Isoparaffin Kerosene Composition

Abstract

Jet boiling range compositions comprising at least a portion of an isoparaffin blend component are provided along with methods for making such blend components. The highly isoparaffinic nature of the blend components may allow the isoparaffinic blend components to be used in combination with both conventional / mineral jet fuel boiling range fractions as well as non-traditional feeds (such as Fischer-Tropsch fractions) to form jet fuel fractions and / or jet fuel blend component fractions.

Description

[Technical field]

[0001] The present disclosure relates to kerosene or jet boiling range compositions having high isoparaffin content, and methods for forming fuel compositions or fuel blend compositions made from such kerosene or jet boiling range compositions. [Background technology]

[0002] The aviation industry is seeking increasingly sustainable sources of jet fuel to lower the carbon intensity of fuel consumed during flight. The aviation industry today contributes 2-3% of global CO2 emissions, which is expected to increase with the projected growth of the aviation sector over the next 30 years. There are many sustainable aviation fuel pathways approved for use in commercial aviation. The feedstocks used in these pathways include vegetable / animal fats, waste materials (e.g., municipal solid waste and forestry waste), and bio-derived alcohols such as ethanol and / or isobutanol. However, there is a growing realization that commercial aviation will require large amounts of fuels of non-biological origin to meet further demand.

[0003] Current Fischer-Tropsch (FT) technology allows for the production of jet fuel from syngas that can be derived from captured CO2 and H2, but FT technology is costly and the products from the FT reaction require additional cracking and hydroisomerization to make suitable aviation fuel. The required cracking reduces the yield of jet fuel from FT. Therefore, new high-yield technologies for converting CO2 and H2 to aviation fuel are needed to improve the availability of low carbon intensity fuels for the aviation sector.

[0004] U.S. Patent No. 7,692,049 describes a process for oligomerizing olefins (including C3-C8 olefins) to produce olefins and alkanes, including a high percentage of branched olefins and alkanes. 20Compositions resulting from this process containing hydrocarbons are described. A 25 wt% blend of one of the compositions with conventional jet fuel is also described. Sources of C3-C8 olefins include conversion of methanol to olefins and formation of olefins via steam cracking.

[0005] US Pat. Nos. 8,318,994 and 7,667,086 also describe processes for oligomerizing olefins and corresponding compositions containing branched olefins and alkanes formed via the oligomerization process.

[0006] A technical paper in the SAE Technical Paper Series (892073) by Gulder et al. 1 This paper describes a methodology for performing H NMR and analyzing the resulting spectra to determine the amount of hydrogen attached to carbon atoms at various positions within a hydrocarbon-like sample. The paper is titled "A Rapid Cetane Number Prediction Method for Petroleum Liquids and Pure Hydrocarbons Using Proton NMR." Summary of the Invention

[0007] In various aspects, blended jet boiling range compositions are provided. The compositions can include an isoparaffin blend component and one or more additional components, such as a mineral jet boiling range fraction and / or a synthetic jet boiling range fraction. The isoparaffin blend component can include at least 80 wt.% isoparaffins, at most 5.0 wt.% olefins, and at most 5.0 wt.% C 19+ In some embodiments, the resulting composition may include a T10 distillation point of 205° C. or less and / or a final boiling point of 300° C. or less.

[0008] In some embodiments, the composition comprises 1.0 wt.% or more, or 1.5 wt.% or more, or 2.0 wt.% or more of C. 17 -C 18In some embodiments, the composition may comprise 10 wt.% or more C9 hydrocarbons. In some embodiments, the composition may comprise a flash point of 50° C. or more and / or a freezing point of −40° C. or less. In some embodiments, the isoparaffin blend component and / or composition may comprise an atypical distribution type of hydrogen in the hydrocarbons of the isoparaffin blend component and / or composition. [Brief description of the drawings]

[0009] [Figure 1] 1 shows compositional information for blends of isoparaffin blend components with conventional jet fuel. [Diagram 2] 1 shows compositional information for blends of different isoparaffin blend components with conventional jet fuel. [Diagram 3] 1 shows results from 1H NMR characterization of iso-olefin and isoparaffin blend components. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In various aspects, kerosene boiling range and / or jet boiling range compositions comprising at least a portion of an isoparaffin blending component are provided along with methods for making such blending components. The highly isoparaffinic nature of the blending components may allow the isoparaffin blending components to be used in combination with both conventional / mineral jet fuel boiling range fractions as well as non-traditional feeds (such as Fischer-Tropsch fractions) to form jet fuel fractions and / or jet fuel blending component fractions. Optionally, a portion of the isoparaffin blending product may correspond to iso-olefins rather than isoparaffins. Optionally, iso-olefin blending components may be formed in place of or in addition to the isoparaffin blending components.

[0011] One of the obstacles to reducing the use of aviation fuel derived from mineral fractions is simply the lack of available supply. One option to overcome this obstacle is to synthesize kerosene / jet boiling range compounds from feedstocks other than mineral fractions. Synthesis of kerosene / jet boiling range components by oligomerization of olefins can provide such a route. For example, the olefins used for oligomerization can be formed by conversion of methanol to olefins. In this option, the problem of producing non-mineral jet boiling range compounds is transformed into the problem of producing non-mineral methanol for subsequent conversion. (More generally, olefins for oligomerization can be obtained from any convenient source of olefins, such as olefins formed by pyrolysis, including pyrolysis of bio-derived feeds.) Forming jet fuel or jet fuel blend components from bio-derived feedstocks containing jet boiling range compounds (or higher boiling range compounds converted to jet boiling range) is another example of a route to "synthesize" jet boiling range compounds.

[0012] With regard to forming jet fuel or jet fuel blend components by synthesis of jet boiling range compounds from a methanol feedstock, various options for producing such methanol are available. One option can be to use bio-derived methanol. Another option can be to synthesize methanol from CO2 and H2. For example, the CO2 can correspond to CO2 sequestered from air or another process, while the H2 can correspond to H2 formed in a renewable manner, such as solar-powered water electrolysis. Because methanol is an easily synthesized feedstock, the source of methanol (and therefore the source of the resulting olefins) can be modified over time to select the option that provides the best overall benefit.

[0013] In addition to enabling the production of non-mineral kerosene / jet boiling range compounds, the synthetic method for forming the high isoparaffin blend component can provide various other advantages. For example, in some embodiments, the isoparaffinic nature of the blend component can be achieved by using a mixture of kerosene and jet boiling range compounds with a high content of C. 17 and / or C. 18 It can enable the incorporation of hydrocarbons into jet fuel. 17 and C 18 The boiling points of n-paraffins are above the final boiling points typically required for jet fuel under standards such as ASTM D1655. However, they contain at least one branch point. 17 Or C 18 Paraffins (i.e., isoparaffins) can have a boiling point below 300° C. The blend components have a relatively low content of n-paraffins, so that up to 15 wt.% C 17 and / or C. 18 Blend components having compounds can be added to potential jet fuels while achieving a final boiling point of 300° C. or less according to ASTM D86.

[0014] As another example, in some embodiments, the isoparaffinic nature of the blend components can have beneficial cold flow properties. While n-paraffins typically have relatively high values ​​for properties such as cloud point or freezing point, various types of isoparaffins generally have much lower values ​​(i.e., cloud points and / or freezing points corresponding to lower temperatures). The beneficial cold flow properties of the isoparaffinic blend components can be used to offset another kerosene / jet boiling range fraction that may have less desirable properties. For example, a Fischer-Tropsch fraction may tend to be composed primarily of n-paraffins and therefore tend to have relatively undesirable cold flow properties. Blending an isoparaffinic blend component with a Fischer-Tropsch fraction can result in a blended synthetic fuel / fuel blend component that incorporates a significant portion of the Fischer-Tropsch fraction yet has sufficient cold flow performance to meet one or more types of jet fuel specifications. Similarly, some synthetic aviation fuel fractions as defined in ASTM 7566 (such as bio-derived aviation fuels) can have relatively high freezing point temperatures. Blending an isoparaffin blending component with such a synthetic aviation fuel fraction can potentially improve the freezing point (and / or other cold flow properties) of the resulting jet fuel while substantially retaining the bio-derived character of the aviation fuel, depending on the source of the olefins that are oligomerized to form the isoparaffin blending component.

[0015] As yet another example, an isoparaffin blend component can have a relatively high energy content (by weight). As a result, the isoparaffin blend component can be a desirable blend component for blending with a variety of other fractions, including sustainable aviation fuel fractions, as well as various types of difficult fractions that may have lower specific energy and / or less desirable cold flow properties.

[0016] In addition to the above, it has further been discovered that the hydrocarbons in the isoparaffin blend components may have unexpected distribution types of carbon atoms, such as an unusual distribution of hydrogens on CH3 groups versus hydrogens on CH2 groups, which may allow for the formation of blends with similarly unexpected distribution types of carbon atoms in the resulting blend.

[0017] definition All numerical values ​​within the detailed description and claims herein are modified by the indicated value as "about" or "approximately" to account for experimental error and variations that would be expected by one of ordinary skill in the art.

[0018] For purposes of this discussion, a jet fuel or jet fuel blend component that contains at least a portion of synthetic jet fuel boiling range compounds (i.e., jet boiling range compounds that are not derived from the processing of a mineral source) is defined as a synthetic jet fuel or synthetic jet fuel blend component.

[0019] In this discussion, when methanol is used as a feedstock to form olefins, methanol obtained by processing a bio-based feedstock and / or methanol obtained by fermentation of the feedstock may be referred to as "sustainable" methanol.

[0020] Current commercial standards for jet fuel typically specify various properties. Examples of property specifications and / or typical properties for commercial jet fuel include a total acidity of 0.1 mg KOH / g or less, or 0.015 mg KOH / g or less, a sulfur content of 3000 wppm or less, a maximum freezing point of -40°C or -47°C, a viscosity at -20°C of 8.0 cSt or less, a flash point of at least 38°C, an initial boiling point of 140°C or more, a T10 distillation point of 205°C or less, and / or a final boiling point of 300°C or less. Another example of a property specification is a specification for a maximum deposit thickness on the surface of the heater tube and / or a maximum pressure increase during a thermal stability test at 260°C (according to ASTM D3241), such as a maximum deposit thickness of 85 nm and / or a maximum pressure increase of 25 mm Hg. Yet another example of a property specification can be a water separation index, such as a water separation index of 85 or more as measured according to ASTM D3948. The water separation index provides an indication of the amount of surfactant present in a jet fuel boiling range sample. Petroleum fractions having an appropriate boiling range and also meeting various requirements of commercial standards can be tested (such as according to ASTM D3241) and certified for use as jet fuel. In some embodiments, the kerosene boiling range fraction can correspond to a jet fuel fraction that meets the specifications for jet fuel under ASTM D1655. This can include a thermal stability breakpoint of 260° C. or greater, or 275° C. or greater, as defined by ASTM D3241.

[0021] Unless otherwise specified, distillation and boiling points may be determined according to ASTM D86. Note that additional methods of boiling point characterization may be provided in the examples. Values ​​generated by such other methods are considered to be indicative of values ​​that would be obtained under ASTM D86.

[0022] For the purposes of this discussion, the jet fuel boiling range or kerosene boiling range is defined as 140° C. to 300° C. The jet fuel boiling range fraction or kerosene boiling range fraction is defined as a fraction having a T10 distillation point of 140° C. to 205° C. and a final boiling point of 300° C. or less. It is noted that jet fuel boiling range fractions can sometimes also have a flash point of 38° C. or greater, but kerosene boiling range fractions do not necessarily have such a requirement.

[0023] In this discussion, hydroprocessed fractions refer to hydrocarbon and / or hydrocarbonaceous fractions that have been exposed to a catalyst having hydroprocessing activity at a temperature of 200° C. or higher and in the presence of hydrogen at 300 kPa-a or higher. Examples of hydroprocessed fractions include hydroprocessed distillate fractions (i.e., hydroprocessed fractions having a distillate boiling range), hydroprocessed kerosene fractions (i.e., hydroprocessed fractions having a kerosene boiling range), and hydroprocessed diesel fractions (i.e., hydroprocessed fractions having a diesel boiling range). It is noted that hydroprocessed fractions derived from biological sources, such as hydroprocessed vegetable oils, can correspond to hydroprocessed distillate fractions, hydroprocessed kerosene fractions, and / or hydroprocessed diesel fractions, depending on the boiling range of the hydroprocessed fraction.

[0024] Various methods may be used to characterize the properties of the kerosene / jet boiling range fractions and / or blends of such fractions with other components to form kerosene / jet boiling range fuels. 3The density of the blend at 100° C. (in wppm or weight %) may be determined according to ASTM D4052. Sulfur (in wppm or weight %) may be determined according to ASTM D2622 and nitrogen (in wppm or weight %) may be determined according to D4629. Kinematic viscosity (cSt) at either −20° C. or −40° C. may be determined according to ASTM D445. Pour point may be determined according to ASTM D5949. Cloud point may be determined according to D5773. Freezing point may be determined according to D5972. Flash point may be determined according to ASTM D56. Cetane number may be determined according to ASTM D613. Aromatic content may be determined according to ASTM D1319.

[0025] In this discussion, the content of n-paraffins, isoparaffins, cycloparaffins, aromatics, and / or olefins may be determined according to test method UOP 990. For aromatics, ASTM D1319 is used for samples with an aromatics content of 5.0 wt% or more. The aromatics content determined according to UOP 990 should only be used to characterize aromatics contents between 1.0 wt% and 5.0 wt%, which corresponds to aromatics contents that are not suitable for characterization according to ASTM D1319. It is noted that even lower aromatics contents could potentially be determined by other methods, such as UV-visible spectroscopy.

[0026] As mentioned above, UOP 990 can be used to determine paraffin, naphthene, and aromatics content. It should be noted that in some cases of the paraffin, n-paraffin, and isoparaffin contents described below, the contents were determined using gas chromatography according to the normal paraffin method. The n-paraffin peaks from a hydrocarbon sample in gas chromatography are well known. The n-paraffin peaks can be incorporated separately to determine the n-paraffin content of the sample using gas chromatography. The peaks in the GC spectrum between the n-paraffin peaks can be assigned as isoparaffins having the same carbon number as the lower peak so that the total amount of paraffins having a given carbon number can be determined. The isoparaffin content for a given carbon number can be determined by subtracting the n-paraffin content from the total paraffin content. The values ​​herein determined by the normal paraffin method are believed to represent the values ​​that would be obtained according to UOP 990.

[0027] As mentioned above, UOP 990 can be used to determine paraffin, naphthene, and aromatic content. For some paraffin, naphthene, and / or aromatic content described herein, supercritical fluid chromatography (SFC) was used. SFC characterization values ​​are believed to represent those that would be obtained according to UOP 990. For SFC characterization, a commercial supercritical fluid chromatographic system was used to perform the characterization, and the methodology represents an extension of the methodology described in ASTM D5186 to allow for separate characterization of paraffins and naphthenes. An extension of the ASTM D5186 methodology was allowed by using an additional separation column to allow for the decomposition of naphthenes and paraffins. The system was equipped with a high pressure pump for delivery of supercritical carbon dioxide mobile phase, a temperature controlled column oven, an autosampler with a high pressure liquid injection valve for delivery of sample material to the mobile phase, a flame ionization detector, a mobile phase splitter (low dead volume tee), a back pressure regulator to keep the CO2 in a supercritical state, and a computer and data system for controlling the components and recording data signals. For analysis, approximately 75 milligrams of sample were diluted in 2 milliliters of toluene and loaded into a standard septum capped autosampler vial. Samples were introduced via a high pressure sampling valve. SFC separations were performed using multiple commercial silica packed columns (with either 5 micron, 60 or 30 Angstrom pores) connected in series (250 mm long, either 2 mm or 4 mm ID). Column temperatures were typically maintained at 35°C or 40°C. For analysis, the column head pressure was typically 250 bar. Liquid CO2 flow rates were typically 0.3 ml / min for the 2 mm ID column or 2.0 ml / min for the 4 mm ID column. The SFC FID signal was integrated into the paraffin and naphthene regions. In addition to characterizing aromatics according to ASTM D5186, samples were analyzed for total paraffin and total naphthene splits using supercritical fluid chromatography.Various standards with representative molecular types can be used to calibrate the paraffin / naphthene split for quantification.

[0028] Carbon number distribution (CND) is obtained by injecting a suitable sample of the olefin-containing reactor product into a hydrogenation GC. The hydrogenation GC is fitted with a zone containing Pt / Al2O3 or other suitable hydrogenation catalyst under conditions such that the olefinic material is nearly or completely saturated with hydrogen co-fed with the sample into the hydrogenation zone before entering the GC column. Thus, the actual GC measurement is not a direct measurement of the olefinic species, but rather a measurement of the corresponding saturated molecules. This provides a more accurate measurement of carbon number by reducing the volatility / retention time dispersion that would be found between the various olefinic species.

[0029] Regardless of the particular GC protocol (injected sample volume, particular column and detector, carrier gas type and speed, split level, and other details well known to those skilled in the art), the carbon numbers are differentiated by the GC retention times of the normal normal paraffins. Typically, in carrying out this analytical method, the selected protocol is calibrated by supplying calibration standards containing all normal normal paraffins of the various carbon numbers of interest, or carbon numbers from C5 to C20. An imperfect but fairly accurate and useful approximation is made that the normal normal paraffin isomer of any given carbon number is the least volatile and therefore has the highest retention time of all the corresponding carbon number isomers. Thus, for example, the C8 species is the one that has a retention time that passes through and includes the peak at n-octane, excluding the peak at n-heptane, then immediately following it, the C9 species is the one that passes through and includes the peak at n-nonane, excluding the peak at n-heptane, then immediately following it, and so on. The drawback is that the C n+1 Certain highly branched paraffins are normal linear C nFor the modest branching levels of the molecules produced by the process of the present invention, this is a small error estimated to be less than about 5% for any given carbon number.

[0030] An exemplary GC protocol uses an Agilent® 8190 GC instrument fitted with the hydrogenation zone described above under appropriate conditions to pass the saturated material through an Agilent® DB-1 column of dimensions 100 m×250 mm×0.5 mm with hydrogen, nitrogen, or helium carrier gas, an FID detector, and a temperature starting at about 40° C. and increasing at a rate of about 1.5-3.5° C. / min to a temperature of about 265° C., with a typical run lasting about 80 minutes.

[0031] In this discussion, the term "paraffin" refers to a saturated hydrocarbon chain. Thus, paraffins are alkanes that do not contain ring structures. Paraffins may be straight or branched chains and are considered to be non-cyclic compounds. "Paraffin" is intended to encompass all structural isomeric forms of paraffins. The term "n-paraffin" has the expected definition of a straight chain alkane (no branches or rings in the carbon chain). The term "isoparaffin" is used herein to refer to any alkane that contains one or more branches in the carbon chain but does not contain any ring structures.

[0032] In this discussion, the term "iso-olefin" is similar to "isoparaffin," but refers to an alkene rather than an alkane. Thus, an iso-olefin is defined as an alkene that contains at least one branch in the carbon chain, but does not contain a ring structure.

[0033] In this discussion, the term "naphthene" refers to a cycloalkane (also known as a cycloparaffin). Thus, naphthenes correspond to saturated ring structures. The term naphthene encompasses single-ring naphthenes and polycyclic naphthenes. Polycyclic naphthenes may have two or more rings, for example, 2, 3, 4, 5, 6, 7, 8, 9, and 10 rings. The rings may be fused and / or bridged. Naphthenes may also include various side chains, such as one or more alkyl side chains of 1 to 10 carbons.

[0034] In this discussion, the term "saturates" refers to all linear, branched, and cyclic paraffins. Saturates therefore correspond to a combination of paraffins and naphthenes.

[0035] In this discussion, the term "aromatic ring" refers to five or six atoms bonded in a ring structure, where (i) at least four of the atoms bonded in the ring structure are carbon atoms, and (ii) all of the carbon atoms bonded in the ring structure are aromatic carbon atoms. Thus, an aromatic ring corresponds to an unsaturated ring structure. Aromatic carbons are, for example, 13 C nuclear magnetic resonance. Aromatic rings that have atoms attached to the ring (e.g., one or more heteroatoms, one or more carbon atoms, etc.) but are not part of a ring structure are within the scope of the term "aromatic ring". Additionally, it should be noted that a ring structure that includes one or more heteroatoms (such as sulfur, nitrogen, or oxygen) can correspond to an "aromatic ring" if the ring structure would otherwise fall within the definition of "aromatic ring."

[0036] In this discussion, the term "non-aromatic ring" means four or more carbon atoms bonded in at least one ring structure, where at least one of the four or more carbon atoms in the ring structure is not an aromatic carbon atom. Non-aromatic rings that have atoms attached to the ring (e.g., one or more heteroatoms, one or more carbon atoms, etc.) but are not part of the ring structure are within the scope of the term "non-aromatic ring."

[0037] In this discussion, the term "aromatic" refers to all compounds that contain at least one aromatic ring. Such compounds that contain at least one aromatic ring include compounds that have one or more hydrocarbon substituents. It should be noted that compounds that contain at least one aromatic ring and at least one non-aromatic ring fall within the definition of the term "aromatic."

[0038] It should be noted that some hydrocarbons present in the feed or product may fall outside the definitions for paraffins, naphthenes, and aromatics. For example, any alkene that is not part of an aromatic compound would fall outside the above definitions. Similarly, non-aromatic compounds that contain heteroatoms such as sulfur, oxygen, or nitrogen are not included in the definition of paraffins or naphthenes.

[0039] Isoparaffin Blend Components In various aspects, isoparaffin blending components can be used to form blended products that can correspond to jet fuel and / or jet fuel blending components. Optionally, iso-olefin blending components can be used in place of or in addition to the isoparaffin blending components.

[0040] In this discussion, to be either an isoparaffin blend component or an iso-olefin blend component, a fraction contains 50 wt% or more, or 60 wt% or more, or 70 wt% or more, or 80 wt% or more of the combined weight of isoparaffins and iso-olefins, e.g., a fraction substantially composed of isoparaffins and iso-olefins (i.e., less than 8.0 wt%, or less than 5.0 wt%, or less than 3.0 wt%, or less than 1.0 wt%, e.g., a minimum of zero other types of hydrocarbons / compounds). In addition to the above, an isoparaffin blend component refers to a fraction containing less than 5.0 wt% iso-olefins and 80 wt% or more, or 85 wt% or more, or 90 wt% or more isoparaffins (by weight of the fraction), e.g., a fraction having substantially all of the fraction corresponding to isoparaffins. Iso-olefin blend component refers to a fraction that a) meets the requirements for the combined amount of iso-olefins and isoparaffins, and b) contains 5.0 wt.% or more, or 25 wt.% or more, or 50 wt.% or more, or 70 wt.% or more of iso-olefins, for example, having substantially all of the fraction corresponding to iso-olefins up to the fraction.

[0041] In various embodiments, the isoparaffin blend components and / or iso-olefin blend components can have one or more of the following characteristics: In some embodiments, 80% or more by weight, or 90% or more by weight, or 94% or more by weight, or 97% or more by weight of the blend components are C9-C 20 In some embodiments, between 2.0 wt.% and 25 wt.%, or between 2.0 wt.% and 15 wt.%, or between 5.0 wt.% and 25 wt.%, or between 5.0 wt.% and 15 wt.%, or between 2.0 wt.% and 10 wt.% of the blend components are made up of C9 hydrocarbons. In some embodiments, between 1.0 wt.% and 15 wt.%, or between 2.5 wt.% and 15 wt.% of the blend components are made up of C9 hydrocarbons. 17+In some embodiments, 1.0 wt.% to 15 wt.%, or 2.5 wt.% to 15 wt.%, or 1.0 wt.% to 10 wt.%, or 2.5 wt.% to 10 wt.% of the blend components are C 17 and / or C. 18 In some embodiments, the blend components have 5.0 wt.% or less, or 3.0 wt.% or less, or 1.0 wt.% or less C 19+ It may contain hydrocarbons, for example, at least C 19+ In some embodiments, the blend components have a hydrocarbon content of 5.0 wt.% or less, or 3.0 wt.% or less, or 1.0 wt.% or less, or 0.5 wt.% or less, for example, as low as 0.1 wt.%, or even lower (i.e., substantially no C 8- (No content) C 8- In some embodiments, the blend components may include a hydrocarbon having a viscosity of 0.730 g / cm at 15° C. 3 ~0.775g / cm 3 It has a specific gravity of .

[0042] In some embodiments, the blend components comprise 60% to 90% by weight of C based on the weight of the blend components. 11 ~C 18 Additionally or alternatively, the blend component may contain 50% to 75% by weight of C based on the weight of the blend component. 12 ~C 16 It may contain isoparaffins, which is particularly advantageous for the flexible use of the composition as an aviation fuel or diesel fuel.

[0043] In various aspects, the blend components can contain reduced or minimized amounts of aromatics, which can correspond to containing 5.0 wt.% or less, or 3.0 wt.% or less, or 1.0 wt.% or less, or 0.5 wt.% or less, or 0.1 wt.% or less aromatics, e.g., substantially no aromatic content.

[0044] In various embodiments, the blend components may have flash points of 38° C. or higher, or 40° C. or higher, or 45° C. or higher, or 50° C. or higher, or 55° C. or higher, such as up to 60° C., or even higher. Additionally or alternatively, the blend components, when tested alone (i.e., before blending with another fraction), may have a Jet Fuel Thermal Oxidation Test (JFTOT) breakpoint result of 260° C. or higher, or 270° C. or higher, or 280° C. or higher, such as up to 320° C., or even higher.

[0045] In some embodiments, the blend components can have an electrical conductivity of 10 pS / m or less (according to ASTM test method D2624) before adding any additives, e.g., a minimum of substantially no electrical conductivity. It is noted that the isoparaffin blend components described herein have good response to conductivity additives. After adding conventional additives for conductivity, the isoparaffin blend components can have a conductivity of 50 pS / m to 600 pS / m.

[0046] One example of a suitable process for making an isoparaffin blend component is described in U.S. Patent No. 7,692,049, which is incorporated herein by reference for the limited purpose of describing how to make an isoparaffin blend component. Briefly, a feed containing at least one C3-C8 olefin is mixed with 10 wt. % or less C2O3 over a molecular sieve catalyst such that a) the recycle feed weight to fresh feed weight ratio is about 0.5-2.0, and b) the difference between the maximum and minimum temperatures in the reactor is 40° F. (22° C.) or less. 10+ Blend components can be produced by oligomerizing together with an olefin recycle stream containing non-normal olefins. The oligomerization product is then separated into an iso-olefin stream and at least one light olefin stream. At least a portion of the light olefin stream is then recycled to the oligomerization process. In various embodiments, the iso-olefin stream can be exposed to hydroprocessing conditions to produce an isoparaffin stream.

[0047] The fresh feed to the oligomerization process can contain any single C3-C8 olefin or any mixture thereof in any proportion. Particularly suitable feeds include mixtures of propylene and butylene having at least 5 wt%, such as at least 10 wt%, such as at least 20 wt%, such as at least 30 wt% or at least 40 wt% C4 olefins. Also useful are mixtures of C3-C5 olefins having at least 40 wt% C4 olefins and at least 10 wt% C5 olefins.

[0048] In one embodiment, the olefin feed is obtained by converting oxygenates such as methanol to olefins, either over a silicoaluminophosphate (SAPO) catalyst, for example according to the methods of U.S. Patents 4,677,243 and 6,673,978, or over an aluminosilicate catalyst, for example according to the methods of WO 04 / 18089, WO 04 / 16572, EP 0 882 692, and U.S. Patent 4,025,575. Alternatively, the olefin feed may be obtained by catalytic cracking of heavier petroleum fractions, or by thermal cracking of various hydrocarbon streams ranging from ethane to naphtha to heavy fuel oil in a mixture with steam in a well-understood process known as "steam cracking".

[0049] In various embodiments, the feed to the oligomerization process also contains 10 wt.% or less C 10 + An olefin recycle stream containing non-normal olefins and / or having a final boiling point of 170° C. or less. In some embodiments, the olefin recycle stream contains 30 wt.% or less, or 10 wt.% or less C 9+It may contain olefins and / or have a final boiling point of 140° C. or less. Additionally or alternatively, in some embodiments, the olefin recycle stream contains 30 wt. % or less, or 5.0 wt. % or less C4 hydrocarbons (thus roughly corresponding to the debutanized stream). The amount of olefin recycle stream fed to the oligomerization process is such that the recycle feed weight to fresh feed weight ratio is from about 0.5 to about 2.0. More specifically, the mass ratio of the olefin recycle stream to the fresh olefin feed can be at least 0.7 or at least 0.9, but is generally not more than 1.8, or not more than 1.5, or not more than 1.3.

[0050] Additionally, the feedstock, the recycle, or both may contain other materials, such as inert diluents, such as saturated hydrocarbons, or other hydrocarbon types, such as aromatics or dienes.

[0051] The catalyst used in the oligomerization process can include any crystalline molecular sieve that is active in olefin oligomerization reactions. In one embodiment, the catalyst includes a medium pore size molecular sieve having a constraint index of about 1 to about 12. The constraint index and methods for determining it are described in U.S. Pat. No. 4,016,218, which is incorporated herein by reference. Examples of suitable medium pore size molecular sieves are those having 10-ring pore openings, including those of the TON framework type (e.g., ZSM-22, ISI-1, theta-1, Nu-10, and KZ-2), MTT framework type (e.g., ZSM-23 and KZ-1), MFI structure type (e.g., ZSM-5), MFS framework type (e.g., ZSM-57), MEL framework type (e.g., ZSM-11), MTW framework type (e.g., ZSM-12), EUO framework type (e.g., EU-1), and members of the ferrierite family (e.g., ZSM-35). In one preferred embodiment, the molecular sieve catalyst comprises ZSM-5.

[0052] Other examples of suitable molecular sieves include those having 12-membered pore openings, such as ZSM-18, zeolite beta, faujasite, zeolite L, mordenite, and members of the MCM-22 family of molecular sieves (including, for example, MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, and MCM-56).

[0053] In one embodiment, the crystalline aluminosilicate molecular sieve has an average (d 50 ) crystal size. Moreover, the molecular sieve is preferably selected to have an alpha value of about 100 to about 600, conveniently about 200 to about 400, or about 250 to about 350. The alpha value of the molecular sieve is an approximate indicator of its catalytic cracking activity compared to the standard silica-alumina catalyst test (which has an alpha value of 1). The alpha test is described in U.S. Pat. No. 3,354,078, Journal of Catalysis, Vol. 4, p. 527 (1965), Vol. 6, p. 278 (1966), and Vol. 61, p. 395 (1980), each of which is incorporated herein by reference for its description. The experimental conditions for the test used herein include a constant temperature of 538° C. and a variable flow rate, which is described in detail in Journal of Catalysis, Vol. 61, p. 395. Conveniently, the crystalline aluminosilicate molecular sieve has a silica to alumina molar ratio of from about 20 to about 300, such as from about 20 to about 150, for example from about 45 to about 90.

[0054] The molecular sieve may be supported or unsupported, for example in powder form, or may be used as an extrudate with a suitable binder. If a binder is used, it is conveniently a metal oxide such as alumina, and is present in an amount such that the oligomerization catalyst contains from about 2 to about 80 weight percent of the molecular sieve.

[0055] The oligomerization reaction produces the desired low levels of C in the reaction product. 17To ensure +oligomerization, it should be carried out with a sufficiently high WHSV of the fresh feed to the reactor. This can correspond to a WHSV (weight hourly space velocity) of 1.5 or more, based on the weight of fresh feed on catalyst basis to the weight of molecular sieve. For combined fresh olefin feed and recycle to the reactor, the WHSV can be 2.3 or more, again based on the amount of molecular sieve in the oligomerization catalyst.

[0056] The oligomerization process may be carried out over a wide range of temperatures, but generally, the temperature in the oligomerization reaction zone should be about 150° C. to 350° C. However, it is important to ensure that the temperature throughout the reaction zone is maintained relatively constant to provide the desired level of C4 olefin conversion at a given WHSV and point in the reaction cycle. Thus, as discussed above, the difference between the maximum and minimum temperatures in the reactor should be maintained at or below 40° F. (22° C.).

[0057] The oligomerization process can be carried out over a wide range of olefin partial pressures, although higher olefin partial pressures are preferred because lower pressures tend to promote cyclization and cracking reactions and are thermodynamically less favorable for the preferred oligomerization reaction.Typical olefin partial pressures of the olefins in the combined olefin feed and light olefins / recycle stream as a total charge to the reactor include at least 400 psig (2860 kPa).

[0058] When synthesized, the resulting oligomerized products can correspond to iso-olefin blend components. The iso-olefin blend components can be converted to isoparaffin blend components by any convenient olefin saturation process, such as a mild hydrotreating process. Mild hydroprocessing generally involves reducing or minimizing the amount of carbon chain size in the fraction, and can convert iso-olefins to isoparaffins. In addition to converting iso-olefins to isoparaffins, hydroprocessing of the kerosene fraction can be used to remove sulfur, nitrogen, saturated olefins, saturated aromatics, and / or other purposes.

[0059] During hydroprocessing, a feedstock consisting partially or entirely of a jet fuel boiling range fraction is treated in a hydrotreating (or other hydroprocessing) reactor that includes one or more hydrotreater stages or hydrotreating beds. Optionally, the reaction conditions in the hydrotreater stage can be suitable for reducing the sulfur content of the feedstream, e.g., suitable for reducing the sulfur content of the feedstream to 500 wppm or less, or 100 wppm or less, or 10 wppm or less, e.g., a minimum of 0.5 wppm, or even lower. The reaction conditions can be from 0.1 to 20.0 hours. -1 The reaction conditions may include an LHSV of about 1000 psig (0.34 MPag), a hydrogen partial pressure of about 50 psig (0.34 MPag) to about 3000 psig (20.7 MPag), a treat gas containing at least about 50% hydrogen, and a temperature of about 450° F. (232° C.) to about 800° F. (427° C.). Preferably, the reaction conditions are for 0.3 to 5 hours. -1 a hydrogen partial pressure of about 100 psig (0.69MPag) to about 1000 psig (6.9MPag), and a temperature of about 700°F (371°C) to about 750°F (399°C).

[0060] Optionally, a hydrotreating reactor operating at a relatively low total pressure value, such as a total pressure of about 200 psig (1.4MPag) to about 800 psig (5.5MPag), can be used. For example, the stage pressure in the hydrotreating reactor can be at least about 200 psig (1.4MPag), or at least about 300 psig (2.1MPag), or at least about 400 psig (2.8MPag), or at least about 450 psig (3.1MPag). The stage pressure in the hydrotreating reactor can be about 800 psig (5.5MPag) or less, or about 700 psig (4.8MPag) or less, or about 600 psig (4.1MPa).

[0061] The hydrotreating stage catalyst may be a conventional hydrotreating catalyst, such as a catalyst composed of a Group VIB metal and / or a Group VIII metal on a support. Suitable metals include cobalt, nickel, molybdenum, tungsten, or combinations thereof. Preferred combinations of metals include nickel and molybdenum, or nickel, cobalt, and molybdenum. Suitable supports include silica, silica-alumina, alumina, and titanium.

[0062] In one embodiment, the amount of treat gas delivered to the hydrotreater stage can be based on the hydrogen consumption rate in the stage. The treat gas rate in the hydrotreater stage can be about 2 to about 5 times the amount of hydrogen consumed per barrel of fresh feed in the stage. A typical hydrotreater stage can have a treat gas rate of about 50 SCF / B (8.4 m), depending on a variety of factors including the nature of the feed being hydrotreated. 3 / m 3 )~Approx. 1000SCF / B(168.5m 3 / m 3 ) of hydrogen. Therefore, the process gas rate is about 100 SCF / B (16.9 m 3 / m 3 )~Approx. 5000SCF / B(842m 3 / m 3). Preferably, the treat gas rate may be about 4 to about 5 times the amount of hydrogen consumed. Note that the treat gas rates above refer to the rate of the hydrogen flow. If hydrogen is delivered as part of a gas stream having less than 100% hydrogen, the treat gas rate for the entire gas stream may be proportionately higher.

[0063] Blended Jet / Kerosene Boiling Range Products The isoparaffin blend component can be blended with one or more other fractions to form a kerosone / jet boiling range product. Examples of fractions that can be blended with the isoparaffin blend component include, but are not limited to, conventional jet fractions, mineral naphtha and / or jet and / or diesel boiling range fractions, and various types of synthetic naphtha, jet, and / or diesel boiling range fractions, such as sustainable aviation fuel fractions and / or Fischer-Tropsch fractions. Other difficult fractions, where at least a portion of the fraction corresponds to a jet / kerosene boiling range component, can also be blended with the isoparaffin blend component.

[0064] In various embodiments, the blended product may contain 1.0% by volume or more, or 10% by volume or more, or 30% by volume or more, or 50% by volume or more, or 65% by volume or more, or 75% by volume or more, such as up to 99% by volume, or even higher. In some embodiments, such blended products may include 1.0% to 20% by volume, or 1.0% to 15% by volume, or 5.0% to 20% by volume, or 5.0% to 15% by volume, or 10% to 20% by volume of the isoparaffin blend component. In other embodiments, such blended components can include 30% to 99% by volume, or 30% to 95% by volume, or 30% to 80% by volume, or 30% to 60% by volume, or 30% to 45% by volume, or 50% to 99% by volume, or 50% to 95% by volume, or 50% to 80% by volume, or 70% to 99% by volume of the isoparaffin blend component.

[0065] In some embodiments, between 0.1% and 15% by weight, or between 1.0% and 15% by weight, or between 2.5% and 15% by weight, or between 0.1% and 10% by weight, or between 1.0% and 10% by weight, or between 2.5% and 10% by weight, or between 1.0% and 6.0% by weight, or between 2.5% and 6.0% by weight, or between 1.0% and 3.0% by weight, or between 0.1% and 6.0% by weight, or between 0.1% and 3.0% by weight of the resulting blended product. 17 In some embodiments, 0.1% to 15% by weight of the resulting blended product may be C 17 and / or C. 18 For example, the resulting blended product may have 0.1 wt% or more, or 1.0 wt% or more, or 1.5 wt% or more, or 2.0 wt% or more, or 4.0 wt% or more, or 6.0 wt% or more, or 10 wt% or more, e.g., up to 15 wt% C 17 -C 18 In some embodiments, the resulting blended product has 5.0 wt.% or less, or 3.0 wt.% or less, or 1.0 wt.% or less, or 0.1 wt.% or less C 19+ It may contain hydrocarbons, for example, at least C 19+ It has substantially no hydrocarbon content.

[0066] In some embodiments, the resulting blended product can have an unexpectedly high content of C9 hydrocarbons. In such embodiments, the resulting blended product can contain 5.0 wt.% or more, or 10 wt.% or more, or 15 wt.% or more, for example, up to 25 wt.%, or even higher.

[0067] In various embodiments, the resulting blended product has a viscosity of 0.775 g / cm at 15° C. 3 ~0.840g / cm 3Additionally or alternatively, the resulting blended product may have a flash point of 38° C. or more, or 40° C. or more, or 45° C. or more, or 50° C. or more, such as up to 60° C., or even higher. Additionally or alternatively, the blend components may furthermore or alternatively, the resulting blended product may have a Jet Fuel Thermal Oxidation Test (JFTOT) breakpoint result of 260° C. or more, or 270° C. or more, or 280° C. or more, such as up to 320° C., or even higher. Additionally or alternatively, the resulting blended product may have a freezing point of −40° C. or less, or −47° C. or less, or −50° C. or less, or −55° C. or less, such as down to −70° C., or even lower.

[0068] In some embodiments, the resulting blended product has a C content of 1.0 wt. % or more. 17+ Despite containing hydrocarbons, they can have a final boiling point of 300° C. or less.

[0069] In various embodiments, the resulting blended product can contain reduced or minimized amounts of aromatics, which can correspond to containing 20 wt% or less, or 15 wt% or less, or 10 wt% or less, or 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, or 0.1 wt% or less aromatics, e.g., substantially no aromatics content. Additionally or alternatively, the sulfur content can be 2000 wppm or less, or 1000 wppm or less, or 500 wppm or less, or 250 wppm or less, or 100 wppm or less, or 10 wppm or less, e.g., as low as 0.5 wppm, or even lower in some cases.

[0070] In some embodiments, the resulting blended product can include at least a portion of one or more conventional jet fuels. Conventional jet fuels are defined herein as fractions that already qualify as jet fuel under at least one of ASTM D1655, UK Ministry of Defence Standard 91-091, and Canadian General Standards Board 3.23. In such embodiments, the resulting blended product can include 1.0% to 99% by volume, or 1.0% to 90% by volume, or 1.0% to 70% by volume, or 1.0% to 50% by volume, or 1.0% to 30% by volume, or 1.0% to 10% by volume, or 10% to 70% by volume, or 10% to 50% by volume, or 10% to 30% by volume, or 30% to 70% by volume of conventional jet fuel fractions. Thus, the resulting blended product may, in some embodiments, contain no more than 50% by volume, or no more than 30% by volume, or no more than 10% by volume, for example, as low as 1.0% by volume, or even lower in some cases.

[0071] In some embodiments, the resulting blended product can include at least a portion of one or more mineral kerosene / jet boiling range fractions. In such embodiments, the resulting blended product can include 1.0% to 99% by volume, or 1.0% to 90% by volume, or 1.0% to 70% by volume, or 1.0% to 50% by volume, or 1.0% to 30% by volume, or 1.0% to 10% by volume, or 10% to 70% by volume, or 10% to 50% by volume, or 10% to 30% by volume, or 30% to 70% by volume of the jet / kerosene boiling range fraction. Thus, the resulting blended product can include, in some embodiments, 50% by volume or less, or 30% by volume or less, or 10% by volume or less, e.g., as low as 1.0% by volume, or even less than 1.0% by volume of the jet / kerosene boiling range fraction.

[0072] In some embodiments, the resulting blended product can optionally include at least a portion of one or more synthetic jet boiling range fractions as defined by ASTM D7566. In such embodiments, the resulting blended product can include 1.0% to 99% by volume, or 1.0% to 90% by volume, or 1.0% to 70% by volume, or 1.0% to 50% by volume, or 1.0% to 30% by volume, or 1.0% to 10% by volume, or 10% to 70% by volume, or 10% to 50% by volume, or 10% to 30% by volume, or 30% to 70% by volume of synthetic jet boiling range fractions. Thus, the resulting blended product can include, in some embodiments, 50% by volume or less, or 30% by volume or less, or 10% by volume or less, e.g., as low as 1.0% by volume, or even less.

[0073] It should be noted that the isoparaffin blending components and / or iso-olefin blending components may be blended with multiple different types of fractions. For example, in some embodiments, the blended product may include two or more (or three or more) conventional jet fuel fractions, a mineral jet boiling range fraction, and a synthetic fraction. Examples of synthetic fractions include bio-derived fractions, sustainable aviation fuel, and / or a Fischer-Tropsch fraction.

[0074] In some embodiments, after the components are blended together to form the kerosene / jet fuel boiling range fraction, it may be desirable to further process the kerosene / jet fuel boiling range fraction for any convenient reason. Examples of further processing methods may include, but are not limited to, hydrous processing, clay processing, acid and / or caustic processing, mercaptan oxidation, salt drying, and hydroprocessing.

[0075] Distribution of carbon atom types in isoparaffin blend components and resulting blends In some aspects, the isoparaffin blend component may be formed according to the synthesis methods described herein, where an iso-olefin blend component is formed via olefin oligomerization and then exposed to hydroprocessing conditions to substantially saturate the olefins to obtain an isoparaffin blend component. When an isoparaffin blend component is formed according to this method, the distribution of carbon atom types within the hydrocarbons of the blend component is different than a fraction containing isoparaffins formed by another method, such as isomerization of an n-paraffin feed. This difference in carbon atom types is due to the fact that 1 H NMR and 13 It can be characterized using various types of nuclear magnetic resonance (NMR) analysis, including C NMR.

[0076] In this study, analysis of the types of hydrogen atoms in hydrocarbon-like samples is performed according to the methodology described in a technical paper in the SAE Technical Paper Series (892073) by Gulder et al., entitled "A Rapid Cetane Number Prediction Method for Petroleum Liquids and Pure Hydrocarbons Using Proton NMR."

[0077] In short, 1H NMR can be used to roughly characterize the amount of hydrogen in a sample that is attached to various types of carbon atoms. Under the analysis used herein, hydrogens are classified into six categories: "Ha" hydrogens correspond to hydrogen atoms attached to aromatic rings; "Hα" hydrogens correspond to hydrogens attached to carbon atoms that are in the "alpha" position relative to the aromatic ring; "Ho" hydrogens correspond to hydrogens attached to carbon atoms that form part of an olefinic bond; "Hc1" hydrogens correspond to hydrogens that are part of a CH or CH2 group that is "beta" to the aromatic ring, and hydrogens that are part of naphthenic or paraffinic CH groups. Note that based on the above definitions, hydrogens from CH or CH2 groups that are in the "alpha" position relative to the aromatic ring would be included as "Hα" and not as part of "Hc1". "Hc2" hydrogens correspond to hydrogens that are part of paraffinic CH2 groups, naphthenic CH2 groups, hydrogens on CH2 groups that are in the "gamma" position or further away from the aromatic ring, and hydrogens that are part of CH3 groups that are in the "beta" position relative to the aromatic ring. "Hd" hydrogens correspond to hydrogens that are part of paraffinic CH groups, as well as hydrogens that are part of CH groups that are in the "gamma" position or further away from the aromatic ring. Based on these definitions, 1 The ratio of various types of hydrogen in a H NMR spectrum can be characterized. Specifically, the peak areas corresponding to each type of hydrogen can be integrated, allowing the ratio of one type of hydrogen to another to be determined. As an example, 1 H NMR can be used to determine the ratio of Hd hydrogens to Hc2 hydrogens (or roughly the ratio of hydrogens in CH3 groups to hydrogens in CH2 groups).

[0078] In various embodiments, the isoparaffin blend component has a ratio of Hd hydrogen to Hc2 hydrogen (Hc2) of 1.01 to 1.35, or 1.01 to 1.25, or 1.01 to 1.15, or 1.10 to 1.35, or 1.10 to 1.25, or 0.95 to 1.25, or 0.95 to 1.15. 1By blending the isoparaffin blend component with another fraction, a ratio of Hd hydrogens to Hc2 hydrogens (HdH2) of 0.50 to 2.30, or 0.60 to 2.30, or 0.75 to 2.30, or 0.91 to 2.30, or 0.91 to 2.00, or 0.91 to 1.80, or 0.91 to 1.50, or 0.91 to 1.15, or 1.01 to 2.30, or 1.01 to 2.00, or 1.01 to 1.80, or 1.01 to 1.50, or 1.01 to 1.15, or 1.36 to 2.30, or 1.36 to 2.00, or 1.36 to 1.80, or 1.70 to 2.30 can be obtained. 1 It is possible to form a resulting blend having a ratio of Hd hydrogen to Hc2 hydrogen (as determined based on H NMR). It is noted that the ratio of Hd hydrogen to Hc2 hydrogen may vary depending on the type of cut that is blended with the isoparaffin blend component. Directionally, blending an isoparaffin blend component with a mineral cut and / or an n-paraffin cut tends to produce a blend having a lower ratio of Hd hydrogen to Hc2 hydrogen. For example, blending an isoparaffin blend component with a mineral jet boiling range cut, a mineral distillate boiling range cut, or a Fischer-Tropsch cut and / or a cut having a high n-paraffin content tends to result in a blend having a lower ratio of Hd hydrogen to Hc2 hydrogen. In contrast, blending an isoparaffin blend component with a cut that has been highly isomerized in a catalytic dewaxing / isomerization process tends to result in a blend having a higher ratio of Hd hydrogen to Hc2 hydrogen.

[0079] In addition to characterizing hydrogen for all samples, 13 Using C NMR, we investigated the C 12 The quaternary carbon content of the fractions was characterized. For this type of measurement, gas chromatography was used to determine the C 12 The compounds can be separated from the remaining hydrocarbons. 12A simple method that can be used to form fractions is normal paraffin (or normal paraffin) gas chromatography. That is, with a suitable gas chromatograph having a separation column of suitable resolution, normal paraffins of a given carbon number can be assumed to exhibit a peak, and beyond that peak, species can be assumed to include the carbon number of the next higher carbon number normal paraffin peak. For example, all peaks for material eluting between the peaks for n-decane and n-undecane are within the C 11 It is assumed to be a species.

[0080] The resulting C 12 The fraction is 13 The isoparaffin blend components made according to the methods described herein can be characterized using C NMR. 12 It has been discovered that the fractions can have unexpectedly low quaternary carbon content relative to fractions made by catalytic isomerization of n-paraffins. In such embodiments, the C of the isoparaffin blend components 12 The quaternary carbon content of the fraction is C 12 It may be no more than 1.5%, or no more than 1.4%, or no more than 1.3% of the total carbon present in the fraction, for example as low as 1.0%, or even lower. EXAMPLES

[0081] Example 1 - Carbon Chain Length Distribution in Isoparaffin Blend Components One of the unusual features of the isoparaffin blend components described herein is that the isoparaffin blend components form blends having a final boiling point of 300° C. or less, as measured according to ASTM D86, while still providing a C 17+The advantage of isoparaffin blends is that they can contain a significant portion of hydrocarbons. To illustrate this, several different samples of isoparaffin blend components were made using the synthesis methods described herein. Table 1 shows the volume percentage of hydrocarbon chain length in the resulting isoparaffin blend components. The samples are designated IPB 1, 2, and 3 (for isoparaffin blend components). For comparison, the hydrocarbon chain length distribution in a representative JET A-1 sample is also shown. [Table 1]

[0082] As shown in Table 1, the representative JET A-1 sample contained less than 2.0 wt.% C. 17 -C 18 Contains the components C 19 The composition is also C 20 In contrast, each of the isoparaffin blend components does not contain more than 3.0 wt.% C 17 -C 18 Hydrocarbons and more than 4.5 wt.% C 17+ Contains hydrocarbons.

[0083] C in isoparaffin blend components 17+ The increase in the concentration of hydrocarbons increases the C in the blends containing a portion of the isoparaffin blend components. 17+ Tables 2-4 show the weight percent of hydrocarbons of various chain lengths that would be incorporated into blended products containing 70% by volume (Table 2), 50% by volume (Table 3), or 30% by volume (Table 4) of the components. [Table 2] [Table 3] [Table 4]

[0084] As shown in Tables 2-4, blends containing 70% by volume of an isoparaffin blend component have 2.0 wt.% or more, or 2.5 wt.% or more, for example, up to 3.0 wt.% C 17 -C 18 For a 50% blend, the isoparaffin blend component may contain 1.6 wt.% or more, e.g., up to 2.2 wt.% C 17 -C 18 Typical C in conventional jet fuel is about 1.8 wt.%. 17 -C 18 Based on content, the isoparaffin blend components described herein provide a higher weight percent of C 17 -C 18 It is clear that it may be possible to incorporate hydrocarbons into a potential blended jet fuel product.

[0085] Example 2 - Blending with conventional jet fuel Isoparaffin blend components corresponding to IPB 1 and IPB 2 of Example 1 were used in combination with conventional jet fuel (JET A-1 or JP-5) to form blended jet boiling range products. Even in the case of blends having 50% or more, or 70% or more by volume of the isoparaffin blend component, the resulting blended jet boiling range product still met the specifications of the corresponding type of jet fuel.

[0086] FIG. 1 shows the results from characterization of a conventional JET A-1 sample, a sample of IPB 1, a blend formed from 30 vol.% IPB 1 and 70 vol.% JET A-1, and a blend formed from 70 vol.% IPB 1 and 30 vol.% JET A-1. As shown in FIG. 1, IPB 1 alone does not meet all of the standard requirements for JET A-1 jet fuel. However, blending 70 vol.% IPB 1 with 30 vol.% conventional JET A-1 resulted in a blended product that met all of the JET A-1 requirements shown in FIG. 1. Note that the minimum aromatic content that can be characterized according to UOP 990 is 1.0 wt.%. The aromatic content reported for the IPB 1 sample in FIG. 1 was determined by alternative methods, including UV-visible spectroscopy.

[0087] As explained in Example 1, the blend containing 70 vol. % IPB 1 had at least 2.0 vol. % C, even without considering the contribution from JET A-1. 17 -C 18 The blends containing 70% by volume of IPB 1 also provided higher JFTOT breakpoint temperatures and higher smoke points. Combined with the generally beneficial cold flow properties of the isoparaffin blend components, Figure 1 shows the value of the isoparaffin blend components described herein that may bring an out-of-specification jet fuel sample back into specification.

[0088] Similar characterizations were performed on the JET A-1 sample, IPB 2, a blend of 30 vol.% IPB 2 with 70 vol.% JET A-1, and a blend of 70 vol.% IPB 2 with 30 vol.% JET A-1. Results from the characterization of these blend products are shown in FIG. 2. Similar to FIG. 1, blending 50 vol.% or more, or 70 vol.% or more of the isoparaffin blend component with a conventional jet fuel sample results in a blend product that can meet all of the required criteria shown in FIG. 2.

[0089] Example 3 - Isoparaffin Blend Components as Lubricity Improvers It has been discovered that in embodiments where the resulting blended product comprises at least 10% by volume of a mineral jet boiling range fraction and 40% or more (or 50% or more) by volume of an isoparaffin blend component, the resulting blended product can have unexpectedly improved lubricity. Lubricity can be measured based on wear scar diameter determined according to ASTM D5001. For example, such blended products can comprise 10% to 50% by volume, or 10% to 60% by volume, or 20% to 50% by volume, or 20% to 60% by volume of a mineral jet boiling range fraction. Such blend components can also comprise 40% to 90% by volume, or 50% to 90% by volume, or 40% to 80% by volume, or 50% to 80% by volume of an isoparaffin blend component.

[0090] The unexpected nature of the lubricity improvement when adding 50% or more by volume of an isoparaffin blend component to a mineral jet boiling range fraction can be understood by comparing the lubricity behavior of the blends shown in Table 5. Table 5 shows the results of testing various jet boiling range fractions under the method of ASTM D5001 to determine the wear scar diameter. In Table 5, the first two samples correspond to pure samples of JET A-1 and JP-5. The remaining samples are blends of an isoparaffin blend component (either IPB-1 or IPB-2) with JET A-1 or JP-5. Traditionally, it would be expected that adding a high paraffin blend component to a mineral jet boiling range fraction would result in poorer lubricity performance. For comparison, it is noted that some jet fuel standards have a maximum wear scar diameter of 0.85 mm or less under ASTM D5001. [Table 5]

[0091] As shown in Table 5, the addition of isoparaffin blend components to conventional jet fuel results in wear scar diameters under ASTM D5001 that are comparable or smaller than those produced by conventional jet fuel alone. This is an unexpected result based on the nature of the isoparaffin blend components. Note that for hydrocarbon fuels, lubricity is typically related to the heteroatom content of a given fuel, with higher heteroatom content directionally resulting in better lubricity (such as reduced scar diameter). The heteroatom content (sulfur, nitrogen, oxygen) is very low. Thus, for mineral jet fractions with typical sulfur / nitrogen content, the isoparaffin blend components are expected to have directionally poor lubricity. Unexpectedly, low heteroatom content isoparaffin blend components can improve the lubricity of mineral jet fuel. Without being bound to any particular theory, the blending results shown in Table 5 suggest that some other aspect of the isoparaffin blend components, such as isoparaffinicity, may contribute to good lubricity performance. Additionally, it is noted that when blending greater amounts of isoparaffin blend components with the JET A-1 sample (such as 50% or more by volume of isoparaffin blend components), the wear scar diameter of the blended composition is reduced by 10% or more compared to the wear scar diameter for the mineral jet boiling range fraction alone.

[0092] Example 4 - Blend Components 1 H NMR analysis Isoparaffin blend component IPB-1 was formed according to the method described herein, where an iso-olefin blend component was formed by olefin oligomerization. A portion of the iso-olefin blend component was then exposed to hydrotreating conditions to saturate the portion, thus forming the IPB-1 sample. Further, mixtures corresponding to 30 wt% iso-olefin blend component / 70 wt% isoparaffin blend component and 70 wt% iso-olefin blend component / 30 wt% isoparaffin blend component were formed.

[0093] an iso-olefin blend component, an isoparaffin blend component, and a mixture of the two; 1 Characterized using H NMR 1 The ratio of Hd hydrogens to Hc2 hydrogens was characterized as determined from H NMR results. 1 3 shows the results from H NMR analysis. In FIG. 3, the first column of data corresponds to the data for the substantially fully saturated isoparaffin blend component (IPB-1-column A). The second and third columns show mixtures corresponding to 70 wt. % isoparaffin (column B) and 30 wt. % isoparaffin (column C), and the last column corresponds to the data for the iso-olefin blend component made from an oligomerization process (column D). As shown in FIG. 3, the isoparaffin blend component had a ratio of Hd hydrogens to Hc2 hydrogens of 1.19.

[0094] For comparison with the values ​​shown in Figure 3, various other types of fractions were also 1 Characterization was performed using H NMR to determine the ratio of Hd hydrogen to Hc2 hydrogen. Table 6 shows the values ​​obtained for these various other types of fractions. Where a range is given, this indicates that several different samples were characterized and the range corresponds to a minimum and maximum value. [Table 6]

[0095] As shown in Table 6, liquids with high n-paraffin content tend to have ratios of Hd hydrogen to Hc2 hydrogen well below 1.00. Commercial fuel products generally have ratios below 1.00, while high isoparaffin content / low aromatic content diesel can approach 1.00. Fluids containing high naphthenes have ratios of Hd hydrogen to Hc2 hydrogen greater than 2.30. Similarly, fractions with high isoparaffin content, where the isoparaffin content is formed by catalytic isomerization, have ratios greater than 2.30.

[0096] Example 5 - Quaternary Carbon Content A sample of IPB-1 was separated using a gas chromatograph to obtain C 12 The resulting fraction was C 12 The fraction is 13 C NMR was used to determine the content of quaternary carbons in the samples. 12 Fractions were also formed from samples derived from other conventional refining processes. Table 7 shows 12 Results from analysis of the fractions are shown. [Table 7]

[0097] As shown in Table 7, the C of IPB-1 12 The quaternary carbon content of the fraction was substantially lower than the other fractions. For both comparative samples, C 12 The fraction had a quaternary carbon content of more than 1.60% relative to the total number of carbons in the sample, while the C from the isoparaffin blend components 12 The fraction has a quaternary carbon content of 1.60% or less, or 1.50% or less, or 1.40% or less, such as a minimum of 1.20%, or optionally even lower.

[0098] Additional Embodiments Embodiment 1. A blended jet boiling range composition comprising 80 wt.% or more isoparaffins, 5.0 wt.% or less olefins, and 5.0 wt.% or less C 19+ % to 70% by volume of a mineral jet boiling range fraction, the composition having a T10 distillation point of 205° C. or less, a final boiling point of 300° C. or less, a freezing point of −40° C. or less, and a C 17 -C 18 A blended jet boiling range composition comprising a hydrocarbon.

[0099] Embodiment 2. A blended jet boiling range composition comprising 80 wt.% or more isoparaffins, 5.0 wt.% or less olefins, and 5.0 wt.% or less C 19+1.0% to 99% by volume of an isoparaffin blend component containing hydrocarbons and 1.0% to 99% by volume of a mineral jet boiling range fraction, wherein the composition has a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, a freezing point of -40°C or less, and i) 10% by weight or more of C9 hydrocarbons, ii) a flash point of 50°C or more, or iii) a combination of i) and ii).

[0100] Embodiment 3. The composition of embodiment 1 or 2, wherein the mineral jet boiling range fraction comprises a conventional jet fuel or kerosene component.

[0101] Embodiment 4. The composition of any one of embodiments 1-3, wherein the composition comprises 50% to 99% by volume of the isoparaffin blend component.

[0102] Embodiment 5. The composition of any one of embodiments 1 to 3, wherein the composition comprises 30% to 95% by volume of the isoparaffin blend component.

[0103] Embodiment 6. The composition of any one of embodiments 1-3, wherein the composition comprises 50% to 90% by volume of the isoparaffin blend component and 10% to 50% by weight of the mineral jet boiling range fraction.

[0104] Embodiment 7. The composition of embodiment 6, wherein the composition provides a wear scar diameter under the ASTM D5001 procedure that is smaller than the wear scar diameter provided by a mineral jet boiling range fraction under the ASTM D5001 procedure.

[0105] Embodiment 8. The composition of embodiment 7, wherein the wear scar diameter produced by the composition is at least 10% smaller than the wear scar diameter produced by the mineral jet boiling range fraction.

[0106] Embodiment 9. The composition of any one of embodiments 1-8, wherein the composition comprises a ratio of Hd hydrogen to Hc2 hydrogen of 1.01 to 2.00.

[0107] Embodiment 10. The composition of any one of embodiments 1-8, wherein the composition comprises a ratio of Hd hydrogen to Hc2 hydrogen of 1.01 to 1.35, and the composition optionally comprises 40% to 70% by volume of an isoparaffin blend component.

[0108] Embodiment 11. The composition of any one of embodiments 1-10, wherein the isoparaffin blend component contains 1.0 wt.% or less aromatics, or the composition contains 20 wt.% or less aromatics, or a combination thereof.

[0109] Embodiment 12. The composition of any one of embodiments 1 to 11, wherein the isoparaffin blend component contains 8.0 wt.% or less, or 5.0 wt.% or less of compounds different from isoparaffins and iso-olefins.

[0110] Embodiment 13. The composition comprises 0.1% by weight to 1.0% by weight of C 19+ 13. The composition of any one of embodiments 1 to 12, comprising a hydrocarbon.

[0111] Embodiment 14. The composition of any one of embodiments 1 to 13, wherein the composition comprises a fuel that meets the specifications for jet fuel according to at least one of ASTM D1655, UK Ministry of Defence Standard 91-091, and Canadian General Standards Board 3.23.

[0112] Embodiment 15. The composition comprises 3.0 wt.% or less of C 8- 15. The composition of any one of embodiments 1 to 14, comprising a compound.

[0113] Embodiment 16. The composition of any one of embodiments 1-15, wherein the isoparaffin blend component comprises a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, and a freezing point of -40°C or less.

[0114] Embodiment 17. C in isoparaffin blend components12 Hydrocarbons are the C components of the isoparaffin blend. 12 17. The composition of any one of the preceding embodiments, comprising 1.5% or less quaternary carbons, based on the total number of carbons in the hydrocarbon.

[0115] Embodiment 18. A blended jet boiling range composition comprising 1.0% to 20% by volume of an isoparaffin blend component and 80% to 99% by volume of a mineral jet boiling range fraction, wherein the isoparaffin blend component has 80% by weight or more isoparaffins, 5.0% by weight or less olefins, and 5.0% by weight or less C. 19+ A blended jet boiling range composition comprising a hydrocarbon, the composition comprising a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, and a freezing point of -40°C or less.

[0116] Embodiment 19. The composition of embodiment 18, wherein the blended jet boiling range composition comprises 1.0 wt% to 10 wt% of an isoparaffin blend component.

[0117] Embodiment 20. The composition of embodiment 18, wherein the blended jet boiling range composition comprises 5.0% to 15% by weight of the isoparaffin blend component.

[0118] Embodiment 21. The composition of any one of embodiments 18-20, wherein the composition comprises a ratio of Hd hydrogen to Hc2 hydrogen of 0.9 to 1.1.

[0119] Embodiment 22. The composition of any one of embodiments 18-21, wherein the isoparaffin blend component contains 1.0 wt.% or less aromatics.

[0120] Embodiment 23. The composition of any one of embodiments 18-22, wherein the isoparaffin blend component comprises 5.0 wt.% or less of compounds different from isoparaffins and iso-olefins.

[0121] Embodiment 24. The composition comprises 0.1% to 1.0% by weight of C19+ 24. The composition of any one of embodiments 18-23, comprising a hydrocarbon.

[0122] Embodiment 25. The composition of any one of embodiments 18-24, wherein the composition comprises a fuel that meets the specifications for jet fuel according to at least one of ASTM D1655, UK Ministry of Defence Standard 91-091, and Canadian General Standards Board 3.23.

[0123] Embodiment 26. The composition comprises 3.0 wt.% or less of C 8- 26. The composition of any one of embodiments 18 to 25, comprising a compound.

[0124] Embodiment 27. The composition of any one of embodiments 18-26, wherein the isoparaffin blend component comprises a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, and a freezing point of -40°C or less.

[0125] Embodiment 28. C in isoparaffin blend components 12 Hydrocarbons are the C components of the isoparaffin blend. 12 28. The composition of any one of embodiments 18-27, comprising 1.5% or less quaternary carbons, based on the total number of carbons in the hydrocarbon.

[0126] Embodiment 29. A blended jet boiling range composition comprising 80% or more by volume of isoparaffins, less than 5.0% by volume of olefins, and 5.0% or less by volume of C. 19+% to 99% by volume of an isoparaffin blend component containing hydrocarbons, and 1.0% to 99% by volume of a synthetic jet boiling range fraction, the synthetic jet boiling range fraction containing less than 80% by weight of isoparaffins; b) having a ratio of Hd hydrogen to Hc2 hydrogen of 1.6 or greater; c) having a ratio of Hd hydrogen to Hc2 hydrogen of 1.0 or less; d) a combination of a) and b), or e) a combination of a) and c), wherein the blended jet boiling range composition comprises a T10 distillation point of 205° C. or less, a final boiling point of 300° C. or less, a freezing point of −40° C. or less, and 1.0 wt.% or more of C 17 -C 18 A blended jet boiling range composition comprising a hydrocarbon.

[0127] Embodiment 30. A blended jet boiling range composition comprising 80 wt.% or more isoparaffins, less than 5.0 wt.% olefins, and 5.0 wt.% or less C 19+ % to 99% by volume of an isoparaffin blend component containing hydrocarbons, and 1.0% to 99% by volume of a synthetic jet boiling range fraction, wherein the synthetic jet boiling range fraction contains less than 80% by weight isoparaffins; b) having a ratio of Hd hydrogen to Hc2 hydrogen of 1.6 or greater; c) having a ratio of Hd hydrogen to Hc2 hydrogen of 1.0 or less; d) a combination of a) and b), or e) a combination of a) and c), wherein the blended jet boiling range composition comprises a T10 distillation point of 205° C. or less, a final boiling point of 300° C. or less, a freezing point of -40° C. or less, and a blended jet boiling range composition comprising i) 10% by weight or more of C9 hydrocarbons, ii) a flash point of 50° C. or more, or iii) a combination of i) and ii).

[0128] Embodiment 31. The composition of embodiment 30, wherein the composition comprises 1.0% to 30% by volume of the isoparaffin blend component.

[0129] Embodiment 32. The composition comprises 30% to 99% by volume of an isoparaffin blend component, and optionally, the composition comprises 1.5% by weight or more of C 17 -C 1832. The composition of any one of embodiments 29-31, comprising a hydrocarbon.

[0130] Embodiment 33. The composition of any one of embodiments 29-32, wherein the synthetic jet boiling range fraction comprises a bio-derived fraction, a Fischer-Tropsch fraction, or a combination thereof.

[0131] Embodiment 34. The composition of any one of embodiments 29-33, wherein the synthetic jet boiling range fraction comprises a jet boiling range fraction derived from a non-conventional source.

[0132] Embodiment 35. The composition of any one of embodiments 29-34, wherein the composition comprises 10% by volume or more of an isoparaffin blend component, 10% by volume or more of a synthetic jet boiling range fraction, or a combination thereof.

[0133] Embodiment 36. The composition of any one of embodiments 29-35, wherein the composition further comprises 1.0 wt.% or more of a conventional jet fuel, a mineral jet boiling range fraction, or a combination thereof.

[0134] Embodiment 37. The composition of any one of embodiments 29-36, wherein the composition comprises a ratio of Hd hydrogen to Hc2 hydrogen of 1.10 to 2.20.

[0135] Embodiment 38. The composition of any one of embodiments 29-36, wherein the composition comprises a ratio of Hd hydrogen to Hc2 hydrogen of 0.50 to 1.0.

[0136] Embodiment 39. The composition of any one of embodiments 29-38, wherein the isoparaffin blend component contains 1.0 volume percent or less aromatics, or the composition contains 20 weight percent or less aromatics, or a combination thereof.

[0137] Embodiment 40. The composition comprises 0.1% by weight to 1.0% by weight of C 19+ 40. The composition of any one of embodiments 29-39, comprising a hydrocarbon.

[0138] Embodiment 41. The composition of any one of embodiments 29-40, wherein the isoparaffin blend component comprises 5.0 wt.% or less of compounds different from isoparaffins and iso-olefins.

[0139] Embodiment 42. The composition of any one of embodiments 29 to 41, wherein the composition comprises a fuel that meets the specifications for jet fuel according to at least one of ASTM D1655, UK Ministry of Defence Standard 91-091, and Canadian General Standards Board 3.23.

[0140] Embodiment 43. The composition comprises 3.0 wt.% or less of C 8- 43. The composition of any one of embodiments 29 to 42, comprising a compound.

[0141] Embodiment 44. The composition of any one of embodiments 29-43, wherein the isoparaffin blend component comprises a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, and a freezing point of -40°C or less.

[0142] Although the present invention has been described and illustrated with reference to specific embodiments, those skilled in the art will recognize that the invention accommodates variations not necessarily exemplified herein, and therefore, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.

Claims

1. 1. A blended jet boiling range composition comprising at least 80% by volume of isoparaffins, at most 5.0% by volume of olefins, and at most 5.0% by volume of C １９＋ % to 99 vol. % of an isoparaffin blend component containing hydrocarbons, and 1.0 vol. % to 99 vol. % of a synthetic jet boiling range fraction, said synthetic jet boiling range fraction comprising: a) less than 80 wt. % isoparaffins; b) a hydrogen to Hc ratio of 1.6 or greater; ２ c) having a ratio of Hd hydrogen to Hc of 1.0 or less; ２ d) a combination of a) and b), or e) a combination of a) and c), wherein the blended jet boiling range composition has a T10 distillation point of 205° C. or less, a final boiling point of 300° C. or less, a freezing point of −40° C. or less, and a C ratio of 1.0 wt. % or greater. １７ -C １８ A blended jet boiling range composition comprising a hydrocarbon.

2. 1. A blended jet boiling range composition comprising at least 80 wt.% isoparaffins, at most 5.0 wt.% olefins, and at most 5.0 wt.% C １９＋ % to 99 vol. % of an isoparaffin blend component containing hydrocarbons, and 1.0 vol. % to 99 vol. % of a synthetic jet boiling range fraction, said synthetic jet boiling range fraction comprising: a) less than 80 wt. % isoparaffins; b) a hydrogen to Hc ratio of 1.6 or greater; ２ c) having a ratio of Hd hydrogen to Hc of 1.0 or less; ２ d) a combination of a) and b), or e) a combination of a) and c), wherein the blended jet boiling range composition comprises a T10 distillation point of 205° C. or less, a final boiling point of 300° C. or less, a freezing point of −40° C. or less, and i) 10 wt. % or more C ９ a blended jet boiling range composition comprising a hydrocarbon, ii) a flash point of 50° C. or greater, or iii) a combination of i) and ii).

3. 3. The composition of claim 2, wherein the composition comprises from 1.0% to 30% by volume of the isoparaffin blend component.

4. The composition comprises 30% to 99% by volume of the isoparaffin blend component, and optionally, the composition comprises 1.5 wt.% or more of C １７ -C １８ The composition of any one of claims 1 to 3, comprising a hydrocarbon.

5. 5. The composition of any one of claims 1 to 4, wherein the synthetic jet boiling range fraction comprises a bio-based fraction, a Fischer-Tropsch fraction, or a combination thereof.

6. 6. The composition of any one of claims 1 to 5, wherein the synthetic jet boiling range fraction comprises a jet boiling range fraction derived from a non-conventional source.

7. 7. The composition of any one of claims 1 to 6, wherein the composition comprises 10% by volume or more of the isoparaffin blend component, 10% by volume or more of the synthetic jet boiling range fraction, or a combination thereof.

8. 8. The composition of any one of claims 1 to 7, wherein the composition further comprises 1.0 wt.% or more of a conventional jet fuel, a mineral jet boiling range fraction, or a combination thereof.

9. The composition has a hydrogen to Hc ratio of 1.10 to 2.

20. ２ The composition of any one of claims 1 to 8, comprising a ratio of hydrogen.

10. The composition has a hydrogen to hydrogen ratio of 0.50 to 1.

0. ２ The composition of any one of claims 1 to 8, comprising a ratio of hydrogen.

11. 11. The composition of any one of claims 1 to 10, wherein the isoparaffin blend component contains 1.0 volume percent or less aromatics, or the composition comprises 20 weight percent or less aromatics, or a combination thereof.

12. The composition comprises 0.1% to 1.0% by weight of C １９＋ The composition of any one of claims 1 to 11, comprising a hydrocarbon.

13. 13. The composition of any one of claims 1 to 12, wherein the isoparaffin blend component comprises up to 8.0 wt.% of compounds different from isoparaffins and iso-olefins.

14. 14. The composition of any one of claims 1 to 13, wherein the composition comprises a fuel that meets jet fuel specifications according to at least one of ASTM D1655, UK Ministry of Defense Standard 91-091, and Canadian General Standards Board 3.

23.

15. The composition comprises 3.0 wt. % or less of C ８－ The composition according to any one of claims 1 to 14, comprising a compound.

16. 16. The composition of any one of claims 1 to 15, wherein the isoparaffin blend component comprises a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, and a freezing point of -40°C or less.

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