Process for Converting C2-C7 Olefins into Fuel

Description

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Patent Application Nos. 63/432,650 and 63/459,523 filed on Dec. 14, 2022 and Apr. 14, 2023, respectively, each 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 on Aug. 2, 2023, entitled “PROCESS FOR CONVERTING C₂-C₇ OLEFINS INTO FUEL,” the disclosures of which are incorporated herein by reference in their entirety.

TECHNICAL FIELD

The subject matter described herein relates to a process for converting one or more C₂-C₇ linear or branched olefins to fuel (e.g., one or more C₈-C₂₄ hydrocarbons).

BACKGROUND

Traditionally, petroleum is used as the starting point for the synthesis of fuels. For example, the oligomerization of light gaseous mono-olefins to form gasoline or diesel type hydrocarbons has been carried out by using acid catalysts such as supported phosphoric acid, and olefin dimers have been generally obtained for gasoline additives after hydrogenation of the dimers. Olefin trimerization has been mainly carried out by using solid acid catalysts, such as heteropoly acid, zirconium, zeolites, amorphous silica alumina and sulfated titania. Ionic liquids are also used for these reactions. However, these catalyst compositions can be expensive and can result in low yields. Moreover, these processes produce oligomers in a non-selective manner by the oligomerization of C₂-C₇ olefins, which typically generate a mathematical distribution (Schulz-Flory or Poisson) of oligomers, which often does not match market demand.

Nickel-based heterogeneous catalysts have also been used for ethylene oligomerization to provide mixtures of C₂-C₈ olefins, which are secondarily oligomerized to C₄-C₂₄ olefins. While these catalysts may be less expensive, the major products of these reactions are lower carbon number olefins and hydrocarbons, and not primarily C₈⁺ oligomers, which is required for efficient production of renewable jet or diesel fuel.

In other implementations, processes have been reported that utilize cation exchange resins for oligomerizing isobutene and other light olefins derived from petroleum to jet fuel range oligomers. Tetramers or pentamers could also be obtained by the oligomerization of pre-formed dimers with ion exchange resins. Moreover, an ion exchange resin, Amberlyst-15, has been used in the oligomerization of light olefins. Similarly, Amberlyst-35 ion exchange resin affords higher levels of trimers, but dimers are present at 30-40% mass yield, which can ultimately decrease the amount of jet and diesel fuel production, thereby increasing cost.

Accordingly, there remains a need for improved catalyst technologies that result in greater yields to fuels from light gaseous mono-olefins (e.g., C₂-C₇).

SUMMARY

Aspects of the current subject matter relate to process for converting one or more C₂-C₇ linear or branched olefins to one or more C₈-C₂₄ hydrocarbons. In some implementations, one or more of the following features may optionally be included in any feasible combination.

In one implementation, an exemplary process for converting one or more C₂-C₇ linear or branched olefins to one or more C₈-C₂₄ hydrocarbons can include contacting a feed stream that includes the one or more C₂-C₇ linear or branched olefins with one or more catalysts in a reactor at a temperature from about 100° C. to 400° C., a pressure from about 200 psig to 1000 psig, and a weight hourly space velocity (WHSV) of at least 0.5 h⁻¹ to form a mixture. The mixture includes one or more C₈-C₂₄ hydrocarbons at a yield of at least 30%; and the one or more catalysts include a doped mixed metal oxide.

In some implementations, the doped metal oxide can include one or more dopants. The one or more dopants can include 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, the nickel can be present in an amount that is from about 0.5 weight percent to 5 weight percent of the one or more catalysts.

In some implementations, the doped mixed metal oxide can include tungsten, zirconium, molybdenum, silica, alumina, or any combination thereof. The tungsten can be present in an amount that is from about 5 weight percent to 25 weight percent of the one or more catalysts.

In another implementation, an exemplary process for converting one or more C₂-C₇ linear or branched olefins to one or more C₈-C₂₄ hydrocarbons, the process can include contacting a feed stream that includes the one or more C₂-C₇ linear or branched olefins with one or more catalysts in a reactor at a temperature from about 100° C. to 400° C., a pressure from about 200 psig to 1000 psig, and a weight hourly space velocity (WHSV) of at least 0.5 h⁻¹ to form a mixture. The mixture includes the one or more C₈-C₂₄ hydrocarbons at a yield of at least 30% and the one or more catalysts includes a first catalyst. The first catalyst can include nickel doped tungstated zirconium, nickel doped tungstated γ-alumina, nickel doped tungstated silica, nickel doped amorphous silica alumina, or nickel doped zeolite.

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.

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

In some implementations, nickel can be present in an amount that is from about 0.5 weight percent to 5 weight percent of the first catalyst.

In some implementations, tungsten can be present in an amount that is from about 5 weight percent to 25 weight percent of the first catalyst.

In some implementations, the first catalyst includes nickel doped tungstated zirconium.

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

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

In some implementations, the one or more C₈-C₂₄ hydrocarbons can include one or more C₈-C₂₀ hydrocarbons.

In some implementations, the one or more C₈-C₂₄ hydrocarbons can include one or more C₈-C₁₆ hydrocarbons.

In some implementations, the feed stream can further include a fusel oil, a residual alcohol, corn oil, water, or any combination thereof. The water can be present in the feed stream in an amount of less than 20 ppm.

In some implementations, the process can further include a recycle stream that can include a portion of the one or more C₈-C₂₄ hydrocarbons of the mixture.

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

In some implementations, the process can further include preparing the feed stream, which can include contacting an input stream with one or more catalysts in one or more reactors to form the 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.

In some implementations, the one or more catalysts can include a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium, titanium, tungsten, or silicon. In some implementations, the one or more catalysts can include a doped or undoped zeolite catalyst.

In some implementations, the process can further include preparing the feed stream, which can include deriving the one or more C₂-C₇ linear or branched olefins from petroleum.

In some implementations, the process can further include recycling a portion of the one or more C₈-C₂₄ hydrocarbons present in the mixture into the feed stream.

In some implementations, the process can further include hydrogenating the one or more C₈-C₂₄ hydrocarbons to produce a product stream.

In some implementations, the process can further include recycling a portion of the one or more C₈-C₂₄ hydrocarbons present in the product stream into the feed stream.

In some implementations, the process can further include separating the one or more C₈-C₂₄ 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 an aromatic compound or a fossil-fuel derived compound. In some implementations, the process can further include blending the renewable diesel fuel with an aromatic compound or a fossil-fuel derived compound.

In some implementations, the yield of the one or more C₈-C₂₄ hydrocarbons can be from about 30% to 99%.

In some implementations, the yield of the one or more C₈-C₂₄ hydrocarbons can be at least about 45%.

In some implementations, the yield of the one or more C₈-C₂₄ hydrocarbons can be at least about 65%.

In some implementations, the yield of the one or more C₈-C₂₄ hydrocarbons can be at least about 80%.

In some implementations, the pressure can be from about 400 psig to 700 psig or from about 600 psig to 800 psig.

In some implementations, the temperature can be from about 150° C. to 300° C.

In some implementations, the weight hourly space velocity (WHSV) can be from about 1 h⁻¹ to about 10 h⁻¹ or from about 1 h⁻¹ to about 5 h⁻¹.

In another implementation, an exemplary process for converting one or more C₂-C₇ linear or branched olefins to one or more C₈-C₂₄ hydrocarbons can include contacting a feed stream that includes the one or more C₂-C₇ linear or branched olefins with one or more catalysts in a reactor at a temperature from about 250° C. to 350° C., a pressure from about 400 psig to 700 psig, and a weight hourly space velocity (WHSV) of at least 2 h⁻¹ to form a mixture. The mixture includes one or more C₈-C₂₄ hydrocarbons at a yield of at least 40% and the one or more catalysts comprise nickel doped tungstated zirconium.

In another implementation, an exemplary for converting one or more C₂-C₇ linear or branched olefins into jet fuel or diesel fuel can include forming, via a single oligomerization step, one or more one or more C₈-C₂₄ hydrocarbons. The single oligomerization step includes contacting a feed stream comprising the one or more C₂-C₇ linear or branched olefins with one or more catalysts in a reactor at a temperature from about 100° C. to 400° C., a pressure from about 200 psig to 1000 psig, and a weight hourly space velocity (WHSV) of at least 0.5 h⁻¹ to form a mixture The mixture includes the one or more C₈-C₂₄ hydrocarbons at a yield of at least 30% and the one or more catalysts comprise a first catalyst, the first catalyst comprising nickel doped tungstated zirconium, nickel doped tungstated γ-alumina, nickel doped tungstated silica, nickel doped amorphous silica alumina, or nickel doped zeolite.

In some implementations, the process can further include hydrogenating the one or more C₈-C₂₄ hydrocarbons to produce a product stream.

In some implementations, the process can further include recycling a portion of the one or more C₈-C₂₄ hydrocarbons present in the product stream into the feed stream.

In some implementations, the process can further include separating the one or more C₈-C₂₄ hydrocarbons from the product stream to produce the renewable jet fuel or the renewable diesel fuel.

In some implementations, the process can further include blending the renewable jet fuel with an aromatic compound or a fossil-fuel derived compound.

In some implementations, nickel can be present in an amount that is from about 0.5 weight percent to 5 weight percent of the first catalyst.

The some implementations, tungsten can be present in an amount that is from about 5 weight percent to 25 weight percent of the first catalyst.

In some implementations, the one or more catalysts further include a second catalyst. The second catalyst can include one or more zeolites or one or more solid acids, or a combination thereof.

In some implementations, the process can further include recycling a portion of the one or more C₈-C₂₄ hydrocarbons present in the mixture into the feed stream.

In some implementations, the one or more the one or more C₂-C₇ linear or branched olefins can be derived from C₂-C₅ monohydric alcohols.

In some implementations, the one or more C₈-C₂₄ hydrocarbons can include one or more low carbon intensity C₈-C₂₄ hydrocarbons.

In some implementations, the one or more C₈-C₂₄ hydrocarbons can include one or more zero carbon intensity C₈-C₂₄ hydrocarbons.

In some implementations, the one or more C₈-C₂₄ hydrocarbons can include one or more negative carbon intensity C₈-C₂₄ hydrocarbons.

The 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 be 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.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated into and constitute a part of this specification, show certain implementations of the subject matter disclosed herein and, together with the description, help explain some of the principles associated with the disclosed implementations. In the drawings:

FIG. 1 is a schematic illustration of an exemplary system for conversion of alcohol(s) to fuel.

When practical, similar reference numbers denote similar structures, features, or elements.

DETAILED DESCRIPTION

Certain exemplary implementations will now be described to provide an overall 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. The features illustrated or described in connection with one exemplary implementation may be combined with the features of other implementations. Such modifications and variations are intended to be included within the scope of the present invention.

Terminology used herein is for the purpose of describing particular implementations and implementations 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 indicates otherwise.

In the description and in the claims, phrases such as “at least one of” or “one or more of” may occur followed by a conjunctive list of elements or features. The term “and/or” may also occur in a list of two or more elements or features. Unless otherwise implicitly or explicitly contradicted by the context in which it used, such a phrase is intended to mean any of the listed elements or features individually or any of the recited elements or features in combination with any of the other recited 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 each intended to mean “A alone, B alone, or A and B together.” A similar interpretation is also intended for lists including three or more 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 and 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,” such that an unrecited feature or element is also permissible.

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 feature/element. Thus, a first feature/element discussed below could be termed a second feature/element, and similarly, a second feature/element discussed below could be termed a first feature/element without departing from the teachings provided herein.

As used herein in the specification and claims, including as used in the examples and unless otherwise expressly specified, all numbers can be read as if prefaced by the word “about” or “approximately,” even if the term does not expressly appear. The phrase “about” or “approximately” may be used when describing magnitude and/or position to indicate that the value and/or position described is within a reasonable expected range of values and/or positions. For example, a numeric value can have a value that is +/−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 values given herein should also be understood to include about or approximately that value, unless the context indicates otherwise. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. It is also understood that when a value is disclosed that “less than or equal to” the value, “greater than or equal to the value” and possible ranges between values are also disclosed, as appropriately understood by the skilled artisan. For example, if the value “X” is disclosed the “less than or equal to X” as well as “greater than or equal to X” (e.g., where X is a numerical value) is also disclosed. It is also understood that the throughout the application, data is provided in a number of different formats, and that this data, represents endpoints and starting points, and ranges for any combination of the data points. For example, if a particular data point “10” and a particular data point “15” are disclosed, it is understood that greater than, greater than or equal to, less than, less than or equal to, and equal to 10 and 15 are considered disclosed as well as between 10 and 15. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

“WHSV” refers to weight hourly space velocity and is defined as the weight of the feed flowing per unit weight of the catalyst per hour.

“Aromatics” or “aromatic compounds” as used herein refer to cyclic organic carbon compounds consisting of six or more carbons (e.g. benzene, etc.).

All yields and conversions described herein are on a weight basis unless specified otherwise.

Carbon intensity, as described herein, is calculated based on the 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 the GHG emissions associated with the combustion (i.e. the use) of a high energy density fuel (i.e. greater than 110,000 BTU/gallon).

While previous reports involve oligomerization of a C₂-C₇ olefin mixture derived from ethanol, the resulting light gaseous effluent from ethanol dehydration, having predominately two carbon atoms, is i) directed to a separate dimerization unit operation in which a nickel based heterogeneous or homogeneous catalyst was used for converting the light hydrocarbon gaseous effluent with primarily two carbon atoms to maximize formation of primarily C₄⁺ olefins, and ii) the resulting C₄⁺ olefins from the dimerization unit is secondly oligomerized to C₈⁺ middle distillate oligomers, followed by iii) recycling the unconverted C₄⁺ olefin fraction to the feed of the secondary oligomerization stage.

Implementations of the current subject matter overcame challenges by developing a oligomerization catalytic process in which linear and/or branched C₂-C₇ olefins may be oligomerized, via doped or undoped mixed metal oxide catalyst, doped or undoped zeolites, doped or undoped solid acid catalyst, or mixtures thereof to either diesel or jet fuel hydrocarbon fractions in single-pass yields of at least 30% and at competitive costs. The processes described herein produce C₈-C₂₄ hydrocarbons in a single-pass with high selectivity (e.g., about 75% C₈₊), high throughput (e.g., about 45% C₉₊), and long catalyst life (e.g., greater than 100 hours) that meet or exceed diesel and/or jet fuel fraction specifications. In other words, these processes includes a single oligomerization stage that converts C₂-C₇ olefins into C₈-C₂₄ hydrocarbons.

In general, the present processes include contacting a feed stream, which includes the one or more C₂-C₇ linear or branched olefins, with one or more catalysts in a reactor at a temperature from about 100° C. to 400° C., a pressure from about 200 psig to 1000 psig, and a weight hourly space velocity (WHSV) of at least 0.5 h⁻¹ to form a mixture, the mixture including one or more C₈-C₂₄ hydrocarbons at a yield of at least 30%. In some implementations, the one or more C₈-C₂₄ hydrocarbons can include one or more C₈-C₂₀ hydrocarbons. Alternatively, or in addition, the one or more C₈-C₂₄ hydrocarbons can include one or more C₈-C₁₆ hydrocarbons.

The one or more C₂-C₇ linear or branched olefins include unsaturated hydrocarbons, e.g., ethylene, propylene, butene, pentene, hexene, or any combination thereof. In one implementation, one or more C₂-C₇ linear or branched olefins can include ethylene, propylene, butene, or any combination thereof.

In some implementations, the feed stream can include additional material. For example, in addition to the one or more C₂-C₇ linear or branched olefins, the feed stream can also include a fusel oil, a residual alcohol, corn oil, water, or any combination thereof. In implementations where the feed stream includes water, the water is present in the feed stream in an amount that is less than 20 ppm. In certain implementations, the water can be present in the feed stream in an amount from about 0.5 to 20 ppm, from about 0.5 to 10 ppm, from about 5 to 20 ppm, from about 5 to 10 ppm, or from about 10 to 20 ppm. It is also contemplated that the water is present in a feed stream in an amount that does not fall outside any of these recited ranges. It is further contemplated that the water is present in a feed stream in an amount can be between any of these recited ranges.

The present oligomerization processes can be carried out in one or more reactors. In one implementation, the one or more reactors includes only a single reactor. In such implementations, 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 comprise two or more reactors. In such configurations, the two or more reactors can be in series, parallel, or a combination of both relative to each other.

In use, the process can be carried out under a variety of temperatures. In some aspects, for example, the temperature of the reactor can be from 100° C. to 400° C. In other implementations, the temperature of the reactor can be from about 150° C. to 370° C., from about 150° C. to 370° C., from about 200° C. to 300° C., or from about 220° C. to 260° C. It is also contemplated that the temperature of the reactor does not fall outside any of these recited ranges. It is further contemplated that the temperature of the reactor can be between any of these recited ranges.

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

Alternatively, or in addition to, the process can be carried out under a variety of a weight hourly space velocities. In some implementations, for example, the WHSV can be at least 0.5 h⁻¹ or at least 1 h⁻¹. In other implementations, the WHSV can be from about 0.5 h⁻¹ to 100 h⁻¹, from about 1 h⁻¹ to 50 h⁻¹, from about 1 h⁻¹ to 10 h⁻¹ or from about 1 h⁻¹ to 5 h⁻¹. It is also contemplated that the WHSV of the reactor does not fall outside any of these recited ranges. It is further contemplated that the process can be carried out at a WHSV between any of these recited ranges.

In the processes described herein, the temperature can be from 100° C. to 400° C., the pressure can be from about 200 psig to 750 psig, and the WHSV can be at least 0.5 h⁻¹. In some implementations, the temperature can be from about 150° C. to 350° C., the pressure can be from about 300 psig to 700 psig, and the WHSV can be from about 0.5 h⁻¹ to 100 h⁻¹. In other implementations, the temperature can be from about 200° C. to 280° C., the pressure can be from about 450 psig to 700 psig, and the WHSV can be from about 1 h⁻¹ to 50 h⁻¹. For example, the temperature can be from about 240° C. to 260° C., the pressure can be from about 450 psig to 700 psig, and the WHSV can be from about 1 h⁻¹ to 5 h⁻¹. Consistent with some implementations of the present disclosure, the oligomerization temperature can be from about 100° C. to 300° C., with reaction pressures ranging from about 200 to 800 psig, and a WHSV from about 0.5 h⁻¹-100 h⁻¹.

The one or more catalysts used in the single oligomerization stage can involve, by way of example, the use of a doped or undoped mixed metal oxide catalyst, a doped or undoped zeolite, a doped or undoped solid acid catalyst, or any combination thereof. Non-limiting examples of suitable mixed metal oxide catalysts include: tungstated zirconium, tungstated alumina, tungstated silica, molybdenum/tungstated zirconium, molybdenum/tungstated alumina, molybdenum/tungstated silica, or any combination thereof. Non-limiting suitable examples of zeolites can be selected from among the zeolites that have a structural type that appears 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 having Si/Al higher than 10, or any combination thereof. Non-limiting examples of solid acid catalysts can include solid phosphoric acid, amorphous silica alumina, amberlyst, sulfonic acid resin, etc. Non-limiting examples of dopants for the 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. One skilled in the art will recognize the above referenced dopants enable tuning the oligomerization catalysts activity and selectivity by modifying surface acidity depending upon desired fuel properties and aromatic content.

In some implementations, the one or more catalyst used in the oligomerization stage can include nickel doped tungstated zirconium, nickel doped tungstated γ-alumina, nickel doped tungstated silica, nickel doped amorphous silica alumina, or nickel doped zeolite. In one implementation, the one or more catalysts can include a first catalyst that is nickel doped tungstated zirconium. In addition, the one or more catalysts can 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 can be nickel doped tungstated zirconium and the second catalyst can be one or more zeolites (e.g., one or more doped zeolites).

In some implementations, the second catalyst can be doped zeolite can be selected from among the zeolites that have a structural type that appears in the following list: MFI, CHA, ERI, MTF, AEI, AEL, FER, BEA, EUO, MEL, MFS, TON, FAU, MOR, MWW, MTT and the zeolites ZBM-30, ZSM-48, IM-5 and IZM-2 having Si/Al higher than 10, taken by themselves or mixed together with another zeolite and/or sulfonic acid mixture.

In some implementations when the one or more catalysts is a doped mixed metal oxide, the one or more dopants present therein can 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 where the one or more dopants is nickel, the nickel can be present in an amount that is from about 0.5 weight percent to 5 weight percent of the total weight of the one or more catalysts. In some implementations where the one or more dopants is nickel, the nickel can be present in an amount that is from about 1 weight percent to 2 weight percent 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 does not fall outside any of these recited ranges. It is further contemplated that the amount of nickel present in the one or more catalysts can be between any of these recited ranges.

Alternatively, or in addition, in some implementations when the one or more catalysts include tungsten, the tungsten can be present in an amount that is from about 5 weight percent to 25 weight percent of the total weight of the one or more catalysts. In other implementations, tungsten can be present in an amount that is from about 10 weight percent to 20 weight percent of the total weight of the one or more catalysts, in an amount that is from about 10 weight percent to 20 weight percent of the total weight of the one or more catalysts, or in an amount that is from about 10 weight percent to 15 weight percent of the total weight of the one or more catalysts. In one implementation, the tungsten can be present in an amount of about 15 weight percent of the total weight of one or more catalysts. It is also contemplated that the amount of tungsten present in the one or more catalysts does 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.

Catalyst preparations can be accomplished via incipient wetness impregnation techniques. The catalysts of the present process can include a nickel doped tungstated zirconium, nickel doped tungstated γ-alumina, nickel doped tungstated silica, nickel doped amorphous silica alumina, or nickel doped zeolite catalysts as a single catalyst or in a stacked bed reactor configuration with zeolites or solid acid catalysts.

The C₂-C₇ olefin oligomerization process with doped WO_x/zirconium catalyst, WO_x/alumina catalyst, WO_x/silica catalyst, solid acid catalyst, amorphous silica alumina or zeolite as a single catalyst or in a stacked bed configuration with a zeolite(s) or solids acid catalyst(s) can result in high yield (e.g., greater than about 60%) to bio-based diesel or jet fuel at relatively low temperatures and pressures (e.g., temperatures of less than about 300° C. and pressures of less than about 800 psig). Other known catalysts for C₂-C₇ linear olefin oligomerization (e.g., standard zeolites, modified zeolites, SPA's, Nafion Resins, etc.) deactivate rapidly requiring re-activation, are relatively expensive, have poor tolerance for the presence of oxygenates, and result in higher levels of oligomer cracking/isomerization as evidenced by higher levels of C₅-7 olefins and lesser amounts of isolated yields to jet and/or diesel fractions.

Granular or extruded catalysts are suitable for the oligomerization stage. The one or more catalysts can have a variety of size and morphology. In some implementations, the one or more catalysts can have a diameter of a size greater than 0.1 mm. In one implementation, the one or more catalysts can have diameter of a size from about 0.2 mm to 3.0 mm or from 1 mm to 10 mm.

The one or more catalysts can be regenerated as necessary under suitable conditions 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 a temperature of 400° C. to 600° C. In one implementation, for example, the catalyst 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 catalyst can be regenerated for 4 to 6 hours.

The oligomerization reaction can be performed in a continuous mode for mass production of oligomers. The continuous mode is operated by using a fixed bed reactor, and reactant flows can be upward or downward. Use of a recycle stream of oligomerized olefinic reaction product or saturated C₈-C₂₄ hydrocarbons, to control the heat of reaction may be useful as the oligomerization reaction is very exothermic. Batch mode oligomerization reactions are also possible, but they tend to result in lower throughput and higher operational costs.

Optionally, the processes described herein can further include preparing the feed stream, referred to herein as the transformation stage. The feed stream can be prepared in a variety of ways from a variety of sources.

In some implementations, feed stream can be prepared by deriving the one or more C₂-C₇ linear or branched olefins from petroleum. Petroleum is a nonrenewable resource and its combustion results in carbon being released into the environment. There is an increasing demand for the use of biomass sources for replacing petroleum as the starting point for the synthesis of fuels. With the increased availability and reduced cost of bioethanol, bioethanol may be an inexpensive and renewable feedstock for making a variety olefins for use producing downstream hydrocarbons. The use of biomass-derived alcohols for the synthesis of base stocks for fuels is therefore of great interest.

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

In some implementations, the one or more C₂-C₇ linear or branched olefins can be produced by contacting an input stream, which includes one or more C₁-C₅ linear or branched alcohols, with one or more catalysts in one or more reactors to form the one or more C₂-C₇ linear or branched olefins. The one or more catalysts can include a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium, titanium, tungsten, or silicon. Alternatively, or in addition, the one or more catalysts can include a doped or undoped zeolite catalyst. In one implementation, conversion of fuel grade ethanol can be carried out over a mixture of a doped or undoped-γ-alumina catalyst admixed with a doped or undoped zeolite in a single fixed bed reactor. The resulting C₂-C₇ olefinic mixture can then be oligomerized in total to produce gasoline, jet fuel, and/or diesel fuel fractions.

By way of example, the conversion of methanol, and/or mixtures of methanol and C₂-C₅ alcohols, proceeds similarly to a C₂-C₇ olefin mixture in high yield and carbon accountability. An exemplary single reaction step encompasses i) dehydration, ii) oligomerization to C₂₊ olefins, iii) skeletal rearrangement, and iv) cracking to primarily produce ethylene and propylene along with minor amounts of C₄₊ olefins and aromatics. Thus, passing a vaporized stream of methanol and ethanol over a single fixed catalyst bed containing a physical mixture of containing the first part of a silicated, zirconated, titanated, niobium, or fluorinated gamma-alumina or gamma-alumina combined with a doped zeolite (boron, phosphor, or combinations thereof) as the second catalyst part at between about 300° C. to about 450° C. can result in a C₂-C₇ olefin mixture, which can be separated for sale, or after removal of condensed water, oligomerized “as-is” to primarily jet and/or diesel fuel. This catalyst combination in a single fixed bed reactor accomplishes i) dehydration, ii) oligomerization to C₂₊ olefins, iii) skeletal rearrangement, and iv) cracking that results in longer catalyst time on stream (ToS), improved hydrothermal stability, improved selectivity to olefins with lesser amounts of saturates and aromatics, and improved alcohol conversions.

In one exemplary implementation, a process for converting one or more C₁-C₅ linear or branched alcohols to one or more C₂-C₇ olefins can include: contacting an input stream that includes the 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 that include the one or more C₂-C₅ olefins, the single bed reactor being at a temperature from about 350° C. to about 750° C., a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) of about 0.5 to about 5.0.

Furthermore, in some implementations, the production of the one or more C₂-C₇ linear or branched olefins can optionally include the recycle of one or more specific olefin fractions (e.g., C₂+C₄+C₅ or C₂+C₅, etc.) in a closed-loop process configuration, while co-feeding the C₁-C₅ alcohols. This can result in the maximization of on-purpose yields to selected olefins. For example, the recycle of the C₂+C₄+C₅ olefin fraction in combination with co-feeding C₁-C₅ alcohols can result in an on-purpose propylene carbon yield exceeding 80 weight percent. As such, selective recycle of the C₂+C₅ olefin fraction can result in an on-purpose propylene and butenes combined carbon yield exceeding 80 weight percent. Additionally, recycle of the C₄+C₅ olefin fraction can result in an on-purpose ethylene and propylene combined carbon yield exceeding 80 wt. %. An exemplary single-step reaction can encompass i) in-situ dehydration, ii) oligomerization to C₃₊ olefins, iii) skeletal rearrangement, and iv) cracking to C₂-C₇ olefins along with aromatics.

Exemplary catalyst combinations, physically mixed within the single-fixed bed reactor, for C₂-C₇ olefin formation can include doped zeolites such as crystalline silicates of the group ZSM-5 (MFI or BEA frameworks), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON having Si/Al higher than 10, or a dealuminated crystalline silicate of the group ZSM5 (MFI or BEA frameworks), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON having Si/Al higher than 10, or a phosphorus and/or boron modified crystalline silicate of the group ZSM-5 (MFI or BEA frameworks), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON having Si/Al higher than 10, or molecular sieves of the type silico-aluminophosphate of the group AEL.

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 combinations thereof. One skilled in the art will recognize the above referenced dopants enable tuning the oligomerization catalysts activity and selectivity by modifying surface acidity depending upon desired fuel properties and aromatic content.

Granular or extruded catalyst(s) can be used for the production of the one or more one or more C₂-C₇ linear or branched olefins described herein. For example, in some implementations, granular or extruded catalyst(s) can have a particle size of greater than at least about 0.05 mm, about 0.1 mm or greater, or from about 0.05 mm to about 2.5 mm, including all the subranges in between. In one implementation, granular or extruded catalysts(s) can have a particle size from about 0.4 to about 2.0 mm.

In some implementations, the C₁-C₅ alcohols can be one or more of methanol, ethanol, propanol, iso-propanol, 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 alcohols can be from bio-based processes, such as, but not limited to, fermentation. For example, the C₁-C₅ linear or branched alcohols can be bio-based and produced by fermentative processes. That is, the C₁-C₅ linear or branched alcohols can be not derived from petroleum but are produced from renewable, bio-based sources.

The resulting yield of the C₈-C₂₄ hydrocarbons produced by the processes described herein can be at least 30%. In some implementations, the resulting yield of the C₈-C₂₄ hydrocarbons can be from about 30% to 99%. In some implementations, the yield of the C₈-C₂₄ hydrocarbons can be at least 35. In other implementations, the yield of the one or more C₈-C₂₄ hydrocarbons can be at least 45%, at least 60%, at least 65% or at least 80%.

In some implementations, the one or more C₈-C₂₄ hydrocarbons can include one or more low carbon intensity C₈-C₂₄ hydrocarbons. In one implementation all the one or more C₈-C₂₄ hydrocarbons can be low carbon intensity hydrocarbons. As used herein, low carbon intensity when used to modify hydrocarbon (e.g., one or more C₈-C₂₄ hydrocarbons) refers to a carbon intensity that is at least about 50% less than a typical carbon intensity for a petroleum derived liquid hydrocarbon fuel. A typical carbon intensity for a petroleum derived liquid hydrocarbon fuel can be from about 90 gCO₂e/MJ to 100 gCO₂e/MJ based on the Argonne GREET® Model.

In some implementations, the one or more C₈-C₂₄ hydrocarbons can include one or more zero carbon intensity C₈-C₂₄ hydrocarbons. In one implementation all the one or more C₈-C₂₄ hydrocarbons can be zero carbon intensity hydrocarbons. As used herein, zero carbon intensity when used to modify hydrocarbon (e.g., one or more C₈-C₂₄ hydrocarbons) refers to a carbon intensity that is at least about 90% to 100% less than a typical carbon intensity for a petroleum derived liquid hydrocarbon fuel.

In some implementations, the one or more C₈-C₂₄ hydrocarbons can include one or more negative carbon intensity C₈-C₂₄ hydrocarbons. In one implementation all the one or more C₈-C₂₄ hydrocarbons can be negative carbon intensity hydrocarbons. As used herein, negative carbon intensity when used to modify olefin or hydrocarbon refers to a carbon intensity that is more than 100% less than a typical carbon intensity for a petroleum derived liquid hydrocarbon fuel.

Further, disclosed herein is a process for converting one or more C₂-C₈ linear or branched olefins, derived from one or more C₁-C₅ alcohols and/or corn oil, to one or more C₈-C₂₄ hydrocarbons, the process can include contacting a feed stream that includes the one or more C₂-C₈ linear or branched olefins, with one or more catalysts in a reactor at a temperature from about 240° C. to 300° C., a pressure from about 450 psig to 750 psig, and a WHSV from about 1 h⁻¹ to 10 h⁻¹, in which the one or more catalysts include a nickel doped tungstated zirconium, nickel doped tungstated γ-alumina, nickel doped tungstated silica, nickel doped amorphous silica alumina, or nickel doped zeolite catalysts as a single catalyst or in a stacked bed reactor configuration with zeolites or solid acid catalysts, in which the nickel is present in the amount from about 1.5 weight percent of the total weight of the one or more catalysts and tungsten is present in the amount from about 15 weight percent of the total weight of the one or more catalysts, to produce a mixture with a yield of C₈-C₂₄ hydrocarbons of at least 35%.

The one or more C₈-C₂₄ hydrocarbons and the subsequent fractions produced in the oligomerization step (e.g., unsaturated one or more C₈-C₂₄ hydrocarbons) can be utilized directly for the production of renewable diesel fuel and renewable jet fuel post-hydrogenation. As such, the processes described herein can further include hydrogenating the one or more C₈-C₂₄ hydrocarbons to product a product stream. The product stream, therefore, can include saturated one or more C₈-C₂₄ hydrocarbons. Hydrogenation catalysts that can be used for this process can be selected from any supported catalysts 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 combinations thereof.

Additionally, the present processes described herein can also include separating the one or more C₈-C₂₄ hydrocarbons post-hydrogenation of the product stream to produce a renewable jet fuel or a renewable diesel fuel. For example, the process can include separating the one or more C₈-C₂₄ hydrocarbons into different fractions to produce a renewable jet fuel or a renewable diesel fuel of the desired composition. The separation process may include distilling the one or more C₈-C₂₄ hydrocarbons to produce the renewable jet fuel or the renewable diesel fuel.

In some implementations, the processes described herein can further include blending the renewable jet fuel or renewable diesel fuel. The blending process may include blending an aromatic compound or a fossil-fuel derived compound with the renewable jet fuel or renewable diesel fuel. In one implementation, blending the one or more C₈-C₂₄ hydrocarbons can include blending an aromatic compound with the renewable jet fuel or the renewable diesel fuel to modify the viscosity, ignition temperature, or other physical and/or chemical characteristics. In another implementation, blending the one or more C₈-C₂₄ hydrocarbons includes blending a fossil-fuel derived compound with the renewable jet fuel or the renewable diesel fuel to modify the heat of combustion, or other chemical and/or physical characteristics.

In some implementations, the present processes can produce renewable diesel fuel. The renewable diesel fuel has a cetane number of 40 or more. The cetane number greater can be adjusted separating and/or blending the C₈-C₂₄ hydrocarbons. In this manner, the renewable diesel fuel can be used in a variety of applications, for example, diesel engines in small displacement automobiles or large displacement machinery.

FIG. 1 illustrates an exemplary system 100 for conversion of alcohol(s) to fuel. The system includes a transformation stage 102, in which an input stream 104 (e.g., alcohols, such as methanol and/or ethanol) are transformed into a feed stream 106 (e.g., one or more olefins, such as one or more of C₂-C₇ olefins), an oligomerization stage 108, in which the feed stream 106 is oligomerized into a mixture stream 110 (e.g., of at least one or more C₈-C₂₄ hydrocarbons), and a hydrogenation stage 112, in which the mixture stream 110 is hydrogenated to produce a product stream 114. In this illustrated system 100, the oligomerization stage 108 includes a single oligomerization step. While this system can include any number and type of reactors, in this illustrated system 100, the transformation 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. Further, the hydrogenation stage 112 is carried out in a hydrotreater 120.

In some implementations, the system 100 can include one or more recycle streams. For example, as shown in FIG. 1, a fraction of the one or more C₂-C₅ olefins in the feed stream can be recycled, via a first recycle stream 122, into the input stream 104. Alternatively, or in addition, as shown in FIG. 1, a fraction of the one or more C₂-C₇ of the mixture stream 110 can be recycled, via a second recycle stream 124, into the feed stream 106.

In some implementations, the oligomerization of linear C₂-C₈ olefins to diesel fractions with doped WO_x/zirconium catalyst, WO_x/alumina catalyst, WO_x/silica catalyst, solid acid catalyst, amorphous silica alumina or zeolite as a single catalyst or in a stacked bed configuration with a zeolite(s), solids acid catalyst(s), or sulfonic acid resin catalyst(s), which are inexpensive to manufacture from commercially available raw materials, can proceed at reaction pressures of 250-1000 psig, reaction temperatures of 125-380° C., and a weight hourly space velocity (WHSV) of 1.0 h⁻¹-10.0 h⁻¹ resulting in a single pass C₂-C₈ olefin conversion of at least 40% as exemplified in the examples below. Removal and recycle of the unreacted C₂-C₅ olefins can provides a final overall yield of at least 40% to naphtha, jet, or diesel products based on the initial mass of olefins fed to the oligomerization step. The catalyst mixtures are stable, and extended reaction on-stream times have been demonstrated. In addition, the catalyst mixture can be regenerated via air to regain activity.

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

EXAMPLES

Reactor Set-Up:

The oligomerization reaction of olefins was carried out at 120° C. to 300° C. by using a fixed bed reactor containing 14 g of specified catalysts and flowing liquefied olefins and recycle downward. The flow rates were controlled by Teledyne Model 500D syringe pumps coupled with D-Series pump controllers, and the olefin flow rate was adjusted to obtain the targeted olefin weight hourly space velocity (WHSV). The reaction temperature was maintained constant via a Lindberg Blue M furnace as manufactured by Thermo-Scientific. Olefin conversion was calculated by analysis of the liquid phase reactor effluent by GC for olefin content and comparing mass accountability fed versus liquid mass collected. Catalyst screening required that mass accountabilities exceeded 90% for continued development and evaluation. Prior to initiation of feeds, the catalysts were pre-treated with nitrogen at 300 C for 1 h.

Example 1: Nickel Impregnated Tungsten Zirconium Catalyst Preparation

The nickel doped WO_x/Zirconium catalyst was prepared by incipient wetness technique. The precursor metal salts (Sigma Aldrich) were added to deionized water in an amount to produce a nickel loading of 1.3 weight percent upon addition to WO_x/Zirconium (15 weight percent tungstate) as support. The nickel impregnated WO_x/Zirconium catalyst was dried at 140° C. for 1 hr, and afterwards calcined at 550° C. for 4 hr.

Example 2: Middle distillate formation via oligomerization of mixed C₂-C₈ linear or branched olefins feed (35% ethylene, 25% propylene, 20% butenes, 8% pentenes, 12% C₂-C₅ saturates) with oligomerization reactor olefinic effluent as recycle over nickel doped WO_x/Zirconium catalyst (14 g). Olefinic recycle to fresh olefin feed mass ratio 1/1. Reaction conditions: T=240° C., WHSV=4.1 h⁻¹, P=640 psig. Liquid mass accountability=92% (total mass fed/mass out as liquid); Mass to vapor=8%; Single pass ethylene conversion=77% (1-ethylene out/ethylene in).

Liquid Effluent Oligomer Composition:

% C4	% C5-C7	% C8	% C9-C11	% C12	% C13-C15	% C16+
9.0	15.7	23.6	18.1	17.8	5.6	10.3

Vapor Effluent Oligomer Composition:

% C2	% C3	% C4	% C5	C2-C5 Saturates
59	15	11.4	2	12.4

Example 3: Middle distillate formation via oligomerization of mixed C₂-C₈ linear or branched olefins feed (35% ethylene, 25% propylene, 20% butenes, 8% pentenes, 12% C₂-C₅ saturates) with oligomerization reactor saturated effluent as recycle over nickel doped WO_x/Zirconium catalyst (14 g). Saturated recycle to fresh olefin feed mass ratio 1/1. Reaction conditions: T=240° C., WHSV=4.1, P=720 psig. Liquid mass accountability=84% (total mass fed/mass out as liquid); Mass to vapor=16%; Single pass ethylene conversion=69% (1-ethylene out/ethylene in).

Liquid Effluent Oligomer Composition:

% C4	% C5-C7	% C8	% C9-C11	% C12	% C13-C15	% C16+
13.3	14.6	25.1	17.2	18.3	5.6	5.9

Vapor Effluent Oligomer Composition:

% C2	% C3	% C4	% C5	C2-C5 Saturates
65	9	15	3	8

Example 4: Middle distillate formation via oligomerization of mixed C₂-C₈ linear or branched olefins feed (35% ethylene, 25% propylene, 20% butenes, 8% pentenes, 12% C₂-C₅ saturates) with oligomerization reactor saturated effluent as recycle over Nickel doped WO_x/Zirconium catalyst (10 g) with ZSM5 catalyst (4 g) in a stacked bed configuration. Saturated recycle to fresh olefin feed mass ratio 1/1. Reaction conditions: T=240° C., WHSV=4.1 h⁻¹, P=720 psig. Liquid mass accountability=92% (total mass fed/mass out as liquid); Mass to vapor=8%; Single pass ethylene conversion=85% (1-ethylene out/ethylene in).

Liquid Effluent Oligomer Composition:

% C4	% C5-C7	% C8	% C9-C11	% C12	% C13-C15	% C16+
13.2	15.2	24.9	17.1	18.2	5.6	5.8

Vapor Effluent Oligomer Composition:

% C2	% C3	% C4	% C5	C2-C5 Saturates
60	9	19	5	7

Example 5: Middle distillate formation via oligomerization of mixed C₂-C₈ linear or branched olefins 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-pentenes, 4.6% 2-methyl-2-butene, 1.7% 2-methyl-1-butene, 1.9% isopentane, 0.5% pentane. Single Stage Oligomerization Reaction Conditions: T=150° C. in reactor, WHSV=3.4 (C₂-C₇ olefin basis), P=19 bar; Catalysts: Ni-impregnated Zeolite (Zeolyst CBV-5524) 2 g+Amberlyst-35 (4 g). Liquid mass accountability=82% (total mass fed/mass out as liquid); Mass to vapor=18%; Single pass ethylene conversion=67% (1-ethylene out/ethylene in).

Liquid Effluent Oligomer Composition: 82% of Reactor Feed (Out/in)

% C4	% C5-C7	% C8	% C9-C11	% C12	% C13-C15	% C16+
3.4	14.2	24.7	20	25.8	11.9	nd

Vapor Effluent Oligomer Composition: Mass=18% of Reactor Feed

% C2	% C3	% C4	% C5	C2-C5 Saturates
63.7	9.2	13.2	2.4	11

Example 6: Middle distillate formation via oligomerization of mixed C₂-C₈ linear or branched olefins feed. Single Stage Oligomerization Reaction Conditions: T=150° C. in reactor, WHSV=3.4 (C₂-C₇ olefin basis), P=19 bar; Catalysts: Ni-impregnated Zeolite (Zeolysts CBV-2314) 2 g+Amberlyst-35 (4 g). Ethylene conversion=66% (1-ethylene in vapor effluent/ethylene fed to olig); Olig Feed Composition: 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-pentenes, 4.6% 2-methyl-2-butene, 1.7% 2-methyl-1-butene, 1.9% isopentane, 0.5% pentane

Liquid Effluent Oligomer Composition: 82% of Reactor Feed (Out/in)

% C4	% C5-C7	% C8	% C9-C11	% C12	% C13-C15	% C16+
2.7	15.9	20.6	16.8	24.7	7	12.3

Vapor Effluent Oligomer Composition: Mass=18% of Reactor Feed

% C2	% C3	% C4	% C5	C2-C5 Saturates
65.6	4.4	8.2	2.3	18

Although various illustrative implementations are described above, any of a number of changes can be made to 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 altogether. Optional features of various system and process implementations may be included in some implementations and not in others. Therefore, the foregoing description is provided primarily for exemplary purposes and should not be interpreted to limit the scope of the claims.

The examples and illustrations included herein show, by way of illustration and not of limitation, specific implementations in which the subject matter may be practiced. As mentioned, other implementations may be utilized and derived there from, such that structural and logical substitutions and changes may be made without departing from the scope of this disclosure. Such implementations of the inventive subject matter may be referred to herein individually or collectively by the term “invention” merely for convenience and without intending to voluntarily limit the scope of this application to any single invention or inventive concept, if more than one is, in fact, disclosed. Thus, although specific implementations have been illustrated and described herein, any arrangement calculated to achieve the same purpose may be substituted for the specific implementations shown. This disclosure is intended to cover any and all adaptations or variations of various implementations. Combinations of the above implementations, and other implementations not specifically described herein, will be apparent to those of skill in the art upon reviewing the above description. Use of the term “based on,” herein and in the claims is intended to mean, “based at least in part on,” such that an unrecited feature or element is also permissible.

The subject matter described herein can be embodied in systems, apparatus, methods, and/or articles depending on the desired configuration. The implementations set forth in the foregoing description do not represent all implementations consistent with the subject matter described herein. Instead, they are merely some examples consistent with implementations related to the described subject matter. Although a few variations have been described in detail herein, other modifications or additions are possible. In particular, further features and/or variations can be provided in addition to those set forth herein. For example, the implementations described herein can be directed to various combinations and subcombinations of the disclosed features and/or combinations and subcombinations of several further features disclosed herein. In addition, the logic flows depicted in the accompanying figures and/or described herein do not necessarily require the particular order shown, or sequential order, to achieve desirable results. Other implementations may be within the scope of the following claims.