Patent Publication Number: US-4096164-A

Title: Process for producing ethanol, acetic acid and/or acetaldehyde, from synthesis gas

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is related to copending U.S. applications Ser. No. 650,799, filed Jan. 20, 1976, U.S. application Ser. No. 541,660, filed Jan. 16, 1975, now abandoned, U.S. application Ser. No. 590,717, filed June 26, 1975, now U.S. Pat. No. 4,014,913, and U.S. application Ser. No. 669,480 filed on even date herewith, now abandoned, and describes a method of increasing the proportion of ethanol among the two-carbon oxygenated compounds produced by the processes described in those applications. 
    
    
     BACKGROUND 
     This invention concerns an improvement in the selective preparation of two-carbon atom oxygenated hydrocarbons, namely acetic acid, ethanol, and/or acetaldehyde, from synthesis gas. More particularly, the invention concerns reaction of synthesis gas in the presence of a catalyst containing rhodium in combination with molybdenum and/or tungsten under heterogeneous reaction conditions to produce a mixture of such two-carbon atom compounds in which ethanol is the major component. 
     The preparation of hydrocarbons and oxygenated hydrocarbons from synthesis gas (essentially a mixture of carbon monoxide and hydrogen with varying amounts of carbon dioxide) has received extensive study and has achieved commercial adoption. Reaction conditions generally involve temperatures on the order of 150°-450° C., pressures from atmospheric to about 10,000 psig, and hydrogen-to-carbon monoxide ratios in the range of 4:1 to about 1:4, with an iron group or a noble metal group hydrogenation catalyst. 
     One serious disability of most synthesis gas processes has been the non-selective or non-specific nature of the product distribution. Catalysts which possess acceptable activity generally tend to give a wide spectrum of products, for example, hydrocarbons and oxygenated hydrocarbons having a broad distribution of carbon atom contents. This not only complicates the recovery of desired products, but results in the wastage of reactants to commercially uninteresting byproducts. 
     Copending application Ser. Nos. 650,799, 541,660, and 590,717 describe processes for the selective preparation of two-carbon atom oxygenated hydrocarbons, namely, acetic acid, ethanol, and/or acetaldehyde, using rhodium-containing catalysts. 
     SUMMARY OF THE INVENTION 
     It has now been discovered that it is possible to modify the catalyst so as to shift the distribution of two-carbon atom oxygenated products in favor of ethanol while retaining the selectivity of the overall reaction toward said two-carbon atom oxygenated compounds. The process of the invention involves contacting synthesis gas with a catalyst comprising rhodium in combination with molybdenum and/or tungsten under suitable reaction conditions. In a preferred embodiment of the invention, the catalyst also contains manganese to improve the kinetics of the reaction with regard to the formation of two-carbon atom products. The use of manganese in conjunction with rhodium as a catalyst for selectively producing two-carbon atom compounds from synthesis gas is disclosed in the aforementioned Ser. No. 590,717. 
    
    
     PROCESS DISCUSSION 
     The reaction is conducted at reaction conditions of temperature, pressure, gas composition and space velocity correlated so as to collectively produce acetic acid, ethanol, and acetaldehyde in an amount which is at least about 50 weight percent, preferably at least about 75 weight percent, of the two and more carbon atom compounds obtained by the reaction. Desirably, the reaction is conducted at these correlated conditions to achieve product efficiencies based on carbon consumption in excess of 10 percent, and frequently in excess of 50 percent. By suitable choice of catalyst composition, that is, the proportions of rhodium, molybdenum and/or tungsten in the catalyst, the reaction may be conducted so that the proportion of ethanol in the two-carbon oxygenated products is at least about 30 percent, and is readily made about 80 percent, and may be as high as 95 percent or more. A characteristic feature of these catalysts is that, in general, as the proportion of ethanol in the two-carbon oxygenated products increases the production of methanol and higher molecular weight alcohols also increases. 
     At optimum reaction conditions, and particularly at relatively low conversions, there is little conversion to three-carbon atom and higher hydrocarbons and oxygenated hydrocarbons, and conversion to methane and methanol may readily be minimized. The reaction efficiency, or selectivity, to these two-carbon atom compounds is invariably at least about 10%, and is usually upwards of about 25%; under the preferred conditions it exceeds 50% and, under optimum conditions, can reach 90% or more. &#34;Selectivity&#34; is defined herein as the percentage of carbon atoms converted from carbon monoxide to a specified compound or compounds other than CO 2 . 
     Thus, the independent reaction variables are correlated so as to favor the formation of a substantial proportion of the desired two-carbon atom oxygenated hydrocarbons (acetic acid, ethanol, and/or acetaldehyde). This proportion, expressed as carbon conversion efficiency, is usually upwards of 25% and frequently exceeds 50%. 
     In one aspect of the invention, this correlation is a combination of conditions which result in maintaining moderate reaction conditions to thereby limit the conversion of CO to not more than about one-fourth, preferably not more than about one-eighth. As will be discussed in detail below, this may be achieved primarily by a combination of high space velocity and low temperature, but other factors (e.g., H 2  /CO ratio, catalyst activity, pressure, bed geometry, etc.) also affect the conversion. At high conversions, it has been noted that hydrocarbons and higher carbon number oxygenated hydrocarbons are produced in excess, with a resulting loss in efficiency to two-carbon atom compounds. 
     Conditions of temperature, of pressure, and of gas composition are usually within the ranges that are essentially conventional for synthesis gas conversions, particularly those employed in the production of methanol. Thus, existing technology and, in some instances, existing equipment may be used to effect the reaction. 
     The reaction is highly exothermic, with both the thermodynamic equilibrium and the kinetic reaction rates being governed by the reaction temperature. Average catalyst bed temperatures are usually within the range of about 150°-450° C., but for optimum conversions, bed temperatures are kept within the range of about 200°-400° C., typically about 250°-350° C. 
     The reaction temperature is an important process variable, affecting not only total productivity but selectivity toward one or more of the desired two-carbon atom products. Over relatively narrow temperature ranges, as for example 10° or 20° C., an increase in temperature may somewhat increase total synthesis gas conversion, tending to increase the efficiency of ethanol production and decrease the efficiency of acetic acid and acetaldehyde production. At the same time, however, higher temperatures favor methane production, and apparently methane production increases much more rapidly at higher temperatures than do conversions to the more desirable two-carbon atom products. Thus, for a given catalyst and with all other variables held constant, the optimum temperature will depend more on product and process economics than on thermodynamic or kinetic considerations, with higher temperatures tending to increase the production of oxygenated products but disproportionately increasing the co-production of methane. 
     In the discussions above the indicated temperatures are expressed as average, or mean, reaction bed temperatures. Because of the highly exothermic nature of the reaction, it is desirable that the temperature be controlled so as not to produce a runaway methanation, in which methane formation is increased with higher temperature, and the resulting exotherm increases the temperature further. To accomplish this, conventional temperature control techniques are utilized, as for example, the use of fluidized bed reaction zones, the use of multi-stage fixed bed adiabatic reactors with inter-stage cooling, or relatively small catalyst particles placed in tube-and-shell type reactors with a coolant fluid surrounding the catalyst-filled tubes. In this regard, reference is made to U.S. application Ser. No. 590,718, filed on June 26, 1975. 
     The reaction zone pressure is desirably within the range of about 15 psig to about 10,000 psig, economically within the range of about 300-5,000 psig. Higher reaction zone pressures increase the total weight of product obtained per unit time and likewise improve the selectivity toward two-carbon atom compounds. 
     The ratio of hydrogen to carbon monoxide in the synthesis gas may vary widely. Normally the mole ratio of hydrogen to carbon monoxide is within the range of 20:1 to 1:20, or preferably within the range of about 5:1 to about 1:5. However, in some instances, it may be advantageous to operate with a hydrogen to carbon monoxide mole ratio as low as about 1:200. In most of the experimental work reported herein the mole ratio of the hydrogen to carbon monoxide is about 1:1. Increasing the ratio tends to increase the total rate of reaction, sometimes quite significantly, and has a small though favorable effect on production of two-carbon atom products, but concurrently increases selectivity to methane. Increasing the hydrogen to carbon monoxide ratio also favors the formation of more highly reduced products, that is, ethanol rather than acetaldehyde or acetic acid. 
     Carbon dioxide, normally present in an amount of up to about 10 mole percent in the synthesis, gas has essentially no effect. If a recycle operation is conducted, in which all or part of the reacted gas is recycled to the catalyst zone, it is desirable to remove oxygenated hydrocarbons before recycling. 
     One of the features of the present invention is the recognition that a low conversion, e.g., preferably less than 20% of the CO, favors the formation or production of a substantial proportion of acetic acid, ethanol and acetaldehyde, generally in excess of 10%. This conversion is conveniently achieved by employing a high space velocity correlated with other reaction variables (e.g., temperature, pressure, gas composition, catalyst, etc.). Space velocities in excess of about 10 3  gas hourly space velocity (volumes of reactant gas, at 0° C and 760 mm mercury pressure, per volume of catalyst per hour, commonly referred to as &#34;GHSV&#34;) are generally employed, although it is preferable that the space velocity be within the range of about 10 4  to about 10 6  per hour. Excessively high space velocities result in uneconomically low conversions, while excessively low space velocities cause the production of a more diverse spectrum of reaction products, including higher boiling hydrocarbons and oxygenated hydrocarbons. 
     The rhodium-molybdenum and rhodium-tungsten catalysts are rhodium provided in combination with molybdenum and/or tungsten upon a support material. This is typically effected by depositing rhodium and molybdenum and/or tungsten onto a particulate support material and placing the supported combination into the reaction zone. For purposes of the invention, the composition of the catalyst may also advantageously include other components, such as, manganese or iron, the use of which, in conjunction with rhodium, is disclosed in the aforementioned copending application Ser. Nos. 590,717, and 541,660, respectively. 
     On the basis of experience to date the amount of catalysts on the support should range from about 0.01 weight percent to about 25 weight percent, based on the combined weight of the metal catalyst and the support material. Preferably, the amount of catalyst is within the range of about 0.1 to about 10 weight percent. 
     The mole ratio of molybdenum and/or tungsten to rhodium in the catalyst should not be less than 1:1000 (i.e., 0.001) in order to gain some advantage. 
     A relatively high surface area particulate support, e.g., one having a surface area upwards of about 1.0 square meters per gram (BET low temperature nitrogen adsorption isotherm method), is preferred, desirably upwards of about 10 square meters per gram, although surface area alone is not the sole determinative variable. Based on research to date, silica gel is preferred as the catalyst base or support, with graphite, graphitized carbon, alpha alumina, manganese oxides, magnesia, eta-alumina, gamma-alumina, and active carbon being less desirable. Zeolitic molecular sieves, primarily the higher silica-to-alumina crystalline zeolites, also have promise. 
     For the purpose of this invention, it is believed that rhodium in combination with molybdenum and/or tungsten deposited on particles of manganese oxides is the same or not significantly different from rhodium and molybdenum and/or tungsten codeposited with manganese on any of the above support materials, including manganese oxides. 
     The rhodium and molybdenum and/or tungsten may be deposited onto the base or support by any of the techniques commonly used for catalyst preparation, as for example, impregnation from an organic or inorganic solution, precipitation, coprecipitation, or cation exchange (on a zeolite). Conveniently, a solution of an inorganic or organic rhodium compound and a molybdenum compound or a tungsten compound is appropriately contacted with the support material, and the support then dried and heated, the latter advantageously under reducing conditions, to form the finely dispersed molybdenum-and/or tungsten-containing rhodium catalyst. These materials may be deposited concurrently or sequentially. It suffices for the present to say that inorganic or organic rhodium and molybdenum and/or tungsten compounds are appropriately contacted with the support material, and the support then dried and heated, the latter advantageously under reducing conditions, to form the finely dispersed rhodium and molybdenum and/or tungsten combination. 
     The rhodium deposited is typically in metal form, desirably as fine discrete particles. The form of the molybdenum or tungsten component is, however, not completely appreciated. It may be chemically associated with the rhodium or it may be in a physical admixture with the rhodium. For example, molybdenum and/or tungsten may be alloyed with the rhodium or not, in the form of a metal or an oxidized state of the metal, or it may be in the form of an oxide, a silicate, carbonate, or the like. 
     DESCRIPTION OF TEST REACTOR 
     The reactors used in these studies were either a 316 stainless steel or an internally gold-plated, bottom-agitated &#34;Magnedrive&#34; autoclave of the J. M. Berty design with a centrally positioned catalyst basket and a side product effluent line. It is of the type depicted in FIG. 1 of the paper by Berty, Hambrick, Malone and Ullock, entitled &#34;Reactor for Vapor-Phase Catalytic Studies&#34;, presented as Preprint 42E at the Symposium on Advances in High-Pressure Technology -- Part II, Sixty Fourth National Meeting of the American Institute of Chemical Engineers (AIChE), at New Orleans, La., on March 16-20, 1969 and obtainable from AIChE at 345 East 47th Street, New York, N.Y. 10017. A variable speed, magnetically driven fan continuously recirculated the reaction mixture over the catalyst bed. The following modifications were found to facilitate operation and inhibit run-away methanation reactions. 
     1. Hydrogen feed gas was introduced continuously at the bottom of the autoclave through the well for the shaft of the Magnedrive agitator. 
     2. Carbon monoxide feed gas was introduced continuously through a separate port at the bottom of the autoclave, in order to avoid a hydrogen-rich zone in the autoclave. 
     Effluent gases are removed through a port in the side of the reactor. Condensable liquid products are removed from the exit stream in a brine-cooled condenser at ca. 5° to 10° C. and are collected in a holding tank under pressure. The non-condensable components of the exit stream are vented through a wet test meter at atmospheric pressure to determine their total volume. A rubber septum in the atmospheric pressure line permits syringe sampling of the non-condensable gases. No external recycle is employed. 
     DESCRIPTION OF THE TEST PROCEDURE 
     The bulk volume of a weighed catalyst sample is determined, and the sample is placed in the catalyst basket. The quantity of catalyst charged varies from about 4 grams to about 60 grams. The quantity of a particular catalyst to be charged is chosen to give an estimated reactant gas conversion of less than 10 percent. Gold-plated screens and thin layers of glass wool are placed above and below the catalyst bed to prevent circulation of solid fines. The catalyst basket is charged to the reactor, and the reactor is sealed. The sealed reactor and the process lines are pressure tested at ambient temperatures to a pressure about 500 to 1000 psig in excess of the maximum anticipated working pressure. Nitrogen, hydrogen, or a mixture of the two is used for this test. 
     When the reactor is shown to be leak free, pure hydrogen is passed through the reactor, and the temperature is raised to about 240° C. The hydrogen and carbon monoxide flows are then adjusted to give the desired steady-state ratio at the desired approximate purge rate. The purge rate is typically from about 250 STP* liters/hr. to about 800 STP* liters/hr. The hydrogen-carbon monoxide ratio is determined by gas chromatographic analysis of an effluent gas aliquot. 
    
     When the appropriate gas composition is obtained, the reactor temperature is raised to the value desired. A period from about 0.5 hour to about one hour is allowed for the reactor to reach a steady state at the new temperature. The liquid product trap is then drained, a wet test meter reading is taken, and the time is noted as the beginning of a run. During the course of a run, one or more effluent gas samples are analyzed for hydrogen, carbon monoxide, acetaldehyde, methane, and other volatile hydrocarbons. At the end of a run, the liquid product is collected, and the volume of effluent gas is noted. The liquid product is analyzed by gas chromatography. 
     Succeeding runs with the same catalyst may be made either at the same conditions or at new conditions of temperature or feed gas flow rates. If any of these conditions are changed, approximately one hour is allowed for the reactor to come to a new steady-state before beginning a new run. 
     PREPARATION OF CATALYSTS 
     Catalysts cited in the table below were all prepared by essentially the following sequence of steps: The desired quantities of rhodium trichloride, and one or more of ammonium heptamolybdate tetrahydrate, ammonium metatungstate, manganese nitrate, and/or iron (III) nitrate, were dissolved in distilled water at ambient temperature. Ammonium metatungstate was prepared as an aqueous solution in accordance with the disclosure of U.S. Pat. No. 1,267,585. The volume of distilled water taken for the preparation of this solution was chosen to just fill the void volume (pores) of the support sample being impregnated. Davison ™ Grade 59 silica gel (8-20 mesh--U.S. Sieves) was placed in a vacuum flask. The top of the flask was sealed with a rubber septum, and the flask was evacuated through the side arm. A syringe needle was then used to inject the solution onto the evacuated support. When addition was complete, the impregnated support was allowed to stand at one atmosphere for ca. 30 minutes. It was then carefully dried in a nitrogen atmosphere using the following sequence: 80° C. (for 1 hr.); 110° C. (2 hrs.); 150° C (2 hrs.); 250° C. (2 hrs.). The dried, impregnated support was placed in a quartz tube through which hydrogen was continuously passed. The temperature was raised from 100° to 500° C., over a six hour period and then held at 500° C. for 1 hour. The reduced catalyst was cooled to ambient temperature in an atmosphere of flowing nitrogen or hydrogen. 
     Table I below summarizes the data for a series of silica-gel supported rhodium catalysts containing one or more of the following elements: molybdenum, tungsten, manganese and iron, which were tested at 300° C., 1,000 psig total pressure, and a hydrogen to carbon monoxide mole ratio of about unity, according to the aforementioned test procedure in the test reactor. Ethyl esters and acetates which were formed were included as ethanol and acetic acid in determining productivities and selectivities as used in the data herein. That is, in calculating ethanol and acetic acid values, credit was taken for quantities obtainable by hydrolysis of esters determined to be present. 
     Table I shows that rhodium-containing catalysts (examples E-AB) are much more active for the synthesis of two-carbon atom oxygenated chemicals than are molybdenum (example A), tungsten (example B), manganese (example C) or iron (example D) catalysts. Test data shown for rhodium (examples E-H) as well as that for iron manganese, and rhodium-manganese (examples I-L) catalysts have been disclosed in copending application Ser. Nos. 650,799, 541,660, and 590,717, and are included herein to provide a basis of comparison for the various catalyst compositions. 
     Examples M and N teach that incorporating molybdenum into a rhodium catalyst produces a catalyst which is active for the synthesis of two-carbon atom chemicals and is capable of producing a mixture of two-carbon atom chemicals in which ethanol is the major component. These examples also demonstrate that rhodium-molybdenum catalysts are more active for the synthesis of methanol and, probably, higher carbon number alcohols than are rhodium or rhodium-manganese catalysts. Copending application Ser. No. 669,480 is directed to a process and catalyst composition for inhibiting such methanol formation while maintaining the selectivity of the reaction toward two-carbon atom products. 
     Examples U and V teach that incorporating tungsten into a rhodium catalyst has a similar effect on reaction kinetics and product distribution as molybdenum addition. That is, the resulting catalyst is active for the synthesis of two-carbon chemicals and can produce a mixture of two-carbon chemicals in which ethanol is the major component. The examples also suggest that rhodium-tungsten catalysts are more selective for other alcohols than are rhodium or rhodium-manganese catalysts. 
     Examples O-T show that rhodium, molybdenum and manganese may be advantageously combined to produce a catalyst which has the enhanced activity associated with rhodium-manganese catalysts as well as the enhanced ethanol preference associated with the rhodium-molybdenum catalysts. 
     Similarly, examples W-Z show that rhodium, molybdenum, tungsten, and iron may be advantageously combined to produce a catalyst which is active for the synthesis of two-carbon atom chemicals and which can produce a mixture of such chemicals in which ethanol is the major component. The effect of incorporating iron into a rhodium catalyst has been previously described in copending application Ser. No. 541,660. 
     Examples AA and AB show that rhodium, molybdenum and tungsten may also be combined to achieve this advantage. 
     
                                           TABLE I                                 
__________________________________________________________________________
COMPARISON.sup.a OF ETHANOL-SELECTIVE, RHODIUM-BASED CATALYSTS            
                      Dis- Carbon Efficiency, %.sup.c                     
                                                     Ethan-               
                                                          Rate to         
                      per- Hydro-      n- n-         ol                   
                                                          C.sub.2 Pro-    
Catalyst              sion.sup.(b)                                        
                           Car-                                           
                               Meth-                                      
                                   Ethan-                                 
                                       Prop                               
                                          But                             
                                             Acetal-                      
                                                 Acetic                   
                                                     ference              
                                                          ducts.sup.(f)   
Ex.                                                                       
   % Rh                                                                   
       % Mo                                                               
           % W                                                            
              % Mn                                                        
                  % Fe                                                    
                      %    bon.sup.(g)                                    
                               anol                                       
                                   ol.sup.(d)                             
                                       anol                               
                                          anol                            
                                             dehyde                       
                                                 Acid.sup.(d)             
                                                     Ratio.sup.(e)        
                                                          (lb/cf/hr)      
__________________________________________________________________________
A  0   5.  0  0   0   NA   96. .2  .2  .02                                
                                          0. 0.  4.  .05  .007            
B  0   0   5. 0   0   NA   92. 0.  .4  .02                                
                                          0. 0.  7.  .06  .006            
C  0   0   0  3.  0   NA   81. 1.5 13.2                                   
                                       1.4                                
                                          .04                             
                                             .68 2.4 4.3  .06             
D  0   0   0  0   1.  NA   69. 12.6                                       
                                   9.9 4.2                                
                                          2.1                             
                                             .32 .20 19.  .15             
E  2.5 0   0  0   0   25.1 34. .69 21. 1.08                               
                                          0  13. 27. .52  2.1             
F  2.5 0   0  0   0   31.7 41. .42 16. .32                                
                                          0  13. 28. .39  2.5             
G  2.5 0   0  0   0   31.7 30. 0   21. .29                                
                                          0  25. 24. .68  3.5             
H  2.5 0   0  0   0   30.0 39. 3.2 23. .82                                
                                          0  21. 13. .68  1.3             
I  2.5 0   0  1.33                                                        
                  0   17.0 65. 0   4.6 .13                                
                                          .01                             
                                             14. 14. .50  12.             
J  2.5 0   0  .80 0   17.4 31. 0   6.8 .26                                
                                          0  31. 26. .12  19.             
K  2.5 0   0  .40 0   22.4 39. 0   5.0 .26                                
                                          0  29. 22. .098 23.             
L  2.5 0   0  .27 0   27.4 30. 0   11. .45                                
                                          .02                             
                                             24. 30. .20  16.             
M  2.5 2.3 0  0   0   9.7  55. 21.5                                       
                                   15. 5.9                                
                                          1.84                            
                                             .3  .3  25.  1.3             
N  2.5 .46 0  0   0   6.7  82. 13.1                                       
                                   4.2 0  0  0   .6  7.   .1              
O  2.5 2.0 0  .8  0   10.1 59. 6.4 23. 6.7                                
                                          3.1                             
                                             .8  1.7 9.2  9.5             
P  2.5 .3  0  .6  0   22.3 57. .56 21. 4.9                                
                                          0  5.8 8.0 1.5  11.1            
Q  2.5 1.5 0  .6  0   25.3 61. 6.8 21. 5.9                                
                                          2.3                             
                                             .7  1.3 10.5 7.3             
R  2.5 .3  0  .3  0   22.7 59. .97 22. 6.6                                
                                          5.6                             
                                             2.1 2.7 4.6  12.5            
S  2.5 1.5 0  .3  0   31.4 57. 11.3                                       
                                   20. 6.4                                
                                          0  .7  2.0 7.4  7.8             
T  2.5 .9  0  .45 0   43.6 64. 2.9 20. 6.0                                
                                          3.5                             
                                             .9  1.6 8.0  10.1            
U  2.5 0   .9 0   0   12.4 57. 3.5 20. 7.8                                
                                          2.8                             
                                             3.0 5.0 2.5  9.9             
V  2.5 0   .18                                                            
              0   0   19.4 50. 1.2 16. 9.6                                
                                          5.0                             
                                             3.7 9.7 1.2  7.3             
W  2.5 .3  .4 0   .6  11.3 40. 27. 26. 3.6                                
                                          .62                             
                                             .5  1.9 10.8 4.3             
X  2.5 .3  1.2                                                            
              0   .6  8.6  42. 28. 23. 3.5                                
                                          .94                             
                                             .5  1.5 11.5 3.6             
Y  2.5 .3  .4 0   .2  19.8 43. 18. 27. 3.2                                
                                          0  4.9 3.7 3.1  4.0             
Z  2.5 .3  1.2                                                            
              0   .2  17.2 52. 8.9 28. 5.3                                
                                          1.5                             
                                             1.0 3.4 6.4  6.1             
AA 2.5 .2  .2 0   0   26.3 50. 5.1 28. 6.6                                
                                          4.1                             
                                             2.4 3.4 4.9  11.6            
AB 2.5 .8  .8 0   0   9.2  53. 20. 19. 4.2                                
                                          1.1                             
                                             0.2 1.4 11.4 7.7             
__________________________________________________________________________
 FOOTNOTES FOR TABLE                                                      
 .sup.(a) Data are from experiments at 300° C and 1000 psig. Values
 are averages of data at various feed gas compositions. The off gas       
 contains approximately 50% CO, 50% H.sub.2. Limits shown are average     
 deviations for multiple (usually two) tests. Catalysts contain the       
 indicated nominal weight percentages of rhodium and other elements       
 supported on Davison TM Grade 59 Silica Gel.                             
 .sup.(b) Dispersion is defined as the fraction of the metal atoms present
 in the catalyst which are present at the surface of metal crystallites an
 so are accessible to gas phase molecules. It is measured by determining  
 the number of moles of CO which will chemisorb on a given quantity of    
 catalyst. These analytical procedures are described by S. J. Gregg and K.
 S. Sing, Adsorption, Surface Area, and Porosity, (Academic Press, Inc.,  
 New York, 1967), where CO adsorption is described at pages 263-267 and th
 dynamic gas chromatographic technique is described at pages 339-343. In  
 this table, the dispersion given is calculated on the assumption that    
 rhodium chemisorbs one molecule of CO per atom of metal exposed but that 
 other elements do not chemisorb CO at all. &#34;NA&#34; is used as an abbreviatio
 for &#34;not available&#34;.                                                     
 .sup. (c) Percent carbon efficiency to a particular product is defined as
 100 times the number of moles of carbon present in that product divided b
 the number of moles of CO converted to products other than CO.sub.2.     
 .sup.(d) Values given in this table for ethanol and for acetic acid      
 include quantities actually present as ethyl esters and as acetates,     
 respectively.                                                            
 .sup.(e) The ethanol preference ratio is the carbon efficiency to ethanol
 divided by the sum of the carbon efficiency to acetaldehyde and the carbo
 efficiency to acetic acid.                                               
 .sup.(f) Units are total pounds of ethanol plus acetic acid plus         
 acetaldehyde produced per cubic foot of catalyst per hour.               
 .sup.(g) Hydrocarbon is aggregated methane, ethane, ethylene, propane,   
 propylene, butane, butenes, and water - insoluble oil.