Methylparafins produced using linear alpha olefins

Abstract

Provided herein is a method for generating a methyl-branched paraffin stream. The method that includes contacting a linear olefin feed stream with hydrogen in the presence of one or more bi-functional supported catalyst comprising a solid acid component and a hydrogenation component, the contacting taking place under conditions to catalytically isomerize the linear olefin feed stream into an intermediate stream comprising one or more branched olefins, wherein the linear olefin feed stream comprises an average carbon (C#) number that is between 18 and 26. Further, the method includes hydrogenating the one or more branched olefins to form an isoparaffin product comprising one or more methyl and ethyl -branched branched paraffins.

Description

METHYLPARAFINS PRODUCED USING LINEAR ALPHA OLEFINSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 602785, filed on November 27, 2023, the entire contents of which is incorporated herein by reference.FIELD

[0002] This disclosure relates to a composition of matter and processes for producing the composition of matter that is a paraffin stream with relatively low aromatic compound content. In particular, the processes may include using a feed stream having relatively large carbon- containing species (e.g., greater than Ci4, greater than Ci6, Cis+, or between Cis and C26) including linear alpha olefins (LAOs). The composition of matter and processes of this disclosure are especially useful for heat transfer applications for electronic components, such as batteries for electric vehicles.BACKGROUND

[0003] In the electric vehicle (EV) industry, numerous advances in battery’ technology have been made in recent years to promote greater power delivery and decreased charging frequency. Among the advancements needed to progress electric vehicle technology even further is the development of more effective cooling systems for promoting heat transfer from various electric vehicle components. Particular components of electric vehicles that may utilize heat transfer include, for example, one or more batteries, axles, electric vehicle power electronics, and / or an electric motor. It may be necessary to utilize improved techniques for cooling for rapid charging stations for electric vehicles. While certain components of an electric vehicle may be cooled to vary ing degrees using conventional jacketed cooling fluids and technology, such as aqueous glycol solutions also used in conjunction with internal combustion engines, effective cooling of the batteries and power components of an electric vehicle through direct cooling fluid contact represents an entirely different challenge due to the electrical conductivity7of commonly used heat transfer fluids.

[0004] All batteries generate heat as they charge or discharge. The more rapid the rate of charge or discharge becomes, the greater the amount of heat generated per unit time. For small batteries, exposure to ambient atmosphere may effectively dissipate the discharged heat, such that separate cooling systems are not required. In electric vehicles, the large battery7size and the rapid discharge rates needed to ensure satisfactory7vehicle performance make heat dissipation much more of a concern. Likewise, rapid battery charging rates at electric vehicle recharging stations may also result in significant battery heating and present similar thermal management issues.

[0005] In addition to influencing or governing vehicle performance, battery temperatures outside a preferred operating range, typically from about 15° C. to 35° C. for lithium-ion batteries, may negatively impact the battery's performance. Internal temperature gradients between the various cells of a battery may similarly impact the batten 's operational performance. In addition to poor battery or vehicle performance, operating a battery outside a preferred temperature range and / or with an internal thermal gradient may increase the risk for battery failure, runaway overheating, or other undesirable effects. Therefore, effective thermal management during battery charge or discharge and vehicle operation may become a limiting factor in how much the performance of electric vehicles may be further advanced. Other technologies in need of advanced thermal management may be similarly limited by existing heat transfer technologies.

[0006] Current strategies for cooling the batteries of electric vehicles may employ one or more of a phase change material, heat dissipation fins, or air cooling. Each of these approaches may have significant limitations, either in terms of the quantity of heat they are able to dissipate directly from the battery and / or due to their impact upon vehicle performance. Heat dissipation fins, for example, introduce excess weight that must be carried by the vehicle as it travels, thereby lowering the vehicle's efficiency and performance.

[0007] Cooling systems employing a heat transfer fluid are another heat dissipation strategy that may be employed for batteries and other heat-generating components of electric vehicles and other apparatuses or locales in need of effective thermal management. Since fluids may exhibit higher thermal conductivity and heat capacity values than does air, fluids may promote more effective heat dissipation from a battery or other heat-generating component, apparatus or locale than do other heat dissipation strategies. Moreover, a fluid may be placed in direct surface contact with a battery, power electronics, electric motor or other heat-generating component to promote optimal heat transfer, including configurations in which the heat-generating component is partially or fully immersed in the heat transfer fluid. Alternately, a suitable heat transfer fluid may be jacketed around and / or circulated through a heat-generating component, such as a battery, power electronics, or electric vehicle power component.

[0008] While immersion or partial immersion of a heat-generating component in a heat transfer fluid may afford optimal heat transfer, many heat transfer fluids presently in common use are unsuitable for immersion of batteries, power components, and / or electric motors therein due to electrical conductivity of the fluid. Aqueous heat transfer fluids, such as aqueous glycol solutions, for example, may be unsuitable for immersion of a battery, power component, or electric motor due to shorting and battery component or motor failure that may occur when the electrically conductive heat transfer fluid contacts the battery's leads or various electrical components.Fluorocarbon fluids are insulators and may meet certain performance requirements for suitable heat transfer fluids, including satisfactory pour point values and flash point values, but fumes from burning of the fluids may lead to undesirable health and environmental effects. Silicone (polysiloxane) heat transfer fluids may be similarly problematic for cooling applications in electric vehicles and other apparatuses and locales in which effective thermal management is required.

[0009] Long-chain methyl-branched paraffins having limited methyl branching are insulators and may provide satis factory heat transfer performance for applications in which aqueous glycol solutions may be unsuitable, but without the disadvantages associated with fluorocarbon, polysiloxane, and other alternative heat transfer fluids. However, efficient syntheses for long- chain methyl-branched paraffins having an acceptable combination of flash point, pour point, and kinematic viscosity have yet to be identified.

[0010] Limitations in heat transfer fluid technology are hindering further development of various fields in need of more effective thermal management, such as in electric vehicles and components therein, high-speed computers, server farms, data processing centers, cloud computing centers, cellular towers (particularly 5G). power stations, stationary battery storage locations, and others. More efficient syntheses for accessing alternative heat transfer fluids are needed to facilitate further advancement in these areas and others in which effective thermal management is needed.SUMMARY

[0011] As discussed above, developing thermal management features that both maintain desired operating temperature for electrical components (e.g., batteries) of electrical vehicle (EV) and maintain a relatively high operating efficiency is a challenging endeavor. Further, a batteiy may be destroyed or otherwise rendered inoperable in the absence of thermal management features. Certain heat transfer fluids, such as aqueous glycol solutions, may be utilized to cool the electrical components, but the heat transfer fluids may have electrical properties (e.g., electrical conductivity) that make the heat transfer fluids unsuitable for certain applications. For example, the relatively high electrical conductivity' of aqueous glycol solutions may render them unsuitable for immersion of the electrical components.

[0012] Methyl-branched paraffins having limited methyl branching, such as a single methyl group located upon a long carbon chain (e.g., 7-methylpentadecane), may have acceptable heat transfer properties for instances in which aqueous glycol solutions and other electrically conductive heat transfer fluids may not be satisfactory. Advantageously, such Methyl-branched paraffins do not present the issues accompanying presently available insulating heat transfer fluids, such as fluorocarbons and polysiloxanes. Unfortunately, specific syntheses for such long-chain methyl-branched paraffins having a single methyl branch located deep within the carbon chain are not economically or technologically feasible at present, especially at commercially viable production scales. For example, hydrogenation of a vinylidene olefin, produced through metallocene-based dimerization of a linear alpha olefin, may afford a single methyl paraffin, but technology to produce vinylidene olefins, and correspondingly the methyl-branched paraffins, are not advanced enough at present to facilitate economically feasible production at large scales. Alternative syntheses of methyl-branched paraffins through hydroisomerization of long-chain alkanes may result in a complex mixture of paraffinic products, often having a wide range of carbon chain lengths and multiple, random branching occurrences, thereby making the mixture unsuitable for many heat transfer applications. Excessive methyl branching of this type may render the methyl-branched paraffins too viscous for effective circulation in heat transfer applications. Pour points may also unacceptably increase when excessive methyl branching is present.

[0013] In anticipation to growing desire for high quality, low viscosity7polyalphaolefin (PAO) basestock in emerging heat-transfer applications, this disclosure provides an alternative process to produce a functionally equivalent product for the same applications. Functionally equivalent here is defined as meeting certain bulk physical properties such as pour point, flash point, and kinematic viscosity at 100 °C (KV100) and 40 °C (KV40).

[0014] The present disclosure relates to techniques for producing a paraffin stream (e.g., a methyl branched paraffin stream and / or methyl and ethyl-branched paraffin stream) using a feed stream containing linear alpha olefins (LAOs). The paraffin stream may include desirable combinations of physical properties, such as viscosity, pour points, flash points, or a combination thereof, that are suitable for providing efficient heat transfer with relatively low conductivity7. In general, the paraffin stream is produced using a feed stream may generally include relatively large LAOs. For example, the feed stream may be characterized by its average C#. As used herein, the ■‘average C#" is a numerical representation that indicates an average number of carbons in a molecule. The feed stream may7have an average C# between 19 and 21, 20 and 20.5, 20.05 and 20.5, 20.01 and 20.3, or 20.1 and 20.2. The feed stream reacts with hydrogen in the presence of a bi-functional catalyst containing a solid acid component and a hydrogenation component that catalyze the formation of hydrogenated products as disclosed herein.

[0015] These and other features and attributes of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description which follows.BRIEF DESCRIPTION OF THE DRAWINGS

[0016] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings, wherein:

[0017] FIG. 1 is a schematic diagram of a system for producing a paraffin stream with relatively low aromatic content, in accordance with the present disclosure;

[0018] FIG. 2 is a graph illustrating thermal conductivity versus temperature of a paraffin stream made in accordance with the system of FIG. 1, in accordance with the present disclosure; and

[0019] FIG. 3 is a graph illustrating specific heat capacity7versus temperature of a paraffin stream made in accordance with the system of FIG. 1. in accordance with the present disclosure.DETAILED DESCRIPTION

[0020] One or more specific embodiments of the present disclosure will be described below. In an effort to provide a concise description of these embodiments, all features of an actual implementation may not be described in the specification. It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers’ specific goals, such as compliance with system-related and business-related constraints, which may vary7from one implementation to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.

[0021] When introducing elements of various embodiments of the present disclosure, 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 numerical values within the detailed description herein are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0022] Reference is now made to the embodiments illustrated in FIGS. 1-3 wherein like numerals are used to designate like parts throughout.

[0023] FIG. 1 illustrates a schematic diagram of a system 10 for producing the paraffin stream with a relatively low aromatic carbon content in accordance with the present disclosure. As shown, the system 10 includes a reactor 12 and a separation unit 14. In general, the system 10 of FIG. 1 receives a feed stream 16 (e.g.. LAO feed stock) that includes an LAO feed and hydrogen 17, and the system 10 produces an output paraffin stream 18. As described herein, the paraffin stream 18 may include advantageous properties, or combinations of properties, such as viscosities (e.g., kinematic viscosities), pour point, flash point, among other physical properties, that provide suitable heat transfer.

[0024] In particular, the paraffin stream may have a relatively high degree of isomerization. As referred to herein, a “degree of isomerization'’ is generally a measure or value indicative of an amount of isomers present in a polymer product, such. In general, each isomer may include branched alkyl groups, such as pendant alky ls. The degree of isomerization may be indicated by a pendant alkyl (e.g., methyl) content and a maximum, a wt% of linear hydrocarbon content, or a combination thereof. In some embodiments, the relatively high degree of isomerization may include a relatively high methyl branching content (MBC). As referred to herein, the “methyl branching content” (mol%) refers to amount of methyl groups off an alkyl chain. In some embodiments, methyl branching content is calculated by Carbon-13 NMR (13C NMR) based on the peak integral from the ppm range correspond to methyl-carbons, such as (the peak integral from 19.2 to 20.8 ppm) / (total carbon integration). The wt% or mol% of linear hydrocarbon content may be calculated using a determined wt% of linear hydrocarbons (e.g., paraffin + olefin) in a sample using gas chromatography, or other suitable techniques as understood by one of ordinary7skill in the art.

[0025] In some embodiments, the methyl branching content of the paraffin stream 18 is greater than or equal to 5 mol% methyl branching based on total C (e.g., mol% of total C) (total carbon integration based on NMR), greater than or equal to 6 mol% methyl branching, greater than or equal to 8 mol% methyl branching, greater than or equal to 9 mol% methyl branching, greater than or equal to 9. 1 mol% methyl branching, greater than or equal to 9.2 mol% methy l branching, or greater than or equal to 9.3 mol% methyl branching. For example, the methyl branching may be about 8.0 mol%, 8.5 mol%, 9.0 mol%, 9. 1 mol%, 9.2 mol%, and so on. In some embodiments, the paraffin stream 18 may have between 5 mol% methyl branching to 10 mol% methyl branching.

[0026] Referring to the reactor 12 of FIG. 1, the reactor 12 may be loaded with a dewaxing catalyst containing both acidic zeolite and metal hydrogenation functionalities to yield an isoparaffin product. More specifically, the reactor 12 may include a solid acid component that promotes formation of branched olefins having a range of methyl group and double bond positions. In some embodiments, the reactor 12 may be a single fixed bed reactor. The reactor 12 may also include a hydrogenation component that hydrogenates the branched olefins produced based on the solid acid component. The hydrogenation component may include one or more metals, such as Pt, Pd, or a combination thereof. In some instances, the hydrogenation component may include a promoter metal, such as Ru, Re, Mn, Zr, Ir, Au, Ag, Ce, Ba or a combination thereof. In some embodiments, the hydrogenation component may include a combination of Pt and / or Pd with one or more of Ru. Re. Mn, Zr, Ir, Au. Ag, Ce, or Ba.

[0027] Suitable solid acid components may include zeolites, particularly those containing 10- or 12-membered rings in the zeolite structural framework. For example, the solid acid component(s) of the reactor 12 may include MRE-type zeolites. Particularly suitable zeolites may include ZSM-48 and ZSM-23, ZSM-12 and ZSM-22, as well as several others. Other suitable zeolite solid acid components may include, for example, ZSM-5, ZSM-11, ZSM-35 (or ferrierite), zeolite Beta, TON (Theta-1), or a combination thereof, for example ZSM-23 and / or ZSM-48, optionally in further combination with one or more of the foregoing zeolites. Other examples of solid acid components that may be suitable for use in the disclosure herein include, for example, EU-1, - ZSM-57, NU-87, SAPO-11, EU-2, EL-11, ZBM-30 and isostructural materials such as NU-10, EU-13, KZ-1, and NU-23. These solid acid components may similarly be used in combination with ZSM-48, ZSM-23. ZSM-22, ZSM-12 or other zeolite materials. In some embodiments, the guard bed unit 26 may include AZ-300 absorbent.

[0028] The reactor 12 may also include solid support components and / or binders that are generally inert toward promoting isomerization and / or reducing cracking and may include substances such as. for example, alumina, titania, silica, silica-alumina, zirconia, or a combination thereof, for example alumina and / or titania or silica and / or zirconia and / or titania. A loading of the hydrogenation component relative to the solid acid component in the bi-functional catalyst may range from about 0.01 wt% to about 10 wt%, or about 0.05 wt% to about 5 wt%, or about 0. 1 wt% to about 2 wt%. or about 0.1 wt. % to about 1 wt%.

[0029] In general operation, the reactor 12 receives the feed stream 16 that includes relatively heavy LAOs and, in some instances, the reactor receives hydrogen 17 (e.g., a hydrogen stream, a hydrogen co-feed stream). For example, the feed stream 16 may include Ci6 carbons or greater, Cis carbons or greater, C20 carbons or greater, C22 carbons or greater, or C24 carbons or greater. In some instances, the average C number, C#, may be between 16-26, 18-26. 20-24, and so on. In some embodiments, the average C# number is about 18, about 19, about 20, about 21, or about 22. For example, the average C number may be between 19 and 21, 20 and 20.5, 20.05 and 20.5, 20.01 and 20.3, or 20. 1 and 20.2.

[0030] To have such a C# number, the feed stream 16 may include varying populations of the relatively heavy LAOs. For example, the feed stream 16 may include one or more of Ci6. Ci8, C20, C22, C24, C26. In some embodiments, the feed stream 16 may include about 0 to 50 weight percent (wt%) % Cis, and about 0 to 50 wt% C20, C22, C24, or a combination thereof. In some embodiments, the feed stream 16 may include about 30 to 40 wt% of Cis carbons and about 70 to 60 wt% by weight of C20 carbons, C22, C24, or a combination thereof. In some embodiments, the feed stream 16 may include about 37 to 40 wt%, of Cis, about 26 to 29 wt% of C20, about 21 to22 wt% of C22, and about 11 to 14 wt% of C24. In some embodiments, the feed stream 16 may be a direct cut from a plant that produces LAO.

[0031] Several non-limiting examples of the composition of the feed stream 16 are described below. However, it should be noted that the specific examples below are meant to be non-limiting. In general, the compositions descried below describe the carbon content of the feed stream 16 (i.e., not including the hydrogen 17 that may be present as a co-feed).

[0032] As one specific non-limiting example, the feed stream 16 may include about 40 wt% of Cis, 20 wt% of C20, 20 wt% of C22, and 20 wt% of C24 (e.g., average C# number is about 20.4). While this specific non-limiting example includes substantially equal percentages of each of the C20, C22, and C24 carbons, it should be noted that in some embodiments, one or more of the percentages of C20. C22, and C24 carbons may be different. For example, the feed stream 16 may include about 30 wt% of Cis, 25 wt% of C20, 20 wt% of C22, and 25 wt% of C24 (e.g., average C# number is about 20.8). As one additionally specific non-limiting example, the feed stream 16 may include about 39 wt% of Cis, 26 wt% of C20, 21 wt% of C22, and 14 wt% of C24 (e.g., average C# number is about 20.2). As one specific non-limiting example, the carbon content of the feed stream 16 may include about 10 wt% of C16, 20 wt% Cis, 30 wt% C20, and 40 wt% C22 (i.e., average C# number of 20). As a further specific non-limiting example, the feed stream 16 may about 38 wt% of Cis, 29 wt% of C20, 22 wt% of C22, and 11 wt% of C24.

[0033] Although the examples described above include each of Cis, C20, C22, and C24, it should be noted that at least some examples of the feed stream 16 may include only two or more of the relatively large carbons. For example, in some embodiments, the feed stream 1 may include Cis and C22 (e.g., not include C20). As another specific non-limiting example, the carbon content of the feed stream 16 may include about 50 wt% of Ci6, 30 wt% of C20, and 20 wt% of C24 (i.e., average C# number of 18.8). As another specific non-limiting example, the carbon content of the feed stream 16 may include about 20 wt% of Ci6, 30 wt% of Cis, and 50 wt% of C24 (i.e., average C# number of 20.6). As another specific non-limiting example, the carbon content of the feed stream 16 may include about 80 wt% of Ci6, 10 wt% of C22, and 10 wt% of C24 (i.e., average C# number of 17.4).

[0034] The hydrogen 17 may be present at a flow rate sufficient to promote hydrogenation of the initially isomerized reaction product. In particular instances, the flow rate may be such that hydrogen is present in a molar amount of about 2:1 to about 7: 1 with respect to the linear olefins undergoing isomerization. For example, the hydrogen 17 may include between 2-5 molar equivalent of H2. between 2-4 molar equivalent of H2. or between 2-3 molar equivalent of H2. Asdescribed herein, the hydrogen 17 may be mixed with the feed stream 16 (e.g., “LAO stream 16 & hydrogen 17) or provided as a separate stream (e.g., “LAO stream 16 + hydrogen 17).

[0035] In any case, to facilitate isomerization of the linear olefins in the feed stream 16, the reactor 12 may be heated to a suitable temperature. For example, the reactor 12 may be heated to and / or maintained (e.g., during the isomerization reaction) at a temperature that is about 200 °C to about 300 °C, or about 200 °C to about 220 °C. or about 220 °C to about 240 °C, or about 240 °C to about 260 °C, or about 260 °C to about 280 °C. or about 280° C to about 300 °C. In some embodiments, the reactor 12 may be maintained (e g., during the isomerization reaction) from about 50 psig to about 200 psig.

[0036] The illustrated embodiment of the system 10 shows a guard bed 26. In general, the guard bed 26 may remove one or more components that may reduce the lifetime of the catalysts and are undesirable to include in the reaction to produce the crude paraffin product 22. For example, the guard bed 26 may be capable of removing trace impurities such as water, oxygen-, nitrogen- or sulfur containing species. However, at least in some instances, the guard bed 26 may be omitted.

[0037] In any case, the separation unit 14 receives the crude paraffin product 22 and separates the crude paraffin product 22 into the light product 24 and the paraffin stream 18 (e.g.. paraffin stream 18). In general, the separation unit 14 may generally include suitable components to separate the components of the crude paraffin product 22. For example, the separation unit 14 may include one or more of strippers, separation columns, distillation columns, fractionators, and the like. In general, it should be noted that the data are from a fractionation of crude paraffin product 22, the BP range for a fraction 18 is from about 500 °F to about 720 °F (e.g., about 260 °C - 382 °C). As shown, the separation unit 14 may also separate a third product, a heavy product 28, from the crude paraffin product 22.

[0038] In some embodiments, the separation unit 14 may include a stripping unit. In some embodiments, the stripping unit may be a heated nitrogen stripper. As referred to herein, a “heated nitrogen stripper” is a device that uses a heated nitrogen flow (e.g., at temperatures greater than 100 °C, greater than 200 °C, greater than 300 °C). The stripping unit may operate at a particular pressure, nitrogen gas flow rate, temperature, or combination thereof. For example, the stripping unit may be operated between 30-50 psig. or 35-45 psig, such as about 30 psig, about 40 psig. or about 50 psig. The stripping unit 14 may be operated at a temperature between 120-150 °C, between 125-145 °C, or between 130 to 140 °C, such as about 130 °C, 135 °C, or 140 °C. In any case, the crude light product passing through the stripping unit may be distilled to obtain a desired product cut with greater than 95%. greater than 96%. greater than 97%, greater than 98%, orgreater than 99% of its components having a boiling point range between about 280 to 380 °C, 290 to 370 °C, or 300 to 360 °C.

[0039] A few specific, non-limiting examples of reaction conditions for operating the system 10 are described in detail below. Table 1 shows a first set of example reaction conditions for producing the disclosed paraffin stream (e.g., the paraffin stream 18) using the system 10. In general, the reaction conditions in Table 1 include a reaction temperature from about 275°C to 285°C and a reaction pressure from about 75 psig to about 175 psig. However, it should be noted that the reaction temperatures and reaction pressures shown in Table 1 are meant to be nonlimiting. For example, the reaction temperature may be a temperature from 260 to 300°C, from 265 to 295°C, from 270 to 290°C, or from 275 to 285°C. Additionally, the reaction pressure may be a pressure from 75 psig to 200 psig, from 75 psig to 150 psig, or from 100 psig to 125 psig. It should be noted that the data are from a fractionation of stream 18 products, the BP range for a fraction from about 500 °F to about 720 °F (e.g., about 260 to 382 °C)

[0040] Kinematic viscosity' at 40 °C (KV40) and Kinematic viscosity at 100 °C (KV100) were determined in accordance with ASTM D445. Unless otherwise noted, pour points (PP) were determined in accordance with ASTM D5950. Flash Points were determined in accordance with ASTM D92.

[0041] Table 1 also includes a pour point between about -70 to -40 °C. For example, the pour point may be between about -65 and -45 °C, -60 and -50 °C, about -55 °C, about -56 °C, about - 57 °C, about -58 °C, about -59 °C, and so on. In some embodiments, the pour point of the paraffin stream 18 is pour point -35 °C or lower, preferably -40 °C or lower, preferably -50 °C or lower.Table 1 shows a first set of example reaction conditions for producing the disclosed paraffin stream.

[0042] In any case, the reaction occurring at the reactor 12 may include from about 2 to about 3 molar equivalents (mol eq.) of H2. By reacting the feed stream 16 under such conditions as shown in Table 1, the paraffin stream 18 (e.g., refined paraffin stream 18) may have a kinematic viscosity at 40°C (KV40) value that is about 5 centistoke (cSt) and a kinematic viscosity at 100°C (KV100) value that is from about 1.6 cSt to about 1.8 cSt. For example, the KV100 value may be about 1.70 cSt, 1.71 cSt, 1.72 cSt, 1.73 cSt, 1.74 cSt, and so on.

[0043] It is noted that aromatization may be part of the catalytic reactivity. Further, the aromatic content in the product may be also associated with high temperature and low pressure, same conditions that favors desired pour point. Accordingly, it may be desirable to tune the reaction conditions such that aromatic content is relatively low while still maintaining on-target pour point of the final product. For example, it may be desirable to have an aromatic content that is 30 mmol / kg or less, 10 mmol / kg or less, 9 mmol / kg or less, 8 mmol / kg or less, 7 mmol / kg or less, 6 mmol / kg or less, 5 mmol / kg or less, or 4 mmol / kg or less, 3 mmol / kg or less. Accordingly, in this case, examples 3 and 4 may be desirable for certain embodiments where a relatively low aromatic content is desired.

[0044] Table 2 shows a second set of example reaction conditions for producing the crude paraffin product 22. In general, the reaction conditions in Table 2 include a reaction temperature from about 265 to 290 °C and a reaction pressure from about 50 psig to about 120 psig. However, it should be noted that the reaction temperatures and reaction pressures shown in Table 2 are meant to be non-limiting. For example, the reaction temperature may be a temperature from about 200 to 350 °C, 260 to 300°C, from 265 to 295 °C, from 270 to 290 °C, or from 275 to 285 °C. In some embodiments, the reaction temperature may be about 265 °C. about 270 °C, 275 °C, 280 °C. 285 °C. Additionally, the reaction pressure may be a pressure from 50 psig to 150 psig, from 60 psig to 140 psig, or from 70 psig to 130 psig. Further, the reaction occurring at the reactor 12 may include from about 1 to about 4 molar equivalents (mol eq.) of H2. For example, the reaction may use 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.8, 2.9, and so on molar equivalents of H2. By reacting the feed stream 16 under such conditions as shown in Table 2, the paraffin stream 18 may have a KV40 value that is from about 5 cSt to about 7 cSt. Further, the paraffin stream 18 may have a KV100 value that is about 2. 1 cSt. For example, the KV100 value may be about 1.8 cSt, 1.9 cSt, 2.0 cSt,2.1 cSt, 2.2 cSt, or 2.3 cSt. In Table 2, the pour points are between about -60 to 0 °C. For example, the pour point may be about -50 °C, about -40 °C, about -30 °C. and so on.Table 2 shows example reaction conditions for producing the disclosed paraffin stream.

[0045] Further, Table 2 shows example wt% of linear hydrocarbons (e.g.. linear content) and mol% of methyl pedant group (MPG) for the crude paraffin product 22. As shown, the wt% of linear hydrocarbons is less than or equal to 5 wt%, less than or equal to 4 wt%, less than or equal to 3 wt%, or less than or equal to 2 wt%. As shown, the MPG is greater than or equal to 5 mol% (e.g., mol% of total C), greater than or equal to 6 mol%, greater than or equal to 8 mol%, greater than or equal to 9 mol%. It is presently recognized that it may be preferred or desired to produce a crude paraffin product 22 (e.g., a methylparaffin product) include methyl-branched paraffins having an MPG that is greater than or equal to 6 mol%, preferably greater than or equal to 8 mol%, preferably greater than or equal to 9 mol%. In some embodiments, the crude paraffin product 22 may include ethyl-branched paraffins. In some embodiments, the crude paraffin product 22 may include a minimum pendant methyl content that is greater than 1 , 2, 3, 4, 5, 6, 7, or 8 mol% on total carbon basis and the maximum linear hydrocarbon content may be less than 1, 2, 3, 4, 5, 6, 7, or 8 wt%.

[0046] It is noted that using LAO feed stream with C20 to C24 carbons (melting point ~ 35 °C) feed stream targeted on optimization process condition, to control the pour point of the product. It is presently recognized that the pour point of the product can be controlled by both reactor temperature and pressure. It is also presently recognized that the pour point of the product may respond to changes in these two conditions. Further still, significant reduction in pour point may also be obtained using combinations of 1) increasing reaction temperature and 2) reducing pressure. The reduction of pour point was unexpected, considering the relatively high melting point of the starting feed stream, achieving -56 °C PP in product corresponds to a > 91 °C reduction of pour point. The examples 5-11 in Table 2 illustrate a > 50 °C PP differential over a change in 25 °C and 40 psi in reaction condition. It was further unexpectedly realized that the viscosity of the product may be insensitive to changes in reaction conditions.

[0047] Thermal conductivity was measured according to ASTM D7896. Specific Heat Capacity was determined according to ASTM El 269.

[0048] FIG. 2 is a graph illustrating thermal conductivity' (y-axis) versus temperature (x-axis) of a paraffin stream (refined stream from 18) made in accordance with the system of FIG. 1. In particular, the graph shows thermal conductivity' versus temperature for a first trace 40 corresponding to the (refined stream from 18), a second trace 42 that corresponds to poly-alpha olefin (PAO) product, and a third trace 44 that corresponds to a reference heat transfer fluid. As shown in FIG. 2, the (refined stream from 18) performs as well as the PAO product, which demonstrates the effectiveness of the paraffin stream 18. Performance of the paraffin (refined stream from 30) is also shown in FIG. 3. For example, FIG. 3 is a graph illustrating specific heat capacity versus temperature of a (refined stream from 18) made in accordance with the system of FIG. 1. In particular, the graph show s thermal conductivity versus temperature for a first trace 50 corresponding to the (refined stream from 18), and a second trace 52 that corresponds to polyalpha olefin (PAO) product. As shown in FIGS. 2 and 3, the paraffin stream 18 performs as well as the PAO product, which demonstrates the effectiveness of the paraffin stream 18. However, as compared to the poly-alpha olefin (PAO) product corresponding to the second trace 42, the (refined stream from 18) is produced using an alternative feedstock, namely the feed stream 16 as described w ith respect to FIG. 1.

[0049] In any case, the (refined stream from 18) may be utilized as a heat transfer fluid for certain heat-generating components. For example, the (refined stream from 30) may be utilized to transfer heat from heat-generating components of electric vehicles and other apparatuses or locales in need of effective thermal management via direct contact (e.g., direct thermal contact). The heat-generating components may include one or more batteries, power electronics, or electric vehicle power components. In some embodiments, the heat-generating components may include components utilized in data center cooling. As described above, the disclosed methyl-branched paraffins may be used in direct cooling applications (e.g., direct cooling fluid contact) due to the relatively low' electrical conductivity of the methyl-branched paraffins. In any case, the (refined stream from 18) may be utilized in systems that include heat-generating components.

[0050] Accordingly, the present disclosure is directed to techniques for producing a methylparaffin stream using LAO streams that include carbons of varying lengths. For example, the LAO streams may include Ci6 carbons, Cis carbons, C20 carbons, C22 carbons, C24 carbons, or larger carbons, or a combination thereof. In general, the LAO streams may be characterized by a C# number that is about 19-21. It is presently recognized that such a LAO stream may produce amethyl -branched paraffin stream having certain physical properties, such as KV100, KV40, pour point, and flash point that are useful for heat transfer applications.

[0051] This written description uses embodiments / examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other embodiments / examples that occur to those skilled in the art. Such other embodiments / examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims. Many alterations, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description without departing from the spirit or scope of the present disclosure and that when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

[0052] Embodiment 1. A method comprising contacting a linear olefin feed stream with hydrogen in the presence of one or more bi-functional catalyst comprising a solid acid component and a hydrogenation component, the contacting taking place under conditions to catalytically isomerize the linear olefin feed stream into an intermediate stream comprising one or more branched olefins, and wherein the linear olefin feed stream comprises an average carbon (C#) number that is between 18 and 26; and hydrogenating the one or more branched olefins to form an isoparaffin product comprising one or more methyl and ethyl-branched paraffins.

[0053] Embodiment 2. A method according to Embodiment 1, wherein the minimum pendant methyl content is greater than 5 mol% on total carbon basis and the maximum linear hydrocarbon content is less than 5 wt%.

[0054] Embodiment 3. A method according to any of Embodiments 1 or 2, wherein the one or more methyl and ethyl-branched paraffins have a pour point less than 0°C.

[0055] Embodiment 4. A method according to any of Embodiments 1-3, wherein the linear olefin feed stream comprises between about 30% by weight to about 50% by weight of Cis hydrocarbons.

[0056] Embodiment 5. A method according to any of Embodiments 1-4, wherein the linear olefin comprises about 0 to 50 weight (wt%) of Cis hydrocarbons and between about 0 to 50 wt% of C20, C22, C24 hydrocarbons, or a combination thereof

[0057] Embodiment 6. A method according to any of Embodiments 1-5, wherein the linear olefin comprises about 30 to 40 wt% of Cis hydrocarbons and about 70 to 60 wt% by weight of C20, C22, C24 hydrocarbons, or a combination thereof.

[0058] Embodiment 7. A method according to any of Embodiments 1-6, wherein the linear olefin comprises about 37 to 40 wt%, of Cis hydrocarbons, about 26 to 29 wt% of C20 hydrocarbons, about 21 to 22 wt% of C22 hydrocarbons, and about 11 to 14 wt% of C24 hydrocarbons.

[0059] Embodiment 8. A method according to any of Embodiments 1-7, wherein the linear olefin comprises about 38 wt% of Cis hydrocarbons, 29 wt% of C20 hydrocarbons, 22 wt% of C22 hydrocarbons, and 11 wt% of C24 hydrocarbons.

[0060] Embodiment 9. A method according to any of Embodiments 1-8. wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 100°C between 1 to 2.5 cSt.

[0061] Embodiment 10. A method according to any of Embodiments 1 -9, wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 40 °C between 3.5 to 7.0 cSt.

[0062] Embodiment 11. A method according to any of Embodiments 1-10, wherein the one or more bi-functional catalysts comprise zeolites having 10- or 12-membered rings.

[0063] Embodiment 12. A method according to any of Embodiments 1-11, wherein the one or more bi-functional catalyst comprises acidic zeolite and metal hydrogenation functionality.

[0064] Embodiment 13. A method according to any of Embodiments 1-12, i) wherein the hydrogenation metal comprises Pt, Pd, or a combination thereof; ii) wherein the promoter metal comprises Ru, Re, Mn, Zr, Ir, Au, Ag, Ce, Ba or a combination thereof; or iii) a combination of i) and ii).

[0065] Embodiment 14. A method according to any of Embodiments 1-13, wherein the one or more bi-functional catalyst further comprises 0. 1 wt% to 5.0 wt% of a hydrogenation metal.

[0066] Embodiment 15. A method according to any of Embodiments 1-14, wherein the one or more methyl and ethyl-branched paraffins have a flash point greater than 100°C.

[0067] Embodiment 16. A method according to any of Embodiments 1-15, wherein a reaction temperature for forming the isoparaffin product is between 200°C to 350°C.

[0068] Embodiment 17. A composition, comprising one or more methyl and ethyl-branched paraffins having pendant methyl groups greater than or equal to 5 mol% on total carbon basis, and at least a pour point less than 0°C. and a flash point greater than 100°C, wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 100°C between 1 to 2.5 cSt,wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 40 °C between 3.5 to 7.0 cSt.

[0069] Embodiment 18. A composition according to Embodiment 17, wherein the minimum pendant methyl content of the one or more methyl and ethyl-branched paraffins is greater than 5 mol% on total carbon basis and the maximum linear hydrocarbon content is less than 5 wt%.

[0070] Embodiment 19. A composition according to any of Embodiments 17 or 18, wherein the one or more methyl-branched paraffins have a pour point less than -40°C.

[0071] Embodiment 20. A composition according to any of Embodiments 17-19, wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 100°C between 1.6 to 1.8 cSt.

[0072] Embodiment 21. A composition according to any of Embodiments 17-20. wherein the one or more methyl and ethyl-branched paraffins have a flash point greater than 150°C.

[0073] Embodiment 22. A system, comprising: a heat transfer fluid comprising one or more methyl and ethyl-branched paraffins, wherein the amount of methyl branching of one or more methyl and ethyl-branched paraffins is greater than or equal to 10 mol%, wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 100 °C between 1 to 2.5 cSt; a pour point of at least less than 0 °C, and flash point of 100 °C or higher, or 150 °C or higher, and wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity7at 40 °C between 3.5 to 7.0 cSt.

[0074] Embodiment 23. A system according to Embodiment 22, comprising a battery, wherein the heat transfer fluid is in direct contact with battery.

[0075] Embodiment 24. A system according to any of Embodiments 22 or 23, comprising one or more electronic components in direct thermal contact with the heat transfer fluid.

[0076] Embodiment 25. A system according to any of Embodiments 22-24, comprising a heatgenerating component, wherein the heat transfer fluid is circulated through the heat-generating component.

[0077] Embodiment 26. A system according to any of Embodiments 22-25, wherein the one or more methyl-branched paraffins have a pour point -35 °C or lower, -40 °C or lower, -50 °C or lower.

[0078] Embodiment 27. A system according to any of Embodiments 22-26, wherein the one or more methyl-branched paraffins have a kinematic viscosity7at 100°C between 1.6 to 1.8 cSt.

Claims

CLAIMS:1 . A method comprising: contacting a linear olefin feed stream with hydrogen in the presence of one or more bifunctional catalyst comprising a solid acid component and a hydrogenation component, the contacting taking place under conditions to catalytically isomerize the linear olefin feed stream into an intermediate stream comprising one or more branched olefins, and wherein the linear olefin feed stream comprises an average carbon (C#) number that is between 18 and 26; and hydrogenating the one or more branched olefins to form an isoparaffin product comprising one or more methyl and ethyl-branched paraffins.

2. The method of claim 1, wherein the minimum pendant methyl content is greater than 5 mol% on total carbon basis and the maximum linear hydrocarbon content is less than 5 wt%.

3. The method of claim 1. wherein the one or more methyl and ethyl-branched paraffins have a pour point less than 0 °C.

4. The method of claim 1, wherein the linear olefin feed stream comprises between about 30% by weight to about 50% by weight of Cis hydrocarbons.

5. The method of claim 1 , wherein the linear olefin comprises about 0 to 50 weight (wt%) of Cis hydrocarbons and between about 0 to 50 wt% of C20, C22, C24 hydrocarbons, or a combination thereof.

6. The method of claim 1, wherein the linear olefin comprises about 30 to 40 wt% of Cis hydrocarbons and about 70 to 60 wt% by weight of C20, C22, C24 hydrocarbons, or a combination thereof.

7. The method of claim 1, wherein the linear olefin comprises about 37 to 40 wt%, of Cis hydrocarbons, about 26 to 29 wt% of C20 hydrocarbons, about 21 to 22 wt% of C22 hydrocarbons, and about 11 to 14 wt% of C24 hydrocarbons.

8. The method of claim 1, wherein the linear olefin comprises about 38 wt% of Cis hydrocarbons, 29 wt% of C20 hydrocarbons, 22 wt% of C22 hydrocarbons, and 11 wt% of C24 hydrocarbons.

9. The method of claim 1 , wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 100°C between 1 to 2.5 cSt.

10. The method of claim 1 , wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 40 °C between 3.5 to 7.0 cSt.

11. The method of claim 1, wherein the one or more bi-functional catalysts comprise zeolites having 10- or 12-membered rings.

12. The method of claim 1, wherein the one or more bi-functional catalyst comprises acidic zeolite and metal hydrogenation functionality.

13. The method of claim 1 , i) wherein the hydrogenation metal comprises Pt, Pd, or a combination thereof; ii) wherein the promoter metal comprises Ru, Re, Mn, Zr, Ir, Au, Ag, Ce, Ba or a combination thereof; or iii) a combination of i) and ii).

14. The method of claim 1 , wherein the one or more bi-functional catalyst further comprises 0.1 wt% to 5.0 wt% of a hydrogenation metal.

15. The method of claim 1. wherein the one or more methyl and ethyl-branched paraffins have a flash point greater than 100°C.

16. The method of claim 1 , wherein a reaction temperature for forming the isoparaffin product is between 200°C to 350°C.

17. A composition, comprising: one or more methyl and ethyl-branched paraffins having pendant methyl groups greater than or equal to 5 mol% on total carbon basis, and at least a pour point less than 0°C, and a flash point greater than 100°C, wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity' at 100°C between 1 to 2.5 cSt, wherein theone or more methyl and ethyl-branched paraffins have a kinematic viscosity at 40 °C between 3.5 to 7.0 cSt.

18. The composition of claim 17, wherein the minimum pendant methyl content of the one or more methyl and ethyl-branched paraffins is greater than 5 mol% on total carbon basis and the maximum linear hydrocarbon content is less than 5 wt%.

19. The composition of claim 17, wherein the one or more methyl-branched paraffins have a pour point less than -40°C.

20. The composition of claim 17. wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 100°C between 1.6 to 1.8 cSt.

21. The composition of claim 15 , wherein the one or more methyl and ethyl-branched paraffins have a flash point greater than 150°C.

22. A system, comprising: a heat transfer fluid comprising one or more methyl and ethyl-branched paraffins, wherein the amount of methyl branching of one or more methyl and ethyl-branched paraffins is greater than or equal to 10 mol%. wherein the one or more methyl and ethyl-branched paraffins have a kinematic viscosity at 100 °C between 1 to 2.5 cSt; a pour point of at least less than 0 °C, and flash point of 100 °C or higher, or 150 °C or higher, and wherein the one or more methyl and ethyl- branched paraffins have a kinematic viscosity at 40 °C between 3.5 to 7.0 cSt.

23. The system of claim 22, comprising a battery, wherein the heat transfer fluid is in direct contact with battery.

24. The system of claim 22, comprising one or more electronic components in direct thermal contact with the heat transfer fluid.

25. The system of claim 22, comprising a heat-generating component, wherein the heat transfer fluid is circulated through the heat-generating component.

26. The system of claim 22, wherein the one or more methyl-branched paraffins have a pour point -35 °C or lower, -40 °C or lower, -50 °C or lower.

27. The system of claim 22, wherein the one or more methyl-branched paraffins have a kinematic viscosity at 100°C between 1.6 to 1.8 cSt.

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