene, 25-50% 1-octene, and 15-50% 1-dodecene. In one such embodiment, the 1-octene comprises renewable carbon. In another such embodiment, the 1-dodecene comprises renewable carbon. In yet another such embodiment, the 1-octene and the 1-dodecene each comprise renewable carbon. As previously noted, certain conventional olefin feedstocks such as 1-decene are less preferred in certain embodiments. In each of the foregoing embodiments, therefore, the olefin feedstock preferably comprises less than 25% 1-decene (as a weight percentage of the olefins comprised by the olefin mixture). By way of further example, in each of the foregoing embodiments, the olefin feedstock may comprise less than 20% 1-decene (as a weight percentage of the olefins comprised by the olefin mixture). By way of further example, in each of the foregoing embodiments, the olefin feedstock may comprise less than 15% 1-decene (as a weight percentage of the olefins comprised by the olefin mixture). By way of further example, in each of the foregoing embodiments, the olefin feedstock may comprise less than 10% 1-decene (as a weight percentage of the olefins comprised by the olefin mixture). By way of further example, in each of the foregoing embodiments, the olefin feedstock may comprise less than 5% 1-decene (as a weight percentage of the olefins comprised by the olefin mixture). By way of further example, in each of the foregoing embodiments, the olefin feedstock may comprise less than 1% 1-decene (as a weight percentage of the olefins comprised by the olefin mixture). By way of further example, in each of the foregoing embodiments, the olefin feedstock may have an absence of 1-decene. In each of the foregoing embodiments, the olefin feedstock may have an average carbon number in the range of 9.5 to 13, such as in the range of from 9.5 to 10.5, and even in the range of from 9.9 to 10.5, such as in the range of from 10.6 to 13.
A second step includes where the olefin mixture is charged to the first stage oligomerization reactor and oligomerized. The reaction is carried out in the presence of a suitable oligomerization catalyst. In one embodiment, the olefin mixture may be treated to remove impurities prior to the oligomerization step.
In a subsequent step optionally a two-stage reaction may be practiced where a second olefin mixture having a different composition than the first olefin mixture is charged to a second stage oligomerization reactor along with the product from the first stage reactor whereupon a second oligomerization catalyst is charged and a second oligomer product is formed.
In a subsequent step the reaction product is discharged and the un-reacted monomer or lights are distilled, in part or in full, and recycled with an optional off-take of the unsaturated lights as a separate product stream.
In a subsequent step, the stripped oligomer product is hydrogenated in either a continuous flow reactor or a batch stirred tank reactor using a nickel (Ni) catalyst, as is known in the art.
In a final step, the hydrogenated oligomer is fractionally distilled using one or more fractional distillation columns and one or more short-path evaporators. In general, long-chain alcohols may be dehydrated, followed by a distillation, that yields a mixture of C8-C16 olefins. Alternatively, in general, ethyl alcohol may be dehydrated, oligomerized, and distilled to provide a mixture of C8-C16 alpha-olefins.
In general, terpenes may be purified and subjected to selective partial hydrogenation to provide a mixture of C8-C16 alpha-olefins.
Oligomerizations typically use suitable catalytic conditions under suitable temperatures to generate PAOs. For example, suitable catalysts used in oligomerizations include Friedel-Crafts catalysts and metallocene catalysts. Exemplary Friedel-Crafts catalysts include Group 13 elements. For example, in one embodiment, the catalyst may be selected from the group consisting of boron trifluoride, aluminum trichloride, gamma-alumina, and combinations thereof. Exemplary metallocene catalysts include titanocenes, zirconocenes, hafnocenes, and the like, and combinations thereof. In some embodiments, suitable co-catalysts may also be used for oligomerizations. Suitable co-catalysts include alcohols, alkyl acetates, methylaluminoxane, and the like. For example, suitable alcohol co-catalysts include C1-C10 alcohols. By way of further example, suitable alcohol co-catalysts include C1-C6 alcohols selected from the group consisting of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, and combinations thereof. By way of further example, suitable alkyl acetate co-catalysts include C1-C10 alkyl acetates. By way of further example, suitable C1-C6 alkyl acetates selected from the group consisting of methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and combinations thereof. In any of the above embodiments, suitable catalysts and/or cocatalysts may be used in amounts known to those of skill in the art to provide oligomerization products, such as PAOs. Suitable temperatures for oligomerization are also known to those of skill in the art. For example, in one embodiment, the oligomerization temperature can vary from about −20° C. to about 90° C. By way of further example, in one embodiment, the oligomerization temperature can vary from about 15° C. to about 70° C.
In some embodiments, distillations following oligomerizations are used to remove unreacted olefin monomers. In other embodiments, distillations are used to remove unreacted monomers and dimers. In yet other embodiments, distillations are used to further remove dimers.
In some embodiments, hydrogenations of purified oligomers are used to saturate remaining trimers and higher oligomers. Conventional hydrogenation conditions are known to those of skill in the art. For example, in certain embodiments, typical hydrogenations include hydrogenation catalysts. By way of further example, in some embodiments, hydrogenation catalysts may be selected from the group consisting of palladium, platinum, nickel, and the like, and combinations thereof.
In some embodiments, a separation includes a plurality of distillations to provide the final base oil. For example, in some embodiments, distillations may include a plurality of fractional distillations as shown in
In some embodiments, the final base oil composition has favorable PAO properties for use as lubricants, and the like. Favorable PAO properties for the base oils generated in the process described herein are dependent on the feedstock composition described herein and may include low Noack volatilities, low kinematic viscosities, and low pour points. Exemplary low Noack volatilities, in one embodiment, include a range of about 10% to about 15% weight loss. By way of further example, in one embodiment, low Noack volatilities include a range of about 11% to about 14% weight loss. Noack volatility is typically determined via the ASTM D5800 method, as known to those of skill in the art, and incorporated herein by reference in its entirety. Exemplary low kinematic viscosities, in one embodiment, include about 6 cSt at 100° C. By way of further example, in one embodiment, low kinematic viscosities include about 4 cSt at 100° C. By way of further example, in one embodiment, low kinematic viscosity may range from at least about 45% of 4 cSt PAO to not more than about 55% of 6 cSt PAO. By way of further example, in one embodiment, low kinetic viscosity may include equal amounts of 4 cSt and 6 cSt PAOs. By way of further example, in one embodiment, low kinetic viscosity may include higher amounts of 4 cSt compared to amounts of 6 cSt. Exemplary low pour points, in one embodiment, may include about −45° C. to about −80° C. By way of further example, in one embodiment, low pour points may include about −60° C. to about −70° C. Pour points are typically determined via the ASTM D5950 method, as known to those of skill in the art, and incorporated herein by reference in its entirety.
In certain embodiments, a plurality of olefinic mixtures may be generated from alcohol-derived olefins described herein, biobased olefins described herein, conventional olefins described herein, and combinations thereof. For example, a first olefin mixture and a second olefin mixture (see
In some embodiments, the process for the generation of polyalphaolefins (PAOs) from alcohol-derived feedstocks may be performed in a single batch mode or a continuous batch mode.
Referring now to
Referring now to
In general, the present disclosure further includes a process for the generation of polyalphaolefins (PAOs) from long-chain alcohol-derived olefins (e.g., linear alpha olefins (LAOs)), and olefin co-monomers. Referring now to
Olefins 1-4 described above may then be subjected to BF3-mediated oligomerization 5, followed by quenching, washing, and separating 6, thereby providing Lights Recycle 7. Lights Recycle 7 may then be purified via distillation before final hydrogenation 8. Distillate from Lights Recycle 7 provides unreacted monomer 13 that may be recycled back to BF3-mediated oligomerization 5, and unsaturated Lights 13 as a by-product. Final hydrogenation 8 then provides Product 9 wherein fractional distillation provides Light Base Oil 10, Mid Base Oil 11, and Heavy Base Oil 12. Exemplary Light Base Oils 13 may include 2 cSt base oil. Exemplary Mid Base Oil may include a range of about 4 cSt to about 8 cSt. By way of further example, in one embodiment, Mid Base oil may include a range of about 4 cSt to about 6 cSt. By way of further example, in one embodiment, Mid Base Oil may include 4 cSt, 6 cSt, or 8 cSt, respectively. Exemplary Heavy Base Oil may include a range of about 7 cSt to about 20 cSt. By way of further example, in one embodiment, Heavy Base Oil may include a range of about 7 cSt to about 17 cSt. By way of further example, in one embodiment, Heavy Base Oil may include a range of about 7 cSt to about 12 cSt. By way of further example, in one embodiment, Heavy Base Oil may include a range of about 7 cSt to about 12 cSt. By way of further example, in one embodiment, Heavy Base Oil may include a range of about 7 cSt to about 9 cSt. By way of further example, in one embodiment, Heavy Base Oil may include 7 cSt, 9 cSt, 12 cSt, 17 cSt, or 20 cSt, respectively.
In general, the present disclosure further provides a process for the generation of LAOs from ethanol. Referring now to
In general, the present disclosure further provides a process for the generation of LAOs from long-chain alcohols. Referring now to
In general, embodiments of the present disclosure further provide a plurality of pilot dehydration reactor trains. Referring now to
The oligomers of the present invention are characterized in that they are formed from several different monomer units, that can vary in carbon number, branch ratio, or reactive double bond position, chemically bonded into larger branched hydrocarbon molecules which comprise the hetero-oligomer reaction product(s), and form a statistical distribution which can be specified and measured. A hetero-oligomer is made of multiple different macromolecules (as opposed to a homo-oligomer that would be formed by a few identical molecules). In cases where the oligomers of the present invention are formed from several different monomer units, a percentage of the olefin monomers in the olefin monomer mixture may have a carbon number difference. For example, in one embodiment, at least 15% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 20% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 25% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 30% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 35% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 40% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 45% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 50% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 55% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 60% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 65% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 70% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 75% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons. By way of further example, in one embodiment, at least 80% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least four carbons.
In another embodiment, for example, at least 15% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 20% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 25% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 30% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 35% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 40% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 45% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 50% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 55% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 60% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 65% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 70% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 75% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons. By way of further example, in one embodiment, at least 80% of the olefin monomers in the olefin mixture may have a carbon number difference of at least five carbons.
In yet another embodiment, for example, at least 15% of the olefin monomers in the olefin monomer mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 20% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 25% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 30% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 35% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 40% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 45% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 50% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 55% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 60% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 65% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 70% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 75% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons. By way of further example, in one embodiment, at least 80% of the olefin monomers in the olefin mixture may have a carbon number difference of at least six carbons.
In cases where the oligomers of the present invention are formed from several different monomer units, a percentage of the olefin monomers in the olefin monomer mixture may have a reactive double bond (olefinic) position. In certain embodiments, the reactive olefinic position may be an internal olefin bond or an external olefin bond. More specifically, a percentage of the olefin monomers in the olefin monomer mixture may have a reactive external olefinic bond, and further include an internal (i.e., non-reactive) olefinic bond. For example, in one embodiment, at least 0.1% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 0.25% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 0.5% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 0.75% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 1% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 1.5% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 1.75% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 2% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 3% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 4% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, at least 5% of the olefin monomers in the olefin monomer mixture have an internal olefin bond.
In certain embodiments, no more than a percentage of the olefin monomers in the olefin monomer mixture include an internal olefin bond. For example, in one embodiment, no more than 4% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, no more than 3% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, no more than 2% of the olefin monomers in the olefin monomer mixture have an internal olefin bond. By way of further example, in one embodiment, no more than 1% of the olefin monomers in the olefin monomer mixture have an internal olefin bond.
The boiling points, carbon numbers, and the molecular weights of the hetero-oligomers are correlated and exist as characteristic distributions which can be described as having some average values and more than one mode for each hetero-oligomer of a given order, such as dimer, trimer, tetramer etc. The modes of the distribution can be defined by considering the distribution along some axis such as molecular weight, carbon number, or actual or simulated boiling point as in
An advantage of the current invention can be seen when one considers that the physical properties of the hetero-oligomers vary continuously and significantly throughout the distribution and the spacing of the modes facilitates the physical separation of the oligomer product by fractional distillation into separate products with properties that can be controlled. In fact the properties of the final products can be more easily controlled and optimized than in the prior art by the careful selection of A) the monomer characteristics as mentioned; B) the relative amounts of each monomer which are incorporated in the oligomers; C) the reaction conditions which can alter selectivity of the reaction and the distribution of oligomers present in the reaction product; and D) the number and efficiency of the fractional separation stages. In one embodiment, fractional distillation is performed to separate the dimer portion of the branched saturated hydrocarbons into two or more product streams differing in boiling point or viscosity. In another embodiment, fractional distillation is performed to separate the trimer portion of the branched saturated hydrocarbons into two or more product streams differing in boiling point or viscosity. In yet another embodiment, fractional distillation is performed to separate the dimer and trimer portions of the branched saturated hydrocarbons into two or more product streams to adjust the Noack volatility, viscosity index and/or pour point of the branched saturated hydrocarbon product. In one embodiment, the branched saturated hydrocarbon mixture has a viscosity of less than 5 centistokes at 100 C, a viscosity index greater than 130 and a cold crank simulation (CCS) of less than 2100 at −35° C.
In one embodiment, base oils prepared as described herein are biodegradable. Biodegradability can be determined using one or more standardized test procedures and can provide valuable insight in comparing the potential risk of different lubricant products to the environment. One such guideline and test method has been set by the Organization for Economic Cooperation and Development (OECD) for degradation and accumulation testing.
The OECD has indicated that several tests may be used to determine the “ready biodegradability” of organic chemicals. Among these, aerobic ready biodegradability by the OECD 301B method tests material over a 28-day period and determines biodegradation of the material by measuring the evolution of carbon dioxide from the microbial oxidation of the material's organic carbon. The carbon dioxide produced is trapped in barium hydroxide solution and is quantified by titration of residual hydroxide with standardized hydrogen chloride. To determine the percent biodegradation, the amount of carbon dioxide (CO2) produced microbially from the test material is compared to its theoretical carbon dioxide content (i.e., the complete oxidation of the carbon in the test material to CO2). Positive controls, using sodium benzoate as a reference material, are run to check the viability of the aerobic microorganisms used in the procedure. Blank controls are also run in parallel. Tests, controls, and blanks are run in duplicate. In one embodiment, branched saturated hydrocarbons in a purified oligomer product have a biodegradability at 28 days as measured in accordance with OECD method 301b of at least 50%. In another embodiment, the branched saturated hydrocarbons may have a biodegradability at 28 days as measured in accordance with OECD method 301b of at least 60%. In another embodiment, the branched saturated hydrocarbons may have a biodegradability at 28 days as measured in accordance with OECD method 301b of at least 70%. In yet another embodiment, the branched saturated hydrocarbons may have a biodegradability at 28 days as measured in accordance with OECD method 301b of at least 75%. In yet a further embodiment, the branched saturated hydrocarbons have a biodegradability at 28 days as measured in accordance with OECD method 301b of at least 80%. In yet another embodiment, the branched saturated hydrocarbons may have a final (ultimate) biodegradability as measured in accordance with OECD method 301b of at least 60%. In yet another embodiment, the branched saturated hydrocarbons have a final (ultimate) biodegradability as measured in accordance with OECD method 301b of at least 70%. In yet another embodiment, the branched saturated hydrocarbons may have a final (ultimate) biodegradability as measured in accordance with OECD method 301b of at least 75%. In yet another embodiment, the branched saturated hydrocarbons may have a final (ultimate) biodegradability as measured in accordance with OECD method 301b of at least 80%. In yet another embodiment, the branched saturated hydrocarbons may have a final (ultimate) as measured in accordance with OECD 301b of at least method 88%. In yet another embodiment, the branched saturated hydrocarbons may have a final (ultimate) biodegradability as measured in accordance with OECD method 301b of at least 90%.
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As various changes could be made in the above articles, compositions and methods without departing from the scope of the disclosure, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
When introducing elements of the present disclosure or the preferred embodiments(s) thereof, the articles “a”, “an”, “the” and “said” are intended to mean that there are one or more of the elements. The terms “comprising”, “including” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.
All directional descriptors, such as top, bottom, left, right, etc., are used solely for ease of reference with respect to the drawings and are not meant as limitations.
This application is a continuation application of U.S. application Ser. No. 15/572,212 filed Nov. 7, 2017, which is a U.S. National Phase application of PCT/US2016/031274 filed May 6, 2016, which claims priority to U.S. Application No. 62/159,153 filed May 8, 2015. The disclosures of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 62159153 | May 2015 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15572212 | Nov 2017 | US |
| Child | 16411384 | US |
