CARBON SOURCE GASES TO AROMATICS

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit priority to U.S. Provisional Patent Application No. 63/409035, filed September 22, 2022; and U.S. Provisional Patent Application No. 63/527479, filed July 18, 2023; the entire contents of each of which are incorporated herein by reference.

BACKGROUND

As carbon dioxide concentrations in the atmosphere increase, it is becoming advantageous from social welfare, human health, and energy security perspectives to develop technologies that remove carbon dioxide from the air. Carbon dioxide conversion technologies have the added benefit of producing commodity chemicals on-site, anywhere on the globe, with no cost or hazard risk of transportation when coupled with air capture of CO2. Additionally, as fossil resources are further depleted, alternate methods to generate commodity chemicals which are principally produced from petroleum-based sources (such as aromatics) are needed.

SUMMARY OF THE INVENTION

In certain aspects, provided herein are catalysts for the production of aromatics comprising: one or more metals; optionally one or more Group VI, VII, VIII, IX, X, XI, or XIII metal additives; and optionally a Group IA or IIA metal promoter.

In further aspects, the present disclosure provides catalytic compositions comprising a catalyst of the disclosure and a support.

In yet further aspects, the present disclosure provides methods of making catalysts and catalytic compositions of the disclosure.

In in yet further aspects, provided herein are methods for the production of aromatics comprising contacting a reduction gas and a carbon source gas with a catalyst or a catalytic composition of the disclosure at an aromatic temperature and an aromatic pressure to afford an aromatic product mixture.

DETAILED DESCRIPTION OF THE INVENTION

Aromatic hydrocarbons are traditionally produced by cracking naphtha derived from petroleum. The majority of the aromatics initially produced by this process are polycyclic. Additional processing is required to access monocyclic aromatics, and existing process steps are limited in their ability to reduce polycyclic aromatics beyond certain limits. Aromatics produced from petroleum also typically contain sulfur-based contaminants, which are difficult to remove.

Additionally, polycyclic aromatics (meaning compounds that contain two or more fused aromatic rings), e.g., naphthalenes, produce a considerably larger amount of hazardous particulate emissions upon combustion than their monocyclic counterparts. For example, n- butylbenzene produces around 62% of the soot of naphthalene when burned. Additionally, with the depletion of petroleum-based resources, alternative sources of aromatics that are not derived from petroleum are needed.

The presently disclosed methods and systems produce a mixture of aromatics that is primarily made up on monocyclic aromatics. In certain embodiments, the aromatics produced by the methods and systems of the present disclosure comprises less than about 1 wt% polycyclic aromatics.

The aromatics produced by the methods and systems of the present disclosure also contain substantially fewer sulfur-containing species than the comparable petroleum-derived aromatics, in certain embodiments less than 1 ppm. This is accomplished by synthesizing the aromatics thermochemically from CO2 and H2.

Both of these features of the aromatics described herein (low polycyclic aromatic and sulfur content) are difficult or impossible to achieve using petroleum-derived feedstocks, as those aromatics are prepared by conventional methods, which ultimately retain various characteristic compounds, e.g., sulfur species and polycyclic aromatics, from the petroleum source which are prohibitively expensive or impossible to remove completely from the final product.

Catalysts for the Conversion of Carbon Source Gases to Aromatics

In certain aspects, the methods of the present disclosure involve the use of catalysts, which may in some embodiments be referred to as “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. In certain aspects, the catalysts of the disclosure comprise: one or more metal oxides; optionally a support; and optionally one or more metal additives. In certain embodiments, catalysts of the disclosure are described as comprising and/or being derived from a particular metal oxide, or a combination of multiple metal oxides. One of ordinary skill in the art will appreciate that during the various catalyst preparation and activation methods known in the art, and in those exemplified herein, some or all of the oxygen atoms of the metal oxide may become bonded to other atoms in the catalyst mixture, and/or may be removed from the catalyst mixture during an activation step (e.g., converted to CO2 and removed). Additionally, one of ordinary skill in the art would appreciate that for such catalysts, e.g., the catalysts described below, the molar ratio of oxygen relative to the total composition may vary.

In certain embodiments, the one or more metal oxides is selected from zinc oxide, copper oxide, chromium oxide, and zirconium oxide. In further embodiments, the one or more metal additives, when present, are selected from a group IA or IIA element, palladium, platinum, and ruthenium. In yet further embodiments, the one or more metal oxides comprises a first metal oxide and a second metal oxide, wherein the first metal oxide is zinc or copper, and the second metal oxide is selected from chromium, aluminum, and zirconium.

In some embodiments, the first metal oxide and second metal oxide are present in a first metallic ratio of from about 1 :5 to about 5: 1. In certain embodiments, the first metallic ratio is about 1 :5. In further embodiments, the first metallic ratio is about 1 :4.5. In yet further embodiments, the first metallic ratio is about 1 :4. In still further embodiments, the first metallic ratio is about 1 :3.5. In certain embodiments, the first metallic ratio is about 1 :3. In further embodiments, the first metallic ratio is about 1 :2.5. In yet further embodiments, the first metallic ratio is about 1:2. In still further embodiments, the first metallic ratio is about 1 : 1.5. In certain embodiments, the first metallic ratio is about 1 : 1. In further embodiments, the first metallic ratio is about 1.5: 1. In yet further embodiments, the first metallic ratio is about 2: 1. In still further embodiments, the first metallic ratio is about 2.5: 1. In certain embodiments, the first metallic ratio is about 3: 1. In further embodiments, the first metallic ratio is about 3.5: 1. In yet further embodiments, the first metallic ratio is about 4: 1. In still further embodiments, the first metallic ratio is about 4.5: 1. In certain embodiments, the first metallic ratio is about 5: 1.

In further aspects, the present disclosure provides a catalyst for the production of aromatics comprising: one or more metals; optionally one or more Group VI, VII, VIII, IX, X, XI, or XIII metal additives; and optionally a Group IA or IIA metal promoter.

In certain embodiments, the one or more metals comprises a first metal and a second metal. In further embodiments, the first metal is zinc oxide. In yet further embodiments, the second metal is selected from zirconium, chromium, aluminum, and copper. In still further embodiments, the first metal is present in the form of an oxide, nitride, or carbide. In certain embodiments, the second metal is present in the form of an oxide, nitride, or carbide.

In certain embodiments, the ratio of the first metal to the second metal is from about 1 : 10 to about 10: 1. In further embodiments, the ratio of the first metal to the second metal is about 1 : 10. In yet further embodiments, the ratio of the first metal to the second metal is about 1 :9. In still further embodiments, the ratio of the first metal to the second metal is about 1 :8. In certain embodiments, the ratio of the first metal to the second metal is about 1 :7. In further embodiments, the ratio of the first metal to the second metal is about 1 :6. In yet further embodiments, the ratio of the first metal to the second metal is about 1 :5. In still further embodiments, the ratio of the first metal to the second metal is about 1 :4. In certain embodiments, the ratio of the first metal to the second metal is about 1 :3. In further embodiments, the ratio of the first metal to the second metal is about 1 :2. In yet further embodiments, the ratio of the first metal to the second metal is about 1 : 1. In still further embodiments, the ratio of the first metal to the second metal is about 2: 1. In certain embodiments, the ratio of the first metal to the second metal is about 3: 1. In further embodiments, the ratio of the first metal to the second metal is about 4: 1. In yet further embodiments, the ratio of the first metal to the second metal is about 5: 1. In still further embodiments, the ratio of the first metal to the second metal is about 6: 1. In certain embodiments, the ratio of the first metal to the second metal is about 7: 1. In further embodiments, the ratio of the first metal to the second metal is about 8: 1. In yet further embodiments, the ratio of the first metal to the second metal is about 9: 1. In still further embodiments, the ratio of the first metal to the second metal is about 10: 1.

In certain embodiments, the metal additive is selected from gallium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, and aluminum. In certain preferred embodiments, the metal additive is gallium. In further embodiments, the metal additive is chromium. In yet further embodiments, the metal additive is molybdenum. In still further embodiments, the metal additive is tungsten. In certain embodiments, the metal additive is manganese. In further embodiments, the metal additive is rhenium. In yet further embodiments, the metal additive is iron. In still further embodiments, the metal additive is ruthenium. In certain embodiments, the metal additive is osmium. In further embodiments, the metal additive is cobalt. In yet further embodiments, the metal additive is rhodium. In still further embodiments, the metal additive is iridium. In certain embodiments, the metal additive is nickel. In further embodiments, the metal additive is palladium. In yet further embodiments, the metal additive is platinum. In still further embodiments, the metal additive is copper. In certain embodiments, the metal additive is silver. In further embodiments, the metal additive is gold. In further embodiments, the additive is aluminum.

In certain embodiments, the metal promoter is selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium. In further embodiments, the metal promoter is selected from lithium, sodium, potassium, rubidium, magnesium, calcium, and cesium. In yet further embodiments, the metal promoter is selected from beryllium, magnesium, calcium, strontium, and barium. In still further embodiments, the metal promoter is potassium.

In certain embodiments, the catalyst is ZnCrC .

In certain preferred embodiments, the metal is zinc; the one or more metal additives is present, wherein the one or more metal additives is gallium; and the catalyst comprises a support, wherein the support is ZSM-5.

Placeholder for new disclosure

In certain embodiments, the catalyst comprises a mixed oxide component comprising iron and zinc; and a zeolite component comprising 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., SAPO11, SAPO31, SAPO41), mordenite zeolites, MCM-49, MCM-22, DA- 114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain preferred embodiments, the zeolite is ZSM-5.

In further embodiments, the zeolite component further comprises a modifier, preferably Ga or Zn. In yet further embodiments, the zeolite component comprises from 0 wt% to about 2 wt% of the modifier. In still further embodiments, the zeolite component comprises from 0.01 wt% to about 2 wt% of the modifier. In certain embodiments, the zeolite component comprises from 0.1 wt% to about 1.5 wt% of the modifier. In some preferred embodiments, the zeolite component comprises from 0.5 wt% to about 1 wt% of the modifier.

In certain embodiments, the aromatic catalyst comprises from about 10 wt% to about

90 wt% of the mixed oxide component and from about 90 wt% to about 10 wt% of the zeolite component. In further embodiments, the aromatic catalyst comprises from about 25 wt% to about 75 wt% of the mixed oxide component and from about 75 wt% to about 25 wt% of the zeolite component. In certain preferred embodiments, the aromatic catalyst comprises from about 40 wt% to about 60 wt% of the mixed oxide component and from about 60 wt% to about 40 wt% of the zeolite component.

In certain embodiments, the mixed oxide component comprises: iron; zinc in a molar ratio of from 0 to about 0.50 relative to iron;

Na, K, Cs, Mg, Ca, or a combination thereof, in a molar ratio of from 0 to about 0.10 relative to iron;

Cu, Cr, Mn, or a combination thereof, in a molar ratio of from 0 to about 0.60 relative to iron.

In some embodiments, the aromatic catalyst comprises K in a molar ratio of from 0 to about 0.10 relative to iron. In certain preferred embodiments, the aromatic catalyst comprises K in a molar ratio of about 0.036 relative to iron.

In certain embodiments, the present disclosure provides catalytic compositions comprising a catalyst of the disclosure and a support. The support may be any suitable material that can serve as a catalyst support.

In some embodiments, the support comprises 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 support comprises y-alumina. In certain embodiments, the support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the support is selected from alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites. In some embodiments, the support is an aluminum oxide that is formed in-situ as part of the paraffin catalyst. In some embodiments, the support is selected from, but not limited to, MgO, AI2O3, ZrCh, SnCh, SiCh, ZnO, WO3, and TiCh. In some embodiments, the support is selected from MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2.

In some embodiments, the 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.

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

In some embodiments, the 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), mordenite zeolites, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain preferred embodiments, the support is ZSM-5. 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.

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

In some embodiments, the support is a mesoporous material. In some embodiments, the support has a mesopore volume from about 0.01 to about 3.0 cc/g. In some embodiments, the support has surface area from about 10 m ² /g to about 1000 m ² /g. In some preferred embodiments, the catalytic composition comprising the support and a catalyst disclosed herein has a surface area from about 10 m ² /g to about 1000 m ² /g.

In some embodiments, the catalytic composition is in a form of particles having an average size from about 10 nm to about 5 pm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 20 nm to about 5 pm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 50 nm to about 1 pm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 100 nm to about 500 nm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 50 nm to about 300 nm.

In some embodiments, the catalytic composition comprises from about 5 wt.% to about 80 wt.% of the catalyst. In some embodiments, the catalytic composition comprises from about 5 wt.% to about 70 wt.% of the catalyst. In some embodiments, the catalytic composition comprises from about 20 wt.% to about 70 wt.% of the catalyst. In some embodiments, the catalytic composition comprises from about 30 wt.% to about 70 wt.% of the catalyst.

In some embodiments, the support is a high surface area scaffold. In some embodiments, the support comprises mesoporous silica. In some embodiments, the support comprises carbon allotropes. In some embodiments, the aromatic catalyst is a nanoparticle catalyst. In some embodiments, the particle sizes of the aromatic catalyst on the surface of the scaffold are about 1 nm to 5 nm. In some embodiments, the particle sizes of the aromatic catalyst on the surface of the scaffold are about 5 nm to 100 nm. In some embodiments, the particle sizes of the aromatic catalyst on the surface of the scaffold are 100-500 nm. In some embodiments, the particles not subjected to agglomeration are 100-500 nm in particle size.

In certain embodiments, catalysts of the disclosure, such as those described above, are active in the conversion of a carbon source gas, such as CO2, to aromatics.

Methods of Makins Catalysts for the Conversion of Carbon Source Gases to Aromatics

In certain embodiments, provided herein are methods of preparing a catalyst or catalytic composition of the disclosure.

In certain embodiments, the method of preparing the catalyst or catalytic composition comprises:

(a) providing a first solution comprising a source of the one or more metals, the optional one or more metal additives, a base, and water;

(b) heating the first solution at a first temperature for a first period of time, thereby producing the first reaction mixture;

(c) heating the first reaction mixture at a second temperature for a second period of time to remove the water, thereby producing a solid precursor; and

(d) heating the solid precursor to a third temperature for a third period of time, thereby isolating the catalyst.

In certain embodiments, the method comprises:

(a) providing a second solution comprising a source of the one or more metals, and water;

(b) providing a third solution comprising a base;

(c) heating the third solution at a third temperature for a third period of time;

(d) adding a source of the optional one or more metal additives to the third solution, thereby producing a second reaction mixture;

(e) adding the second solution to the second reaction mixture at a fourth temperature for a fourth period of time, thereby producing a third reaction mixture;

(f) heating the third reaction mixture at a fifth temperature for a fifth period of time, thereby producing a solid precursor;

(g) isolating the solid precursor; (h) contacting the solid precursor with a solution comprising the metal promoter, thereby producing a catalyst precursor; and

(i) heating the catalyst precursor to a sixth temperature for a sixth period of time, thereby isolating the catalyst.

In certain embodiments, the method comprises: providing a first solution comprising a source of the one or more metals and a source of the one or more metal additives; combining the first solution with a basic precipitant, such as a carbonate, to increase the pH of the metal salt containing solution thereby precipitating solid particles; drying and calcining the solid particles to form a solid catalyst.

In certain embodiments, the method comprises: providing a first solution comprising a zinc source and a chromium source and introducing it to a pre-made support material via incipient wetness or wet impregnation, followed by drying and calcining to form a solid catalyst.

In certain embodiments, the method comprises: mixing a source of the one or more metals and a support in a mill jar to provide a first mixture; ball milling the first mixture for between 2 hours to 2 weeks to thereby provide a first precipitate; filtering the first precipitate and heating to a first temperature to provide a ball milled metal source; mixing the ball milled metal source with a source of the one or more metal additives to provide a second mixture; and isolating a solid material from the second mixture to provide the catalyst.

In certain embodiments, the method further comprises combining the solid material with a source of the one or more Group IA metals.

In certain embodiments, the method further comprises pressing the solid material into pellets. In further embodiments, the method further comprises pressing the solid material into pellets prior to introduction into a flow reactor.

Methods for the Conversion of Carbon Source Gases to Aromatics

In certain aspects, the present disclosure provides methods for the production of aromatics comprising contacting a reduction gas and a carbon source gas with a catalyst or a catalytic composition of the disclosure to afford an aromatic product mixture.

In certain embodiments, the reduction gas is 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. In further embodiments, the reduction gas is H2. In yet further embodiments, the reduction gas is synthesis gas. In still further embodiments, the reduction gas is a hydrocarbon, such as CH4, ethane, propane, or butane. In certain embodiments, the reduction gas is, or is derived from, flare gas, waste gas, or natural gas. In further embodiments, the reduction gas is CH4.

In certain embodiments, the carbon source gas is CO2. In further embodiments, the carbon source gas comprises CO2. In yet further embodiments, the carbon source gas is CO. In still further embodiments, the carbon source gas comprises CO.

In certain embodiments, the molar ratio of the reduction gas to the carbon source gas is from about 10: 1 to about 1 : 10. In further embodiments, the molar ratio of the reduction gas to the carbon source gas is from about 5:1 to about 0.5: 1. In yet further embodiments, the molar ratio of the reduction gas to the carbon source gas is about 5: 1. In still further embodiments, the molar ratio of the reduction gas to the carbon source gas is about 4.5: 1. In certain embodiments, the molar ratio of the reduction gas to the carbon source gas is about 3: 1. In further embodiments, the molar ratio of the reduction gas to the carbon source gas is about 2.5 : 1. In yet further embodiments, the molar ratio of the reduction gas to the carbon source gas is about 2: 1. In still further embodiments, the molar ratio of the reduction gas to the carbon source gas is about 1.5: 1. In certain embodiments, the molar ratio of the reduction gas to the carbon source gas is about 1 : 1. In further embodiments, the molar ratio of the reduction gas to the carbon source gas is about 0.5: 1.

In certain embodiments, contacting the reduction gas and the carbon source gas with the catalyst occurs at an aromatic temperature from about 100 °C to about 500 °C, preferably from about 100 °C to about 450 °C. The aromatic temperature may be at least 80 °C, or at least 100 °C, or at least 120 °C. The aromatic temperature may be 550 °C or less, or 500 °C or less, or preferably 450 °C or less. In certain embodiments, the aromatic temperature is from about 250 °C to about 350 °C. In some such embodiments, the aromatic temperature is about 250 °C, about 275 °C, about 300 °C, about 325 °C, or about 350 °C. In certain preferred embodiments, the aromatic temperature is about 300 °C.

In some embodiments, contacting the reduction gas and the carbon source gas with the catalyst occurs at an aromatic pressure is from about 50 psi to about 3000 psi, preferably from about 50 psi to about 1000 psi. In certain such embodiments, the aromatic pressure is about 50 psi, about 150 psi, about 250 psi, about 350 psi, about 450 psi, about 550 psi, about 650 psi, about 750 psi, about 850 psi, about 950 psi, or about 1000 psi. In certain preferred embodiments, the aromatic pressure is about 450 psi.

In certain embodiments, contacting a reduction gas and a carbon source gas with ancatalyst to afford an aromatic product mixture comprising one or more aromatics and/or cyclic paraffins is carried out at an aromatic standard Gas Hourly Space Velocity (aromatic GHSV) of from about 8000 mL/g*h to about 12000 mL/g*h. In further embodiments, the aromatic GHSV is from about 8750 mL/g*h to about 9250 mL/g*h. In still further embodiments, the aromatic GHSV is about 8750 mL/g*h, about 9000 mL/g*h, or about 9250 mL/g*h. In preferred embodiments, the paraffin GHSV is about 9000 mL/g*h.

In certain embodiments, methods of the disclosure further comprise capturing the carbon source gas from a gas feed stream.

As used herein, the term “wt% polycyclic aromatics” in the aromatic product mixture is a percentage of polycyclic aromatics based on total aromatics content. In certain embodiments, the aromatic product mixture comprises from about 0 wt% to about 2 wt% polycyclic aromatics. In further embodiments, the aromatic product mixture comprises from about 0.1 wt% to about 2 wt% polycyclic aromatics. In yet further embodiments, the aromatic product mixture comprises from about 0.1 wt% to about 1 wt% polycyclic aromatics. In still further embodiments, the aromatic product mixture comprises from about 1 wt% to about 2 wt% polycyclic aromatics.

Definitions

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.

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).

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). 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.

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.

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).

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.

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).

EXAMPLES

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.

Example 1 : Exemplary CCh-to-aromatic catalyst compositions

Exemplary catalysts of the disclosure comprise a mixed metal oxide and a zeolite support. The ratio of the mixed metal oxide and zeolite may be: a. Mixed oxide: 10% to 90%, zeolite: 90% to 10% b. Mixed oxide: 25% to 75%, zeolite: 75% to 25% c. Mixed oxide: 40% to 60%, zeolite: 60% to 40% The mixed oxide component of the exemplary catalysts comprises iron and zinc oxide modified with additional metals which is donated as A _a BbFeiooZn _x O _y where a, b, and x represent the atomic composition of each metal and y is the number of oxygen atoms to complement the metal. A consists of at least one of Na, K, Cs, Mg, or Ca, and B consists of at least one of Cu, Cr, or Mn. The range of a, b, and x are shown below: a. 0 < a < 10 b. 0 <= b < 60 c. 0 <= x < 50

The zeolite component of the exemplary catalyst is ZSM5 or metal- or metalloid- modified ZSM5 having the formula M _x ZSM5 _y where x and y are the weight percentage of metal and ZSM5. M consists of Ga or Zn and the range of x and y are shown below: a. ZSM5ioo b. Gao.oiZSM599,99 to Ga2ZSM598 c. Gao.iZSM599,9 to Gai.5ZSM598.5 d. Gao.5ZSM599,5 to GaiZSM599 e. Zno.oiZSM599,99 to Zn2ZSM598 f. Zno.iZSM599,9 to Z ZSMSgs.s g. Zno.5ZSM599,5 to ZniZSM599

Example 2: General Procedure for Preparation of Catalysts for Conversion of CO2 to Aromatics

An exemplary catalyst of the disclosure is synthesized via incipient wetness impregnation of zinc nitrate and chromium nitrate (Zn/Cr ratio = 0.5) onto the H-ZSM-5 support. The metal content of zinc and chromium is 38 wt%. The HZSM-5 support is made through hydrothermal reformation of tetraethyl orthosilicate and aluminum nitrate (Si/ Al = 70) at 180 °C for 48 hours. The resulting product was dried overnight at 110 °C. Calcination was performed at 450 °C for 2 hours.

Example 3: Synthesis of exemplary CCh-to-aromatic catalysts

Mixed Metal Oxide preparation'. 109.1 g of ferric nitrate nonahydrate and 20.1 g zinc nitrate hexahydrate were dissolved in 675 mL water to obtain solution I. 47.2 g of sodium carbonate was dissolved in 891 mL water to obtain solution II. Solution I and solution II were added to a flask containing 100 mL water heated to 338 K under stirring. The feed rate of solution II is 1.3 times of the feed rate of solution I so that the addition of both solutions completed at the same time. After the addition, the temperature of the solution was increased to 353 K and the precipitated solid was aged in the solution for 1 hour. After the aging, the solid was separated from the solution by filtration. The resulting solid was then washed by water until the sodium level in the solid was below 0.1 wt%. The washed solid was then dried at 395 K for 6 hours to obtain solid I. 1.34 g potassium carbonate was dissolved in 1.5 mL of water to obtain solution III. Solution III was combined with solid I to obtain mixture I which was dried at 395 K for 6 hours to obtain solid II. Solid II was then calcined at 623 K for 6 hours. The obtained mixed oxide was Ks.eFeiooZnieOy.

Ga-ZSM5 support preparation: 3.7 g of gallium nitrate was dissolved in 3mL water to obtain solution I. Solution I was then mixed with 99 g of ZSM5 to obtain mixture I. Mixture I was dried at 395 K for 6 hours to obtain solid I. Solid I was calcined at 773 K for 12 hours. The obtained solid was GaiZSM599.

Zn-ZSM5 support preparation: 2.9 g of zinc nitrate hexahydrate was dissolved in 3mL water to obtain solution I. Solution I was then mixed with 99 g of ZSM5 to obtain mixture I. Mixture I was dried at 395 K for 6 hours to obtain solid I. Solid I was calcined at 773 K for 12 hours. The obtained solid was ZmZSM599.

Example 4: General procedure for conversion of CO2 to aromatics

Aromatic formation from CO2 and hydrogen is carried out in a fixed bed flow reactor. The flow reactor is loaded with 1 kg of ZnCnCL on HZSM-5 catalyst. The catalyst is reduced in situ in a hydrogen environment at 350 °C for 2 hours. The reactor is heated to 300 °C after pretreatment. A feed mixture of 75% hydrogen and 25% CO2 is introduced to the reactor at 300 psi and a gas hourly space velocity of 5,000 h' ¹ . The CO2 is converted into a mixture of alkylated aromatics with a selective range of carbon chain numbers (C8-C12).

Example 5: Exemplary Procedure I for CO2 hydrogenation to aromatics (commercial ZSM5) Catalyst made by the method from Example 1, Ks.eFeiooZmeOy was granulated to 40 to 60 mesh size. Commercial ZSM5 was granulated to the same 40 to 60 mesh size. Equal weight of granulated Ks.eFeiooZnieOy and ZSM5 was mixed by a rotating mixer at 60 rpm for 1 minute to obtain the final catalyst I. 2 grams of catalyst I was loaded into a ’A” tubing fixed- bed reactor. Catalyst I was activated by a gas stream of 5% H2 diluted with nitrogen. The activation was operated at 200 PSIG and 623 K. The activation duration was 5 hours. After activation, a mix gas of CO2 and H2 was introduced into the reactor. The H2/CO2 molar ratio was 3: 1. The reactor was operated at pressure of 450 PSIG and temperature of 573 K with a standard gas hourly space velocity of 9000 mL/g*h. The reactor effluent of liquid and gas was measured and the per-pass CO2 conversion and the major component carbon selectivity was reported in Table 5.1.:

Table 5.1. Product distribution of Example 5

Example 6: Exemplary Procedure II for CO2 hydrogenation to SAF -range aromatics (modified ZSM-5)

A mixed-metal oxide made by the method from Example 3, e.g., Ks.eFeiooZnieOy was granulated to 40 to 60 mesh size. A catalyst support, e.g., GaiZSM599 made by the method from Example 3 was granulated to the same 40 to 60 mesh size. Equal weight of granulated Ks.eFeiooZnieOy and GaiZSM599 was mixed by a rotating mixer at 60 rpm for 1 minute to obtain catalyst II. 2 grams of catalyst II was loaded into a ’A” tubing fixed-bed reactor.

Catalyst II was activated by a gas stream of 5% EE diluted with nitrogen. The activation was operated at 200 PSIG and 623 K. The activation duration was 5 hours. After activation, a mix gas of CO2 and EE was introduced into the reactor. The H2/CO2 molar ratio was 3: 1. The reactor was operated at pressure of 450 PSIG and temperature of 573 K with a standard gas hourly space velocity of 9000 mL/g*h. The reactor effluent of liquid and gas was measured and the per-pass CO2 conversion and the major component carbon selectivity was reported in Table 6.2.:

Table 6.2 Product distribution obtained by exemplary procedure II for hydrogenation to aromatics

Polycyclic aromatics in aromatics was between 1 and 2 wt%

INCORPORATION BY REFERENCE All publications and patents mentioned herein are hereby incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of conflict, the present application, including any definitions herein, will control. EQUIVALENTS

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 the claims 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.