Abstract:
An eta phase composition in powder form, prepared in the absence of sulfur or sulfur bearing compounds, having a surface area greater than about 2m 2  /g and consisting of X 6  Y 6  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, Ni, Mo and W, Z is at least one element selected from the group consisting of C, N and combinations thereof such that when Z is N, a is greater than or equal to 1 but less than or equal to 2 and when Z is C, a is greater than 1 but less than or equal to 2 except when Z is C and Y is Fe, then a is greater than or equal to 1 but less than or equal to 2. The eta phase may be a carbide, nitride or carbonitride. 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, nitrogen or combinations thereof. The precursor compound is thermally decomposed in a nonoxidizing atmosphere, free of sulfur or sulfur bearing compounds, and reacts with carbon or nitrogen derived from the decomposition 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. These eta-phase composition may be used for producing or converting hydrocarbons or alchols. 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), isomerization and dehydrogenation.

Description:
This a continuation-in-part of U.S. Ser. No. 336,998 filed Apr. 12, 1989, now abandoned, which is a continuation-in-part of U.S. Ser. No. 197,356 filed May 23, 1988, now abandoned, which is based on Information and Belief. 
    
    
     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. Eta-phases can be present in steels containing, for example, nickel and molybdenum and 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, this thermal processing involves heating in the presence of sulfur or sulfur bearing compounds. For example, U.S. Pat. No. 4,595,672, Ho et al, teaches a method of producing self-promoted molybdenum sulfide and tungsten sulfide hydrotreating catalysts. The method involves heating one or more molybdate and/or tungstate catalyst precursors of the general formula ML(Mo y  W 1-y  O 4 ), where M is one or more divalent promoter metals selected from Mn, Fe, Co, Ni, Cu, Zn, and mixtures thereof and L is one or more, neutral, nitrogen-containing ligands, at least one or more of which is a chelating ligand polydentate ligand. The heating is conducted in a non-oxidizing atmosphere and in the presence of sulfur or sulfur bearing compounds, such as H 2  S. Sulfur reacts with these catalyst precursors to form sulfided materials. 
     P. Ettmayer and R. Suchentrunk, &#34;Thermal Stability of n-Carbides&#34;, Monatsh. Chem., Vol. 101(4), p. 1098-1103 (1970) also printed in Chem. Abstracts, Equilibriums and Solutions, Vol. 73, p. 313, reference article 92208g, 1970 Edition, disclose the formation of eta-phase carbides having the general formula n-M 6  M 1   6  C where M is Fe, Co or Ni and where M 1  is Mo or W. Eta-phase carbides covered in this article include: Fe 6  W 6  C, Co 6  Mo 6  C, Co 6  W 6  C, Ni 6  Mo 6  C and Ni 6  W 6  C. However, the stoichiometry of these eta-phase carbides employ a single carbon atom and only a single metal from groups M and M 1 . Moreover, the formation of Fe 6  Mo 6  C eta-phase carbides was not observed. 
     Conventional eta-phase structures have low surface area and are difficult to synthesize Therefore, they have not been known or considered for use as catalysts Also, conventional methods for making eta-phase structures do not produce high surface area eta-phase materials and are not formulated in a non-oxidizing atmosphere free of sulfur or sulfur bearing compounds. 
     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 non-oxidizing atmosphere free of sulfur or sulfur bearing compounds to react with carbon, nitrogen or combinations thereof, at an elevated temperature and pressure. 
     Another object of the invention is to provide eta-phase powder for use as a catalyst effective for hydrocarbon or alcohol production or conversion that provides results similar to those achieved with more expensive noble metals, such as platinum and palladium, conventionally used for this purpose. 
     Additional objects and advantages of this invention are set forth in the description and examples that follow. Other objectives falling within the scope of the invention 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 herein. 
     SUMMARY OF THE INVENTION 
     In accordance with the invention, the composition thereof comprises an eta-phase in powder form, prepared in the absence of sulfur or sulfur bearing compounds. The powder has a surface area greater than 2 meters 2  /gram (m 2  /g). The eta-phase is a eta-phase carbide, eta-phase nitride or eta-phase carbonitride, present either singly or in combination. The eta-phase material has a composition of the general formula X 6  Y 6  Z a  wherein X is at least one element selected from the group consisting of Mo (molybdenum) and W (tungsten), Y is at least one element selected from the group consisting of Fe (iron), Co (cobalt), Ni (nickel), Mo (molybdenum) and W (tungsten), Z is at least one element selected from the group consisting of C (carbon), N (nitrogen) and combinations thereof, and a is such that when Z is N, a is greater than or equal to 1 but less than or equal to 2 and when Z is C, a is greater than 1 but less than or equal to 2 except when Z is C and Y is Fe, then a is greater than or equal to 1 but less than or equal to 2. 
     Specifically, the eta phase materials in accordance with the invention may be: 
     Mo 6  Fe 6  Z a , Mo 6  Co 6  Z a , Mo 6  Ni 6  Z a , 
     Mo 6  (FeCo) 6  Z a , Mo 6  (FeNi) 6  Z a , Mo 6  (CoNi) 6  Z a , 
     Mo 6  (FeCoNi) 6  Z a , W 6  Fe 6  Z a , W 6  Co 6  Z a , 
     W 6  Ni 6  Z a , W 6  (FeCo) 6  Z a , W 6  (FeNi) 6  Z a , 
     W 6  (Co,Ni) 6  Z a , W(Fe,Co,Ni) 6  Z a , (W,Mo) 6  Fe 6  Z a , 
     (W,Mo) 6  Co 6  Z a , (W,Mo) 6  Ni 6  Z a , 
     (W,Mo) 6  (Fe,Co) 6  Z a , 
     (W,Mo) 6  (Fe,Ni) 6  Z a , (W,Mo) 6  (Co,Ni) 6  Z a , 
     (W,Mo) 6  (Fe,Co,Ni) 6  Z a , 
     wherein Z is at least one element selected from the group consisting of C, N and combinations thereof, and a is such that when Z is N, a is greater than or equal to 1 but less than or equal to 2 and when Z is C, a is greater than 1 but less than or equal to 2 except when Z is C and Y is Fe, then a is greater than or equal to 1 but less than or equal to 2. 
     Further in accordance with the invention, a method is provided for producing eta phase compositions. 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 that is free of sulfur or sulfur bearing compounds, and reacts 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 meters 2  /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. 
     The invention is also a method for producing or converting hydrocarbons and alcohols, including hydrogenation reactions using these eta-phase materials. 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. 
    
    
     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. The reduction is carried out in a non-oxidizing atmosphere free of sulfur or sulfur bearing compounds. 
     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: H 2  +CO C n  H 2n+2  +C n  H 2n+1  OH. 
     Specific examples demonstrating the effectiveness of Applicants&#39; eta phase composition and method employing the same in producing hydrocarbons and alcohols or converting hydrocarbons are set forth hereinafter. 
     EXAMPLE 1 
     Ni(en) 3  MoO 4  Catalyst Precursor Preparation 
     A tris(ethylenediamine) nickel molybdate, Ni(en) 3  MoO 4 , 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) 3  MoO 4  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, (NH 4 ) 6  Mo 7  O 24 .4H 2  O, was added to 500 ml of ethylenediamine, NH 2  CH 2  CH 2  NH 2 , 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, NiCl 2 .6H 2  O, were dissolved into 300 ml of distilled water. This Ni 2+   was added slowly, in aliquots, to the molybdate solution with agitation after each addition. The precipitate, Ni(en) 3  MoO 4 , 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) 3  MoO 4  were recovered. 
     EXAMPLE 2 
     Co(en) 3  MoO 4  and Fe(en) 3  MoO 4  Preparation 
     The method of Example 1 was used with the substitution of either CoCl 2 .6H 2  O or FeCl 2 .4H 2  O for the NiCl 2 .6H 2  O. In the synthesis of Fe(en) 3  MoO 4  the solutions and the precipitate were handled under an inert blanket of nitrogen gas to prevent the oxidation of Fe 2+   to Fe 3+ . 
     EXAMPLE 3 
     Preparation of [Fe(en) 3  ] 0 .5 [Ni(en) 3  ] 0 .5 MoO 4 , [Fe(en) 3  ] 0 .5 [Co(en) 3  ] 0 .5 MoO 4 , [Co(en) 3  ] 0 .5 [Ni(en) 3  ] 0 .5 MoO 4 , etc. 
     The methods of Example 1 and Example 2 were used with equimolar mixtures of aqueous Fe 2+   and Ni 2+   Fe 2+   and Co 2+ , and Co 2+  and Ni 2+   substituted respectively for the Ni 2+   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&#39;(en) 3  ] x  MoO 4  where both M and M&#39;=Fe, Co, Ni 
     The methods of Example 1 and Example 2 were used with mixtures of aqueous M 2+   and M&#39; 2+   in the molar ratio (1-x):x, where x is greater than or equal to zero less than or equal to 1, substituted for the Ni 2+   aqueous solution of Example 1. A nitrogen gas blanket was used as in the previous examples. 
     EXAMPLE 5 
     Preparation of Ni(en) 3  WO 4   
     14.5 grams of tungstric acid, H 2  WO 4 , were dissolved in 150 ml of a 1:1 mixture of concentrated NH 4  OH and water, and 150 ml of ethylenediamine. A clear solution was obtained by heating and stirring. In a separate vessel, 13.5 grams of NiCl 2 .6H 2  O was dissolved in distilled water and added to the hot tungstric acid solution. A precipitate, Ni(en) 3  WO 4 , 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) 3  WO 4  and Fe(en) 3  WO 4   
     The method of Example 5 was used with the substitution of CoCl 2 .6H 2  O or FeCl 2 .4H 2  O for NiCl 2  O.6 H2  O. In the synthesis of Fe(en) 3  WO 4  the procedure is carried out under an inert atmosphere to prevent the oxidation of Fe 2+   to Fe 3+ . 
     EXAMPLE 7 
     Preparation of [M(en) 3  ] 1-x  [M&#39;(en) 3  ] x  WO 4  where both M and M&#39;=Fe, Co, Ni 
     The methods of Example 5 and Example 6 were used with mixtures of aqueous M 2+   and M&#39; 2+   in the molar ratio (1-x):x, where x is defined as in Example 4, substituted for the Ni 2+   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&#39;(en) 3  MoO 4  salt and were synthesized by the methods of Examples 1 and 2, where M&#39; is Ni, Co and Fe. The transition metal coordination compound was placed in a quartz boat in a 1.5&#34; I.D. quartz tubular furnace and heated in a flowing mixture of equal parts by volume of He and H 2  at 1 atm 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 H 2  /He flow was replaced with He and the heating continued to 1000° C. The flow rate was then replaced with a CO 2  /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 Fe 6  Mo 6  C, Co 6  Mo 6  C, Co 6  Mo 6  C (at an elevated temperature), and Ni 6  MO 6  C. 
     
                       TABLE I______________________________________Molybdenum Eta Carbide Phases           CO.sub.2      He   Temp.   (cc/   CO     (cc/ Carbon Pco.sup.+ PcoEta-Phase   (C.°)           min)   (cc/min)                         min) Activity                                     (Torr)______________________________________Ni.sub.6 Mo.sub.6 C   1000    64.8   200    200  0.011  433Co.sub.6 Mo.sub.6 C   1000    64.8   200    200  0.011  433Fe.sub.6 Mo.sub.6 C   1000    64.8   200    200  0.011  433Co.sub.6 Mo.sub.6 C   1010    14.0   100     0   0.048  760______________________________________ 
    
     EXAMPLE 9 
     Thermodynamically Controlled Preparation of Tungsten Carbide Eta Phases 
     The reactive precursor for the synthesis of a pure Co 6  W 6  C was prepared by reductive decomposition of Co(en) 3  WO 4 . The transition metal coordination compound was placed in a quartz boat in a 1.5&#34; I.D. quartz tubular furnace and heated in a flowing mixture of equal parts by volume of He and H 2  at 1 atm 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/O 2  gas mixtures by successive addition of O 2  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) 3  WO 4  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 CO 2  /CO mixture with total pressure (P) and CO 2  /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 CO 2  /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 Co 6  W 6  C eta carbide had occurred for the precursor processed at a carbon activity, ac, of 0.1. 
     EXAMPLE 10 
     Kinetically Controlled Preparation of Ni 6  Mo 6  Z a  Eta Phase 
     A small quartz boat was filled with Ni(en) 3  MoO 4 . The boat was then placed into a 1.5&#34; I.D. quartz tubular furnace which had been preheated to 700° C. and which contained a 1:1 H 2  /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 Fe 3  Ni 3  Mo 6  Z a , Where a=1 and Fe 3  Ni 3  Mo 6  Z a , Where a=2 Eta Phase 
     A small quartz boat was filled with [Fe(en) 3  ] 0 .5 [Ni(en) 3  ] 0 .5 MoO 4 . The boat was then placed into a 1.5&#34; 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 H 2  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% O 2  in He for 1 hour 
     4% O 2  in He for 1 hour 
     6% O 2  in He for 15 minutes 
     10% O 2  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, Fe 3  Ni 3  Mo 6  Z a , where a is greater than zero but less than or equal to 1 and Fe 3  Ni 3  Mo 6  Z a , where a is greater than zero but less than or 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 pressure. The H 2  /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 CO 2 . 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%. 
     
                       TABLE II______________________________________Molybdenum Nickel Eta Phase Catalyst      Run Number      2-1   2-2       2-3     2-4______________________________________Temp.(°C.)        249     250       252   249Pressure (atm)        1.0     5.0       10.0  15.0H.sub.2 /CO inlet        3.0     3.0       3.0   3.0Feed Rate (cc/min)        40      40        80    120% CO Conversion        1.2     2.8       2.3   1.9Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons        63.8    44.0      33.5  29.2C.sub.2 hydrocarbons        27.5    14.5      9.7   7.9C.sub.3 hydrocarbons        8.6     5.0       3.5   2.8C.sub.4 hydrocarbons        --      1.6       1.5   1.3C.sub.5 hydrocarbons        --      0.5       0.4   0.5C.sub.1 alcohols        --      29.8      46.1  52.2C.sub.2 alcohols        --      4.6       5.3   5.9C.sub.3 alcohols        --      --        --    0.3______________________________________ 
    
     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 H 2  /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 and H 2  =3.0 atm. 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 H 2  /CO=3.0 and a total pressure of 4.0 atm. Both hydrocarbons and alcohols are among the products. Increasing the H 2  /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 H 2  /CO ratio to 9.0 increased the alcohol selectivity still further. When the H 2  partial pressure reached 9.0 atm, the CO partial pressure was systematically increased first to 2.0 atm, then 4.0 atm, and finally 6.0 atm. The H 2  /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 H 2  /CO ratio. 
     
                                           TABLE III__________________________________________________________________________Molybdenum Nickel Eta Phase Catalyst       Run Number       3-1 3-2   303 3-4  3-5 3-6__________________________________________________________________________Temp. (°C.)       253 253   252 256  252 252Total Pressure (atm)       4.0 7.0   10.0                     11.0 13.0                              15.0H.sub.2 Pressure (atm)       3.0 6.0   9.0 9.0  9.0 9.0CO Pressure (atm)       1.0 1.0   1.0 2.0  4.0 6.0H.sub.2 /CO inlet       3.0 6.0   9.0 4.5  2.2 1.5Feed Rate (cc/min)       40  70    100 110  130 150% CO Conversion       1.8 2.9   4.4 2.2  1.1 0.7Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons       46.1           40.0  38.8                     33.4 29.7                              27.2C.sub.2 hydrocarbons       15.8           10.6  8.8 8.5  8.5 8.7C.sub.3 hydrocarbons       5.3 3.1   2.5 2.7  3.0 3.2C.sub.4 hydrocarbons       1.2 0.5   0.5 1.4  1.3 1.2C.sub.5 hydrocarbons       0.4 0.3   0.3 0.2  0.4 0.5C.sub.1 alcohols       31.2           41.4  46.3                     49.2 51.2                              51.4C.sub.2 alcohols       --  4.0   2.9 4.7  5.9 7.9C.sub.3 alcohols       --  --    --  --   --  --__________________________________________________________________________ 
    
     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 H 2  /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 H 2  /CO ratio was maintained at 3.0 and the total pressure was 10 atmospheres. 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+2H 2 . Increased reaction temperature has a substantial effect on the rate of CO conversion to hydrocarbons. 
     
                       TABLE IV______________________________________Molybdenum Nickel Eta Phase Catalyst      Run Number      4-1   4-2       4-3     4-4______________________________________Temp.(°C.)        199     250       275   302Pressure (atm)        10.0    10.0      10.0  10.0H.sub.2 /CO inlet        3.0     3.0       3.0   3.0Feed Rate (cc/min)        40      80        120   120% CO Conversion        0.8     2.5       4.2   12.0Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons        24.2    32.6      46.4  74.2C.sub.2 hydrocarbons        9.2     7.5       7.9   8.8C.sub.3 hydrocarbons        5.4     3.1       2.5   2.7C.sub.4 hydrocarbons        2.7     1.0       0.9   0.8C.sub.5 hydrocarbons        1.3     1.1       0.5   0.3C.sub.5+ hydrocarbons        2.1     0.6       0.5   0.4C.sub.1 alcohols        49.0    49.1      38.2  11.7C.sub.2 alcohols        6.2     5.0       2.9   1.1C.sub.3 alcohols        --      --        --    --______________________________________ 
    
     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. Pat. No. 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 pressure, and a H 2  /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. 
     
                       TABLE V______________________________________Comparison of Molybdenum Nickel Eta Phase WithMolybdenum Oxycarbonitride For CO Hydrogenation          Run Number          5-1    5-2          Catalyst          MoNi          eta phase                 MoO.sub. xC.sub.y N.sub.z______________________________________Temp. (°C.)            250      249Pressure (atm)   10.0     10.0H.sub.2 /CO inlet            1.0      1.0Feed Rate (cc/min)            100      120% CO Conversion  0.66     1.60Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons            28.0     50.2C.sub.2 hydrocarbons            10.8     18.9C.sub.3 hydrocarbons            4.4      8.5C.sub.4 hydrocarbons            1.5      3.2C.sub.5 hydrocarbons            0.8      1.6C.sub.5+ hydrocarbons            0.9      12.2C.sub.1 alcohols 37.5     5.1C.sub.2 alcohols 14.4     0.4C.sub.3 alcohols 1.3      --C.sub.4 alcohols 0.5      --______________________________________ 
    
     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 H 2  /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 H 2  /CO inlet ratio was maintained at 3.0 and the total pressure was 10 atmospheres. 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. 
     
                       TABLE VI______________________________________Molybdenum Cobalt Eta Phase Catalyst      Run Number      6-1   6-2       6-3     6-4______________________________________Temp.(°C.)        203     250       275   299Pressure (atm)        10.0    10.0      10.0  10.0H.sub.2 /CO inlet        3.0     3.0       3.0   3.0Feed Rate (cc/min)        120     120       120   120% CO Conversion        0.8     9.6       20.4  54.2Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons        17.1    32.0      44.1  57.9C.sub.2 hydrocarbons        13.4    19.9      23.4  24.8C.sub.3 hydrocarbons        11.1    12.4      11.9  9.8C.sub.4 hydrocarbons        6.2     5.8       4.7   3.1C.sub.5 hydrocarbons        4.1     3.2       2.3   1.4C.sub.5+ hydrocarbons        10.3    7.7       5.3   2.2C.sub.1 alcohols        29.3    14.5      7.5   0.7C.sub.2 alcohols        8.5     4.2       0.9   0.1C.sub.3 alcohols        --      0.3       --    --______________________________________ 
    
     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 H 2  /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 and H 2  =3.0 atm. 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 H 2  /CO 3.0 and a total pressure of 4 atm. Both hydrocarbons and alcohols are among the products. Increasing the H 2  /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 H 2  /CO ratio to 9.0 continued the trend toward more alcohols and lighter hydrocarbon products. When the H 2  inlet partial pressure reached 9.0 atm, the CO inlet partial pressure was systematically increased, first to 2.0 atm and then to 4.0 atm. Increased CO pressure reduced the catalyst selectivity toward methane and increased selectivity toward methanol and other light alcohols. 
     
                       TABLE VII______________________________________Molybdenum Cobalt Eta Phase Catalyst     Run Number     7-1   7-2     7-3      7-4   7-5______________________________________Temp.(°C.)       249     247     254    247   248Pressure (atm)       4.0     7.0     10.0   11.0  13.0H.sub.2 Pressure       3.0     6.0     9.0    9.0   9.0CO Pressure 1.0     1.0     1.0    2.0   4.0H.sub.2 /CO inlet       3.0     6.0     9.0    9.0   9.0Feed Rate (cc/min)       40      70      100    110   130% CO Conversion       11.2    15.3    20.5   8.5   3.9Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons       33.5    40.5    45.3   35.2  28.9C.sub.2 hydrocarbons       25.7    22.3    20.4   19.4  18.2C.sub.3 hydrocarbons       16.7    11.9    10.0   11.0  11.4C.sub.4 hydrocarbons       7.4     5.1     4.1    4.5   5.0C.sub.5 hydrocarbons       4.2     2.5     1.8    2.5   2.9C.sub.5+ hydrocarbons       10.0    7.2     4.7    5.8   7.2C.sub.1 alcohols       2.6     9.5     12.6   17.8  19.7C.sub.2 alcohols       --      1.1     1.2    3.7   6.2C.sub.3 alcohols       --      --      --     0.2   0.6______________________________________ 
    
     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 H 2  /CO reactions. Tests were carried out at 10.0 atm pressure and a constant inlet H 2  /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 pressure increased reaction rate and shifted the product distribution toward lower molecular weights. 
     
                       TABLE VIII______________________________________Molybdenum Iron Eta Phase Catalyst       Run Number       8-1      8-2     8-3______________________________________Temp.(°C.)         200        249     302Pressure (atm)         10.0       10.0    10.0H.sub.2 /CO inlet         3.0        3.0     3.0Feed Rate (cc/min)         40         80      120% CO Conversion         3.2        9.7     38.4Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons         15.0       25.6    44.5C.sub.2 hydrocarbons         11.4       17.9    26.2C.sub.3 hydrocarbons         11.5       14.4    14.2C.sub.4 hydrocarbons         7.2        7.3     5.6C.sub.5 hydrocarbons         5.5        4.4     2.9C.sub.5+ hydrocarbons         19.4       12.4    6.6C.sub.1 alcohols         15.2       12.7    0.8C.sub.2 alcohols         12.4       4.5     0.2C.sub.3 alcohols         2.5        0.9     --______________________________________ 
    
     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 total pressure, a H 2  /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. 
     
                       TABLE IX______________________________________Potassium Promoter Affects onMolybdenum Iron Eta Phases      Run Number      9-1   8-2       9-2     8-3______________________________________% Potassium  3.2     0.0       3.2   0.0Temp.(°C.)        253     249       304   302Pressure (atm)        10.0    10.0      10.0  10.0H.sub.2 /CO inlet        3.0     3.0       3.0   3.0Feed Rate (cc/min)        80      80        80    80% CO Conversion        1.0     9.7       5.0   38.4Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons        12.8    25.6      22.4  44.5C.sub.2 hydrocarbons        12.9    17.9      19.9  26.2C.sub.3 hydrocarbons        9.8     14.4      12.6  14.2C.sub.4 hydrocarbons        6.2     7.3       6.7   5.6C.sub.5 hydrocarbons        4.8     4.4       4.9   2.9C.sub.5+ hydrocarbons        16.9    12.4      11.8  6.6C.sub.1 alcohols        19.0    12.7      10.6  0.8C.sub.2 alcohols        16.3    4.5       9.9   0.2C.sub.3 alcohols        1.4     0.9       1.3   --______________________________________ 
    
     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 H 2  /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 H 2  /CO inlet ratio was 3.0 and the total pressure was 10.0 atm. 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. 
     
                       TABLE X______________________________________Molybdenum Nickel-Iron Eta Phase Catalyst       Run Number       10-1     10-2    10-3______________________________________Temp.(°C.)         199        251     300Pressure (atm)         10.0       10.0    10.0H.sub.2 /CO inlet         3.0        3.0     3.0Feed Rate (cc/min)         40         80      120% CO Conversion         2.6        6.9     25.9Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons         18.8       30.8    52.3C.sub.2 hydrocarbons         12.0       16.1    22.0C.sub.3 hydrocarbons         9.2        9.9     10.4C.sub.4 hydrocarbons         5.4        4.8     4.3C.sub.5 hydrocarbons         2.9        2.6     2.1C.sub.5+ hydrocarbons         7.8        6.1     4.5C.sub.1 alcohols         29.5       22.3    3.9C.sub.2 alcohols         12.5       6.5     0.5C.sub.3 alcohols         2.0        1.0     --______________________________________ 
    
     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 pressure and H 2  /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. 
     
                       TABLE XI______________________________________Comparison of Molybdenum Eta Phase Catalysts      Run Number      10-2  4-2       6-2     8-2      Group VIII Metals      NiFe  Ni        Co      Fe______________________________________Temp.(°C.)         251     250       250   249Pressure (atm)        10.0    10.0      10.0  10.0H.sub.2 /CO inlet        3.0     3.0       3.0   3.0Feed Rate (cc/min)        80      80        120   80% CO Conversion        6.9     2.5       9.6   9.7Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons        30.8    32.6      32.0  25.6C.sub.2 hydrocarbons        16.1    7.5       19.9  17.9C.sub.3 hydrocarbons        9.9     3.1       12.4  14.4C.sub.4 hydrocarbons        4.8     1.0       5.8   7.3C.sub.5 hydrocarbons        2.6     1.1       3.2   4.4C.sub.5+ hydrocarbons        6.1     0.6       7.7   12.4C.sub.1 alcohols        22.3    49.1      14.5  12.7C.sub.2 alcohols        6.5     5.0       4.2   4.5C.sub.3 alcohols        1.0     --        0.3   0.9______________________________________ 
    
     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 H 2  /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 H 2  /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. 
     
                       TABLE XII______________________________________Tungsten Nickel Eta Phase Catalyst      Run Number      12-1  12-2      12-3    12-4______________________________________Temp.(°C.)        172     199       223   252Pressure (atm)        10.0    10.0      10.0  10.0H.sub.2 /CO inlet        3.0     3.0       3.0   3.0Feed Rate (cc/min)        40      40        40    40% CO Conversion        0.73    1.7       2.1   6.0Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons        45.0    46.8      53.3  65.2C.sub.2 hydrocarbons        12.8    11.1      10.2  9.0C.sub.3 hydrocarbons        5.1     4.1       3.6   2.7C.sub.4 hydrocarbons        1.6     1.2       1.0   0.6C.sub.5 hydrocarbons        0.7     0.4       0.5   0.3C.sub.5+ hydrocarbons        2.1     0.7       0.9   0.3C.sub.1 alcohols        28.1    31.1      27.8  20.5C.sub.2 alcohols        4.6     4.6       2.6   1.4C.sub.3 alcohols        --      --        --    --______________________________________ 
    
     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 H 2  /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 H 2  /CO ratio was maintained at 3.0 and the total pressure was maintained at 10 atm. 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. 
     
                       TABLE XIII______________________________________Tungsten Cobalt Eta Phase Catalyst     Run Number     13-1  13-2    13-3     13-4  13-5______________________________________Temp.(°C.)       201     227     252    278   304Pressure (atm)       10.0    10.0    10.0   10.0  10.0H.sub.2 /CO inlet       3.0     3.0     3.0    3.0   3.0Feed Rate (cc/min)       40      40      40     80    120% CO Conversion       1.5     4.2     10.3   13.1  20.9Product Selectivity(wt. %, CO.sub.2 free)C.sub.1 hydrocarbons       27.1    29.9    36.6   44.0  54.5C.sub.2 hydrocarbons       18.1    20.1    23.0   25.1  26.4C.sub.3 hydrocarbons       13.7    13.3    13.6   12.7  10.5C.sub.4 hydrocarbons       6.9     6.1     5.7    4.7   3.3C.sub.5 hydrocarbons       3.6     3.9     3.2    2.4   1.5C.sub.5+ hydrocarbons       9.9     9.2     7.4    5.3   3.3C.sub.1 alcohols       12.9    11.2    8.4    4.6   0.6C.sub.2 alcohols       7.8     6.3     2.0    1.2   --C.sub.3 alcohols       --      --      --     --    --______________________________________ 
    
     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. A sample of tungsten cobalt eta phase catalyst weighing 1.02 g was loaded into the reactor and reduced in flowing hydrogen at 90 cc/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 with hydrogen, the saturator filled with 1-hexene and thermostated to 0° C., and the hydrogen flow rate controlled at 50 cc/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. 
     
                       TABLE XIV______________________________________Tungsten Cobalt Eta Phase Catalyst         Run Number         feed     14-1    14-2______________________________________Temp.(°C.)           --         24      97Pressure (atm)  --         9.9     9.9H.sub.2 Feed Rate (cc/min)           --         50      50H.sub.2 /HC inlet           --         140     140WHSV (g/g/hr)*  --         0.08    0.08Analysis (wt. %)n-hexane        0.0        11.0    100.0hexenes         100.0      89.0    0.00CH.sub.4        0.00       0.00    0.00Other C.sub.2 -C.sub.6           0.00       0.00    0.00______________________________________ *weight hourly space velocity 
    
     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 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 between 1 and 60 atmospheres. A sample of tungsten nickel eta phase cataylst weighing 1.00 g was loaded into the reactor and reduced in flowing hydrogen at 80 cc/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 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. 
     
                       TABLE XV______________________________________Tungsten Nickel Eta Phase Catalyst       Run Number       feed   15-1    15-2      15-3______________________________________Temp.(°C.)         --       255     201     152Pressure (atm)         --       21.3    21.3    21.3H.sub.2 Feed Rate (cc/min)         --       80      80      80HC Feed Rate (g/hr)         --       0.50    0.50    0.50H.sub.2 /HC inlet         --       33      33      33WHSV (g/g/hr)*         --       0.5     0.5     0.5Analysis (wt. %)cyclohexane   0.07     100.0   100.0   100.0benzene       97.93    0.00    0.00    0.00CH.sub.4      0.00     0.00    0.00    0.00Other C.sub.2 -C.sub.6         0.00     0.00    0.00    0.00______________________________________ *weight hourly space velocity 
    
     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% naphthylene in benzene. The reactor temperature was raised from room temperature to 250° C. and the unit pressurized with hydrogen to 21.3 atm. 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 naphthylene 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%. 
     
                       TABLE XVI______________________________________Tungsten Nickel Eta Phase Catalyst       Run Number       feed   16-1    16-2      16-3______________________________________Temp.(°C.)         --       267     313     361Pressure (atm)         --       21.3    21.3    21.3H.sub.2 Feed Rate (cc/min)         --       80      80      80HC Feed Rate (g/hr)         --       1.33    1.33    1.33H.sub.2 /HC inlet         --       13      13      13WHSV (g/g/hr)*         --       1.33    1.33    1.33Analysis (wt. %)cyclohexane   0.06     85.20   67.25   32.76benzene       85.21    0.02    16.71   51.13trans-decalin 0.01     9.26    9.86    4.51cis-decalin   0.02     5.15    3.74    1.85tetralin      0.08     0.25    1.06    2.58naphthalene   14.61    0.05    0.11    0.92CH.sub.4      0.00     0.00    0.03    0.56Other C.sub.2 -C.sub.6         0.00     0.05    0.46    2.19Other C.sub.7 -C.sub.10         0.00     0.02    0.78    3.49______________________________________ *weight hourly space velocity 
    
     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 C 7  &#39;s were paraffins produced by isomerization of the methylcyclohexane, and the methane and other C 2  -C 6  &#39;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 C 7  paraffin isomers. Both benzene and xylene products were evident as well as hydrogenolysis products of methane and C 2  -C 6  paraffins. The tungsten cobalt eta phase catalyst showed only 10.2% methane and C 2  -C 6  paraffins under conditions where most of the products were either aromatics or branched C 7  paraffin isomers. 
     
                       TABLE XVII______________________________________Tungsten Cobalt Eta Phase Catalyst         Run Number         feed    17-1    17-2______________________________________Temp.(°C.)           --        351     401Pressure (atm)  --        10.0    10.0H.sub.2 Feed Rate (cc/min)           --        50      50HC Feed Rate (g/hr)           --        0.02    0.02H.sub.2 /HC inlet           --        625     625WHSV (g/g/hr)*  --        0.02    0.02Analysis (wt. %)methylcyclohexane           99.69     43.55   9.77toluene         0.31      8.11    52.26Other C.sub.7   --        42.80   25.09xylenes         --        --      0.68benzene         --        0.15    2.00Other C.sub.2 -C.sub.6           --        0.15    3.45CH.sub.4        --        5.23    6.74______________________________________ *weight hourly space velocity 
    
     In these specific examples, for equilibration at constant carbon activity, the following reaction may be employed: 
     
         2(CO) (g) CO.sub.2 (g)+C(s)                                (I) 
    
     where the CO and CO 2  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/CO 2  gas mixture is ##EQU1## where G° 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 CO 2  (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/CO 2  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/CO 2  mixture used should be below that for which any oxide phase is stable at the reaction temperature. The equilibrium oxygen activity of a CO/CO 2  gas mixture can be calculated from the reaction: 
     
         2CO.sub.2 2CO+O.sub.2                                      (III) 
    
     for which the oxygen partial pressure (p O2 ) is given by ##EQU2## where G° III  is standard free energy of formation of one mole of O 2  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 71/2% 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.