Synthetic aviation fuel compositions, and systems and methods of making the same

Abstract

A CO2-derived synthetic aviation fuel composition is disclosed comprising distilled paraffine, cycloparaffin and aromatic product mixtures and having an average carbon number between about 10 and about 11.4, and less than about 500 ppm oxygenates. Methods for converting CO2 and a reduction gas, such as H2 or a hydrocarbon, using a reduction catalyst and an aromatic catalyst into mixtures of paraffins, and aromatics into the CO2-derived synthetic aviation fuel are also disclosed.

Description

SYNTHETIC AVIATION FUEL COMPOSITIONS, AND SYSTEMS AND METHODS OF MAKING THE SAMEBACKGROUND

[0001] Development of transportation technologies that afford decreased CO2 emissions, is a priority. One such means is development of synthetic aviation fuel (SAF).

[0002] Conventional jet fuel (Jet- A) consists of normal paraffins, iso-paraffins, naphthenes, and aromatics refined from crude oil. In order to produce SAF that can be directly substituted for Jet-A without blending, the SAF has to be within the current compositional range of Jet-A derived from crude oil. Current technologies for SAF production involve making SAF from vegetable oils, animal fats, and waste oils. However, the SAF made from these processes contains mainly paraffins, and does not have enough naphthenes and aromatics to be directly substituted for Jet-A derived from crude oil. Accordingly, there is a need for technologies that produce SAF that can be directly substituted for Jet-A derived from crude oil.SUMMARY OF THE DISCLOSURE

[0003] A fully formulated synthetic aviation fuel is disclosed comprising: a distilled paraffin product mixture, a distilled cycloparaffin product mixture, and a distilled aromatic product mixture. The fuel composition may be derived CO2. The fuel composition may have an average carbon number between about 10 and about 11.4. The fuel composition may comprise less than about 500 ppm oxygenates. The fuel composition may comprise about 200 ppm to about 500 ppm, or about 250 ppm to about 450 ppm oxygenates.

[0004] The fuel composition of may include: about 16 wt% to about 30 wt%, or about 16 wt% to about 28 wt% n-alkanes; and / or about 20 wt% to about 47 wt% iso-alkanes. The fuel composition of may include: about 16 wt% to about 30 wt% monocycloalkanes; about 1 wt% to about 9 wt% polycycloalkanes; and / or about 9 wt% to about 20 wt%, or about 9 wt% to about 18 wt% aromatics. The fuel composition may contain about 16 wt% to about 30 wt% n-alkanes, about 20 wt% to about 47 wt% iso-alkanes, about 16 wt% to about 30 wt% monocycloalkanes, about 1 wt% to about 9 wt% polycycloalkanes, and about 9 wt% to about 20 wt% aromatics.

[0005] The fuel composition may include one or more of the following: about 21 wt% to about 30 wt% C10 hydrocarbons; about 18 wt% to about 25 wt% Cn hydrocarbons; about 6wt% to about 17 wt% C9 hydrocarbons; about 12 wt% to about 20 wt% C12 hydrocarbons; about 5 wt% to about 15 wt % C13 hydrocarbons; about 1 wt% to about 10 wt% C14 hydrocarbons; about 1 wt% to about 5 wt% Cs hydrocarbons; and / or about 1 wt% to about 5 wt% C15 hydrocarbons.

[0006] Methods of making the fully formulated SAF are also disclosed herein. Those methods may include i) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford a paraffin product mixture comprising one or more paraffins; ii) contacting a second reduction gas and a second carbon source gas with an aromatic catalyst to afford an aromatic product mixture comprising one or more aromatics and / or cycloparaffins; iii) separating the aromatic product mixture into a separated aromatic product mixture and a cycloparaffin product mixture; iv) distilling the paraffin product mixture, the separated aromatic product mixture, and the cycloparaffin product mixture to remove hydrocarbons outside of the SAF range; and v) blending the distilled paraffin product mixture, the distilled aromatic product mixture and the distilled cycloparaffin product mixture to afford a crude product mixture comprising hydrocarbons in the SAF range. The method may include converting oxygenates in the paraffin product mixture, the separated aromatic product mixture, and / or the cycloparaffin product mixture (before or after distillation) into paraffins.

[0007] A method of making the fuel composition may include: contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a medium hydrocarbon product mixture comprising one or more C4-9 paraffins and / or olefins; a light hydrocarbon product mixture comprising one or more C2-4 paraffins and / or olefins; and a target hydrocarbon product mixture comprising one or more Cio-16 paraffins and / or olefins; and converting oxygenates in the medium hydrocarbon product mixture, the light hydrocarbon product mixture, and the target hydrocarbon product mixture into paraffins; contacting the medium hydrocarbon product mixture, optionally a second reduction gas, and optionally a second carbon source gas with an aromatic catalyst to afford a target aromatic product mixture comprising one or more C9-16 aromatics, and a light aromatic product mixture comprising one or more Ce-8 aromatics; contacting the light hydrocarbon product mixture and the light aromatic product mixture with analkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics; contacting the light hydrocarbon product mixture with an oligomerization catalyst to afford: a target oligomerized product mixture comprising one or more Cio-16 paraffins and / or olefins; hydrogenating the target hydrocarbon product mixture, the target aromatic product mixture, the target oligomerized product mixture, the target alkyl arene product mixture to make paraffin product mixture, a aromatic product mixture, and a cycloparaffin product mixture; distilling the paraffin product mixture, the separated aromatic product mixture, and the cycloparaffin product mixture to remove hydrocarbons outside of the SAF range; and blending the distilled paraffin product mixture, the distilled aromatic product mixture and the distilled cycloparaffin product mixture to produce fully formulated fuel composition.

[0008] The method may include converting oxygenates in the medium hydrocarbon product mixture, the light hydrocarbon product mixture, and the target hydrocarbon product mixture into paraffins.BRIEF DESCRIPTION OF THE FIGURES

[0009] Figure l is a process flow diagram for making, treating and blending components for the production of fully formulated SAF.

[0010] Figure 2A is a bar graph showing carbon number distribution for a sample of a distilled paraffin product mixture.

[0011] Figure 2B is a graph showing the distillation curve of the distilled paraffin product mixture shown in Figure 2 A.

[0012] Figure 3 A is a bar graph showing carbon number distribution for a sample of a distilled cycloparaffin product mixture.

[0013] Figure 3B is a graph showing the distillation curve of the distilled cycloparaffin product mixture shown in Figure 3 A.

[0014] Figure 4A is a bar graph showing carbon number distribution for a sample of a distilled aromatic product mixture.

[0015] Figure 4B is a graph showing the distillation curve of the distilled aromatic product mixture shown in Figure 4 A.

[0016] Figure 5 A is a bar graph showing carbon number distribution for a sample of a blended fully formulated SAF sample made according to the process scheme of Figure 1.

[0017] Figure 5B is a graph showing the distillation curve of the blended fully formulated SAF sample of Figure 5 A.

[0018] Figure 6 is another process flow diagram for making, treating and blending components for the production of fully formulated SAF compared to conventional jet range.

[0019] Figure 7A is a bar graph showing carbon number distribution for a sample of a blended fully formulated SAF sample made according to the process scheme of Figure 6.

[0020] Figure 7B is a graph showing the distillation curve of the blended fully formulated SAF sample of Figure 7A compared to conventional jet range.DETAILED DESCRIPTION OF THE DISCLOSURE

[0021] Synthetic fuels, such as aviation fuel and diesel fuel, are disclosed herein. A synthetic aviation fuel may comprise: a distilled paraffin product mixture, a distilled cycloparaffin product mixture, and a distilled aromatic product mixture. The fuel composition may be a CO2 derived fully formulated product. The fuel composition may be a CO derived fully formulated product. The fuel composition comprises hydrocarbons Cs-Ci7. The fuel composition may have an average carbon number between 10 and 11.4. The fuel composition may have an average carbon number of about 10.0 to about 11.1, about 10.0 to about 10.8, about 10.1 to about 10.8, about 10.2 to about 10.8, about 10.3 to about 11.4, about 10.5 to about 11.4, about 10.7 to about 11.4, or about 10.3 to about 10.7.

[0022] The term “distilled” when used with a distilled paraffin product mixture, a distilled cycloparaffin product mixture, and a distilled aromatic product mixture means that the mixture has been distilled to remove the majority of, or substantially all of the light (below Cs) and heavy compounds (above C17). As will readily be understood by one of skill in the art, the distilled paraffin product mixture, distilled cycloparaffin product mixture, and distilled aromatic product mixture may be distilled separately or in certain embodiments, one or more of the product mixtures may be combined prior to distillation. The distillation is important to arriving at the desired carbon number and to achieve the jet fuel properties of the SAF composition. Because the components of the fuel composition are distilled, the fully formulated fuel composition may contain less than about 2 wt%, less than about 1 wt%, or less than about 0.5 wt% of each of Ce, C7,Ci7 and / or Cis hydrocarbons. In an embodiment, the fully formulated fuel composition contains less than about 1 wt% of Ce, less than about 1 wt% of C7, less than about 1 wt% of C17 and less than about 1 wt% of Cis hydrocarbons.

[0023] The present disclosure provides systems and methods for producing fuel compositions from a carbon source gas (e.g., CO2) and a reduction gas (e.g., H2). The fuel compositions produced by these systems and / or methods, e.g., the compositions described below, exhibit certain unique properties and compositional features. For example, these compositions have low total sulfur content because they (or their major components) are produced synthetically from CO2. As another example, the systems and processes disclosed herein for preparing the aromatic component heavily favor the creation of monocyclic aromatics, and disfavor the creation of polycyclic aromatics. These compositional features (e.g., low sulfur content and low polycyclic aromatic content), which arise a result of the systems and processes described herein, are advantageous compared with conventional (petroleum-derived) fuels.

[0024] The fuel composition may comprise about 16 wt% to about 30 wt% n-alkanes, about 16 wt% to about 28 wt% n-alkanes, about 18 wt% to about 28 wt% n-alkanes, about 17 wt% to about 26 wt% n-alkanes, or about 23 wt% to about 25 wt% n-alkanes. The fuel composition may comprise about 20 wt% to about 47 wt% iso-alkanes, about 30 wt% to about 47 wt% iso-alkanes, about 32 wt% to about 42 wt% iso-alkanes, about 34 wt% to about 46 wt% iso-alkanes, about 20 wt% to about 40 wt% iso-alkanes, or about 35 wt% to about 38 wt% iso-alkanes. The fuel composition may comprise about 16 wt% to about 30 wt% monocycloalkanes, about 17 wt% to about 26 wt% monocycloalkanes, about 21 wt% to about 28 wt% monocycloalkanes, or about 22 wt% to about 26 wt% monocycloalkanes. The fuel composition may comprise about 0.1 wt% to about 6 wt% polycycloalkanes, about 0.2 wt% to about 5 wt% polycycloalkanes, about 0.2 wt% to about 4 wt% poly cycloalkanes, about 0.5 wt% to about 1 wt% poly cycloalkanes, about 0.2 wt% to about 1 wt% polycycloalkanes, about 4 wt% to about 6 wt% polycycloalkanes, or about 5 wt% to about 6 wt% polycycloalkanes.

[0025] The fuel composition may comprise about 9 wt% to about 20 wt% aromatics, about 9 wt% to about 18 wt% aromatics, about 10 wt% to about 17 wt% aromatics, about 10 wt% to about 13 wt% aromatics, about 11 wt% to about 19 wt% aromatics, or about 11 wt% to about 12 wt% aromatics. The term “aromatics” includes monoaromatics,cycloaromatics and polyaromatics. Cycloaromatics may be present in the fuel compositions herein. Cycloaromatics are understood to be beneficial to thermostability.

[0026] The fuel composition may comprise about 16 wt% to about 30 wt% n-alkanes, about 20 wt% to about 47 wt% iso-alkanes, about 16 wt% to about 30 wt% monocycloalkanes, about 1 wt% to about 9 wt% polycycloalkanes, and about 9 wt% to about 20 wt% monocyclic aromatics. The fuel composition may comprise about 16 wt% to about 28 wt% n-alkanes, about 30 wt% to about 47 wt% iso-alkanes, about 16 wt% to about 30 wt% monocycloalkanes, about 2 wt% to about 9 wt% poly cycloalkanes, and about 9 wt% to about 18 wt% aromatics. The fuel composition may comprise about 17 wt% to about 26 wt% n-alkanes, about 34 wt% to about 46 wt% iso-alkanes, about 17 wt% to about 26 wt% monocycloalkanes, about 2 wt% to about 7 wt% poly cycloalkanes, and about 10 wt% to about 17 wt% aromatics.

[0027] The fuel composition may comprise about 21 wt% to about 30 wt%, about 21 wt% to about 25 wt%, or about 25 wt% to about 30 wt% Cio hydrocarbons. The fuel composition may comprise about 18 wt% to about 25 wt%, about 20 wt% to about 25 wt%, or about 20 wt% to about 23 wt% Cn hydrocarbons. The fuel composition may comprise about 6 wt% to about 17 wt%, about 6 wt% to about 10 wt%, or about 12 wt% to about 17 wt% C9 hydrocarbons. The fuel composition may comprise about 12 wt% to about 20 wt%, about 15 wt% to about 20 wt%, or about 12 wt% to about 17 wt% C12 hydrocarbons. The fuel composition may comprise about 5 wt% to about 15 wt%, about 10 wt% to about 15 wt%, or about 5 wt% to about 10 wt% C13 hydrocarbons. The fuel composition may comprise about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt% C14 hydrocarbons.

[0028] The fuel composition may comprise about 1 wt% to about 5 wt% of each of Cs, and C15 hydrocarbons.

[0029] The distilled paraffin product mixture comprises hydrocarbons Cs-Cn. The distilled paraffin product mixture may have an average carbon number between 10.5 and 11.5. The distilled paraffin product mixture may have an average carbon number of about 10.6 to about 11.4, about 10.8 to about 11.2, or about 10.9 to about 11.2.

[0030] The distilled paraffin product mixture may comprise about 30 wt% to about 45 wt% n- alkanes, about 33 wt% to about 43 wt% n-alkanes, or about 36 wt% to about 40 wt% n-alkanes. The distilled paraffin product mixture may comprise about 42 wt% to about 58 wt% iso-alkanes, about 45 wt% to about 55 wt% iso-alkanes, or about 49 wt% toabout 52 wt% iso-alkanes. The distilled paraffin product mixture may comprise about 7 wt% to about 13 wt% monocycloalkanes, or about 9 wt% to about 11 wt% monocycloalkanes. The distilled paraffin product mixture may comprise about 0.1 wt% to about 4 wt% poly cycloalkanes, about 0.5 wt% to about 4 wt% poly cycloalkanes, about 0.5 wt% to about 3 wt% poly cycloalkanes, about 0.5 wt% to about 2 wt% polycycloalkanes or about 1 wt% to about 2 wt% polycycloalkanes. The distilled paraffin product mixture may comprise about 0 wt% aromatics.

[0031] The distilled paraffin product mixture may comprise about 20 wt% to about 30 wt% Cio hydrocarbons, about 15 wt% to about 23 wt% Cn hydrocarbons, about 15 wt% to about 20 wt% C9 hydrocarbons, about 1 wt% to about 5 wt% Cs hydrocarbons, about 12 wt% to about 18 wt% C12 hydrocarbons, about 5 wt% to about 11 wt% C13 hydrocarbons, about 2 wt% to about 7 wt% of each of C14, and C15 hydrocarbons.

[0032] The distilled cycloparaffin product mixture comprises hydrocarbons C9-C14. The cycloparaffin product mixture may have an average carbon number between 10.5 and 11.5. The distilled cycloparaffin product mixture may have an average carbon number of about 10.7 to about 11.3, about 10.8 to about 11.2, or about 10.9 to about 11.1.

[0033] The distilled cycloparaffin product mixture may comprise about 6 wt% to about 15 wt% n-alkanes, about 7 wt% to about 11 wt% n-alkanes, or about 8 wt% to about 10 wt% n- alkanes. The distilled cycloparaffin product mixture may comprise about 22 wt% to about 32 wt% iso-alkanes, about 25 wt% to about 30 wt% iso-alkanes, or about 26 wt% to about 28 wt% iso-alkanes. The distilled cycloparaffin product mixture may comprise about 45 wt% to about 60 wt% monocycloalkanes, about 47 wt% to about 56 wt% monocycloalkanes, or about 50 wt% to about 53 wt% monocycloalkanes. The distilled cycloparaffin product mixture may comprise about 0.5 wt% to about 7 wt% polycycloalkanes, about 1 wt% to about 6 wt% polycycloalkanes, or about 4 wt% to about 5.5 wt% poly cycloalkanes. The distilled cycloparaffin product mixture may comprise about 9 wt% to about 14 wt%, or about 11 wt% to about 13 wt% aromatics.

[0034] The distilled cycloparaffin product mixture may comprise about 30 wt% to about 35 wt% Cio hydrocarbons, about 25 wt% to about 30 wt% Cn hydrocarbons, about 5 wt% to about 10 wt% C9 hydrocarbons, about 16 wt% to about 23 wt% C12 hydrocarbons, about 7 wt% to about 13 wt% C13 hydrocarbons, and about 1 wt% to about 5 wt% of C14 hydrocarbons.

[0035] The distilled aromatic product mixture comprises Cs-Ci6 aromatics. The distilled aromatic product mixture may have an average carbon number between 10 and 12.5. The distilled aromatic product mixture may have an average carbon number of about 10.5 to about 12, about 10.5 to about 11, or about 11 to about 12.

[0036] In certain embodiments, the disclosure includes mixtures comprising aromatics. These aromatics may be described in terms of a carbon number e.g, “CX-Y aromatics.” As will be appreciated by one of skill in the art, this carbon number refers to the total number of carbon atoms in the molecule, and not necessarily to the number of ring atoms. For example, the group of compounds described by the term “Cio aromatics” may include naphthalene (CioHs), butylbenzene (C10H14), etc.

[0037] The distilled aromatic product mixture may comprise about 2 wt% to about 7 wt% n- alkanes, about 3 wt% to about 6 wt% n-alkanes, or about 3.5 wt% to about 4.5 wt% n- alkanes. The distilled aromatic product mixture may comprise about 4 wt% to about 11 wt% iso-alkanes, about 5 wt% to about 10 wt% iso-alkanes, or about 6 wt% to about 8 wt% iso-alkanes. The distilled aromatic product mixture may comprise about 11 wt% to about 18 wt% monocycloalkanes, about 12 wt% to about 16 wt% monocycloalkanes, or about 13 wt% to about 14 wt% monocycloalkanes. The distilled aromatic product mixture may comprise about 1 wt% to about 10 wt% poly cycloalkanes, about 4 wt% to about 10 wt% poly cycloalkanes, about 5 wt% to about 9 wt% poly cycloalkanes, or about 6 wt% to about 7 wt% polycycloalkanes. The distilled aromatic product mixture may comprise about 65 wt% to about 71 wt%, or about 67 wt% to about 69 wt% aromatics.

[0038] The distilled aromatic product mixture may comprise about 35 wt% to about 40 wt% Cio hydrocarbons, about 15 wt% to about 20 wt% Cn hydrocarbons, about 22 wt% to about 27 wt% C9 hydrocarbons, about 1 wt% to about 5 wt% Cs hydrocarbons, about 6 wt% to about 12 wt% C12 hydrocarbons, about 1 wt% to about 6 wt% C13 hydrocarbons, and about 0.5 wt% to about 4 wt% of each of C14, C15 hydrocarbons.

[0039] In the processing of the fuel composition, each of the paraffin product mixture, the cycloparaffin product mixture, and the aromatic product mixture is distilled using a bench scale distillation setup to remove C15+ hydrocarbons and C7- or Cs- hydrocarbons. Paraffin distillation cuts may be performed as follows (ambient-125, 125-145, 145-200, 200-266 °C), The 145-266°C fraction may preferably be used for the final blended SAF. Cycloparaffin distillation cuts may be as follows (ambient-95, 95-120, 120-140, 140-160 and 160-250°C) The 140-250°C fraction may preferably be used for the final blended SAF. The aromatic distillation cuts may be performed as follows (ambient- 120, 120-155, 155+ °C). The 155+ °C fraction may preferably be used for the final SAF blend.

[0040] The distilled product mixtures predominantly contain Cs-i5 hydrocarbons in the SAF range, which provide the desirable properties for fuel, in particular aviation fuel, e.g. Jet-A. The blend for the final fuel may be determined by prioritizing fuel properties that affect engine operability (specifically focusing on density, viscosity, freeze point, flashpoint, DCN, LHV, surface tension and smoke point) measured according to its respective ASTM method as documented in D7566. The distillation may be performed by any means known in the art

[0041] The composition may comprise less than about 5 wt% tetralins and indanes, or less than about 1 wt% tetralins and indanes. The composition may comprise from 0 wt% to about 5 wt% tetralins and indanes. The composition may comprise from 0 wt% to about 1 wt% tetralins and indanes. The composition may comprise less than about 1 wt% tetralins and less than about 1 wt% indanes, or less than about 0.5 wt% tetralins and less than about 0.5 wt% indanes. In certain embodiments, the composition comprises essentially no tetralins and indanes.

[0042] The composition may comprise less than about 5 wt%, less than about 1 wt%, or less than about 0.5 wt% polycyclic aromatics. The composition may comprise from 0 wt% to about 5 wt%, from 0.5 wt% to about 5 wt%, from 1 wt% to about 5 wt%, from 0 wt% to about 0.5 wt% polycyclic aromatics. The composition may comprise about 0.1 wt% to about 1 wt% polycyclic aromatics. The composition may comprise about 0.1 wt% or less, about 0.2 wt% or less, about 0.3 wt% or less, about 0.4 wt% or less, or about 0.5 wt% or less polycyclic aromatics. In certain embodiments, the composition comprises essentially no polycyclic aromatics, e.g., as determined by GC-MS.

[0043] In other embodiments, substantially all or essentially all of the aromatic compounds present in fuel compositions of the present disclosure are monocyclic aromatics. The composition may comprise about 5 wt% to about 25 wt%, about 8 wt% to about 20 wt%, or about 8 wt% to about 15 wt% monocyclic aromatics. The composition may comprise greater than about 8 wt%, greater than about 9 wt%, greater than about 10 wt%, or greater than about 14 wt% monocyclic aromatics. In certain embodiments, the composition comprises about 14.5 wt% monocyclic aromatics.

[0044] The composition may comprise about 15 wt% to about 65 wt%, about 15 wt% to about 45 wt%, about 15 wt% to about 45 wt%, about 15 wt% to about 35 wt%, about 20 wt% to about 45 wt%, or about 20 wt% to about 40 wt% cyclo-paraffins. In further embodiments, the composition comprises about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, or about 35 wt% cyclo-paraffins.

[0045] The composition may comprise about 5 wt% to about 40 wt%, about 5 wt% to about 20 wt%, about 10 wt% to about 40 wt%, or about 10 wt% to about 35 wt% iso-paraffins.

[0046] The composition may comprise about 5 wt% to about 50 wt%, about 5 wt% to about 40 wt%, about 5 wt% to about 30 wt%, about 10 wt% to about 40 wt%, or about 10 wt% to about 35 wt% n-paraffins.

[0047] The composition and properties thereof may be compliant with ASTM D4054 - Tier 1. The composition may be compliant with ASTM DI 655. The composition may be compliant with ASTM D7566. The composition may be compliant with ASTM D4054 - Tier 1, ASTM D7566 and ASTM D1655.

[0048] The composition may have a total acidity of less than about 0.10 mg KOH / g. The composition may have a total acidity of greater than 0.00 to about 0.10 mg KOH / g, about 0.005 mg KOH / g to about 0.10 mg KOH / g, about 0.01 mg KOH / g to about 0.10 mg KOH / g, about 0.01 mg KOH / g to about 0.05 mg KOH / g, or about 0.05 mg KOH / g to about 0.10 mg KOH / g. In certain embodiments, the composition has a total acidity of about 0.05 mg KOH / g, about 0.06 mg KOH / g, about 0.07 mg KOH / g, about 0.08 mg KOH / g, about 0.09 mg KOH / g, or about 0.10 mg KOH / g.

[0049] The composition may comprise less than about 0.3 wt% total sulfur, for example as measured by ASTM D2622. The composition may comprise less than about 1 ppm sulfur-containing impurities. In certain embodiments, the composition comprises essentially no sulfur-containing impurities. In other embodiments, the composition comprises less than about 0.003 wt% sulfur mercaptan. In certain preferred embodiments, the composition comprises about 0 wt% sulfur mercaptan, for example as measured by ASTM D3227.

[0050] The composition may have a flash point of at least about 38 °C. The composition may have a flash point from about 38 °C to about 150 °C, or about 38 °C to about 50 °C.

[0051] The composition may have a density from about 775 kg / m3to about 850 kg / m3at 15 °C, about 775 kg / m3to about 840 kg / m3at 15 °C, from about 780 kg / m3to about 810 kg / m3, or about 785 kg / m3to about 810 kg / m3at 15 °C at 15 °C. In certainembodiments, the composition has a density of about 775 kg / m3, about 778 kg / m3, about 780 kg / m3, about 782 kg / m3, about 785 kg / m3, about 790 kg / m3, about 795 kg / m3, about 800 kg / m3, or about 810 kg / m3at 15 °C.

[0052] The composition may have a freezing point of less than about -40 °C. The composition may have a freezing point of about -70 °C to about -40 °C, about -60 °C to about -40 °C, or about -65 °C to about -45 °C. In further embodiments, the composition has a freezing point of about -70 °C, about -65 °C, about -60 °C, about -55 °C, about -51 °C, about -50 °C, about -45 °C, or about -40 °C.

[0053] The composition may have a viscosity of less than about 8.0 cSt at -20 °C. In certain embodiments, the composition has a viscosity of less than about 12 mm2 / s at -40 °C or of about 3.2 mm2 / s at -20 °C.

[0054] The composition may have a net heat of combustion of at least about 42.8 MJ / kg. The composition may have a net heat of combustion of about 42.8 MJ / kg to about 51 MJ / kg. In further embodiments, the composition has a net heat of combustion of about 42.8 MJ / kg, about 43.4 MJ / kg, about 45 MJ / kg, about 47 MJ / kg, about 49 MJ / kg, or about 51 MJ / kg.

[0055] The composition may have a smoke point of at least about 18 mm. The composition may have a smoke point of at least about 25 mm. The composition may have a smoke point of from about 25 mm to about 45 mm. In further embodiments, the composition has a smoke point of about 25 mm, about 30 mm, about 35 mm, about 36 mm, about 40 mm, or about 45 mm.

[0056] The composition may give a filter pressure drop of less than about 25 mm Hg. The composition may give a filter pressure drop of from 0 mm Hg to about 25 mm Hg, or of about 0 mm Hg.

[0057] The composition may give a tube deposit rating of less than about 3, with essentially no peacock or abnormal color deposits. The composition may give a tube deposit rating of 1 VTR Color Code.

[0058] The composition may have a lubricity of less than about 0.85 mm wear scar diameter (WSD). The composition may have a lubricity of from 0 mm WSD to about 0.85 mm WSD, or of about 0.52 mm WSD.

[0059] In certain embodiments, the monocyclic aromatics are not petroleum-derived. In some embodiments, the monocyclic aromatics are derived from CO2. In certain embodiments, the monocyclic aromatics, cyclo-paraffins, n-paraffins, and iso-paraffinsare not petroleum-derived. In other embodiments, the monocyclic aromatics, cycloparaffins, n-paraffins, and iso-paraffins are CO2 derived. In an embodiment, a portion of one or more of the monocyclic aromatics, cyclo-paraffins, n-paraffins, and isoparaffins are not derived from CO2.

[0060] The composition may comprise less than about 500 ppm, less than about 400 ppm, less than about 350 ppm, or less than about 300 ppm of oxygenates. The composition may comprise about 200 ppm to about 500 ppm, about 250 ppm to about 450 ppm about 250 ppm to about 400 ppm, or about 300 ppm to about 400 ppm of oxygenates. By incorporating oxygenate conversion, hydrogenation of paraffins (e.g., C9+ (150-310°C fraction) obtained from distilling the hydrocarbon fraction from the CO2 hydrogenation and oligomerization products), and an optional step to remove impurities as a final step, the fuel composition may contain less than 500 ppm of oxygenates. Oxygenate conversion may be performed by any means known in the art to convert oxygenate impurities (e.g., acids, ketones, aldehydes and / or alcohols) to olefins and a minority amount of aromatics. For example, oxygenate conversion may be performed by feeding an oxygenate-containing hydrocarbon stream through a fixed bed reactor packed with a oxygenate conversion catalyst. Oxygenate conversion may convert over about 95%, or over about 98% of alcohol; and / or over about 95%, or over about 98% of aldehydes to olefins and aromatics. Oxygenate conversion may convert over about 80%, over about 85%, about 87% or about 88% of acids; and / or over about 80%, over about 85%, about 87%, or about 88% of ketones.

[0061] The oxygenate conversion catalyst may comprise a zeolite. In certain embodiments, the zeolite is selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g, SAPO-11, SAPO-31, SAPO-41), L zeolite (LTL), mordenite zeolites, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain embodiments, the zeolite is ZSM-5, MCM-49, PSH-3, or MCM-22. The zeolite may be ZSM-5. The ZSM-5 may have a silicon to aluminum ratio (SAR) of about 30 to about 1000, about 80 to about 400, or about 30 to about 280. The zeolite may be SAPO-11.

[0062] The composition may further comprise at least one fuel additive.

[0063] As used herein, certain components, fractions, and feeds are described in terms of the carbon numbers (e.g., CX-Y) in said component, fraction, feed, etc. These descriptions indicate the possible (non-limiting) carbon numbers of the hydrocarbons present in said component, but do not require the presence of each and every carbon number within the range. For example, a feed described as comprising C9-15 hydrocarbons must comprise at least one component falling within the range of carbon numbers listed.

[0064] The synthetic aviation fuel compositions disclosed herein may be made by any method or system for making a paraffin product mixture, an aromatic product mixture, a fuel composition, or otherwise disclosed in co-owned U.S. Patent Application Publication No. 2024 / 0124792, published on April 18, 2024, titled: SYNTHETIC FUELS, AND METHODS AND APPARATUS FOR PRODUCTION THEREOF; or in co-owned U.S. Patent App. No. 18 / 934,440, filed on November 21, 2024, titled: SYSTEMS, METHODS AND CATALYSTS FOR THE PRODUCTION OF SUSTAINABLE AVIATION FUEL; the entire contents of the foregoing applications are incorporated by reference herein.

[0065] One embodiment disclosed herein in a method for the production of aviation fuel comprising: i) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford a comprising one or more paraffins; ii) contacting a second reduction gas and a second carbon source gas with an aromatic catalyst to afford an aromatic product mixture comprising one or more aromatics and / or cyclic paraffins; iii) separating the aromatic product mixture into a separated aromatic product mixture and a cycloparaffin product mixture; iv) distilling the paraffin product mixture, the separated aromatic product mixture, and the cycloparaffin product mixture to remove hydrocarbons outside of the SAF range; and v) blending the distilled paraffin product mixture, the distilled aromatic product mixture and the distilled cycloparaffin product mixture to afford a crude product mixture comprising hydrocarbons in the SAF range.

[0066] Another method for the production of the fully formulated SAF disclosed herein may include: (a) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a medium hydrocarbon product mixture comprising one or more C5-9 paraffins and / or olefins; and a target hydrocarbon product mixture comprising one or more Cio-16 paraffins and / or olefins; (b) distilling the medium hydrocarbon product mixture and the target hydrocarbon product mixture; (c) converting oxygenates in the medium hydrocarbon product mixture and the targethydrocarbon product mixture to hydrocarbons; and (d) contacting the medium hydrocarbon product mixture with an aromatic catalyst to afford a target aromatic product mixture comprising one or more C9-14 aromatics. The step of contacting the medium hydrocarbon product mixture with an aromatic catalyst may also include providing a second reduction gas and / or a second carbon source gas, to afford a target aromatic product mixture comprising one or more C9-14 aromatics.

[0067] The method may further comprise: contacting the medium hydrocarbon product mixture with the aromatic catalyst further affords a light aromatic product mixture comprising one or more Ce-8 aromatics; and / or contacting the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics; and / or contacting the light hydrocarbon product mixture with an oligomerization catalyst to afford a target oligomerized product mixture comprising one or more Cio-16 paraffins and / or olefins.

[0068] The method may further comprise: contacting the light hydrocarbon product mixture with the oligomerization catalyst further affords a light oligomerized product mixture comprising one or more C1-2 hydrocarbons; and, optionally, combining the carbon source gas with the light oligomerized product mixture prior to contacting with the reduction catalyst.

[0069] Another embodiment is directed to a method for the production of aviation fuel comprising: i) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a medium hydrocarbon product mixture comprising one or more C4-9 paraffins and / or olefins; and a target hydrocarbon product mixture comprising one or more Cio-16 paraffins and / or olefins; ii) converting oxygenates in the medium hydrocarbon product mixture and the target hydrocarbon product mixture to hydrocarbons; iii) contacting the medium hydrocarbon product mixture, optionally a second reduction gas, and optionally a second carbon source gas with an aromatic catalyst to afford a target aromatic product mixture comprising one or more C9-16 aromatics; iv) distilling the target hydrocarbon product mixture and the target aromatic product mixture to remove hydrocarbons outside of the SAF range; and v) blending the distilled target hydrocarbon product mixture, the distilled target aromatic product mixture and a distilled cycloparaffin product mixture to afford a crude product mixture comprising hydrocarbons in the SAF range. The method may further comprise anymethod or system disclosed in co-owned U.S. Provisional Patent Application No. 63 / 635,982, filed on April 18, 2024, titled: ISOMERIZATION OF N-PARAFFINS USING PLATINUM OR PALLADIUM IMPREGNATED SAPO CATALYST.

[0070] Catalysts for Conversion of Carbon Sources to Olefins and Paraffins

[0071] Any reduction catalyst known for use in the art of CO2 hydrogenation may be used in the present disclosure. The conversion of carbon dioxide and carbon dioxide containing mixtures can be achieved through catalytic carbon dioxide transformations, where the reduction catalyst plays the key role in the process. Reduction catalysts, as used herein may also be understood to be carbon dioxide hydrogenation catalysts, which are catalysts that enhance carbon dioxide activation and conversion, and may also control the selectivity of the hydrogenation products. The reduction catalysts are active in the conversion of a carbon source gas, such as CO2, to hydrocarbons comprising olefins and / or paraffins.

[0072] Transition metal catalysts, especially base metals, are particularly effective as reduction catalysts due to their high electron density, various oxidation states and rich spectrum of metal-ceramic materials, which provides enhanced carbon dioxide activations and flexible tuning of transformation pathways. In addition to the metal elements, the reduction catalyst may contain one or more additional materials, such as a binder, lubricant and / or supporting material, which can be added to optimize the forming catalyst process, metal dispersity and other chemical and physical properties.

[0073] Certain commonly known reduction catalysts contain copper, iron, zinc, cobalt, or some combination thereof. The reduction catalyst may comprise copper. Copper catalysts are known to be one of the most efficient reduction catalysts producing oxygenates as the major products. These catalysts may include copper as the core metal with various supporting elements including but not limited to zinc, zirconium, aluminum, chromium, alkali metal and alkali earth metals. The supporting element, metal alloy and metal oxide provide electronic and structure support to better tune the reactivity and selectivity of carbon dioxide hydrogenation.

[0074] The reduction catalyst may be any of the reduction catalysts disclosed in co-owned U.S. Patent App. No. 18 / 934,440, filed on November 21, 2024, titled: SYSTEMS, METHODS AND CATALYSTS FOR THE PRODUCTION OFSUSTAINABLE AVIATION FUEL, which is incorporated by reference herein in entirety.

[0075] In an embodiment, the reduction catalyst may comprise iron, optionally in combination with an additional metal. The reduction catalyst may comprise: iron; K, Li, Zr, Cs, Mg, Ca, or a combination thereof, optionally at a molar ratio of from 0 to about 0.20 relative to iron; and / or Au, Cu, Na, Cr, Al, Ga, Mn, or a combination thereof, optionally at a molar ratio from 0 to about 0.60 relative to iron; and / or Zn, optionally at a molar ratio from 0 to about 0.50 relative to iron. The reduction catalyst may comprise: iron; K, Cs, Mg, Ca, or a combination thereof, optionally at a molar ratio of from 0 to about 0.20 relative to iron; and / or Na, Cu, Cr, Mn, or a combination thereof, optionally at a molar ratio of from 0 to about 0.60 relative to iron; and / or Co, Ru, Ni, or a combination thereof, optionally at a molar ratio of from 0 to about 0.50 relative to iron. The reduction catalyst may comprise iron and at least one element selected from K, Cs, Mg, Ca, Na, Cu, Cr, Mn, Co, Ru, or Ni. The reduction catalyst may comprise iron, zinc, and at least one element selected from K, Cs, Mg, Ca, Na, Cu, Cr, Mn, Co, Ru, or Ni. The iron may be in the form of an iron oxide, and the iron oxide is magnetite (FesCU), hematite (Fe20s), or a combination thereof.

[0076] In further aspects, provided herein are reduction catalysts comprising: one or more metals; optionally one or more second elements selected from copper and zinc; optionally one or more Group VI, VII, VIII, IX, X, or XI metal additives; optionally a Group IA or IIA metal, which acts as a promoter.

[0077] The one or more metals may be selected from cobalt, iron, nickel, indium, yttrium, a lanthanide, and combinations thereof. In certain embodiments, the one or more metals is cobalt. In other embodiments, the one or more metals is iron. In still further embodiments, the one or more metals is a combination of iron and cobalt.

[0078] The one or more metals may be present in the form of an oxide, nitride, or carbide. In certain embodiments, the one or more metals is present in the form of an iron oxide.

[0079] In certain embodiments, the one or more Group VI, VII, VIII, IX, X, or XI metal additives, when present, is selected from manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel. In further embodiments, the Group IA or IIA metal, when present, are Group IA elements. In yet further embodiments, the one or more Group IA or IIA metals, when present, are magnesium,calcium, lithium, sodium, potassium, or cesium. In yet further embodiments, the Group I A or II A metal, when present, is lithium, sodium, potassium, or cesium. In still further embodiments, the one or more second elements is present in an amount of about 0.5 to about 40 wt.% of the total amount of the one or more metals, the second element, the optional one or more Group VI, VII, VIII, IX, X, or XI metal additives, and the optional Group IA or IIA metal. The reduction catalyst may comprise: iron; a first element selected from copper, zinc, cobalt, or combinations thereof; and optionally one or more second elements selected from Group IA and IIA metals.

[0080] The reduction catalyst may also include one or more third elements selected from a Group V, VI, VII, VIII, IX, X, and XI metal (e.g., manganese, chromium, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel).

[0081] The reduction catalyst may include: iron; and the first element being zinc. One or both of the iron and zinc may be present in oxide or carbide forms. The iron oxide may be in the form of FeO, Fe20s (hematite), FesCU (magnetite) or a combination thereof. The iron oxide may be substantially (e.g., over about 80%, or over about 90%) in the form of Fe20s. The iron oxide may be substantially (e.g., over about 80%, or over about 90%) in the form of FesC

[0082] The reduction catalyst may comprise zinc at a molar ratio of about 0.2 to about 3 relative to iron, or about 0.3 to about 3 relative to iron. In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.2 to about 1 relative to iron, or about 0.4 to about 1 relative to iron. In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 1.5 relative to iron. In other embodiments, the reduction catalyst comprises zinc at a molar ratio of about 1.0 relative to iron. In certain embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.75 relative to iron, about 0.6 relative to iron, about 0.5 relative to iron, about 0.4 relative to iron, about 0.3 relative to iron, or about 0.25 relative to iron. In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.5 relative to iron.

[0083] The reduction catalyst may comprise a molar ratio of iron to zinc of about 1 : 1 to about 7: 1, about 1: 1 to about 6: 1; about 2:2 to about 6: 1, about 1 : 1 to about 4: 1, about 1 : 1 to about 3: 1, or about 2:1 to about 3: 1. The reduction catalyst may comprise a molar ratio of iron to zinc of about 1 : 1 to about 4.5: 1, about 1.5: 1 to about 3.5: 1, about 1.5: 1 to about 3: 1, or about 1.5: 1 to about 2.5: 1. The reduction catalyst may comprise a molar ratio of iron to zinc of about 2: 1.

[0084] In some embodiments, the reduction catalyst comprises: iron; zinc at a molar ratio of about 0.2 to about 3 relative to iron; and one or more Group IA or IIA metals.

[0085] The one or more Group IA or IIA metals may be present at a molar ratio from 0 to about 0.60 relative to iron; and Zn at a molar ratio from 0 to about 0.50 relative to iron.

[0086] The reduction catalyst may comprise K, Na, Cs, Rh, or a combination thereof at a molar ratio of about 0.01 to about 0.20, about 0.01 to about 0.10, about 0.01 to about 0.08, about 0.01 to about 0.05, or about 0.02 to about 0.4 relative to iron. In other embodiments, the reduction catalyst comprises Na at a molar ratio of about 0.01 to about 0.20, about 0.01 to about 0.10, about 0.01 to about 0.08, about 0.01 to about 0.05, or about 0.02 to about 0.4 relative to iron.

[0087] The reduction catalyst may comprise K, Na, Cs, Rh, or a combination thereof in an amount of about 0.2% to about 1.5%, or about 0.5% to about 1.0% of the total weight of iron plus the first element. In certain embodiments, the reduction catalyst comprises Na in an amount of about 0.2% to about 1.5%, or about 0.5% to about 1.0% of the total weight of iron plus the first element. In other embodiments when the first element is zinc, the reduction catalyst may comprise Na in an amount of about 0.2% to about 1.5%, or about 0.5% to about 1.0% of the total weight of iron plus zinc.

[0088] Catalysts for Conversion of Carbon Sources and Reduction Gas to Aromatics

[0089] In certain aspects, the systems and methods of the present disclosure involve the use of aromatic catalysts. As used herein, the term “aromatic catalyst” refers to a catalyst used for the conversion of carbon sources and reduction gases to aromatics, but which does not necessarily itself comprise aromatics. Use of an aromatic catalyst may also produce other hydrocarbons in a lesser amount.

[0090] Any aromatic catalyst known for use in the art of carbon conversion and aromatization may be used in the present disclosure. The aromatic catalyst may comprise a zeolite component comprising a zeolite. The aromatic catalyst may comprise: a mixed oxide component comprising iron, zinc, or a combination thereof; and a zeolite component comprising a zeolite. The aromatic catalyst may comprise a zeolite component comprising a zeolite and a modifier selected from Fe, Ga, Zn, or a combination thereof.

[0091] In certain embodiments, the aromatic catalyst comprises a zeolite. In certain embodiments, the zeolite is selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g.,SAP011, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain embodiments, the zeolite is ZSM-5, MCM-49, PSH-3, or MCM-22. The zeolite may be ZSM-5. The ZSM-5 may have a silicon to aluminum ratio (SAR) of about 30 to about 1000, about 80 to about 400, about 30 to about 280, or about 80 to about 280.

[0092] The zeolite may comprise a modifier. The modifier may be Ga, Fe, Mn, Zn, P, Pt or a combination thereof. In certain embodiments, the zeolite comprises from 0 wt% to about 10 wt% of the modifier. In further embodiments, the zeolite comprises from 0.01 wt% to about 10 wt% of the modifier, from 0.01 wt% to about 5 wt% of the modifier, from 0.01 wt% to about 3 wt% of the modifier, from 0.1 wt% to about 1.5 wt% of the modifier, or from 0.5 wt% to about 1 wt% of the modifier. In certain embodiments, the zeolite is ZSM-5 modified with Ga, Fe, Mn, Zn, P, Pt, or a combination thereof. The zeolite may be ZSM-5 modified with Zn, optionally in an amount of 0 wt% to about 10 wt% of the total catalyst composition.

[0093] Optional features of the invention relating to catalysts for conversion of carbon sources and reduction gas to aromatics described above may also constitute optional features in relation to catalysts for conversion of carbon sources to paraffins or catalysts for conversion of carbon source gases and reduction gases to linear alpha olefins, and vice versa.

[0094] The aromatic catalyst may include a binder. The binder may be any binder known for use in the art. In certain embodiments, the binder may be selected from the group consisting of: boehmite (e.g., PURAL® TH 100, PURAL® TH 80, PURAL® TH 200, PURAL® 200), silica-alumina hydrate (e.g., SIRAL® 1, SIRAL® 5, SIRAL® 10, SIRAL® 20, SIRAL® 40), aluminate, silicon, zirconium, silica, pseudoboehmite alumina (e.g., VERSAL® V-250), bentonite, or any combination thereof. The binder may be present in an amount of about 0% to about 60% by weight, or about 0% to about 40% by weight of the total catalyst composition. In certain embodiments, the binder is present in about 0.1% to about 30%, about 0.1% to about 20%, about 1% to about 30%, about 1% to about 20%, about 1% to about 15%, about 5% to about 30%, about 5% to about 20%, about 5% to about 15%, about 0.5% to about 10%, about 0.5% to about 5% by weight of the total catalyst composition. In an embodiment, the aromatic catalystincludes a silica binder in amount of about 15% to about 25%, or about 20% by weight of the total catalyst composition.

[0095] In certain embodiments, aromatic catalysts of the disclosure are active in the conversion of a carbon source gas, such as CO2, to aromatics. In other embodiments, aromatic catalysts of the disclosure are active in the conversion of a carbon source gas, such as CO2, and an olefin source to aromatics. The olefin source may be a hydrocarbon product mixture, such as a medium hydrocarbon product mixture comprising one or more C4-9 paraffins and / or olefins, or an olefin product mixture, such as a stream comprising one or more C4-9 olefins, to aromatics.

[0096] The feed stream through the aromatic catalyst may be a carbon source gas. The carbon source gas may be a mixture of hydrocarbons, including, but not limited to, olefins. Accordingly, the selectivity for the aromatic catalyst refers to conversion of hydrocarbons, including, but not limited to, olefins, to the specified aromatic molecule(s). Optionally, the selectivity for the aromatic catalyst refers to conversion of hydrocarbons, including, but not limited to, olefins, in the presence of a carbon gas source to the specified aromatic molecule(s). The aromatic catalyst used herein may have a selectivity for aromatics of over about 50 carbon mole%, over about 55 carbon mole%, over about 60 carbon mole%, or over about 65 carbon mole%. The aromatic catalyst may have a selectivity for aromatics of about 50 carbon mole% to about 90 carbon mole%, about 55 carbon mole% to about 85 carbon mole%, about 60 carbon mole% to about 85 carbon mole%, or about 65 carbon mole% to about 80 carbon mole%. The aromatic catalyst used herein may have a selectivity for target aromatic of about 5 carbon mole% to about 20 carbon mole%, or about 7 carbon mole% to about 15 carbon mole%. The aromatic catalyst used herein may have a selectivity for methane of less than about 8 carbon mole%, less than about 5 carbon mole%, or less than about 4 carbon mole%. The aromatic catalyst used herein may have a selectivity for methane of about 1 carbon mole% to about 8 carbon mole%, about 2 carbon mole% to about 6 carbon mole%, about 2 carbon mole% to about 5 carbon mole%, or about 3 carbon mole% to about 4 carbon mole%.

[0097] The aromatic reactor may afford an aromatic product mixture comprising a light aromatic product mixture and a target aromatic product mixture. The aromatic product mixture may comprise the light aromatic product mixture in about 70% to about 93% by weight of the total aromatic product mixture and the target aromatic product mixturein about 7% to about 15% by weight of the total aromatic product mixture. The aromatic product mixture may comprise the light aromatic product mixture in about 80% to about 93% by weight of the total aromatic product mixture and the target aromatic product mixture in about 7% to about 10% by weight of the total aromatic product mixture.

[0098] The light aromatic product mixture may include a mixture of benzene, toluene, As (aromatic molecules having 8 carbons). The aromatic product mixture may comprise about 10% to about 20% by weight of benzene and about 40% to about 50% by weight of toluene. The aromatic product mixture may comprise about 12% to about 18% by weight of benzene and about 40% to about 46% by weight of toluene, and optionally about 25% to about 35% by weight of As aromatics. The aromatic product mixture may comprise less than about 5% by weight, less than about 3% by weight, less than about 2% by weight of naphthalene. The aromatic product mixture may comprise about 10% to about 20% by weight of benzene, about 40% to about 50% by weight of toluene, and less than about 5%, or less than about 2% by weight of napthalene. The aromatic product mixture may comprise about 12% to about 18% by weight of benzene and about 40% to about 46% by weight of toluene, about 25% to about 35% by weight of As aromatics, and less than about 5%, or less than about 2% by weight of naphthalene.

[0099] Catalysts for Hydrogenation

[0100] In certain aspects, the systems and methods of the present disclosure involve the use of hydrogenation catalysts for hydrogenating percentages of the hydrocarbons produced. In certain embodiments, the hydrogenation catalyst may be independently selected from the catalysts described below.

[0101] In certain embodiments, the hydrogenation catalyst of the present disclosure is a aluminosilicate catalyst, such as a zeolite. In further embodiments, the isomerization catalyst and / or the hydrogenation catalyst is AlCh. In yet further embodiments, the hydrogenation catalyst is doped with a transition metal, such as Pt, Pd, etc. In still further embodiments, the hydrogenation catalyst is Pt on beta-zeolite. In certain embodiments, the hydrogenation catalyst of the disclosure comprises an isomerization catalyst metal, and a zeolite support. In further embodiments, the isomerization catalyst metal is selected from Pd, Pt, Ni-Co, Ni-W, and Ni-Mo.

[0102] The additional support may comprise one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon,titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some preferred embodiments, the additional support comprises y-alumina. In certain embodiments, the additional support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the additional support is selected from alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites. In some embodiments, the additional support is an aluminum oxide that is formed in-situ as part of the reduction catalyst. In some embodiments, the additional support is selected from, but not limited to, MgO, AI2O3, ZrCh, SnCh, SiCh, ZnO, WO3, and TiCh. In some embodiments, the additional support is selected from MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2.

[0103] The hydrogenation catalyst support may comprise: A) one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin, such as MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2; B) a carbon-based material such as activated carbon, carbon nanotubes, graphene, and graphene oxide; C) SiA10x, SO4-ZrO2, zirconium tungstate, tungstated- titania, and anatases (SiO2-AhO3, SiO2-TiO2); D) an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites; or E) a zeolite such as Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. Optionally, the zeolites comprise a modifier such as Zn, Ga, Fe, or other transition metals; and / or optionally the modifier is present as a zeolite- supported metal or as isomorphous substitution in the zeolite framework.

[0104] The additional support may include one or more carbon-based materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0105] The additional support may be selected from SiAlOx, SCU-ZrCh, zirconium tungstate, tungstated-titania, and anatases (SiCh-AhCh, SiCh-TiCh). In further embodiments, the additional support is an aluminum-based material such as alumina (e.g., y-alumina),boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites.

[0106] The additional support may be a zeolite such as Y-type zeolites, beta-zeolites, ZSM- type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline US Y zeolite, microcrystalline US Y zeolite, and combinations thereof. In further embodiments, the zeolites comprise additional metals such as Zn, Ga, Fe, or other transition metals. In yet further embodiments, the additional metals are present as zeolite supported metals or as isomorphous substitution in the zeolite framework. The additional support may be modified with molybdenum, chlorine, and / or sulfur.

[0107] In still further embodiments, the hydrogenation catalyst may be selected from Pt / ZrO2 / WO3, Pt / ZrWO4, Pt / SiA10x, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni- W / SiA10x, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22, and Ni-W / SAPO.

[0108] Catalysts for Hydrocracking

[0109] The systems and methods of the present disclosure can use any suitable hydrocracking catalyst, including those known in the art. In some embodiments, similar catalysts to those described for the hydrogenation and isomerization step (above) are also used for hydrocracking.

[0110] Any suitable hydrocracking catalysts known in the art may be used in these processes. However, the particular embodiments set forth below are provided both to exemplify the use of such catalysts and to identify catalysts particularly well-suited for use in conjunction with the other features of the systems and methods disclosed herein.

[0111] In further embodiments, the hydrocracking catalyst comprises a hydrocracking metal, such as Pd, Pt, Ni, Co, Co-W, Ni-W, and Ni-Mo, and a hydrocracking support. The hydrocracking support may be any suitable material that can serve as a catalyst support.

[0112] The hydrocracking support may comprise one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some embodiments, the hydrocracking support comprises y-alumina. In certain embodiments, the hydrocracking support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, thehydrocracking support is selected from alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites. In some embodiments, the hydrocracking support is an aluminum oxide that is formed in-situ as part of the reduction catalyst. In some embodiments, the hydrocracking support is selected from, but not limited to, MgO, AI2O3, ZrCh, SnCh, SiCh, ZnO, WO3, and TiCh. In some embodiments, the hydrocracking support is selected from MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2.

[0113] In some embodiments, the hydrocracking support comprises one or more carbon-based materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0114] In some embodiments, the hydrocracking support is selected from SiAlOx, SO4-ZrO2, zirconium tungstate, tungstated-titania, and anatases (SiO2-AhO3, SiO2-TiO2). In further embodiments, the hydrocracking support is an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites.

[0115] In some embodiments, the hydrocracking support is a zeolite such as Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In further embodiments, the zeolites comprise a modifier such as Zn, Ga, Fe, or other transition metals. In yet further embodiments, the modifier is present as a zeolite supported metal or as isomorphous substitution in the zeolite framework.

[0116] In some embodiments, the hydrocracking support is modified with molybdenum, chlorine, and / or sulfur.

[0117] In certain embodiments, the hydrocracking metal comprises from about 0.5 wt% to about 40 wt% of the hydrocracking catalyst. In further embodiments, the hydrocracking metal comprises about 0.5 wt% of the hydrocracking catalyst. In yet further embodiments, the hydrocracking metal comprises about 1 wt% of the hydrocracking catalyst. In still further embodiments, the hydrocracking metal comprises about 10 wt% of the hydrocracking catalyst. In certain embodiments, the hydrocracking metal comprises about 20 wt% of the hydrocracking catalyst. In further embodiments, the hydrocracking metal comprises about 30 wt% of the hydrocracking catalyst. In yetfurther embodiments, the hydrocracking metal comprises about 40 wt% of the hydrocracking catalyst.

[0118] Optional features of the invention relating to catalysts for hydrocracking described above may also constitute optional features in relation to catalysts for conversion of carbon sources to paraffins, catalysts for conversion of carbon source gases and reduction gases to linear alpha olefins, catalysts for conversion of carbon sources and reduction gas to aromatics or catalysts for hydrogenation and isomerization, and vice versa.

[0119] Catalysts for Alkylation of Aromatics

[0120] The alkylation step may be performed with any suitable catalyst. In certain embodiments, the alkylation catalyst is a liquid acid, such as HF, SPA (solid phosphoric acid), a Friedel-Crafts alkylation catalyst (e.g., HF / AlCh), tungsten, platinum, or a zeolite. In further embodiments, the alkylation catalyst is a zeolite, such as an acidic zeolite. In yet further embodiments, the zeolite is selected from Y-type zeolites, betazeolites, ZSM-type zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g, SAPO-11, SAPO-5, SAPO-31, SAPO-41), L zeolite (LTL), mordenite zeolite, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, DA-114, USY zeolite, and combinations thereof. In certain embodiments, the zeolite is MCM-22, MCM-49, PSH-3, mordenite zeolite, Y- type zeolite, or beta-zeolite.

[0121] The weight-based space velocity is measured as the amount of reactant mass per unit catalyst mass per unit time. The range for the weight-based space velocity for the alkylation catalyst is between about 0.1 g of reactant per g of catalyst per hour (0.1 h- 1) and about 50 h-1, or between about 0.5 h-1 to about 20 h-1.

[0122] Catalysts for Oligomerization

[0123] The oligomerization catalyst may be a heterogeneous acid catalyst, such as a zeolite or a molecular sieve. The oligomerization catalyst may be an amorphous or crystalline aluminosilicate molecular sieve. The oligomerization catalyst may be a zeolite. The oligomerization catalyst may be an aluminosilicate zeolite. The oligomerization catalyst may be selected from ZSM-5, ZSM-11, ZSM-22, Theta-1, ZSM-23, ZSM-12, ZSM-57, ZSM-35, beta-zeolite, a faujasite, a mordenite, SAPO-5, SAPO-11, a zeoliteof the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof. The oligomerization catalyst may be ZSM-5, beta-zeolite, MCM-22, MCM-49, PSH-3, mordenite, SAPO-5, or a combination thereof. The oligomerization catalyst may be selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, and any combination thereof. The oligomerization catalyst may be ZSM-5. The oligomerization catalyst may MCM-22, PSH-3, or MCM-49.

[0124] The weight-based space velocity is measured as the amount of reactant mass per unit catalyst mass per unit time. The range for the weight-based space velocity for the oligomerization catalyst is between about 0.1 g of reactant per g of catalyst per hour (0.1 h-1) and about 50 h-1, between about 0.5 h-1 about 20 h-1, or between about 0.5 h-1 and about 5 h-1.

[0125] When the oligo-alkylation reactor is used, a combination of one or more alkylation catalyst and one or more oligomerization catalysts may be combined within the oligo- alkylation reactor. The one or more alkylation catalyst and the one or more oligomerization catalysts may be mixed, layered within the reactor optionally with an intermediate quench. In other embodiments, an oligo-alkylation catalyst may be used. The oligo-alkylation catalyst may be a liquid acid, such as HF, SPA (solid phosphoric acid), a Friedel -Crafts alkylation catalyst (e.g., HF / AlCh), an amorphous heterogeneous acid catalyst, such as tungsten / Zr oxide, a heterogeneous acid catalyst, such as a zeolite or a molecular sieve, and a combination thereof. In some embodiments, the oligo-alkylation catalyst is an amorphous or crystalline aluminosilicate molecular sieve. In other embodiments, the oligo-alkylation catalyst is selected from the group consisting of: ZSM-5, ZSM-11, ZSM-22, Theta-1, ZSM-23, ZSM-12, ZSM-57, ZSM- 35, zeolite beta, a faujasite, a mordenite, SAPO-5, SAPO-11, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof. In further embodiments, the oligo-alkylation catalyst is ZSM-5, beta-zeolite, MCM-22, PSH-3, MCM-49, mordenite zeolite, SAPO-5, or any combination thereof.

[0126] Reduction Gases, Carbon Source Gases, and Ratios Thereo f

[0127] The systems and methods of the present disclosure can be designed to utilize any combination of suitable reduction gases and suitable carbon source gases. Said carbon source and reduction gases may in certain embodiments be provided into the requisitereaction vessels separately, or they may in certain embodiments be pre-mixed (e.g., the first reduction gas feed and the first carbon source gas feed can, in some embodiments refer to the same physical feature, as can the second reduction as feed and the second carbon source gas feed) to provide a single feed stream comprising both a carbon source gas and a reduction gas, which is coupled to the appropriate reactor.

[0128] Additionally, a single gas feed comprising the first reduction gas feed, the first carbon source gas feed, the second reduction gas feed, and the second carbon source gas feed can be pre-mixed to provide a single feed stream comprising both a carbon source gas and a reduction gas, coupled to both the aromatic reactor and the reduction reactor.

[0129] In certain embodiments, the single gas feed may include CO2, H2, CO, C2, C3, CH4, and any combination thereof. The feed stream may contain H2 / CO2, in a range of about 10% to about 95%, and each of CO, C2, C3, and CH4 in the range of about 0% to about 65%. The source of CO, C2, C3, and / or CH4 may be from a recycle stream or may be introduced in the fresh feed stream.

[0130] In certain embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and the fourth reduction gas are independently selected from H2, a hydrocarbon, synthesis gas (CO / H2), or from a gas that is, or is derived from, flare gas, waste gas, or natural gas.

[0131] In certain embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is H2. In further embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is synthesis gas. In yet further embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is a hydrocarbon, such as CH4, ethane, propane, or butane. In still further embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is, or is derived from, flare gas, waste gas, or natural gas. In certain embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is CH4.

[0132] In certain embodiments, the first carbon source gas and / or the second carbon source gas is CO2. In further embodiments, the first carbon source gas and / or the second carbon source gas comprises CO2. In yet further embodiments, the first carbon source gas and / or the second carbon source gas is CO. In still further embodiments, the first carbon source gas and / or the second carbon source gas comprises CO.

[0133] As will be understood by those of skill in the art, the flow rate of carbon source gas and / or reduction gas, or various product mixtures through the paraffin and / or aromatic reactors (or elsewhere in the disclosed systems and methods) can be adjusted as needed to afford the desired product output characteristics.

[0134] Additionally, as will be understood by those of skill in the art, the carbon source gases and the reduction gases may be provided in any suitable ratio that affords the desired product output characteristics. In certain embodiments, the molar ratio of the first reduction gas to the first carbon source gas is from about 10: 1 to about 1 : 10. In further embodiments, the molar ratio of the first reduction gas to the first carbon source gas is from about 5: 1 to about 0.5: 1. In yet further embodiments, the molar ratio of the second reduction gas to the second carbon source gas is from about 10: 1 to about 1 : 10. In still further embodiments, the molar ratio of the second reduction gas to the second carbon source gas is from about 5:1 to about 0.5: 1.

[0135] Definitions

[0136] Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings that are commonly understood by those of ordinary skill in the art. Generally, nomenclature used in connection with, and techniques of, chemistry, cell and tissue culture, molecular biology, cell and cancer biology, neurobiology, neurochemistry, virology, immunology, microbiology, pharmacology, genetics and protein and nucleic acid chemistry, described herein, are those well known and commonly used in the art.

[0137] The methods and techniques of the present disclosure are generally performed, unless otherwise indicated, according to conventional methods well known in the art and as described in various general and more specific references that are cited and discussed throughout this specification. See, e.g. “Principles of Neural Science”, McGraw-Hill Medical, New York, N.Y. (2000); Motulsky, “Intuitive Biostatistics”, Oxford University Press, Inc. (1995); Lodish et al., “Molecular Cell Biology, 4th ed.”, W. H. Freeman & Co., New York (2000); Griffiths et al., “Introduction to Genetic Analysis, 7th ed.”, W. H. Freeman & Co., N.Y. (1999); and Gilbert et al., “Developmental Biology, 6th ed.”, Sinauer Associates, Inc., Sunderland, MA (2000).

[0138] Chemistry terms used herein, unless otherwise defined herein, are used according to conventional usage in the art, as exemplified by “The McGraw-Hill Dictionary of Chemical Terms”, Parker S., Ed., McGraw-Hill, San Francisco, C.A. (1985).

[0139] All of the above, and any other publications, patents and published patent applications referred to in this application are specifically incorporated by reference herein. In case of conflict, the present specification, including its specific definitions, will control.

[0140] The term “Log of solubility”, “LogS” or “logS” as used herein is used in the art to quantify the aqueous solubility of a compound. The aqueous solubility of a compound significantly affects its absorption and distribution characteristics. A low solubility often goes along with a poor absorption. LogS value is a unit stripped logarithm (base 10) of the solubility measured in mol / liter.

[0141] The term “monocyclic aromatic(s)” as used herein refer to compounds comprising only one single aromatic ring, which may be substituted or unsubstituted (e.g., alkylbenzenes), and which may optionally be fused with non-aromatic rings (e.g., tetralins and indanes).

[0142] The term “polycyclic aromatic(s)” as used herein refers to compounds comprising at least two aromatic rings, which may be fused (e.g., two distinct rings sharing two adjacent ring atoms). As a non-limiting example, the term “polycyclic aromatics” may be used to refer to a group of compounds comprising naphthalene and / or naphthalene derivatives.

[0143] The term “petroleum-derived” as used herein refers to compounds and compositions that are derived by physical and chemical processes from petroleum feedstocks, but does not include compounds and compositions whose carbon is derived from carbon dioxide or carbon monoxide, even if that carbon dioxide or carbon monoxide was produced from petroleum feedstocks (e.g., by combusting petroleum).

[0144] When the amount of an impurity is specified at a level of "about 0", it is understood by those of skill in the art that such a measurement is accurate to a certain number of significant figures based on the relevant detection method used.

[0145] As used herein, certain components, fractions, and feeds are described in terms of the carbon numbers (e.g., CX-Y) in said component, fraction, feed, etc. These descriptions indicate the possible (non-limiting) carbon numbers of the hydrocarbons present in said component, but do not require the presence of each and every carbon number withinthe range. For example, a feed described as comprising C9-15 hydrocarbons must comprise at least one component falling within the range of carbon numbers listed.

[0146] As used herein, the term “selectivity” and grammatical variants thereof refer to how selective a particular process or catalyst is for producing a particular product. The term refers to an exemplary selectivity value observed for a reaction performed with suitable reagents under conditions that have been selected, by a person of ordinary skill in the art, to maximize or minimize the production of a given product of interest. A value for selectivity may refer to the proportion of product(s) of interest compared to other products produced (which may not be of interest), or may refer to the proportion of other product(s) produced compared to product(s) of interest. Selectivity may be a function of the catalyst used in a process, and / or may be a function of process design or parameters (e.g., temperature, pressure, reagent concentration, GHSV, etc.), as would be understood by a person of ordinary skill in the art. Those of skill in the art are familiar with how to calculate selectivity for a given product. However, where an explicit calculation for selectivity is provided herein, that calculation method controls.

[0147] As used herein, the term “oligomerization,” and grammatical variants thereof, will be understood by those of skill in the art to refer to a process that may involve dimerization, trimerization, tetramerization, pentamerization, hexamerization, heptamerization, octamerization, nonamerization, decamerization, higher-order oligomerization, and combinations thereof. The extent of oligomerization in a particular reaction will determine the composition of the product stream, and depends on aspects of the reactant stream, as well as the reaction conditions.EXAMPLES

[0148] The invention now being generally described, it will be more readily understood by reference to the following examples which are included merely for purposes of illustration of certain aspects and embodiments of the present invention, and are not intended to limit the invention.

[0149] EXAMPLE 1

[0150] A fuel composition was prepared according to a scheme for making paraffins from CO2 (CTP) and aromatics from CO2 (CTA). That scheme is provided in Figure 1.

[0151] Sample analysis: Before distillation, each of the paraffin product mixture, cycloparaffin product mixture and aromatic product mixture was analyzed usingGCxGC to determine the carbon number breakdown and distilled after applying Jet Fuel Blend Optimization platform tJudO) (See Yang, Z., et al., “Maximizing Sustainable aviation fuel usage through optimization of distillation cut points and blending,” Fuel, Vol. 353, Dec. 1, 2023, 129136, available at: https: / / www.sciencedirect.com / science / article / pii / S0016236123017507) to predict the properties and distillation cuts.

[0152] Paraffin: The paraffin product mixture was distilled. The distribution of the paraffin based on GCXGC was Cs to C17 and an average carbon number of 11.1 vs. 11.4 for conventional jet fuel. BP range between IBP=120°C to FBP=298°C (based on ASTM D2887, simdist). Table 1 and Figure 2A and 2B show the carbon makeup and distillation curve of the distilled paraffin product mixture.Table 1 : Carbon Distribution and Properties of the Distilled Paraffin Product Mixture

[0153] Cycloparaffin: The cycloparaffin product mixture was distilled. BP range between IBP=142°C to FBP=263°C (based on ASTM D288, simdist). Table 2 and Figure 3A and 3B show the carbon makeup and distillation curve of the distilled cycloparaffin product mixture. A freezing point anomaly was observed during the testing.Table 2: Carbon Distribution and Properties of the Distilled Cycloparaffin Product Mixture

[0154] Aromatics - The aromatic product mixture was distilled. The distribution of the aromatics based on GCXGC was Cs to Ci6 with an average carbon number of 10.4 vs. 11.4 for conventional jet fuel. BP range between IBP=139OC to FBP=399°C. Table 3 and Figure 4A and 4B show the carbon makeup and distillation curve of the distilled cycloparaffin product mixture.Table 3: Carbon Distribution and Properties of the Distilled Aromatic Product Mixture

[0155] Final fuel composition: A fuel composition was prepared with a 55 / 30 / 15 (paraffin / cycloparaffm / aromatic) blend. The carbon range of the final blended fuel was Cs-Ci? with an average carbon number of 10.9 (vs. 11.4 for conventional jet fuel). The IBP=125°C and final boiling point (FBP)=334°C. The properties of the fuel composition can also be found in Tables 4 and 5, and in Figure 5A and 5B.Table 4: Carbon distribution in the Fuel CompositionTable 5: Properties of Each Component and Blended Fuel

[0156] EXAMPLE 2

[0157] A fuel composition was prepared according to a scheme for converting CO2 and hydrogen into paraffins and olefins, and subsequently into cycloparaffins and aromatics. That scheme is provided in Figure 6.

[0158] CO2 hydrogenation: A mixture of hydrogen gas and CO2 was fed into a fixed bed reactor loaded with a FeZn catalyst at 320°C and 450 psig. The reactor was run under recycle mode for over 1000 hours.

[0159] Distillation: After separating out the aqueous product, the remaining liquid hydrocarbon mixture was distilled to separate a mixed stream of the light and medium hydrocarbons from the heavy C9+ hydrocarbons. The light hydrocarbons (distilled below 150°C) were separated out and slated for waterwash followed by oxygenate conversion. The 150-310°C fraction cut was directed to hydrogenation (HYD-2).

[0160] Water wash: After separation, the light and medium mixed hydrocarbon stream was processed with a water wash to primarily remove acids, alcohols, ketones, aldehydes and other water soluble oxygenates.

[0161] Aromatization (OTA): A feed of CO2, propylene, Ce-8 paraffins, N2 and commercially purchased C3-5 olefins was provided into a fixed bed reactor loaded with a modified ZSM-5 catalyst at 500°C and 50 psig. The aromatization process produced a heavy aromatic product containing benzene, toluene and xylene (together “BTX”).

[0162] Oxygenate conversion: The water-washed mixed light and medium hydrocarbon stream was fed to a fixed bed reactor packed with a SAPO catalyst at 330-350°C and ambientpressure to convert the oxygenates to primarily olefins. Over 98% of alcohol and aldehyde conversion was achieved. About 87-88% of conversion of acids and ketones.

[0163] Alkylation: The aromatization product (over about 75% BTX) plus C3-C6 olefins from the oxygenate conversion and hexane from a recycle stream were fed into the alkylation process over a MWW family catalyst at 160°C and 500 psig, With this process, over 95% of the propylene, butylene and hexene was converted, along with about 75% of the benzene and xylene, and about 80% of the toluene was converted.

[0164] Oligomerization: Oligomerization was performed at 200°C and 800 psig by running the product from the oxygenate conversion (Ce-8 hydrocarbons, propylene, butylene, and hexane diluent) over an MWW-type family catalyst. In this step, over 90% of the propylene, butylene and hexene was successfully converted.

[0165] Hydrogenation 1 (HYD-1): The alkylation product was split into a first split stream and a second split stream. The first split stream was fed into a hydrogenation reactor with conditions set to convert aromatics to cycloparaffins and convert trace amounts of olefins. The HYD-1 reactor was set at 120-160°C and 100-200 psig and packed with a NISAT™ 310 catalyst.

[0166] Hydrogenation 2 (HYD-2): The second split stream of the alkylation product was combined with the C9+ (150-310°C fraction) hydrocarbon mixture obtained from distilling the hydrocarbon fraction from the CO2 hydrogenation and oligomerization outputs to make a stream of about 70-90% C5-16; about 5-10% Ci6+; less than 1% of each of alcohol, aldehyde, and ketone; about 1% acid; about 10-15% Ae+, and then fed to a second hydrogenation reactor for hydrogenation (“HYD-2”), which converts olefins, aromatics, and oxygenates. The HYD-2 reactor was set at 160-200°C and 300- 400 psig and packed with a NISAT™ 370 catalyst.

[0167] The products of HYD-1 and HYD-2 steps were distilled separately to recover the 150 °C plus fraction and then blended at a ratio of 10 vol% HYD-1 product and 90 vol% HYD-2 product to make the fully formulated SAF sample. This final distillation step was performed to remove all hydrocarbons outside of the jet fuel range (i.e., C9-C16).

[0168] The product was then treated with commercial clay to remove any residual impurities. A final distillation step was performed to provide the blended fuel sample having the desired properties within the acceptable limits for Jet Fuel A properties.

[0169] The fuel produced according to the process above has the properties shown in Tables 6 and 7 and in FIGS. 7A and 7B.able 6: Carbon Distribution in the Blended FuelTable 7: Properties of Jet Fuel A and Blended Fuel*Greater content of aromatics results in a lower freezing point.

[0170] While specific embodiments of the subject invention have been discussed, the above specification is illustrative and not restrictive. Many variations of the invention will become apparent to those skilled in the art upon review of this specification and theclaims below. The full scope of the invention should be determined by reference to the claims, along with their full scope of equivalents, and the specification, along with such variations.

Claims

WHAT IS CLAIMED1. A fully formulated synthetic aviation fuel composition comprising: a distilled paraffin product mixture, a distilled cycloparaffin product mixture, and a distilled aromatic product mixture; wherein the fuel composition is derived from CO2; and wherein the fuel composition has an average carbon number between about 10 and about 11.4.

2. The fuel composition of claim 1, wherein the fuel composition has the average carbon number between 10.0 and about 11.1.

3. The fuel composition of claim 1 or 2, wherein the fuel composition comprises less than about 500 ppm oxygenates.

4. The fuel composition of claim 1 or 2, wherein the fuel composition comprises about 200 ppm to about 500 ppm oxygenates.

5. The fuel composition of claim 3, wherein the fuel composition comprises about 250 ppm to about 450 ppm oxygenates.

6. The fuel composition of any one of the preceding claims, wherein the fuel composition comprises about 16 wt% to about 30 wt% n-alkanes.

7. The fuel composition of claim 6, wherein the fuel composition comprises about 16 wt% to about 28 wt% n-alkanes,8. The fuel composition of any one of the preceding claims, wherein the fuel composition comprises about 20 wt% to about 47 wt% iso-alkanes9. The fuel composition of claim 8, wherein the fuel composition comprises about 30 wt% to about 47 wt% iso-alkanes.

10. The fuel composition of any one of the preceding claims, wherein the fuel composition comprises about 16 wt% to about 30 wt% monocycloalkanes.

11. The fuel composition of any one of the preceding claims, wherein the fuel composition comprises about 0.1 wt% to about 6 wt% polycycloalkanes.

12. The fuel composition of claim 11, wherein the fuel composition comprises about 0.2 wt% to about 5 wt% polycycloalkanes.

13. The fuel composition of any one of the preceding claims, wherein the fuel composition comprises about 9 wt% to about 20 wt% aromatics.

14. The fuel composition of claim 13, wherein the fuel composition comprises about 9 wt% to about 18 wt% aromatics.

15. The fuel composition of any one of claims 1-5, wherein the fuel composition comprises about 16 wt% to about 30 wt% n-alkanes, about 20 wt% to about 47 wt% iso-alkanes, about 16 wt% to about 30 wt% monocycloalkanes, about 0.1 wt% to about 6 wt% polycycloalkanes, and about 9 wt% to about 20 wt% aromatics.

16. The fuel composition of any one of claims 1-5, wherein the fuel composition comprises about 16 wt% to about 28 wt% n-alkanes, about 30 wt% to about 47 wt% iso-alkanes, about 16 wt% to about 30 wt% monocycloalkanes, about 0.2 wt% to about 5 wt% polycycloalkanes, and about 9 wt% to about 18 wt% aromatics.

17. The fuel composition of any one of claims 1-16, wherein the fuel composition comprises about 21 wt% to about 30 wt% Cio hydrocarbons.

18. The fuel composition of claim 17, wherein the fuel composition comprises about 21 wt% to about 25 wt% Cio hydrocarbons.

19. The fuel composition of any one of claims 1-18, wherein the fuel composition comprises about 18 wt% to about 25 wt% Cn hydrocarbons.

20. The fuel composition of claim 19, wherein the fuel composition comprises about 20 wt% to about 25 wt% Cn hydrocarbons.

21. The fuel composition of any one of claims 1-20, wherein the fuel composition comprises about 6 wt% to about 17 wt% C9 hydrocarbons.

22. The fuel composition of any one of claims 1-21, wherein the fuel composition comprises about 12 wt% to about 20 wt% C12 hydrocarbons.

23. The fuel composition of any one of claims 1-22, wherein the fuel composition comprises about 5 wt% to about 15 wt % C13 hydrocarbons.

24. The fuel composition of claim 23, wherein the fuel composition comprises about 1 wt% to about 10 wt% C14 hydrocarbons.

25. The fuel composition of claim 23 or 24, wherein the fuel composition comprises about 1 wt% to about 5 wt% Cs hydrocarbons and / or about 1 wt% to about 5 wt% C15 hydrocarbons.

26. The fuel composition of any one of claims 1-16, wherein the fuel composition comprises about 21 wt% to about 30 wt% Cio hydrocarbons, about 18 wt% to about 25 wt% Cn hydrocarbons, about 6 wt% to about 17 wt% C9 hydrocarbons, about 12 wt% to about 20 wt% C12 hydrocarbons, and about 5 wt% to about 15 wt% C13 hydrocarbons.

27. The fuel composition of claim 26, wherein the fuel composition further comprises one or more of: about 1 wt% to about 10 wt% of C14 hydrocarbons; about 1 wt% to about 5 wt% Cs hydrocarbons; and / or about 1 wt% to about 5 wt% C15 hydrocarbons.

28. The fuel composition of any one of claims 1-16, wherein the fuel composition comprises about 25 wt% to about 30 wt% Cio hydrocarbons, about 20 wt% to about 25 wt% Cn hydrocarbons, about 12 wt% to about 17 wt% C9 hydrocarbons, about 12 wt% to about 17 wt% C12 hydrocarbons, and about 5 wt% to about 10 wt% C13 hydrocarbons.

29. The fuel composition of any one of claims 1-16, wherein the fuel composition comprises about 21 wt% to about 25 wt% Cio hydrocarbons, about 20 wt% to about 23 wt% Cn hydrocarbons, about 6 wt% to about 10 wt% C9 hydrocarbons, about 15 wt% to about 20 wt% C12 hydrocarbons, and about 10 wt% to about 15 wt% C13 hydrocarbons.

30. The fuel composition of claim 28 or 29, wherein the fuel composition comprises about 1 wt% to about 10 wt% C14 hydrocarbons.

31. The fuel composition of any one of claims 28-30, wherein the fuel composition comprises about 1 wt% to about 5 wt% Cs hydrocarbons and / or about 1 wt% to about 5 wt% C15 hydrocarbons.

32. The fuel composition of any one of claims 1-31, wherein the fuel composition comprises less than about 2 wt% of each of Ce, C7, C17 and / or Cis hydrocarbons.

33. A fully formulated synthetic aviation fuel composition comprising: about 16 wt% to about 30 wt% n-alkanes, about 20 wt% to about 47 wt% iso-alkanes, about 16 wt% to about 30 wt% monocycloalkanes, about 0.1 wt% to about 6 wt% polycycloalkanes, and about 9 wt% to about 20 wt% aromatics.

34. The fuel composition claim 33, wherein the fuel composition comprises about 16 wt% to about 28 wt% n-alkanes, about 30 wt% to about 47 wt% iso-alkanes, about 16 wt% to about30 wt% monocycloalkanes, about 0.2 wt% to about 5 wt% polycycloalkanes, and about 9 wt% to about 18 wt% aromatics.

35. The fuel composition of claim 33 or 34, wherein the fuel composition comprises about 21 wt% to about 30 wt% Cio hydrocarbons.

36. The fuel composition of claim 35, wherein the fuel composition comprises about 21 wt% to about 25 wt% Cio hydrocarbons.

37. The fuel composition of any one of claims 33-35, wherein the fuel composition comprises about 18 wt% to about 25 wt% Cn hydrocarbons.

38. The fuel composition of claim 37, wherein the fuel composition comprises about 20 wt% to about 25 wt% Cn hydrocarbons.

39. The fuel composition of any one of claims 33-38, wherein the fuel composition comprises about 6 wt% to about 17 wt% C9 hydrocarbons.

40. The fuel composition of any one of claims 33-39, wherein the fuel composition comprises about 12 wt% to about 20 wt% C12 hydrocarbons.

41. The fuel composition of any one of claims 33-40, wherein the fuel composition comprises about 5 wt% to about 15 wt % C13 hydrocarbons.

42. The fuel composition any one of claims 33-41, wherein the fuel composition comprises about 1 wt% to about 10 wt% C14 hydrocarbons.

43. The fuel composition of any one of claims 33-42, wherein the fuel composition comprises about 1 wt% to about 5 wt% Cs hydrocarbons and / or about 1 wt% to about 5 wt% C15 hydrocarbons.

44. A fully formulated synthetic aviation fuel composition comprising: about 21 wt% to about 30 wt% Cio hydrocarbons, about 18 wt% to about 25 wt% Cn hydrocarbons, about 6 wt% to about 17 wt% C9 hydrocarbons, about 12 wt% to about 20 wt% C12 hydrocarbons, and about 5 wt% to about 15 wt% C13 hydrocarbons.

45. The fuel composition of claim 44, wherein the fuel composition further comprises one or more of: about 1 wt% to about 10 wt% of C14 hydrocarbons; about 1 wt% to about 5 wt% Cs hydrocarbons; and / or about 1 wt% to about 5 wt% C15 hydrocarbons.

46. The fuel composition claim 44 or 45, wherein the fuel composition comprises about 25 wt% to about 30 wt% Cio hydrocarbons, about 20 wt% to about 25 wt% Cn hydrocarbons, about 12 wt% to about 17 wt% C9 hydrocarbons, about 12 wt% to about 17 wt% C12 hydrocarbons, and about 5 wt% to about 10 wt% C13 hydrocarbons.

47. The fuel composition of any one of claims 44-46, wherein the fuel composition comprises about 21 wt% to about 25 wt% Cio hydrocarbons, about 20 wt% to about 23 wt% Cn hydrocarbons, about 6 wt% to about 10 wt% C9 hydrocarbons, about 15 wt% to about 20 wt% C12 hydrocarbons, and about 10 wt% to about 15 wt% C13 hydrocarbons.

48. The fuel composition of any one of claims 45-47, wherein the fuel composition comprises about 1 wt% to about 10 wt% C14 hydrocarbons.

49. The fuel composition of claim 44, wherein the fuel composition comprises about 1 wt% to about 5 wt% Cs hydrocarbons and / or about 1 wt% to about 5 wt% C15 hydrocarbons.

50. The fuel composition of any one of claims 44-49, wherein the fuel composition comprises less than about 2 wt% of each of Ce, C7, C17 and / or Cis hydrocarbons.

51. The fuel composition of any one of claims 1-50, wherein the fuel composition comprises less than about 0.3 wt% total sulfur.

52. The fuel composition of any one of claims 1-51, wherein the fuel composition comprises less than about 1 ppm sulfur-containing impurities.

53. The fuel composition of any one of claims 1-52, wherein the composition comprises essentially no sulfur-containing impurities.

54. The fuel composition of any one of claims 1-53, wherein the fuel composition is compliant with ASTM DI 655.

55. The fuel composition of any one of claims 1-54, wherein the aromatics are not petroleum-derived.

56. The fuel composition of any one of claims 1-55, wherein the aromatics are derived from CO2.

57. The fuel composition of any one of claims 1-56, wherein the monocyclic aromatics, cyclo-paraffins, n-paraffins, and iso-paraffins are not petroleum-derived.

58. The fuel composition of any one of claims 1-57, wherein the monocyclic aromatics, cyclo-paraffins, n-paraffins, and iso-paraffins are derived from CO2.

59. A method of making the fuel composition of any one of claims 1-58 comprising: i) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford a paraffin product mixture comprising one or more paraffins; ii) contacting a second reduction gas and a second carbon source gas with an aromatic catalyst to afford an aromatic product mixture comprising one or more aromatics and / or cycloparaffins; iii) separating the aromatic product mixture into a separated aromatic product mixture and a cycloparaffin product mixture; iv) distilling the paraffin product mixture, the separated aromatic product mixture, and the cycloparaffin product mixture to remove hydrocarbons outside of the SAF range; and v) blending the distilled paraffin product mixture, the distilled aromatic product mixture and the distilled cycloparaffin product mixture to afford a crude product mixture comprising hydrocarbons in the SAF range.

60. A method of making the fuel composition of any one of claims 1-58 comprising: contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a medium hydrocarbon product mixture comprising one or more C4-9 paraffins and / or olefins; a light hydrocarbon product mixture comprising one or more C2-4 paraffins and / or olefins; and a target hydrocarbon product mixture comprising one or more Cio-16 paraffins and / or olefins; and converting oxygenates in the medium hydrocarbon product mixture, the light hydrocarbon product mixture, and the target hydrocarbon product mixture into paraffins; contacting the medium hydrocarbon product mixture, optionally a second reduction gas, and optionally a second carbon source gas with an aromatic catalyst to afford a target aromatic product mixture comprising one or more C9-16 aromatics, and a light aromatic product mixture comprising one or more Ce-8 aromatics; contacting the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics;contacting the light hydrocarbon product mixture with an oligomerization catalyst to afford: a target oligomerized product mixture comprising one or more Cio-16 paraffins and / or olefins; hydrogenating the target hydrocarbon product mixture, the target aromatic product mixture, the target oligomerized product mixture, the target alkyl arene product mixture to make paraffin product mixture, a aromatic product mixture, and a cycloparaffin product mixture; distilling the paraffin product mixture, the separated aromatic product mixture, and the cycloparaffin product mixture to remove hydrocarbons outside of the SAF range; and blending the distilled paraffin product mixture, the distilled aromatic product mixture and the distilled cycloparaffin product mixture to produce fully formulated fuel composition.

61. The method of claim 60, further comprising contacting the light hydrocarbon product mixture with the oligomerization catalyst further affords: a medium oligomerized product mixture comprising one or more C3-7 hydrocarbons; and / or a light oligomerized product mixture comprising one or more C1-2 hydrocarbons.

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