Methods for converting C2-C7 olefins into fuels

Abstract

One or more C2-C7 linear or branched olefins and one or more C8-C 24 A method for converting to hydrocarbons is provided.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application Nos. 63 / 432,650 and 63 / 459,523, filed December 14, 2022 and April 14, 2023, respectively, entitled "Two-Step Process for Transformation of Ethanol into Jet Fuel and / or Diesel Fuel," and U.S. Provisional Patent Application No. 63 / 530,408, filed August 2, 2023, entitled "PROCESS FOR CONVERTING C2-C7 OLEFINS INTO FUEL," the disclosures of which are incorporated herein by reference in their entireties.

[0002] The subject matter described herein includes a method for preparing a fuel (e.g., a refrigerant containing one or more C2 to C7 linear or branched olefins) from a fuel (e.g., one or more C8 to C9 24 This relates to a process for converting hydrocarbons into

[0003] Background technology Traditionally, petroleum has been used as the starting point for fuel synthesis. For example, the oligomerization of light gaseous monoolefins to form gasoline or diesel-type hydrocarbons has been carried out using acid catalysts such as supported phosphoric acid, and olefin dimers are commonly obtained for use as gasoline additives after hydrogenation of the dimers. Olefin trimerization has primarily been carried out using solid acid catalysts such as heteropolyacids, zirconium, zeolites, amorphous silica-alumina, and sulfated titania. Ionic liquids have also been used in these reactions. However, these catalyst compositions are expensive and can result in low yields. Furthermore, these processes produce oligomers nonselectively through the oligomerization of C2–C7 olefins, which typically produces mathematical distributions (Schultz-Flory or Poisson) of oligomers that often do not match market demand.

[0004] Nickel-based heterogeneous catalysts are also used in ethylene oligomerization to provide a mixture of C2-C8 olefins, which are then converted secondarily to C4-C 24 These catalysts may be inexpensive, but the primary products of these reactions are lower carbon number olefins and hydrocarbons, not the C8 needed for efficient production of renewable jet or diesel fuels. + Oligomers are not the main component.

[0005] In other implementations, a method utilizing cation exchange resins to oligomerize isobutene and other petroleum-derived light olefins into jet fuel-range oligomers has been reported. Tetramers or pentamers can also be obtained by oligomerizing preformed dimers with ion exchange resins. Additionally, Amberlyst-15 ion exchange resins have been used to oligomerize light olefins. Similarly, Amberlyst-35 ion exchange resins yield higher levels of trimer, but the dimers are present at a mass yield of 30–40%, which can ultimately reduce jet and diesel fuel production and thereby increase costs.

[0006] Therefore, there remains a need for improved catalyst technology that increases the yield of light gaseous monoolefins (e.g., C2-C7) to fuels.

[0007] Summary of the Invention Aspects of the present subject matter include the use of one or more C2-C7 linear or branched olefins in combination with one or more C8-C 24 In some implementations, one or more of the following features may be included in any workable combination:

[0008] In one implementation, one or more C2-C7 linear or branched olefins are combined with one or more C8-C 24 An exemplary process for converting the hydrocarbons is to heat the mixture in a reactor at a temperature of about 100° C. to 400° C., a pressure of about 200 psig to 1000 psig, and for at least 0.5 hours.-1 The method may include contacting a feed stream comprising one or more C2 to C7 linear or branched olefins with one or more catalysts at a weight hourly space velocity (WHSV) of 1000 to 2000 rpm to form a mixture. The mixture may include contacting a feed stream comprising one or more C8 to C9 linear or branched olefins with one or more catalysts at a weight hourly space velocity (WHSV) of 1000 to 2000 rpm to form a mixture. 24 The hydrocarbons are produced in at least a 30% yield, and the one or more catalysts comprise a doped mixed metal oxide.

[0009] In some implementations, the doped metal oxide can include one or more dopants, such as nickel, cobalt, yttrium, rhodium, ruthenium, palladium, platinum, ion, lanthanum, silica, alumina, scandium, titanium, niobium, copper, chromium, rhenium, zinc, vanadium, iridium, or any combination thereof. In certain implementations, nickel can be present in an amount of about 0.5 to 5 weight percent of the one or more catalysts.

[0010] In some implementations, the doped mixed metal oxide may include tungsten, zirconium, molybdenum, silica, alumina, or any combination thereof. Tungsten may be present in an amount of about 5 weight percent to 25 weight percent of the one or more catalysts.

[0011] In another implementation, one or more C2-C7 linear or branched olefins are combined with one or more C8-C 24 An exemplary process for converting ethylene glycol into hydrocarbons is provided in a reactor at a temperature of about 100° C. to 400° C., a pressure of about 200 psig to 1000 psig, and for at least 0.5 hours. -1 The method may include contacting a feed stream comprising one or more C2 to C7 linear or branched olefins with one or more catalysts at a weight hourly space velocity (WHSV) of 1000 to 2000 rpm to form a mixture. The mixture may include contacting a feed stream comprising one or more C8 to C9 linear or branched olefins with one or more catalysts at a weight hourly space velocity (WHSV) of 1000 to 2000 rpm to form a mixture. 24The one or more catalysts comprise a first catalyst, which may comprise nickel-doped zirconium tungstated, nickel-doped γ-alumina tungstated, nickel-doped silica tungstated, nickel-doped amorphous silica-alumina, or nickel-doped zeolite.

[0012] In some implementations, the reactor can be a single-bed reactor. The single-bed reactor can be a fixed-bed reactor or a fluidized-bed reactor.

[0013] In some implementations, the reactor can be a stacked bed reactor.

[0014] In some implementations, nickel can be present in an amount of about 0.5 weight percent to 5 weight percent of the first catalyst.

[0015] In some implementations, tungsten can be present in an amount between about 5 percent and 25 percent by weight of the first catalyst.

[0016] In some implementations, the first catalyst comprises nickel-doped zirconium tungstated.

[0017] In some implementations, the one or more catalysts can further include a second catalyst. The second catalyst can include one or more zeolites, one or more solid acids, or a combination thereof. In some implementations, the one or more solid acids can include one or more sulfonic acid resins.

[0018] In some implementations, the one or more zeolites can include one or more doped zeolites.

[0019] In some implementations, one or more of C8-C 24 Hydrocarbons contain one or more C8-C 20 Hydrocarbons may be included.

[0020] In some implementations, one or more of C8-C 24 Hydrocarbons contain one or more C8-C 16 Hydrocarbons may be included.

[0021] In some implementations, the feed stream may further include fusel oil, residual alcohol, corn oil, water, or any combination thereof. Water may be present in the feed stream in an amount less than 20 ppm.

[0022] In some implementations, the process comprises: 24 It may further include a recycle stream which may include a portion of the hydrocarbons.

[0023] In some implementations, the one or more C2-C7 linear or branched olefins can include ethylene, propylene, butene, pentene, hexene, or any combination thereof.

[0024] In some implementations, the process can further include preparing a feed stream, which can include contacting an input stream with one or more catalysts in one or more reactors to form one or more C2-C7 linear or branched olefins. The input stream can include one or more C1-C5 linear or branched alcohols. The one or more C1-C5 linear or branched alcohols can include ethanol, propanol, butanol, or any combination thereof.

[0025] In some implementations, the one or more catalysts may include a doped or undoped alumina catalyst containing one or more of zirconium, titanium, tungsten, or silicon in neutral or ionic form. In some implementations, the one or more catalysts may include a doped or undoped zeolite.

[0026] In some implementations, the process can further include preparing a feedstream, which can include deriving one or more C2 to C7 linear or branched olefins from petroleum.

[0027] In some implementations, the process further comprises: 24 It may further include recycling a portion of the hydrocarbons to the feed stream.

[0028] In some implementations, the process comprises one or more C8-C9 catalysts to produce a product stream. 24 It can further include hydrogenating the hydrocarbon.

[0029] In some implementations, the process further comprises: 24 It may further include recycling a portion of the hydrocarbons to the feed stream.

[0030] In some implementations, this process involves one or more C8-C 24 The process can further include separating hydrocarbons from the product stream to produce a renewable jet fuel or a renewable diesel fuel. In some implementations, the process can further include blending the renewable jet fuel with aromatic compounds or fossil fuel-derived compounds. In some implementations, the process can further include blending the renewable diesel fuel with aromatic compounds or fossil fuel-derived compounds.

[0031] In some implementations, one or more of C8-C 24 The yield of hydrocarbons can be about 30% to 99%.

[0032] In some implementations, one or more of C8-C 24 The yield of hydrocarbons may be at least about 45%.

[0033] In some implementations, one or more of C8-C24 The yield of hydrocarbons may be at least about 65%.

[0034] In some implementations, one or more of C8-C 24 The yield of hydrocarbons may be at least about 80%.

[0035] In some implementations, the pressure can be between about 400 psig and 700 psig, or between about 600 psig and 800 psig.

[0036] In some implementations, the temperature may be between about 150°C and 300°C.

[0037] In some implementations, the weight hourly space velocity (WHSV) is about 1 h -1 ~about 10h -1 or about 1 hour -1 ~about 5h -1 It could be.

[0038] In another implementation, one or more C2-C7 linear or branched olefins are combined with one or more C8-C 24 An exemplary process for converting the hydrocarbons is to heat the mixture in a reactor at a temperature of about 250° C. to 350° C., a pressure of about 400 psig to 700 psig, and for at least 2 hours. -1 The method may include contacting a feed stream comprising one or more C2 to C7 linear or branched olefins with one or more catalysts at a weight hourly space velocity (WHSV) of 1000 to 2000 rpm to form a mixture. The mixture may include contacting a feed stream comprising one or more C8 to C9 linear or branched olefins with one or more catalysts at a weight hourly space velocity (WHSV) of 1000 to 2000 rpm to form a mixture. 24 The hydrocarbons are produced in at least a 40% yield, and the one or more catalysts comprise nickel-doped zirconium tungstated.

[0039] In another implementation, an example of converting one or more C2 to C7 linear or branched olefins to jet fuel or diesel fuel includes converting one or more C8 to C9 linear or branched olefins to jet fuel or diesel fuel via a single oligomerization step. 24The single oligomerization step involves forming hydrocarbons in a reactor at a temperature of about 100°C to 400°C, a pressure of about 200 psig to 1000 psig, and for at least 0.5 hours. -1 The method includes contacting a feed stream containing one or more C2 to C7 linear or branched olefins with one or more catalysts at a weight hourly space velocity (WHSV) of 0.05 to 0.15 to form a mixture. The mixture includes one or more C8 to C9 linear or branched olefins. 24 The hydrocarbons are included in at least a 30% yield, and the one or more catalysts include a first catalyst, the first catalyst including nickel-doped tungstated zirconium, nickel-doped tungstated gamma-alumina, nickel-doped tungstated silica, nickel-doped amorphous silica-alumina, or nickel-doped zeolite.

[0040] In some implementations, the process comprises one or more C8-C9 catalysts to produce a product stream. 24 It can further include hydrogenating the hydrocarbon.

[0041] In some implementations, the process further comprises: 24 It may further include recycling a portion of the hydrocarbons to the feed stream.

[0042] In some implementations, this process involves one or more C8-C 24 It can further include separating hydrocarbons from the product stream to produce renewable jet fuel or renewable diesel fuel.

[0043] In some implementations, the process can further include blending the renewable jet fuel with aromatic compounds or fossil fuel-derived compounds.

[0044] In some implementations, nickel can be present in an amount of about 0.5 weight percent to 5 weight percent of the first catalyst.

[0045] In some implementations, tungsten can be present in an amount between about 5 percent and 25 percent by weight of the first catalyst.

[0046] In some implementations, the one or more catalysts further comprise a second catalyst, which can include one or more zeolites, one or more solid acids, or a combination thereof.

[0047] In some implementations, the process further comprises: 24 It may further include recycling a portion of the hydrocarbons to the feed stream.

[0048] In some implementations, one or more of the one or more C2-C7 linear or branched olefins can be derived from a C2-C5 monohydric alcohol.

[0049] In some implementations, one or more of C8-C 24 Hydrocarbons contain one or more low carbon strength C8-C 24 Hydrocarbons may be included.

[0050] In some implementations, one or more of C8-C 24 Hydrocarbons include C8-C8 with one or more zero carbon intensities. 24 Hydrocarbons may be included.

[0051] In some implementations, one or more of C8-C 24 Hydrocarbons contain one or more C8-C8 with negative carbon strength. 24 Hydrocarbons may be included.

[0052] Details of one or more implementations of the subject matter described herein are set forth in the accompanying drawings and the description below. Other features and advantages of the subject matter described herein will become apparent from the description and drawings, and from the claims. The claims that follow this disclosure are intended to define the scope of the protected subject matter.

[0053] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate certain implementations of the subject matter disclosed herein and, together with the description, serve to explain some of the principles associated with the disclosed implementations. [Brief explanation of the drawings]

[0054] [Figure 1] 1 is a schematic diagram illustrating an exemplary system for converting alcohol to fuel.

[0055] MODE FOR CARRYING OUT THE INVENTION Wherever practical, like reference numerals refer to like structures, features, or elements.

[0056] Certain exemplary implementations will now be described to provide a general understanding of the principles of the structure, function, manufacture, and use of the systems and processes disclosed herein. One or more examples of these implementations are illustrated in the accompanying drawings. Those skilled in the art will understand that the systems and processes specifically described herein and illustrated in the accompanying drawings are non-limiting exemplary implementations, and that the scope of the present invention is not defined solely by the claims. Features shown or described in connection with one exemplary implementation may be combined with features of other implementations. Such modifications and variations are intended to be within the scope of the present invention.

[0057] The terminology used herein is for the purpose of describing particular implementations and embodiments only and is not intended to be limiting. For example, as used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0058] In the description and claims, phrases such as "at least one of" or "one or more of" may appear followed by a concatenated list of elements or features. The term "and / or" may also appear with a list of two or more elements or features. Unless implicitly or explicitly contradicted by the context of use, such phrases are intended to mean any of the listed elements or features individually, or any of the listed elements or features in combination with any of the other listed elements or features. For example, the phrases "at least one of A and B," "one or more of A and B," and "A and / or B" are intended to mean "A alone, B alone, or A and B together," respectively. A similar interpretation is intended for lists containing more than two items. For example, the phrases "at least one of A, B, and C," "one or more of A, B, and C," and "A, B, and / or C" are each intended to mean "A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B, and C together." Use of the term "based on" above and in the claims is intended to mean "based at least in part on," allowing for unrecited features or elements.

[0059] Although the terms "first" and "second" may be used herein to describe various features / elements (including steps), these features / elements should not be limited by these terms unless the context indicates otherwise. These terms may be used to distinguish one feature / element from another. Thus, a first feature / element described below could be referred to as a second feature / element, and similarly, a second feature / element described below could be referred to as a first feature / element, without departing from the teachings provided herein.

[0060] As used in this specification and claims, including in the examples, unless expressly specified otherwise, all numbers can be read as if preceded by the word "about" or "approximately," even if the term does not explicitly appear. The phrase "about" or "approximately" can be used in describing a magnitude and / or location to indicate that the stated value and / or location is within a reasonably expected range of value and / or location. For example, a numerical value can have a value of + / - 0.1% of the stated value (or range of values), + / - 1% of the stated value (or range of values), + / - 2% of the stated value (or range of values), + / - 5% of the stated value (or range of values), + / - 10% of the stated value (or range of values), etc. Any numerical value set forth herein should be understood to include approximately or approximately that value unless the context indicates otherwise. For example, if the value "10" is disclosed, "about 10" is also disclosed. Any numerical range recited herein is intended to include all subranges subsumed therein. As will be appreciated by those skilled in the art, when a value is disclosed, it is understood that "less than or equal to" that value, "greater than or equal to" that value, and possible ranges between those values ​​are also disclosed. For example, if a value "X" is disclosed, "less than or equal to X" and "greater than or equal to X" (e.g., where X is a number) are also disclosed. It is also understood that throughout this application, data is provided in several different formats, and this data represents endpoints and starting points, as well as ranges for any combination of the data points. For example, if a specific data point "10" and a specific data point "15" are disclosed, it is understood that greater than, greater than, less than, less than, less than, and equal to 10 and 15, as well as 10 to 15, are considered disclosed. It is also understood that each unit between two specified units is disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0061] "WHSV" refers to weight hourly space velocity and is defined as the weight of feed flowing per unit weight of catalyst per hour.

[0062] As used herein, "aromatic" or "aromatic compound" refers to a cyclic organic carbon compound of six or more carbons, such as benzene.

[0063] All yields and conversions reported herein are by weight unless otherwise specified.

[0064] The carbon intensities described herein are calculated based on Argonne National Laboratory's (Argonne) Greenhouse gases, Regulated Emissions, and Energy use in Technologies (GREET®) Model. In the processes described herein, carbon intensity (CI) (gCO2e / MJ) is used as a measure of GHG emissions associated with the combustion (i.e., use) of high energy density fuels (i.e., greater than 110,000 BTU / gallon).

[0065] Previous reports have involved the oligomerization of a mixture of C2-C7 olefins derived from ethanol, but the light gaseous effluent obtained from ethanol dehydration, having primarily two carbon atoms, is sent to a separate dimerization unit operation, where primarily C4 + In order to maximize the formation of olefins, a nickel-based heterogeneous or homogeneous catalyst is used to convert the light hydrocarbon gaseous effluent, mainly having two carbon atoms, and ii) the C4 obtained from the dimerization unit. + Olefins are secondarily oligomerized to C8 + middle distillate oligomers, and then iii) unconverted C4 + The olefin fraction is recycled to the feed of the second oligomerization stage.

[0066] Implementations of the present subject matter have overcome challenges by developing catalytic oligomerization processes capable of oligomerizing linear and / or branched C2-C7 olefins over doped or undoped mixed metal oxide catalysts, doped or undoped zeolites, doped or undoped solid acid catalysts, or mixtures thereof, into either diesel fuel or jet fuel hydrocarbon fractions in a single pass yield of at least 30% and at a competitive cost. The processes described herein provide high selectivity (e.g., about 75% C) that meets or exceeds specifications for diesel fuel and / or jet fuel fractions. 8+ ), high throughput (e.g., approximately 45% C 9+ ) and long catalyst life (e.g., over 100 hours) for single-pass C8 to C 24 In other words, these processes convert C2-C7 olefins into C8-C 24 It involves a single oligomerization step to convert the hydrocarbons.

[0067] Generally, the process of the present invention is carried out in a reactor at a temperature of about 100° C. to 400° C., a pressure of about 200 psig to 1000 psig, and for at least 0.5 hours. -1 and contacting a feed stream comprising one or more C2 to C7 linear or branched olefins with one or more catalysts at a weight hourly space velocity (WHSV) of 1000 to 1500 rpm to form a mixture, the mixture comprising one or more C8 to C9 linear or branched olefins. 24 In some implementations, the hydrocarbons include one or more C8-C10 in a yield of at least 30%. 24 Hydrocarbons contain one or more C8-C 20 Alternatively or additionally, one or more C to C hydrocarbons may be included. 24 Hydrocarbons contain one or more C8-C 16 Hydrocarbons may be included.

[0068] The one or more C2-C7 linear or branched olefins include unsaturated hydrocarbons such as ethylene, propylene, butene, pentene, hexene, or any combination thereof. In one implementation, the two or more different C2-C7 linear or branched olefins can include ethylene, propylene, butene, or any combination thereof.

[0069] In some implementations, the feed stream can contain additional materials. For example, in addition to one or more C2-C7 linear or branched olefins, the feed stream can also contain fusel oil, residual alcohol, corn oil, water, or any combination thereof. In implementations in which the feed stream contains water, the water is present in the feed stream in an amount less than 20 ppm. In certain implementations, the water can be present in the feed stream in an amount of about 0.5-20 ppm, about 0.5-10 ppm, about 5-20 ppm, about 5-10 ppm, or about 10-20 ppm. It is also contemplated that water may be present in the feed stream in an amount outside any of these recited ranges. It is further contemplated that water may be present in the feed stream in an amount between any of these recited ranges.

[0070] The oligomerization process of the present invention can be carried out in one or more reactors. In one implementation, the one or more reactors include only a single reactor. In such an implementation, the single reactor can be a single-bed reactor or a stacked-bed reactor. In implementations where a single-bed reactor is used, the single-bed reactor can be a fixed-bed reactor or a fluidized-bed reactor. In other implementations, the one or more reactors include two or more reactors. In such configurations, the two or more reactors can be in series, parallel, or a combination of both with respect to one another.

[0071] In use, the process can be carried out at a variety of temperatures. In some implementations, for example, the reactor temperature can be between 100°C and 400°C. In other implementations, the reactor temperature can be between about 150°C and 370°C, between about 150°C and 370°C, between about 200°C and 300°C, or between about 220°C and 260°C. It is contemplated that the reactor temperature will not fall outside any of these recited ranges. It is further contemplated that the reactor temperature can be between any of these recited ranges.

[0072] Alternatively or additionally, the process can be carried out under a variety of pressures. In some implementations, for example, the reactor pressure can be about 200 psig to 1000 psig. In other implementations, the reactor pressure can be about 300 psig to 800 psig, about 400 psig to 800 psig, about 400 psig to 700 psig, about 600 psig to 800 psig, or about 650 psig to 750 psig. It is also contemplated that the reactor pressure will not fall outside any of these recited ranges. It is further contemplated that the reactor pressure can be between any of these recited ranges.

[0073] Alternatively or additionally, the process can be carried out under various weight hourly space velocities. In some implementations, for example, the WHSV is at least 0.5 h -1 Or at least 1h -1 In other implementations, the WHSV may be about 0.5 h -1 ~100 h-1 , about 1 h-1 ~50 h-1 , about 1 h-1 ~10 h-1 , or about 1 h-1 ~5 h-1 It is also contemplated that the WHSV of the reactor will not fall outside any of these recited ranges. It is further contemplated that the process may be carried out at a WHSV between any of these recited ranges.

[0074] In the process described herein, the temperature is between 100°C and 400°C, the pressure is between about 200 psig and 750 psig, and the WHSV is at least 0.5 h. -1 In some implementations, the temperature may be about 150°C to 350°C, the pressure may be about 300 psig to 700 psig, and the WHSV may be about 0.5 h. -1 ~100h -1 In other implementations, the temperature may be about 200°C to 280°C, the pressure may be about 450 psig to 700 psig, and the WHSV may be about 1 h. -1 ~50h -1 For example, the temperature may be about 240°C to 260°C, the pressure may be about 450 psig to 700 psig, and the WHSV may be about 1 h. -1 ~5h -1 Consistent with some implementations of the present disclosure, the oligomerization temperature may be about 100°C to 300°C, the reaction pressure may range from about 200 to 800 psig, and the WHSV may be about 0.5 h -1 ~100h -1 It could be.

[0075] The one or more catalysts used in the single oligomerization stage may, for example, include doped or undoped mixed metal oxide catalysts, doped or undoped zeolites, doped or undoped solid acid catalysts, or any combination thereof. Non-limiting examples of suitable mixed metal oxide catalysts include zirconium tungstated, alumina tungstated, silica tungstated, molybdenum / zirconium tungstated, molybdenum / alumina tungstated, molybdenum / silica tungstated, or any combination thereof. Non-limiting examples of suitable zeolites may be selected from those having the structure types appearing in the following list: MFI, CHA, ERI, MTF, AEI, AEL, FER, BEA, EUO, MEL, MFS, TON, FAU, MOR, MWW, MTT, zeolites ZBM-30, ZSM-48, IM-5, and IZM-2, or any combination thereof, with Si / Al greater than 10. Non-limiting examples of solid acid catalysts include solid phosphoric acid, amorphous silica alumina, amberlyst, sulfonic acid resins, etc. Non-limiting examples of dopants for metal oxides, zeolites, or solid acid catalysts include Fe, Sr, Co, Ni, La, Cr, Zr, Ru, Mo, Ir, In, Mg, W, Cu, Mn, V, Zn, Ti, Rh, Re, Ga, Bi, Hf, Sn, Pt, Pd, Ag, In, K, Na, Ca, P, B, Li, or any combination thereof. Those skilled in the art will recognize that the above-mentioned dopants can adjust the activity and selectivity of the oligomerization catalyst by changing the surface acidity depending on the desired fuel properties and aromatic content.

[0076] In some implementations, the one or more catalysts used in the oligomerization step may include nickel-doped zirconium tungstated, nickel-doped tungstated gamma-alumina, nickel-doped tungstated silica, nickel-doped amorphous silica-alumina, or nickel-doped zeolite. In one implementation, the one or more catalysts may include a first catalyst that is nickel-doped zirconium tungstated. Additionally, the one or more catalysts may include a second catalyst that is one or more zeolites or one or more solid acids, or a combination thereof. In one implementation, the first catalyst may be nickel-doped zirconium tungstated, and the second catalyst may be one or more zeolites (e.g., one or more doped zeolites).

[0077] In some implementations, the second catalyst can be a doped zeolite, which can be selected from among zeolites having structure types appearing in the following list: MFI, CHA, ERI, MTF, AEI, AER, FER, BEA, EUO, MEL, MFS, TON, FAU, MOR, MWW, MTT, and zeolites ZBM-30, ZSM-48, IM-5, and IZM-2, with Si / Al greater than 10, used alone or in mixtures with other zeolites and / or sulfonic acid mixtures.

[0078] In some implementations, when the one or more catalysts are doped mixed metal oxides, the one or more dopants present therein may include nickel, cobalt, yttrium, rhodium, ruthenium, palladium, platinum, ion, lanthanum, silica, alumina, scandium, titanium, niobium, copper, chromium, rhenium, zinc, vanadium, iridium, iron, zirconium, or any combination thereof. In implementations in which the one or more dopants are nickel, the nickel may be present in an amount of about 0.5 wt% to 5 wt% of the total weight of the one or more catalysts. In some implementations in which the one or more dopants are nickel, the nickel may be present in an amount of about 1 wt% to 2 wt% of the total weight of the one or more catalysts. It is also contemplated that the amount of nickel present in the one or more catalysts will not fall outside any of these recited ranges. It is further contemplated that the amount of nickel present in the one or more catalysts may be between any of these recited ranges.

[0079] Alternatively or additionally, in some implementations, when one or more catalysts include tungsten, the tungsten can be present in an amount of about 5 wt% to 25 wt% of the total weight of the one or more catalysts. In other implementations, the tungsten can be present in an amount of about 10 wt% to 20 wt% of the total weight of the one or more catalysts, in an amount of about 10 wt% to 20 wt% of the total weight of the one or more catalysts, or in an amount of about 10 wt% to 15 wt% of the total weight of the one or more catalysts. In one implementation, the tungsten can be present in an amount of about 15 wt% of the total weight of the one or more catalysts. It is also contemplated that the amount of tungsten present in the one or more catalysts will not fall outside any of these recited ranges. It is further contemplated that the amount of tungsten present in the one or more catalysts can be between any of these recited ranges.

[0080] Catalyst preparation can be accomplished by incipient wetness impregnation techniques. The catalyst for the process of the present invention can include nickel-doped zirconium tungstated, nickel-doped tungstated gamma-alumina, nickel-doped silica tungstated, nickel-doped amorphous silica-alumina, or nickel-doped zeolite catalyst as a single catalyst or in a stacked bed reactor configuration with a zeolite or solid acid catalyst.

[0081] Doped WO x / Zirconium catalyst, WO x / Alumina catalyst, WO x A C2-C7 olefin oligomerization process using a silica catalyst, a solid acid catalyst, amorphous silica alumina, or a zeolite as a single catalyst or in a stacked bed configuration with one or more zeolites or one or more solid acid catalysts can produce high yields (e.g., greater than about 60%) of bio-based diesel or jet fuel at relatively low temperatures and pressures (e.g., temperatures less than about 300°C and pressures about 800 psig). Other known catalysts for the oligomerization of C2-C7 linear olefins (e.g., standard zeolites, modified zeolites, SPAs, Nafion resins, etc.) are rapidly deactivated and require reactivation, are relatively expensive, have poor tolerance to the presence of oxygenates, and are C 5-7 High levels of oligomer cracking / isomerization occur as evidenced by high levels of olefins and low isolated yields of jet and / or diesel fractions.

[0082] Granular or extruded catalysts are suitable for the oligomerization step. The catalyst(s) can have a variety of sizes and morphologies. In some implementations, the catalyst(s) can have a diameter greater than 0.1 mm. In one implementation, the catalyst(s) can have a diameter between about 0.2 mm and 3.0 mm or between 1 mm and 10 mm.

[0083] The one or more catalysts can be regenerated as needed under conditions suitable for the processes described herein. Consistent with some implementations of the present disclosure, the one or more catalysts can be regenerated in situ in air. In certain implementations, the one or more catalysts can be regenerated at temperatures between 400°C and 600°C. In one implementation, for example, the catalysts can be regenerated at 500°C. Further, consistent with some implementations of the present disclosure, the one or more catalysts can be regenerated for 30 minutes to 6 hours. In one implementation, for example, the catalysts can be regenerated for 4 to 6 hours.

[0084] The oligomerization reaction can be carried out in a continuous mode for large-scale production of oligomers. Continuous mode is operated by using a fixed-bed reactor, and the reactant flow can be either upflow or downflow. Because the oligomerization reaction is highly exothermic, the oligomerized olefin reaction product or saturated C8-C8 is added to control the heat of reaction. 24 It can be useful to use a hydrocarbon recycle stream. Batch mode oligomerization reactions are also possible, but tend to have lower throughput and higher operating costs.

[0085] Optionally, the processes described herein can further include preparing a feed stream, referred to herein as a conversion step. The feed stream can be prepared in a variety of ways from a variety of sources.

[0086] In some implementations, the feedstream can be prepared by deriving one or more C2-C7 linear or branched olefins from petroleum. Petroleum is a non-renewable resource, and its combustion results in carbon emissions into the environment. There is a growing demand to use biomass sources to replace petroleum as a starting point for fuel synthesis. As the availability and cost of bioethanol increases and decreases, bioethanol has the potential to become an inexpensive, renewable feedstock for producing various olefins for use in downstream hydrocarbon production. Therefore, the use of biomass-derived alcohols in the synthesis of fuel base stocks is of great interest.

[0087] In other implementations, one or more C2-C7 linear or branched olefins in the feedstream can be derived from renewable resources obtained from biomass (e.g., sugar-producing plants, amylase plants, or lignocellulosic biomass). By way of example, in certain implementations, one or more C2-C7 linear or branched olefins in the feedstream can be derived from one or more bio-derived C1-C5 alcohols and / or corn oil.

[0088] In some implementations, one or more C2-C7 linear or branched olefins can be produced by contacting an input stream containing one or more C1-C5 linear or branched alcohols with one or more catalysts in one or more reactors to form one or more C2-C7 linear or branched olefins. The one or more catalysts can include a doped or undoped alumina catalyst containing one or more of zirconium, titanium, tungsten, or silicon, in neutral or ionic form. Alternatively or additionally, the one or more catalysts can include a doped or undoped zeolite catalyst. In one implementation, fuel-grade ethanol conversion can be carried out over a mixture of doped or undoped zeolite gamma-alumina catalysts mixed with doped or undoped zeolites in a single fixed-bed reactor. The resulting C2-C7 olefin mixture can then be oligomerized in its entirety to produce gasoline, jet fuel, and / or diesel fuel fractions.

[0089] As an example, the conversion of methanol and / or mixtures of methanol with C2-C5 alcohols proceeds with high yields and carbon accountability, as well as mixtures of C2-C7 olefins. Exemplary single reaction steps include: i) dehydration; ii) C 2+ olefin oligomerization, iii) skeletal rearrangement, and iv) mainly ethylene and propylene with small amounts of C 4+It involves cracking to produce olefins along with aromatics. Thus, by passing a vaporized stream of methanol and ethanol at about 300°C to about 450°C through a single fixed catalyst bed containing a physical mixture containing a first portion of silicided, zirconated, titanated, niobium, or fluorinated γ-alumina or γ-alumina combined with a doped zeolite (boron, phosphor, or combinations thereof) as the second catalyst portion, a mixture of C2 to C7 olefins can be obtained that can be separated for sale or oligomerized "in situ" to primarily jet fuel and / or diesel fuel after removing condensed water. This catalyst combination in a single fixed bed reactor can be used for: i) dehydration; ii) C 2+ iii) oligomerization to olefins, iii) backbone rearrangement, and iv) cracking are achieved, resulting in longer catalyst on-stream time (ToS), improved hydrothermal stability, improved selectivity to olefins with less saturates and aromatics, and improved alcohol conversion.

[0090] In one exemplary implementation, a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C7 olefins may include contacting an input stream comprising one or more C1-C5 linear or branched alcohols with at least a first catalyst and a second catalyst in a single-bed reactor to form an output stream comprising one or more C2-C5 olefins, wherein the single-bed reactor has a temperature of about 350° C. to about 750° C., a gauge pressure of 0 to about 30 bar, and a weight hourly space velocity (WHSV) of about 0.5 to about 5.0.

[0091] Furthermore, in some implementations, the production of one or more C2-C7 linear or branched olefins can include recycling one or more specific olefin fractions (e.g., C2+C4+C5 or C2+C5, etc.) in a closed-loop process configuration, optionally while co-feeding C1-C5 alcohols. This can result in maximizing the intended yield of selected olefins. For example, combining recycling of the C2+C4+C5 olefin fraction with co-feeding of C1-C5 alcohols can result in an intended propylene carbon yield of greater than 80 weight percent. Thus, selective recycling of the C2+C5 olefin fraction can result in an intended propylene and butene combined carbon yield of greater than 80 weight percent. Additionally, recycling of the C4+C5 olefin fraction can result in an intended ethylene and propylene combined carbon yield of greater than 80 weight percent. Exemplary single-step reactions include: i) in situ dehydration; ii) C 3+ These processes can include oligomerization to olefins, iii) backbone rearrangement, and iv) cracking to C2-C7 olefins along with aromatics.

[0092] Exemplary catalyst combinations physically mixed in a single fixed bed reactor for C2 to C7 olefin formation include doped zeolites, such as crystalline silicates of the group ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON, with Si / Al greater than 10, or crystalline silicates of the group ZSM5 (MFI or BEA framework), CHA, FER, FA, with Si / Al greater than 10. The molecular sieve may comprise a dealuminated crystalline silicate of group U, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON, or a phosphor- and / or boron-modified crystalline silicate of group ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON, with Si / Al greater than 10, or a silico-aluminophosphate type molecular sieve of group AEL.

[0093] Non-limiting examples of suitable dopants for zeolites, metal oxides or sulfonic acid resins include Fe, Sr, Co, Ni, La, Cr, Zr, Ru, Mo, Ir, Mg, W, Cu, Mn, V, Zn, Ti, Rh, Re, Ga, Bi, Hf, Sn, Pt, Ag, In, K, Na, Ca, P, B, Li, or any combination thereof. Those skilled in the art will recognize that the above-mentioned dopants can tune the activity and selectivity of the oligomerization catalyst by altering the surface acidity depending on the desired fuel properties and aromatic content.

[0094] One or more granular or extruded catalysts can be used in the production of one or more of the one or more C2 to C7 linear or branched olefins described herein. For example, in some implementations, the one or more granular or extruded catalysts can have a particle size of at least about 0.05 mm, about 0.1 mm or more, or from about 0.05 mm to about 2.5 mm, including all subranges therebetween. In one implementation, the one or more granular or extruded catalysts can have a particle size of about 0.4 mm to about 2.0 mm.

[0095] In some implementations, the C1-C5 alcohol can be one or more of methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, tert-butanol, pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-pentanol, 2-pentanol, 3-methyl-2-butanol, or 2-methyl-2-butanol. The C1-C5 alcohol can be obtained from a biobased process, such as, but not limited to, fermentation. For example, the C1-C5 straight-chain or branched alcohol can be biobased and produced by a fermentation process. That is, the C1-C5 straight-chain or branched alcohol is produced from a renewable biobased resource rather than from petroleum.

[0096] C8-C9 produced by the processes described herein 24The resulting yield of hydrocarbons may be at least 30%. In some implementations, 24 The resulting yield of hydrocarbons can be about 30% to 99%. In some implementations, C8 to C9 24 The yield of hydrocarbons may be at least 35. In other implementations, one or more C to C 24 The yield of hydrocarbons may be at least 45%, at least 60%, at least 65% or at least 80%.

[0097] In some implementations, one or more of C8-C 24 Hydrocarbons contain one or more low carbon strength C8-C 24 In one implementation, one or more C to C hydrocarbons may be included. 24 All hydrocarbons may be low carbon strength hydrocarbons. As used herein, hydrocarbons (e.g., one or more C to C 24 Low carbon intensity when used to reformulate petroleum-derived liquid hydrocarbon fuels refers to a carbon intensity that is at least about 50% lower than the typical carbon intensity of petroleum-derived liquid hydrocarbon fuels, which may be about 90 g CO2e / MJ to 100 g CO2e / MJ based on the Argonne GREET® model.

[0098] In some implementations, one or more of C8-C 24 Hydrocarbons include C8-C8 with one or more zero carbon intensities. 24 In one implementation, one or more C to C hydrocarbons may be included. 24 All hydrocarbons may be hydrocarbons with zero carbon intensity. As used herein, hydrocarbons (e.g., one or more C to C 24 When used to reformulate petroleum-derived liquid hydrocarbon fuels, zero carbon intensity refers to a carbon intensity that is at least about 90% to 100% lower than the typical carbon intensity of petroleum-derived liquid hydrocarbon fuels.

[0099] In some implementations, one or more of C8-C 24 Hydrocarbons contain one or more C8-C8 with negative carbon strength. 24In one implementation, one or more C to C hydrocarbons may be included. 24 Any hydrocarbon may be a negative carbon strength hydrocarbon. As used herein, negative carbon strength when used to reform olefins or hydrocarbons refers to a carbon strength that is 100% or more lower than the typical carbon strength of petroleum-derived liquid hydrocarbon fuels.

[0100] Further disclosed herein are methods for preparing corn oil-derived olefins, comprising: one or more C1 to C5 alcohols and / or one or more C2 to C8 linear or branched olefins derived from corn oil; 24 2. A process for converting a feed stream containing one or more C2-C8 linear or branched olefins into hydrocarbons, the process comprising: subjecting a feed stream containing one or more C2-C8 linear or branched olefins to a temperature of about 240° C. to 300° C., a pressure of about 450 psig to 750 psig, and a temperature of about 1 hour in a reactor. -1 ~10h -1 with one or more catalysts, wherein the one or more catalysts comprise nickel-doped tungstated zirconium, nickel-doped tungstated gamma-alumina, nickel-doped tungstated silica, nickel-doped amorphous silica-alumina, or nickel-doped zeolite catalyst, either as a single catalyst or in a stacked bed reactor configuration with a zeolite or solid acid catalyst, wherein the nickel is present in an amount of about 1.5 weight percent of the total weight of the one or more catalysts and the tungsten is present in an amount of about 15 weight percent of the total weight of the one or more catalysts, and 24 A mixture is produced with a hydrocarbon yield of at least 35%.

[0101] One or more C8-C produced in the oligomerization step 24 Hydrocarbons and subsequent fractions (e.g., unsaturated one or more C8-C 24 Hydrocarbons) can be directly utilized in the production of renewable diesel fuel and, after hydrogenation, renewable jet fuel. Thus, the process described herein can be used to generate one or more C8-C9 hydrocarbons. 24 The product stream can further include hydrogenating the hydrocarbon to produce a product stream. Thus, the product stream can include one or more saturated C-C hydrocarbons.24 The hydrogenation catalyst that can be used in this process can be selected from any supported catalyst such as Pd / C, Pd / alumina, Pd / silica, Pd / silica-alumina, Pt / C, Pt / alumina, Pt / silica, Pt / silica-alumina, Ru / C, Ru / alumina, Ru / silica, Ru / silica-alumina, Ni / C, Ni / alumina, Ni / silica, Ni / silica-alumina, or any combination thereof.

[0102] Additionally, the processes described herein may comprise, after hydrogenation of the product stream, the addition of one or more C8-C 24 The process may also include separating the hydrocarbons to produce renewable jet fuel or renewable diesel fuel. For example, the process may include separating one or more C8-C9 hydrocarbons. 24 The process can include separating hydrocarbons into different fractions to produce renewable jet fuel or renewable diesel fuel of a desired composition. The separation process can include separating one or more C8-C9 hydrocarbons. 24 This may include distilling hydrocarbons to produce renewable jet fuel or renewable diesel fuel.

[0103] In some implementations, the processes described herein can further include blending a renewable jet fuel or a renewable diesel fuel. The blending process can include blending aromatic compounds or fossil fuel-derived compounds with the renewable jet fuel or renewable diesel fuel. In one implementation, one or more C8-C9 24 Blending hydrocarbons can include blending aromatic compounds with renewable jet fuel or renewable diesel fuel to modify viscosity, ignition temperature, or other physical and / or chemical properties. In another implementation, one or more C8-C9 aromatic compounds can be blended with renewable jet fuel or renewable diesel fuel to modify viscosity, ignition temperature, or other physical and / or chemical properties. 24 Hydrocarbon blending involves blending fossil fuel-derived compounds with renewable jet fuel or renewable diesel fuel to modify the heat of combustion, or other chemical and / or physical properties.

[0104] In some implementations, the process of the present invention can produce renewable diesel fuel. Renewable diesel fuel has a cetane number of 40 or greater. Higher cetane numbers include C8 to C 24 The hydrocarbons can be separated and / or blended to produce a renewable diesel fuel that can be used in a variety of applications, such as diesel engines in small-displacement vehicles or large-displacement machinery.

[0105] 1 shows an exemplary system 100 for converting one or more alcohols into fuel. The system includes a conversion stage 102 in which an input stream 104 (e.g., an alcohol, such as methanol and / or ethanol) is converted into a feed stream 106 (e.g., one or more olefins, such as one or more of C2 to C7 olefins), and a conversion stage 103 in which the feed stream 106 is oligomerized (e.g., to produce at least one or more C8 to C9 olefins). 24 The system 100 includes an oligomerization stage 108 that converts the converted hydrocarbons into a mixture stream 110 (of hydrocarbons), and a hydrogenation stage 112 that hydrogenates the mixture stream 110 to produce a product stream 114. In the illustrated system 100, the oligomerization stage 108 includes a single oligomerization step. While the system can include any number and type of reactors, in the illustrated system 100, the conversion stage 102 is carried out in a first fixed bed reactor 116 and the oligomerization stage 108 is carried out in a second, separate fixed bed reactor 118. Additionally, the hydrogenation stage 112 is carried out in a hydrotreater 120.

[0106] In some implementations, system 100 can include one or more recycle streams. For example, as shown in Figure 1, a portion of one or more C2-C5 olefins in the feed stream can be recycled to input stream 104 via first recycle stream 122. Alternatively, or additionally, as shown in Figure 1, a portion of one or more C2-C7 olefins in mixture stream 110 can be recycled to feed stream 106 via second recycle stream 124.

[0107] In some implementations, the oligomerization of linear C2-C8 olefins into diesel fractions is carried out using doped WO x / Zirconium catalyst, WO x / Alumina catalyst, WO x Silica catalyst, solid acid catalyst, amorphous silica alumina, or zeolite is used as a single catalyst, or in a stacked bed configuration (which can be inexpensively produced from commercially available raw materials) with one or more zeolites, one or more solid acid catalysts, or one or more sulfonic acid resin catalysts, at a reaction pressure of 250 to 1000 psig, a reaction temperature of 125 to 380°C, and a weight hourly space velocity (WHSV) of 1.0 h -1 ~10.0h -1 By proceeding with this process, single-pass C2-C8 olefin conversions of at least 40% can be obtained, as illustrated in the following examples. Removal and recycling of unreacted C2-C5 olefins allows for a final overall yield of at least 40% for naphtha, jet, or diesel products, based on the initial mass of olefins fed to the oligomerization step. The catalyst mixture is stable, and extended on-stream reaction times have been demonstrated. Furthermore, the catalyst mixture can be regenerated via air to restore activity.

[0108] The following specific examples are intended to be illustrative and should not be construed as limiting the scope of the claims.

[0109] Example Reactor setup:

[0110] Olefin oligomerization reactions were carried out at temperatures between 120 and 300 °C using a fixed-bed reactor containing 14 g of the designated catalyst and with liquefied olefins flowing through and recycled downward. The flow rate was controlled by a Teledyne Model 500D syringe pump connected to a D-series pump controller, and the olefin flow rate was adjusted to obtain the target olefin weight hourly space velocity (WHSV). The reaction temperature was maintained constant by a Thermo-Scientific Lindberg Blue M furnace. The liquid-phase reactor effluent was analyzed for olefin content by GC and the olefin conversion was calculated by comparing the feed mass accountability with the recovered liquid mass. Catalyst screening required a mass accountability greater than 90% for further development and evaluation. Before the start of the feed, the catalyst was pretreated with nitrogen at 300 °C for 1 h.

[0111] Example 1: Preparation of nickel-impregnated tungsten zirconium catalyst

[0112] Nickel-doped WO x The zirconium / zirconium catalysts were prepared by the incipient wetness impregnation technique. Precursor metal salts (Sigma Aldrich) were impregnated onto WO as the support. x Nickel-impregnated WO was added to deionized water in an amount that, when added to zirconium (15 wt. % tungstate), would produce a nickel loading of 1.3 wt. %. x The zirconium catalyst was dried at 140°C for 1 hour and then calcined at 550°C for 4 hours.

[0113] Example 2: Nickel-doped WO x Formation of middle distillates by oligomerization of a mixed C2-C8 linear or branched olefin feed (35% ethylene, 25% propylene, 20% butene, 8% pentene, 12% C2-C5 saturates) using the olefin effluent of the oligomerization reactor as recycle over a zirconium catalyst (14 g). Mass ratio of olefin recycle to fresh olefin feed: 1 / 1. Reaction conditions: T = 240 °C, WHSV = 4.1 h. -1, P = 640 psig. Liquid mass accountability = 92% (total mass fed / mass discharged as liquid); mass to vapor = 8%; single-pass ethylene conversion = 77% (1 - ethylene output / ethylene input).

[0114] Oligomeric composition of liquid effluent: [Table 1]

[0115] Oligomer composition of vapor emissions: [Table 2]

[0116] Example 3: Nickel-doped WO x Formation of middle distillates by oligomerization of a mixed C2-C8 linear or branched olefin feed (35% ethylene, 25% propylene, 20% butenes, 8% pentenes, 12% C2-C5 saturates) using the saturated effluent of the oligomerization reactor as recycle over a zirconium catalyst (14 g). The mass ratio of saturated recycle to fresh olefin feed was 1 / 1. Reaction conditions: T = 240 °C, WHSV = 4.1, P = 720 psig. Liquid mass accountability = 84% (total mass feed / mass discharge as liquid); mass to vapor = 16%; single-pass ethylene conversion = 69% (1 - ethylene output / ethylene input).

[0117] Oligomeric composition of liquid effluent: [Table 3]

[0118] Oligomer composition of vapor emissions: [Table 4]

[0119] Example 4: Nickel-doped WO in a stacked bed configuration xFormation of middle distillates by oligomerization of a mixed C2-C8 linear or branched olefin feed (35% ethylene, 25% propylene, 20% butene, 8% pentene, 12% C2-C5 saturates) using the saturated effluent of the oligomerization reactor as recycle over a zirconium catalyst (10 g) and a ZSM5 catalyst (4 g). Mass ratio of saturated recycle to fresh olefin feed: 1 / 1. Reaction conditions: T = 240 °C, WHSV = 4.1 h. -1 , P = 720 psig. Liquid mass accountability = 92% (total mass fed / mass discharged as liquid); mass to vapor = 8%; single-pass ethylene conversion = 85% (1 - ethylene output / ethylene input).

[0120] Oligomeric composition of liquid effluent: [Table 5]

[0121] Oligomer composition of vapor emissions: [Table 6]

[0122] Example 5: Oligomerization of a mixed C2-C8 linear or branched olefin feed (34.6% ethylene, 13.3% propylene, 9.6% heptane (diluent), 10.6% isobutylene, 6.7% 1-butene, 6.7% trans-2-butene, 6.7% cis-2-butene, 3.1% 2-pentene, 4.6% 2-methyl-2-butene, 1.7% 2-methyl-1-butene, 1.9% isopentane, 0.5% pentane) to form middle distillates. One-stage oligomerization reaction conditions: reactor temperature = 150 °C, WHSV = 3.4 (based on C2-C7 olefins), P = 19 bar; catalyst: 2 g Ni-impregnated zeolite (Zeolyst CBV-5524) + 4 g Amberlyst-35. Liquid mass accountability = 82% (total mass fed / mass discharged as liquid); mass to vapor = 18%; single pass ethylene conversion = 67% (1 - ethylene output / ethylene input).

[0123] Oligomeric composition of liquid effluent: 82% of reactor feed (output / input) [Table 7]

[0124] Oligomer composition of vapor effluent: Mass = 18% of reactor feed [Table 8]

[0125] Example 6: Oligomerization of mixed C2-C8 linear or branched olefin feed to form middle distillates. One-stage oligomerization reaction conditions: reactor temperature = 150 °C, WHSV = 3.4 (based on C2-C7 olefins), P = 19 bar; catalyst: Ni-impregnated zeolite (Zeolysts CBV-2314) 2 g + Amberlyst-35 (4 g). Ethylene conversion = 66% (1 - ethylene in vapor effluent / ethylene fed to oligomers); composition of oligomer feed: 34.6% ethylene, 13.3% propylene, 9.6% heptane (diluent), 10.6% isobutylene, 6.7% 1-butene, 6.7% trans-2-butene, 6.7% cis-2-butene, 3.1% 2-pentene, 4.6% 2-methyl-2-butene, 1.7% 2-methyl-1-butene, 1.9% isopentane, 0.5% pentane

[0126] Oligomeric composition of liquid effluent: 82% of reactor feed (output / input) [Table 9]

[0127] Oligomer composition of vapor effluent: Mass = 18% of reactor feed [Table 10]

[0128] While various exemplary implementations have been described above, any of numerous modifications can be made to the various implementations without departing from the teachings herein. For example, the order in which various described method steps are performed may often be changed in alternative implementations, and in other alternative implementations, one or more method steps may be skipped entirely. Optional features of various system and process implementations may be included in some implementations and not in others. Accordingly, the foregoing description has been provided primarily for illustrative purposes and should not be construed as limiting the scope of the claims.

[0129] The examples and illustrations contained herein illustrate, by way of illustration and not limitation, specific implementations in which the subject matter may be practiced. As noted above, other implementations may be utilized and derived therefrom, such that structural and logical substitutions and changes may be made without departing from the scope of the present disclosure. Such implementations of the inventive subject matter may be individually or collectively referred to herein by the term "invention," if more than one is actually disclosed, merely for convenience and without any intention to intentionally limit the scope of the present application to any single invention or inventive concept. Thus, while specific implementations are shown and described herein, any configuration calculated to achieve the same purpose may be substituted for the specific implementation shown. The present disclosure is intended to cover any and all adaptations or modifications of various implementations. Combinations of the above implementations, as well as other implementations not specifically described herein, will be apparent to those skilled in the art upon reviewing the above description. The use of the term "based on" in the specification and claims is intended to mean "based at least in part on," allowing for unrecited features or elements.

[0130] The subject matter described herein may be embodied in systems, devices, methods, and / or articles, depending on the desired configuration. The implementations described in the foregoing description do not represent all implementations consistent with the subject matter described herein. Instead, they are merely some examples of implementations consistent with the described subject matter. While some variations have been described in detail herein, other modifications or additions are possible. In particular, additional features and / or variations may be provided in addition to those described herein. For example, the implementations described herein may be directed to various combinations and subcombinations of the disclosed features and / or combinations and subcombinations of certain additional features disclosed herein. Additionally, the logic flow depicted in the accompanying figures and / or described herein does not necessarily require the particular order shown or sequence to achieve desirable results. Other implementations may be within the scope of the following claims.

Claims

1. One or more C ２ ~C ７ A linear or branched olefin is one or more C ８ ~C ２４ 1. A process for converting hydrocarbons comprising: In the reactor, a temperature of about 100° C. to 400° C., a pressure of about 200 psig to 1000 psig, and a temperature of at least 0.5 h are applied. －１ At a weight hourly space velocity (WHSV) of ２ ~C ７ contacting a feedstream comprising linear or branched olefins with one or more catalysts to form a mixture, said mixture comprising one or more C ８ ~C ２４ and wherein the hydrocarbons are present in a yield of at least 30%. The method wherein the one or more catalysts comprise a doped mixed metal oxide.

2. 10. The method of claim 1, wherein the doped metal oxide comprises one or more dopants, the one or more dopants comprising nickel, cobalt, yttrium, rhodium, ruthenium, palladium, platinum, ion, lanthanum, silica, alumina, scandium, titanium, niobium, copper, chromium, rhenium, zinc, vanadium, iridium, or any combination thereof.

3. The method of claim 2, wherein the nickel is present in an amount of about 0.5% to 5% by weight of the one or more catalysts.

4. 4. The method of claim 1, wherein the doped mixed metal oxide comprises tungsten, zirconium, molybdenum, silica, alumina, or any combination thereof.

5. 5. The method of claim 4, wherein the tungsten is present in an amount of about 5% to 25% by weight of the one or more catalysts.

6. One or more C ２ ~C ７ A linear or branched olefin is one or more C ８ ~C ２４ 1. A method for converting hydrocarbons, comprising: In the reactor, a temperature of about 100° C. to 400° C., a pressure of about 200 psig to 1000 psig, and a temperature of at least 0.5 h are applied. －１ At a weight hourly space velocity (WHSV) of ２ ~C ７ contacting a feedstream comprising linear or branched olefins with one or more catalysts to form a mixture, said mixture comprising one or more C ８ ~C ２４ and wherein the hydrocarbons are present in a yield of at least 30%. The method, wherein the one or more catalysts comprise a first catalyst, the first catalyst comprising nickel-doped zirconium tungstated, nickel-doped tungstated gamma-alumina, nickel-doped tungstated silica, nickel-doped amorphous silica-alumina, or nickel-doped zeolite.

7. 7. The process of any one of claims 1 to 6, wherein the reactor is a single-bed reactor.

8. 8. The process of claim 7, wherein the single-bed reactor is a fixed-bed reactor or a fluidized-bed reactor.

9. 9. The process according to any one of claims 1 to 8, wherein the reactor is a stacked bed reactor.

10. 10. The method of any one of claims 6 to 9, wherein nickel is present in an amount of about 0.5% to 5% by weight of the first catalyst.

11. 11. The method of any one of claims 6 to 10, wherein tungsten is present in an amount of about 5% to 25% by weight of the first catalyst.

12. 12. The method of any one of claims 6 to 11, wherein the first catalyst comprises nickel-doped zirconium tungstate.

13. 13. The method of any one of claims 6 to 12, wherein the one or more catalysts further comprise a second catalyst.

14. 14. The method of claim 13, wherein the second catalyst comprises one or more zeolites, one or more solid acids, or a combination thereof.

15. 15. The method of claim 14, wherein the one or more solid acids comprise one or more sulfonic acid resins.

16. 15. The method of claim 14, wherein the one or more zeolites comprise one or more doped zeolites.

17. The one or more C ８ ~C ２４ The hydrocarbon may comprise one or more C ８ ~C ２０ 17. The method of any one of claims 1 to 16, comprising a hydrocarbon.

18. The one or more C ８ ~C ２４ The hydrocarbon is one or more C ８ ~C １６ 17. The method of any one of claims 1 to 16, comprising a hydrocarbon.

19. 19. The method of any one of claims 1 to 18, wherein the feed stream further comprises fusel oil, residual alcohol, corn oil, water, or any combination thereof.

20. 20. The method of claim 19, wherein the water is present in the feed stream in an amount less than 20 ppm.

21. The feed stream is a mixture of one or more C ８ ~C ２４ 21. The process of any one of claims 1 to 20, further comprising a recycle stream comprising a portion of the hydrocarbons.

22. The one or more C ２ ~C ７ 22. The process of any one of claims 1 to 21, wherein the linear or branched olefin comprises ethylene, propylene, butene, pentene, hexene, or any combination thereof.

23. 23. The method of any one of claims 1 to 22, further comprising preparing the feed stream.

24. Preparing the feed stream comprises one or more C １ ~C ５ An input stream comprising linear or branched alcohols is contacted with one or more catalysts in one or more reactors to produce said one or more C ２ ~C ７ 24. The method of claim 23, comprising forming a linear or branched olefin.

25. 25. The method of claim 24, wherein the one or more catalysts comprise a doped or undoped alumina catalyst containing one or more of zirconium, titanium, tungsten, or silicon in neutral or ionic form.

26. 26. The method of claim 24 or 25, wherein the one or more catalysts comprise a doped or undoped zeolite catalyst.

27. The one or more C １ ~C ５ 27. The method of any one of claims 23 to 26, wherein the linear or branched alcohol comprises ethanol, propanol, butanol, or any combination thereof.

28. Preparing the feed stream comprises preparing the one or more C ２ ~C ７ 24. The method of claim 23, comprising deriving the linear or branched olefin from petroleum.

29. The one or more C present in the mixture ８ ~C ２４ 29. The process of any one of claims 1 to 28, further comprising recycling a portion of the hydrocarbons into the feed stream.

30. The one or more C ８ ~C ２４ 30. The process of any one of claims 1 to 29, further comprising hydrogenating the hydrocarbon to produce a product stream.

31. The one or more C present in the product stream ８ ~C ２４ 31. The method of claim 29 or 30, further comprising recycling a portion of the hydrocarbons into the feed stream.

32. The one or more C ８ ~C ２４ 32. The method of claim 30 or 31, further comprising separating hydrocarbons from the product stream to produce renewable jet fuel or renewable diesel fuel.

33. 33. The method of claim 32, further comprising blending the renewable jet fuel with aromatic compounds or fossil fuel-derived compounds.

34. 33. The method of claim 32, further comprising blending the renewable diesel fuel with aromatic compounds or fossil fuel derived compounds.

35. The one or more C ８ ~C ２４ 35. The process of any one of claims 1 to 34, wherein the yield of hydrocarbons is about 30% to 99%.

36. The one or more C ８ ~C ２４ 36. The method of any one of claims 1 to 35, wherein the yield of hydrocarbons is at least about 45%.

37. The one or more C ８ ~C ２４ 37. The method of any one of claims 1 to 36, wherein the yield of hydrocarbons is at least about 65%.

38. The one or more C ８ ~C ２４ 38. The method of any one of claims 1 to 37, wherein the yield of hydrocarbons is at least about 80%.

39. 39. The method of any one of claims 1 to 38, wherein the pressure is about 400 psig to 700 psig or about 600 psig to 800 psig.

40. 40. The method of any one of claims 1 to 39, wherein the temperature is about 150°C to 300°C.

41. The weight hourly space velocity (WHSV) is about 1 h －１ ~about 10 hours －１ Or about 1 hour －１ ~about 5 hours －１ 41. The method of any one of claims 1 to 40, wherein

42. One or more C ２ ~C ７ A linear or branched olefin is one or more C ８ ~C ２４ 1. A process for converting hydrocarbons comprising: In the reactor, a temperature of about 250° C. to 350° C., a pressure of about 400 psig to 700 psig, and a temperature of at least 2 h are added. －１ At a weight hourly space velocity (WHSV) of ２ ~C ７ contacting a feedstream comprising linear or branched olefins with one or more catalysts to form a mixture, said mixture comprising one or more C ８ ~C ２４ and wherein the hydrocarbons are present in a yield of at least 40%. The method wherein the one or more catalysts comprise nickel-doped zirconium tungstate.

43. One or more C ２ ~C ７ 1. A process for converting linear or branched olefins into jet fuel or diesel fuel, comprising: One or more C ８ ~C ２４ forming hydrocarbons, said single oligomerization step comprising: In the reactor, a temperature of about 100° C. to 400° C., a pressure of about 200 psig to 1000 psig, and a temperature of at least 0.5 h are applied. －１ At a weight hourly space velocity (WHSV) of ２ ~C ７ contacting a feed stream comprising linear or branched olefins with one or more catalysts to form a mixture, said mixture comprising one or more C ８ ~C ２４ containing hydrocarbons in at least 30% yield; The method, wherein the one or more catalysts comprise a first catalyst, the first catalyst comprising nickel-doped zirconium tungstated, nickel-doped tungstated gamma-alumina, nickel-doped tungstated silica, nickel-doped amorphous silica-alumina, or nickel-doped zeolite.

44. The one or more C ８ ~C ２４ 44. The method of claim 43, further comprising hydrogenating the hydrocarbon to produce a product stream.

45. The one or more C present in the product stream ８ ~C ２４ 45. The method of claim 44, further comprising recycling a portion of the hydrocarbons into the feed stream.

46. The one or more C ８ ~C ２４ 46. ​​The method of claim 44 or 45, further comprising separating hydrocarbons from the product stream to produce the renewable jet fuel or the renewable diesel fuel.

47. 47. The method of any one of claims 43 to 46, further comprising blending the renewable jet fuel with an aromatic compound or a fossil fuel-derived compound.

48. 48. The method of any one of claims 43 to 47, wherein nickel is present in an amount of about 0.5% to 5% by weight of the first catalyst.

49. 49. The method of any one of claims 43 to 48, wherein tungsten is present in an amount of about 5% to 25% by weight of the first catalyst.

50. 50. The method of any one of claims 43 to 49, wherein the one or more catalysts further comprise a second catalyst.

51. 51. The method of claim 50, wherein the second catalyst comprises one or more zeolites, one or more solid acids, or a combination thereof.

52. The one or more C present in the mixture ８ ~C ２４ 52. The method of any one of claims 43 to 51, further comprising recycling a portion of the hydrocarbons into the feed stream.

53. The one or more C ２ ~C ７ The linear or branched olefin is C ２ ~C ５ 53. The method of any one of claims 43 to 52, wherein the alcohol is derived from a monohydric alcohol.

54. The one or more C ８ ~C ２４ The hydrocarbon may be one or more low carbon intensity C ８ ~C ２４ 54. The method of any one of claims 43 to 53, comprising a hydrocarbon.

55. The one or more C ８ ~C ２４ The hydrocarbon may be one or more C ８ ~C ２４ 55. The method of any one of claims 43 to 54, comprising a hydrocarbon.

56. The one or more C ８ ~C ２４ The hydrocarbon has one or more negative carbon intensities C ８ ~C ２４ 56. The method of any one of claims 43 to 55, comprising a hydrocarbon.

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