ETA PHASE MATERIALS, METHODS OF PRODUCING THE SAME, AND USE THEROF AS CATALYSTS FOR ALCOHOL SYNTHESIS, HYDROCARBON SYNTHESIS, HYDROCARBON HYDROGENATION AND HYDROCARBON CONVERION REACTIONS

Abstract: An eta phase composition in powder form having a surface area greater than about 2m²/g and consisting of X₆Y₆Z a , wherein X is at least one of Mo or W, Y is at least one of Fe, Co or Ni and up to one of Mo and W, Z is at least one of C and N and a is greater than or equal to 1 but less than or equal to 2. The eta phase may be a carbide, nitride or carboni­ tride. The eta-phase composition may be used for producing or converting hydrocarbons or alcohols. This includes hydrogenation of CO to produce at least one hydrocarbon or at least one alcohol and hydrogenation of unsaturated hydrocarbons, aromatic hydrocarbons and olefinic hydrocarbons. The eta-phase composition may be used in hydrocarbon conversion reactions, including isomerization and dehydrogenation. A method for producing the eta-phase composition includes providing a precursor compound including at least two eta-phase forming metals, and a ligand containing carbon, nitro­ gen or combinations thereof. The precursor compound is thermally decomposed in a nonoxidizing atmosphere to react the carbon or nitrogen derived from the decompo­ sition of the ligand with the metals to form the eta-phase. The eta phase forming metals are at least two of the metals tungsten, molybdenum, nickel, cobalt and iron.

Description: FIELD OF THE INVENTION This invention relates to powder of an eta-phase structure having an increased surface area and to a method for using the same in producing or converting hydrocarbons. BACKGROUND OF THE INVENTION Eta-phase structures, such as eta-phase carbides, nitrides and carbonitrides are known in the art for use as hardening dispersions in a metal or alloy matrix. Eta-phase materials are conventionally produced by heating metals with a source of carbon or nitrogen. This may be achieved, for example, by vacuum arc melting. These eta-phases can be present in steels containing, for example, nickel and molybdenum. They may be formed in situ during thermal processing of these steels. These eta-phases may be crushed and milled to a desired particle size distribution. Typically, heating is done in the presence of sulfur or sulfur bearing compounds. U.S. Patent 4,595,672, Ho et al, teaches a method of producing self-promoted molybdenum and tungsten sulfide hydrotreating catalysts. The reduction of the catalyst precursor salt, Co(en)₃MoO₄, supported on alumina, is carried out in the presence of sulfur or sulfur bearing compounds, such as H₂S, in a non-oxidizing atmosphere. Sulfur converts the catalyst precursor to sulfide materials. Conventional eta-phase structures also have low surface area and are difficult to synthesize. Therefore, they have not been known or considered for use as catalysts. Conventional methods for making eta-phase structures fail to reveal a method for producing high surface area eta-phase materials in a sulfur-free, non-oxidizing atmosphere. SUMMARY OF THE INVENTION It is accordingly a primary object of the present invention to provide an eta-phase structure in powder form and a method for using the same as a catalyst in converting or producing hydrocarbons in a more efficient manner, particularly from the cost standpoint, than catalysts conventionally used for this purpose. A more specific object of the invention is to provide a method for producing a high surface area eta-phase powder for use as a catalyst wherein a precursor salt compound is thermally decomposed in a sulfur-free, non-oxidizing atmosphere to react with carbon, nitrogen or combinations thereof at an elevated temperature and pressure effective for hydrocarbon or alcohol production or conversion. The catalyst material of the invention will provide results similar to those achieved with the more expensive noble metals, such as platinum and palladium, conventionally used for this purpose. Another object of the invention is to provide eta-phase powder for use as a catalyst in practices of this type wherein the catalyst material of the invention provides results similar to those achieved with the more expensive noble metals, such as platinum and palladium, conventionally used for this purpose. Additional objects and advantages of this invention will be set forth in part in the description that follows and in part will be obvious from the description or may be learned by the practice of the invention. The objects and advantages of the invention may be realized and obtained by the compositions and methods particularly set forth in the appended examples and claims. In accordance with the invention, the composition thereof comprises an eta-phase in powder form. The powder has a surface area greater than 2 meters²/gram (m²/g). The eta phase is of a composition X₆Y₆Z a wherein X is at least one element selected from the group consisting of molybdenum and tungsten, Y is at least one element selected from the group consisting of iron, cobalt and nickel and up to one element selected from the group consisting of molybdenum and tungsten, Z is at least one element selected from the group consisting of carbon and nitrogen and a is greater than or equal to 1 but less than or equal to 2. The eta-phase may be a carbide phase, a nitride phase or a carbonitride phase, with these phases being present either singly or in combination. Specifically, the eta phase in accordance with the invention may be Mo₆Fe₆Z a , Mo₆Co₆Z a , Mo₆Ni₆Z a , Mo₆(FeCo)₆Z a , Mo₆(FeNi)₆Z a , Mo₆(CoNi)₆Z a , Mo₆(FeCoNi)₆Z a , W₆Fe₆Z a , W₆Co₆Z a , W₆Ni₆Z a , W₆(FeCo)₆Z a , W₆(FeNi)₆Z a , W₆(Co,Ni)₆Z a , W₆(Fe,Co,Ni)₆Z a , (W,Mo)₆Fe₆Z a , (W,Mo)₆Co₆Z a , (W,Mo)₆Ni₆Z a , (W,Mo)₆(Fe,Co)₆Z a , (W,Mo)₆(Fe,Ni)₆Z a , (W,Mo)₆(Co,Ni)₆Z a , (W,Mo)₆(Fe,Co,Ni)₆Z a , wherein Z is at least one element selected from the group consisting of carbon and nitrogen and a is greater than or equal to 1 but less than or equal to 2. The method in accordance with the invention is for producing or converting hydrocarbons and alcohols, including hydrogenation reactions. The method comprises contacting a fluid, carbon-containing feedstock with a catalyst of an eta-phase composition in accordance with the invention as set forth above. This takes place in a reducing atmosphere at an elevated temperature and pressure effective for the desired hydrocarbon or alcohol production or conversion. In this regard, with respect to hydrogenation reactions, such may include the hydrogenation of CO to produce a hydrocarbon or an alcohol. Hydrogenation may be of unsaturated hydrocarbons, such as aromatic hydrocarbons and olefinic hydrocarbons. Hydrocarbon conversion reactions may be isomerization or dehydrogenation. The method for producing or converting hydrocarbons in accordance with the invention may include the specific eta phase listed above in accordance with the invention used as catalysts. Further in accordance with the invention, a method is provided for producing an eta phase composition. The method includes providing a precursor compound that includes at least two eta phase forming metals and a ligand containing carbon, nitrogen or combinations thereof. The precursor compound is thermally decomposed in a nonoxidizing atmosphere to react carbon, nitrogen or combinations thereof derived from the decomposition of the ligand with the metals of the precursor compound to form the eta phase. The eta phase forming metals may be tungsten, molybdenum, nickel, cobalt and iron, with preferred combinations thereof being molybdenum and nickel, molybdenum and cobalt, molybdenum and iron, tungsten and nickel, tungsten and cobalt, and tungsten and iron. The conditions for thermal decomposition of the ligand will vary depending upon the precursor compound including the ligand thereof. The temperature must be sufficiently high to remove the ligand from the metals and decompose the ligand, at least in part, to provide the required carbon and/or nitrogen necessary to react with the metals of the precursor compound. However, the temperature is not so high as to reduce the surface area of the final eta phase powder to 2 meters²/gram or less. This temperature will also be dependent upon the reactor size, reactor geometry, the amount of precursor and so forth. This may be readily determined by routine experimentation as demonstrated by the specific examples herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to presently preferred embodiments of the invention, specific examples of which are described below. The eta phase compositions in accordance with the invention are produced for example by the reduction decomposition of a suitable mixed metal coordination compound or mixed metal organometallic precursor at a temperature sufficient to yield an atomically mixed high surface area reactive product. A specific, typical reaction employing a catalyst in accordance with the eta-phase compositions of the invention in a hydrogenation reaction wherein hydrogen and carbon monoxide are reacted at a suitable elevated temperature and pressure with a catalyst of the invention to produce a hydrocarbon and alcohol would be as follows: H₂+CO→C n H 2n+2 + C n H 2n+1 OH. Specific examples demonstrating the effectiveness of Applicants' eta phase composition and method employing the same in producing hydrocarbons and alcohols or converting hydrocarbons are set forth hereinafter. Example 1 Ni(en)₃MoO₄ Catalyst Precursor Preparation A tris(ethylenediamine) nickel molybdate, Ni(en)₃MoO₄, catalyst precursor was prepared by dissolving ammonium molybdate into ethylenediamine (en) and the resulting solution cooled to 0°C in an ice bath. An aqueous solution of nickel chloride was slowly added, in aliquots, to the above solution, with agitation after the addition of each aliquot. A precipitate was formed and recovered by vacuum filtration. This precipitate was Ni(en)₃MoO₄ which was washed with water and acetone and then dried in a vacuum oven at 50°C. More specifically, 20.5 g of ammonium heptamolybdate, (NH₄)₆Mo₇O₂₄.4H₂O, was added to 500 ml of ethylenediamine, NH₂CH₂CH₂NH₂, in a 1000 ml Erlenmeyer flask. The amount of ethylenediamine was greatly in excess of the stochiometric amount required to form the precursor compound and aids in its precipitation. In a separate flask 27 g of nickel chloride, NiCl₂.6H₂O, were dissolved into 300 ml of distilled water. This Ni²⁺ was added slowly, in aliquots, to the molybdate solution with agitation after each addition. The precipitate, Ni(en)₃MoO₄, which formed immediately, was collected on a Buchner funnel, washed with a small amount of water and then acetone. It was dried in a vacuum oven for 16 hours. 46 g of Ni(en)₃MoO₄ were recovered. Example 2 Co(en)₃MoO₄ and Fe(en)₃MoO₄ Preparation The method of Example 1 was used with the substitution of either CoCl₂.6H₂O or FeCl₂.4H₂O for the NiCl₂.6H₂O. In the synthesis of Fe(en)₃MoO₄ the solutions and the precipitate were handled under an inert blanket of nitrogen gas to prevent the oxidation of Fe²⁺ to Fe³⁺. Example 3 Preparation of [Fe(en)₃] 0.5 [Ni(en)₃] 0.5 MoO₄, [Fe(en)₃] 0.5 [Co(en)₃] 0.5 MoO₄, [Co(en)₃] 0.5 [Ni(en)₃] 0.5 MoO₄, etc. The methods of Example 1 and Example 2 were used with equimolar mixtures of aqueous Fe²⁺ and Ni²⁺ Fe²⁺ and Co2+, and Co²⁺ and Ni²⁺ substituted respectively for the Ni²⁺ aqueous solution used in Example 1. Again a nitrogen gas blanket was used where necessary to prevent the oxidation of these ions. Example 4 Preparation of [M(en)₃] 1-x [M'(en)₃] x MoO₄ where both M and M' = Fe, Co, Ni The methods of Example 1 and Example 2 were used with mixtures of aqueous M²⁺ and M'²⁺ in the molar ratio (1-x):x, where x is greater than or equal to zero but less than or equal to 1, substituted for the Ni²⁺ aqueous solution of Example 1. A nitrogen gas blanket was used as in the previous examples. Example 5 Preparation of Ni(en))₃WO₄ 14.5 grams of tungstric acid, H₂WO₄, were dissolved in 150 ml of a 1:1 mixture of concentrated NH₄OH and water, and 150 ml of ethylenediamine. A clear solution was obtained by heating and stirring. In a separate vessel, 13.5 grams of NiCl₂.6H₂O was dissolved in distilled water and added to the hot tungstric acid solution. A precipitate, Ni(en)₃WO₄, formed as the volume of the mixture was reduced 50% by evaporating the solution. After cooling the mixture to room temperature, the product was collected by filtration on a Buchner funnel, washed with acetone, and dried. Example 6 Preparation of Co(en)₃WO₄ and Fe(en)₃WO₄ The method of Example 5 was used with the substitution of CoCl₂.6H₂O or FeCl₂.4H₂O for NiCl₂O.6 H2 O. In the synthesis of Fe(en)₃WO₄ the procedure is carried out under an inert atmosphere to prevent the oxidation of Fe²⁺ to Fe³⁺. Example 7 Preparation of [M(en)₃] 1-x [M'(en))₃] x WO₄ where both M and M' = Fe, Co, Ni The methods of Example 5 and Example 6 were used with mixtures of aqueous M²⁺ and M'²⁺ in the molar ratio (1-x):x, where x is defined as in Example 4, substituted for the Ni²⁺ aqueous solution of Example 5. Example 8 Thermodynamically Controlled Preparation of Molybdenum Carbide Eta Phases The reactive precursors were prepared in identical manners from the appropriate M'(en)₃MoO₄ salt and were synthesized by the methods of Examples 1 and 2, where M' is Ni, Co and Fe. The transition metal coordination compound was placed in a quartz boat in a 3.81 cm (1.5'') I.D. quartz tubular furnace and heated in a flowing mixture of equal parts by volume of He and H₂ at 1 atm (101.36 kPa) pressure and at a total flow rate of 160 cc/min. The furnace temperature was ramped from room temperature to 650°C at a heating rate of 15°C/min and held at temperature for 0.5 hours. The H₂/He flow was replaced with He and the heating continued to 1000°C. The flow rate was then replaced with a CO₂/CO/He mixture appropriate for the desired thermodynamic conversion. The conversion was allowed to proceed at 1000°C for at least three hours. Finally the reactor was purged with He and cooled to room temperature. In this manner, the following four molybdenum eta phases were produced: Fe₆Mo₆C, Co₆Mo₆C, Co₆Mo₆C (at an elevated temperature), and Ni₆MO₆C. Example 9 Thermodynamically Controlled Preparation of Tungsten Carbide Eta Phases The reactive precursor for the synthesis of a pure Co₆W₆C was prepared by reductive decomposition of Co(en)₃WO₄. The transition metal coordination compound was placed in a quartz boat in a 3.81 cm (1.5'') I.D. quartz tubular furnace and heated in a flowing mixture of equal parts by volume of He and H₂ at 1 atm (101.36 kPa) pressure and total flow rate of 160 cc/min. The furnace was ramped from room temperature to a temperature of 650°C at a heating rate of 15°C/min, held there for three hours and cooled to room temperature in flowing gas. At room temperature, the reactive gas was replaced by helium at a flow rate of 40 cc/min. The resulting reactive precursor was subsequently passivated in He/O₂ gas mixtures by successive addition of O₂ of increasing concentration prior to removal from the furnace tube. The reactive high surface area precursor produced by the low temperature reductive decomposition of Co(en)₃WO₄ described above was placed in a quartz boat at the center of a uniform hot zone of a quartz tubular furnace in flowing argon at 900 Torr pressure and 250 cc/min flow rate. The furnace temperature was raised rapidly to the conversion temperature (typically 700 to 1000°C). The argon flow was quickly replaced by the CO₂/CO mixture with total pressure (P) and CO₂/CO ratio necessary to achieve the desired carbon and oxygen activities at the conversion temperatures. The sample was held isothermally in the flowing reactive gas at a flow rate of 500 cc/min for a time sufficient to allow complete equilibration of the carbon activity of the precursor with the flowing gas. The CO₂/CO gas mixture was then purged from the reaction tube by argon at a flow rate of 500 cc/min and the furnace was rapidly cooled to room temperature. Samples were removed at room temperature without passivation. It was determined that complete conversion to the pure Co₆W₆C eta carbide had occurred for the precursor processed at a carbon activity, a c , of 0.1. Example 10 Kinetically Controlled Preparation of Ni₆Mo₆Z a Eta Phase A small quartz boat was filled with Ni(en)₃MoO₄. The boat was then placed into a 1.5'' (3.81 cm) I.D. quartz tubular furnace which had been preheated to 700°C and which contained a 1:1 H₂/He mixture flowing at 500 cc/min. The reactor was maintained at these conditions for 3 hours after which the resulting catalyst was cooled to room temperature in the flowing gas mixture. The catalyst was removed from the reactor without passivation. The structure of the catalyst was determined by x-ray powder diffraction and elemental analysis. Example 11 Kinetically Controlled Preparation of Fe₃Ni₃Mo₆Za, Where a = 1 and Fe₃Ni₃Mo₆Z a , Where a = 2 Eta Phase A small quartz boat was filled with [Fe(en)₃]0.5[Ni(en)₃] 0.5 MoO₄. The boat was then placed into a 1.5'' (3.81 cm) I.D. quartz tubular furnace which had been preheated to 700°C and which contained He flowing at 500 cc/min. The temperature was allowed to stabilize and the flow increased to 525 cc/min with the addition of a H₂ gas stream. The reactor was maintained at these conditions for 3 hours after which the catalyst was cooled to room temperature in the flowing gas mixture. The catalyst was passivated at room temperature according to the following schedule. 2% O₂ in He for 1 hour 4% O₂ in He for 1 hour 6% O₂ in He for 15 minutes 10% O₂ in He for 15 minutes The samples were removed from the reactor. X-ray and chemical analysis showed that the catalyst sample contained two forms of eta phase catalyst, Fe₃Ni₃Mo₆Z a , where a is equal to 1 and Fe₃Ni₃Mo₆Z a , where a is equal to 2. Example 12 Molybdenum Nickel Eta Phase Catalyst for CO Hydrogenation: Effect of Pressure on Alcohol Synthesis Samples of eta phase catalysts were evaluated for CO hydrogenation reactions in a continuous flow unit with separate mass flow controllers for metering the feed rates of carbon monoxide and hydrogen to a stainless steel upflow reactor temperature controlled in a fluidized sand bath with 2.0 cc catalyst volume between porous frits. An on-line gas chromatograph was used for analyzing both reactants and products, and a back pressure regulator was used for controlling the reaction pressure between 1 and 60 atmospheres. A sample of molybdenum nickel eta phase catalyst weighing 0.53 g, prepared by the methods of Example 1 and Example 10, was loaded into the reactor and flushed with flowing hydrogen at room temperature. The catalyst was heated in stages, first to 120°C, then to 250°C and finally to 400°C. The sample was reduced for at least 1 hour at 400°C prior to lowering the temperature for reaction studies. A temperature of 250°C was used as a typical temperature for evaluating new materials. The effect of pressure on catalyst performance of molybdenum nickel eta phase catalyst is shown in Table II. The feed rates were varied from 40 to 80 to 120 cc (STP) per minute as the pressure was increased from 1 to 5 to 10 to 15 atmospheres (0.101 to 0.507 to 1.014 to 1.520 MPa) pressure. The H₂/CO ratio was maintained at 3.0. The product distribution changed substantially as the pressure was increased from 1 atmosphere. Initially the products were exclusively light hydrocarbons, water and CO₂. As the pressure was raised, substantial quantities of alcohols appeared in the products. Increasing the pressure increased the methanol selectivity from 29.8% to 46.1% to 52.2%. Example 13 Molybdenum Nickel Eta Phase Catalyst For CO Hydrogenation: Effect of Partial Pressure on Selectivity The sample of molybdenum nickel eta phase catalyst described in Example 12 was tested to determine the effect of H₂/CO ratio on performance. The catalyst sample was heated to 250°C and the initial reactant inlet partial pressures were set at CO = 1.0 atm (0.101 MPa) and H₂ = 3.0 atm (0.304 MPa). Conversions were maintained at a low level so that the changes in reactant concentration would be low in moving from the reactor inlet to the outlet. The reactant concentrations were changed systematically, first by maintaining the CO partial pressure and increasing the hydrogenation pressure, then by holding the hydrogen partial pressure constant and increasing the CO partial pressure. The results of this set of runs are presented in Table III. The run 3-1 starting the sequence has H₂/CO = 3.0 and a total pressure of 4.0 atm (0.405 MPa). Both hydrocarbons and alcohols are among the products. Increasing the H₂/CO ratio to 6.0 while maintaining the CO partial pressure increased the reaction rate and increased the selectivity to methanol relative to hydrocarbon products. Increasing the H₂/CO ratio to 9.0 increased the alcohol selectivity still further. When the H₂ partial pressure reached 9.0 atm (0.912 MPa), the CO partial pressure was systematically increased first to 2.0 atm (0.203 MPa), then 4.0 atm (0.405 MPa), and finally 6.0 atm (0.608 MPa). The H₂/CO ratio decreased from 9.0 to 1.5 over the full range. The high selectivity to light alcohols was maintained over this broad range of H₂/CO ratio. Example 14 Molybdenum Nickel Eta Phase Catalyst For CO Hydrogenation: Effect of Temperature on Selectivity A 0.51 g sample of molybdenum nickel eta phase catalyst was evaluated at constant pressure and H₂/CO ratio while the temperature was varied. Table IV shows changes in the rate and product distribution when the reaction temperature was increased from 199 to 302°C. The H₂/CO ratio was maintained at 3.0 and the total pressure was 10 atmospheres (1.014 MPa). Run 4-1 shows high selectivity to methanol at 199°C. This selectivity stayed at 49% when the temperature was increased to 250°C, but dropped to 38% at 275°C and to 12% at 302°C. Decreased selectivity to methanol at the higher temperatures was predicted by thermodynamic considerations. Higher reaction temperatures require higher pressures to prevent methanol from decomposing to the reactants CO + 2H₂. Increased reaction temperature has a substantial effect on the rate of CO conversion to hydrocarbons. Example 15 Comparison of Molybdenum Nickel Eta Phase With Molybdenum Oxycarbonitride for CO Hydrogenation A comparison of the catalytic properties of molybdenum nickel eta phase was made with molybdenum oxycarbonitride for CO hydrogenation reactions. Molybdenum oxycarbonitride is a high surface area, high activity catalyst for CO hydrogenation as described in U.S. Patent 4,418,154. It produces hydrocarbon product distributions typical of traditional molybdenum carbide and molybdenum nitride materials, but has high activity due to its high surface area. A comparison of 1.08 g of molybdenum oxycarbonitride with 0.53 g of molybdenum nickel eta phase catalyst using the continuous flow unit described in Example 12 is shown in Table V. At 250°C, 10 atmospheres (1.014 MPa) pressure, and a H₂/CO ratio of 1.0, the molybdenum nickel eta phase catalyst produced a product distribution containing 46.3% hydrocarbons and 53.7% alcohols. By contrast, the molybdenum oxycarbonitride catalyst produced 94.5% hydrocarbons and only 5.5% alcohols. The high selectivity to alcohols distinguishes the molybdenum eta phase catalyst from catalyst containing molybdenum alone in a carbide, nitride, oxycarbide, carbonitride, or oxycarbonitride form. Example 16 Molybdenum Cobalt Eta Phase Catalyst For CO Hydrogenation: Effect of Temperature on Selectivity A 0.51 g sample of molybdenum cobalt eta phase catalyst was evaluated at constant pressure and H₂/CO ratio while the temperature was varied. Table VI shows how rate and product distribution changed when the reaction temperature was increased from 203 to 299°C. The H₂/CO inlet ratio was maintained at 3.0 and the total pressure was 10 atmospheres (1.014 MPa). Run 6-1 shows product selectivities for both hydrocarbons and alcohols. The major individual product at 203°C is methanol. A comparison of molybdenum cobalt with molybdenum nickel at similar conditions shows that changing from nickel to cobalt increased the hydrocarbon yield relative to alcohols and also caused the hydrocarbon distribution to shift toward higher molecular weights. Increasing reaction temperature increases reaction rates and selectivities toward hydrocarbons. Example 17 Molybdenum Cobalt Eta Phase Catalyst For CO Hydrogenation: Effect of Reactant Partial Pressure on Selectivity A 0.51 g sample of molybdenum cobalt eta phase catalyst was tested to determine the effect of H₂/CO ratio on performance. The catalyst sample was heated to 250°C and the initial reactant inlet partial pressures were set at CO = 1.0 atm (0.101 MPa) and H₂ = 3.0 atm (0.304 MPa). The reactant concentrations were changed systematically, first by maintaining the CO partial pressure and increasing the hydrogen pressure, then by holding the hydrogen partial pressure constant and increasing the CO partial pressure. The results of this set of experiments are presented in Table VII. The run 7-1 starting the sequence has H₂/CO = 3.0 and a total pressure of 4 atm (0.405 MPa). Both hydrocarbons and alcohols are among the products. Increasing the H₂/CO ratio to 6.0 while maintaining the CO partial pressure increased reaction rates and increased selectivity towards alcohols. The hydrocarbon product distribution became slightly lighter with increasing hydrogen partial pressure. Increasing the H₂/CO ratio to 9.0 continued the trend toward more alcohols and lighter hydrocarbon products. When the H₂ inlet partial pressure reached 9.0 atm (0.912 MPa), the CO inlet partial pressure was systematically increased, first to 2.0 atm (0.203 MPa) and then to 4.0 atm (0.405 MPa). Increased CO pressure reduced the catalyst selectivity toward methane and increased selectivity toward methanol and other light alcohols. Example 18 Molybdenum Iron Eta Phase Catalyst For CO Hydrogenation A 0.50 g sample of molybdenum iron eta phase catalyst was tested in the continuous flow reactor described in Example 12 to determine its activity and selectivity for H₂/CO reactions. Tests were carried out at 10.0 atm (1.014 MPa) pressure and a constant inlet H₂/CO ratio of 3.0 while the temperature was varied. Table VIII shows how the conversion and product distributions changed as the temperature was increased from 200 to 302°C. Run 8-1 shows that at 200°C the iron molybdenum eta phase catalyst has low methane selectivity, a broad distribution of hydrocarbon products, and high selectivity to both methanol and ethanol. Catalyst samples containing iron had broader product distributions than their analogs containing cobalt (run 6-1) or nickel (run 4-1). Increasing reaction temperature at 10 atm (1.014 MPa) pressure increased reaction rate and shifted the product distribution toward lower molecular weights. Example 19 Preparation of Potassium Promoted Molybdenum Iron Eta Phase Catalyst A 0.487 M solution of potassium carbonate was prepared by dissolving 1.01 g of potassium carbonate in 15.0 g of distilled water. 0.87 cc of the resulting solution was added dropwise to 0.99 g of molybdenum iron eta phase catalyst. The sample was stirred to provide an even distribution of liquid over the solid sample and then permitted to air dry. The concentration of potassium on the sample is calculated to be 3.2%. Example 20 Potassium Promoted Molybdenum Iron Eta Phase Catalyst For CO Hydrogenation: A Comparison With Unpromoted Molybdenum Iron Eta Phase Catalyst A 0.51 g sample of potassium promoted molybdenum iron eta phase catalyst was tested at conditions similar to those used in Example 18 to determine the effect of the potassium addition on the catalyst performance. The comparison was made at 10.0 atm (1.014 MPa) total pressure, a H₂/CO ratio of 3.0 and at both 250 and 300°C. The results were presented in Table IX. At approximately 250°C, the potassium promoted catalyst showed a substantially heavier product than the unpromoted sample. Methane selectivity was 12.8% as compared to 25.6%. The heavier hydrocarbon liquids were analyzed at 16.9% as compared to 12.4%, and the alcohol selectivity showed a substantial increase with potassium addition. At 300°C, similar results were observed with methane from the potassium promoted sample being about half that produced by the unpromoted sample. Again, heavier hydrocarbon liquids were observed, as well as substantially more alcohol products. Example 21 Molybdenum Nickel-Iron Eta Phase Catalyst For CO Hydrogenation A 0.50 g sample of molybdenum nickel-iron eta phase catalyst as prepared in Example 11 was evaluated at constant pressure and H₂/CO ratio while the temperature was varied. Table X shows how rate and product distribution changed when the reaction temperature was increased from 199 to 300°C. The H₂/CO inlet ratio was 3.0 and the total pressure was 10.0 atm (1.014 MPa). The product contains both hydrocarbons and alcohols. At 199°C, the major product is methanol. Raising the temperature reduces the selectivity to alcohols with hydrocarbons being the predominant product at 300°C. Example 22 Comparison of Molybdenum Eta Phase Catalysts For CO Hydrogenation Reactions: Effect of Group VIII Metals on Selectivity A comparison of the molybdenum eta phase catalysts described in Examples 14, 16, 18 and 21 is made in Table XI. The molybdenum nickel-iron eta phase catalyst is compared with its molybdenum nickel, molybdenum cobalt and molybdenum iron analogs. The comparison is made for reactions at approximately 250°C, 10.0 atm (1.014 MPa) pressure and H₂/CO = 3.0. All of the catalyst make similar products, but variations do occur in a systemic way. Molybdenum nickel is most selective to methanol. Methanol selectivity decreases as the Group VIII metal changes from nickel to cobalt to iron. While methanol selectivity is decreasing, the hydrocarbon products are becoming more significant, and they are shifting from primarily light products to heavier products. Comparing the mixed Group VIII metal eta phase catalyst to the others, the nickel-iron combination produces a product state similar to that produced by cobalt. The mixed Group VIII metal eta phase catalyst is clearly not just the average of nickel properties and iron properties, for were that the case, yield of methanol would be higher. This similarity between molybdenum nickel-iron and molybdenum cobalt can also be observed at 200 and 300°C by comparing the data provided in Table X with Table VI. Example 23 Tungsten Nickel Eta Phase Catalysts For CO Hydrogenation A 1.02 g sample of tungsten nickel eta phase catalyst was evaluated at constant pressure and H₂/CO ratio while the temperature was varied. Table XII shows how rate and product distribution changed when the temperature was increased from 172 to 252°C. The H₂/CO ratio was maintained at 3.0 and the total pressure was maintained at 10 atm. Run 12-1 shows high selectivity to methanol at 172°C. This initial selectivity of 28% methanol remained nearly constant as the temperature was increased to 223°C, then decreased slightly to 20% on raising the reaction temperature to 252°C. The hydrocarbon distribution is comprised primarily of methane and other light hydrocarbon products. Example 24 Tungsten Cobalt Eta Phase Catalysts For CO Hydrogenation A 1.02 g sample of tungsten cobalt eta phase catalyst was evaluated at constant pressure and H₂/CO ratio while the temperature was varied. Table XIII shows rate and product distribution changes when the temperature was increased from 201 to 304°C. The H₂/CO ratio was maintained at 3.0 and the total pressure was maintained at 10 atm (1.014 MPa). Run 13-1 shows high selectivity to light hydrocarbons and alcohols at 201°C. Increasing the temperature increases conversion and shifts both the hydrocarbons and alcohols toward lighter products. Example 25 1-Hexene Hydrogenation With Tungsten Cobalt Eta Phase Catalyst Samples of eta phase catalyst were evaluated for olefin hydrogenation in a continuous flow unit with mass flow controllers for metering flows of hydrogen and helium, a gas saturator in a constant temperature bath for adding controlled amounts of hydrocarbons to the hydrogen or helium stream, a stainless steel upflow reactor temperature controlled in a sand bath with 2.0 cc catalyst volume between porous frits , an on line gas chromatograph for analyzing both reactants and products, and a back pressure regulator for controlling the reaction pressure between 1 and 60 atmospheres (0.103 and 6.081 MPa). A sample of tungsten cobalt eta phase catalyst weighing 1.02 g was loaded into the reactor and reduced in flowing hydrogen at 90 cm³/min (STP) at 400°C for 1.5 hours. The reactor temperature was lowered to room temperature to evaluate this material as a catalyst for olefin hydrogenation. The unit was pressurized to 9.9 atmospheres (1.003 MPa) with hydrogen, the saturator filled with 1-hexene and thermostated to 0°C, and the hydrogen flow rate controlled at 50 cm³/min (STP). The saturator temperature set the 1-hexene concentration at 0.7 volume percent, a weight hourly space velocity of approximately 0.08 grams of feed per gram of catalyst per hour. Run 14-1 shows that 11.0% of the 1-hexene fed was hydrogenated to n-hexane at 24°C. The olefins that were not hydrogenated were isomerized so that the product contained not only 1-hexene and n-hexane but also 2-hexenes and 3-hexenes as well. The reactor temperature was raised to 97°C and all of the feed was hydrogenated to n-hexane at this temperature. No methane or light hydrocarbon products indicative of carbon-carbon bond hydrogenolysis were observed. The results and conditions for these experiments are listed in Table XIV. Example 26 Benzene Hydrogenation With Tungsten Nickel Eta Phase Catalyst Samples of eta phase catalyst were evaluated for aromatics hydrogenation and carbon-carbon bond hydrogenolysis in a continuous flow unit with mass flow controllers for metering flows of hydrogen and helium, a liquid chromatrography pump for maintaining low feed rates of liquid reactants, a stainless steel upflow reactor temperature controlled in a sand bath with 2.0 cm³ catalyst volume between porous frits, an on line gas chromatograph for analyzing both reactants and products, and a back pressure regulator for controlling the reaction between 1 and 60 atmospheres (0.101 to 6.081 MPa). A sample of tungsten nickel eta phase catalyst weighing 1.00 g was loaded into the reactor and reduced in flowing hydrogen at 80 cm³/min (STP) at 400°C for 2.5 hours. The reactor temperature was lowered to 250°C to evaluate this material as a catalyst for benzene hydrogenation. The unit was pressurized to 21.3 atmospheres (2.159 MPa) with hydrogen and a benzene feed was introduced at 0.50 g/hr, at weight hourly space velocity of 0.5 grams of feed per gram of catalyst per hour. Run 15-1 shows that all of the benzene was hydrogenated to cyclohexane at these conditions. None of the cyclohexane was cracked by carbon-carbon bond hydrogenolysis to lighter products at 252°C. The reactor temperature was lowered to 201°C to reduce reaction rate. Again 100% of the benzene was hydrogenated to cyclohexane. Finally the reactor was cooled to 152°C where the conversion of benzene to cyclohexane was again 100%. The results and conditions for these experiments are listed below in Table XV. Example 27 Aromatics Hydrogenation With Tungsten Nickel Eta Phase Catalyst The tungsten nickel eta phase catalyst used for Example 26 was tested again for aromatics hydrogenation using a mixture comprised of 14.6% naphthalene in benzene. The reactor temperature was raised from room temperature to 250°C and the unit pressurized with hydrogen to 21.3 atm (2.159 MPa). The aromatic feed mixture was introduced at 1.33 g/hr, a weight hourly space velocity of 1.33 grams of feed per gram of catalyst per hour. Introducing the feed at this rate raised the reaction temperature above that of the sand bath. Run 16-1 shows that at 267°C, 99.98% of the benzene was hydrogenated to cyclohexane and 99.66% of the naphthalene was hydrogenated to either tetralin (1.7%) or one of the decalin isomers (98%). Only traces of other hydrocarbon products due to either isomerization or carbon-carbon bond hydrogenolysis were observed. Raising the reaction temperature from 267 to 313°C caused the extent of aromatic hydrogenation to decrease since increasing temperature shifts the thermodynamic equilibrium away from the totally hydrogenated product and toward the aromatic forms. Raising the temperature caused only a small increase in carbon-carbon bond breaking or skeletal rearrangements. The methane product was only 0.03% while the total hydrocarbon converted to other structural forms was 1.3%. A final increase in reaction temperature to 361°C reduced aromatics saturation still further due to changing equilibrium position and increased the extent of rearranged or cracking products to 6.3%. Example 28 Methylcyclohexane Conversion With Tungsten Cobalt Eta Phase Catalyst A tungsten cobalt eta phase catalyst was tested for converting cycloparaffins to aromatics and isoparaffins. Using the catalyst and test unit described in Example 25, methylcyclohexane was added to the saturator thermostated at 0°C, the pressure was raised to 350°C. A hydrogen flow of 50 cc/min (STP) carrying 0.16 volume percent methylcyclohexane made the weight hourly space velocity of hydrocarbons approximately 0.02 grams of feed per gram of catalyst per hour. Run 17-1 shows that at 351°C, about 56% of the methylcyclohexane had reacted, yielding 8.1% toluene, 42.8% heptane isomers, and 5.2% methane. Toluene was the dehydrogenation product, the other C₇'s were paraffins produced by isomerization of the methylcyclohexane, and the methane and other C₂-C₆'s were products of carbon-carbon bond hydrogenolysis and various conversion reactions. Raising the temperature to 401°C increased the toluene selectivity to 53% with lower selectivity to other C₇ paraffin isomers. Both benzene and xylene products were evident as well as hydrogenolysis products of methane and C₂-C₆ paraffins. The tungsten cobalt eta phase catalyst showed only 10.2% methane and C₂-C₆ paraffins under conditions where most of the products were either aromatics or branched C₇ paraffin isomers. In these specific examples, for equilibration at constant carbon activity, the following reaction may be employed: 2(CO) (g) ⇄ CO₂(g) + C(s) where the CO and CO₂ are gas phase species and C(s) is the solid carbon phase available for reaction to form the desired carbide phase, dissolved carbon or free carbon. From equation (I) the equilibrium carbon activity (a c ) of a CO/CO₂ gas mixture is a c = p²co p co2 exp (- ΔG · I /RT) where ΔG · I is the standard free energy of formation of 1 mole of carbon in reaction I above at the reaction temperature T, molar gas constant R. For a fixed total reactive gas pressure and ratio of the partial pressure of CO (p CO ) to the partial pressure of CO₂ (p CO2 ) p CO /p CO2 the equilibrium carbon activity of the gas environment is fixed by equation (II). Two issues are considered in fixing the carbon activity with CO/CO₂ gas mixtures for the method of the invention: control of carbon activity should be easy and accurate and the equilibrium oxygen activity of the CO/CO₂ mixture used should be below that for which any oxide phase is stable at the reaction temperature. The equilibrium oxygen activity of a CO/CO₂ gas mixture can be calculated from the reaction: 2CO₂⇄2CO + O₂ for which the oxygen partial pressure (p O2 ) is given by p O2 = (p CO2 ) p CO exp(- ΔG · III RT ) where ΔG · III is standard free energy of formation of one mole of O₂ in equation (III) at the reaction temperature T. Equations (IV) and (II) show that the oxygen partial pressure and carbon activity at constant total reactive gas pressure P t (where P t = p CO +p CO2 ) and temperature are coupled. At constant T and P t , measurement of the oxygen partial pressure of the gas phase therefore is a unique determination of the carbon activity of the gas phase. This observation provides a simple and precise method for the determination and control of the carbon activity. The oxygen partial pressure of the gas phase may, for example, be continuously measured by means of a 7-1/2% calcia stabilized zirconia oxygen probe located ideally in the hot zone of the furnace in which the thermodynamic conversion of the reactive precursor is carried out. The carbon activity of the gas phase is then calculated by equation (II) from a knowledge of the total reaction pressure, temperature and p CO /p CO2 as determined by equation (IV). Generally, the coupling of equations I and III requires that the total pressure in the system be adjusted so that no undesirable oxide phase is stable at conditions required to form the desired carbide phase.

Claims: An eta phase composition in powder form, said powder having a surface area greater than about 2m²/g and said eta phase consisting essentially of X₆ Y₆ Z a wherein X is at least one element selected from the group consisting of Mo and W, Y is at least one element selected from the group consisting of Fe, Co and Ni and up to one element selected from the group consisting of Mo and W, Z is at least one element selected from the group consisting of C and N and a is greater than or equal to 1 but less than or equal to 2. An eta phase composition according to claim 1 comprising at least one eta phase composition selected from the group consisting of Mo₆Fe₆Z a , Mo₆Co₆Z a , Mo₆Ni₆Z a , Mo₆(FeCo)₆Z a , Mo₆(FeNi)₆Z a , Mo₆(CoNi)₆Z a , Mo₆(FeCoNi)₆Z a , W₆Fe₆Z a , W₆Co₆Z a , W₆Ni₆Z a , W₆(FeCo)₆Z a , W₆(FeNi)₆Z a , W₆(Co,Ni)₆Z a , W₆(Fe,Co,Ni)₆Z a , (W,Mo)₆Fe₆Z a , (W,Mo)₆Co₆Z a , (W,Mo)₆Ni₆Z a , (W,Mo)₆(Fe,Co)₆Z a , (W,Mo)₆(Fe,Ni)₆Z a , (W,Mo)₆(Co,Ni)₆Z a , (W,Mo)₆(Fe,Co,Ni)₆Z a , wherein Z is at least one element selected from the group consisting of carbon and nitrogen and a is greater than or equal to 1 but less than or equal to 2. A method for producing or converting hydrocarbons or alcohols, said method comprising contacting in a reducing environment at elevated temperature and pressure effective for hydrocarbon production or conversion, a fluid, carbon-containing feedstock with a catalyst comprising an eta phase composition according to claim 1 or claim 2. The method of claim 3 wherein the catalyst comprises at least one of the following eta phase compositions: Mo₆Fe₆Z a , Mo₆Co₆Z a , Mo₆Ni₆Z a , Mo₆(FeCo)₆Z a , Mo₆(FeNi)₆Z a , Mo₆(CoNi)₆Z a , Mo₆(FeCoNi)₆Z a , W₆Fe₆Z a , W₆Co₆Z a , W₆Ni₆Z a , W₆(FeCo)₆Z a , W₆(FeNi)₆Z a , W₆(Co,Ni)₆Z a , W₆(Fe,Co,Ni)₆Z a , (W,Mo)₆Fe₆Z a , (W,Mo)₆Co₆Z a , (W,Mo)₆Ni₆Z a , (W,Mo)₆(Fe,Co)₆Z a , (W,Mo)₆(Fe,Ni)₆Z a , (W,Mo)₆(Co,Ni)₆Z a , (W,Mo)₆(Fe,Co,Ni)₆Z a , wherein Z is at least one element selected from the group consisting of carbon and nitrogen. The method of claim 3 or claim 4 wherein said feedstock contains CO and the temperature and pressure conditions are selected to produce at least one hydrocarbon. The method of claim 3 or claim 4 wherein the feedstock contains CO and the temperature and pressure conditions are selected to produce at least one alcohol. The method of claim 3 or claim 4 wherein the feedstock is selected from the group consisting of unsaturated hydrocarbons, aromatic hydrocarbons and olefinic hydrocarbons and the temperature and pressure conditions are selected to reduce the feedstock. The method of claim 3 or claim 4 wherein the temperature and pressure conditions are selected to convert hydrocarbons by isomerization or dehydrogenation. A method for producing an eta phase composition, said method comprising providing a precursor compound, said precursor compound including at least two eta phase forming metals, and a ligand containing carbon, nitrogen or combinations thereof, thermally decomposing said precursor compound in a nonoxidizing atmosphere to react said carbon, nitrogen or combinations thereof derived from decomposition of said ligand with said metals to form said eta phase. The method of claim 9 wherein said eta phase forming metals are at least two metals selected from the group consisting of tungsten, molybdenum, nickel, cobalt and iron.

Inventors: CHIANELLI, RUSSELL ROBERT, JACOBSON, ALLAN JOSEPH, KUGLER, EDWIN LEE, MCCANDLISH, LARRY EUGENE
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1989
Main classification: C01B31
IPC codes: C07C29, B01J27, C07C15, C07C9, C07C5, C01B21, C01B31, C07C4, C07C1, C07C13, C07B61, C07C31