Templated active material

Abstract

The invention relates to templated active material, including those deriving order from organic and/or inorganic templating agents. The invention also relates to methods for producing templated active material, and to active material produced by such methods, and the use of such templated active material for producing oxygenate.

Claims

1. A templated active material, comprising: (a) a first metal M.sub.1, wherein M.sub.1 includes at least one metal selected from Groups 7-12 of the Periodic Table; (b) 0.5 wt. % of a second metal M.sub.2, wherein (i) M.sub.2 is not the same as M.sub.1 and (ii) M.sub.2 includes at least one metal selected from Groups 7-12 of the Periodic Table; (c) 1.0 wt. % of oxide of M.sub.1 and (d) 1.0 wt. % of oxide of M.sub.2, the templated active material having (i) an M.sub.2 to M.sub.1 molar ratio in the range of from 0.1 to 10, (ii) a plurality of pores having an average pore size in the range of from 2 nm to 50 nm, and (iii) an average surface area 50 m.sup.2/g wherein the templated active material's template is produced from a carbonaceous structure-directing agent, the carbonaceous structure-directing agent comprising one or more of siloxane, urea, and surfactant.

2. The templated active material of claim 1, wherein M.sub.1 includes one or more of Cu, Fe, Co, Mn, Zn, Rh, and Ru.

3. The templated active material of claim 1, wherein M.sub.2 includes one or more of Cu, Fe, Co, Mn, Zn, Rh, and Ru.

4. The templated active material of claim 1, wherein M.sub.1 is Fe, and the templated active material comprises 1.0 wt. % to 50.0 wt. % Fe.

5. The templated active material of claim 1, wherein M.sub.2 is Cu, and the templated active material comprises 1.0 wt. % to 50.0 wt. % Cu.

6. The templated active material of claim 1, wherein the M.sub.2 to M.sub.1 molar ratio is in the range of from 0.25 to 4, and the templated active material contains 0.05 wt. % of any oxide of M.sub.1 and/or any oxide of M.sub.2.

7. The templated active material of claim 1, where the average pore size is in the range of from 4 nm to 25 nm.

8. The templated active material of claim 1, wherein the average surface area is in the range of from 50 m.sup.2/g to 350 m.sup.2/g.

9. The templated active material of claim 1, wherein the templated active material's template includes one or more of MCM-41, MCM-48, SBA-15, KIT-6-100, and KIT-6-40.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Definitions

(2) For the purpose of this description and appended claims, the following terms are defined:

(3) The term C.sub.n hydrocarbon means hydrocarbon having n carbon atom(s) per molecule, wherein n is a positive integer. The term C.sub.n+ hydrocarbon means hydrocarbon having at least n carbon atom(s) per molecule, wherein n is a positive integer. The term C.sub.n hydrocarbon means hydrocarbon having no more than n number of carbon atom(s) per molecule, wherein n is a positive integer. The term hydrocarbon means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon, (ii) unsaturated hydrocarbon, and (iii) mixtures of hydrocarbons, including mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n.

(4) The term C.sub.n alcohol means alcohol having n carbon atom(s) per molecule, wherein n is a positive integer. The term C.sub.n+ alcohol means alcohol having at least n carbon atom(s) per molecule, wherein n is a positive integer. The term C.sub.n alcohol means alcohol having no more than n number of carbon atom(s) per molecule, wherein n is a positive integer. The term oxygenate means a class of compounds which include at least one oxygen atom, e.g., alcohol and ether. The term alcohol means a class of compounds which include at least one aliphatic carbon bound to a hydroxyl group, but excluding aldehyde, ketone, and carboxylic acid. The term alcohol encompasses (i) saturated and unsaturated alcohol, (ii) alcohol having one hydroxyl group per alcohol molecule (mono-alcohol) and alcohol having a plurality of hydroxyl groups per alcohol molecule (di-alcohol, tri-alcohol, etc.), (iii) primary, secondary, and tertiary alcohol, (iv) alcohol having a terminal hydroxyl group (1-alcohol) and alcohol having a hydroxyl group in a non-terminal position (2-alcohol, 3-alcohol, etc.), and (iv) mixtures of two or more alcohol compounds, including mixtures of alcohol compounds having different values of n.

(5) The term long chain alcohol means a class of saturated, primary, mono-alcohol compounds having (i) the form of a single unbranched chain which includes four or more carbon atoms, the chain beginning with a first terminal carbon atom and ending with a second terminal carbon atom, (ii) each of the chain's non-terminal carbon atoms tetravalently bound to two nearest-neighbor hydrogen atoms and to two nearest-neighbor carbon atoms of the chain, and (iii) a sole hydroxyl group, the sole hydroxyl group and two hydrogen atoms each being directly bound to the first terminal carbon atom, the second terminal carbon atom being directly bound to three hydrogen atoms (namely: normal, C.sub.4+, saturated, primary, mono-, 1-alcohol). Typically, the number of carbon atoms in the single unbranched chain is in the range of from 5 to 21, more typically in the range of from 5 to 15, e.g., in the range of from 6 to 12.

(6) The term alkane means substantially-saturated compounds containing hydrogen and carbon only, e.g., those containing 1% (molar basis) of unsaturated carbon atoms. As an example, the term alkane encompasses C.sub.2 to C.sub.20 linear, iso, and cyclo-alkanes.

(7) The term unsaturate or unsaturated hydrocarbon mean a C.sub.2+ hydrocarbon containing at least one carbon atom directly bound to another carbon atom by a double or triple bond. The term olefin means an unsaturated hydrocarbon containing at least one carbon atom directly bound to another carbon atom by a double bond. In other words, an olefin is a compound which contains at least one pair of carbon atoms, where the first and second carbon atoms of the pair are directly linked by a double bond.

(8) The term Periodic Table means the Periodic Chart of the Elements, as it appears on the inside cover of The Merck Index, Twelfth Edition, Merck & Co., Inc., 1996.

(9) The term reaction zone or reactor zone means a location within a reactor, e.g., a specific volume within a reactor and/or a specific volume between two reactors for carrying out a reaction which produces alcohol. The term fixed bed catalytic reactor means a catalytic reactor having at least one bed of catalyst, wherein the catalyst is substantially retained within the bed and remains in a substantially fixed location within the bed.

(10) The term selectivity refers to the production of a specified compound in a catalytic reaction. As an example, the phrase the reaction has a 100% selectivity for 1-alcohol means that the reaction produces 100% 1-alcohol. When used in connection with a specified reactant, the term conversion means the amount of the reactant consumed in the reaction. For example, when the specified reactant is CO, 100% conversion means 100% of the CO is consumed in the reaction.

(11) A templated active material is one deriving structure from at least one structure-directing agent, typically called a template. Templated active materials which contain at least some template used during active material synthesis, and or fragments thereof (atomic and/or molecular) are within the scope of the invention, although typically the templated active material contains 1 wt. % of template or fragments thereof based on the weight of the active material, e.g., 0.1 wt. %, such as 0.01 wt. %.

(12) Certain aspects the invention relate templated active materials having structure derived from at least one inorganic template, e.g., from an ordered mesoporous siliceous material, or from at last one organic templating agent, e.g., from surfactant. These aspects will now be described in more detail. The invention is not limited to these aspects, and this description is not meant to foreclose other aspects within the broader scope of the invention.

(13) Templated Active Material

(14) The templated active material is multi-metallic in that it comprises first and second metals (M.sub.1 and M.sub.2). M.sub.1 and M.sub.2 are each one or more metal selected from Groups 7-12 of the Periodic Table. Although M.sub.1 and M.sub.2 can each be a mixture of metals, they each typically comprise substantially one metal only. M.sub.1 is not the same as M.sub.2; in other words, M.sub.1 comprises a different metal or different mixture of metals than does M.sub.2. Typically, M.sub.1 and M.sub.2 are each one or more of M.sub.1 includes one or more of Cu, Fe, Co, Mn, Zn, Rh, and Ru. More typically, M.sub.1 comprises, consists essentially of, or consists of iron, and M.sub.2 comprises, consists essentially of, or consists of copper. While not wishing to be bound by any theory or model, it is believed that the copper provides the templated active material with oxygenate synthesis functionality and the iron provides it with Fischer-Tropsch synthesis (carbon atom chain growth) functionality.

(15) The templated active material is mesoporous in that it has a plurality of pores, the pores having an average pore size in the range of from 2 nm to 50 nm. When the templated active material is in the form of a particulate, typically each particle has a plurality of pores having an average pore size in the specified range. While not wishing to be bound by any theory or model, it is believed that an average pore size in the specified range favors the formation of relatively long chain hydrocarbonaceous oxygenate over hydrocarbonaceous oxygenate having three or fewer carbon atoms. The templated active material has an average surface area 50 m.sup.2 per gram of templated active material. Conventional methods can be utilized for determining (i) the type, amount, electronic structure, and physical structure of templated active material components, e.g., those of M.sub.1 and/or M.sub.2, (ii) average pore size, (iii) average surface area, (iv) the amount of order, if any, exhibited by the plurality of pores and the boundaries thereof, and (v) templated active material morphology (including the size and shape of particles when the templated active material is at least partly in the form of particulates). For example, the amounts of M.sub.1 and/or M.sub.2 can be determined using energy-dispersive mapping methods disclosed in Y. Lu, et al., Applied Catalysis A: General 429-430 (2012). Templated active material morphology can be determined using SEM and TEM methods disclosed in this article. X-ray diffraction methods disclosed in this article can be used for deterring the physical structure (and phases) of metals, including M.sub.1 and/or M.sub.2, present in the templated active material, and can also for determining templated active material particle size. Average surface area, average pore size, and pore size distribution can be determined using N.sub.2 adsorption/desorption methods disclosed in Cao, at al., J. Mater. Sci. (2009) 44:6663-6669. The amount of mesoporous order, if any, exhibited by the pores can be determined using x-ray diffraction methods disclosed in J. S. Beck, et al., J. Am. Chem. Soc., Vol. 114, No. 127, 10834-10843 (1992). Should the templated active material have insufficient mesoporous order to exhibit diffraction peaks at a scattering angle 24 when utilizing the x-ray scattering methods of the J. Am. Chem. Soc. article, average pore size and the amount of ordered mesoporosity (if any) can be determined using the direct HREM imaging methods disclosed in Sakamoto, et al., Nature, 408, 449-452 (2000). The electronic structure of templated active material components such as copper and iron can be determined using photoemission methods including XPS and Auger Electron Spectroscopy methods disclosed in Y. Lu et al., ChemCatChem 6, 473-476 (2014), which is incorporated by reference herein in its entirety.

(16) Typically, the templated active material comprises M.sub.1 in an amount in the range of 0.75 wt. % to 50.0 wt. %, based on the weight of the templated active material, more typically in the range of 1.0 wt. % to 10 wt. %. Typically, the amount of M.sub.2 is in the range of from 0.75 wt. % to 50.0, based on the weight of the templated active material, more typically in the range of from more typically in the range of 1.0 wt. % to 10 wt. %. In certain aspects, the templated active material has an M.sub.1 to M.sub.2 molar ratio in the range of from 0.25 to 4, e.g., an iron to copper molar ratio in the range of from 0.25 to 4.

(17) All or a portion of M.sub.1 can be located in the templated active material, e.g., comprising a templated active material framework which separates nearest-neighbor pores (framework M.sub.1). In certain aspects, at least a portion of M.sub.1 is located on the surface of the templated active material (surface M.sub.1), e.g., M.sub.1 located at or proximate to templated active material's pore openings and/or inside the pores. M.sub.1 (surface M.sub.1 and/or framework M.sub.1) can be, e.g., in one or more metallic phases of M.sub.1 (M.sub.1 atoms bound to neighboring M.sub.1 atoms) and/or in one or more carbide phases such as FeC.sub.2. All or a portion of the M.sub.2 can be located in the templated active material, e.g., comprising a templated active material framework which separates nearest-neighbor pores (framework M.sub.2). In certain aspects, at least a portion of M.sub.2 is located on the surface of the templated active material (surface M.sub.2), e.g., M.sub.2 located at or proximate to templated active material pore openings and/or inside the pores. M.sub.2 (surface M.sub.2 and/or framework M.sub.2) can be, e.g., in one or more metallic phases (e.g., copper atoms bound to neighboring copper atoms) and/or in one or more carbide phases, such as CuC.sub.2. Typically, the metallic and carbide phases of M.sub.1 and/or M.sub.2 are substantially crystalline (e.g., substantially polycrystalline), but this is not required. Typically, 50.0 wt. % of M.sub.1 is framework M.sub.1, e.g., 75.0 wt. %, based on the weight of the templated active material, such as 90.0 wt. %, or in the range of from 50.0 wt. % to 100.0 wt. %, or 75.0 wt. % to 99.0 wt. %. Typically, 50.0 wt. % of M.sub.2 is surface M.sub.2, e.g., 75.0 wt. %, based on the weight of the templated active material, such as 90.0 wt. %, or in the range of from 50.0 wt. % to 100.0 wt. %, or 75.0 wt. % to 99.0 wt. %.

(18) When M.sub.1 is iron and M.sub.2 is copper, or vice versa, the templated active material can further comprise additional materials, e.g. additional metal (M.sub.3). When present, the amount of M.sub.3 is 10.0 wt. %, e.g., in the range of about 0.1 wt. % to about 10.0 wt. %, or about 0.5 wt. % to about 5 wt. %. M.sub.3 can be a mixture of metals, and can include, for example, one or more of Mn, Zn, Rh, and Co. M.sub.3 can be located on the templated active material surface (on internal and/or external surfaces as surface metal). Instead or in addition, M.sub.3 can be located in the templated active material's framework (framework metal). Besides or in addition to M.sub.3, the templated active material can further comprise other material, such as carbon (including surface carbon and/or framework carbon), e.g., carbon introduced during synthesis of a templated active material precursor. Carbon can also accumulate on the precursor and/or templated active material during precursor processing, e.g., when the templated active material is produced from the precursor by exposing the precursor to reducing conditions in the presence of a reducing agent such as syngas. Carbon can also accumulate on the templated active material when it is present during the conversion of a carbon monoxide+molecular hydrogen mixture to oxygenate. When the templated active material includes carbon, the templated active material typically comprises 95 wt. % carbon, based on the weight of the templated active material, e.g., 90 wt. %, such as in the range of from 1 wt. % to 90 wt. %, or 10 wt. % to 85 wt. %. When present, the carbon is typically in the form of one or more of (i) carbonaceous deposits, such as coke and/or soot deposits, (ii) carbonaceous layers, e.g., graphitic carbon layers, and (iii) metal carbide, e.g., FeC.sub.2, CuC.sub.2, etc. When present, coke/soot deposits and carbonaceous layers are typically located on and/or in the templated active material, e.g., in templated active material pores, e.g., as coke particles. When present, metal carbides can be located on and/or in the templated active material, e.g., as carbide particulates on the templated active material surface and/or in the templated active material pores. Metal carbide can also be a component of the templated active material framework, e.g., when the templated active material framework comprises iron.

(19) The templated active material comprises 1.0 wt. % of oxide of M.sub.1 and 1.0 wt. % of oxide of M.sub.2. Typically, the templated active material comprises 0.5 wt. % of oxide of M.sub.1 and/or 0.5 wt. % of oxide of M.sub.2, e.g., 0.1 wt. % of oxide of M.sub.1 and/or 0.1 wt. % of oxide of M.sub.2, such as in the range of 0.05 wt. % of oxide of M.sub.1 to 1.0 wt. % of oxide of M.sub.1 and/or in the range of 0.05 wt. % of oxide of M.sub.2 to 1.0 wt. % oxide of M.sub.2. In certain aspects, the templated active material is substantially free of any oxide of M.sub.2 (e.g., CuO, Cu.sub.2O, etc.) and/or substantially free of any oxide of M.sub.1 (e.g., Fe.sub.3O.sub.4, Fe.sub.2O.sub.3, etc.). The term substantially free in this context means 0.05 wt. % based on the weight of the templated active material. When the templated active material is produced from one or more precursors which contain oxides of M.sub.1 and/or oxides of M.sub.2, the method for producing the templated active material from the precursor typically includes a step for reducing these oxides, e.g., by exposing the precursor to a reducing gas such as syngas under conditions effective for reducing the templated active material. Typically, the templated active material comprises 15.0 wt. % of oxygen atoms, based on the weight of the templated active material, whether as unbound oxygen ions, oxygen atoms bound to at least one other oxygen atoms, oxygen atoms bound to at least one hydrogen atoms, and/or oxygen atoms bound to at least one of M.sub.1 (e.g., oxide of iron) and M.sub.2 (oxide of copper). More typically, the templated active material comprises 10.0 wt. % of oxygen atoms, e.g., 1.0 wt. %, such as in the range of 0.1 wt. % to 10.0 wt. %, or 0.5 wt. % to 5.0 wt. %.

(20) The templated active material comprises a plurality of pores having an average pore size in the range of from 2 nm to 50 nm; and an average surface area 50 m.sup.2/g. Typically, the average pore size is in the range of from 4 nm to 25 nm, and the average surface area is in the range of from 50 m.sup.2/g to 350 m.sup.2/g, such as from 60 m.sup.2/g to 250 m.sup.2/g. Although at least some pores in the specified size range can exhibit a substantially regular order (an ordered mesoporous templated active material), this is not required, and in certain aspects the templated active material includes at least some disordered mesoporous templated active material, namely templated active material having few or no pores of the specified average size that are arranged in regular order. Disordered templated active materials can include non-crystalline or poorly-crystalline framework material, but typically has a substantially crystalline (e.g., substantially polycrystalline) framework. Examples of ordered mesoporous materials appear in F. Jiao, et al., J. Mater. Chem. A, 2, 3065-3071 (2014), and examples of disordered mesoporous materials appear in the Microporous and Mesoporous Materials article. For the purpose of this description and appended claims, the terms ordered and disordered have the same meanings as used in those articles.

(21) The templated active material can be a component of a templated active material system, e.g., one component of a templated active material composite. Besides templated active material, such a system or composite can further comprise one or more inorganic oxides, e.g., one or more of silica, alumina, magnesia, zirconia, oxide of zinc, etc. Such oxides can be present in the system as binder and/or as a support material, for example.

(22) Templated Active Material Synthesis

(23) The templated active material is typically synthesized using at least one structure-directing agent, typically called a template. For example, a template can be used to produce a calcined multi-metallic templated precursor, which is then reduced to produce the templated active material. Certain synthesis methods utilizing one or more templates will now be described in more detail. The invention is not limited to these aspects, and this description is not meant to foreclose other synthesis methods within the broader scope of the invention.

(24) Suitable templates include, e.g., (i) ordered mesoporous inorganic materials such as one or more of MCM-41, MCM-48, SBA-15, KIT-6-100, and KIT-6-40 (hard templating) and/or (ii) carbonaceous material, e.g., hydrocarbonaceous material, such as one or more of siloxane, urea, and surfactant (soft templating).

(25) Producing a Calcined Multi-Metallic Templated Precursor from a Hard Template

(26) In certain aspects, the templated active material is produced from a hard template comprising oxide of silicon, e.g., MCM-41. Conventional methods can be utilized for producing the template, such as the methods disclosed in U.S. Pat. No. 6,096,288 and in J. S. Beck, et al., J. Am. Chem. Soc., Vol. 114, No. 127, 10834-10843 (1992), which are incorporated by reference herein in their entireties. A metal-substituted template is produced by substituting first metal M.sub.1 and/or second metal M.sub.2 for at least a portion of the silicon atoms in the template's framework. Conventional methods can be used for carrying out the substitution, such as those which include heating a synthesis mixture comprising (i) hexane, (ii) nitrate of M.sub.1 and/or nitrate of M.sub.2, and (iii) mesoporous silica template to a temperature of 70 C. for 20 hours. Suitable methods are disclosed in the J. Mater. Chem. A. article, which is incorporated by reference herein in its entirety. The metal-substituted template is recovered, e.g., by vacuum filtration. When the synthesis mixture comprises M.sub.1 and M.sub.2, the relative amount of nitrate of M.sub.1 and nitrate of M.sub.2 is selected is selected to achieve a molar ratio of M.sub.1 to M.sub.2 in the in the range of from 0.1 to 10, e.g., about 0.25 to 4.

(27) The recovered metal-substituted template is calcined to produce a templated precursor. In aspects where only one of M.sub.1 or M.sub.2 is substituted for the template's framework silicon, the templated precursor is called a monometallic templated precursor. In aspects where M.sub.1 and M.sub.2 are substituted for the template's framework silicon, the templated precursor is called a multi-metallic templated precursor. The templated precursor is calcined, e.g., by exposing the metal-substituted template to an oxidant at a temperature 350 C. Conventional recovery and calcining conditions can be used, such as those disclosed in the J. Mater. Chem. A. article, but the invention is not limited thereto. Following calcination, at least a portion of any silica in the templated precursor is removed, e.g., 90.0 wt. % of any silica based on the weight of the templated precursor. Silica removal can be carried out by conventional methods, such as by exposing the metal-substituted template to a 2M solution of NaOH at a temperature of approximately 25 C., but the invention is not limited thereto. Suitable silica removal methods are disclosed in the J. Mater. Chem. A. article, for example.

(28) In aspects where the templated precursor is a monometallic templated precursor comprising the first metal (M.sub.1 or M.sub.2 as the case may be), a multi-metallic templated precursor is produced by depositing a second metal on and/or in the monometallic templated precursor. This can be carried out, e.g., by depositing the second metal (M.sub.1 or M.sub.2 as the case may be) on the monometallic templated precursor's external surface and/or impregnating in the pores of the monometallic templated precursor. In certain aspects, the first metal is M.sub.1, e.g., iron, and the second metal is M.sub.2, e.g., copper. Typically, the amount of second metal deposited on and/or in the monometallic templated precursor is selected to achieve a molar ratio of first to second metal in the in the range of from 0.1 to 10, e.g., about 0.25 to 4. Conventional methods can be used for impregnating the second metal, e.g., by exposing the monometallic templated precursor to an impregnation solution containing nitrate of the second metal, but the invention is not limited thereto. Optionally, the impregnation solution further comprises nitrate of M.sub.3 in an amount to produce a multi-metallic templated precursor of the desired M.sub.3 content. Examples of suitable impregnation methods are disclosed, e.g., in J.-L. Cao, et al., J. Mater. Sci., 44, 6663-6669 (2009), which is incorporated by reference herein in its entirety. The multi-metallic templated precursor is calcined, e.g., by exposure to an oxidant at a temperature 350 C. Conventional calcining conditions can be used, such as those disclosed in the J. Mater. Chem. A. and J. Mater. Sci. articles. In alternative aspects, co-impregnation and/or co-deposition of the first and second metal is carried out, the relative amount of first and second metal deposited on and/or impregnated in the template is selected to achieve a molar ratio of first to second metal in the multi-metallic templated precursor in the range of from 0.1 to 10, e.g., about 0.25 to 4. Co-impregnation can simplify production of the templated active material because the second calcining step is not needed.

(29) Producing a Calcined Multi-Metallic Templated Precursor from a Soft Template

(30) In certain aspects, the templated active material is produced from a soft template by reacting a synthesis mixture comprising at least one carbonaceous structure-directing agent and nitrate of a first metal (e.g., M.sub.1 and/or M.sub.2 as the case may be) to produce a mesoporous oxide template. A templated precursor is then produced by calcining the mesoporous oxide template. A multi-metallic templated precursor is produced by (i) including a nitrate of a second metal (M.sub.1 or M.sub.2 as the case may be) in the synthesis mixture and/or by depositing the second metal on and/or in the monometallic templated precursor, e.g., on the monometallic templated precursor's external surface and/or in the pores of the monometallic templated precursor. In certain aspects, the first metal is M.sub.1, e.g., iron and the second metal is M.sub.2, e.g., copper. The multi-metallic templated precursor is calcined and reduced to produce the templated active material.

(31) The structure-directing agent is typically one or more of siloxane, polymeric glycol, urea, and surfactant, more typically surfactant. The surfactant can be an individual surfactant compound, or a mixture of individual surfactant compounds, but is typically an individual surfactant compound. The surfactant can include one or more of cationic surfactant, non-ionic surfactant, zwitterionic surfactant, and anionic surfactant, but is typically cationic. The surfactant can comprise unbranched surfactant, e.g., cetyltrimethylammonium bromide. Alternatively or in addition, the surfactant can comprise branched surfactant, such as quaternary ammonium surfactant including those having at least one alkyl spacer; oligomeric quaternary ammonium surfactant including those having (i) at least one polar spacer such as at least one hydroxyl group and/or (ii) at least one aromatic (including alkyl aromatic) spacer group; dimeric surfactant including gemini surfactant and/or dimeric surfactant which includes siloxane; trimeric surfactant including (i) polyoxyethylene ether trimeric quaternary ammonium surfactant, (ii) polyoxyethylene trimeric surfactant, (iii) ring-type trimeric surfactant, (iv) trimeric surfactant derived from amine, and (v) n-alkylphenol polyoxyethylene trimeric surfactant; tetrameric surfactant; tetrameric surfactant, including those having at least one ring spacer; star-shaped trimeric tetrameric, and hexameric quaternary ammonium surfactant, including those having at least one amide group; and tyloxopol. Conventional surfactant can be used, but the invention is not limited thereto. Certain suitable gemini surfactants are disclosed in Sakamoto, et al., Nature, 408, 449-452 (2000), which is incorporated by reference herein in its entirety. Certain suitable trimeric surfactants are disclosed in T. Yoshimura, et al., Langmuir 28, 9322-9331 (2012), which is incorporated by reference herein in its entirety.

(32) In certain aspects, a mesoporous oxide template is produced by combining a structure-directing agent, e.g., surfactant, and nitrate of M.sub.1, e.g., Fe(NO.sub.3).sub.3, water, and optionally urea to produce a synthesis mixture. The synthesis mixture is then aged to produce mesoporous oxide template, e.g., by exposing the mixture to a temperature in the range of from about 50 C. to 150 C., at a pressure of about 1 bar (absolute) for a time in the range of about 1 hour to about 50 hours. The mesoporous oxide template can be recovered from the aged mixture, e.g., by centrifuging and washing. Suitable soft templating methods for producing the mesoporous oxide template are disclosed in Q. Liu, et al., Microporous and Mesoporous Materials, 100, 233-240 (2007), which is incorporated by reference herein in its entirety.

(33) A mono-metallic templated precursor is then produced by calcining the mesoporous oxide template, e.g., by exposing the mesoporous oxide template to an oxidant at a temperature 350 C. Conventional calcining can be used, such as the calcining disclosed in the Microporous and Mesoporous Materials article, but the invention is not limited thereto.

(34) Following calcination, a multi-metallic templated precursor is produced by depositing a second metal on and/or in the monometallic templated precursor, e.g., on the monometallic templated precursor's external surface and/or in the pores of the monometallic templated precursor. In certain aspects, the first metal is M.sub.1, e.g., iron, and the second metal is M.sub.2, e.g., copper. Typically, the amount of second metal deposited on and/or in the monometallic templated precursor is selected to achieve a molar ratio of M.sub.1 to M.sub.2 in the in the range of from 0.1 to 10, e.g., about 0.25 to 4. Conventional methods can be used for impregnating the second metal, e.g., by exposing the monometallic templated precursor to a solution containing nitrate of the second metal, but the invention is not limited thereto. Suitable impregnation methods are disclosed, e.g., in J.-L. Cao, et al., J. Mater. Sci., 44, 6663-6669 (2009), which is incorporated by reference herein in its entirety. The multi-metallic templated precursor is calcined, e.g., by exposure to an oxidant at a temperature 350 C. Conventional calcining conditions can be used, such as those disclosed in the J. Mater. Chem. A. article, the J. Mater. Sci. article, and in the Microporous and Mesoporous Materials article. In aspects where the synthesis mixture further comprises nitrate of the second metal (e.g., copper nitrate), the relative amount of copper nitrate and iron nitrate is selected to achieve a molar ratio of first to second metal in the multi-metallic templated precursor in the range of from 0.1 to 10, e.g., about 0.25 to 4. Utilizing a synthesis mixture comprising nitrate of M.sub.1 and nitrate of M.sub.2 can simplify templated active material production because the steps for impregnating the second metal and the second calcining are not needed. Optionally, the synthesis mixture further comprises nitrate of M.sub.3 in an amount to produce a multi-metallic templated precursor of the desired M.sub.3 content.

(35) Producing the Templated Active Material

(36) The templated active material is produced by reducing the calcined multi-metallic templated precursor. For example, the reduction can be carried out by exposing the calcined multi-metallic templated precursor to a reducing agent (e.g., a reducing gas such as molecular hydrogen and/or syngas) in a reactor vessel such as a tube reactor. Surprisingly, it has been found that repeated thermal treatments during processing, e.g., the calcination and reduction, do not result in templated precursor decomposition even though the templated precursor is multi-metallic. Reducing conditions can be conventional conditions for producing macroporous oxygenate synthesis catalysts from metal-substituted macroporous metal oxide, but the invention is not limited thereto. In certain aspects, the reduction is carried out under conditions which include exposing the calcined multi-metallic templated precursor to a 1:1 molar mixture of carbon monoxide and molecular hydrogen at a temperature in the range of from 200 C. to 350 C., at a pressure in the range of from 0.5 bar (absolute) to 5 bar (absolute) at a space velocity (GHSV) in the range of from 10 hr.sup.1 to 10,000 hr.sup.1, for a time in the range of about 1 hour to about 100 hours. Typically, the templated active material is maintained in a reducing environment or an inert environment until the start of the oxygenate synthesis reaction. When the maximum temperature achieved by the precursor during calcination is T.sub.1, the reduction is typically carried out at a temperature T.sub.2, where T.sub.1 is T.sub.2 and T.sub.1-T.sub.2 is 10 C., e.g., 25 C., such as 50 C., or 75 C.

(37) The templated active material is useful for producing oxygenate from carbon monoxide and molecular hydrogen. Certain aspects of the invention relating to the use of the templated active material for producing oxygenate comprising long chain alcohol will now be described in more detail. The invention is not limited to these aspects, and this description is not meant to foreclose other aspects within the broader scope of the invention.

(38) Process for Producing Long Chain Alcohol

(39) Certain aspects of the invention relate to a process for catalytically producing long chain alcohol by exposing a carbon monoxide+molecular hydrogen feed mixture to a catalytically effective amount of the specified templated active material under catalytic long chain alcohol synthesis process conditions. Suitable feed mixtures and process conditions will now be described in more detail. The invention is not limited to these, and this description is not meant to foreclose other process conditions within the broader scope of the invention.

(40) The feed mixture typically comprises molecular hydrogen and 1 wt. % carbon monoxide, based on the weight of the feed mixture, such as 5 wt. %, and optionally further comprises diluent such as carbon dioxide. For example, the feed mixture can comprise 5 wt. % to 95 wt. % of carbon monoxide, and can have a molecular hydrogen molar ratio in the range of from 0.25 to 20, e.g., 0.25 to 20, such as 0.5 to 20. Such mixtures are typically referred to as synthesis gas (or syngas). In certain aspects, the feed mixture includes syngas comprising molecular hydrogen, 10 wt. % carbon monoxide, and diluent. The diluent typically comprises carbon dioxide. The syngas typically has an H.sub.2:(CO+CO.sub.2) molar ratio in the range of from 0.25 to 20, or 0.5 to 20, e.g., an H.sub.2:CO ratio in the range of from 0.25 to 20, or 0.5 to 20. Certain suitable syngas mixtures have an H.sub.2:CO molar ratio in the range of from 0.25 to 4.

(41) The syngas can be produced from a carbon-containing source material, such as hydrocarbon, e.g., hydrocarbon in the form of one or more of natural gas, petroleum, coal, biomass, including mixtures thereof, derivatives thereof, and mixtures of such derivatives. The type of carbon-containing source material used is not critical. The source material typically comprises 10 vol. %, such as 50 vol. %, based on the volume of the source material, of at least one hydrocarbon, especially methane.

(42) Any convenient method for producing syngas can be used, including conventional methods. Suitable methods include those described in U.S. Patent Application Publications Nos. 2007/0259972 A1, 2008/0033218 A1, and 2005/0107481, each of which is incorporated by reference herein in its entirety. For example, natural gas can be converted to syngas by steam reforming. The first step normally involves the removal of inert components in the natural gas, such as nitrogen, argon, and carbon dioxide. Natural gas liquids will also be recovered and directed to other processing or transport. The treated natural gas will comprise primarily methane and some ethane with small amounts of higher alkanes, such as propane. Preferably, the natural gas comprises more than 90 vol. % methane. The treated natural gas is then contacted with steam in the presence of a catalyst, such as one or more metals or compounds thereof selected from Groups 7 to 10 of the Periodic Table supported on at least one attrition-resistant refractory support, such as alumina. The contacting is normally conducted at high temperature, such as in the range of from 800 C. to 1100 C., and pressures 5000 kPa. Under these conditions, methane converts to carbon monoxide and hydrogen according to reactions, such as:
CH.sub.4+H.sub.2.fwdarw.CO+3H.sub.2.

(43) Steam reforming is energy intensive in that the process consumes over 200 kJ/mole of methane consumed. A second method is partial oxidation, in which the methane is burned in an oxygen-lean environment. The methane is partially-oxidized to carbon monoxide (reaction (i)), with a portion of the carbon monoxide being exposed to steam reforming conditions (reaction (ii)) to produce molecular hydrogen and carbon dioxide, according to the following representative reactions:
CH.sub.4+3/2O.sub.2.fwdarw.CO+2H.sub.2O(i),
CO+H.sub.2O.fwdarw.CO.sub.2+H.sub.2(ii).

(44) Partial oxidation is exothermic and yields a significant amount of heat. Because one reaction is endothermic and the other is exothermic, steam reforming and partial oxidation are often performed together for efficient energy usage. Combining the steam reforming and partial oxidation yields a third process wherein the heat generated by the partial oxidation is used to drive the steam reforming to yield syngas.

(45) The feed mixture, typically syngas, is reacted to produce long chain alcohol in the presence of the at least one specified templated active material. Suitable process conditions will now be described in more detail.

(46) In certain aspects, the reaction is carried out under conditions which include a reaction temperature 150 C., a total pressure 0.7 MPa (absolute), and a space velocity (GHSV) 50 hr.sup.1. Typically, the reaction conditions include a temperature in the range of from 150 C. to 300 C., e.g., 200 C. to 280 C. In certain aspects, the reaction is carried out at a temperature in the range of from 150 C. to 250 C. Total pressure is typically in the range of from 0.7 MPa to 5 MPa, such as in the range of from 1.0 MPa to 4 MPa, or 1.5 MPa to 3.5 MPa. The space velocity (GHSV) is typically in the range of from 100 hr.sup.1 to 10,000 hr.sup.1, such as in the range of from 500 hr.sup.1 to 5000 hr.sup.1. The process can be carried out in at least one reaction zone, the reaction zone being located within at least one reactor vessel, e.g., a tube reactor. The templated active material is resistant to deactivation during use, and the process can be operated continuously without interruption for catalyst regeneration, rejuvenation, or replacement for a time 10 hours, e.g., 100 hours, such as 1000 hours, or 10,000 hours.

(47) A reaction effluent comprising long chain alcohol is conducted away from the reaction zone. Typically the reaction effluent further comprises any unreacted feed mixture components and byproducts from side reactions such as short chain alcohols. Conventional technology can be utilized for separating the long chain alcohol from the remainder of the reaction effluent, e.g., fractional distillation. If desired, other oxygenate can be produced from the long chain alcohol. For example, the process can further comprise dehydrogenating the long chain alcohol to produce corresponding aldehyde (long-chain aldehyde). The aldehyde can be converted to olefin, e.g., by removing the aldehyde's formyl group.

(48) While the present invention has been described and illustrated with respect to certain aspects, it is to be understood that the invention is not limited to the particulars disclosed and extends to all equivalents within the scope of the claims. Unless otherwise stated, all percentages, parts, ratios, etc. are by weight. Unless otherwise stated, a reference to a compound or component includes the compound or component by itself as well as in combination with other elements, compounds, or components, such as mixtures of compounds. Further, when an amount, concentration, or other value or parameter is given as a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of an upper preferred value and a lower preferred value, regardless of whether ranges are separately disclosed. All patents, test procedures, and other documents cited herein, including priority documents, are fully incorporated by reference to the extent such disclosure is not inconsistent and for all jurisdictions in which such incorporation is permitted.