CATALYST COMPOSITIONS AND METHODS FOR ALCOHOL PRODUCTION FROM SYNTHESIS GAS

PRIORITY DATA

[0001] This international patent application claims the priority benefit of U.S. Provisional Patent Application Nos. 61/013,958; 61/013,965; and 61/013,975, each filed December 14, 2007; and of U.S. Non-Provisional Patent Application Nos. 12/330,172; 12/330,222; 12/330,276, each filed December 8, 2008; all disclosures of which are hereby incorporated by reference herein for all purposes.

FIELD OF THE INVENTION

[0002] The present invention generally relates to catalysts and methods for converting syngas into alcohols, such as ethanol.

BACKGROUND OF THE INVENTION

[0003] Synthesis gas (hereinafter referred to as syngas) is a mixture of hydrogen (H ₂ ) and carbon monoxide (CO). Syngas can be produced, in principle, from virtually any material containing carbon. Carbonaceous materials commonly include fossil resources such as natural gas, petroleum, coal, and lignite, and renewable resources such as lignocellulosic biomass and various carbon-rich waste materials. It is preferable to utilize a renewable resource to produce syngas because of the rising economic, environmental, and social costs associated with fossil resources.

[0004] There exist a variety of conversion technologies to turn these feedstocks into syngas. Conversion approaches can utilize a combination of one or more steps

comprising gasification, pyro lysis, steam reforming, and/or partial oxidation of a carbon-containing feedstock.

[0005] Syngas is a platform intermediate in the chemical and biorefining industries and has a vast number of uses. Syngas can be converted into alkanes, olefins, oxygenates, and alcohols. These chemicals can be blended into, or used directly as, diesel fuel, gasoline, and other liquid fuels. Syngas can also be directly combusted to produce heat and power.

[0006] Since the 1920s it has been known that mixtures of methanol and other alcohols can be obtained by reacting syngas over certain catalysts (Forzatti et al., Cat. Rev. — ScL andEng. 33(1-2), 109-168, 1991). Fischer and Tropsch observed around the same time that hydrocarbon-synthesis catalysts produced linear alcohols as byproducts (Fischer and Tropsch, Brennst.-Chem. 7:97, 1926).

[0007] There is a continuing need for catalyst compositions, and methods for making and using these catalyst compositions, to produce C1-C4 alcohols from syngas. An especially preferred alcohol is ethanol, which can replace gasoline and other liquid fuels.

BRIEF SUMMARY OF THE INVENTION

[0008] The present invention provides several aspects that address the aforementioned needs in the art.

[0009] In one aspect, the invention provides a compound of the formula wherein: M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 2 or 3; x is 2 when M ² is Ni or Pd; x is 3 when M ¹ is Mo and M ² is Co; and R is a C3-C8 alkyl group.

[0010] In some embodiments, M ¹ is Mo, W, or both Mo and W. In some embodiments, M ² is Co, Ni, Pd, two of these, or all of these elements. In some embodiments, R is an n-alkyl group, such as n-butyl, n-pentyl, or n-hexyl.

[0011] In some embodiments, the compound has a formula selected from the group consisting Of [NR ₄ ]S[Mo ₂ CoS ₈ ], [NR ₄ MMo ₂ NiS ₈ ], [NR ₄ ]S[W ₂ CoS ₈ ], [NR ₄ MW ₂ CoSg], and [NR ₄ J ₂ [W ₂ NiS ₈ ]. Some compositions include at least two such compounds. For example, some compositions include both [NR ₄ J ₂ [Mo ₂ NiS ₈ ] and [NR ₄ J ₂ [Mo ₂ CoS ₈ ]. Some compositions include both [NR ₄ ] ₂ [W ₂ NiS ₈ ] and [NR ₄ ] ₂ [W ₂ CoS ₈ ]. Certain compositions include Pd in economically viable amounts. Compositions of the invention can further include a solvent.

[0012] In some embodiments, the compound has the formula A _x [M^M ² S ₈ ], wherein: A is selected from the group consisting of K, Rb, Cs; M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 2 or 3; x is 2 when M ² is Ni or Pd; and x is 3 when M ¹ is Mo and M ² is Co. For example, the compound can be selected from the group consisting of A ₃ [Mo ₂ CoS ₈ ], A ₂ [Mo ₂ NiS ₈ ], A ₃ [W ₂ CoS ₈ ], A ₂ [W ₂ CoS ₈ ], and A ₂ [W ₂ NiS ₈ ].

[0013] In other embodiments, the compound has the formula A _x [M^M ² S ₈ ], wherein: A is selected from the group consisting of Sr and Ba; M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 1 or 1.5; x is 1 when M ² is Ni or Pd; and x is 1.5 when M ¹ is Mo and M ² is Co. For example, the compound can be selected from the group consisting of AL ₅ [MO ₂ COS ₈ ], A[Mo ₂ NiS ₈ ], AL ₅ [W ₂ COS ₈ ], A[W ₂ COS ₈ ], and A[W ₂ NiS ₈ ].

[0014] Certain embodiments employ at least two compounds each in accordance with the foregoing description.

[0015] In another aspect, this invention provides a method for generating a catalyst (derived from [R ₄ N] _x [M^M ² S ₈ ]) capable of converting syngas into one or more reaction products comprising at least one Ci-C ₄ alcohol when in the presence of a catalytic promoter, the method comprising the following steps:

(a) preparing a solution A of a compound of the formula [NH ₄ J _x [M ¹ S ₄ ] in a first polar solvent, wherein M ¹ is Mo or W, and wherein x is 2;

(b) preparing a solution B of a salt or compound of a Group VIII element M ² in a second polar solvent, wherein M ² is Co, Ni, or Pd, wherein x is 2 when M ² is Ni or Pd, and wherein x is 3 when M ¹ is Mo and M ² is Co;

(c) when x is 3, preparing a solution C containing a reducing agent dissolved in a third polar solvent miscible in the first or second polar solvents;

(d) preparing a solution D of a compound of the formula R ₄ NZ in a fourth polar solvent, wherein R is a C ₃ -Cg alkyl group, and wherein Z is a monovalent anion;

(e) combining solutions A, B, C (if any), and D, to form a precipitate comprising a compound of the formula [R ₄ N] _x [M^M ² S ₈ ];

(f) removing the first, second, third (if any), and fourth solvents from the precipitate; and

(g) calcining the precipitate under inert atmosphere to form the catalyst.

[0016] In some embodiments, solutions A and B are mixed to form a solution comprising a compound of the formula prior to mixing with solution C and/or solution D. In some embodiments, solutions B and D are mixed prior to mixing with solution A. Various orders of steps are possible.

[0017] Steps (f) and (g) are preferably performed under inert atmospheres. Steps (f) and (g) can be performed without exposing the precipitate to oxygen between the steps. In some embodiments, step (g) is performed in an alcohol-synthesis reactor. Optionally, the catalytic promoter can be combined with the compound [R ₄ N] _x [M^M ² S ₈ ] prior to step (g).

[0018] In some embodiments, solution D further comprises a base, such as a compound of the formula R ₄ NZ. Z can be selected from the group consisting of acetate, formate, bicarbonate, and hydroxide. A base can deprotonate ammonium cations and drive precipitation reactions.

[0019] The salt of a Group VIII element M ² is selected from the group consisting of acetate salt, chloride salt, bromide salt, and nitrate salt.

[0020] In other embodiments, the invention provides a method for generating a catalyst, derived from E _y [M^M ² S ₈ ], the catalyst being capable of converting syngas into one or more reaction products comprising at least one Ci-C ₄ alcohol when in the

presence of a catalytic promoter, wherein: E is selected from the group consisting of K, Cs, Rb, Sr, and Ba; M ¹ is Mo or W; M ² is a Group VIII element Co, Ni, or Pd; x is 2 when M ² is Ni or Pd; x is 3 when M ¹ is Mo and M ² is Co; y is x when E is K, Cs, or Rb; and y is x/2 when E is Sr or Ba. This method comprises the following steps:

(a) preparing a solution A of a compound of the formula [NH ₄ J ₂ [M ¹ S ₄ ] in a first polar solvent;

(b) preparing a solution B of a salt or compound of M ² in a second polar solvent,

(c) when x is 3, preparing a solution C containing a reducing agent dissolved in a third polar solvent miscible in said first or second polar solvents;

(d) preparing a solution D of a compound of the formula selected from the group consisting of KOH, CsOH, RbOH, Sr(OH) ₂ , and Ba(OH) ₂ in a fourth polar solvent;

(e) combining said solutions A, B, C (if any), and D, to form a precipitate comprising a compound of the formula

(f) removing said first, second, third (if any), and fourth solvents from said precipitate; and

(g) calcining said precipitate under inert atmosphere to form said catalyst.

[0021] Step (d) can be conducted in the presence of a complexing agent suitable to promote solubilization of the compound provided in step (d). The complexing agent can, for example, be a crown ether.

[0022] Steps (f) and (g) are preferably performed under inert atmospheres. In some embodiments, steps (f) and (g) are performed without exposing the precipitate to oxygen between the steps. Step (g) can be performed at a temperature selected from about 350-500 ⁰ C for a time selected from about 1-10 hours. In some embodiments, step (g) is performed in an alcohol-synthesis reactor. Optionally, the catalytic promoter can be combined with the compound prior to step (g).

[0023] Each of the first, second, third, and fourth polar solvents can be separately selected from the group consisting of acetonitrile, dimethylformamide,

tetrahydrofuran, C ₁ -C ₄ alcohols, and mixtures thereof. In some embodiments, the first, second, third (if present), and fourth polar solvents are the same. Removal of solvent can be accomplished, for example, by filtration, heating, or some other means.

[0024] In some embodiments, the molar ratio of sulfur to the combined total of molybdenum (if present), tungsten (if present), and the Group VIII element(s) in the catalyst is at least about 1.5:1. In certain embodiments, this molar ratio is at least about 1.9:1, 2.0:1, or 2.1 :1.

[0025] Variations of the invention further include a method of producing at least one C ₁ -C ₄ alcohol from syngas, the method comprising contacting hydrogen and carbon monoxide with a catalyst, produced according to the methods described herein, and combined with a suitable catalytic promoter. Certain embodiments produce ethanol, such as at least 25%, 50%, or more by weight of the total C1-C4 alcohols produced.

[0026] In some of these variations, the catalyst is exposed to O ₂ for less than six hours prior to contacting the catalyst with hydrogen and carbon monoxide. In certain embodiments, the catalyst is exposed to O ₂ for less than one hour prior to contacting the catalyst with hydrogen and carbon monoxide. Optionally, the catalyst is not substantially exposed to O ₂ prior to contacting the catalyst with hydrogen and carbon monoxide.

[0027] Another aspect relates to compositions produced by methods of the invention. In some embodiments, a composition is produced by the method comprising: (a) obtaining a compound having the formula wherein: (i) M ¹ is Mo or W; (ii) M ² is Co, Ni, or Pd; (iii) x is 2 or 3; (iv) R is a C ₃ -C ₈ alkyl group; (v) x is 2 when M ² is Ni or Pd; and (vi) x is 3 when M ¹ is Mo and M ² is Co; and (b) calcining the compound under a substantially inert atmosphere.

[0028] In some embodiments, the compound obtained or produced in step (a) has a formula selected from the group consisting of [NR4] ₃ [Mo ₂ CoS ₈ ], [NR ₄ J ₂ [Mo ₂ NiS ₈ ], [NR ₄ ]S[W ₂ CoS ₈ ], [NR ₄ MW ₂ CoS ₈ ], and [NR ₄ MW ₂ NiS ₈ ].

[0029] Some compositions produced include more than one compound having the formula For instance, the at least two compounds can be [NR ₄ MW ₂ NiS ₈ ] and [NR ₄ J ₂ [W ₂ CoS ₈ ].

[0030] Preferably, solvent in contact with the compound(s) is substantially removed prior to calcining. In some embodiments, the composition is not exposed to oxygen between solvent removal and calcining. Step (b) can be performed, for example, at a temperature selected from about 350-500 ⁰ C and a time selected from about 1-10 hours. In some embodiments, step (b) is performed in an alcohol- synthesis reactor. Optionally, a catalytic promoter can be combined, prior to step (b), with the compound [NR ₄ ] _X [M^M ² S ₈ ] obtained in step (a).

[0031] In other embodiments, a composition is produced by the method comprising: (a) obtaining a compound having the formula A _x [M^M ² S ₈ ], wherein: A is selected from the group consisting of K, Rb, Cs; M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 2 or 3; x is 2 when M ² is Ni or Pd; x is 3 when M ¹ is Mo and M ² is Co; and (b) calcining the compound under a substantially inert atmosphere.

[0032] In still other embodiments, a composition is produced by the method comprising: (a) obtaining a compound having the formula A _x [M^M ² S ₈ ], wherein: A is selected from the group consisting of Sr and Ba; M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 1 or 1.5; x is 1 when M ² is Ni or Pd; and x is 1.5 when M ¹ is Mo and M ² is Co; and (b) calcining the compound under a substantially inert atmosphere.

[0033] Additionally, new and useful compositions can be produced from at least two compounds of formula A _x [M^M ² S ₈ ], as described above and in more detail herein.

[0034] Preferably, solvent in contact with the compound(s) is substantially removed prior to calcining. In some embodiments, the composition is not exposed to oxygen between solvent removal and calcining. Step (b) can be performed, for example, at a temperature selected from about 350-500 ⁰ C and a time selected from about 1-10 hours. In some embodiments, step (b) is performed in an alcohol-

synthesis reactor. Optionally, a catalytic promoter can be combined, prior to step (b), with the compound obtained in step (a).

[0035] In some variations, these compositions are capable of catalytically converting syngas into one or more reaction products comprising at least one C ₁ -C ₄ alcohol when in the presence of a catalytic promoter. The catalytic promoter can be K2CO3, CS2CO3, or another effective promoter for alcohol synthesis.

[0036] In certain embodiments, a composition includes: (a) at least one Group VIB element selected from molybdenum and tungsten; (b) at least one Group VIII element selected from cobalt, nickel, and palladium; and (c) sulfur; wherein the molar ratio of sulfur to the combined total of the at least one Group VIB element and the at least one Group VIII element is at least about 1.9:1; wherein the molar ratio of the at least one Group VIB element to the at least one Group VIII element is 2:1; wherein the composition is essentially free of crystalline phase disulfide of the at least one Group VIII element; and wherein the composition is capable of catalyzing the conversion of syngas into one or more reaction products comprising at least one C ₁ - C ₄ alcohol, such as ethanol, when in the presence of a suitable catalytic promoter.

[0037] The present invention will now be described by reference to the following detailed description, which characterizes some preferred embodiments but is by no means limiting.

DETAILED DESCRIPTION OF SOME EMBODIMENTS OF THE INVENTION

[0038] Provided herein are catalytic compositions, intermediates for making the compositions, methods for making the compositions, and methods of using the compositions for the catalytic conversion of syngas into C ₁ -C ₄ alcohols such as ethanol.

[0039] "Synthesis gas" and "syngas" are used interchangeably herein, and mean a mixture OfH ₂ and CO. Syngas may be produced, for example, from fossil resources

such as natural gas, petroleum, coal, and lignite, and from renewable resources such as lignocellulosic biomass and various carbon-rich waste materials.

[0040] As used herein and in the appended claims, the singular forms "a", "an" and "the" include plural forms, unless the context clearly dictates otherwise. Unless defined otherwise or clearly indicated by context, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0041] Unless otherwise indicated, all numbers expressing reaction conditions, stoichiometries, concentrations of components, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Numerical parameters set forth in this specification and the attached claims are approximations that may vary depending at least upon the specific analytical technique. Any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in its respective testing measurements.

[0042] As used herein, a catalyst that is "capable of catalytically converting syngas into one or more reaction products comprising at least one C ₁ -C ₄ alcohol when in the presence of a catalytic promoter" refers to a catalyst that produces at least one C ₁ -C ₄ alcohol (e.g., methanol, ethanol, propanol, butanol) when contacted with H ₂ , CO, and a suitable catalytic promoter under reaction conditions suitable for synthesizing Ci-C ₄ alcohols.

[0043] In some variations, catalytic intermediate compounds of the formula are provided, wherein: M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 2 or 3; and R is a C3-C8 alkyl group. In preferred embodiments, x is 2 when M ² is Ni or Pd; and x is 3 when M ¹ is Mo and M ² is Co. These intermediate compound(s) may be present in one or more solvents, or may be isolated by filtering and/or heating. Calcining the catalytic intermediate compound(s), preferably under inert atmosphere, results in formation of the catalyst that can then be loaded into a reactor. Optionally, the calcination may be performed in an alcohol-synthesis reactor, wherein a catalytic

promoter can be mixed with the catalytic intermediate compound(s) prior to calcination.

[0044] Mixed intermediate compounds comprising more than one M ² (e.g., Co and Ni, Co and Pd, Ni and Pd, or all of Co, Ni, and Pd) may be produced, as discussed below. Mixed intermediate compounds containing both Mo and W may also be produced.

[0045] R may be a straight-chain alkyl (n-alkyl) group. R may also be branched (e.g. isopropyl, isobutyl, sec-butyl, etc.) or cyclic (e.g. cyclopropyl, cyclohexyl, cyclopropyl-methyl, etc.), provided that the steric bulk around the nitrogen is not too high to prevent formation of the tetraalkylammonium salt [NR ₄ J ⁺ . In some embodiments, R is selected from the group consisting of n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.

[0046] Non- limiting examples of intermediate compounds of the invention include: [NR ₄ ]S[Mo ₂ CoS ₈ ], [NR ₄ MMo ₂ NiS ₈ ], [NR ₄ ]S[W ₂ CoS ₈ ], [NR ₄ J ₂ [W ₂ CoS ₈ ], and [NR ₄ ] ₂ [W ₂ NiS ₈ ], wherein R is a Cs-C ₈ alkyl group.

[0047] Compositions comprising a single intermediate compound may be produced by methods of the invention. Alternatively, mixed compositions comprising more than one, such as two, three, four or more, of the intermediate compounds may be produced and mixed in any ratio (e.g., when two compositions are mixed, 90:10, 75:25, 50:50, 25:75, or 10:90).

[0048] In some embodiments, when Pd and Ni and/or Co are present in the catalytic composition, the Pd is present at a much lower concentration than either Ni or Co. For example, Pd may be present at a ratio of Pd to (Ni+Co) of less than about 50:50, preferably less than about 10:90, and more preferably less than about 1 :99. The mixed intermediates may either be created by mixing two or more of the intermediate compounds that are synthesized separately, or may also be synthesized by co-producing two or more intermediate compounds in a single reaction vessel. In the case of co-production of two or more intermediate compounds, in some

embodiments, when M ² is Co and Ni for the at least two intermediate compounds, then x is 2 and M ¹ is W; and when M ² is Co and Pd for the at least two intermediate compounds, then M ¹ is W.

[0049] In another aspect, catalytic intermediate compounds of the formula A _x [M^M ² S ₈ ] (x = 2 or 3) are provided, wherein: M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 2 when M ² is Ni or Pd; x is 3 when M ¹ is Mo and M ² is Co; and A is selected from the group consisting of K, Rb, and Cs. In a related aspect, catalytic intermediate compounds of the formula (x = 1 or 1.5) are provided, wherein: M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 1 when M ² is Ni or Pd; x is 1.5 when M ¹ is Mo and M ² is Co; and A is selected from Sr and Ba.

[0050] Mixtures comprising both NR ₄ and the cation A are also possible. For example, in some embodiments related to sulfϊded molybdenum/nickel catalysts, KNR ₄ [Mo ₂ NiSg] is produced. Optionally, KNR ₄ [Mo ₂ NiSg] can be co-produced with K ₂ [Mo ₂ NiSg] and [NR ₄ ] ₂ [Mo ₂ NiSg], all of which are effective intermediates suitable for producing effective catalytic compositions.

[0051] In some variations of the invention, catalytic compositions are provided, wherein the catalytic composition, when in the presence of a catalytic promoter, is capable of catalyzing the conversion of syngas into one or more reaction products comprising at least one Ci-C ₄ alcohol.

[0052] In some embodiments, the catalytic composition is produced by the method comprising: (a) obtaining one or more intermediate compounds as described herein; and (b) calcining the compound(s) under inert atmosphere, as described herein.

[0053] In some embodiments, the catalytic composition comprises: (a) at least one Group VIB element selected from molybdenum and tungsten; (b) at least one Group VIII element selected from cobalt, nickel, and palladium; and (c) sulfur; wherein the molar ratio of sulfur to the combined total of the at least one Group VIB element and the at least one Group VIII element is preferably at least about 1.9:1.

Preferably, the molar ratio of the at least one Group VIB element to the at least one Group VIII element is 2:1. Preferably, the catalytic composition is essentially free of a crystalline disulfide phase of the at least one Group VIII element. In these embodiments, the catalytic composition, when in the presence of a catalytic promoter, is capable of catalyzing the conversion of syngas into reaction products comprising at least one C ₁ -C ₄ alcohol.

[0054] The molar ratio of sulfur to the combined total of the at least one Group VIB element and the at least one Group VIII element may be at least about 1.5:1, preferably at least about 1.9:1, more preferably at least about 2.0:1, and most preferably at least about 2.1 :1.

[0055] The catalytic compositions may comprise one or more metal disulfides, such as molybdenum disulfide or tungsten disulfide. The compositions may comprise one or more metal persulfides, such as one or more of nickel persulfide, cobalt persulfide, and palladium persulfide. As used herein, "persulfide" indicates an anion of the form S ₂ ^{2 ~} .

[0056] Non-limiting examples of catalytic compositions of the invention include: 2MoS ₂ -NiS ₂ , 2WS ₂ -NiS ₂ , 2WS ₂ -CoS ₂ , 4WS ₂ -CoS ₂ -NiS ₂ and 2MoS ₂ -CoS ₂ . It is to be understood that a composition with a given empirical formula, e.g. 2MoS ₂ -NiS ₂ , may vary in its precise elemental composition, and that the ratios of elements given (2 Mo + 6 S + 1 Ni) are only approximate.

[0057] The catalytic compositions may be essentially free of a crystalline disulfide phase of a Group VIII element. X-ray diffraction is one technique that can be used to make such a determination. Namely, when a composition is essentially free of crystalline disulfide phase of a Group VIII element, the intensity of the most- intense reflection of CoS ₂ , NiS ₂ , and PdS ₂ will be less than about half that of the most-intense reflection OfMoS ₂ or WS ₂ , as measured by X-ray diffraction.

[0058] In some embodiments, catalytic compositions include small amounts of a crystalline disulfide phase of a Group VIII element. In these embodiments, the

intensity of the most-intense disulfide reflection Of CoS ₂ , NiS ₂ , and PdS ₂ , as measured by X-ray diffraction, will be less than about 45%, less than about 35%, or less than about 25% that of the most-intense reflection OfMoS ₂ or WS ₂ .

[0059] The catalytic compositions of the invention may have a high surface area, such as at least about 10 m ² /gram (surface area per gram of total material). In some embodiments, the catalytic compositions have a surface area at least about 25 m ² /gram, at least about 50 m ² /gram, at least about 75 m ² /gram, or at least about 100 m ² /gram. Use of increasingly large R groups (in embodiments relating to may result in increasing surface area for the resulting catalytic compositions described herein.

[0060] The catalytic composition may be produced from a single intermediate compound, or may be produced from more than one intermediate compounds. When making mixed catalytic compositions from more than one intermediate compound, the intermediate compounds may be produced and/or mixed in any ratio prior to calcining, to result in mixed catalytic compositions. In some embodiments, when Pd and Ni and/or Co are present in the catalytic composition, the Pd is present at a much lower concentration than either Ni or Co. The mixed catalytic compositions may either be created by mixing two or more of the catalytic compositions that are synthesized separately, or may be synthesized by co-producing the mixed composition from two or more intermediate compounds in a single reaction vessel. The two or more intermediate compounds may be synthesized separately and then mixed, or they may be co-produced in a single reaction vessel.

[0061] When Ci-C ₄ alcohols are desired, the catalytic compositions described herein are preferably combined with a suitable catalytic promoter. In the absence of the catalytic promoter, hydrocarbons can be produced in high selectivities. Suitable promoters include alkali promoters such as potassium, cesium, and rubidium, preferably incorporated as anhydrous carbonates, acetates, or hydroxides. Non- limiting examples of suitable promoters include K ₂ Cθ3, KO ₂ C ₂ H ₃ , Cs ₂ CO ₃ ,

CsO ₂ C ₂ H ₃ , Rb ₂ CO ₃ , RbO ₂ C ₂ H ₃ , and formates or propionates of potassium, rubidium, or cesium.

[0062] Without wishing to be bound by theory, one role of a basic promoter is to shift selectivity away from predominantly methane production to provide for selectivity for alcohol synthesis. Another role of the basic promoter may be to suppress acid-catalyzed alcohol dehydration to yield olefins. The promoter may be an inherent constituent of a catalytic intermediate compound, as recited above. Alternatively, or additionally, a promoter may be added to the catalyst, for example, by grinding together with the catalyst. In this case, it is typically convenient to grind, under a substantially inert atmosphere, a salt of a base promoter such as potassium or cesium. It is preferred to grind acetate or carbonate salts with the catalytic materials. Alternatively, the promoter may be mixed with the intermediate compound prior to isolation and calcination of the intermediate to form the catalyst.

[0063] The catalyst can take the form of a powder, pellets, granules, beads, extrudates, and so on. When a catalyst support is optionally employed, the support may assume any physical form such as pellets, spheres, monolithic channels, etc. The supports may be coprecipitated with active metal species, or the support may be treated with the catalytic metal species and then used as is or formed into the aforementioned shapes, or the support may be formed into the aforementioned shapes and then treated with the catalytic species.

[0064] In embodiments of the invention that employ a catalyst support, the support is preferably (but not necessarily) a carbon-rich material with large mesopore volume, and further is preferably highly attrition-resistant. One carbon support that can be utilized is "Sibunit" activated carbon (Boreskov Inst, of Catalysis, Novosibirsk, Russia) which has high surface area as well as chemical inertness both in acidic and basic media (Simakova et al., Proceedings of SPIE — Volume 5924, 592413, 2005). An example of Sibunit carbon as a catalyst support can be found in U.S. Patent No. 6,617,464, issued to Manzer.

[0065] Methods for making catalytic compositions described herein are provided in some variations. These catalytic compositions, when in the presence of a catalytic promoter, are capable of catalyzing the conversion of syngas into one or more reaction products comprising at least one C ₁ -C ₄ alcohol.

[0066] In some embodiments, a catalytic composition is produced by the method comprising: (a) obtaining one or more intermediate compounds as described herein, and (b) calcining the compound(s) under inert atmosphere, as described herein.

[0067] In some embodiments, the method for making a catalytic composition derived from a precipitate of the formula [R ₄ N] _x [M^M ² Ss] (x = 2 or 3) comprises the following steps:

(a) preparing a solution A of a compound of the formula [NELi] ₂ [M ¹ S ₄ ] in a first polar solvent, wherein M ¹ is Mo or W;

(b) preparing a solution B of a salt of a Group VIII element M 2 in a second polar solvent, wherein M ² is Co, Ni, or Pd, wherein x is 2 when M ² is Ni or Pd, and wherein x is 3 when M ¹ is Mo and M ² is Co;

(c) when x is 3, preparing a solution C containing a reducing agent dissolved in a third polar solvent miscible in the first or second polar solvents;

(d) preparing a solution D of a compound of the formula R ₄ NZ in a fourth polar solvent, wherein R is a C ₃ -Cs alkyl group, and wherein Z is a monovalent anion;

(e) combining solutions A, B, C (if present), and D, to form a precipitate comprising a compound of the formula [R ₄ N] _x [M^M ² Ss];

(f) removing the first, second, third (if present), and fourth solvents from the precipitate; and

(g) calcining the precipitate under inert atmosphere to form the catalyst. Steps (f) and (g) are preferably (but not necessarily) performed without exposing the precipitate to oxygen between the steps.

[0068] The solution C, used when x is 3, can contain a reducing agent such as a soluble salt of the [SCeH ₅ ] ^" anion, a salt of the BH ₄ ^" anion, or hydrazine. Step (c) is

not necessary when x is 2. In some embodiments, in step (e), a non-polar solvent is added to induce or aid precipitation. This non-polar solvent is preferably deoxygenated and free of water, and it is preferably miscible in at least one, more preferably at least two, and most preferably all of the first, second, third (if present) and fourth polar solvents.

[0069] In some embodiments, solutions A and B are mixed to form a solution comprising a compound of the formula prior to mixing with solution C and/or solution D. In some embodiments, solution B and solutions C and/or D are mixed prior to mixing with solution A. These particular embodiments may be useful, for example, when the ammonium salts are not soluble.

[0070] Optionally, a base may be added to solution D. For example, when smaller alkyl chains (e.g. propyl) are used as a precipitant (e.g. for [MoS ₄ ] ^2" ), tetraalkylammonium hydroxide may be used. Using such an approach, ammonium is deprotonated and cannot compete for the anion, so precipitation is driven forward. The base may be added to solution D, or the tetraalkylammonium hydroxide may be used to prepare solution D.

[0071] Monovalent anion Z may be, for example, acetate, formate, hydroxide, or bicarbonate. The salt of a Group VIII element M ² may be, for example, an acetate, chloride, bromide, or nitrate salt. In some embodiments, the salt of a Group VIII element M ² is an acetate, chloride, or bromide salt.

[0072] Examples of suitable polar solvents for the first, second, third, and fourth polar solvents include, for example, acetonitrile, dimethylformamide, tetrahydrofuran, Ci-C ₄ alcohols, water, and mixtures thereof. The first, second, third, and fourth polar solvents may be the same, or they may be different. In some embodiments, the first, second, third, or fourth polar solvent is methanol, acetonitrile, or a mixture of methanol and acetonitrile. Water is a less-preferred solvent.

[0073] A base, such as KOH, may be added to solutions containing (x = 2 or 3) yielding solutions containing together with H ₂ O and NH3. If it is desired to separate the compound(s) from solution by filtering, a non-polar solvent miscible in solvent mixtures A, B, and C (if present) may be added to induce precipitation of the In analogous fashion, other salts of may be made using hydroxides of rubidium, cesium, barium, and so forth. The mixed solvent (solutions A, B, and C, if present) and additional non-polar solvent (such as hexane, cyclohexane, decane, toluene, ethylbenzene, and xylenes) may, after separation from the salt of [M ¹ ₂ M ² ₁ Sg], be separated by, for instance, distillation and reused. These compositions effectively incorporate catalyst promoters during synthesis.

[0074] The first, second, third (if present), and fourth solvents may be removed, for example, by filtering and/or heating. In some embodiments, the filtering is performed under air. In some embodiments, the filtering is performed under inert atmosphere. For example, for compounds comprising Ni, filtering under air or under inert atmosphere may be used. For compounds comprising Mo and Co, and for compounds comprising [W ₂ CoS ₈ ] ^{3 "} , filtering under inert atmosphere is preferred. Generally, the filter cake is not truly dried but remains moist with mother liquor from the initial suspension. Final drying of the catalyst, by either filtering or heating, may be performed under air or under inert atmosphere. In general, the temperature used to remove the solvent and dry the compound can be a temperature near or slightly above the atmospheric-pressure boiling point of the solvent. Between drying the precipitate and calcining, the precipitate may be exposed to air, or may be kept under inert atmosphere. In some embodiments, the precipitate is exposed to air between drying and calcination. In preferred embodiments, the precipitate is kept under inert atmosphere between drying and calcination.

[0075] The catalytic compositions are produced by calcining one or more of the intermediate compounds. The calcination temperature and time may be selected so as to maximize production of persulfide, and minimize thermal reduction and loss of sulfur. For example, preferred calcination of [NR ₄ J ₂ [Mo ₂ NiS ₈ ] will result in a catalyst

having an empirical formula of about 2MoS ₂ -NiS ₂ . If calcination, however, runs for too long or too high of a temperature, more sulfur will be lost, resulting in a catalyst with an empirical formula closer to 2MoS ₂ -NiS. Further, drying the compounds under air, followed by calcination under inert atmosphere, can also be associated with the loss of more sulfur, resulting in compositions with an empirical formula closer to MoS ₂ -NiS, whereas drying and calcination under inert atmosphere will yield 2MoS ₂ -NiS ₂ . In another example, calcination of a mixture of [NR ₄ J ₂ [W ₂ CoSs] and [NILi] ₂ [W ₂ NiSg] can be conducted to yield a composition with an empirical formulation of about 4WS ₂ -CoS ₂ -NiS ₂ ; calcination for too long of a time or too high of a temperature can result in larger amounts of thermal reduction and a composition approximating 4WS ₂ -CoS-NiS. These latter compositions (2MoS ₂ -NiS and 4WS ₂ -CoS-NiS) will be catalytically active for alcohol production, but will typically have reduced catalytic activity. The calcination may be performed at a temperature of, for example, about 350-500 ⁰ C for about, for example, 1-10 hours.

[0076] In some embodiments, the method for making a catalytic composition comprises similar steps as recited herein above, to produce a precipitate comprising compound of the M^M ² Ss anion with an effective cation. These catalytic intermediate compounds can generally have the formula A _x [M^M ² Ss] (x = 2 or 3) when M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 2 when M ² is Ni or Pd; x is 3 when M ¹ is Mo and M ² is Co; and A is selected from the group consisting of K, Rb, and Cs. Or, these catalytic intermediate compounds can have the formula (x = 1 or 1.5) when M ¹ is Mo or W; M ² is Co, Ni, or Pd; x is 1 when M ² is Ni or Pd; x is 1.5 when M ¹ is Mo and M ² is Co; and A is selected from Sr and Ba.

[0077] The catalytic compositions described herein, in certain variations of the invention, may be used to produce Ci-C ₄ alcohols (methanol, ethanol, propanol, and butanol, including all isomers) from syngas by contacting hydrogen, carbon monoxide, and a catalytic promoter with the catalyst. Methods of synthesizing alcohols from syngas using catalysts and catalyst promoters are described in, for example, U.S. Patent App. No. 12/166,203, filed July 1, 2008 and which is hereby incorporated by reference herein in its entirety for all purposes.

[0078] In general, a reactor (such as a fixed-bed reactor with continuous gas flow) may be loaded with a catalytic composition (described herein) and a catalytic promoter (such as CS2CO3 or K2CO3). The catalyst may be loaded into the reactor with minimum exposure to air. In some embodiments, the catalyst is exposed to O ₂ for less than about six hours, less than about an hour, less than about 10 minutes, or less than about 1 minute prior to contacting the catalyst with hydrogen and carbon monoxide. In some embodiments, the catalyst is not exposed to O ₂ prior to contacting the catalyst with hydrogen and carbon monoxide. In some embodiments, the catalyst is produced from the intermediate directly in the reactor. After loading the catalytic composition and the catalytic promoter, the reactor is charged with syngas (pressurized, at e.g. 1500 psi), and the reactor is taken to operating conditions appropriate for the synthesis of alcohols.

[0079] In some embodiments, conditions effective for producing alcohols from syngas include a feed hydrogen/carbon monoxide molar ratio (H ₂ /CO) from about 0.2-4.0, preferably about 0.5-2.0. These ratios are indicative of certain embodiments and are not limiting. It is possible to operate at feed H ₂ /CO ratios less than 0.2 as well as greater than 4, including 5, 10, or even higher. It is well-known that high H ₂ /CO ratios can be obtained with extensive steam reforming and/or water-gas shift in operations prior to the syngas-to-alcohol reactor.

[0080] In some embodiments, conditions effective for producing alcohols from syngas include reactor temperatures from about 200-400 ⁰ C, preferably about 250- 35O ⁰ C; and reactor pressures from about 20-500 atm, preferably about 50-200 atm or higher. Generally, productivity increases with increasing reactor pressure. Temperatures and pressures outside of these ranges can be employed.

[0081] In some embodiments, conditions effective for producing alcohols from syngas include average reactor residence times from about 0.1-10 seconds, preferably about 0.5-2 seconds. "Average reactor residence time" is the mean of the residence- time distribution of the mobile-phase reactor contents under actual operating conditions. Catalyst space times and/or catalyst contact times can also be calculated

by a skilled artisan and these times will typically also be in the range of 0.1-10 seconds, although it will be appreciated that it is certainly possible to operate at shorter or longer times.

[0082] In general, the specific selection of catalyst configuration (geometry), H2/CO ratio, temperature, pressure, residence time (or feed rate), and other reactor- engineering parameters will be selected to provide an economical process. These parameters are not regarded as critical to the present invention. It is within the ordinary skill in the art to experiment with different reactor conditions to optimize selectivity to a particular product or some other parameter.

[0083] Product selectivities can be calculated on a carbon-atom basis. "Carbon- atom selectivity" means the ratio of the moles of a specific product to the total moles of all products, scaled by the number of carbon atoms in the species. This definition accounts for the mole-number change due to reaction. The selectivity S _j to general product species C _x H O ₂ is

S, = — ^LJ -

∑ ^x . ^F .

wherein F ₁ is the molar flow rate of speciesy which contains x _} carbon atoms. The summation is over all carbon-containing species C ₁ H ₁ , O ₂ produced in the reaction.

[0084] In some embodiments, wherein all products are identified and measured, the individual product selectivities sum to unity (plus or minus analytical error). In other embodiments, wherein one or more products are not identified in the exit stream, the selectivities can be calculated based on what products are in fact identified, or instead based on the conversion of reactants. In the latter case, the selectivities may not sum to unity if there is some mass imbalance. This method can, however, be preferable as it tends to determine more accurate selectivities to identified products when it is suspected that at least one reaction product is not measured.

[0085] "Cθ ₂ -free carbon-atom selectivity" or "Cθ ₂ -free selectivity" mean the percent of carbon in a specific product with respect to the total carbon converted from carbon monoxide to some product other than carbon dioxide. It is the same equation above for S _j , except that i ≠ CO ₂ andy ≠ CO ₂ .

[0086] In various embodiments of the present invention, the product stream from the reactor may be characterized by CO ₂ -free selectivities of about 10-40% to methanol and about 20-60% or higher to ethanol. In some preferred embodiments, the ethanol CO ₂ -free selectivity is higher, preferably substantially higher, than the methanol CO ₂ -free selectivity, such as a CO ₂ -free selectivity ratio of ethanol/methanol in the product of about 1.0, 1.5, 2.0, 2.5, 3.0, or higher. The product stream can also contain more methanol than ethanol, on either a mole basis or a carbon-atom basis, in certain embodiments. The CO ₂ -free selectivity ratio of ethanol to all other alcohols is preferably at least 1, more preferably at least 2.

[0087] The method produces one or more reaction products, including at least one C1-C4 alcohol. In some embodiments, at least about 25% of the total C1-C4 alcohols produced is ethanol. In certain embodiments, at least about 50% of the total C ₁ -C ₄ alcohols produced is ethanol.

[0088] The product stream from the reactor may include up to about 25% CO ₂ - free selectivity to C3 ₊ alcohols, and up to about 10% to other non-alcohol oxygenates such as aldehydes, esters, carboxylic acids, and ketones. These other oxygenates can include, for example, acetone, 2-butanone, methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetic acid, propanoic acid, and butyric acid.

[0089] This invention has been described and specific examples of the invention have been portrayed. While the invention has been described in terms of particular variations, those of ordinary skill in the art will recognize that the invention is not limited to the variations described. In addition, where methods and steps described above indicate certain events occurring in certain order, those of ordinary skill in the art will recognize that the ordering of certain steps may be modified and that such modifications are in accordance with the variations of the invention. Additionally,

certain of the steps may be performed concurrently in a parallel process when possible, as well as performed sequentially as described above.

[0090] All publications, patents, and patent applications cited in this specification are incorporated herein by reference in their entirety as if each publication, patent, or patent application were specifically and individually put forth herein.

[0091] In this detailed description, reference has been made to multiple embodiments. Other embodiments that do not provide all of the features and advantages set forth herein may be utilized, without departing from the spirit and scope of the present invention. To the extent there are variations of the invention, which are within the spirit of the disclosure or equivalent to the inventions found in the claims, it is intended that this patent will cover those variations as well.