INVENTORS: Jeffrey C. Bunquin, Wenyih Frank Lai, Chuansheng Bai, Paul F.

Keusenkothen

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Application No. 62/832,059, filed April 10, 2019, and European Patent Application No. 19185760.6, filed July 11, 2019, the disclosures of which are incorporated herein by their reference.

FIELD

[0002] This disclosure generally relates to processes for preparing lower hydrocarbons and oxygenates from a feedstream, and more particularly to processes for preparing a mixture that includes C2 to C4 olefins from a synthesis gas feedstream in the presence of a multicomponent catalyst.

BACKGROUND

[0003] Synthesis gas (syngas) is a mixture of hydrogen and carbon monoxide generated from the upgrading of chemical feedstocks such as natural gas and coal. Syngas has been used industrially for the production of value-added chemicals including chemical intermediates such as olefins and alcohols, and fuels. Fischer-Tropsch catalysis is one route for syngas conversion to value-added products. Generally, Fischer-Tropsch catalysis involves the use of iron and cobalt catalysts for the production of gasoline range products for transportation fuels, heavy organic products including distillates used in diesel fuels, and high purity wax for a range of applications including food production.

[0004] Similar catalysts can be used for the production of value-added chemical intermediates including olefins and alcohols that can be used, for example, for the production of polymers and fuels. Often the production of value-added chemicals includes the production of saturated hydrocarbons including paraffins. The selectivity of Fischer-Tropsch catalysts towards production of value-added chemical intermediates may be adjusted by addition of promoters including group 1 and group 2 cations and transition metals. Fischer-Tropsch catalysts have been prepared as metal oxides or sulfides of iron and cobalt. The iron and cobalt catalysts are frequently supported on solid carriers including oxides such as alumina, silica, or various clays or on carbonaceous materials. Fischer-Tropsch catalysts have been used to produce hydrocarbons in the gasoline range and lighter hydrocarbons.

[0005] In addition to Fischer-Tropsch synthesis, recent developments in direct syngas conversion technologies involve the conversion of syngas to oxygenated intermediate(s) (e.g., methanol, lower alcohols, ketene), and in situ conversion of the oxygenated intermediate(s) to hydrocarbons. These multicomponent catalyst systems make use of mixtures of (a) oxide catalysts for syngas conversion to alcohols and/or other oxygenated species (e.g., ketenes), and (b) acid catalysts (e.g., zeolites) for conversion of the oxygenated intermediate to hydrocarbons. Conventional multicomponent catalyst systems, however, suffer from limited activity and stability at high temperatures (>300°C), as well as high selectivity to low-value co-products (e.g., methane).

[0006] Therefore, what is needed are multicomponent catalyst systems that demonstrate higher conversion to C2 to C4 hydrocarbons, show selectivity for producing olefins (e.g., ethylene and propylene), and show reduced levels of undesired products (e.g., methanol, methane, C2-C3 paraffins, and C5 and higher products.

[0007] References for citing in an Information Disclosure Statement (37 C.F.R. 1.97(h)): U.S. Patent No. 8,513,315; U.S. Patent Application Nos. 15/769,871; U.S. Patent Application Publication 2018/0305272 and 2008/0319245; International Publications WO 2018/144840, WO 2018/093880, and WO 2010/068364; Chinese Patent Publication CN 103508828; Simard et ak,“Zn0-Cr ₂ 0 ₃ +ZSM-5 catalyst with very low Cr/Zn ratio for the transformation of synthesis gas to hydrocarbons,” Appl. Catal. A: Gen., 125, 81-98 (1995); Erena et ak,“Study of physical mixtures of Cr ₂ 0 ₃ -Zn0 and ZSM-5 catalysts for the transformation of syngas into liquid hydrocarbon,” Ind. Eng. Chem. Res. 37, 1211-1219 (1998); Li et ak,“Direct conversion of syngas into hydrocarbons over a core-shell Cr-Zn@Si0 _2@ -SAP0-34 catalyst,” Chinese J. Catal. 36, 1131-1135 (2015); Chen et ak,“C2-C4 hydrocarbons synthesis from syngas over Cu0-Zn0Al ₂ 0 ₃ /SAP0-34 bifunctional catalyst,” J. Chem. Technol. Biotechnok, 90, 415-422 (2015); Yu et ak,“Transformation of syngas to light hydrocarbons over bifunctional CuO- ZnO/SAPO-34 catalysts: the effect of preparation methods,” Reaction Kinetics, Mechanisms and Catalysis, voh 112, 489-497 (Apr. 26, 2014).

SUMMARY

[0008] It has been found, in a surprising manner, that multicomponent catalysts having a first catalytic component that includes a metal oxide or mixed metal oxide (e.g., ZrCL’ZnO or ZnCrAlO _x ) and a second catalytic component that includes a solid acid (e.g., a zeolite) can be used for the direct conversion of synthesis gas to lower hydrocarbons (e.g., C2-C4 hydrocarbons). The multicomponent catalysts show selectivity for C2-C4 hydrocarbons, e.g., C2-C4 olefins and paraffins, over methane, C5+ hydrocarbons, oxygenates, carbon dioxide, and water.

[0009] A first aspect of this disclosure relates to a catalyst composition such as a catalyst composition for converting syngas that includes a first catalytic component, the first catalytic component that includes zinc, a metal M ¹ selected from Al, Zr, and combinations of A1 and Zr at any proportion, optionally Cr, and oxygen, and having a molar ratio of M ¹ and Cr to Zn of rl and r2, respectively, indicated by the following formula: M ¹ :Cr:Zn = rl:r2:l, where 0.25 < rl< 20, and 0 < r2 < 4.0.

[0010] A second aspect of this disclosure relates to a catalyst composition such as a catalyst composition for converting syngas that includes a first catalytic component and a second catalytic component, the first catalytic component that includes zinc, a metal M ¹ selected from Al, Zr, and combinations of Al and Zr at any proportion, optionally Cr, and oxygen, wherein Al, Zr, and Cr, if any, are substantially uniformly distributed in the first catalytic component, and the second catalytic component is a solid acid consisting essentially of a molecular sieve having an 8 -member ring in a crystal structure thereof.

[0011] A third aspect of this disclosure relates to a catalyst composition such as a catalyst composition for converting syngas that includes a first catalytic component, the first catalytic component that includes zinc, a metal M ¹ selected from Al, Zr, and combinations of Al and Zr at any proportion, optionally Cr, and oxygen, wherein Al, Zr, and Cr, if any, are substantially uniformly distributed in the first catalytic component.

[0012] A fourth aspect of this disclosure relates to a process for making a catalytic composition, the process including contacting a feed that includes syngas with a catalyst composition of the first aspect or second aspect described summarily above under conversion conditions to produce a conversion product mixture.

[0013] A fifth aspect of this disclosure relates to a process for preparing C2-C4 hydrocarbons that includes introducing a feedstream containing hydrogen gas and carbon monoxide gas into a reactor; introducing a catalyst composition of the present disclosure to the reactor, under reactor conditions effective to produce a product mixture, the reactor conditions including a reactor temperature of from 200°C to 450°C; a pressure of from 0.05 MPa to 6 MPa; and (c) forming the product mixture that includes C2-C4 hydrocarbons. [0014] A sixth aspect of this disclosure relates to a process for making a catalytic composition, the process including (I) contacting, in water, a first water soluble compound with a second water soluble compound or mixture and optionally with a third water soluble compound under alkaline conditions to obtain a precipitate, wherein the first water soluble compound that includes Zn, the second water soluble compound or mixture that includes Zr, or Al, or a combination of Zr and Al, and the third water soluble compound that includes Cr, and the precipitate that includes Zn, one or both of Al and Zr, and optionally Cr; and (II) obtaining from the precipitate a first catalytic component that includes zinc, a metal M ¹ selected from Al, Zr, and combinations of Al and Zn at any proportion, optionally Cr, and oxygen, with a molar ratio of M ¹ and Cr to Zn of rl and r2, respectively, indicated by the following formula: MFCr:Zn = rl:r2:l, where 0.25 < rl< 20, and 0 < r2 < 4.0.

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.

[0016] FIG. 1 is a x-ray diffraction (XRD) pattern of an example chabazite according to some embodiments.

[0017] FIG. 2 is a XRD pattern of an example chabazite according to some embodiments.

[0018] FIG. 3 is a XRD pattern of an example chabazite according to some embodiments.

[0019] FIG. 4 is a XRD pattern of an example chabazite according to some embodiments.

[0020] FIG. 5 is a XRD pattern of an example mordenite according to some embodiments.

[0021] FIG. 6 is a XRD pattern of an example mordenite according to some embodiments.

[0022] FIG. 7 is a plot showing the CO conversion of Zn-Cr/A10 _x + H-chabazite according to some embodiments.

[0023] FIG. 8 is a plot showing the C2-C4 hydrocarbon selectivity of (a) Zn-Cr/A10 _x + H- chabazite (Si/AF = 20), (b) Zn-Cr/A10 _x + H-chabazite (Si/AF = 40), and (c) Zn-Cr/A10 _x + H- mordenite (Si/AF = 50) according to some embodiments.

[0024] FIG. 9 is a plot showing the C2-C4 olefin selectivity and C2-C4 paraffin selectivity of (a) Zn-Cr/A10 _x + H-chabazite (Si/AF = 20), (b) Zn-Cr/A10 _x + H-chabazite (Si/AF = 40), and (c) Zn-Cr/A10 _x + H-mordenite (Si/AF = 50) according to some embodiments. DETAILED DESCRIPTION

[0025] In this disclosure, a process is described as including at least one“step.” It should be understood that each step is an action or operation that may be carried out once or multiple times in the process, in a continuous or discontinuous fashion. Unless specified to the contrary or the context clearly indicates otherwise, multiple steps in a process may be conducted sequentially in the order as they are listed, with or without overlapping with one or more other step, or in any other order, as the case may be. In addition, one or more or even all steps may be conducted simultaneously with regard to the same or different batch of material. For example, in a continuous process, while a first step in a process is being conducted with respect to a raw material just fed into the beginning of the process, a second step may be carried out simultaneously with respect to an intermediate material resulting from treating the raw materials fed into the process at an earlier time in the first step. In some embodiments, the steps are conducted in the order described.

[0026] For purposes of this disclosure, and unless otherwise indicated, a“composition” includes components of the composition and/or reaction products of two or more components of the composition.

[0027] Unless otherwise indicated, all numbers indicating quantities in this disclosure are to be understood as being modified by the term“about” in all instances. It should also be understood that the numerical values used in the specification and claims constitute specific embodiments. Efforts have been made to ensure the accuracy of the data in the examples. However, it should be understood that any measured data inherently contain a certain level of error due to the limitation of the technique and equipment used for making the measurement.

[0028] As used herein, the indefinite article“a” or“an” shall mean“at least one” unless specified to the contrary or the context clearly indicates otherwise. Thus, embodiments comprising“a metal” include embodiments comprising one, two, or more metals, unless specified to the contrary or the context clearly indicates only one metal is included.

[0029] For the purposes of this disclosure, the nomenclature of elements is pursuant to the version of Periodic Table of Elements as described in CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985). Abbreviations for atoms are as given in the periodic table (Zn = zinc, for example).

[0030] The following abbreviations may be used herein for the sake of brevity: RT is room temperature (and is 23 °C unless otherwise indicated), kPag is kilopascal gauge, psig is pound- force per square inch gauge, psia is pound- force per square inch absolute, and WHSV is weight hourly space velocity, and GHSV is gas hourly space velocity.

[0031] The phrases, unless otherwise specified,“consists essentially of’ and“consisting essentially of’ do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of this disclosure. Additionally, they do not exclude impurities and variances normally associated with the elements and materials used. “Consisting essentially of’ a component in this disclosure can mean, e.g., comprising, by weight, at least 80 wt%, of the given material, based on the total weight of the composition comprising the component.

[0032] “Soluble” refers to, with respect to a given solute in a given solvent at a given temperature, at most 100 mass parts of the solvent is required to dissolve 1 mass part of the solute under a pressure of 1 atmosphere. “Insoluble” refers to, with respect to a given solute in a given solvent at a given temperature, more than 100 mass parts of the solvent is required to dissolve 1 mass part of the solute under a pressure of 1 atmosphere.

[0033] The term“Cn” compound or group, where n is a positive integer, refers to a compound or a group comprising carbon atoms therein at the number of n. The term“Cm” compound or group, where m is a positive integer, refers to a compound or a group comprising carbon atoms therein at the number of m. Thus,“Cm to Cn” alcohols refers to an alcohol comprising carbon atoms therein at a number in a range from m to n, or a mixture of such alcohols. Thus, C1-C2 alcohols refers to methanol, ethanol, or mixtures thereof.

[0034] The term“conversion” refers to the degree to which a given reactant in a particular reaction (e.g., dehydrogenation, hydrogenation, etc.) is converted to products. Thus 100% conversion of carbon monoxide refers to complete consumption of carbon monoxide, and 0% conversion of carbon monoxide refers to no measurable reaction of carbon monoxide.

[0035] The term“selectivity” refers to the degree to which a particular reaction forms a specific product, rather than another product. For example, for the conversion of syngas, 50% selectivity for C2-C4 olefins refers to that 50% of the products formed are C2-C4 olefins, and 100% selectivity for C2-C4 olefins refers to that 100% of the products formed are C2-C4 olefins. The selectivity is based on the product formed, regardless of the conversion of the particular reaction. The selectivity for a given product produced from a given reactant can be defined as weight percent (wt%) of that product relative to the total weight of the products formed from the given reactant in the reaction. [0036] Provided below is a detailed description of the catalyst compositions of this disclosure, including the catalyst composition of the first aspect of this disclosure, the catalyst composition of the second aspect of this disclosure, and the catalyst composition of the third aspect of this disclosure, the process for making a catalyst composition, and the processes for converting syngas utilizing a catalyst composition. In the description, unless specified or the context clearly indicates otherwise, a“catalyst composition of this disclosure” refers to a catalyst composition of the first aspect of this disclosure, a catalyst composition of the second aspect of this disclosure, catalyst composition of the third aspect of this disclosure, or a mixture or a combination thereof.

[0037] As described herein, a multicomponent catalyst composition (e.g., a metal oxide- solid acid catalyst) can be used to prepare a mixture that includes C2 to C4 olefins from a synthesis gas feedstream. The metal oxide-solid acid catalyst compositions can demonstrate high activity in converting syngas into organic products, especially C2-C4 olefins and C2-C4 alcohols, which have significantly higher value than syngas. Moreover, these catalysts can be highly selective toward C2-C4 olefins, C2-C4 alkanes, and C1-C4 alcohols, and particularly toward C2-C4 olefins, among all C2-C4 products produced.

Catalyst Compositions

[0038] In some embodiments of the catalyst compositions of this disclosure, the catalyst composition includes a first catalytic component and a second catalytic component. The first catalytic component is a metal oxide or a mixed metal oxide. Metal oxide and mixed metal oxides include materials wherein the bonding between the metal and oxygen is undetermined, e.g., a mixed phase. The second catalytic component is a solid acid.

[0039] In some embodiments, the first catalytic component includes Zn, a metal M ¹ selected from Al, Zr, and combinations of A1 and Zr at any proportion, optionally Cr, and oxygen, and having a molar ratio 1 (rl) of M ¹ to Zn and a molar ratio 2 (r2) of Cr to Zn indicated by the following formula:

M ¹ :Cr:Zn = rl:r2:l,

respectively, where 0.25 < rl< 20, such as 0.25 < rl < 10, such as 0.25 < rl < 4.0, and 0 < r2 < 4.0, such as 0 < r2 < 2.0. In some embodiments, 0.25 < r2 < 4.0, such as 0.25 < r2 < 2.0.

[0040] In some embodiments, the distribution of zinc in the first catalytic component is substantially uniform. Without intending to be bound by a particular theory, it is believed that the uniformity results from the unique process for making the catalyst: co-precipitation of Zr and Zn, instead of supporting Zn on a pre-fabricated ZrCh support. The resulting ZnO/ZrCh first catalytic component may be a mixed oxide, glass, or an intricate atom network, or a mixture of all these different forms. In these and other embodiments, the distribution of M ¹ in the first catalytic component is substantially uniform. In these and other embodiments, the distribution of Cr, if any, in the first catalytic component, is substantially uniform. In some embodiments, Al, Zr, and Cr, if any, are substantially uniformly distributed in the first catalytic component.

[0041] In some embodiments, M ¹ is Zr and is free or substantially free of Al. In some embodiments, the catalyst is free of Cr (e.g., r2=0) and the first catalytic component is e.g., a ZrCh-ZnO mixed oxide or a ZrCh-AkCb-ZnO mixed oxide.

[0042] In some embodiments, M ¹ is Al and is free or substantially free of Zr.

[0043] In some embodiments, the first catalytic component consists essentially of Zn, Zr, and oxygen. In some embodiments, the first catalytic component consists essentially of Al, Cr, Zn, and oxygen. In some embodiments, the first catalytic component consists essentially of Al, Zn, and oxygen. The identification of the presence of an oxide phase in a catalyst composition can be conducted by comparing the XRD data of the catalyst composition against an XRD peak database of known oxides, such as those available from International Center for Diffraction Data (“ICDD”). Without intending to be bound by a particular theory, the presence of oxygen can promote the catalytic effect of the catalyst composition. The oxygen may be present as an oxide of one or more metals of M ¹ , Cr, and Zn.

[0044] In some embodiments, the second catalytic component is a solid acid, such as a molecular sieve. In these and other embodiments, the solid acid consists essentially of a molecular sieve having an 8-member ring in a crystal structure thereof. In some embodiments, the 8-member ring structure has a zeolite framework type defined by the Structure Commission of the international Zeolite Association (IZA) as chabazite (CHA), mordenite (MOR), aluminophosphate-eighteen (AEI), silico-aluminophosphate-fifty-six SAPO-56 (AFX), erionite (ERI), Linde Type A (LTA), UOP Zeolitic Material - five (UFI), Ruhr University Bochum - thirteen (RTH), and a combination thereof. In some embodiments, the 8-member ring structure is meso-mordenite (meso-MOR). Examples of zeolites with 8-membered ring structures include ZSM-35 and ZSM-57.

[0045] In some embodiments, the MOR framework type zeolite has a S1O2 to AI2O3 molar ratio (also abbreviated as“Si/Ah molar ratio”“Si/Ah ratio,” or“S1O2 to AI2O3 ratio” in this disclosure) or of from about 6 to about 2000, such as from about 6 to about 200, such as from about 10 to about 60. [0046] In some embodiments, the CHA framework type zeolite has a S1O2 to AI2O3 molar ratio that is from about 10 to about 1000, such as from about 10 to about 100, such as from about 10 to about 50.

[0047] In some embodiments, the MOR framework type zeolite has a S1O2 to AI2O3 molar ratio that is from about 10 to about 1000, such as from about 10 to about 100, such as from about 10 to about 50.

[0048] In some embodiments, the meso-MOR framework type zeolite has a S1O2 to AI2O3 molar ratio that is from about 10 to about 1000, such as from about 10 to about 100, such as from about 10 to about 50.

[0049] Notwithstanding the above, the CHA, MOR, and/or meso-MOR may be used in its acid form (also known as protonated form or H-form). Persons of ordinary skill in the art will understand that in its acid form the cations charge balancing the framework consists predominantly of proton ions H ⁺ .

[0050] In some embodiments, the first catalytic component is supported on the surface of the second catalytic component. In some embodiments, the catalyst composition is a physical mixture of particles of the first catalytic component and particles of the second catalytic component.

[0051] The catalyst compositions of this disclosure may consist essentially of the first and second catalytic components of this disclosure, e.g., including > about 85 wt%, or > about 90 wt%, or > about 95 wt%, or > about 98 wt%, or even > about 99 wt% of the first and second catalytic components, based on a total weight of the catalyst composition. Such catalyst compositions may be considered as a“bulk catalyst” in that they include a minor amount of a carrier or a support material in their compositions, if any at all. Bulk catalysts can be made by procedures described below.

[0052] The catalyst compositions of this disclosure can include a catalyst support material (which may be called a carrier or a binder), at any suitable quantity, e.g., > about 20 wt%, > about 30 wt%, > about 40 wt%, > about 50 wt%, > about 60 wt%, > about 70 wt%, > about 80 wt%, > about 90 wt%, or even > about 95 wt%, based on a total weight of the catalyst composition. In supported catalyst compositions, the first and second catalytic components can be desirably disposed on the internal or external surfaces of the catalyst support material. Catalyst support materials may include porous materials that provide mechanical strength and a high surface area. Non-limiting examples of suitable support materials can include oxides (e.g. silica, alumina, titania, zirconia, and mixtures thereof), treated oxides (e.g. sulphated), crystalline microporous materials (e.g. zeolites), non-crystalline microporous materials, cationic clays or anionic clays (e.g. saponite, bentonite, kaoline, sepiolite, hydrotalcite), carbonaceous materials, or combinations and mixtures thereof. Deposition of the first and second catalytic components on a support can be effected by, e.g., incipient impregnation. A support material can be sometimes called a binder in a catalyst composition.

Producing Catalytic Components and Catalyst Compositions

[0053] As discussed above, the catalyst compositions include a first catalytic component (e.g., a metal oxide or a mixed metal oxide) and a second catalytic component (e.g., a solid acid). The first catalytic component may be prepared prior to combining it with the second catalytic component. The second catalytic component may be prepared prior to combining it with the first catalytic component.

[0054] The first catalytic component may be prepared by a method that includes (1-1) contacting, in water, a first water soluble compound with a second water soluble compound or mixture and optionally with a third water soluble compound under alkaline conditions (e.g., aqueous sodium carbonate) to obtain a precipitate, wherein the first water soluble compound includes Zn, the second water soluble compound or mixture includes Zr, Al, or a combination of Zr and Al, and the third water soluble compound includes Cr, and the precipitate includes Zn, one or both of Al and Zr, and optionally Cr. In some embodiments, the first water soluble compound may be zinc nitrate hexahydrate, the second water soluble compound may be zirconyl nitrate hydrate or chromium nitrate nonahydrate, and/or the third water soluble compound, if any, may be aluminum nitrate nonahydrate. In some embodiments, the method further includes (l-II) obtaining from the precipitate a first catalytic component that includes zinc, a metal M ¹ selected from Al, Zr, and combinations of Al and Zn at any proportion, optionally Cr, and oxygen, with a molar ratio 1 (rl) of M ¹ to Zn and a molar ratio 2 (r2) of Cr to Zn indicated by the following formula:

M ¹ :Cr:Zn = rl:r2:l,

where 0.25 < rl< 20, such as 0.25 < rl < 10, such as 0.25 < rl < 4.0, and 0 < r2 < 4.0, such as 0 < r2 < 2.0. In some embodiments, 0.25 < r2 < 4.0, such as 0.25 < r2 < 2.0.

[0055] In some embodiments, operation (l-II) further includes drying and/or calcining the precipitate.

[0056] The second catalytic component may be prepared by a method that includes (2-1) contacting, in water, a template (e.g., a tetralkylammonium compound such as trimethyl adamantylammonium (TMAA) hydroxide, tetraethylammonium bromide (TEABr), tetrapropylammonium hydroxide (TPAOH), or tetrapropylammonium bromide (TPABr)), a silica source (e.g., silica particles, colloidal silicic acid, or an alkali silicate), an alkali source (a sodium hydroxide solution), and an aluminum source (e.g., an alkali aluminate, such as a sodium aluminate, for example one of a sodium aluminate sol or a sodium aluminate solution) to obtain a precipitate. In the method, a material can perform several functions; for example a material can operate as an aluminum source and as an alkali source, or as a silicon source and as an alkali source, or also as an aluminum source, an alkali source, and a silicon source. Operation 2-1 may further include mixing (e.g., by stirring) with a stirring speed from about 100 rpm and about 900 rpm, such as about 350 rpm. Operation 2-1 may be performed at a temperature from about 100°C to about 200°C, such as about 138°C or about 160°C. Operation 2-1 may be performed for a period of time from about 40 h to about 90 h, such as about 48 h or about 72 h.

[0057] The method of making a second catalytic component may further include (2-II) separating (e.g., filtering) the precipitate, drying the precipitate (at a temperature from about 100°C to about 200°C, such as about 120°C or about 160°C, for a period of time of about 2 h to about 20 h), and/or calcining the precipitate (at a temperature of about 200°C to about 800°C, such as about 540°C, for a period of time of about 2 h to about 20 h) to obtain the second catalytic component. To form the H-form (protonated form) of the second catalytic component, the method may further include (2-III) exchanging the alkali ions of the precipitate in an aqueous medium with a proton-containing substance or a substance that yields protons when heated. In some embodiments, operation (2-III) may further include one or more of a washing with water, a drying operation (at a temperature from about 100°C to about 200°C, such as about 120°C or about 160°C, for a period of time of from about 2 h to about 20 h), or a calcining operation (at a temperature of about 200°C to about 800°C, such as about 540°C, for a period of time of from about 2 h to about 20 h) to form the H-form of the second catalytic component.

[0058] Non-limiting characteristics of the second catalytic component and the H-form of the second catalytic component are discussed herein.

[0059] In some embodiments, the second catalytic component and/or the H-form of the second catalytic component can be mixed with a binder by techniques known in the art.

[0060] In some embodiments, a method of forming a catalyst composition includes (3-1) combining the first catalytic component with second catalytic component which is a solid acid to form a catalyst composition. Non-limiting characteristics of the catalyst composition are described above. The method of forming a catalyst composition may further include (3-II) disposing the first catalytic component on the surface of the second catalytic component and/or forming a physical mixture of the first catalytic component and the second catalytic component.

[0061] The thus made catalyst composition can be used as is as a catalyst composition for its intended use (e.g., converting syngas), e.g., as a bulk catalyst. Alternatively, one can combine the catalyst composition with a catalyst support material, a co-catalyst, or a solid diluent material, to form a second catalyst composition. Suitable catalyst support materials for combining with the catalyst composition are described earlier in this disclosure in connection with the catalyst composition. The combination of the support material and the catalyst composition can be processed in any known catalyst forming processes, including but not limited to grinding, milling, sifting, washing, drying, calcination, and the like, to obtain a catalyst composition. The catalyst composition may be then disposed in an intended reactor to perform its intended function, such as a syngas converting reactor in a syngas converting process.

[0062] It is contemplated that prior to combining the first catalytic component and the second catalytic component (in operation 3-1), the first catalytic component and/or the second catalytic component may be combined with a catalyst support material to obtain a mixture thereof, which is subsequently subject to operation (3-1). In such processes, the first catalytic component and/or the second catalytic component may be disposed on the internal and/or external surfaces of the support material. The operation (3-1) can be performed in a reactor where the catalyst composition is normally used, such as a syngas converting reactor. Alternatively, operation (3-1) can be performed in a reactor other than the reactor the catalyst composition is intended for to obtain a catalyst composition that includes a support material and the catalytic component(s), which can be stored, shipped, and then disposed in a reactor it is intended for.

[0063] It is also contemplated that prior to operation (3-1), the first catalytic component and/or the second catalytic component may be combined or formed with a precursor of a support material to obtain a support/catalytic component mixture. Suitable precursors of various support materials can include, e.g., alkali metal aluminates, water glass, a mixture of alkali metal aluminates and water glass, a mixture of sources of a di-, tri-, and/or tetravalent metal, such as a mixture of water-soluble salts of magnesium, aluminum, and/or silicon, chlorohydrol, aluminum sulfate, or mixtures thereof. The support/catalytic component mixture is subsequently subject to operation (3-1) together, resulting in the formation of the catalytic component and the support material substantially in the same operation. Likewise, operation (3-1) can be performed in a reactor where the catalyst composition is normally used, such as a syngas converting reactor. Alternatively, operation (3-1) can be performed in a reactor other than the reactor the catalyst composition is intended for to obtain a catalyst composition that includes a support material and the catalytic component, which can be stored, shipped, and then disposed in a reactor it is intended for.

Process for Converting Syngas

[0064] A catalyst composition of this disclosure can be used in any suitable process where a metal oxide-solid acid catalyst can perform a catalytic function. The catalyst compositions of this disclosure can be advantageously used in processes for converting syngas into various products such as hydrocarbons, for example C2-C4 olefins and/or C1-C4 alcohols, by the Fischer-Tropsch processes. The Fischer-Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into hydrocarbons and/or alcohols. These reactions occur in the presence of metal catalysts, typically at temperatures of from about 100°C to about 500°C (from about 212°F to about 932°F) and pressures of from about one to about several tens of atmospheres.

[0065] The term“syngas” as used herein relates to a gaseous mixture consisting essentially of hydrogen (¾) and carbon monoxide (CO). In some embodiments, the syngas, which is used as a feed stream, may include up to about 10 mol% of other components such as CO2 and lower hydrocarbons (lower HC), depending on the source and the intended conversion processes. Said other components may be side-products or unconverted products obtained in the process used for producing the syngas. The syngas may contain such a low amount of molecular oxygen (O2) so that the quantity of O2 present does not interfere with the Fischer-Tropsch synthesis reactions and/or other conversion reactions. For example, the syngas may include not more than about 1 mol% O2, not more than about 0.5 mol% O2, or not more than about 0.4 mol% O2. The syngas may have a hydrogen (¾) to carbon monoxide (CO) molar ratio of from about 1:3 to about 3:1, such as from about 0.5:1 to about 3:1. The partial pressures of Fp and CO may be adjusted by introduction of a nonreactive gas (such as N2, Ar, He, or a combination thereof) to the reaction mixture.

[0066] Syngas can be formed by reacting steam and/or oxygen with a carbonaceous material, for example, natural gas, coal, biomass, or a hydrocarbon feedstock through a reforming process in a syngas reformer. The reforming process can be based on any suitable reforming process, such as Steam Methane Reforming, Auto Thermal Reforming, or Partial Oxidation, Adiabatic Pre Reforming, or Gas Heated Reforming, or a combination thereof. Example steam and oxygen reforming processes are detailed in U.S. Patent No. 7,485,767.

[0067] In some embodiments, the syngas formed from steam or oxygen reforming includes hydrogen and one or more carbon oxides (CO and CO2). The hydrogen to carbon oxide ratio of the syngas produced will vary depending on the reforming conditions used. In some embodiments, the syngas reformer product(s) should contain ¾, CO, and CO2 in amounts and ratios which render the resulting syngas blend suitable for subsequent processing into either oxygenates comprising methanol/dimethyl ether or in Fischer-Tropsch synthesis.

[0068] In some embodiments, a process for converting syngas includes contacting a feed that includes syngas with one or more catalyst compositions of the present disclosure under conversion conditions to produce a product mixture. In some embodiments, the product mixture includes a C2-C4 hydrocarbon, e.g., a C2-C4 olefin, a C2-C4 alkane, and/or a C1-C4 alcohol. In some embodiments, the product mixture includes C2-C4 hydrocarbons, in aggregate, at a concentration greater than about 30 wt%, such as greater than about 35 wt%, such as from about 35 wt% to about 99 wt%, such as from about 35 wt% to about 90 wt%, such as from about 40 wt% to 80 about wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.

[0069] In some embodiments, the product mixture includes C2-C4 hydrocarbons having an olefins/alkanes weight ratio of from about 0.1 to about 7, such as from about 0.1 to about 6.

[0070] In some embodiments, the product mixture includes methane at a concentration no greater than 15 wt%, such as no greater than 10 wt%, such as no greater than 5 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.

[0071] In some embodiments, the product mixture includes a combined saturated and unsaturated C5 and higher hydrocarbon content of less than about 50 wt%, such as from about 0.00001 wt% to about 30 wt%, such no greater than about 10 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2. In some embodiments, the product mixture includes an oxygenate content of no greater than about 20 wt%, such as no greater than about 10 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.

[0072] In some embodiments, the product mixture includes (excluding hydrogen (i.e., ¾), CO, and CO2), a combined C2-C4 alkane content of from about 0.0 wt% to about 90 wt%, such as from about from about 0.1 wt% to about 80 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2. In some embodiments, the product mixture includes, a combined C2-C4 alkene (e.g., olefin) content of from about 0.0 wt% to about 90 wt%, such as from about 0.1 wt % to about 80 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.

[0073] In some embodiments, the syngas to be used in Fischer-Tropsch synthesis may have a molar ratio of H2 to CO, unrelated to the quantity of CO2, of about 1.9 or greater, such as from about 2.0 to about 2.8, or from about 2.1 to about 2.6. In some embodiments, and on a water-free basis, the CO2 content of the syngas may be about 10 mol% or less, such as about 5.5 mol% or less, or from about 2 mol% to about 5 mol%, or from about 2.5 mol% to about 4.5 mol%.

[0074] It is possible to alter the ratio of components within the syngas and the absolute CO2 content of the syngas by removing, and optionally recycling, some of the CO2 from the syngas produced in one or more reforming processes. Several commercial technologies are available (e.g., acid gas removal towers) to recover and recycle CO2 from syngas as produced in the reforming process. In some embodiments, CO2 can be recovered from the syngas effluent from a steam reforming unit, and the recovered CO2 can be recycled to a syngas reformer.

[0075] Suitable Fischer-Tropsch catalysis procedures may be found in: U.S. Patent Nos. 7,485,767, 6,211,255, and 6,476,085, the relevant portions of their contents being incorporated herein by reference. In some embodiments, the catalyst composition may be contained in a fixed bed reactor, a fluidized bed reactor, or any other suitable reactor. In some embodiments, the reaction conditions may include contacting the catalyst composition with syngas, to provide a reaction mixture, at a pressure of about 0.05 MPa to about 10 MPa, at a temperature of about 150°C to about 450°C, and/or a gas hourly space velocity of about 1000 h ^-1 to about 10,000 h ¹ for a reaction period.

[0076] The reaction conditions may include a wide range of temperatures. In some embodiments, the reaction temperature is from about 100°C to about 450°C, such as from about 200°C to about 450°C, or from about 300°C to about 400°C, or from about 150°C to about 350°C, such as from about 200°C to about 300°C.

[0077] The reaction conditions may include a wide range of pressures. In some embodiments, the absolute reaction pressure is from pi to p2 kilopascal (“kPa”), wherein pi and p2 can be, independently, e.g., about 100 kPa, about 150 kPa, about 200 kPa, about 250 kPa, about 300 kPa, about 350 kPa, about 400 kPa, about 450 kPa, about 500 kPa, about 600 kPa, about 700 kPa, about 800 kPa, about 900 kPa, about 1000 kPa, about 1500 kPa, about 2000 kPa, about 2500 kPa, about 3000 kPa, about 3500 kPa, about 4000 kPa, about 4500 kPa, or about 5,000 kPa, as long as pi < p2. In some embodiments, the absolute reaction pressure is from about 0.05 MPa to about 10 MPa, such as from about 0.01 MPa to about 6 MPa, such as from about 1 MPa to about 3 MPa.

[0078] Gas hourly space velocities used for converting the syngas to olefins and/or alcohols can vary depending upon the type of reactor that is used. In some embodiments, the gas hourly space velocity of the flow of gas through the catalyst bed is from about 100 hr ^-1 to about 100,000 hr ^-1 , such as from about 100 hr ^-1 to about 50,000 hr ^-1 , such as from about 500 hr ^-1 to about 25,000 hr ^-1 , such as from about 1000 hr ^-1 to about 20,000 hr ^-1 , or from about 100 hr ^-1 to 10,000 hr ¹ .

[0079] Reaction conditions may have an effect on the catalyst performance. For example, selectivity on a carbon basis is a function of the probability of chain growth. Factors affecting chain growth include the temperature of the reaction, the gas composition and the partial pressures of the various gases in contact with the catalyst composition. Altering these factors may lead to a high degree of flexibility in obtaining a type of product in a certain carbon range. Without being limited by theory, an increase in operating temperature shifts the selectivity to lower carbon number products. Desorption of growing surface species is one of the main chain termination steps and since desorption is an endothermic process so a higher temperature should increase the rate of desorption which will result in a shift to lower molecular mass products. Similarly, the higher the CO partial pressure, the more catalyst surface that is covered by adsorbed monomers. The lower the coverage by partially hydrogenated CO monomers, the higher the probability of chain growth. Accordingly, it is probable that the two key steps leading to chain termination are desorption of the chains yielding alkenes and hydrogenation of the chains to yield alkanes.

EXAMPLES

Part A. Preparation of the Metal Oxides

[0080] Preparation of ZrO»ZnQ by Na^CCL addition (Sample 1). Zinc nitrate hexahydrate (21.4 g) and zirconyl nitrate hydrate (50.01 g) were dissolved in 300 g of distilled water (Solution A). Sodium carbonate (Na ₂ C0 ₃ , 23.45 g) was dissolved in 300 g of distilled water (Solution B). Solution A was heated in a water-bath with temperature maintained at 70°C, and Solution B was slowly added to Solution A under vigorous stirring to form a slurry, while maintaining a temperature of about 70°C, and the addition of Solution B was stopped when the pH of the slurry reached a pH of about 7.0. While maintaining the temperature of the slurry at about 70°C, the slurry was aged for about 2 h with stirring. The slurry was allowed to cool to a temperature of about room temperature (e.g., from about 15°C to about 25°C). The slurry was filtered, the slurry cake recovered, and the slurry cake was washed thoroughly with distilled water. The sample was dried at about 120°C in air for about 16 h and then grinded to a sample powder. After grinding, the sample powder was placed in a box furnace. The furnace was ramped from room temperature to about 932°F (500°C) at a rate of about 10°F/min (about 5.5°C/min) in air. The air flowing rate was set at about 5 volume/volume catalyst/minute. The sample was held at about 500°C in air for about 5 hr. In the sample of ZrCk-ZnO, the molar ratio of Zr/Zn is about 2.

[0081] Preparation of ZnCrAlO _x by Na _? COr addition (Sample 2). Zinc nitrate hexahydrate (58.4 g), chromium nitrate nonahydrate (22.4 g), and aluminum nitrate nonahydrate (21.0 g) were dissolved in 300 g of distilled water (Solution C). Sodium carbonate (Na2CC>3, 38.56 g) was dissolved in 300 g of distilled water (Solution D). Solution C was heated in a water-bath with temperature maintained at 70°C, and Solution D was added to Solution C under vigorous stirring, while maintaining a temperature of about 70°C to form a slurry, and the addition of Solution D was stopped when the pH of the slurry reached a pH of about 7.0. While maintaining the temperature of the slurry at about 70°C, the slurry was aged for about 2 h with stirring. The slurry was allowed to cool to a temperature of about room temperature (e.g., from about 15°C to about 25 °C). The slurry was filtered, the slurry cake recovered, and the slurry cake was washed thoroughly with distilled water. The sample was dried at about 120°C in air for about 16 h, and then grinded to a sample powder. After grinding, the sample powder was placed in a box furnace. The furnace was ramped from room temperature to about 932°F (500°C) at a rate of about 10°F/min (about 5.5°C/min) in air. The air flowing rate was set at about 5 volume/volume catalyst/minute. The sample was held at about 500°C in air for about 3 h. In the sample of ZnCrAlO _x , the weight percentage of ZnO is about 69%, and C12O3 is about 19%, and AI2O3 is about 12%.

[0082] Properties of Sample 1 and Sample 2 are provided in Table 1.

Table 1

Part B. Preparation of the Solid Acid Component

[0083] Example 1: Preparation of chabazite crystals and the H-form of the chabazite crystals with SiO/APCh of about 21/1. A mixture of water, a 43% sodium aluminate sol, a 25% trimethyl adamantylammonium (TMAA) hydroxide solution, Ultrasil silica, seeds, and a 50% sodium hydroxide solution was prepared. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 26; H2O/S1O2 of about 16; NaOH/SiCh of about 0.25; and TMAA/S1O2 of about 0.20. The mixture was reacted at about 320°F (about 160°C) in a 2-liter autoclave with stirring at about 350 rpm for about 72 h. The product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C). The XRD pattern (FIG. 1) of the as-synthesized material showed the typical phase of chabazite topology. The scanning electron microscope (SEM) image of the as-synthesized material showed that the material was composed of crystals mainly with size of less than about 1 micron. The resulting chabazite crystals had a S1O2/AI2O3 molar ratio of about 21/1. The as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h. The resulting H-form chabazite crystals had a Hexane sorption of about 115.4 mg/g, a total surface area(SA)/(micro pore SA + mesopore SA) of about 687/(675+11.6) m ² /g, and an Alpha value of about 270.

[0084] Example 2: Preparation of chabazite crystals and H-form of the chabazite crystals with of about 40/1. A mixture of water, a 43% sodium aluminate sol, a 25%

trimethyl adamantylammonium (TMAA) hydroxide solution, Ultrasil silica, seeds, and a 50% sodium hydroxide solution was prepared. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 45; H2O/S1O2 of about 15; NaOH/SiCF of about 0.2; and TMAA S1O2 of about 0.2. The mixture was reacted at about 320°F (about 160°C) in a 2-liter autoclave with stirring at about 350 rpm for about 48 h. The product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C). The XRD pattern (FIG. 2) of the as-synthesized material showed the typical phase of chabazite topology. The SEM of the as-synthesized material showed that the material was composed of crystals mainly with size of less than about 1 micron. The resulting chabazite crystals had a S1O2/AI2O3 molar ratio of about 40/1. The as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h. The resulting H-form chabazite crystals had a Hexane sorption of about 119.1 mg/g, a total surface area(SA)/(micro pore SA + mesopore SA) of about 724/(715+8.7) m ² /g, and an Alpha value of about 85.

[0085] Example 3: Preparation of chabazite crystals and H-form of the chabazite crystals with about 70/1. A mixture of water, a 43% sodium aluminate sol, a 25%

trimethyl adamantylammonium (TMAA) hydroxide solution, Ultrasil silica, seeds, and a 50% sodium hydroxide solution was prepared. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 80; H2O/S1O2 of about 11.3; NaOH/SiCh of about 0.15; and TMAA/S1O2 of about 0.18. The mixture was reacted at about 320°F (about 160°C) in a 2-liter autoclave with stirring at about 350 rpm for about 48 h. The product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C). The XRD pattern (FIG. 3) of the as-synthesized material showed the typical phase of chabazite topology. The SEM of the as-synthesized material showed that the material was composed of crystals mainly with size of less than about 1 micron. The resulting chabazite crystals had a S1O2/AI2O3 molar ratio of about 70/1. The as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h.

[0086] Example 4: Preparation of chabazite crystals and H-form of the chabazite crystals with SiCb/AFOi of about 140/1. A mixture of water, a 43% sodium aluminate sol, a 25% trimethyl adamantylammonium (TMAA) hydroxide solution, Ultrasil silica, seeds, and a 50% sodium hydroxide solution was prepared. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 160; H2O/S1O2 of about 11.3; NaOH/SiCh of about 0.05; and TMAA/S1O2 of about 0.20. The mixture was reacted at about 320°F (about 160°C) in a 2-liter autoclave with stirring at about 350 rpm for about 48 h. The product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C). The XRD pattern (FIG. 4) of the as-synthesized material showed the typical phase of chabazite topology. The SEM of the as-synthesized material showed that the material was composed of crystals mainly with size of less than about 1 micron. The resulting chabazite crystals had a S1O2/AI2O3 molar ratio of about 140/1. The as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h.

[0087] Example 5 : Preparation of meso-mordenite crystals and H-form of meso-mordenite crystals with of about 20/1. A mixture of tetraethylammonium bromide (TEABr,

50% solution, the template), Ultrasil silica a sodium aluminate solution (43%), and a 50% sodium hydroxide solution was prepared. Then 10 g of mordenite seeds was added to the mixture. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 25; H2O/S1O2 of about 25; NaOH/SiC of about 0.29; and Template/SiC of about 0.05. The mixture was reacted at about 280°F (about 138°C) in a 2-liter autoclave with stirring at about 350 rpm for about 72 h. The product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C). The XRD pattern (FIG. 5) of the as-synthesized material showed the typical pure phase of mordenite topology. The SEM of the as-synthesized material showed that the material was composed of small crystals with size of less than about 0.1 micron. The resulting mordenite crystals had a S1O2/AI2O3 molar ratio of about 20/1. The as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h. The resulting H- form mordenite crystals had a Hexane sorption of about 61.7 mg/g, a total surface area(SA)/(micro pore SA + mesopore SA) of about 603/(558 + 45) m ² /g, and an Alpha value of about 910.

[0088] Example 6: Preparation of mordenite Crystals and the H-form of the mordenite Crystals with of about 50/1. A mixture of tetraethylammonium bromide (TEABr,

50% solution, the template), Ultrasil silica, a sodium aluminate solution (43%), and a 50% sodium hydroxide solution was prepared. Then 10 g of mordenite seeds was added to the mixture. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 60; H2O/S1O2 of about 14.7; NaOH/Si0 ₂ of about 0.27; and Template/Si0 ₂ of about 0.05. The mixture was reacted at about 280°F (about 138°C) in a 2-liter autoclave with stirring at about 350 rpm for about 72 h. The product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C). The XRD pattern (FIG. 6) of the as-synthesized material showed the typical pure phase of mordenite topology. The SEM of the as-synthesized material showed that the material was composed of small crystals with size of less than about 1 micron. The resulting mordenite crystals had a S1O2/AI2O3 molar ratio of about 50/1. The as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h. The resulting H- form mordenite crystals had a Hexane sorption of about 33.5 mg/g, a total surface area(SA)/(micro pore SA + mesopore SA) of about 512/(468 + 44) m ² /g, and an Alpha value of about 180.

Part C. Catalyst synthesis and XRD characterization

[0089] Example Cl: Preparation of co-extrusion of alumina bound of mixed ZrZnO _x and Chabazite extrudates. About 40 parts of calcined ZrZnO _x (Sample 1, Part A) and about 40 parts of calcined H-formed Chabazite crystals (Example 1 , Part B) were mixed with about 20 parts of high surface area alumina oxide and water (an amount of water sufficient to form a slurry) in a muller. The mixture of ZrZnO _x , Chabazite, alumina, and water was extruded into a 1/16” cylinder extrudates and then dried at about 121°C overnight. The dried extrudate was calcined in nitrogen at about 400°C for about 2 h before testing.

[0090] Example C2: Preparation of co-extrusion of alumina bound mixed ZnCrAlO _x and Mordenite extrudate. About 40 parts of calcined ZnCrAlO _x (Sample 2, Part B) and about 40 parts of calcined H-formed Mordenite crystals (Example 5, Part B) were mixed with about 20 parts of high surface area alumina oxide (an amount of water sufficient to form a slurry) in a muller. The mixture of ZnCrAlO _x , Mordenite, alumina, and water was extruded into a 1/16” cylinder extrudates and then dried at about 121°C overnight. The dried extrudate was calcined in nitrogen at about 400°C for about 2 h before testing.

Part D: General procedure for converting syngas using the metal oxide-solid acid catalyst of this disclosure

[0091] The catalyst was loaded into a fixed-bed reactor system. The catalyst was dried at about 110°C under an N2 purge at about 15 bar absolute pressure and about GHSV=2000 h ¹ for about 2 h. Maintaining the N2 purge, reactor pressure, and GHSV, the reactor temperature was then increased to about 400°C at about a 1 °C/min ramp rate. The reactor was kept at about 400°C for about 2 h. The reactor was then cooled to the Fischer-Tropsch reaction synthesis temperature (e.g., about 250°C). Once the temperature stabilized, the reactor feed was switched to a mixture of ¾ and CO (e.g., syngas). The range of conditions explored were as follows: (1) temperature, from about 150°C to about 400°C; (2) pressure, from about 1 bar to about 50 bar; (3) thiCO ratio, from about 1:3 to about 3:1, and (4) GHSV, from about 1000 h ¹ to about 10,000 h ¹ .

[0092] FIG. 7 shows the CO conversion for ZnCrO _x and H-CHA (Si/A12 = 40) showing that high CO conversions and an exceedingly low catalyst deactivation rate can be achieved. For example, CO conversions higher than 60% were achieved at 400 °C, pressure of 18 bar (1800 kPa) and GHSV = 2000 h ¹ , without observable deactivation (time on stream = 155-235 h).

[0093] FIG. 8 shows the C2-C4 selectivity of various example catalysts at various CO conversion levels. The catalyst having Zn-Cr/A10 _x + H-chabazite (Si/ Ah = 20) shows a C2- C4 hydrocarbon selectivity of about 70%. The catalyst having Zn-Cr/A10 _x + H-chabazite (Si/ Ah = 40) shows a C2-C4 hydrocarbon selectivity of about 90%. The catalyst having Zn- Cr/A10 _x + H-mordenite (Si/ Ah = 50) shows a C2-C4 hydrocarbon selectivity of about 70%.

[0094] FIG. 9 is a plot showing the percentage C2-C4 olefins versus the C2-C4 hydrocarbon selectivity of various example catalysts. For example, the catalyst having Zn- Cr/A10 _x + H-chabazite (Si/Ah = 20) shows that at a 70% C2-C4 hydrocarbon selectivity, the percentage of C2-C4 products is about 60% C2-C4 olefins and about 40% C2-C4 paraffins. The catalyst having Zn-Cr/A10 _x + H-chabazite (Si/ Ah = 40) shows that at about 95% C2-C4 hydrocarbon selectivity, the percentage of C2-C4 products is about 5-10% C2-C4 olefins and about 90-95% C2-C4 paraffins. The catalyst having Zn-Cr/A10 _x + H-mordenite (Si/AF = 50) shows that at about 25% C2-C4 hydrocarbon selectivity, the percentage of products is about 80% C2-C4 olefins and about 20% C2-C4 paraffins. In addition, the Zn-Cr/A10 _x + H- mordenite (Si/A12 = 50) catalyst also shows that at about 70% C2-C4 hydrocarbon selectivity, the percentage of products is about 55% C2-C4 olefins and about 45% C2-C4 paraffins.

[0095] The catalytic components of all these catalyst compositions contain oxygen, at least part of which in the form of metal oxide(s). The metal elements contained in these catalytic components as well as the solid acid component are indicated in the following Table 2, along with several performance parameters at about 300°C to about 400°C, about 2:1 H2/CO ratio, absolute pressure of about 1800 kPa, and GHSV=about 2000 h ¹ : Table 2

[0096] In Table 2, MOR refers to mordenite, and CHA refers to chabazite. As can be seen from the data in Table 2 above, the metal oxide-solid acid catalyst compositions comprising metal oxide(s) demonstrated high activity in converting syngas into organic products, especially C2-C4 olefins and C2-C4 alcohols, which have significantly higher value than syngas. Moreover, these catalysts are highly selective toward C2-C4 olefins, C2-C4 alkanes, and C1-C4 alcohols, and particularly toward C2-C4 olefins, among all C2-C4 products produced.

[0097] In a comparison of conversion between CHA with Si/ Ah = 40 and 20 (Examples 5 and 6). The lower acidity CHA (Si/Ak = 40) gave a higher conversion. This may be attributed to a lower propensity of CHA (Si/Al ₂ =40) to form coke, meaning that the catalyst has less active sites and has less deactivation.

[0098] In some demonstrations, the C2-C4 product fraction comprises from about 10 wt% to about 90 wt% olefins, from about 10 wt% to about 90 wt% alkanes, from about 0 wt% to about 5 wt% alcohols. The Figures and the Table 2 further show that multicomponent catalysts have very low methane selectivity (<5 %).

[0099] Other non-limiting aspects and/or embodiments of the present disclosure can include:

[00100] Al. A catalyst composition for converting syngas, comprising a first catalytic component, the first catalytic component comprising zinc, a metal M ¹ selected from Al, Zr, and combinations of A1 and Zr at any proportion, optionally Cr, and oxygen, and having a molar ratio of M ¹ and Cr to Zn of rl and r2, respectively, indicated by the following formula:

M ¹ :Cr:Zn= rl:r2:l,

where 0.25 < rl< 20, and 0 < r2 < 4.0.

[00101] A2. The catalyst composition of Al, wherein 0.25 < rl < 10, 0 < r2 < 2.0, or a combination thereof.

[00102] A3. The catalyst composition of Al or A2, wherein the distribution of zinc in the first catalytic component is substantially uniform.

[00103] A4. The catalyst composition of any of Al to A3, wherein the distribution of M ¹ in the first catalytic component is substantially uniform.

[00104] A5. The catalyst composition of any of Al to A4, wherein the distribution of Cr, if any, in the first catalytic component, is substantially uniform.

[00105] A6. The catalyst composition of any of Al to A5, wherein M ¹ is Zr.

[00106] A7. The catalyst composition of any of Al to A6, wherein r2=0.

[00107] A8. The catalyst composition of any of Al to A7, wherein 0.25 < rl < 10.

[00108] A9. The catalyst composition of any of A6 to A8, wherein the first catalytic component consists essentially of Zn, Zr, and oxygen.

[00109] A10. The catalyst composition of any of Al to A5, wherein M ¹ is Al.

[00110] Al l. The catalyst composition of A10, wherein 0.25 < rl < 4.0.

[00111] A12. The catalyst composition of A10 or Al 1, wherein 0.25 < r2 < 4.0.

[00112] A13. The catalyst composition of A10 or Al 1, wherein 0.25 < r2 < 2.0.

[00113] A 14. The catalyst composition of any of A10 to A13, wherein the first catalytic component consists essentially of Al, Cr, Zn, and oxygen.

[00114] A15. The catalyst composition of any of Al to A 14, further comprising a second catalytic component which is a solid acid, such as a molecular sieve.

[00115] A 16. The catalyst composition of A15, wherein the solid acid consists essentially of a molecular sieve having an 8-member ring in a crystal structure thereof.

[00116] A17. The catalyst composition of A15 or A16, wherein the first catalytic component is supported on a surface of the second catalytic component.

[00117] A18. The catalyst composition of A15 or A16, which is a physical mixture of particles of the first catalytic component and particles of the second catalytic component. [00118] A 19. The catalyst composition of any of A15 to A18, wherein the molecular sieve is selected from zeolites the following frame work types: MOR, CHA, and mixtures and combinations thereof.

[00119] A20. The catalyst composition of any of A15 to A19, wherein the molecular sieve comprises a MOR framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 6 to 200.

[00120] A21. The catalyst composition of any of A15 to A19, wherein the molecular sieve comprises a MOR framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 10 to 60.

[00121] A22. The catalyst composition of any of A15 to A21, wherein the molecular sieve comprises a CHA framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 10 to 200.

[00122] A23. The catalyst composition of any of A15 to A21, wherein the molecular sieve comprises a CHA framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 10 to 60.

[00123] A24. The catalyst composition of any of A1-A23, wherein the first catalytic component and the second catalytic component are co-extruded.

[00124] Bl. A catalyst composition comprising a first catalytic component, the first catalytic component comprising zinc, a metal M ¹ selected from Al, Zr, and combinations of A1 and Zr at any proportion, optionally Cr, and oxygen, wherein Al, Zr, and Cr, if any, are substantially uniformly distributed in the first catalytic component.

[00125] B2. The catalyst composition of Bl, wherein the first catalytic component consists essentially of Zn, Zr, and oxygen.

[00126] B3. The catalyst composition of Bl, wherein the first catalytic component consists essentially of Al, Zn, and oxygen.

[00127] B4. The catalyst composition of any of Bl to B3, wherein the molar ratios of M ¹ and Cr, if any, to Zn are rl and r2 respectively, indicated by the following formula:

M ¹ :Cr:Zn = rl:r2:l,

where 0.25 < rl< 20, and 0 < r2 < 4.0.

[00128] B5. The catalyst composition of any of Bl to B4, wherein 0.25 < rl < 10, 0 < r2 <

2.0, or a combination thereof.

[00129] B6. The catalyst composition of any of B 1 to B5, wherein M ¹ is Zr.

[00130] B7. The catalyst composition of any of B 1 to B6, wherein r2=0. [00131] B8. The catalyst composition of any of B1 to B7, wherein M ¹ is Al, and 0.25 < rl

< 4.0.

[00132] B9. The catalyst composition of any of B 1 to B8, wherein 0.25 < r2 < 4.0.

[00133] B 10. The catalyst composition of B 10 or B 11 , wherein 0.25 < r2 < 2.0.

[00134] Bll. The catalyst composition of any of B1-B10, wherein the first catalytic component and the second catalytic component are co-extruded.

[00135] Cl. A process for converting syngas, comprising contacting a feed comprising syngas with a catalyst composition of any of Al to A19 and/or a catalyst composition of any of B 1 to B 11 under conversion conditions to produce a product mixture.

[00136] C2. The process of Cl, wherein the product mixture comprises a C2-C4 olefin and/or a C1-C4 alcohol.

[00137] C3. The process of Cl or C2, wherein the conversion conditions comprise a temperature of from 250°C to 450°C, a pressure of from 5 bar (0.5 MPa) to 50 bar (5.0 MPa), and a gas hourly space velocity of from 1,000 hour ¹ to 100,000 hour ¹ .

[00138] C4. The process of Cl or C2, wherein: the temperature is from 300°C to 400°C, the pressure is from 1.0 MPa to 3.0 MPa, and the gas hourly space velocity is from 1,000 hour ¹ to 10,000 hour ¹ .

[00139] C5. The process of any of Cl to C4, wherein the product mixture comprises C2 to

C4 hydrocarbons, in aggregate, at a concentration from 40 wt% to 80 wt%, based on the total weight of the product mixture excluding hydrogen (H2), CO, and CO2.

[00140] C6. The process of C5, wherein the C2 to C4 hydrocarbons have an olefins/alkanes weight ratio from 0.1 to 6.

[00141] Cl. The process of any of Cl to C6, wherein the product mixture further comprises methane at a concentration no greater than 10 wt%, based on the total weight of the product mixture excluding hydrogen (H2), CO, and CO2.

[00142] C8. The process of any of Cl to C7, wherein the feed has a hydrogen gas to the carbon monoxide gas molar ratio of from 0.5 to 3.

[00143] Dl. A process for making a catalyst composition, comprising:

[00144] (I) contacting, in water, a first water soluble compound with a second water soluble compound or mixture and optionally with a third water soluble compound under alkaline conditions to obtain a precipitate, wherein the first water soluble compound comprises Zn, the second water soluble compound or mixture comprises Zr, or Al, or a combination of Zr and Al, and the third water soluble compound comprises Cr, and the precipitate comprises Zn, one or both of A1 and Zr, and optionally Cr; and (II) obtaining from the precipitate a first catalytic component comprising zinc, a metal M ¹ selected from Al, Zr, and combinations of A1 and Zn at any proportion, optionally Cr, and oxygen, with a molar ratio of M ¹ and Cr to Zn of rl and r2, respectively, indicated by the following formula:

M ¹ :Cr:Zn = rl:r2:l,

where 0.25 < rl< 20, and 0 < r2 < 4.0.

[00145] D2. The process of Dl, wherein M ¹ is Zr.

[00146] D3. The process of Dl or D2, wherein r2=0.

[00147] D4. The process of any of Dl to D3, wherein M ¹ is Al.

[00148] D5. The process of D4, wherein 0.25 < r2 < 4.0.

[00149] D6. The process of D4, wherein 0.25 < r2 < 2.0.

[00150] D6. The process of any of Dl to D5, wherein operation (II) comprises drying and/or calcining the precipitate.

[00151] D7. The process of any of Dl to D6, further comprising: (III) combining the first catalytic component with second catalytic component which is a solid acid.

[00152] D8. The process of D7, wherein the solid acid comprises a molecular sieve having an 8-member ring in a crystal structure thereof.

[00153] D9. The process of D7 or D8, wherein operation (III) comprises disposing the first catalytic component on the surface of the second catalytic component.

[00154] D10. The process of any of D7 to D9, wherein operation (III) comprises forming a physical mixture of the first catalytic component and the second catalytic component.

[00155] Dl l. The process of any of D7 to D10, wherein the molecular sieve is selected from zeolites the following frame work types: MOR, CHA, and mixtures and combinations thereof.

[00156] D12. The process of any of D7 to Dll, wherein the molecular sieve comprises a

MOR framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 6 to 200.

[00157] D13. The process of any of D7 to D12, wherein the molecular sieve comprises a

MOR framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 6 to 60.

[00158] D14. The process of any of D7 to D13, wherein the molecular sieve comprises a CHA framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 10 to 200.

[00159] D15. The process of any of D7 to D14, wherein the molecular sieve comprises a

CHA framework type zeolite having a S1O2 to AI2O3 molar ratio in the range 10 to 60. [00160] El. A catalyst composition for preparing C2 to C4 hydrocarbons, comprising: a solid acid that is a molecular sieve having 8-membered ring crystals; and a metal oxide on a support, wherein: (a) the metal oxide comprises ZnO and the support comprises Z1O2, or

(b) the metal oxide comprises ZnO and C12O3, and the support comprises AI2O3.

[00161] E2. The catalyst composition of El, wherein a molar ratio of Zn to Zr is from 0.25 to 20.

[00162] E3. The catalyst composition of El, wherein: molar ratio of Zn to Cr, is from 4:1 to 1 :4; and a molar ratio of Zn to A1 is from 4: 1 to 1 :4.

[00163] E4. The catalyst composition of any of El to E3, wherein the solid acid comprises a chabazite, a mordenite, a meso-mordenite, or a combination thereof.

[00164] E5. The catalyst composition of E4, wherein the solid acid is a chabazite having a molar ratio of S1O2/AI2O3 from 10 to 1000.

[00165] E6. The catalyst composition of E4, wherein the solid acid is a chabazite having a molar ratio of S1O2/AI2O3 is less than 50.

[00166] E7. The catalyst composition of E4, wherein the solid acid is a chabazite in protonated form.

[00167] E8. The catalyst composition of E4, wherein the solid acid is a mordenite having a molar ratio of S1O2/AI2O3 from 10 to 1000.

[00168] E9. The catalyst composition of E4, wherein the solid acid is a mordenite having a molar ratio of S1O2/AI2O3 is less than 50.

[00169] E10. The catalyst composition of E4, wherein the solid acid is a mordenite in protonated form.

[00170] El l. The catalyst composition of E4, wherein the solid acid is a meso-mordenite having a molar ratio of S1O2/AI2O3 from 10 to 1000.

[00171] E12. The catalyst composition of E4, wherein the solid acid is a meso-mordenite having a molar ratio of S1O2/AI2O3 is less than 50.

[00172] E13. The catalyst composition of E4, wherein the solid acid is a meso-mordenite in protonated form.

[00173] El 4. The catalyst composition of any of El to E13, wherein the solid acid and the metal oxide on support are co-extruded.

[00174] FI. A process for preparing C2-C4 hydrocarbons, comprising: introducing a feedstream comprising hydrogen gas and carbon monoxide gas into a reactor; introducing the catalyst composition of any of paragraphs El -22 to the reactor, under reactor conditions effective to produce a product mixture, the reactor conditions comprising: a reactor temperature of from 200°C to 450°C; a pressure of from 0.1 MPa to 5.0 MPa; and (c) forming the product mixture comprising C2-C4 hydrocarbons.

[00175] F2. The process of FI, wherein the product mixture comprises a combined C2-C4 alkane content of from 30 wt% to 90 wt%; and a combined C2-C4 alkene content of from 0 wt% to 85 wt%, wherein each wt% is based on the total weight of the product mixture excluding hydrogen (H2), CO, and CO2.

[00176] F3. The process of FI, wherein the product mixture further comprises a methane content of no greater than 15 wt%; a combined saturated and unsaturated C5 and higher hydrocarbon content of no greater than 50 wt%; and an oxygenate content of no greater than 20 wt%, wherein each wt% is based on the total weight of the product mixture excluding hydrogen (H2), CO, and CO2.

[00177] F4. The process of any of FI to F3, wherein the reactor temperature is from 300°C to 400°C.

[00178] F5. The process of any of FI to F4, wherein the pressure is from 1.0 MPa to 3.0

MPa.

[00179] F6. The process of any of FI to F5, wherein the reactor conditions further comprise a gas hourly space velocity of from 1,000 h ¹ to 10,000 h ^-1 .

[00180] F7. The process of any of FI to F8, wherein a molar ratio of the hydrogen gas to the carbon monoxide gas is from 0.5:1 to 3:1.

[00181] As described herein, a multicomponent catalyst composition (e.g., a metal oxide- solid acid catalyst) can be used to prepare a mixture that includes C2 to C4 olefins from a synthesis gas feedstream. The metal oxide-solid acid catalyst compositions can demonstrate high activity in converting syngas into organic products, especially C2-C4 olefins and C2-C4 alcohols, which have significantly higher value than syngas.

[00182] The phrases, unless otherwise specified,“consists essentially of’ and“consisting essentially of’ do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of this disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[00183] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[00184] All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of this disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of this disclosure. Accordingly, it is not intended that this disclosure be limited thereby. Likewise, the term“comprising” is considered synonymous with the term“including” for purposes of United States law. Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases“consisting essentially of,”“consisting of,”“selected from the group of consisting of,” or“is” preceding the recitation of the composition, element, or elements and vice versa.

[00185] While this disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of this disclosure.