Process for converting C2 + olefins to higher carbon number olefins useful for producing isoparaffin kerosene compositions

Abstract

A process for producing a blended jet boiling range composition stream can include: oligomerizing an ethylene stream to a C4 + olefin stream in a first olefin oligomerization unit, wherein the C4 + olefin stream contains no greater than 10 wt% combined methane, ethylene, and ethane; wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and each no more than 20 wppm carbon monoxide and hydrogen; oligomerizing the C4 + olefin stream and the propylene / C4 + olefin stream in a second oligomerization unit to produce an isoolefin stream; subjecting at least a portion of the isoolefin stream to a hydrotreating process with hydrogen as a process gas to produce an isoparaffin stream having an olefin content of not greater than 10 wt%; and generating a blended jet boiling range using at least a portion of the isoparaffin stream.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 202380032729.4, filed on April 4, 2023, with International Application No. PCT / US2023 / 017451, entitled "Method for converting C2+ olefins into higher carbon number olefins that can be used to produce isoparaffinic kerosene compositions". Technical Field

[0002] This application relates to a method for converting C2+ olefins into olefins with higher carbon numbers. The higher carbon olefins can be used to produce isoparaffinic kerosene compositions. Background Technology

[0003] Olefins are valuable feedstocks in chemical manufacturing. For example, light olefins such as ethylene and propylene can be used in polymerization reactions. Higher carbon olefins, such as C6+ and C8+ olefins, which can be produced by oligomerizing light olefins, can be used to produce specialty surfactants, lubricants, jet / aviation fuels, diesel fuels, fuel additives, etc. Many oligomerization catalyst systems have been studied to increase the yield of preferred higher carbon olefins, and even achieve higher yields. However, the steps for upgrading light olefins to higher carbon olefins remain reasonably unchanged. Summary of the Invention

[0004] This application relates to a method for converting C2+ olefins into olefins with higher carbon numbers.

[0005] A non-limiting example method for producing a blended jet-boiling-range composition stream includes: oligomerizing an ethylene stream into a C4+ olefin stream in a first olefin oligomerization unit comprising a series reactor and a light removal tower, wherein the C4+ olefin stream contains no more than 10 wt% of combined methane, ethylene, and ethane; wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm each of carbon monoxide and hydrogen; oligomerizing the C4+ olefin stream and a propylene / C4+ olefin stream in a second oligomerization unit to produce an isoolefin stream; subjecting at least a portion of the isoolefin stream to a hydrogenation process using hydrogen as a process gas to produce an isoparaffin stream with an olefin content of no more than 10 wt%; and using at least a portion of the isoparaffin stream to produce the blended jet-boiling-range composition, the blended jet-boiling-range composition comprising: 30 vol% to 99 vol%. The isoparaffin blend component, vol%, derived from the isoparaffin stream containing 80 wt% or more isoparaffins, 5.0 wt% or less olefins and 5.0 wt% or less C19+ hydrocarbons; 1.0 vol% to 70 vol% mineral jet boiling range fraction; and a T10 distillation point of 205°C or lower, a final boiling point of 300°C or lower, a freezing point of -40°C or lower, and 2.0 wt% or more C17-C18 hydrocarbons.

[0006] A non-limiting example method for producing a blended jet boiling range composition includes: providing a raw olefin stream comprising ethylene, propylene, and C4+ olefins, wherein at least 10 wt% of all olefins in the raw olefin stream is ethylene, and further containing at least 1000 wppm of methane and ethane, and at least 100 wppm of carbon monoxide and hydrogen, respectively; subjecting the raw olefin stream to a separation operation to remove hydrogen, carbon monoxide, propylene, and C4+ olefins from the raw olefin stream, and producing an ethylene stream containing at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm of carbon monoxide and hydrogen, respectively, wherein at least 95 wt% of all ethylene in the raw olefin stream is recovered in the ethylene stream; and providing at least a portion of the ethylene stream to a first olefin oligomerization unit comprising one or more tandem reactors and a light-removal tower to convert at least 90% of the ethylene contained in the ethylene stream into a mixture containing no more than 10 wt% ethylene in a single pass through the tandem reactors. A second C4+ olefin stream comprising wt% of combined methane, ethylene, and ethane; providing at least a portion of each of the propylene and the C4+ olefins removed from the original olefin stream and at least a portion of the second C4+ stream to a second olefin oligomerization unit to produce an isoolefin stream; subjecting at least a portion of the isoolefin stream to a hydrogenation process using hydrogen as a process gas to produce an isoparaffin stream with an olefin content not exceeding 10 wt%; and using at least a portion of the isoparaffin stream to produce the blended jet boiling range composition comprising: 30 vol% to 99 vol% of an isoparaffin blend component derived from the isoparaffin stream containing 80 wt% or more of isoparaffins, 5.0 wt% or less of olefins, and 5.0 wt% or less of C19+ hydrocarbons; 1.0 vol% to 70 vol% of... vol% of mineral jet boiling range fractions; and T10 distillation point of 205°C or lower, final boiling point of 300°C or lower, freezing point of -40°C or lower, and 2.0 wt% or more of C17-C18 hydrocarbons.

[0007] These and other features and properties of the methods disclosed herein, and their advantageous applications and / or uses, will become apparent from the following detailed description. Attached Figure Description

[0008] To assist those skilled in the art in making and using the subject matter herein, reference is made to the accompanying drawings. These drawings are included to illustrate certain aspects of this disclosure and should not be considered an exclusive configuration. As will be apparent to those skilled in the art who benefit from this disclosure, the disclosed subject matter is capable of considerable modifications, alterations, combinations, and equivalents in form and function.

[0009] Figure 1 Non-limiting examples of the methods disclosed herein are shown.

[0010] Figure 2 Non-limiting examples of the methods disclosed herein are shown.

[0011] Figure 3 Non-limiting examples of the methods disclosed herein are shown.

[0012] Figure 4 Non-limiting examples of the methods disclosed herein are shown.

[0013] Figure 5 Non-limiting examples of the methods disclosed herein are shown.

[0014] Figure 6 The compositional information of the isoparaffin blend components and the blend of conventional jet fuel is shown.

[0015] Figure 7 The composition information of another isoparaffin blend component and a blend of conventional jet fuel is shown.

[0016] Figure 8 The components of the blend of isoolefins and isoalkanes are shown. 1 H NMR characterization results. Detailed Implementation

[0017] This application relates to a method for converting C2+ olefins into higher carbon number olefins. The olefins and / or the olefins converted into alkanes can be used in a variety of other applications, including fuels and fuel blend feedstocks. More specifically, the conversion may involve two oligomerization processes that can advantageously increase the overall ethylene conversion rate, while offering flexibility and efficiency that can provide energy and cost savings.

[0018] definition

[0019] All numerical values ​​in the specific embodiments and claims herein are modified by values ​​indicated by “about” or “approximately”, and take into account experimental errors and variations that can be expected by one of ordinary skill in the art.

[0020] In this discussion, a jet fuel or jet fuel blend component containing at least a portion of a synthetic jet fuel boiling range compound (i.e., a jet fuel boiling range compound not derived from processed mineral sources) is defined as a synthetic jet fuel or synthetic jet fuel blend component.

[0021] In this discussion, methanol obtained through various processes can be referred to as “sustainable” methanol if it is used as a feedstock for the formation of olefins. Examples of such processes may include, but are not limited to, reforming municipal waste, reforming biomass, fermenting biomass, electrolyzing water to produce hydrogen for reaction with carbon monoxide and / or carbon dioxide, and any combination thereof.

[0022] Commercial standards for jet fuels typically specify various properties. Examples of typical properties and specifications for commercial jet fuels 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 of 8.0 cSt or less at -20°C, a flash point of at least 38°C, an initial boiling point of 140°C or higher, a T10 distillation point of 205°C or less, and / or a final boiling point of 300°C or less. Another example of property specifications is the maximum deposit thickness on the heater tube surface and / or the 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 property specifications can be a water separation rating, such as 85 or higher, as measured according to ASTM D3948. The water separation grade provides an indication of the amount of surfactant present in a jet fuel boiling range sample. Various petroleum fractions with appropriate boiling ranges that also meet commercial standards can be tested (e.g., according to ASTM D3241) and certified for use as jet fuels. In some respects, kerosene boiling range fractions can correspond to jet fuel fractions that meet the specifications for jet fuels according to ASTM D1655. This can include thermal stability breaks of 260°C or higher, or 275°C or higher, as defined by ASTM D3241.

[0023] Unless otherwise specified, distillation point and boiling point can be determined according to ASTM D86. Note that other methods for characterizing boiling point may also be provided in the examples. Values ​​obtained by such other methods are considered indicative of values ​​obtained according to ASTM D86.

[0024] In this discussion, the boiling range of jet fuel or kerosene is defined as 140°C to 300°C. Jet fuel boiling range fractions or kerosene boiling range fractions are defined as fractions with a T10 distillation point of 140°C to 205°C or lower and a final boiling point of 300°C or lower. Note that the flash point of jet fuel boiling range fractions can sometimes be 38°C or higher, although kerosene boiling range fractions do not necessarily have such requirements.

[0025] In this discussion, hydrotreated fractions refer to hydrocarbon fractions and / or hydrocarbon-containing fractions that have been exposed to a catalyst with hydrotreated activity at a temperature of 200°C or higher in the presence of hydrogen at 300 kPa-a or higher. Examples of hydrotreated fractions include hydrotreated distillate fractions (i.e., hydrotreated fractions with a distillate boiling range), hydrotreated kerosene fractions (i.e., hydrotreated fractions with a kerosene boiling range), and hydrotreated diesel fractions (i.e., hydrotreated fractions with a diesel boiling range). Note that hydrotreated fractions derived from biological sources, such as hydrotreated vegetable oils, can be correlated with hydrotreated distillate fractions, hydrotreated kerosene fractions, and / or hydrotreated diesel fractions, depending on the boiling range of the hydrotreated fraction.

[0026] Various methods can be used to determine the properties of kerosene / jet boiling range fractions and / or blends of such fractions with other components to form kerosene / jet boiling range fuels. The density of the blend at 15°C (kg / m³) is also considered. 3 The following parameters can be determined according to ASTM D4052: Sulfur (in wppm or wt%) can be determined according to ASTM D2622, while nitrogen (in wppm or wt%) can be determined according to D4629. Kinematic viscosity at -20°C or -40°C (in cSt) can be determined according to ASTM D445. Pour point can be determined according to ASTM D5949. Cloud point can be determined according to D5773. Freezing point can be determined according to D5972. Flash point can be determined according to ASTM D56. Aromatic compound content can be determined according to ASTM D1319. Cetane number can be determined according to ASTM D613.

[0027] In this discussion, the contents of n-alkanes, isoalkanes, cycloalkanes, aromatic compounds, and / or alkenes can be determined according to the test method UOP 990. Note that for some alkanes, n-alkanes, and isoalkanes described below, the contents are determined by gas chromatography using the linear alkanes method. The n-alkanes peaks from hydrocarbon samples are well-known in gas chromatography. The n-alkanes peaks can be individually integrated to determine the n-alkanes content of the sample using gas chromatography. Peaks in the GC spectrum between n-alkanes peaks can be designated as isoalkanes with the same number of carbons as the next peak so that the total amount of alkanes with a given number of carbons can be determined. The isoalkanes content with a given number of carbons can be determined by subtracting the n-alkanes content from the total alkanes content. It is believed that the values ​​determined herein by the linear alkanes method represent values ​​obtained according to UOP 990.

[0028] As described above, UOP 990 can be used to determine the content of alkanes, cycloalkanes, and aromatic compounds. Note that supercritical fluid chromatography (SFC) was used for the content of some alkanes, cycloalkanes, and / or aromatic compounds described herein. SFC characterization values ​​are believed to represent values ​​obtained according to UOP 990. For SFC characterization, a commercial supercritical fluid chromatography system was used, and the method is an extension of the method described in ASTM D5186 to allow for the separate characterization of alkanes and cycloalkanes. The extension of the ASTM D5186 method is achieved by using additional separation columns to allow for the resolution of cycloalkanes and alkanes. The system is equipped with the following components: a high-pressure pump for delivering the supercritical carbon dioxide mobile phase; a temperature-controlled column oven; an autosampler with a high-pressure liquid injection valve for delivering sample material into the mobile phase; a flame ionization detector; a mobile phase separator (low dead volume tee); a back pressure regulator for maintaining CO2 in a supercritical state; and a computer and data system for controlling the components and recording data signals. For analysis, approximately 75 mg of sample is diluted in 2 mL of toluene and placed in a standard soundproof autosampler vial. The sample is introduced via a high-pressure sampling valve. SFC separation is performed using multiple commercial silica packed columns (5 μm, with 60 or 30 Å pores) connected in series (250 mm long, 2 mm or 4 mm ID). Column temperatures are typically maintained at 35 or 40 °C. For analysis, the column head is typically 250 bar. Liquid CO2 flow rates are typically 0.3 mL / min for 2 mm ID columns or 2.0 mL / min for 4 mm ID columns. The SFCFID signal is integrated into the alkane and cycloalkane regions. In addition to characterizing aromatic compounds according to ASTM D5186, supercritical fluid chromatography is used to analyze the splitting of total alkane and total cycloalkane in the sample. Various standards for typical molecular types can be used to calibrate the alkane / cycloalkane splitting for quantification.

[0029] As used herein, the term "alkanes" refers to saturated hydrocarbons that can be straight-chain or branched. Alkanes can be straight-chain or branched and are considered acyclic compounds. "Alkanes" is intended to encompass all structural isomers of alkanes. The term "n-alkanes" has the expected definition of straight-chain alkanes (without branches or rings in the carbon chain). The term "iso-alkanes" is used herein to refer to any alkane that contains one or more branches in its carbon chain but does not contain any ring structure. The term "alkanes" encompasses both the terms "n-alkanes" and "iso-alkanes".

[0030] In this discussion, the term "isoolefin" is similar to "isoalkane," but refers to an olefin rather than an alkane. Therefore, an isoolefin is defined as an olefin that contains at least one branch in its carbon chain but not a ring structure.

[0031] In this discussion, the term "naphthene" refers to a cycloalkane (also known as a cycloparaffin). Therefore, cycloalkane corresponds to a saturated ring structure. The term cycloalkane encompasses both monocyclic and polycyclic cycloalkanes. Polycyclic cycloalkane can have two or more rings, such as bicyclic, tricyclic, tetracyclic, pentacyclic, hexacyclic, heptacyclic, octacyclic, nonacyclic, and decacyclic rings. These rings can be fused and / or bridged. Cycloalkane can also contain various side chains, such as one or more alkyl side chains of 1-10 carbons.

[0032] In this discussion, the term "saturate" refers to all straight-chain, branched-chain, and cyclic-chain alkanes. Therefore, saturates correspond to combinations of alkanes and cycloalkanes.

[0033] In this discussion, the term "aromatic ring" refers to a ring structure in which five or six atoms are bonded, wherein (i) at least four of the atoms bonded in the ring structure are carbon atoms, and (ii) all the carbon atoms bonded in the ring structure are aromatic carbon atoms. Therefore, aromatic rings correspond to unsaturated ring structures. For example, 13 Aromatic carbons are identified using nuclear magnetic resonance (NMR). An aromatic ring has atoms attached to it (e.g., one or more heteroatoms, one or more carbon atoms, etc.) but not part of the ring structure, which fall within the scope of the term "aromatic ring." Additionally, note that ring structures containing one or more heteroatoms (such as sulfur, nitrogen, or oxygen) can also correspond to "aromatic ring" if the ring structure otherwise falls within the definition of "aromatic ring."

[0034] In this discussion, the term "non-aromatic ring" means four or more carbon atoms bonded in at least one ring structure, wherein at least one of the four or more carbon atoms in the ring structure is not an aromatic carbon atom. Non-aromatic rings having atoms attached to the ring (e.g., one or more heteroatoms, one or more carbon atoms, etc.) but not part of the ring structure fall within the scope of the term "non-aromatic ring".

[0035] In this discussion, the term "aromatic compound" refers to all compounds containing at least one aromatic ring. Such compounds containing at least one aromatic ring include compounds having one or more hydrocarbon substituents. Note that compounds containing at least one aromatic ring and at least one non-aromatic ring fall within the definition of the term "aromatic compound".

[0036] Note that some hydrocarbons present in the feed or product may fall outside the definitions of alkanes, cycloalkanes, and aromatic compounds. For example, any olefin that is not part of an aromatic compound falls outside the above definitions. Similarly, non-aromatic compounds containing heteroatoms such as sulfur, oxygen, or nitrogen are not included in the definitions of alkanes or cycloalkanes.

[0037] As used herein, the term "Cx hydrocarbon" or "Cx" indicates a hydrocarbon molecule with the number of carbon atoms expressed in "x". The term "Cx+ hydrocarbon" indicates the aforementioned molecule having a number of carbon atoms expressed in "x" or greater. For example, "C17+ hydrocarbon" would include hydrocarbons with C17, C18, and higher carbon numbers. Similarly, "Cx- hydrocarbon" indicates the aforementioned molecule having a number of carbon atoms expressed in "x" or fewer.

[0038] Methods and compositions

[0039] Figure 1 A non-limiting example of method 100 of this disclosure is shown. The shown method 100 includes a first oligomerization 104 and a second oligomerization 110, and optionally a hydrogenation treatment 114. In short, an ethylene stream 102 undergoes the first oligomerization 104, which produces a C4+ olefin stream 106. The C4+ olefin stream 106 and the propylene / C4+ olefin stream 108 then undergo the second oligomerization 110. The second oligomerization 110 produces an isoolefin stream 112. The isoolefin stream 112 has many potential uses. In a non-limiting example, the isoolefin stream 112 undergoes hydrogenation treatment 114 and produces an isoalkane stream 116.

[0040] Ethylene stream 102 may contain at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm each of carbon monoxide and hydrogen (or (i) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen, or (ii) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 1 wppm each of carbon monoxide and hydrogen). Ethylene may be present in ethylene stream 102 in an amount of at least 50 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99.9 wt%, or 50 wt% to 99 wt%, or 60 wt% to 95 wt%, or 70 wt% to 90 wt%. Ethane may be present in ethylene stream 102 in an amount of at least 2000 wppm, or at least 5000 wppm, or at least 1 wt%, or at least 10 wt%, or at least 25 wt%, or at least 45 wt%, or 2000 wppm to 45 wt%, or 2000 wppm to 25 wt%, or 5000 wppm to 10 wt%. Methane may be present in ethylene stream 102 in an amount of not more than 1000 wppm, or not more than 500 wppm, or not more than 250 wppm, or 10 wppm to 1000 wppm, or 10 wppm to 250 wppm, or 100 wppm to 500 wppm, or 250 wppm to 1000 wppm. Each of carbon monoxide and hydrogen may be present in the ethylene stream 102 in amounts not greater than 20 wppm, not greater than 5 wppm, not greater than 1 wppm, or not greater than 0.5 wppm, or not greater than 0.1 wppm, or from 0.001 wppm to 20 wppm, or from 0.001 wppm to 5 wppm, or from 0.001 wppm to 1 wppm, or from 0.001 wppm to 0.5 wppm.

[0041] These two oligomers have similar chemical reactions, but are not the same steps. The chemicals involved in these steps can be achieved through very different processes. For example, the first oligomer 104 can be achieved with high efficiency and power in the liquid phase using a homogeneous catalyst. Conversely, the second oligomer 110, which produces higher molecular weight olefins such as propylene and butene, can be carried out more efficiently and effectively using a heterogeneous catalyst under conditions where some or all components are supercritical. By oligomerizing ethylene separately into higher molecular weight olefins (the first oligomer 104), the resulting olefins can be included as part of the feedstock in the second oligomer 110, thereby increasing the overall yield of higher molecular weight olefins (e.g., C10+ olefins). That is, the feedstock for the second oligomer 110 has a minimal amount of ethylene. In general, the process may benefit from using (a) a first oligomer catalyst specific for high-yield ethylene oligomerization and (b) a second oligomer catalyst that yields a high-yield range of olefins from an olefin feedstock with minimal ethylene content. Because the two oligomers are completed as separate processes (although the processes can be carried out in different parts of the same vessel), the overall method and system can have a higher yield of distillate range of olefins, which can then be used to produce isoparaffin streams and additional fuel products (e.g., distillates, jet fuel, kerosene, etc.).

[0042] When ethylene stream 102 undergoes a first oligomerization 104, at least 95% of the ethylene present in ethylene stream 102 can be converted to C4+ olefins (e.g., C4 olefins, C6 olefins, C8 olefins, and C10 olefins). C4+ olefin stream 106 contains no more than 10 wt% of combined methane, ethylene, and ethane (or (i) no more than 5 wt% of combined methane, ethylene, and ethane, or (ii) no more than 2000 wppm of combined methane, ethylene, and ethane, or (iii) no more than 1000 wppm of combined methane, ethylene, and ethane, or (iv) at least 10 wt% and no more than 10 wt% (or 2000 wppm or 1000 wppm) of combined methane, ethylene, and ethane). C4+ olefins may be present in the C4+ olefin stream 106 in an amount of at least 99 wt%, or at least 99.5 wt%, or at least 99.999 wt%, or from 99 wt% to 99.999 wt%.

[0043] The presence of small amounts of carbon monoxide and hydrogen in the ethylene stream 102 can allow for high conversion rates of ethylene to C4+ olefins in the first oligomer 104. For example, carbon monoxide and hydrogen can be detrimental to the catalyst system in the first oligomer 104, especially if nickel is used. However, the first oligomer 104 may be largely unaffected by saturated hydrocarbons such as methane and ethane, which can allow for higher concentrations of saturated hydrocarbons.

[0044] Ethylene stream 102 can originate from any suitable source, including but not limited to ethylene derived from ethanol dehydration reactions, steam crackers, fluidized catalytic crackers (FCCs), methanol catalytic conversion reactions commonly referred to as "methanol to olefins (MTO)," and any combination of sources. Note that most MTO processes can also satisfactorily convert other alcohols, such as ethanol or butanol, and / or ethers, such as dimethyl ether (DME) or diethyl ether (DEE), typically in proportion to methanol, to useful olefins, using the same catalysts and equipment, with fine-tuning of the rates and / or concentrations of various reaction products and contaminants. Other oxygen-containing molecules, such as ketones, aldehydes, and esters, can also be converted to olefins, but this is undesirable given their relative hydrogen deficiency compared to alcohols, which also results in more carbonaceous coke on the catalyst. Nevertheless, small amounts of the aforementioned oxygen-containing compounds are produced as byproducts of the MTO reaction, recovered in some form, and recycled back to the MTO reactor along with the main alcohol feed. Therefore, the more general term commonly used for these types of technologies is "oxygen-containing compound conversion to olefins."

[0045] The first oligomer 104 may occur in a first oligomer unit, which may include one or more reactors in series, typically a fixed-bed adiabatic reactor containing (or otherwise containing) an oligomer catalyst, or a continuous stirred tank reactor (CSTR) or pump circulation pipeline system for containing a homogeneous oligomer catalyst.

[0046] Examples of catalysts used in the first oligomer 104 may include, but are not limited to: (a) homogeneous catalysts, including (a1) homogeneous catalysts containing organoaluminum, nickel, titanium and / or zirconium or (a2) Ziegler-type catalysts, wherein (a1) or (a2) may optionally contain ligands for activating the metal and may optionally contain solvents such as hydrocarbons or ionic liquids such as cyclohexane; (b) heterogeneous catalysts, such as (b1) solid phosphoric acid, (b2) microporous materials, such as zeolites, for example ZSM-5 catalyst, ZSM-57 catalyst, ZSM-22 catalyst, ZSM-48 catalyst, ZSM-12 catalyst, or (b3) aluminosilicate phosphate (SAPO) molecular sieves; (c) such catalysts; and (d) any mixture thereof.

[0047] The first oligomer 104 can utilize a homogeneous organometallic catalyst. This can include, for example, nickel and other metal coordination catalysts, as described in "Oligomerization of Monoolefins by Homogeneous Catalysts," A. Forestière, *Oil & Gas Science and Technology - Rev. IFP*, Vol. 64 (2009), No. 6, pp. 649-667. Limiting the concentration of C10+ olefins to a small amount (e.g., no more than about 15 wt% of the total C4+ oligomer product) may be optimal for feeding the second oligomer 110. This can be achieved using the ethylene oligomerization process called DIMERSOL-E®, licensed by IFP (now Exxon), and the ethylene oligomerization process called Linear-1®, licensed by UOP. Second oligomer 110 can operate acceptablely well with C10+ olefins in the reactor system feed, but it operates most efficiently at relatively low concentrations of those components. C10+ molecules are already within the carbon number range of distillate products such as diesel and jet fuel, so the main benefit of feeding them to second oligomer 110 is to provide alkyl branches to the molecules (by adding lighter olefins) to lower their freezing point, but there is an increased risk of harmful cracking reactions that make higher carbon number olefins more susceptible to its effects.

[0048] The contact between the ethylene stream 102 and the first oligomerizing catalyst can be carried out under conditions suitable for low polyethylene. For example, the temperature can be from about 25°C to about 300°C (or from about 50°C to about 200°C). For example, the pressure can be from about 100 psia to about 2000 psia (or from about 200 psia to about 1200 psia, or from about 250 psia to about 1000 psia).

[0049] Propylene / C4+ olefin stream 108 and C4+ olefin stream 106 undergo a second oligomerization 110 (e.g., in a second oligomerization unit) to produce an isoolefin stream 112. Although shown as entering the second oligomerization 110 separately, the method may include mixing (or otherwise blending) propylene / C4+ olefin stream 108 and C4+ olefin stream 106 before undergoing the second oligomerization 110.

[0050] The second oligomer 110 that generates the isoolefin stream 112 may optionally utilize the method described in U.S. Patent 7,692,049, which is incorporated herein by reference in its entirety.

[0051] The propylene / C4+ olefin stream 108 may contain any single C3 to C9 olefin or a mixture thereof in any proportion. The propylene / C4+ olefin stream 108 may contain at least 50 wt% of C3+ olefins. The C3+ olefins may be present in the propylene / C4+ olefin stream 108 in amounts of at least 50 wt%, at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 95 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 95 wt%. The carbon number distribution of the C3+ olefins may vary based on the source of the propylene / C4+ olefin stream 108. For example, the propylene / C4+ olefin stream 108 may include at least 5 wt% propylene, at least 5 wt% C4 olefins, and C5+ olefins, such that the C3+ olefin concentration is at least 50 wt% of the propylene / C4+ olefin stream 108. C3 olefins may be present in the propylene / C4+ olefin stream 108 in an amount of at least 5 wt%, at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or 5 wt% to 80 wt%, or 5 wt% to 30 wt%, or 10 wt% to 50 wt%, or 25 wt% to 75 wt%, or 40 wt% to 80 wt%. C4 olefins may be present in the propylene / C4+ olefin stream 108 in an amount of at least 5 wt%, at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or 5 wt% to 80 wt%, or 5 wt% to 30 wt%, or 10 wt% to 50 wt%, or 25 wt% to 75 wt%, or 40 wt% to 80 wt%. C5 olefins may be present in the propylene / C4+ olefin stream 108 in an amount of at least 5 wt%, at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or 5 wt% to 80 wt%, or 5 wt% to 30 wt%, or 10 wt% to 50 wt%, or 25 wt% to 75 wt%, or 40 wt% to 80 wt%. C6 olefins may be present in the propylene / C4+ olefin stream 108 in an amount of at least 5 wt%, at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or 5 wt% to 80 wt%, or 5 wt% to 30 wt%, or 10 wt% to 50 wt%, or 25 wt% to 75 wt%, or 40 wt% to 80 wt%.In a non-limiting example, the propylene / C4+olefin stream 108 may include propylene, at least 5 wt% C4 olefins, at least 40 wt% C5 olefins, and at least 10 wt% C6 olefins. In another non-limiting example, the propylene / C4+olefin stream 108 may include propylene, at least 20 wt% C4 olefins, at least 40 wt% C5 olefins, and at least 10 wt% C6 olefins. In yet another non-limiting example, the propylene / C4+olefin stream 108 may include propylene, at least 40 wt% C4 olefins, at least 40 wt% C5 olefins, and at least 10 wt% C6 olefins.

[0052] The propylene / C4+ olefin stream 108 can come from any suitable source, including but not limited to C4+ byproducts derived from propane dehydrogenation reactors, butane dehydrogenation reactors, steam crackers, fluidized catalytic crackers (FCCs), methanol catalytic conversion reactions commonly referred to as "methanol to olefins (MTO)," and any combination of sources.

[0053] The second oligomer 110 can occur in an oligomer unit, which may include a fixed-bed adiabatic reactor containing (or otherwise containing) an oligomer catalyst, or an isothermal tubular reactor containing (or otherwise containing) an oligomer catalyst.

[0054] Examples of oligomerization catalysts that can be used for the second oligomer 110 may include, but are not limited to, zeolite families, including the MWW family (e.g., MCM-22). BEA family (e.g., zeolite β), FAU catalysts, MTW family (e.g., ZSM-12), TON family (e.g., ZSM-22), MTT family (e.g., ZSM-23). MRE family (e.g., ZSM-48), MFS family (e.g., ZSM-57), SAPO molecular sieves, and any mixture thereof.

[0055] The contact between the propylene / C4+ olefin stream 108 and the C4+ olefin stream 106 (introduced as a mixture or separately) and the second oligomerizing catalyst can be carried out under conditions suitable for oligomerizing the olefins. For example, the temperature can be from about 150°C to about 300°C (or from about 150°C to about 250°C, or from about 200°C to about 300°C). For example, the pressure can be from about 600 psia to about 2000 psia (or from about 600 psia to about 1200 psia, or from about 1000 psia to about 2000 psia).

[0056] The second oligomerization unit, or the unit between the second oligomerization unit and the hydrogenation treatment unit, can remove at least one light olefin (e.g., C3-C9 olefin, or C3 to C6 olefin, or C3 to C8 olefin) from the isoolefin stream 112. The light olefin can be recycled back as part of the feed to the oligomerization unit along with the propylene / C4+ olefin stream 108 and the C4+ olefin stream 106.

[0057] The second oligomer 110 produces an isoolefin stream 112. The composition of the isoolefin stream 112 depends in particular on the conditions of the second oligomer 110, the composition of the propylene / C4+ olefin stream 108, the composition of the C4+ olefin stream 106, and the catalyst.

[0058] The isoolefin stream 112 may primarily contain C6+ olefins (or C8+ olefins, or C9+ olefins). For example, the isoolefin stream 112 may contain at least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of C6+ olefins (e.g., C6 to C20 olefins) having no more than 20 wt% C5-olefins (or no more than 10 wt% C5-olefins, or no more than 5 wt% C5-olefins). In another example, the isoolefin stream 112 may contain at least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of C8+ olefins (e.g., C8 to C20 olefins) having no more than 20 wt% C7-olefins (or no more than 10 wt% C7-olefins, or no more than 5 wt% C7-olefins). In yet another example, the isoolefin stream 112 may contain at least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of C9+ olefins (e.g., C9 to C20 olefins) having no more than 20 wt% C8-olefins (or no more than 10 wt% C8-olefins, or no more than 5 wt% C8-olefins).

[0059] At least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of the olefins in the isoolefin stream 112 may be isoolefins.

[0060] For example, 80 wt% or more, or 90 wt% or more, or 94 wt% or more, or 97 wt% or more of the isoolefin stream 112 may be composed of C9 to C20 isoolefins. Further, 2.0 wt% to 25 wt%, or 2.0 wt% to 15 wt%, or 5.0 wt% to 25 wt%, or 5.0 wt% to 15 wt%, or 2.0 wt% to 10 wt% of the isoolefin stream 112 may be composed of C9 olefins (e.g., C9 isoolefins). Further, 1.0 wt% to 15 wt%, or 2.5 wt% to 15 wt% of the isoolefin stream 112 may be composed of C17+ olefins (e.g., C17+ isoolefins). In some aspects, 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 isoolefin stream 112 may consist of C17 and / or C18 olefins (e.g., C17 and / or C18 isoolefins). Further, the isoolefin stream 112 may contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less of C19+ olefins (e.g., C19+ isoolefins), such as being substantially free of C19+ hydrocarbons. Further, the isoolefin stream 112 may contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less of C8-olefins, such as being as low as 0.1 wt% or possibly still lower (i.e., substantially free of C8-olefins).

[0061] In another example, isoolefin stream 112 may contain 60 wt% to 90 wt% of C11 to C18 olefins (e.g., C11 to C18 isoolefins). Alternatively or concurrently, isoolefin stream 112 may contain 50 wt% to 75 wt% of C12 to C16 olefins (e.g., C12 to C16 isoolefins). This is particularly advantageous for suitability for further processing (e.g., hydrotreating), where the resulting product can be flexibly used as an aviation or diesel fuel.

[0062] Isoolefin stream 112 may contain reduced or minimal amounts of aromatic compounds. This may 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 of aromatic compounds, or as little as substantially no aromatic compounds.

[0063] The composition of isoolefin stream 112, or a portion thereof or fraction thereof, may be a suitable product for a variety of applications, or may be adapted for further processing into a suitable product for a variety of applications. For example, isoolefin stream 112 may be adapted for further processing to produce blend compositions (e.g., jet fuel blend feedstock, diesel fuel blend feedstock, distillate blend feedstock, kerosene blend feedstock, etc.), specialty chemicals (e.g., surfactants, lubricants, solvents, hydraulic and other working fluids, etc.). In a non-limiting example, a portion or all of isoolefin stream 112 may be further subjected to hydrogenation treatment 114 to produce isoalkane stream 116 (preferably with an olefin content of not more than 10 wt%).

[0064] Mild hydrotreating can typically convert isoolefins to isoalkanes while reducing or minimizing the reduction in carbon chain size in the fraction. Besides converting isoolefins to isoalkanes, hydrotreating kerosene fractions can also be used for desulfurization, denitrification, saturation of olefins, saturation of aromatic compounds, and / or for other purposes.

[0065] During hydrotreating, the feedstock, consisting part or all of a jet fuel boiling range fraction, is processed in a hydrotreating (or other hydrotreating) reactor containing one or more hydrotreating stages or beds. Optionally, the reaction conditions in the hydrotreating stages can be conditions suitable for reducing the sulfur content of the feed stream, such as conditions suitable for reducing the sulfur content of the feed stream to 500 wppm or less, or 100 wppm or less, or 10 wppm or less, such as as low as 0.5 wppm or possibly still lower. Reaction conditions can consist of 0.1 to 20.0 hr. -1 The reaction conditions include an LHSV of about 50 psig (0.34 MPag) to about 3000 psig (20.7 MPag), a process gas containing at least about 50% hydrogen, and a temperature of about 450℉ (232°C) to about 800℉ (427°C). Preferably, the reaction conditions include about 0.3 to about 5 hours. -1 The LHSV, hydrogen partial pressure of about 100 psig (0.69 MPag) to about 1000 psig (6.9 MPag), and temperature of about 700℉ (371℃) to about 750℉ (399℃).

[0066] Optionally, a hydrotreating reactor operating at a relatively low total pressure can be used, such as a total pressure of about 200 psig (1.4 MPag) to about 800 psig (5.5 MPag). For example, the pressure in a stage of the hydrotreating reactor can be at least about 200 psig (1.4 MPag), or at least about 300 psig (2.1 MPag), or at least about 400 psig (2.8 MPag), or at least about 450 psig (3.1 MPag). The pressure in a stage of the hydrotreating reactor can be about 800 psig (5.5 MPag) or less, or about 700 psig (4.8 MPag) or less, or about 600 psig (4.1 MPa) or less.

[0067] The catalyst in the hydrotreating stage can be a conventional hydrotreating catalyst, such as a catalyst composed of Group VIB and / or Group VIII metals on a support. Suitable metals include cobalt, nickel, molybdenum, tungsten, or combinations thereof. Preferred metal combinations include nickel and molybdenum, or nickel, cobalt, and molybdenum. Suitable supports include silica, silica-alumina, alumina, and titanium dioxide.

[0068] The isoalkane stream 116 from hydrotreating 114 is suitable for producing blend compositions (e.g., jet fuel blend feedstock, diesel fuel blend feedstock, distillate blend feedstock, kerosene blend feedstock, etc.). Advantageously, the isoolefin stream 112 and the resulting isoalkane stream 116 can have a low aromatic content, which may be advantageous for producing fuels with low aromatic content (e.g., jet fuel, jet fuel blend feedstock).

[0069] The isoalkane stream 116 may have a similar carbon number distribution to the isoolefin stream 112, but is an alkane rather than an olefin. Therefore, the isoalkane stream 116 may mainly contain C6+ isoalkane (or C8+ isoalkane, or C9+ isoalkane). For example, the isoparaffin stream 116 may contain at least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of C6+ alkanes (e.g., C6 to C20 alkanes) having no more than 20 wt% of C5-alkanes (or no more than 10 wt% of C5-alkanes, or no more than 5 wt% of C5-alkanes). In another example, the isoalkane stream 116 may contain at least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of C8+ alkanes (e.g., C8 to C20 alkanes) having no more than 20 wt% of C7-alkanes (or no more than 10 wt% of C7-alkanes, or no more than 5 wt% of C7-alkanes). In yet another example, the isoalkane stream 116 may contain at least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of C9+ alkanes (e.g., C9 to C20 alkanes) having no more than 20 wt% of C8-alkanes (or no more than 10 wt% of C8-alkanes, or no more than 5 wt% of C8-alkanes).

[0070] At least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of the alkanes in stream 116 may be isoparaffins.

[0071] For example, 80 wt% or more, or 90 wt% or more, or 94 wt% or more, or 97 wt% or more of the isoparaffin stream 116 may be composed of C9 to C20 isoparaffins. Further, 2.0 wt% to 25 wt%, or 2.0 wt% to 15 wt%, or 5.0 wt% to 25 wt%, or 5.0 wt% to 15 wt%, or 2.0 wt% to 10 wt% of the isoparaffin stream 116 may be composed of C9 alkanes (e.g., C9 isoparaffins). Further, 1.0 wt% to 15 wt%, or 2.5 wt% to 15 wt% of the isoparaffin stream 116 may be composed of C17+ alkanes (e.g., C17+ isoparaffins). In some aspects, 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 isoparaffin stream 116 may consist of C17 and / or C18 alkanes (e.g., C17 and / or C18 isoparaffins). Further, the isoparaffin stream 116 may contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less of C19+ alkanes (e.g., C19+ isoparaffins), such as being virtually free of C19+ hydrocarbons. Furthermore, the isoparaffin stream 116 may contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less of C8-paraffins, such as as low as 0.1 wt% or possibly still lower (i.e., substantially free of C8-paraffins).

[0072] In another example, the isoparaffin stream 116 may contain 60 wt% to 90 wt% of C11 to C18 alkanes (e.g., C11 to C18 isoparaffins). Alternatively or additionally, the isoparaffin stream 116 may contain 50 wt% to 75 wt% of C12 to C16 alkanes (e.g., C12 to C16 alkanes). This is particularly advantageous for suitability for further processing (e.g., hydrotreating), where the resulting product can be flexibly used as an aviation or diesel fuel.

[0073] Isoparaffin stream 116 may contain reduced or minimal amounts of aromatic compounds. This may 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 of aromatic compounds, or as little as substantially no aromatic compounds.

[0074] Although Figure 1 The description provides non-limiting examples of the sources of ethylene stream 102 and propylene / C4+ olefin stream 108, but... Figure 1 The source was not cited. Figure 2 Non-limiting examples of processes are shown that include potential sources of both ethylene stream and propylene / C4+ olefin stream for converting oxygen-containing compounds into olefins and then separating the olefin products.

[0075] Figure 2 A non-limiting example method 200 of this disclosure is illustrated, showing an oxygen-to-olefin reaction 220 followed by separation 226 of the products from the oxygen-to-olefin process 220, a first oligomer 204, and a second oligomer 210. In short, an oxygen-containing compound stream 218 (e.g., comprising methanol and optionally dimethyl ether) undergoes the oxygen-to-olefin reaction 220, producing a water stream 222 and a raw olefin stream 224. The raw olefin stream 224 then undergoes separation 226 to produce an ethylene stream 202 and a propylene / C4+ olefin stream 208. The ethylene stream 202 then undergoes the first oligomer 204 to produce a C4+ olefin stream 206. The propylene / C4+ olefin stream 208 and the C4+ olefin stream 206 can then be used for various applications. In the illustrated example, the propylene / C4+ olefin stream 208 and the C4+ olefin stream 206 are inputs to the second oligomer 210 to produce an isoolefin stream 212. In alternative embodiments, the second oligomer can be excluded, and propylene / C4+olefin stream 208 and C4+olefin stream 206 can be used as feedstocks for other processes.

[0076] The oxygen-containing compound stream 218 can originate from any suitable source. In non-limiting examples, the oxygen-containing compound (e.g., methanol) can be produced by reforming natural gas, reforming coal, reforming municipal waste, reforming biomass, fermenting biomass, electrolyzing water to produce hydrogen for reaction with carbon monoxide and / or carbon dioxide, and any combination thereof. Typically, water electrolysis produces hydrogen and oxygen. The hydrogen can then react with carbon monoxide and / or carbon dioxide to produce methanol.

[0077] Examples of methanol conversion catalysts that can be used for reactions 220 involving oxygen-containing compounds to olefins may include, but are not limited to, microporous materials such as zeolites, SAPO, and ALPO. Such materials may include, but are not limited to, the zeolite family, specifically the MWW family (e.g., MCM-22). The BEA family (e.g., zeolite β), ZSM-11, (MEL) family (e.g., ZSM-12), TON family (e.g., ZSM-22), and MTT family (e.g., ZSM-23) are all mentioned. MRE family (e.g., ZSM-48), MFS family (e.g., ZSM-57), ZSM-5 (MFI), ALPO-18 (AEI) and SAPO-34 (CHA) or mixtures thereof (containing symbionts).

[0078] The contact between the oxygen-containing compound stream 218 and the methanol conversion catalyst can be carried out under conditions suitable for olefin production. For example, the inlet temperature can be from about 300°C to about 625°C (or from about 400°C to about 600°C, or from about 450°C to about 550°C). For example, the pressure can be from about 20 psia to about 300 psia (or from about 30 psia to about 250 psia, or from about 50 psia to about 150 psia).

[0079] The reaction 220 from oxygenated compounds to olefins can occur in a fixed-bed adiabatic reactor that contains (or otherwise contains) a methanol conversion catalyst and receives an input of an oxygenated compound stream 218.

[0080] The resulting primary olefin stream 224 may include ethylene, propylene, and C4+ olefins, wherein at least 10 wt% of all olefins in the stream may be ethylene. Primary olefin stream 224 may further include at least 1000 wppm each of methane and ethane, and at least 100 wppm each of carbon monoxide and hydrogen. In other aspects, primary olefin stream 224 may include other components with volatility ranging from hydrogen to butane, such as propane or dimethyl ether. The exact composition of primary olefin stream 224 will depend on the specific method used to produce primary olefin stream 224, and further on the specific means of operating these methods.

[0081] The raw olefin stream 224 may have been treated by various methods (e.g., in the unit where the reaction 220 from oxygen-containing compounds to olefins occurs or downstream) to remove some byproducts generated by the given olefin-producing method. Such methods and related systems can be used for the raw olefin stream 224 within the scope of this disclosure, but not in… Figure 2 The following is illustrated. Examples of such methods may include, but are not limited to, reactor effluent quenching and large-volume water removal, gas compression, washing with a caustic alkali solution to remove carbon dioxide, gas drying to complete dryness, separation of C5+ species from C4 species, or selective saturation with hydrogen to remove acetylene and methylacetylene, as well as other methods well described in the art. Those skilled in the art can readily modify this disclosure to use a raw olefin stream 224 derived from various olefin-generating processes. It is also useful to combine olefin streams from different sources or processes. In a non-limiting example, ethylene derived from an ethanol dehydration reaction may be combined with hydrogen, CO, propylene, unreacted propane, and C4+ byproducts derived from a propane dehydrogenation reaction to produce raw olefin stream 224.

[0082] The original olefin stream 224 then undergoes separation 226 to produce an ethylene stream 202 and a propylene / C4+ olefin stream 208. Separation 226 can occur within a separation system. Examples of separation devices that can be included in a separation system include, but are not limited to, fractionators, membranes, and any combination thereof.

[0083] Separation 226 can occur in the same unit or downstream unit as reaction 220 from oxygen-containing compounds to olefins.

[0084] Separation 226 involves the use of equipment such as flash tanks and distillation columns to address differences in component volatility, which can be configured in various ways to produce an ethylene stream 202 exiting separation 226. Hydrogen, carbon monoxide, propylene, and C4+ olefins can be separated from the original olefin stream 224 to produce ethylene stream 202. Ethylene stream 202 may contain at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm each of carbon monoxide and hydrogen (or (i) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen, or (ii) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 1 wppm each of carbon monoxide and hydrogen), and at least 95 wt% of all ethylene in the original olefin stream 224 may be recovered in ethylene stream 202. Ethylene stream 202 may also contain at least 90% of the ethane present in the original olefin stream 224. Separator 226 creates a separate pipeline for lower volatile components, such as propylene and C4+ olefins, to be separated from ethylene and ethane in ethylene stream 202. These components exit the separation as propylene / C4+ olefin stream 208. Instead of distillation columns, or in addition to distillation columns, the separation process may also include membrane and absorption systems. Figure 1 The compositional description of ethylene stream 102 is applicable Figure 2 Ethylene flow 202.

[0085] Figure 2 The propylene / C4+ olefin stream 208 after separation 226 is shown as a single stream, but propylene / C4+ olefin stream 208 can be two separate streams (e.g., a first stream comprising relatively pure propylene and a second stream comprising relatively pure C4+ olefins). This additional separation can be carried out using a separate distillation column and can include the separation of propylene from propane and similar or lower volatile components such as dimethyl ether. This process, referred to in the art as a "propylene concentrator," is particularly useful if the olefin source is an oxygen-containing compound conversion that can produce a significant amount of dimethyl ether, or a catalytic cracking that can produce a significant amount of propane, neither of which is particularly desirable to provide for an optional second oligomer 210.

[0086] Figure 1 The disclosures for ethylene stream 102, first oligomer 104, C4+ olefin stream 106, propylene / C4+ olefin stream 108, second oligomer 110, and isoolefin stream 112 are applicable to Figure 2The ethylene stream 202, the first oligomer 204, the C4+ olefin stream 206, the propylene / C4+ olefin stream 208, the second oligomer 210, and the isoolefin stream 212. Further embodiments may include additional processing of the isoolefin stream 212, such as as discussed in relation to additional processing of the isoolefin stream 112, including hydrogenation to produce an isoalkane stream.

[0087] Figure 3 Non-limiting examples of the method 300 of this disclosure are shown, wherein a non-limiting example separation 326 is described. This relates to having with Figure 1 and / or Figure 2 The disclosure of steps, flows, processes, units, etc. (e.g., propylene / C4+ olefin flow 108) corresponding to the last two reference numerals in the aforementioned figures is applicable to those having the same... Figure 3 The last two labels in the figure correspond to the same steps, streams, processes, units, etc. (e.g., propylene / C4+ olefin stream 308). However, in Figure 3 The separation 326 shown is a non-limiting example of a separation and is one of many possible separations that can be used for the separations shown in any other figures in this disclosure.

[0088] As shown, the original olefin stream 324 undergoes separation 326 to remove hydrogen, carbon monoxide, propylene, and C4+ olefins from ethylene and ethane. In short, separation 326 produces three separate streams, wherein (1) a higher volatile component (e.g., methane, hydrogen, and carbon monoxide) forms a high-volatility stream 334, (2) a lower volatile component (e.g., propylene and C4+ olefins) forms a propylene / C4+ olefin stream 308, and (3) a medium volatile component (e.g., ethylene and ethane) forms an ethylene stream 302.

[0089] In separation 326, the raw olefin stream 324 is first introduced into a deethanizer distillation column 328, which separates lower volatile components (e.g., propylene and C4+ olefins) from higher and medium volatile components (e.g., ethylene, ethane, methane, carbon monoxide, and hydrogen) to produce a propylene / C4+ olefin stream 308 and a first overhead stream 330, respectively. The first overhead stream 330 is then directed to a demethanizer distillation column 332 to separate higher volatile components from medium volatile components to produce a high-volatility stream 334 and an ethylene stream 302. Ethylene stream 302 may contain at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm each of carbon monoxide and hydrogen (or (i) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen, or (ii) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 1 wppm each of carbon monoxide and hydrogen), and at least 95 wt% of all ethylene in the original olefin stream 324 may be recovered in ethylene stream 302. In this embodiment, ethylene stream 302 may also contain at least 90% of the ethane present in the original olefin stream in line 324, which eliminates the need for a distillation column (referred to in the art as a "C2 splitter") for separating ethylene from ethane.

[0090] The ethylene stream 302 then undergoes a first oligomerization 304, which produces a C4+ olefin stream 306. The C4+ olefin stream 306 and the propylene / C4+ olefin stream 308 are then used as feed in a second oligomerization 310. As shown, the C4+ olefin stream 306 and the propylene / C4+ olefin stream 308 are combined into a feed stream 338, which enters the second oligomerization 310. The second oligomerization 310 produces the desired isoolefin stream 312. Further embodiments may include additional processing of the isoolefin stream 312, such as as discussed regarding additional processing relative to the isoolefin stream 112, including hydrogenation to produce an isoalkane stream.

[0091] Figure 4 Non-limiting examples of the method 400 of this disclosure are shown, wherein a non-limiting example first oligomer 404 is described. This relates to having with Figure 1 , Figure 2 and / or Figure 3 The disclosure of steps, flows, processes, units, etc. (e.g., propylene / C4+ olefin flow 108) corresponding to the last two reference numerals in the aforementioned figures is applicable to those having the same... Figure 3The last two labels in the figure correspond to the same steps, streams, processes, units, etc. (e.g., propylene / C4+ olefin stream 308). However, in Figure 4 The first oligomeric 404 shown is a non-limiting example of a separation and is one of many possible separations that can be used for the separations shown in any other figures in this disclosure.

[0092] In short, the original olefin stream 424 undergoes separation 426 to produce at least two streams: an ethylene stream 402 and a propylene / C4+ olefin stream 408, and optionally a highly volatile stream 434 (e.g., when according to...). Figure 3 (During separation 326, separation 426 is performed). Ethylene stream 402 then undergoes a first oligomerization 404, which can convert at least 95% of the ethylene present in ethylene stream 402 into C4+ olefin stream 406. C4+ olefin stream 406 may contain no more than 10 wt% of combined methane, ethylene, and ethane (or (i) no more than 5 wt% of combined methane, ethylene, and ethane, or (ii) no more than 2000 wppm of combined methane, ethylene, and ethane, or (iii) no more than 1000 wppm of combined methane, ethylene, and ethane, or (iv) at least 10 wt% and no more than 10 wt% (or 2000 wppm or 1000 wppm) of combined methane, ethylene, and ethane). C4+ olefin stream 406 and propylene / C4+ olefin stream 408 then undergo a second oligomerization 410. Although optional, as shown, streams 406 and 408 are combined into feed stream 438 before the second oligomer 410 to produce isoolefin stream 412. Other embodiments may include further processing of isoolefin stream 412, such as as discussed in relation to further processing of isoolefin stream 112, including hydrogenation to produce isoalkane streams.

[0093] The first oligomerization process 404 may involve introducing an ethylene stream 402 into a reactor 442, where an oligomerization reaction occurs from the ethylene stream 402 to an intermediate C4+ olefin stream 444. The oligomerization may convert at least 95% of the ethylene in the ethylene stream 402 into C4+ oligomers in a single pass through reactor 442. The first oligomerization unit may comprise two or more reactors arranged in series, in which some product oligomers and unreacted ethylene hydrocarbon products from one reactor are fed as feed to the next reactor in series to convert additional ethylene into oligomer products. Alternatively, the first oligomerization unit may comprise two or more reactors arranged in parallel, for example, by splitting the feed into two streams to enter two separate reactors, increasing the overall capacity of the first oligomerization unit. Further, the first oligomerization unit may include a mixture of the aforementioned reactors, some arranged in parallel and others arranged in series.

[0094] The intermediate C4+ olefin stream 444 from reactor 442 is then introduced into a light fuel stream 446 to remove components with higher volatility than butene, as well as a potential trace amount of butene, to produce a light fuel stream 436. The higher volatile components in the light fuel stream 436 may primarily consist of methane, ethane, and unreacted ethylene. Using the light fuel stream 446 to separate saturated hydrocarbons like methane and ethane from the intermediate C4+ olefin stream 444 can advantageously reduce energy intensity and / or require fewer complex components compared to separating saturated hydrocarbons from the more readily volatile ethylene in an earlier separation 426. That is, the upstream separation may only produce two streams, with the higher volatile components remaining in the ethylene stream. These higher volatile components can then be removed in a first oligomerization reactor by including a light fuel stream downstream of the oligomerization reactor. The light fuel stream can be located within or downstream of the first oligomerization unit.

[0095] Another advantage of including a light hydrocarbon removal tower downstream of reactor 442 is that the first oligomerization reaction and the first oligomerization catalyst can be largely unaffected by saturated hydrocarbons, as saturated hydrocarbons are essentially inert in the first oligomerization reaction. Therefore, the requirement to separate saturated hydrocarbons in separator 426 can be relaxed or eliminated, resulting in significant energy and cost benefits.

[0096] Figure 5 Non-limiting examples of the methods 500 of this disclosure are shown, wherein a non-limiting example second oligomer 510 is described. This relates to having with Figure 1 , Figure 2 , Figure 3 and / or Figure 4 The disclosure of steps, flows, processes, units, etc. (e.g., propylene / C4+ olefin flow 108) corresponding to the last two reference numerals in the aforementioned figures is applicable to those having the same... Figure 3 The last two labels in the figure correspond to the same steps, streams, processes, units, etc. (e.g., propylene / C4+ olefin stream 308). However, in Figure 5 The second oligomer 510 shown in the figure is a non-limiting example of a separation and is one of many possible separations that can be used for the separations shown in any other figures in this disclosure.

[0097] As shown, the original olefin stream 524 enters separation 526, which produces an ethylene stream 502 and a propylene / C4+ olefin stream 508, as well as optionally a highly volatile stream 534 (e.g., when according to...). Figure 3 When separation 326 is performed (separation 526). Ethylene stream 502 undergoes first oligomerization 504 and separation, the first oligomerization and separation producing C4+ olefin stream 506 and optionally light fuel stream 436 (e.g., when using a light fuel removal tower, for example, like the first oligomerization 504, it can be adjusted according to the desired light fuel flow rate). Figure 4 The first oligomer 404 occurs.

[0098] The C4+ olefin stream 506 and the propylene / C4+ olefin stream 508 then undergo a second oligomerization 510. Optionally, as shown, the streams 506 and 508 are combined into a feed stream 538 before the second oligomerization 510 to produce an isoolefin stream 512.

[0099] The second oligomer 510 is shown to be carried out in a second oligomer unit, which includes a reactor 552, a mogas / distillate fractionation column 556, and a butane fractionation column 562.

[0100] Feed stream 538 is combined with top recirculation stream 568 and bottom recirculation stream 566 to form a combined second oligomerizing reactor feed stream 550 comprising C4-C10+ olefins, which may contain no more than about 10 wt% of C10+ olefins. The combined feed stream 550 is supplied to reactor 552, which produces reactor product 554 rich in distillate range C10+ olefins (e.g., C10+ isoolefins), as well as unreacted and freshly prepared C4-C9 olefins of various isomers.

[0101] The reactor product 554 is directed to a Murcos / distillate fractionator 556, which separates a C9- or C10- first Murcos stream 558 from a C10+ isoolefin stream 512. The C10+ isoolefin stream 512 is removed from the second oligomerization unit 510 and can be used for various applications. The C9- first Murcos stream 558 is split into two streams, typically the majority becoming the top recycle stream 568, and the remainder becoming the butanizer feed stream 560. The butanizer feed stream 560 is sent to a butanizer fractionator 562, which separates a C4- purge stream 540 from a C5+ second Murcos stream 564. The C4- purge stream 540 is removed from the second oligomerization unit 510, while the C5+ second Murcos stream 564 is split into two streams, with most of it becoming the bottom circulation stream 566 and the remainder becoming the Murcos product purge stream 548, which is also removed from the second oligomerization unit 510.

[0102] As described above, propylene / C4+ olefin stream 508 and C4+ olefin stream 506 can be introduced into reactor 552, respectively. Within the scope of this disclosure, depending on the exact composition involved, containing olefins and potentially low concentrations of contaminants, it may be desirable to supply each of streams 506 and 508 to a separation point within the second oligomerization unit. For example, C4+ olefin stream 508 may contain up to 15 wt% or even more of C10+ olefins already in the distillate range. To minimize the load on reactor 552, propylene / C4+ olefin stream 508 can be the feed gas to reactor 552, and C4+ olefin stream 506 can be added directly to the Murcox / distillate fractionation column 556. In this way, the Murcox / distillate fractionation column 556 directly separates C10+ molecules in the C4+ olefin stream 506 into an isoolefin stream 512, and separates low-carbon molecules in the C4+ olefin stream 506 into Murcox range material 558, most of which becomes the recycle feed to reactor 552 to generate another isoolefin stream 512.

[0103] Another embodiment may include further processing of the isoolefin stream 512, such as the further processing discussed relative to the isoolefin stream 112, including hydrogenation to produce an isoalkane stream.

[0104] Isoparaffin blend components for use in blending jet / kerosene boiling range products

[0105] In all aspects, isoparaffin blend components (e.g., Figure 1-5 All or part of the isoalkane stream discussed herein can be used to form products that can be blended with jet fuel and / or jet fuel blending components. Optionally, isoolefin blending components can be used instead of isoalkane blending components or in addition to isoalkane blending components.

[0106] In this discussion, for isoparaffin blends or isoolefin blends, the fraction will contain 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 isoolefins, such as a fraction consisting at most substantially of isoparaffins and isoolefins (i.e., less than 5.0 wt%, or less than 3.0 wt%, or less than 1.0 wt% of other types of hydrocarbons / compounds, such as as low as zero). Apart from the foregoing, an isoparaffin blend refers to a fraction containing less than 5.0 wt% of isoolefins and 80 wt% or more, or 85 wt% or more, or 90 wt% or more of isoparaffins (relative to the weight of the fraction), such as at most substantially all fractions corresponding to isoparaffins. An isoolefin blend component refers to a fraction that: a) meets the requirement of combining isoolefins and isoalkanes in sufficient quantities; and b) contains 5.0 wt% or more, or 25 wt% or more, or 50 wt% or more, or 70 wt% or more of isoolefins, as at most substantially all fractions correspond to isoolefins.

[0107] In various aspects, the isoalkane blend component and / or isoolefin blend component may have one or more of the following properties. In some aspects, 80 wt% or more, or 90 wt% or more, or 94 wt% or more, or 97 wt% or more of the blend component are C9 to C6. 20 Composed of isoolefins, isoalkanes, or combinations thereof. In some aspects, 2.0 wt% to 25 wt%, or 2.0 wt% to 15 wt%, or 5.0 wt% to 25 wt%, or 5.0 wt% to 15 wt%, or 2.0 wt% to 10 wt% of the blended components are composed of C9 hydrocarbons. In some aspects, 1.0 wt% to 15 wt%, or 2.5 wt% to 15 wt% of the blended components are composed of C9 hydrocarbons. 17 +hydrocarbon composition. In some aspects, the blended components comprise 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 C 17 and / or C 18 Hydrocarbon composition. In some respects, the blended components may contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less C. 19+ Hydrocarbons, such as those containing virtually no carbon. 19+ Hydrocarbons. In some respects, the blended components may contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less C. 8- Hydrocarbons, such as as low as 0.1 wt% or possibly even lower (i.e., essentially C-free). 8-In some respects, the specific gravity of the blended components at 15°C is 0.730 g / cm³. 3 Up to 0.775 g / cm 3 .

[0108] In some respects, based on the weight of the blend components, the blend components may contain 60 wt% to 90 wt% C. 11 To C 18 Isoalkanes. Alternatively or additionally, the blend components may contain 50 wt% to 75 wt% C based on their weight. 12 To C 16 Isoalkanes. This is particularly advantageous for the flexible use of the composition as an aviation or diesel fuel.

[0109] In all aspects, the blend components may contain reduced or minimal amounts of aromatic compounds. This may 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 of aromatic compounds, or even as little as substantially no aromatic compounds.

[0110] In all respects, the flash point of the blend components may be 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 possibly still higher. Additionally or alternatively, when tested alone (i.e., before blending with another fraction), the jet fuel thermal oxidation test (JFTOT) breakpoint results for the blend components may be 260°C or higher, or 270°C or higher, or 280°C or higher, such as up to 320°C or possibly still higher.

[0111] In some respects, the conductivity of the blend component can be 10 pS / m or less (according to ASTM Test Method D2624) before the addition of any additives, such as as low as essentially no conductivity. Note that the isoparaffin blend component, as described herein, exhibits a good response to conductive additives. After the addition of conventional additives for conductivity, the conductivity of the isoparaffin blend component can range from 50 pS / m to 600 pS / m.

[0112] The isoparaffinic blend component can be blended with one or more other fractions to form a kerosene / jet boiling range product. Examples of fractions that can be blended with the isoparaffinic blend component include, but are not limited to, conventional jet fractions, mineral naphtha and / or jet and / or diesel boiling range fractions, as well as various types of synthetic naphtha, jet and / or diesel boiling range fractions, such as sustainable aviation fuel fractions and / or Fischer-Tropsch fractions. Other challenging fractions, at least a portion of which correspond to jet and / or diesel boiling range components, can also be blended with the isoparaffinic blend component.

[0113] In various aspects, the blended product may contain 1.0 vol% or more, or 10 vol% or more, or 30 vol% or more, or 50 vol% or more, or 65 vol% or more, or 75 vol% or more of an isoparaffin blend component, such as up to 99 vol% or possibly still higher. In some aspects, the product of such blends may contain 1.0 vol% to 20 vol%, or 1.0 vol% to 15 vol%, or 5.0 vol% to 20 vol%, or 5.0 vol% to 15 vol%, or 10 vol% to 20 vol% of an isoparaffin blend component. In other respects, such blends may contain 30 vol% to 99 vol%, or 30 vol% to 95 vol%, or 30 vol% to 80 vol%, or 30 vol% to 60 vol%, or 30 vol% to 45 vol%, or 50 vol% to 99 vol%, or 50 vol% to 95 vol%, or 50 vol% to 80 vol%, or 70 vol% to 99 vol% of isoparaffinic blend components.

[0114] In some respects, the resulting blended product may contain 0.1 wt% to 15 wt%, or 1.0 wt% to 15 wt%, or 2.5 wt% to 15 wt%, or 0.1 wt% to 10 wt%, or 1.0 wt% to 10 wt%, or 2.5 wt% to 10 wt%, or 1.0 wt% to 6.0 wt%, or 2.5 wt% to 6.0 wt%, or 1.0 wt% to 3.0 wt%, or 0.1 wt% to 6.0 wt%, or 0.1 wt% to 3.0 wt% of C 17 +hydrocarbons. In some respects, the resulting blend product may contain 0.1 wt% to 15 wt% C24. 17 and / or C 18 Hydrocarbons. For example, the resulting blend may contain 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 C. 17 -C 18 Hydrocarbons, such as up to 15 wt%. In some respects, the resulting blend may contain 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+ Hydrocarbons, such as those containing virtually no carbon. 19+ hydrocarbon.

[0115] In some respects, the resulting blends may have an unexpectedly high content of C9 hydrocarbons. In such respects, the resulting blends may contain 5.0 wt% or more, or 10 wt% or more, or 15 wt% or more of C9 hydrocarbons, such as up to 25 wt% or possibly still higher.

[0116] In all aspects, the specific gravity of the resulting blend at 15°C can be 0.775 g / cm³. 3 Up to 0.840 g / cm 3 Alternatively or alternatively, the flash point of the resulting blend may be 38°C or higher, or 40°C or higher, or 45°C or higher, or 50°C or higher, such as up to 60°C or possibly still higher. Further, alternatively or alternatively, the jet fuel thermal oxidation test (JFTOT) breakpoint of the resulting blend may be 260°C or higher, or 270°C or higher, or 280°C or higher, such as up to 320°C or possibly still higher. Still further, alternatively or alternatively, the freezing point of the resulting blend may be -40°C or lower, or -47°C or lower, or -50°C or lower, or -55°C or lower, such as as low as -70°C or possibly still lower.

[0117] In some respects, the final boiling point of the resulting blend can be 300°C or lower, even if the resulting blend contains 1.0 wt% or more of C. 17+ hydrocarbon.

[0118] In all respects, the resulting blends may contain reduced or minimal amounts of aromatic compounds. This may correspond to 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 of aromatic compounds, such as as low as substantially no aromatic compounds. Alternatively or alternatively, the sulfur content may be 500 wppm or less, or 250 wppm or less, or 100 wppm or less, or as low as 0.5 wppm or possibly still lower.

[0119] In some respects, the resulting blend may contain at least a portion of one or more conventional jet fuels. Conventional jet fuel is defined herein as a fraction that has qualified as a jet fuel according to at least one of ASTM D1655, UK Ministry of Defence Standard 91-091, and Canadian General Standards Committee 3.23. In such respects, the resulting blend may contain 1.0 vol% to 99 vol%, or 1.0 vol% to 90 vol%, or 1.0 vol% to 70 vol%, or 1.0 vol% to 50 vol%, or 1.0 vol% to 30 vol%, or 1.0 vol% to 10 vol%, or 10 vol% to 70 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 30 vol% to 70 vol%. Therefore, in some respects, the resulting blended product may contain 50 vol% or less, or 30 vol% or less, or 10 vol% or less of conventional jet fuel fractions, such as as low as 1.0 vol% or possibly even lower.

[0120] In some aspects, the resulting blend product may contain at least a portion of one or more mineral kerosene / jet boiling range fractions. In such aspects, the resulting blend product may contain 1.0 vol% to 99 vol%, or 1.0 vol% to 90 vol%, or 1.0 vol% to 70 vol%, or 1.0 vol% to 50 vol%, or 1.0 vol% to 30 vol%, or 1.0 vol% to 10 vol%, or 10 vol% to 70 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 30 vol% to 70 vol%. Thus, in some aspects, the resulting blend product may contain 50 vol% or less, or 30 vol% or less, or 10 vol% or less of a jet / kerosene boiling range fraction, such as as low as 1.0 vol% or possibly even lower.

[0121] In some aspects, the resulting blend may contain at least a portion of one or more synthetic jet-boiling range fractions, optionally as defined in ASTM D7566. In these aspects, the resulting blend may contain 1.0 vol% to 99 vol%, or 1.0 vol% to 90 vol%, or 1.0 vol% to 70 vol%, or 1.0 vol% to 50 vol%, or 1.0 vol% to 30 vol%, or 1.0 vol% to 10 vol%, or 10 vol% to 70 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 30 vol% to 70 vol%. Therefore, in some aspects, the resulting blend may contain 50 vol% or less, or 30 vol% or less, or 10 vol% or less of a synthetic jet-boiling range fraction, such as as low as 1.0 vol% or possibly even lower.

[0122] Note that isoparaffins and / or components can be blended with a variety of different types of fractions. For example, in some aspects, the blended product may contain two or more (or three or more) of conventional jet fuel fractions, mineral jet boiling range fractions, and synthetic fractions. Examples of synthetic fractions include bio-derived fractions, sustainable aviation fuels, and / or Fischer-Tropsch fractions.

[0123] In some respects, after the components are blended together to form a kerosene / jet fuel boiling range fraction, further processing of the kerosene / jet fuel boiling range fraction may be desired for any convenient reason. Examples of additional processing methods may include, but are not limited to, wet processing, clay processing, acid and / or caustic alkali processing, mercaptan oxidation, salt drying, and hydrotreating.

[0124] Distribution of carbon atom types in isoalkane streams and related blend components and blends

[0125] In some respects, the carbon atom type distribution within the hydrocarbons of the isoalkane stream formed according to this method differs from the carbon atom type distribution of the isoalkane-containing fraction formed by another method, such as isomerization of a n-alkane feed. This difference in carbon atom type can be characterized using various types of nuclear magnetic resonance (NMR) analysis, including... 1 H NMR and 13 C NMR.

[0126] 1 ¹H NMR can be used to roughly characterize the amount of hydrogen in a sample corresponding to CH₃ groups (primary or terminal carbons), CH₂ groups (secondary carbons), and CH groups (tertiary carbons). This is only an approximate characterization because the presence of aromatic rings can alter the resonance positions of certain types of hydrogen. However, this effect of aromatic rings is not significant for all types of hydrogen.1 For H NMR, this is universal, and for any sample containing less than 60 wt% aromatic compounds, the variation in the detection of CH3, CH2, and CH groups is minimal. Therefore, 1 H NMR can be used to characterize the content of CH3 groups, CH2 groups and CH groups in a sample in a reproducible manner.

[0127] generally, 1 ¹H NMR can be used to characterize the number of CH₃, CH₂, and CH groups in a sample in the following ways: based on peak positions, 1 ¹H NMR typically characterizes hydrogen in hydrocarbon (or hydrocarbon-like) samples as falling into one of six types of groups: 1) hydrogen attached to an aromatic ring; 2) hydrogen attached to a carbon that is part of an olefinic bond; 3) hydrogen attached to a carbon located at the α-axis relative to the aromatic ring (i.e., hydrogen attached to the first carbon, which in turn is attached to a second carbon that is part of the aromatic ring); 4) hydrogen as part of CH₃; 5) hydrogen as part of a CH₂ group; and 6) hydrogen as part of a CH group. The peaks corresponding to these six types of hydrogen can then be integrated. This provides a relative ratio of the amount of each type of hydrogen present. These ratios can then be used to determine the relative percentage of the corresponding type of carbon present in the sample. Specifically, for hydrogen attached to CH₃ and CH₂ groups, the amount of hydrogen present needs to be divided by 3 or 2, respectively, to convert the relative amount of hydrogen detected by NMR into the relative amount of CH₃ or CH₂ groups.

[0128] In this discussion, "CH3 group" is defined as based on 1 The presence of an alkane / aliphatic CH3 group is determined by ¹H NMR. This is determined by integrating the hydrogen peaks corresponding to the peaks in the NMR spectrum, which correspond to hydrogens that are part of the CH3 group. Note that hydrogens from any CH3 group are not part of this peak, where the carbon of the CH3 group is located in the α or β position relative to the aromatic ring (e.g., CH3 is part of a methyl or ethyl group attached to an aromatic ring). Here, the CH3 group is contained in the side chain of the aromatic ring at the γ position or further away. Therefore, the degree of presence of the aromatic compound is based on… 1 The amount of CH3 groups detected by H NMR may be slightly lower than the actual content of CH3 groups. However, for samples with aromatic compound content less than 60 wt%, this is a small error. Therefore, in this discussion, the reference to CH3 groups in a sample is defined as as obtained by... 1 The CH3 group was detected by H NMR without attempting to correct the NMR values ​​based on the possible undercount error due to the presence of aromatic compounds.

[0129] In this discussion, "CH2 group" is defined as based on 1 The alkane / aliphatic CH2 group is determined by ¹H NMR. This is determined by integrating the hydrogen peaks corresponding to the peaks in the NMR spectrum, which correspond to hydrogens that are part of the CH2 group. Note that hydrogens from any CH2 group located in the α or β position relative to the aromatic ring are not part of this peak. Additionally, hydrogens from CH3 groups located in the β position relative to the aromatic ring are also included in this peak. Therefore, the extent of the presence of aromatic compounds is determined based on… 1 The amount of CH2 groups detected by H NMR may be slightly lower, slightly higher, or equal to the actual content of CH2 groups. However, for samples with an aromatic compound content of less than 60 wt%, this is a small error. Therefore, in this discussion, the reference to CH2 groups in a sample is defined as follows: 1 The CH2 group was detected by 1H NMR without attempting to correct the NMR values ​​based on possible undercounting and / or overcounting errors due to the presence of aromatic compounds. Note that the CH2 group, as part of a cycloalkane ring, is included in the CH2 NMR peak.

[0130] In this discussion, "CH group" is defined as based on 1 The alkane / aliphatic CH group is determined by 1H NMR. This is determined by integrating the hydrogen peaks corresponding to the peaks in the NMR spectrum, which correspond to hydrogens that are part of the CH group. As mentioned above, any hydrogens directly attached to the aromatic ring are not included in this peak. Additionally, note that hydrogens from any CH group located at α or β relative to the aromatic ring are not part of this peak. Furthermore, hydrogens from CH2 groups located at β relative to the aromatic ring are also included in this peak. Therefore, the extent of the presence of aromatic compounds is determined based on... 1 The amount of CH groups detected by H NMR may be slightly lower, slightly higher, or equal to the actual content of CH groups. However, for samples with aromatic compound content less than 60 wt%, this is a small error. Therefore, in this discussion, the reference to CH groups in a sample is defined as follows: 1 The ¹H NMR detected alkane / aliphatic CH groups without attempting to correct the NMR values ​​based on possible undercounting and / or overcounting errors due to the presence of aromatic compounds. Note that CH groups that are part of a cycloalkane ring are included in the ¹H NMR peak.

[0131] In various aspects, isoparaffin streams (e.g., Figure 1-5 The CH3 group (such as those based on the isoalkane stream discussed in the text) 1 HNMR determination) and CH2 groups (such as based on 1The ratio (determined by H NMR) can be 1.01 to 1.35, or 1.01 to 1.25, or 1.10 to 1.35, or 1.10 to 1.25. By blending at least a portion of the isoparaffin stream (also referred to as the isoparaffin blend component) with another fraction, CH3 groups and CH2 groups (both based on...) can be formed. 1 The ratios (determined by H NMR) of the resulting blends are 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. Note that the ratio of CH3 to CH2 groups can vary depending on the type of fraction blended with the isoparaffinic blend component. For example, blending the isoparaffinic blend component with mineral jet boiling range fractions, mineral distillate boiling range fractions, or Fischer-Tropsch fractions and / or fractions with high n-paraffin content tends to yield blends with lower ratios. In contrast, blending the isoparaffinic blend component with fractions that are highly isomerized during catalytic dewaxing / isomerization tends to yield blends with higher ratios.

[0132] In addition to hydrogen gas characterizing the entire sample, 13 C10 NMR is also used to characterize the C10 of various samples. 12 The quaternary carbon content of the fraction. For this type of measurement, gas chromatography can be used to detect C present in the sample. 12 The compound is separated from the remaining hydrocarbons. It can be used to form C... 12 The direct method for fractionation is the gas chromatography method for n-chain alkanes (or straight-chain alkanes). That is, for a suitable gas chromatograph with a separation column having sufficient resolution, it is assumed that a given number of carbon atoms in a n-chain alkane will depict a peak, and above that peak, species can be assumed to include the next n-chain alkane peak with a higher carbon number. For example, all peaks of the material eluted between the peaks of n-decane and n-undecane are assumed to be C10. 11 Species.

[0133] Then you can use 13 C10 NMR characterization 12 Fractions. It has been found that the C1 of iso-alkane blend components prepared according to the method described herein is higher than that of fractions prepared by catalytic isomerization of n-alkane. 12 The fraction can have a surprisingly low quaternary carbon content. In this respect, the C content of the isoparaffin blend component is... 12 The quaternary carbon content of the fraction can be found in C 12 The fraction contains 1.5% or less of total carbon, or 1.4% or less, or 1.3% or less, such as as low as 1.0% or possibly still lower.

[0134] Unless otherwise specified, all numerical values ​​used in this specification and related claims to represent quantities of components, properties such as molecular weight, reaction conditions, etc., are to be understood as being modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained through the embodiment of the invention. To a minimum, and without attempting to limit the application of the equivalence principle to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying general rounding techniques.

[0135] This document presents one or more illustrative embodiments incorporating one or more inventive elements. For clarity, not all features of the physical embodiments are described or shown in this application. It should be understood that in the development of physical embodiments incorporating one or more elements of the invention, numerous implementation-specific decisions must be made to achieve the developer's objectives, such as compliance with system-related, business-related, governmental-related, and other constraints that vary with the implementation and over time. While the developer's efforts may be time-consuming, such efforts will be routine for those skilled in the art who benefit from this disclosure.

[0136] Although this document describes compositions and methods as “comprising” various components or steps, the compositions and methods may also “consist substantially of various components and steps” or “comprise various components and steps”.

[0137] Other embodiments

[0138] Example 1. A method for producing a blended jet-boiling-range composition stream, the method comprising: oligomerizing an ethylene stream into a C4+ olefin stream in a first olefin oligomerization unit comprising a series reactor and a light removal tower, wherein the C4+ olefin stream contains no more than 10 wt% of combined methane, ethylene, and ethane; wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm each of carbon monoxide and hydrogen; oligomerizing the C4+ olefin stream and a propylene / C4+ olefin stream in a second oligomerization unit to produce an isoolefin stream; subjecting at least a portion of the isoolefin stream to a hydrogenation process using hydrogen as a process gas to produce an isoparaffin stream with an olefin content of no more than 10 wt%; and using at least a portion of the isoparaffin stream to produce the blended jet-boiling-range composition, the blended jet-boiling-range composition comprising: 30 vol% to 99 vol%. The isoparaffin blend component, vol%, derived from the isoparaffin stream containing 80 wt% or more isoparaffins, 5.0 wt% or less olefins and 5.0 wt% or less C19+ hydrocarbons; 1.0 vol% to 70 vol% mineral jet boiling range fraction; and a T10 distillation point of 205°C or lower, a final boiling point of 300°C or lower, a freezing point of -40°C or lower, and 2.0 wt% or more C17-C18 hydrocarbons.

[0139] Example 2. The method according to Example 1, wherein the C4+ olefin stream contains no more than 5 wt% of combined methane, ethylene and ethane.

[0140] Example 3. The method according to any one of Examples 1 to 2, wherein the C4+ olefin stream contains no more than 2000 wppm of combined methane, ethylene and ethane.

[0141] Example 4. The method according to any one of Examples 1 to 3, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen.

[0142] Example 5. The method according to any one of Examples 1 to 4, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 1 wppm each of carbon monoxide and hydrogen.

[0143] Example 6. The method according to any one of Examples 1 to 5, wherein the C4+ olefin stream and the propylene / C4+ olefin stream are combined prior to the second oligomerization.

[0144] Example 7. The method according to any one of Examples 1 to 6, wherein the first oligomer unit utilizes a homogeneous catalyst, and wherein the second oligomer unit utilizes a heterogeneous catalyst.

[0145] Example 8. The method according to any one of Examples 1 to 7, wherein the second oligomerization recycles a portion of the non-oligomery C4+ olefin stream so that it passes through the second oligomer again.

[0146] Example 9. The method according to any one of Examples 1 to 8, further comprising: converting methanol into olefins to produce a raw olefin stream; wherein the raw olefin stream comprises ethylene, propylene, and C4+ olefins, wherein at least 10 wt% of all olefins in the raw olefin stream is ethylene, and further contains at least 1000 wppm of methane and ethane, and at least 100 wppm of carbon monoxide and hydrogen, respectively; and separating the raw olefin stream to remove hydrogen, carbon monoxide, propylene, and C4+ olefins from the raw olefin stream, and producing the ethylene stream.

[0147] Example 10. The method according to Example 9, wherein the ethylene stream contains at least 90% of the ethane present in the original olefin stream.

[0148] Example 11. The method according to Example 9, wherein the methanol is converted to olefins using a silica-aluminophosphate catalyst, an aluminosilicate catalyst, or steam cracking.

[0149] Example 13. A method for producing a blended jet boiling range composition, the method comprising: providing a raw olefin stream comprising ethylene, propylene, and C4+ olefins, wherein at least 10 wt% of all olefins in the raw olefin stream is ethylene, and further comprising at least 1000 wppm of methane and ethane, and at least 100 wppm of carbon monoxide and hydrogen, respectively; subjecting the raw olefin stream to a separation operation to remove hydrogen, carbon monoxide, propylene, and C4+ olefins from the raw olefin stream, and producing an ethylene stream containing at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm of carbon monoxide and hydrogen, respectively, wherein at least 95 wt% of all ethylene in the raw olefin stream is recovered in the ethylene stream; providing at least a portion of the ethylene stream to a first olefin oligomerization unit comprising one or more tandem reactors and a light-removal tower to convert at least 90% of the ethylene contained in the ethylene stream into a concentration of no more than 10 wt% ethylene in a single pass through the tandem reactors. A second C4+ olefin stream comprising wt% of combined methane, ethylene, and ethane; providing at least a portion of each of the propylene and the C4+ olefins removed from the original olefin stream and at least a portion of the second C4+ stream to a second olefin oligomerization unit to produce an isoolefin stream; subjecting at least a portion of the isoolefin stream to a hydrogenation process using hydrogen as a process gas to produce an isoparaffin stream with an olefin content not exceeding 10 wt%; and using at least a portion of the isoparaffin stream to produce the blended jet boiling range composition comprising: 30 vol% to 99 vol% of an isoparaffin blend component derived from the isoparaffin stream containing 80 wt% or more of isoparaffins, 5.0 wt% or less of olefins, and 5.0 wt% or less of C19+ hydrocarbons; 1.0 vol% to 70 vol% of... vol% of mineral jet boiling range fractions; and T10 distillation point of 205°C or lower, final boiling point of 300°C or lower, freezing point of -40°C or lower, and 2.0 wt% or more of C17-C18 hydrocarbons.

[0150] Example 14. The method according to Example 13, wherein the C4+ olefin stream contains no more than 5 wt% of combined methane, ethylene and ethane.

[0151] Example 15. The method according to any one of Examples 13 to 14, wherein the C4+ olefin stream contains no more than 2000 wppm of combined methane, ethylene and ethane.

[0152] Example 16. The method according to any one of Examples 13 to 15, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen.

[0153] Example 17. The method according to any one of Examples 13 to 16, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 1 wppm each of carbon monoxide and hydrogen.

[0154] Example 18. The method according to any one of Examples 13 to 17, wherein the ethylene stream contains at least 90% of the ethane present in the original olefin stream.

[0155] Example 19. The method according to any one of Examples 13 to 18, wherein the separation operation comprises: a deethanizer distillation column for separating propylene and C4+ from the original olefin stream; and a demethanizer distillation column for separating methane, hydrogen and carbon monoxide from the original olefin stream to produce the ethylene stream.

[0156] Example 20. The method according to Example 19 further includes: an additional distillation column in the separation operation, wherein the propylene is separated from C4+ olefins and then further separated from propane and similar or lower volatile components.

[0157] Example 21. The method according to any one of Examples 13 to 20, wherein the first oligomer unit utilizes a homogeneous catalyst, and wherein the second oligomer unit utilizes a heterogeneous catalyst.

[0158] Example 22. The method according to any one of Examples 13 to 21, wherein the second oligomer unit comprises: a series reactor; a distillation column for outputting the isoolefin stream; and a debutanizing column for purging C4-olefins.

[0159] Example 23. According to the method of Example 22, wherein the distillate fractionation column also outputs C9-olefins, a first portion of which is recycled to the tandem reactor and a second portion is sent to the butane fractionation column.

[0160] Example 24. According to the method of Example 22, wherein the butane-de-butane fractionation column also outputs C5+ olefins, wherein a first portion is recycled to the series reactor and a second portion is purged.

[0161] Example 25. The method according to Example 22, wherein when entering the second oligomerization unit, the second C4+ stream first proceeds to the distillate fractionation tower, while the propylene and the C4+ olefins removed from the original olefin stream first proceed to the tandem reactor.

[0162] Example 26. The method according to any one of Examples 13 to 25, further comprising: converting methanol into olefins to produce a raw olefin stream.

[0163] Example 27. The method according to Example 26, wherein the methanol is converted to olefins using a silica-aluminophosphate catalyst, an aluminosilicate catalyst, or steam cracking.

[0164] To facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are provided. These examples should not be construed as limiting or restricting the scope of the invention.

[0165] Example

[0166] Example 1 - Carbon chain length distribution in isoparaffin blend components

[0167] One of the unusual characteristics of isoparaffin blends described in this article is that they can contain C 17+ The essential hydrocarbon fraction, while still forming blends with a final boiling point of 300°C or lower, as measured according to ASTM D86. To illustrate this, samples of several different isoparaffinic blend components were formed using the synthetic methods described herein. Table 1 shows the volume percentage of hydrocarbon chain length in the resulting isoparaffinic blend components. The samples are referred to as IPB 1, 2, and 3 (for the isoparaffinic blend components). For comparison, the hydrocarbon chain length distribution in a representative JET A-1 sample is also shown.

[0168] Table 1 - Hydrocarbon chain length distribution

[0169] As shown in Table 1, the representative JET A-1 sample contains less than 2.0 vol% C. 17 -C 18 Components, and C-free 19 Or C 20 Components. In contrast, each component in the isoparaffin blend contains more than 3.0 vol% C. 17 -C 18 Hydrocarbons, and more than 4.5 vol% C 17+ hydrocarbon.

[0170] C in the isoparaffin blend component 17+An increase in hydrocarbon concentration may lead to an increase in the C content of blends containing a portion of isoparaffinic hydrocarbon blend components. 17+ The corresponding increase in hydrocarbons. Tables 2-4 show the volume percentages of hydrocarbons of various chain lengths that will be incorporated into blends containing 70 vol% (Table 2), 50 vol% (Table 3), and 30 vol% (Table 4) of isoparaffinic blend components.

[0171] Table 2 - Contribution of 70 vol% to the blend

[0172] Table 3 - Contribution of 50 vol% to the blend

[0173] Table 4 - Contribution of 30 vol% to the blend

[0174] As shown in Table 2-4, blends containing 70 vol% of isoparaffinic blend components may contain 1.6 vol% or more, or 2.0 vol% or more of C 17 -C 18 Hydrocarbons, such as up to 2.3 vol%. For a 50% blend, the isoalkane blend component can contribute 1.2 vol% or more of C. 17 -C 18 Hydrocarbons, such as up to 1.6 vol%. Based on the typical C content of approximately 1.5 vol% in conventional jet fuel. 17 -C 18 The content, clearly, as described in this article, of the isoparaffin blend components allows for a higher volume percentage of C. 17 -C 18 Hydrocarbons are incorporated into the potential blended jet fuel products.

[0175] Example 2 - Blend with conventional jet fuel

[0176] The isoparaffinic blend components corresponding to IPB 1 and IPB 2 in Example 1 are used in combination with conventional jet fuel (JETA-1 or JP-5) to form blended jet boiling range products. Even for blends with 50 vol% or more, or 70 vol% or more of isoparaffinic blend components, the resulting blended jet boiling range products still meet the specifications of the corresponding type of jet fuel.

[0177] Figure 6The results of characterization of conventional JET A-1 samples, IPB 1 samples, blends formed from 30 vol% IPB 1 and 70 vol% JET A-1, and blends formed from 70 vol% IPB 1 and 30 vol% JET A-1 are shown. Figure 6 As shown, IPB1 alone cannot meet all the standard requirements of JET A-1 jet fuel. However, the blend obtained by blending 70 vol% IPB1 with 30 vol% conventional JET A-1 meets the requirements. Figure 6 All JET A-1 requirements are shown, except for electrical conductivity. However, the electrical conductivity of potential jet fuel products can be easily increased to meet the required standards using conventional additives.

[0178] As explained in Example 1, a blend containing 70 vol% IPB 1 contains at least 2.0 vol% C. 17 -C 18 Hydrocarbons, even without considering contributions from JET A-1. Blends containing 70 vol% IPB 1 also provide higher JFTOT breakpoint temperatures and higher smoke points. Combined with the generally beneficial cold flow properties of isoparaffin blend components, Figure 6 The value of isoparaffinic blends, as described herein, for potentially restoring non-compliant jet fuel samples to specifications is demonstrated.

[0179] Similar characterizations were performed on the JET A-1 sample, IPB 2, blends of 30 vol% IPB 2 and 70 vol% JET A-1, and blends of 70 vol% IPB 2 and 30 vol% JET A-1. The characterization results of these blend products are as follows: Figure 7 As shown in the image. (and) Figure 6 Similarly, blends obtained by blending 50 vol% or more, or 70 vol% or more, of isoparaffinic blend components with conventional jet fuel samples can still meet the requirements. Figure 7 All the required standards are shown.

[0180] Example 3 - Isoalkane blend components as lubrication improvers

[0181] It has been found that the resulting blends, in which the product comprises at least 10 vol% of a mineral jet boiling range fraction and 40 vol% or more (or 50 vol% or more) of an isoparaffin blend component, can exhibit unexpectedly improved lubricity. Lubricity can be measured based on the wear track diameter as determined according to ASTM D5001. For example, such blends may comprise 10 vol%–50 vol%, or 10 vol%–60 vol%, or 20 vol%–50 vol%, or 20 vol%–60 vol% of a mineral jet boiling range fraction. The components of such blends may also comprise 40 vol%–90 vol%, or 50 vol%–90 vol%, or 40 vol%–80 vol%, or 50 vol%–80 vol% of an isoparaffin blend component.

[0182] The unexpected improvement in lubricity when 50 vol% or more of an isoparaffin blend is added 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 to determine the wear track diameter according to the method of ASTM D5001. In Table 5, the first two samples correspond to pure samples of JET A-1 and JP-5. The remaining samples are blends of isoparaffin blend components (IPB-1 or IPB-2) with JET A-1 or JP-5. Traditionally, adding a high alkane blend component to a mineral jet boiling range fraction is expected to result in poor lubricity performance. For comparison, note that some diesel fuel standards specify a maximum wear track diameter of 0.85 mm or less according to ASTM D5001.

[0183] Table 5 - Measured lubricity values ​​of jet boiling range fractions

[0184] As shown in Table 5, when the blend of IPB-1 or IPB-2 with the JET A-1 sample is 30 vol%, the linear weighted average model predicts a wear track diameter of approximately 0.60 mm for IPB-1 or IPB-2 alone when used to describe the wear track diameter results. In contrast, for blends containing 50 wt% or more of IPB-1 or IPB-2, the linear weighted average model predicts a wear track diameter of less than 0.60 mm. Further note that for blends with higher contents of isoparaffinic components with the JET A-1 sample (e.g., 50 vol% or more of isoparaffinic components), the wear track diameter of the blended composition is reduced by 10% or more relative to the wear track diameter of the individual mineral jet boiling range fraction.

[0185] Similarly, for a blend of 25 vol% IPB-1 and JP-5, the linear weighted average model predicted a wear track diameter of approximately 0.63 mm for IPB-1. Indeed, the addition of IPB-1 appears to increase the wear track diameter when blended with JP-5, consistent with conventional expectations. However, increasing the amount of IPB-1 in the blend to 50 wt% resulted in a decrease in the wear track diameter relative to pure JP-5, with a predicted wear track diameter of approximately 0.58 mm for pure IPB-1.

[0186] Based on Table 5, a synergistic effect was observed in blends with 50% or more of the isoparaffin blend component, where a surprisingly large amount of isoparaffin blend component in the blend resulted in a reduction in the wear track diameter.

[0187] Example 4 - Blended components 1 H NMR analysis

[0188] The isoalkane blend component IPB-1 was formed according to the method described herein, wherein the isoolefin blend component was formed by olefin oligomerization. A portion of the isoolefin blend component was then exposed to hydrogenation conditions to saturate the portion, thus forming the IPB-1 sample. In addition to forming the isoalkane blend component, two other portions of the isoolefin blend component were exposed to olefin-saturated conditions, such that the component contained approximately 30 wt% olefin / 70 wt% alkane and 70 wt% olefin / 30 wt% alkane.

[0189] use 1 ¹H NMR characterizes the isoolefin blend components, isoalkane blend components, and two partially saturated components to characterize the ratio of CH₃ groups to CH₂ groups, such as by… 1 The results confirmed this with H NMR. Figure 8 It shows 1 Results of H NMR analysis. Figure 8 In the table, the first column of data corresponds to the data for the essentially fully saturated isoalkane blend component (IPB-1). The second and third columns show the partially saturated products, while the last column corresponds to the data for the isoolefin blend component obtained by the oligomerization process.

[0190] like Figure 8 As shown, the isoolefin blend component (before any saturation) has the highest CH3 to CH2 group ratio. With increasing saturation, the CH3 to CH2 group ratio decreases, with the isoalkane blend component (IPB-1) having the highest CH3 to CH2 group ratio (as based on...). 1 The value (determined by H NMR) is 1.18.

[0191] In order to Figure 8 The values ​​shown are compared, and also using 1 ¹H NMR was used to characterize various other types of fractions to determine the ratio of CH₃ groups to CH₂ groups. Table 6 shows the values ​​obtained from these various other types of fractions. Where ranges are given, this indicates that multiple different samples were characterized, with the range corresponding to a minimum and a maximum value.

[0192] Table 6 - If passed 1 CH3 / CH2 ratio of other components determined by H NMR

[0193] As shown in Table 6, liquids with high n-alkane content tend to have a CH3 to CH2 ratio well below 1.00. The ratio for commercial fuel products is typically below 1.00, although diesel fuels with high isoalkane content and low aromatic content can approach 1.00. Fluids containing high cycloalkanes have a CH3 to CH2 ratio above 2.30. Similarly, fractions with high isoalkane content have a CH3 to CH2 ratio above 2.30, where the isoalkane content is formed through catalytic isomerization.

[0194] Example 5 - Quarterly Carbon Content

[0195] The sample of IPB-1 was separated using gas chromatography to form C 12 Fraction. Use 13 C10 NMR analysis yielded C10 NMR results 12 Fractions were collected to determine the quaternary carbon content in the sample. For comparison, after exposing the source to deep catalytic isomerization, C... 12 The fraction was also formed from two other mineral sources. Table 7 shows the C... 12 Results of fraction analysis.

[0196] Table 7 - C 12 distillate 13 C NMR analysis

[0197] As shown in Table 7, C 12 The quaternary carbon content of the fraction is generally lower than that of other fractions. For two comparative samples, C is lower relative to the total carbon content in the sample. 12 The fraction has a quaternary carbon content greater than 1.60%, while the C content from the isoparaffin blend component is higher. 12 The quaternary carbon content of the fraction is 1.60% or less, or 1.50% or less, or 1.40% or less, such as as low as 1.20% or possibly still lower.

[0198] Therefore, the present invention is well suited to achieving the stated objects and advantages, as well as their inherent objects and advantages. The specific examples and configurations disclosed above are merely illustrative, as the invention can be modified and practiced in different but equivalent ways that will be apparent to those skilled in the art who benefit from the teachings herein. Furthermore, no limitation is intended to be made on the details of the constructions or designs shown herein, except as set forth in the following claims. Thus, it is apparent that the specific illustrative examples disclosed above can be changed, combined, or modified, and all such changes are considered to be within the scope and spirit of the invention. The invention illustratively disclosed herein can be suitably practiced in the absence of any elements not specifically disclosed herein and / or any optional elements disclosed herein. While compositions and methods are described as “comprising,” “containing,” or “including” various components or steps, compositions and methods may also be “substantially composed of various components or steps” or “composed of various components or steps.” All numbers and ranges disclosed above can differ by a certain amount. Whenever a numerical range with a lower and upper limit is disclosed, any numerical value falling within the range and any range included therein is specifically disclosed. Specifically, each range of values ​​disclosed herein (in the form of "about a to about b" or equivalently "about a to b" or equivalently "about ab") should be understood as listing each number and range covered within a broader range of values. Furthermore, unless otherwise explicitly and clearly defined by the patent holder, the terms in the claims have their general, ordinary meaning. Additionally, the indefinite article "a / an" used in the claims is defined herein as referring to one or more of the elements it introduces.

Claims

1. A method for producing a blended jet boiling range composition stream, comprising the following steps: In a first olefin oligomerization unit, an ethylene stream is oligomerized into a C4+ olefin stream, the first olefin oligomerization unit comprising a series reactor and a light-weight removal tower; The C4+ olefin stream contains a total of no more than 10 wt% methane, ethylene and ethane; and the ethylene stream contains at least 50 wt% ethylene and no more than 1000 wppm methane. In the second oligomerization unit, the C4+ olefin stream is oligomerized with the propylene / C4+ olefin stream to produce an isoolefin stream; Hydrogen is used as the process gas to hydrogenate at least a portion of the isoolefin stream to produce a hydrogenated stream comprising a total of 50 wt% or more of isoolefins and isoalkanes. The blended jet boiling range composition is prepared using at least a portion of the hydrogenation process stream, comprising: 30 vol% to 99 vol% of the blend component from the hydrotreating stream, the blend component comprising a total of 50 wt% or more of isoolefins and isoalkanes, and 5.0 wt% or less of C19+ hydrocarbons; Mineral jet boiling range fractions from 1.0 vol% to 70 vol%; and T10 distillation point of 205°C or lower, final boiling point of 300°C or lower, freezing point of -40°C or lower, and 2.0 wt% or more of C17-C18 hydrocarbons.

2. The method of claim 1, wherein the hydrogenation process stream comprises a total of 60 wt% or more of isoolefins and isoalkanes, or the blend components comprise a total of 60 wt% or more of isoolefins and isoalkanes, or a combination of both.

3. The method of claim 1, wherein the hydrogenation process stream comprises a total of 70 wt% or more of isoolefins and isoalkanes, or the blend components comprise a total of 70 wt% or more of isoolefins and isoalkanes, or a combination of both.

4. The method of claim 1, wherein the C4+ olefin stream comprises a total of no more than 5 wt% methane, ethylene and ethane.

5. The method of claim 1, wherein the C4+ olefin stream comprises a total of not more than 2000 wppm of methane, ethylene, and ethane.

6. The method of claim 1, wherein the ethylene stream comprises at least 2000 wppm of ethane, and carbon monoxide and hydrogen, each not exceeding 5 wppm.

7. The method of claim 1, wherein the C4+ olefin stream and the propylene / C4+ olefin stream are combined before entering the second oligomer unit.

8. The method of claim 1, wherein the first oligomer unit is a homogeneous catalyst and the second oligomer unit is a heterogeneous catalyst.

9. The method of claim 1, wherein the second oligomer unit recycles the unoligomery portion of the C4+ olefin stream to pass it through the second oligomer unit again.

10. The method of claim 1, further comprising the following steps: Methanol is converted into olefins to produce a crude olefin stream comprising ethylene, propylene and C4+ olefins, wherein at least 10 wt% of all olefins in the crude olefin stream is ethylene, and further comprises at least 1000 wppm each of methane and ethane, and at least 100 wppm each of carbon monoxide and hydrogen. and The crude olefin stream is separated to remove hydrogen, carbon monoxide, propylene, and C4+ olefins from the crude olefin stream, thereby producing an ethylene stream.

11. The method of claim 10, wherein the ethylene stream comprises at least 90% ethane in the crude olefin stream.

12. The method of claim 10, wherein methanol is converted into olefins via a silica-aluminophosphate catalyst, an aluminosilicate catalyst, or steam cracking.

13. The method of claim 10, wherein separating the crude olefin stream further comprises generating at least a portion of the propylene / C4+ olefin stream.

14. A method for producing a blended jet boiling point composition stream, comprising the following steps: In a first olefin oligomerization unit, an ethylene stream is oligomerized into a C4+ olefin stream, the first olefin oligomerization unit comprising a series reactor and a light-weight removal tower; The C4+ olefin stream contains a total of no more than 10 wt% methane, ethylene and ethane; and the ethylene stream contains at least 50 wt% ethylene and no more than 1000 wppm methane. And each of the following: carbon monoxide and hydrogen, not exceeding 20 wppm; In the second oligomerization unit, the C4+ olefin stream is oligomerized with the propylene / C4+ olefin stream to produce an isoolefin stream; Hydrogen is used as the process gas to hydrogenate at least a portion of the isoolefin stream to produce a hydrogenated stream comprising a total of 50 wt% or more of isoolefins and isoalkanes. The blended jet boiling range composition is prepared using at least a portion of the hydrogenation process stream, comprising: 30 vol% to 99 vol% of the blend component from the hydrotreating stream, the blend component comprising a total of 50 wt% or more of isoolefins and isoalkanes, and 5.0 wt% or less of C19+ hydrocarbons; Mineral jet boiling range fractions from 1.0 vol% to 70 vol%; and T10 distillation point of 205°C or lower, final boiling point of 300°C or lower, freezing point of -40°C or lower, and 2.0 wt% or more of C17-C18 hydrocarbons.

15. The method of claim 14, wherein the hydrogenation process stream comprises a total of 70 wt% or more of isoolefins and isoalkanes, or the blend components comprise a total of 70 wt% or more of isoolefins and isoalkanes, or a combination of both.

16. The method of claim 14, wherein the C4+ olefin stream comprises a total of no more than 5 wt% methane, ethylene, and ethane.

17. The method of claim 14, wherein the ethylene stream comprises at least 2000 wppm of ethane, and carbon monoxide and hydrogen, each not exceeding 5 wppm.

18. The method of claim 14, wherein the C4+ olefin stream and the propylene / C4+ olefin stream are combined before entering the second oligomer unit.

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