Hydrocarbon synthesis catalyst and method of preparation

A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint.

FIELD OF THE INVENTION 
This invention relates to the synthesis of hydrocarbons by the reaction of 
carbon monoxide and hydrogen in the presence of a catalyst, commonly known 
as the Fischer-Tropsch synthesis. More particularly, this invention 
relates to novel catalysts for use in such process, methods for 
preparation of such catalysts, and methods for use of such catalysts. 
DESCRIPTION OF THE PRIOR ART 
The so-called Fischer-Tropsch synthesis wherein liquid aliphatic 
hydrocarbons, alcohols and minor amounts of aldehydes, fatty acids and 
ketones are produced by the hydrogenation of carbon monoxide has been 
known for about 60 years. Initially, alkalized iron turnings were 
utilized as the catalytic material. Typical effective catalysts are 
supported cobalt-thoria or supported iron catalysts. The reaction 
temperature is about 250.degree.-300.degree. C. and pressures range from 1 
atm. to about 20 atm. A large commercial plant using iron catalysts is in 
operation in South Africa. Additionally, various methods for conducting 
the specific contacting of the reactants with one another and the 
catalytic material have been utilized, e.g. fixed bed, fluidized bed, etc. 
A thorough discussion of the chemistry of this immensely important 
reaction is set forth in "The Fischer-Tropsch and Related Synthesis" by 
Henry H. Storch, Norma Golumbic, Robert B. Anderson, published by John 
Wiley & Sons, New York, 1951. 
Numerous attempts have been made to refine this synthesis in terms of 
improved effectiveness of the catalyst, product yield, improved production 
of more desirable product fractions, control of the product distribution, 
etc. Additionally, efforts have been made to achieve more stable 
catalysts. As a general rule, the materials which have been known to be 
effective as Fischer-Tropsch catalysts are extremely sensitive to air and 
moisture and consequently, must be used either shortly after preparation 
or prepared in situ. 
In more recent years, the catalysts used for such reactions were composed 
of cobalt, sometimes in conjunction with nickel on a support, such as a 
clay. These catalysts have generally been characterized by instability and 
low activity. Additionally, such catalysts require the use of either a 
fixed or fluidized bed type system. Such contacting methods often produce 
severe heat transfer problems which place an additional burden upon the 
process as well as affect the uniformity of the products obtained. 
SUMMARY OF THE INVENTION 
We have discovered a novel catalytic material which can be used for the 
synthesis of hydrocarbons from carbon monoxide and hydrogen. This 
catalytic material is unique in both its physiochemical constitution as 
well as the properties which it exhibits. Thus, the catalytic composition 
of the present invention exhibits superior activity as compared to 
conventional Fischer-Tropsch type catalysts. In addition, such activity 
can be obtained in dilute slurry from which substantially improves the 
heat transfer factors involved in the Fischer-Tropsch synthesis. 
Furthermore, the catalytic composition of the present invention exhibits 
superior stability and can be stored for long periods of time in either a 
dry or slurry form. Finally, the catalytic composition of the present 
invention produces a very desirable product composed of a fraction of 
linear hydrocarbons ranging from C.sub.1 to C.sub.40 with a low degree of 
branching. 
The catalyst composition of the present invention is easily prepared by a 
new process which also comprises a part of the present invention. This 
process allows the composition to be prepared and separated for use at a 
later time. 
The method and use of the present invention is also unique as compared with 
conventional Fischer-Tropsch catalysts. Of great importance is the fact 
that this catalyst can be used in dilute slurry form and with dilute 
concentrations of gaseous reactants to obtain high yields of desirable 
product fractions. This avoids the heat transfer problems commonly 
encountered with alternative contacting systems. 
More particularly, the catalyst composition of the present invention is 
composed of palladium or platinum and cobalt supported on a solid phase. 
The solid phase material, commonly referred to as a support or carrier, 
may be chosen material such as: talc; dolomite; limestone; clay; activated 
carbon; zeolite; pumice; the oxides, hydroxides or carbonates of aluminum, 
silicon, zinc, chromium, magnesium, calcium, titanium, or zirconium; 
alumina; silica gel; kieselguhr; barium sulfate; or any inert material. 
This catalyst produces improved yields significantly greater than 
conventionally known systems. Additionally, the catalyst is able to 
operate effectively under wider ranges of pressure and temperature than 
the previously known catalysts and can also operate effectively under 
dilute feed gas conditions, that is in the presence of synthesis gas 
diluents or impurities such as nitrogen, so long as the ranges of carbon 
monoxide and hydrogen are within the ranges set forth below. 
The catalyst of the present invention is prepared by first heating a 
heterogeneous component. As used herein, the term heterogeneous component 
means a component formed from two different materials, i.e, a metal and a 
support. Typically, the heterogeneous component would be palladium or 
platinum on a solid phase support. This heterogeneous component is heated 
in a homogeneous phase which is composed of a metal carbonyl or metal 
precursor compound. As used herein, the term metal precursor compound 
means a compound, which, on heating, forms the metal carbonyl in situ. 
This metal carbonyl or precursor is in a suitable solvent and the heating 
takes place in a gaseous stream of hydrogen and carbon monoxide. The 
heating time and temperature as well as the pressure of the hydrogen and 
carbon monoxide can be varied, but in any event, must be sufficient to 
form the catalyst. The completion of the catalyst preparation is indicated 
by a disappearance of the color of the metal carbonyl. Alternately, or 
simultaneously, the process can be monitored by infrared analysis to 
detect the metal carbonyl absorption. When this absorption no longer 
exists, the preparation of the catalyst is complete. 
The catalyst of the present invention can be used to synthesize 
hydrocarbons from a mixture of hydrogen and carbon monoxide by contacting 
the gaseous mixture with a solvent and an effective amount of the catalyst 
in a slurry form.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 
More particularly, the catalyst of the present invention is formed from 
palladium or platinum on a solid phase having cobalt supported thereon 
wherein the amount of palladium or platinum is in the range from about 0.1 
to 10 weight percent based on the total weight of the catalyst. The cobalt 
may be present in the range from about 10 to 70 weight percent based on 
the total weight of the catalyst. 
A variety of supports may be used and these are well known in the art. 
Typically, such supports would include alumina, silica gel, kieselguhr and 
zinc oxide. 
The catalytic composition of the present invention possesses a unique 
structure which can be characterized by the X-ray diffraction patterns of 
the catalytic composition. In particular, reference is made to FIGS. 1 and 
2. FIG. 1 is an X-ray diffraction pattern of a catalyst in accordance with 
the present invention composed of cobalt and palladium on an aluminum 
oxide carrier. In contrast, FIG. 2 is an X-ray diffraction pattern of a 
cobalt/aluminum oxide catalyst prepared by standard precipitation 
techniques. It is clear that as a result of the unique structure of the 
present catalyst, the aluminum oxide peak between 65 and 70 does not 
appear. (In X-ray diffraction patterns of this type, 2.theta. equals 
around 65-70, where .theta. equals the angle of refraction.) Thus, because 
of the actual physical structure of the present catalyst, the aluminum 
oxide pattern is comletely masked. In each case, however, it is clear that 
the cobalt peaks at about 45 come through. 
A comparison of the X-ray diffraction patterns of the catalyst of FIG. 1 
and a similar catalyst having a lower cobalt loading, (catalyst of FIG. 1 
is 55% by weight cobalt while the catalyst in FIG. 3 is 28% by weight 
cobalt) is shown in FIG. 3. This comparison indicates that while the 
cobalt peaks still appear around 45, the aluminum oxide peak present in 
the standard catalyst between 65 and 70 still is not seen. 
It is believed that the reason for this is that the structure of the 
present catalyst is one wherein the cobalt and palladium or platinum coats 
the support in a manner which completely shields the support from the 
X-ray analysis as compared to the prior art materials wherein the 
deposited metal was sufficiently diffused to allow the support to be 
reached by the X-ray beam. What is of particular interest, however, is the 
fact that even at relatively low cobalt, loadings, the support is still 
not seen in the X-ray diffraction pattern. The coating of the support that 
takes place in the preparation of the catalysts of the present invention 
could theoretically occur in such a way as to produce structures as 
depicted in FIGS. 4 and 5. 
In particular, as shown in FIG. 4, the catalyst of the present invention 
may comprise particles of a catalytic support which are surrounded by an 
X-ray impermeable layer of a solid solution of platinum or palladium with 
cobalt. The same effect may be achieved by the structure shown in FIG. 5 
wherein a first inner layer of platinum or palladium surrounds the support 
in a manner to be X-ray impermeable and a second layer of cobalt is 
superimposed thereon. However, as the palladium peaks are clearly visible 
in FIG. 3, but not in FIG. 1, reflecting the shielding effect of cobalt, 
FIG. 5 would appear to best represent the idealized structure of this 
catalyst. 
The unique catalytic composition of the present invention is obtained by a 
novel process. The first step of the process involves the conventional 
deposition of palladium or platinum or mixtures thereof on to a solid 
phase. 
Typically, this is accomplished by impregnation of the support with an 
aqueous solution of a salt of the particular metal. For example, such 
preparations are shown in U.S. Pat. No. 3,988,334, incorporated herein by 
reference. In the usual process, the support, such as alumina, silica, 
zirconia, silica-alumina, kieselguhr, and the like, in particulate form is 
immersed in an aqueous solution of a salt of the particular metal. After 
sufficient time for impregnation of the support, the mixture is dried at 
temperatures between 80.degree.-200.degree. C., usually in air, and 
ultimately calcined in air for a period from one half to one and one half 
hours at temperatures between 300.degree.-600.degree. C. Those skilled in 
the art will readily recognize that other methods are available, such as 
the known techniques of sputtering, other methods of precipitation, vapor 
deposition, electrical deposition and electrochemical deposition. 
In accordance with a novel aspect of the present invention, the thus 
prepared platinum or palladium on the support is then immersed into a 
solution of cobalt carbonyl, or hybride cobalt carbonyl precursors 
thereof, in an appropriate solvent. The forms of the cobalt can be 
selected from either the metallic form, the complexed form, or the salt 
form. In the latter, the salt can be any inorganic salt or organic salt 
capable of being converted into an organic solvent soluble form under 
reaction conditions. Of course, it is understood, that any cobalt compound 
which might be known to inhibit the ultimate action of the catalyst is to 
be avoided. 
One of the interesting characteristics of cobalt carbonyl is that solutions 
containing cobalt carbonyl generally have a dark color, usually brown. 
This is important in determining when the reaction of the cobalt carbonyl 
with the other components of the catalyst is complete. 
The cobalt carbonyl or the precursor thereof and the support carrying the 
platinum or palladium are placed in an appropriate organic solvent which 
can be selected from a wide variety of known materials. Suitable solvents 
include, for example, saturated hydrocarbon, such as n-hexane, and cetane, 
slack wax, aliphatic alcohols, such as butanol and isooctanol, aldehydes, 
and the like or the alcohol or ether by-products of the oxo process, such 
as, isooctanol, isobutanol, and ethers, either taken alone or mixed. Those 
skilled in the art may readily recognize that the use of less inert 
solvents, such as olefins, is possible, resulting in their incorporation 
into the product. Particularly preferred solvents are cyclohexane, xylene, 
decalin, and tetrahydrofuran. 
The mixture of the support carrying the platinum or palladium with the 
cobalt carbonyl or its precursor in the solvent is placed under an inert 
atmosphere and then subjected to pressure using "syngas", i.e., carbon 
monoxide and hydrogen. The process can be carried out under either a 
static pressure or in a continuous manner. Typically, the partial pressure 
of syngas utilized is between about 3 to 3,000 psi and the mixture is 
agitated at a temperature from about 100.degree. to 350.degree. C. If the 
carbon monoxide pressure is too high, the cobalt tends to go back into the 
solution. 
In the static type situation, the entire mixture is placed into a pressure 
bomb which is agitated, as by shaking. Alternatively, an internal mixing 
or stirring device can be utilized. 
In any event, the reaction is continued until the color of the cobalt 
carbonyl disappears from the solution which can be determined either 
visually or by infrared spectroscopy by measuring the disappearance of the 
characteristic metal carbonyl absorptions in the range of 2100-1600 
cm.sup.-1. 
Insofar as the gaseous composition utilized in the preparation process is 
concerned, one can use a ratio of hydrogen to carbon monoxide in the range 
from about 11:1 to 1:4, and preferably in the range from 2:1 to 1:1. 
Hydrogen gas alone may be used in place of syngas for the preparation of 
the catalyst. 
After the reaction has been completed, the catalyst, still in particulate 
form, can be separated from the solvent by standard separation techniques, 
e.g., magnetic techniques, precipitation, filtration, centrifugation, and 
the like. The catalyst can then be stored either in the moist form or 
after having been dried at relatively low temperatures, i.e., under 
300.degree. C., and preferably under 120.degree. C., for extended periods 
of time without any additional precautions being taken. Thus, the catalyst 
of the present invention does not lose its activity as a result of contact 
with air, even after long periods of time on the shelf. 
The catalyst thus prepared exhibits the X-ray diffraction characteristics 
as exhibited in FIG. 1. Of particular interest, however, is a comparison 
of the X-ray diffraction patterns of a catalyst prepared in accordance 
with the present invention as shown in FIG. 1 and that wherein cobalt 
carbonyl is deposited solely on an aluminum oxide support without having 
any palladium or platinum deposited thereon. The X-ray diffraction of this 
latter catalyst is shown in FIG. 2. As can be seen, the single sharp peak 
found in FIG. 1 at around 45 shows that the cobalt in the catalyst of the 
present invention has a highly structured crystalline form which is 
believed to be face centered cubic in contrast to the multiple diffuse 
peaks of FIG. 2, which shows a mixture of cobalt crystalline forms. 
The method of use of the present catalyst is also novel and advantageous. 
Not only can the present catalyst be used in the conventional so-called 
fixed bed or fluidized bed reactions, but it can also be used in a slurry 
type reactor. The conventional contacting techniques, i.e., fixed or 
fluidized bed, suffer from the disadvantages that localized hot spots can 
develop due to poor heat transfer and the relatively high concentration of 
catalyst. This can affect both the efficiency of the process and the 
product distribution and uniformity. When the catalyst of the present 
invention is used in the slurry type reactor, the catalyst can be used in 
relatively dilute form and can also be used efficiently with dilute 
gaseous mixtures. 
In contrast to the conventional contacting techniques, with a relatively 
dilute slurry of the catalyst in a solvent, the heat transfer within the 
system is more efficient than with the other techniques and these problems 
can be avoided. Additionally, the synthesis reaction with the present 
catalyst can be carried out at a wide variety of temperatures and 
pressures. 
In particular, the catalyst of the present invention can be utilized in 
slurry form in the conventional solvents used for such reactions. The 
slurry concentration can generally be in the range from about 0.3 to 50 
percent by volume. This can, of course, be varied depending on the desired 
results. Slurry concentrations of from about 1 to 300 g/l are preferred. 
Suitable temperatures for carrying out a synthesis reaction with the 
present invention range from about 30.degree. to 400.degree. C., and, 
preferably, are in the range from about 130.degree. to 250.degree. C. 
As noted, relatively dilute concentrations of gaseous reactants, i.e, 
hydrogen and carbon monoxide, can be used. Conditions for use are 
essentially the same as conditions for preparation; however, as the syngas 
pressure increases, the product distribution begins to favor oxygenates 
such as alcohols, ketones, and the like. Overall partial pressures of 
hydrogen in the total mixture from about 2 to 2500 psi can be employed, 
with pressures from about 100 to 1000 psi being preferred; and carbon 
monoxide pressures from about 1 to 2000 psi, and preferably, from about 60 
to 600 psi can be used. 
Of particular importance is the fact that despite the wide range of 
pressures and temperatures which can be used as well as the diluteness of 
the gaseous feed streams, the product obtained is composed of highly 
desirable fractions of hydrocarbons. Typically, for example, the product 
obtained with the present invention would have an analysis as shown by gas 
phase chromatography exemplified in FIG. 6. The distribution for diesel 
fuel is shown in FIG. 7. In particular, analysis of typical reaction 
products indicates a broad distribution of C.sub.1 to C.sub.40 paraffins. 
Only small amounts of C.sub.1 -C.sub.5 alcohols have been detected with 
the catalyst of the invention. For example, a reaction employing 3 g of 
the present catalyst in 100 ml of xylene carried out under three separate 
synthesis gas chargings yielded a light yellow solution and water. The 
xylene was distilled under vacuum, a yellow oil resulted. Infrared 
analysis of the reaction solution and oil indicated only a small amount of 
oxygenated product and olefins and no metal carbonyl. Integrated nuclear 
magnetic resonance spectra of the yellow oil, shown in FIG. 8, indicated 
highly linear paraffinic products of an average chain length of 18 with 
little or no aromatics, unsaturates, oxygenates or branched products. Gas 
phase analysis of the gaseous components from the cooled reactor, as 
determined by gas-solid chromatography employing a thermal conductivity 
detector, indicated methane (generally less than 10 weight percent of 
hydrocarbon in the product), ethane, propane, butane, and only small 
amounts of unsaturated hydrocarbons. 
An additional experiment was carried out to determine the efficacy of the 
catalyst in accordance with the present invention in dilute synthesis gas 
feed conditions. In particular, a catalyst was prepared from 3.4 grams of 
dicobalt octacarbonyl and 1.0 grams 5% palladium on alumina in cyclohexane 
under 400 psi of nitrogen and 1200 psi of hydrogen. The reactor was heated 
to about 180.degree. C. However, no pressure drop was observed. On cooling 
the reactor, ammonia could not be detected in either the gas or liquid 
phases. Upon venting the gases and recharging with 500 psi of nitrogen and 
500 psi of synthesis gas (2 H.sub.2 :1 CO) and thereafter heating, the 
catalyst exhibited normal activity for hydrocarbon synthesis. This is to 
be contrasted with ordinary Fischer-Tropsch catalysts which show a marked 
decrease in activity in the presence of a diluent. 
That the catalyst of the present invention is substantially more reactive 
than conventionally known Fischer-Tropsch catalysts is shown in Table 1. 
TABLE 1 
______________________________________ 
REPRESENTATIVE HYDROCARBON 
PRODUCTION RATES OF 
FISCHER TROPSCH CATALYSTS 
Activity 
g prod. per 
Temperature 
Kg metal per 
Catalyst .degree.C. hour 
______________________________________ 
Catalyst of Example 4 
225.degree. 
3000 
Catalyst of Example 9 
225.degree. 
1080 
Catalyst of the Present 
Invention.sup.a 125.degree. 
40 
Lurgi catalyst (10Fe:10Cu: 
2K.sub.2 CO.sub.3 :9Al.sub.2 O.sub.3 :30SiO.sub.2).sup.b 
225.degree. 
24 
Brabag catalyst (100Fe:20Cu: 
20Zn:1K.sub.2 CO.sub.3).sup.b 
225.degree. 
10 
Bureau of Mines 2A catalyst 
(100Co:18ThO.sub.2 :100 kieselguhr).sup.c 
195.degree. 
50 
Pichler acid-promoted Ru/Al.sub.2 O.sub.3 
catalyst for polymethylene.sup.d 
120.degree. 
120 
Kolbel slurry catalyst 
(100Fe:0.1Cu:0.05K.sub.2 O).sup.e 
268.degree. 
450 
Vannice (5% Fe on glassy 
carbon).sup.f 235.degree. 
4 
______________________________________ 
.sup.a 2.2 g catalyst, containing 1.2 g metal on low surface area (80-100 
mesh) Al.sub.2 O.sub.3, 100 mL cyclohexane, 1200 psi charge 2.1 syngas, 
300 mL AE reactor, catalyst prepared in situ. 
.sup.b H. H. Storch, N. Golumbic, and R. B. Anderson, The FischerTropsch 
and Related Syntheses, p. 308 (Table 86), Wiley, New York, 1951. 
.sup.c Ibid., p. 132 (Table 5). 
.sup.d H. Pichler and F. Bellstedt, Erdol u. Kohle 26, 560 (1973). 
.sup.e H. Kolbel, P. Ackermann, and F. Engelhardt, Erdol u. Kohle 9, 153, 
225, 303 (1956). 
.sup.f M. A. Vannice, paper presented at 181st Am. Chem. Soc. Meet., 
Atlanta, GA, March 29-April 3, 1981. 
Table 1 shows rate comparisons of a number of conventional Fischer-Tropsch 
catalysts with catalysts of the present invention under isothermal 
conditions. The activity of the present catalysts as expressed in 
conversions per catalytic volume per unit time or of conversions per mole 
of metal atoms per unit time are superior by about two orders of magnitude 
as compared to those catalysts studied by the Bureau of Mines. 
Of particular interest is the fact that the conventional catalysts for 
hydrocarbon synthesis are generally used at about atmospheric pressure. In 
contrast, the catalysts of the present invention have their best activity 
at pressures between about 300 to 500 psi. An experiment utilizing a 
conventional Fischer-Tropsch catalyst, such as, 100 Co:18 ThO.sub.2 :100 
kieselguhr, under comparable conditions to those used with the present 
catalyst (cyclohexane slurry, 225.degree. C., 1200 psi cold synthesis gas 
pressure), show that the rate of gas consumption was more than 10 times 
faster with the present catalyst, while the product of the present 
catalyst contained less of the undesired oxygenates. 
Table 2 shows a comparison of several other types of catalysts with that of 
the present invention under the slurry conditions preferably employed when 
using the catalysts of the present invention. 
TABLE 2 
__________________________________________________________________________ 
COMISON OF SEVERAL CATALYST SYSTEMS IN CYCLOHEXANE SLURRY.sup.a 
Activity Rate of Syngas 
Gaseous Products, 
Consumption 
Catalyst g prod/(kg metal*hr) 
Consumption 
mmol Ratio Products 
__________________________________________________________________________ 
Catalyst of Example 4 
3000 55%/20 min 
8.3 CH.sub.4 
2.2 principally linear 
0.09 C.sub.2 H.sub.4, 1.4 C.sub.3 
H.sub.6 .sup. 2.0.sup.b 
paraffins 
0.1 C.sub.4 H.sub.10 3.1 CO.sub.2 
Catalyst of the Present 
860 50%/70 min 
17 CH.sub.4, 2.0 C.sub.2 H.sub.6, 
2.0 principally linear 
Invention prepared from 1.0 CO.sub.2 
.sup. 1.9.sup.b 
paraffins 
1 g 5% Pd on 80-100 mesh 
Al.sub.2 O.sub.3 and 3.4 g Co.sub.2 (CO).sub.8, 
in situ (1.4 g catalyst 
containing 1.2 g metal) 
Catalyst of Example 9 
1080 33%/80 min 
13 CH.sub.4, 1.4 C.sub.2 H.sub.6 
3.2 principally hydro- 
0.5 CO.sub.2 carbons with small 
amounts of alcohols 
Catalyst of Example 5 
640 44%/60 min 
16 CH.sub.4 , 0.1 C.sub.2 H.sub.4 
1.7 principally linear 
0.3 C.sub.2 H.sub.6, 
paraffins 
16 CO.sub.2 
Co on Al.sub.2 O.sub.3, prepared 
270 33%/120 min 
18 CH.sub.4, 0.9 C.sub.2 H.sub.6, 
3.2 hydrocarbons and 
from lg 80-100 mesh 2.3 CO.sub.2 alcohols 
Al.sub.2 O.sub.3 and 3.4 g 
Co.sub.2 (CO).sub.8 (2.2 g catalyst 
containing 1.2 g metal) 
5% Pd on 80-100 mesh Al.sub.2 O.sub.3 
0 None -- -- no hydrocarbons or 
(1 g of catalyst containing alcohols detected 
0.05 g metal) 
100Co:18ThO.sub.2 :100 Kieselguhr 
71 66%/350 min 
3.4 CH.sub.4, 0.2 C.sub.2 H.sub.6, 
2.3 hydrocarbons, rich in 
(7.5 g of K.sub.2 CO.sub.3 precipitated 
0.5 CO.sub.2 lower molecular 
weight 
catalyst, reduced at 400.degree. oxygenates 
with H.sub.2, containing 1.3 g Co) 
4Fe:1Cu (3 g of precipitated 
180 40%/120 min 
2.4 CH.sub.4, 24 CO.sub.2 
1.8 hydrocarbons rich in 
catalyst, reduced at 400.degree. C. 
1.2 C.sub.2 H.sub.4, 0.8 C.sub.2 
H.sub.6 olefins 
with H.sub.2, containing 1.3 g Fe) 
5% Ru/Al.sub.2 O.sub.3 (2.2 g catalyst, 
21000 48%/25 min 
27 CH.sub.4, 0.02 C.sub.2 H.sub.4 
2.1 principally linear 
containing 0.11 g metal) 0.13 C.sub.2 H.sub.6 
paraffins, rich in 
high 
0.14 C.sub.3 H.sub.8, 1.6 
molecular weight 
waxes.sup.c 
__________________________________________________________________________ 
.sup.a General Conditions: 100 mL cyclohexane, 300 mL AE reactor charged 
with 800 psi H.sub.2 and 400 psi CO with reaction carried out at 
225.degree. C. (18 min to temperature). 
.sup.b Consumption ratio, exclusive of methane formation. 
.sup.c Significant quantities of soluble hydrocarbonyl and alkylcarbonyl 
ruthenium complexes detected in solution by infrared. 
While it is possible to prepare the present catalyst in the manner noted 
above and isolate the catalyst for storage and subsequent use, it is also 
possible to utilize the catalyst after it has been prepared in situ. In 
such a case, the catalyst would be prepared in the manner described 
hereinabove and one would simply continue to maintain the temperature and 
pressure conditions along with the appropriate amount of agitation to 
produce reaction of the gaseous materials and synthesis thereof into the 
desired hydrocarbons. The reaction is normally followed by continuous 
measurement of the pressure. When the pressure ceases to decrease, i.e., 
remains constant or decreases only slowly, it is apparent that the 
reaction is ceasing. Upon cooling, the hydrocarbons obtained are normally 
liquid and, in particular, dissolve in the solvent used. These can be 
isolated in the normal manner. 
The catalysts of the present invention, their method of preparation and use 
are shown in the following examples: 
EXAMPLE 1 
The reactor configuration employed in most experiments is as follows. The 
reactor system consists of a 300 ml Autoclave Engineers Magne-Drive 
reactor, equipped with liquid and gas sampling valves. The heater is 
controlled by a Love Controls proportioning temperature controller, 
employing an iron-constantan thermocouple. Fine control of the temperature 
is achieved by means of alternating heating and cooling cycles in the 
vicinity of the set point. Cooling is controlled by the flow of compressed 
air through a solenoid-actuated internal, spiral cooling coil. Temperature 
may be readily controlled to within 2.degree. C. Ordinarily, 100 mL of 
slurry solvent is employed, allowing for 200 mL of gas space. The system 
is normally purged with synthesis gas before final charging. 
The above reactor was purged, 1 g of commercially obtained 5% palladium on 
alumina was added, followed by 3.4 g of commercially obtained 
octacarbonyldicobalt. While purging is continued, 100 mL of cyclohexane is 
added. The reactor is then sealed, purged with 500 psi synthesis gas, and 
after venting, charged with 1200 psi synthesis gas (nominally 2 H.sub.2 :1 
CO). The reactor is checked for leaks. Stirring and heating are commenced 
with the temperature controller. 
Approximately 18 minutes are required to bring the reactor to set 
temperature. As the temperature is increased, the pressure increases due 
to thermal expansion of the gases; however, in the range of 
200.degree.-225.degree. C., the pressure levels off, then decreases, 
indicating that hydrocarbon synthesis has commenced. The reaction was 
carried out for a total elapsed time of 40 minutes, during which the 
pressure dropped from 2200 to 1590 psi at 225.degree. C., affording an 
average pressure drop of 28 psi/min which corresponds to an average 
activity of 1200 g prod-(Kg metal).sup.-1 hr.sup.-1 neglecting the 
formation of volatiles. The reactor was cooled to room temperature, at 
which the pressure was found to be 790 psi. Thus, taking into account 
those volatile materials which substantially condense at ambient pressure, 
the gross activity is 1300 g prod-(Kg metal).sup.-1 hr.sup.-1. 
Theoretically, 2.2 g of the catalyst was formed. 
EXAMPLE 2 
The reaction mixture from Example 1 was allowed to stand overnight. The 
gases were vented, the solvent was drawn off, and the catalyst washed with 
cyclohexane. While purging with argon, 100 ml fresh cyclohexane was added. 
During the solvent removal and washing, approximately 0.3 g of the 
catalyst was lost. The reactor was again recharged with 1200 psi synthesis 
gas and brought to 225.degree. C. During the 50 minutes of use the 
pressure dropped from 2080 to 1520 psi, affording an activity of 840 g 
prod-(Kg metal).sup.-1 hr.sup.-1. Upon cooling, the pressure was found to 
be 610 psi. Thus, using the pressure drop at room temperature, the 
activity is found to be 1490 g prod-(Kg metal).sup.-1 hr.sup.-1. 
The cooled reaction mixture was subjected to gas analysis. This is 
accomplished by injecting 0.500 ml of reaction gas into a gas 
chromatograph equipped with dual thermistor-type thermal conductivity 
detectors. Gas analysis for hydrogen is achieved with a 6 foot.times.1/4 
inch glass column, packed with Linde 13.times. molecular sieve, and 
employing nitrogen as carrier gas at ambient temperatures. Gas analysis 
for carbon monoxide and methane is achieved with a 1 meter.times.1/4 inch 
polyethylene column, also packed with Linde 13.times. molecular sieve and 
employing helium as carrier gas at ambient temperature. Gas analysis for 
carbon dioxide, ethylene and ethane is achieved with a 41/2 foot.times.1/4 
inch polyethylene column packed with Chromosorb 102 and also employing 
helium as carrier gas at ambient temperature. Gas analysis for higher 
volatile hydrocarbons is achieved on a gas chromatograph equipped with hot 
wire-type thermal conductivity detectors by means of a gas sampling value, 
and using a 12 foot.times.1/8 inch Porapak Q stainless steel column at 
150.degree. C., employing helium as carrier gas. 
The areas of the respective peaks are integrated digitally and compared to 
the areas of corresponding injections of the pure components. For the 
instant example, the gas phase was found to consist of 59% H.sub.2, 35% 
CO, 5% CH.sub.4, 0.5% CO.sub.2, 0.4% C.sub.2 H.sub.6 and 0.03% C.sub.2 
H.sub.4. The ideal gas law is then employed to estimate the quantity of 
each gas present in the gas phase. In this particular case, the gas phase 
consisted of 202 mmol H.sub.2, 119 mmol CO, 18 mmol CH.sub.4, 1.6 mmol 
CO.sub.2, 1.5 mmol C.sub.2 H.sub.6 and 0.1 mmol C.sub.2 H.sub.4. The 
consumption ratio is then 2.3, with 247 mmol H.sub.2 and 106 mmol CO 
having been consumed. The methane fraction corresponds to approximately 
4.5% by weight of the hydrocarbon product. 
The bulk of the solution, containing dissolved hydrocarbons is transferred 
to a bottle by means of the liquid sampling valve. The remainder of the 
solution is removed by pipette after the reactor is vented and opened. 
Ordinarily, copious amounts of water are present at the bottom of the 
reactor, near the catalyst. The catalyst is then removed from the reactor 
by use of a magnet and transferred to a petri dish, in which it is dried 
in an oven at 100.degree.-120.degree. C.; 1.86 g of catalyst was so 
recovered. 
EXAMPLE 3 
1.35 g of the catalyst recovered in Example 2 was packed into a stainless 
steel tube of 1/2" nominal diameter. The catalyst was retained by glass 
wool plugs at each end of the bed. Synthesis gas (66% H.sub.2, 34% CO) at 
5 psi was passed through the catalyst bed, affording a flow rate of 0.16 
ft.sup.3 /hr. The gas passed through the column was analyzed periodically 
by gas chromatography (He carrier gas) by means of a metering gas sampling 
valve. 
The temperature was gradually increased, and at 125.degree. C., only a 
small portion (0.04%) was found to have been consumed. At 150.degree. C, 
approximately 1% of the carbon monoxide was converted to products. 
Increasing the temperature to 225.degree. C. led to very high conversions 
(initially about 80% after 5 min and 98% after 15 min). However, the 
activity gradually dropped (78% after 1 hour, 72% after 2 hours, 49% after 
3 hours, 54% after 4 hours, and 37% CO conversion after 6 hours). Flushing 
hydrogen over the catalyst at 225.degree. C. failed to restore the high 
activity, although a modest improvement in activity was observed. At the 
end of the reaction the material in the cold trap was found to weigh 1.7 g 
and consisted almost exclusively of water; that is the products were 
predominately low-boiling. 
EXAMPLE 4 
The 0.3L autoclave was purged with argon. One gram of commercially obtained 
5% platinum on alumina hydrogenation catalyst was added, followed by 100 
ml cyclohexane. After further purging, 3.4 g of commercially obtained 
octacarbonyldicobalt was added. The reactor was then sealed, purged two 
times with 200 psi syngas and then charged with 1200 psi of syngas, 
consisting of two parts hydrogen to one part carbon monoxide. The reactor 
was checked for leaks. Approximately 18 minutes were required to achieve 
an operating temperature of 225.degree. C. During the warm-up cycle, the 
pressure increased to 2075, after which time the pressure decreased at an 
average rate of 39.5 psi/min (see Table E-4 which follows). 
TABLE E-4 
______________________________________ 
RATE OF SYNGAS CONSUMPTION 
Time, min Temp, .degree.C. 
Pressure, psi 
______________________________________ 
0 25 1200 
15 200 1950 
18 225 2075 
20 225 2000 
22 230 1825 
25 225 1625 
28 225 1500 
30 225 1425 
32 225 1375 
35 225 1300 
40 225 1210 
______________________________________ 
The reactor was cooled to room temperature, at which the pressure was found 
to be 540 psi. The gas phase was analyzed and contained 39.9% hydrogen, 
50.1% carbon monoxide, 8.3% methane, 0.03% ethylene, 0.45% ethane, 0.34% 
propane, and 1.0% carbon dioxide. The consumption ratio was found to be 
2.2; when corrected for the methane produced, the consumption ratio was 
calculated to be 2.0. 
Upon opening the reactor, the liquid phase was clear and slightly yellow. A 
small amount of black liquid consisting of water and suspended catalyst, 
was found at the bottom of the reactor. The catalyst was removed 
magnetically and dried overnight at 120.degree. C. The sample of recovered 
catalyst weighed 1.5 g. Gas chromatography analysis of the liquid phase 
indicates predominately linear aliphatic hydrocarbons are formed. 
EXAMPLE 5 
A sample of 7.2 g commercial zinc oxide was suspended in 15 mL distilled 
water. A solution of 0.5 g palladium (II) chloride, 8 ml concentrated 
hydrochloric acid and 10 ml water was added. The slurry was heated to 
dryness with constant stirring by means of a glass rod, yielding a 
red-brown solid. This solid was dried for 20 hrs at 120.degree. C. in an 
oven. Reduction in a stream of hydrogen at 220.degree.-240.degree. C. for 
3 hrs afforded 7.55 g of 4% palladium on zinc oxide. 
One gram of said 4% Pd/ZnO was added to the 0.3L reactor purged with argon 
and containing 100 mL cyclohexane as slurry solvent. 3.4 g of 
octacarbonyldicobalt, containing considerable amounts of the purple 
contaminant familiar to those acquainted with this reagent was added. The 
reactor was purged two times with 200 psi syngas, then pressurized to 1200 
psi with syngas consisting of 67% H.sub.2 and 33% CO. 
The reactor was warmed to 225.degree. C., at which time a liquid sample 
indicated little soluble cobalt species. Over an hour period little 
activity for syngas consumption was observed. The reactor was cooled to 
80.degree. C. and maintained at this temperature for 3 hours. A liquid 
sample indicated the presence of Co.sub.2 (CO).sub.8. The reactor was 
cooled to room temperature. 
On the following day, the reactor was heated again to 225.degree. C. During 
the following hour, the pressure decreased at a rate of 8 psi/min. Upon 
cooling the pressure was 560 psi. Gas analysis indicated the following 
mmol quantities of gaseous products: 
16 CH.sub.4, 0.1 C.sub.2 H.sub.4, 0.3 C.sub.2 H.sub.6, and 16 CO.sub.2. The 
consumption ratio was 1.7. 
The solution removed from the reactor was slightly yellow. Washing the 
reactor and catalyst with tetrahydrofuran led to a blue solution. Addition 
of water to this blue solution led to a pale pink color, suggesting that 
some cobalt was not tightly bound to the heterogeneous catalyst. The 
catalyst was washed with tetrahydrofurn until the washings were colorless. 
1.9 g of catalyst was recovered magnetically; approximately 0.2 g of 
material was non-magnetic, and this is ascribed to impurities in the 
octacarbonyldicobalt starting material. 
EXAMPLE 6 
A 250 ml three neck round bottom flask was purged with argon. One gram of 
5% Pd/Al.sub.2 O.sub.3 and a magnetic stirring bar was added. With 
continued purging, 100 ml of decalin was added, followed by 3.4 g Co.sub.2 
(CO).sub.8. The argon was replaced with a slow, steady flow of hydrogen. 
The reaction mixture was heated with stirring and was maintained at 
135.degree. C.-140.degree. C. After 3 hours, the infrared spectrum of the 
reaction solution indicated the absence of any metal carbonyl species. On 
cooling, it was found that a magntic catalyst, clinging to the magnetic 
stirring bar, was formed. Upon filtration and drying this catalyst 
displayed comparable activities for hydrocarbon synthesis as those 
prepared by the method of Example 1. 
EXAMPLE 7 
The 0.3L autoclave was purged with argon. Two grams of 5% Pd/Al.sub.2 
O.sub.3 was added, followed by 150 ml cyclohexane, then 6.8 g cobalt 
carbonyl. The reactor was charged with 870 psi H.sub.2 and 430 psi CO. The 
reactor was heated to 225.degree. C., after which the pressure was found 
to decrease at an average rate of 54 psi/min. Gas chromatographic analysis 
indicated the following gas composition: 65.6% H.sub.2, 27.6% CO, 4.4% 
CH.sub.4, 1.1% CO.sub.2 and 0.17% C.sub.2 H.sub.6. 
EXAMPLE 8 
In this reaction, a 310 ml packed cone autoclave, manufactured by Parr 
Instruments was employed. The reactor was purged with argon. 3.42 g 
Co.sub.2 (CO).sub.8, 1.06 g 5% Pd/Al.sub.2 O.sub.3 and 100 ml 
tetrahydrofuran were added. The reactor was charged with 1300 psi 
synthesis gas, consisting of hydrogen and carbon monoxide in equal 
proportions. The reactor was heated to 200.degree. C. The pressure dropped 
from 1600 to 1100 psi over 3.5 hrs. Upon cooling, the pressure was 350 
psi. Very little hydrogen was found in the gas phase. A significant 
quantity of white, waxy, tetrahydrofuran-insoluble material was observed. 
Infrared spectra and toluene solubility indicate this to be higher 
molecular weight paraffins. 
EXAMPLE 9 
Chromatographic alumina was sieved to be 80 to 100 mesh. Five grams of this 
alumina was suspended in 5 g water. A solution of 0.44 g PdCl.sub.2, 7 ml 
hydrochloric acid and 10 ml H.sub.2 O was added. The slurry was heated 
with stirring to dryness on a hot plate, then dried at 120.degree. C. for 
16 hrs. 
The resulting solid was carefully ground to achieve approximately the same 
dimensions as the starting support. It was then reduced for 2 hrs at 
220.degree.-250.degree. C. under a stream of H.sub.2. 
One gram of the said 5% palladium dispersed on alumina was added to the 
0.3L autoclave. The reactor was purged with argon and 100 ml cyclohexane 
was added. 1.13 g cobalt carbonyl was then added. The reactor was purged 
with syngas, then pressurized to 1200 psi (2H.sub.2 :1CO). The reactor was 
heated to 225.degree. C. During the following 80 minutes, the pressure 
dropped 510 psi. 
Upon cooling, the final pressure was 800 psi. The gas phase consisted of 
55% H.sub.2, 42% CO, 2.8% CH.sub.4, 0.3% C.sub.2 H.sub.6 and 0.1% CO.sub.2 
.