Catalysts for the conversion of syn gas

A catalyst system for the conversion of synthesis gas in a single stage to liquid hydrocarbons comprises PA0 (a) a copper-containing alcohol synthesis catalyst, PA0 (b) an iron-containing modifier for the alcohol synthesis catalyst to promote the formation of hydrocarbons, and PA0 (c) a metallosilicate wax cracking catalyst. The alcohol synthesis catalyst (a) can contain thorium, zinc, uranium or zirconium in addition to the copper. The iron-containing modifier (b) can contain an iron-containing zeolite such as ferrierite or an inorganic support containing ferrous or ferric ions. The metallosilicate can be a zeolite or gallosilicate. The zeolite can have a pore diameter of at least 5 Angstroms and can have the faujasite structure. A Group VIIIA metal e.g., Pd may be incorporated on the zeolite to suppress coke formation. A hydrocarbon product from the conversion can be obtained containing at least 70 percent by weight of hydrocarbons in the range C.sub.3 to a boiling point of 340.degree. C., and less than 10 percent by weight of methane.

BACKGROUND OF THE INVENTION 
This invention relates to a catalyst system suitable for the conversion of 
synthesis gas to hydrocarbons, more particularly to a catalyst system 
comprising a copper-containing component together with an iron-containing 
component and a wax cracking component such as a Zeolite. This invention 
also relates to a process for the conversion of synthesis gas to 
hydrocarbons using the above-described catalyst system. 
The conversion of synthesis gas to hydrocarbons by the Fischer-Tropsch 
process is well known. Usually the catalyst employed in the 
Fischer-Tropsch process is an iron oxide-containing material although 
other metal oxides such as those of cobalt, nickel, ruthenium, thorium, 
rhodium and osmium have been described. However, it is a feature of known 
Fischer-Tropsch catalysts that a significant proportion of the hydrocarbon 
product is either in the form of methane and/or wax and this is a 
disadvantage because the need at the present time is for liquid 
hydrocarbons suitable for use as transportation fuels. 
To reduce the wax content of the product it has been previously proposed to 
either incorporate with the Fischer-Tropsch catalyst a cracking component 
such as a Zeolite or to pass the product from the Fischer-Tropsch catalyst 
over a cracking catalyst in a separate stage. 
For example, U.S. Pat. Nos. 4,046,830 and 4,279,830 describe the conversion 
of synthesis gas to oxygenates and hydrocarbons by first contacting the 
synthesis gas with a Fischer-Tropsch catalyst in a first stage and then 
passing the product from the first stage over an acidic crystalline 
Zeolite in a second stage. The process is operated as two stages because 
the conditions under which the cracking catalyst is operated are more 
severe than those required for the hydrocarbon synthesis. It would be an 
advantage to be able to operate both reactions in a single stage since 
this would eliminate a reactor vessel and it is an object of the present 
invention to provide such a process. 
U.S. Pat. No. 4,086,262 discloses a process for the conversion of synthesis 
gas using a single stage process wherein the catalyst is a mixture of (i) 
a carbon monoxide reducing catalyst such as a methanol catalyst or an 
iron-containing Fischer-Tropsch catalyst and (ii) a ZSM-5 type Zeolite. 
However, the products described in this patent contain significant amounts 
of gaseous hydrocarbons, particularly methane which in all cases exceeds 
10 percent by weight of the hydrocarbon product. 
It is therefore an object of the present invention to provide a single 
stage process for the conversion of synthesis gas to hydrocarbons and 
thereby avoid the disadvantage of the two stages described in U.S. Pat. 
Nos. 4,046,830 and 4,279,830 and at the same time to produce a hydrocarbon 
product that either contains less than 10 percent by weight of methane or 
contains at least 70 percent by weight of hydrocarbons in the range 
C.sub.3 to a boiling point of 340.degree. C. 
SUMMARY OF THE INVENTION 
According to the present invention, a catalyst system suitable for the 
conversion of synthesis gas to hydrocarbons comprises the components: 
(a) a copper-containing alcohol synthesis catalyst, 
(b) an iron-containing modifier for the alcohol synthesis catalyst in an 
amount to promote the formation of hydrocarbons, and 
(c) a metallosilicate wax cracking catalyst in an effective amount to 
reduce the wax content of the hydrocarbon product. 
According to another aspect of the present invention, a process for the 
conversion of synthesis gas to hydrocarbons comprises contacting synthesis 
gas at elevated temperature and pressure with a catalyst system comprising 
the components: 
(a) a copper-containing alcohol synthesis catalyst, 
(b) an iron-containing modifier for the alcohol synthesis catalyst in an 
amount to promote the formation of hydrocarbons, and 
(c) a metallosilicate wax cracking catalyst. 
DETAILED DESCRIPTION OF THE INVENTION 
The component (a) of the catalyst system can be any of the 
copper-containing alcohol synthesis catalysts, for example, a partially 
reduced mixed metal oxide containing copper and thorium and optionally 
other metals as disclosed, for example, in U.S. Pat. No. 4,298,354 or a 
partially reduced mixed metal oxide containing copper and zinc as 
described in the Journal of Catalysis Volume 56, 407-429 (1979) promoted 
with alkali metal. Other copper zinc catalysts which may be used include 
(i) copper-zinc oxide-aluminum oxide-potassium catalysts described by C. 
E. Hofstadt et al in Preparation of Catalysts III, page 709, Elsevier 
Science Publishers BV Amsterdam 1983 (ii) copper-zinc oxide-potassium 
catalysts described by K. J. Smith et al in the Canadian Journal of 
Chemical Engineering Vol. 61. pages 40-45 (1983) (iii) copper-zinc oxide 
with alkali or alkaline earth metals described by G. A. Vedage et al in 
American Chemical Society Division of Petroleum Chemistry Preprints 
Washington, D.C. Meeting. Aug. 29 to Sept. 2, 1983, page 1261. 
Further copper-containing alcohol catalysts which may be used include 
copper zirconium catalysts described in our co-pending patent application 
U.S. Ser. No. 653,946. Copper beryllium and copper uranium catalysts may 
also be employed and may be prepared in a manner similar to that described 
in U.S. Pat. No. 4,298,354 for the copper thorium catalysts or in U.S. 
Ser. No. 653,946 for the copper zirconium catalysts i.e., by precipitation 
of the oxides or their precursors from a solution of the metal salts, 
followed by calcination and partial reduction. 
The iron-containing modifier for the alcohol catalyst can be an 
iron-containing zeolite such as ferrierite or an inorganic oxide support 
or zeolite exchanged or impregnated with either ferrous or ferric ions. 
The purpose of the iron-containing modifier is to alter the products from 
the reaction from being mainly alcohols to mainly hydrocarbons. Suitable 
amounts of modifier are such as provides an atomic ratio of iron to copper 
of at least 0.003 to 1 preferably from 0.03 to 1 to 10 to 1. 
Preferably the iron-containing modifier is supported for example on a 
zeolite which may be naturally occurring such as ferrierite, the iron 
content of the supported modifier conveniently being from about 0.001 to 
80 percent by weight of iron (calculated as metal and based on the weight 
of the modifier and support) preferably from about 0.5 to 2.0 percent. The 
supported iron modifier can be prepared by impregnation, ion exchange, 
coprecipitation or vapor deposition. Naturally occurring iron-containing 
minerals can be employed. 
A preferred support is an inorganic oxide such as silica, titania, 
magnesia. lanthanum oxide, alumina, a Zeolite or a clay. 
The metallosilicate wax cracking catalysts are conveniently zeolite (i.e. 
an aluminosilicate) wax cracking catalysts which are well known in the 
art. However, metallosilicates not containing aluminum can be used, for 
example iron silicates as described, for example. in U.S. Pat. No. 
4,350,772 or chromium silicate described, for example in German 
Offenlegungschrift No. 2831630. 
The zeolite preferably has a pore diameter of at least 5 Angstroms, more 
preferably from about 5 to about 9 Angstroms. The zeolite can be, for 
example an erionite, offretite, or ferrierite each having a pore diameter 
of about 5 Angstroms. or mordenite or X zeolite or Y zeolite of the 
faujasite type each having a pore diameter of about 9 Angstroms, or a 
zeolite of the ZSM series having an intermediate pore diameter of 5 to 9 
Angstroms. Zeolites having pore diameters of from 5 to 9 Angstroms are 
particularly suitable for obtaining a product containing gasoline. Typical 
of such zeolites are those of the ZSM series developed by Mobil such as 
ZSM-5, ZSM-11, ZSM-12, ZSM-21, ZSM-35 and ZSM-38. The silica to alumina 
ratio is desirably at least 12. 
The zeolite cracking catalyst can have Group VIIIA metals such as palladium 
or platinum added by impregnation or ion exchange to suppress coke 
formation and can be any of the Group VIIIA metal containing ZSM-5 
catalysts described in European Patent Application No. 027,380. 
The amount of the cracking catalyst in the catalyst system can vary within 
wide limits but should preferably be from 20 to 80 percent by weight more 
preferably 30 to 70 percent by weight of the catalyst system. 
The process conditions for the conversion of synthesis gas to hydrocarbons 
are preferably at temperatures of from 200.degree. C. to 450.degree. C. 
and pressures of from 1 to 300 atmospheres. 
More preferred conditions are a temperature of from 260.degree. C. to 
400.degree. C. of from 20 to 75 atmospheres and a gas hourly space 
velocity of 10 to 100,000, more preferably 500 to 6,000. 
The synthesis gas employed in the present invention can contain hydrogen 
and carbon monoxide in a molar ratio of less than 1:1 particularly less 
than 1:2, for example from 1:1 to 1:5. 
The form of the Periodic Table referred to in the present specification is 
that published in 1979 by Sargent-Welch Scientific Company of Skokie, 
Illinois in which the rare gases constitute Group VIII and the iron group 
metals Group VIIIA.

The invention is illustrated by the following examples. Different catalyst 
mixtures were prepared, some of which were used with Zeolites. 
The catalysts were tested under the conditions set out in Table 1 which 
also records the results obtained. 
Preparation of Catalysts 
Preparation A: Cu.sub.0.4 ZnO.sub.y 
The procedure follows that described in J Catalysis 56 407-429 (1979). 
52.4 g of Cu(NO.sub.3).sub.2 . 3H.sub.2 O (Formula weight 241.6; moles 
0.217) and 156 g of Zn(NO.sub.3).sub.2 . 6H.sub.2 O (Formula weight 
297.47; moles 0.524) were dissolved in 1500 ml of distilled water. The 
solution was heated with stirring to between 85.degree. and 90.degree. C., 
at which temperature a 1 Molar solution of sodium carbonate was added 
dropwise over a period of one and a half hours (total volume added 500 
ml). At this point the precipitate which was initially pale blue became 
greyish in color. The mixture was allowed to cool over a period of one and 
a half hours, the precipitate filtered off. washed thoroughly with water 
and dried in an oven overnight at 110.degree. C. The dried material was 
placed in an oven set at 200.degree. C. and after one and a half hours the 
temperature raised to 250.degree. C., after a further half hour to 
300.degree. C., after a further half hour to 350.degree. C. and maintained 
at this temperature for four and a half hours. The material was then 
allowed to cool and stored in a sealed bottle. 
Preparation B: Potassium Doped Catalyst of Formula Cu.sub.0.4 Znk.sub.x 
O.sub.y 
7.9 g of potassium carbonate (K.sub.2 CO.sub.3) were dissolved in 100 ml of 
distilled water. 15 ml of the solution were used to impregnate 10 g of the 
Cu.sub.0.4 ZnO.sub.y catalyst prepared in Preparation A. The impregnated 
catalyst was dried at 120.degree. C. and calcined at 400.degree. C. for 
six hours. The thus prepared catalyst contained 6.2 percent by weight of 
potassium. 
Preparation C: Sodium Doped Catalyst of Formula Cu.sub.0.4 ZnNa.sub.x 
O.sub.y 
3.5 g of anhydrous sodium carbonate were dissolved in 90 ml of water and 
used to impregnate 30 g of the Cu.sub.0.4 ZnO.sub.y catalyst prepared in 
Preparation A. The impregnated catalyst was dried at 120.degree. C. and 
calcined at 400.degree. C. for six hours. The thus prepared catalyst 
contained 5 percent by weight of sodium. 
Preparation D: Pd-Containing Zeolite HLZY62 
Zeolite LZY62 (which is an ammonium exchanged Y zeolite obtained from Linde 
in extrudate form) was converted to its acid form (HLZY62) by calcination 
at 400.degree. C. 0.4 g of [Pd(NH.sub.3).sub.4 ] Cl.sub.2 . H.sub.2 O were 
dissolved in 7 ml of water and the solution used to impregnate 8.9 g of 
the zeolite HLZY62. The impregnated material was dried in an oven at 
120.degree. C. and then calcined at 400.degree. C. for six hours to give a 
zeolite containing 1 percent Pd. 
Preparation E: H Zeolon 700 
Zeolon 700 is a natural ferrierite obtained from the Norton Company 
containing 1 percent by weight of iron. H Zeolon 700 is the acid form of 
Zeolon 700 and was prepared by exchanging cations in the zeolite with 
ammonium ions as follows: 1OO g. of Zeolon 700 was added to 500 ml. of a 5 
percent (w/v) ammonium chloride solution and the solution stirred for one 
hour at 95.degree. C. The Zeolite was filtered off and washed. The 
procedure was repeated 3 more times. The Zeolite was then dried at 
120.degree. C. and calcined at 400.degree. C. to convert it to the acid 
form. 
Preparation F: 6.2 Percent Potassium Cu.sub.0.4 Zn O.sub.y /H Zeolon 700 
10 g of the potassium doped catalyst prepared in Preparation B and 10 g of 
H Zeolon 700 and 0.8 g graphite were ground together in a McCrone Mill and 
pressed into pellets, and meshed to between 5 and 30 mesh. then calcined 
at 400.degree. C. for two hours. 
Preparation G: 5 Percent Sodium Cu.sub.0.4 Zn O.sub.y /H Zeolon 700 
The procedure of Preparation F was followed except 10 g of the sodium doped 
Cu.sub.0.4 Zn O.sub.y catalyst of Preparation C were used in place of the 
potassium doped Cu.sub.0.4 Zn O.sub.y catalyst. 
Preparation H: 6 Percent Na on Cu.sub.1.5 Th Na.sub.x O.sub.y Catalyst/H 
Zeolon 700 
125.50 g of Cu(NO.sub.3).sub.2 . 21/2 H.sub.2 O and 192.19 g of 
Th(NO.sub.3).sub.4 . 4 H.sub.2 O were dissolved in 2.75 liters of 
distilled water and heated to 90.degree. C. The solution was stirred 
vigorously and hot aqueous 2M Na.sub.2 CO.sub.3 solution was added slowly 
over 1 1/4 hours until the pH was 9.5. The mixture was kept at 90.degree. 
C. for one hour and then cooled to room temperature. The pH was adjusted 
to 7.0 with 1.2 M HNO.sub.3 and then the mixture vacuum filtered. The 
filter cake was not allowed to become completely dry and was reslurried 
with one litre of distilled water and heated to 60.degree. C. then again 
vacuum filtered. 
The filter cake was allowed to dry, was broken up using a pestle and mortar 
and reslurried with one liter of distilled water again heated to 
60.degree. C. and refiltered. The filter cake was dried in an oven at 
150.degree. C. for four hours and then calcined in a muffle furnace for 4 
1/2 hours at 400.degree. C. This material contained 0.7 percent by weight 
of sodium. 
1.85 g of Na NO.sub.3 were dissolved in 4.8 ml of distilled water and the 
solution used to impregnate 10 g of the above prepared catalyst and dried 
at 120.degree. C. for two hours. 10 g of the impregnated catalyst 
containing 6 percent by weight of sodium was mixed with H Zeolon 700 (10 
g) and graphite (1 g) and ground using a McCrone Mill. The mixture was 
pressed into pellets, broken and sieved to collect particles between 5 and 
30 mesh, and then calcined at 400.degree. C. for 48 hours. 
Preparation I: 4 Percent Na on Cu.sub.1.5 Th Na.sub.x O.sub.y Catalyst/H 
Zeolon 700 
104.4 g of Cu(NO.sub.3).sub.2 . 3 H.sub.2 O and 153.8 g of 
Th(NO.sub.3).sub.4 . 4 H.sub.2 O were dissolved in 2.5 liters of distilled 
water. The solution was heated with stirring to about 90.degree. C., then 
hot 2M Na.sub.2 CO.sub.3 added dropwise over a period of one hour to give 
a final solution of pH 9.5. The solution was kept at 95.degree. C. for one 
hour and then allowed to cool to room temperature. The solution was 
filtered and the filter cake reslurried with one liter of distilled water 
and heated with stirring to 60.degree.-90.degree. C. for one hour, cooled 
and filtered again. The filter cake was reslurried as previously described 
filtered and the filter cake dried at 120.degree. C. in an oven then 
calcined at 400.degree. C. for four hours. 1.85 g of sodium nitrate were 
dissolved in 6.6 ml of distilled water and 2.7 ml of this solution used to 
impregnate 10 g of the above-described catalyst and then the catalyst 
dried at 120.degree. C. for two hours and calcined at 400.degree. C. for 
four hours. The calcined catalyst contained 4 percent by weight of sodium, 
10 g of which was mixed with 10 g of H Zeolon 700 and 0.8 g graphite and 
ground together in a McCrone Mill and pressed into pellets, ground and 
meshed to particles between 5 and 30 mesh and finally calcined at 
400.degree. C. for two hours. 
Preparation J: 2.4 Percent Na on Cu.sub.1.5 Th Na.sub. x O.sub.y 
Catalyst/HZSM35 
104.4 g of Cu(NO.sub.3).sub.2 . 3 H.sub.2 O and 153.8 g of 
Th(NO.sub.3).sub.4 . 4 H.sub.2 O were dissolved in 2.5 liters of distilled 
water and the solution heated with stirring to 90.degree. C. Then 2M 
Na.sub.2 CO.sub.3 solution was added dropwise over a period of one hour 
until the pH was 9.5. The solution was kept at 95.degree. C. for one hour 
and then allowed to cool to room temperature. 2M HNO.sub.3 was then added 
to bring the solution to a pH of 7 and filtered. The filter cake was 
reslurried in 1200 ml of water, heated to 60.degree. C. and the 
precipitate allowed to settle. The liquid was decanted off and the volume 
of the residue made up to 1400 ml with distilled water and heated with 
stirring to 60.degree. C., then filtered and dried at 120.degree. C. for 
48 hours and calcined at 400.degree. C. for four hours. The catalyst 
contained 2.4 percent by weight of sodium. 
10 g of the catalyst and 10 g of zeolite HZSM35 and 0.8 g graphite were 
mixed, ground in a McCrone Mill, pressed into pellets, broken sieved to 
between 5 and 30 mesh and calcined at 400.degree. C. for two hours. 
HZSM35 was prepared by stirring 50 g of ZSM35 prepared as described in the 
literature with 25 g of NH.sub.4 Cl in 500 ml of water at 85.degree. C. 
for one hour. The operation was repeated three more times, filtered, 
washed until washings were free of chloride ions, dried at 125.degree. C. 
and calcined at 550.degree. C. for six hours to convert to the hydrogen 
form HZSM35. 
Preparation K: 6.7 Percent K on Cu.sub.0.4 Zn K.sub.x O.sub.y Catalyst/Na 
Zeolon 700 
7.94 g of K.sub.2 CO.sub.3 were dissolved in 100 ml of distilled water and 
37.5 ml of this solution were used to impregnate 20 g of the Cu.sub.0.4 Zn 
O.sub.y catalyst which was then dried at 120.degree. C. and then calcined 
at 400.degree. C. for three hours to yield a catalyst containing 6.7 
percent by weight of K. 10 g of the calcined catalyst and 10 g of Na 
Zeolon 700 from preparation M described below together with 0.8 g of 
graphite were ground together in a McCrone Mill, pressed into pellets, 
ground and meshed to between 5 and 30 mesh, then finally calcined at 
400.degree. C. for two hours. 
Preparation L: 1.8 Percent Pd on HZSM5 
HZSM5 was prepared by stirring 50 g of ZSM5 prepared as described in the 
literature with 25 g of NH.sub.4 Cl in 500 ml of water at 85.degree. C. 
for one hour. The operation was repeated three more times, filtered, 
washed until washings were free of chloride ions, dried at 125.degree. C. 
and calcined at 550.degree. C. for six hours to convert to the hydrogen 
form HZSM5. 
0.45 g of Pd(NH.sub.3).sub.4 Cl.sub.2. H.sub.2 O were dissolved in 18.4 ml 
of distilled water and 10 g of the zeolite HZSM5 were impregnated with the 
solution. 4 g of alumina (Catapal supplied by Conoco Chemicals) were added 
and thoroughly mixed and the solids pressed into pellets ground and meshed 
to between 5 and 30 mesh, then dried at 120.degree. C. overnight and 
calcined at 550.degree. C. for three hours. 
Preparation M: Na-Zeolon 700 
Zeolon 700 is a natural ferrierite obtained from the Norton Company. 
H-Zeolon 700, the acid form of Zeolon 700, was prepared first by 
exchanging cations in the zeolite with ammonium ions as follows: 200 g of 
Zeolon 700 was added to 1000 ml of a 5 percent (w/v) ammonium chloride 
solution and the solution was stirred for one hour at 95.degree. C. The 
zeolite was filtered off and washed. The procedure was repeated three more 
times. The zeolite was then dried at 120.degree. C. for three hours and 
calcined at 400.degree. C. for three hours to convert it to the acid form. 
84 g of H-Zeolon 700 was added to 1700 ml of a 1 percent (w/v) sodium 
nitrate solution and the solution was stirred for one hour at 90.degree. 
C. The zeolite was filtered and washed with 2000 ml distilled water. The 
zeolite was then dried at 120.degree. C. for two hours and calcined at 
400.degree. C. for three hours to form the Na-Zeolon 700. 
Preparation N: Cu U Al.sub.0.1 O.sub.y /Na Zeolon 700 
217.44 g of UO.sub.2 (NO.sub.3).sub.2 . 6H.sub.2 O (formula weight 502.13; 
moles 0.433), 100.94 g of Cu(NO.sub.3).sub.2 . 2 1/2H.sub.2 O (formula 
weight 232.6; moles 0.434), and 19.69 g Al(NO.sub.3).sub.3 . 9H.sub.2 O 
(formula weight 375.14; moles 0.053) were dissolved in 2000 ml of absolute 
methanol. A 2 molar solution of sodium hydroxide in methanol was added 
dropwise to the nitrate solution while stirring until the pH of the 
solution reached 7. The slurry was filtered and the filtercake was 
resuspended in 1OOO ml of absolute methanol. The solution was once again 
filtered and the filtercake resuspended in 1000 ml of absolute methanol. A 
final filtration was performed with the resultant solids dried in a 
calcining oven which was programmed to increase from room temperature to 
400.degree. C. at 1.degree. C./minute, hold at 400.degree. C. for 120 
minutes, and then cool gradually to room temperature. The calcined 
material was suspended in 1000 ml distilled water. The slurry was stirred 
for one hour prior to filtration. The filtercake was washed with 300 ml 
distilled water, then dried in an oven at 120.degree. C. for two hours. 
Retained sodium was 5.5 percent by weight. 
10.38 g of the above prepared catalyst was mixed with 10.36 g of Na-Zeolon 
700, and 0.79 g of graphite. The mixture was ground using a McCrone mill 
with the resultant powder pressed into pellets. The pellets were crushed 
and sieved to collect particles between 5 and 30 mesh. The particles were 
then calcined at 400.degree. C. for two hours. 
Preparation O: H, LZY-82 
Zeolite LZY-82 (which is an ammonium exchanged Y zeolite obtained from 
Linde in powder form) was pressed into pellets. The pellets were crushed 
and sieved to collect particles between 5 and 30 mesh. The particles were 
calcined at 500.degree. C. for two hours to convert the zeolite to its 
acid form (H, LZY-82). 
Preparation P: SK-500 
Zeolite SK-500 (which is a rare earth exchanged Y zeolite obtained from 
Linde in extrudate form) was converted to its active form by calcination 
at 500.degree. C. for two hours. 
Preparation Q: Pd-Containing Zeolite HZSM-11 
7.22 g of sodium aluminate was dissolved in 432 ml of a 12 percent 
tetrapropyl ammonium hydroxide solution at 60.degree. C. This solution was 
allowed to cool to room temperature prior to the addition of 129.13 g of 
Ludox AS 40 (colloidal silica dispersion from DuPont) accompanied by 
vigorous stirring. The resultant viscous mixture was poured into a 2000 ml 
Teflon liner, which was in turn placed into a stainless steel Parr 
autoclave. The autoclave was tightly sealed and placed into an oven at 
170.degree. C. The autoclave was removed from the oven after three days 
and quenched in a sink of cold water. After cooling, the autoclave was 
opened and the solids collected through filtration. The zeolite was washed 
twice with 800 ml distilled water, dried at 120.degree. C., and calcined 
at 550.degree. C. for three hours. 
The ZSM-11 zeolite was converted to its acid form (HZSM-11) by exchanging 
cations in the zeolite with ammonium ions as follows: 48 g of ZSM-11 was 
added to 1000 ml of a 1.1 percent (w/v) ammonium chloride solution and the 
solution was stirred for one hour at 95.degree. C. The zeolite was 
filtered off and washed. The procedure was repeated three more times. The 
zeolite was then dried at 120.degree. C. and calcined at 550.degree. C. 
for three hours to convert it to the acid form. 
0.06 g Pd(NH.sub.3).sub.4 Cl.sub.2 . H.sub.2 O (41.0 percent Pd by weight) 
was dissolved in 2.5 ml of distilled water and the solution used to 
impregnate 5.0 g of zeolite HZSM-11 to give a zeolite containing 0.50 
percent Pd. The impregnated material was dried in an oven at 120.degree. 
C. for two hours. 5.00 g of alumina (Catapal SB AL-179-L14 supplied by 
Conoco) was mixed with the Pd, HZSM-11. The powder was pressed into 
pellets which were crushed and sieved to collect particles between 5 and 
30 mesh. The particles were then calcined at 550.degree. C. for three 
hours. 
Preparation R: Cu.sub.1.5 Th O.sub.y 
101.0 g Cu(NO.sub.3).sub.2 . 2 1/2H.sub.2 O (formula weight 232.6; moles 
0.433) and 158.6 g Th(NO.sub.3).sub.4 . 4H.sub.2 O (formula weight 552.12; 
moles 0.287) were dissolved in 2000 ml of absolute methanol. A two molar 
solution of sodium hydroxide in methanol was added dropwise to the 
nitrate, with stirring, until the pH of the solution reached 7. The slurry 
was filtered and the filtercake was resuspended in 1000 ml of absolute 
methanol. The solution was again filtered and the filtercake resuspended 
in 1000 ml of absolute methanol. A final filtration was performed with the 
resultant solids dried in a calcining oven programmed to ramp from room 
temperature to 400.degree. C. at 1.degree. C./min., hold at 400.degree. C. 
for 120 minutes, and gradually cool to room temperature. The calcined 
material was suspended in 1000 ml of distilled water and stirred for one 
hour. The slurry was filtered and the filtercake washed with 300 ml of 
distilled water. The catalyst was then dried at 110.degree. C. 
Preparation S: Sodium Doped Catalyst of Formula Cu.sub.0.1 ZrNa.sub.x 
O.sub.y 
A solution of 50.1 g of zirconium hydroxide (Pflatz and Bauer) suspended in 
150 ml of distilled water was refluxed for 24 hours. The solution was 
filtered and the filtercake was washed with 200 ml of distilled water. The 
solids were dried at 100.degree. C. for two hours. 
2.31 g of Cu(NO.sub.3).sub.2 . 2 1/2H.sub.2 O were dissolved in 5 ml of 
distilled water and the solution used to impregnate 12.2 g of the refluxed 
zirconia. The impregnated material was dried in an oven at 120.degree. C. 
for two hours. 
1.10 g of sodium carbonate were dissolved in 10 ml of distilled water and 
the solution used to impregnate 7.96 g of the Cu.sub.0.1 ZrO.sub.y 
catalyst. The impregnated material was dried in an oven at 120.degree. C. 
for two hours to give a catalyst containing 5.9 percent Na and 4.3 percent 
Cu by weight. 
Preparation T: Aluminum Doped Gallosilicate Catalyst 
1.70 g of gallium oxide (Aesar) was added to a solution of 5.16 g of sodium 
hydroxide dissolved in 50.05 g of distilled water. The resultant mixture 
was heated to 80.degree. C. to insure complete dissolution of the oxide. 
The solution was filtered and allowed to cool to room temperature. A 
second solution was prepared by adding 120.86 g of a 20 percent 
tetrapropyl ammonium hydroxide solution to a mixture of 54.01 g of 
distilled water and 150.00 g of Ludox AS 40 (colloidal silica dispersion 
from DuPont). The cooled oxide solution was slowly added to this second 
solution with rapid stirring. Upon mixing the two solutions, a viscous 
white gel immediately formed which became mobile with further stirring. 
After 15 minutes of vigorous stirring, the white paste was poured into the 
Teflon liner of a 2000 ml stainless steel Parr autoclave. The autoclave 
was tightly sealed and placed into an oven at 170.degree. C. The autoclave 
was removed from the oven after four days and quenched in a sink of cold 
water. After cooling, the autoclave was opened and the solids collected 
through filtration. The zeolite was washed with 300 ml of distilled water, 
dried at 120.degree. C., and calcined at 550.degree. C. for three hours. 
The gallosilicate zeolite was converted to its acid form (HGaSiO.sub.x) by 
exchanging cations in the zeolite with ammonium ions as follows: 53.35 g 
of GaSiO.sub.x was added to 1000 ml of a 5 percent (w/v) ammonium chloride 
solution and the solution stirred for four hours at 80.degree. C. The 
zeolite was filtered off and dried at 120.degree. C. This procedure was 
repeated once more with the drying of the zeolite at 120.degree. C. 
followed by calcination at 550.degree. C. for three hours to convert it to 
the acid form. 
7.56 g of HGaSiO.sub.x were dissolved in 15.23 g of distilled water and the 
flask was placed on a Rotovapor RE120 unit to achieve constant mixing. A 
solution of 1.58 g of Al(NO.sub.3).sub.3 . 9H.sub.2 O dissolved in 523.3 g 
of distilled water was gradually added to the continuously mixed zeolite 
solution over a three hour period. The aluminum exchanged gallosilicate 
zeolite collected through filtration was dried at 120.degree. C. for two 
hours, and then calcined at 550.degree. C. for two hours. 
6.61 g of the aluminum exchanged gallosilicate zeolite was mixed with 6.61 
g of alumina (Catapal SB AL-179-L14 supplied by Conoco). The powder was 
pressed into pellets which were crushed and sieved to collect particles 
between 5 and 30 mesh. The particles were then calcined at 550.degree. C. 
for two hours. 
Preparation U: 2.7 Percent Na on Cu.sub.1.5 Th O.sub.y /Na Zeolon 700 
0.79 g of sodium carbonate was dissolved in 10 ml of distilled water. 8 ml 
of the solution were used to impregnate 10.06 g of the Cu.sub.1.5 Th 
O.sub.y catalyst prepared in Preparation R. The impregnated catalyst was 
dried at 110.degree. C. for two hours. 
The above prepared catalyst was mixed with 11.11 g of Na-Zeolon 700 and 
0.89 g of graphite. The mixture was ground using a McCrone mill with the 
resultant powder being pressed into pellets. The pellets were crushed and 
sieved to collect particles between 5 and 30 mesh. The particles were then 
calcined at 400.degree. C. for two hours. 
Preparation V: 4 Percent Na on Cu.sub.1.5 Th O.sub.y /Na Zeolon 700 
0.66 g of sodium carbonate was dissolved in 8 ml of distilled water. This 
solution was used to impregnate 7.02 g of a Cu.sub.1.5 Th O.sub.y catalyst 
prepared as in Preparation R. The impregnated catalyst was dried at 
120.degree. C. for two hours. 
In each case 6.00 g of the above prepared alcohol catalyst was mixed with 
5.93 g of Na-Zeolon 700 and 0.61 g of graphite. In every case the mixture 
was ground using a McCrone mill with the resultant powder pressed into 
pellets. The pellets were crushed and sieved to collect particles between 
5 and 30 mesh. The particles were then calcined at 400.degree. C. for two 
hours. 
Preparation W: 6 Percent Na on Cu.sub.0.1 Zr O.sub.y /Na-Zeolon 700 
7.21 g of Cu.sub.0.1 Zr Na.sub.x O.sub.y, as prepared in Preparation S. 
7.22 g of Na-Zeolon 700, and 0.82 g of graphite were mixed together. The 
mixture was ground using a McCrone mill with the resultant powder pressed 
into pellets. The pellets were crushed and sieved to collect particles 
between 5 and 30 mesh. The particles were then calcined at 400.degree. C. 
for two hours. 
EXAMPLE 1 
The catalyst system employed was a mixture of: (1) 6.2 percent potassium 
CuOZnO/H Zeolon 700 prepared in Preparation F and (2) 1 percent Pd on 
zeolite HLZY62 prepared in Preparation D components 1 and 2 being employed 
in a volume ratio of 4:3 (12 mls and 9 mls respectively) and randomly 
mixed in the reactor tube. The catalyst was reduced by passing a mixture 
of hydrogen (20 SCCM) and nitrogen (200 SCCM) in a volume ratio of 1:10 
and the temperature raised as follows: 10 minutes to 100.degree. C., two 
hours 100.degree. to 150.degree. C., two hours 150.degree. to 250.degree. 
C. and three hours at 250.degree. C. The catalyst was allowed to cool 
overnight. The catalysts in Examples 2-7 and 10 and 12 were subjected to a 
similar reduction treatment. 
EXAMPLE 2 
The catalyst system employed was a mixture of: (1) 5 percent potassium 
Cu.sub.0.4 ZN O.sub.y /H Zeolon 700 prepared in Preparation G and (2) 
HLZY62 prepared in Preparation D. 
Components 1 and 2 were employed in a volume ratio of 4:3, component 1 
being added to the reactor tube first and then component 2, the two 
components being separated by a plug of glass wool. 
Experiment A 
In Experiment A, no supported iron catalyst was present. The mixture of 
alcohol catalyst and zeolite used was prepared in Preparation J. 
EXAMPLES 3 and 4 
In Examples 3 and 4 the iron-containing component and the zeolite cracking 
catalyst were both provided by the H-Zeolon 700. In Example 4, separate 
catalyst particles of Zeolite and the modified catalyst were randomly 
mixed in the reactor tube. 
TABLE 1 
______________________________________ 
CATALYST TESTING CONDITIONS AND 
PRODUCT SELECTIVITIES 
Catalyst System Example 1 Example 2 
______________________________________ 
Alcohol FROM FROM PRE- 
Catalyst PREATION ATION G 
F 
Supported Fe 
Zeolite 1 wt Percent HLZY62 
Pd on HLZY62 
Vol ratio of 4:3 4:3 
modified catalyst 
to zeolite 
GHSV (h.sup.-1) 1245 1285 
Feed H.sub.2 /CO molar ratio 
0.41 0.34 
Pressure, (psig) 
750 750 
Reactor Temperature (.degree.C.) 
Set 306 303 
Average Hot Spot 
321 325 
Run length (hours) 
18.2 24.5 
Syngas Conversion Percent 
H.sub.2 59.7 60 
CO (total) 33.6 33.3 
CO to CO.sub.2 14.9 16.0 
CO to hydrocarbons 
16.3 14.7 
CO to oxygenates 
trace trace 
H.sub.2 /CO consumption 
0.73 0.62 
Hydrocarbon Product 
Distribution Wt Percent 
CH.sub.4 9.0 8.8 
C.sub.2 9.8 7.3 
C.sub.3 -C.sub.4 
23.3 21.0 
gasoline (&lt;180.degree. C.) 
36.7 38.0 
diesel (&lt;340.degree. C.) 
18.7 21.3 
Higher MW (&gt;340.degree. C.) 
2.6 3.6 
Hydrocarbons in the 
78.7 80.3 
range C.sub.3 to a boiling 
point of 340.degree. C. 
______________________________________ 
The Table illustrates that in both Examples 1 to 2 a hydrocarbon product 
was obtained containing less than 10 percent by weight of methane and more 
than 75 percent by weight of hydrocarbons in the range C.sub.3 to a 
boiling point of 340.degree. C. 
TABLE 2 
______________________________________ 
CATALYST TESTING CONDITIONS AND 
PRODUCT SELECTIVITIES 
Example Example Experiment 
Catalysy System 
3 4 A 
______________________________________ 
Alcohol FROM FROM Cu.sub.1.5 ThNa.sub.x O.sub.y 
Catalyst PRE- PRE- (2.4 Wt 
A- A- Percent Na) 
TION H TION I 
Supported Fe -- 
Zeolite -- H-zeolon HZSM35 
700 
Vol ratio of -- 1:1 -- 
modified catalyst 
to zeolite 
GHSV (h.sup.-1) 
1526 2820 1545 
Feed H.sub.2 /CO Molar 
0.57 0.63 0.62 
Ratio 
Pressure, (psig) 
750 750 750 
Reactor Temperature (.degree. C.) 
Set 306 306 349 
Average Hot Spot 
358 .+-. 4 
327 360 
Run length (h) 2.4 18.8 4.3 
Syngas Conversion 
Percent 
H.sub.2 77.4 50 45.1 
CO (total) 66.4 40 28.6 
CO to CO.sub.2 29.9 20.9 9.0 
CO to hydrocarbons 
27.8 19.1 3.2 
CO to oxygenates 
2.2 1.0 9.4 
H.sub.2 /CO consumption 
0.66 0.78 0.98 
Hydrocarbon Product 
Distribution Wt Percent 
CH.sub.4 17.4 17.2 24.4 
C.sub.2 9.3 9.8 8.0 
C.sub.3 -C.sub.4 
17.6 21.4 54.9 
gasoline (&lt;180.degree. C.) 
39.5 36.6 12.7 
diesel (&lt; 340.degree. C.) 
13.5 13.7 -- 
Higher MW (&gt;340.degree. C.) 
2.7 1.3 -- 
Hydrocarbons in the 
70.6 71.7 67.6 
range C.sub.3 to a 
boiling point of 340.degree. C. 
______________________________________ 
In Example 3 the catalyst system comprised (1) 6 percent sodium on 
Cu.sub.1.5 Th Na.sub.x Oy/H Zeolon 700 prepared as described in 
Preparation H. 
In Example 4 the catalyst system comprised (1) 4 percent sodium on 
Cu.sub.1.5 Th Na.sub.x Oy/H Zeolon 700 as prepared in Preparation I. 
This Table shows that for both Examples 3 and 4 the hydrocarbon product 
contained at least 70 percent by weight of hydrocarbons in the range 
C.sub.3 to a boiling point of 340.degree. C. the amounts being 70.6 and 
71.7 for Examples 3 and 4 respectively. 
Examples 3 shows that an iron-containing zeolite can be both the iron 
modifier and the zeolite of the catalyst system. 
Experiment A shows that omission of the iron modifier from the catalyst 
system results in a product in which oxygenates predominate over 
hydrocarbons and that of the latter the percentage in the range C.sub.3 to 
a boiling pint of 340.degree. C. is below 70. 
TABLE 3 
______________________________________ 
CATALYST TESTING CONDITIONS AND 
PRODUCT SELECTIVITIES 
Catalyst System 
Example 5 Example 6 Example 7 
______________________________________ 
Alcohol Catalyst 
PREED IN PREATION K 
Iron Modifier PREED IN PREATION M 
Zeolite PREED IN PREATION L 
Wax Cracking 
Catalyst 
Vol Ratio of 1:3 9:7 3:5 
Modified Catalyst 
to Zeolite 
GHSV (hour.sup.-1) 
2184 2113 1820 
Feed 0.44 0.41 0.42 
H.sub.2 /CO Molar Ratio 
Pressure psig 750 750 750 
Reactor Temperature 
Set 314 315 315 
Hot Spot 321 321 321 
Run Length 46.3 48.2 45.4 
(hours) 
Synthesis Gas 
Conversion Percent 
H.sub.2 41.5 36.9 40.9 
CO (total) 22.1 24.0 25.5 
CO to CO.sub.2 
10.7 12.4 10.4 
CO to hydrocarbons 
11.5 13.1 11.1 
CO to oxygenates 
trace trace trace 
H.sub.2 /CO 
consumption 0.83 0.64 0.67 
Hydrocarbon Product 
Distribution, Wt Percent 
CH.sub.4 5.8 5.0 5.8 
C.sub.2 11.2 6.5 10.5 
C.sub.3 -C.sub.4 
62.1 24.2 47.3 
Gasoline (&lt;180 C.) 
11.4 35.9 22.5 
Diesel (&lt;340 C.) 
3.8 10.2 4.5 
Higher (&gt;340 C.) 
0 18.2 9.4 
Hydrocarbons in 
77.3 70.3 74.3 
the range C.sub.3 to 
a boiling point of 
340.degree. C. 
______________________________________ 
The above examples show that as zeolite content of the catalyst system 
decreases the yield of higher molecular weight hydrocarbons increases. 
EXAMPLE 8 
The catalyst system employed was a mixture of: (1) Cu U Al.sub.0.1 O.sub.y 
/Na-Zeolon 700 prepared in Preparation N and (2) H, LZY-82 prepared in 
Preparation O. Components 1 and 2 were employed in a volume ratio of 1:1 
(9 ml each) and randomly mixed in the reactor tube. The catalyst was 
reduced by passing a mixture of hydrogen (50 SCCM) and nitrogen (400 SCCM) 
in a volume ratio of 1:8 over the catalyst bed with the temperature raised 
as follows: 10 minutes to 100.degree. C., two hours 100.degree. C. to 
150.degree. C., two hours 150.degree. C. to 250.degree. C. and three hours 
at 250.degree. C. The catalysts in Examples 9 and 11 were subjected to a 
similar reduction treatment. 
EXAMPLE 9 
The catalyst system employed was a mixture of: (1) 6 percent Na on 
Cu.sub.0.1 Zr O.sub.y /Na-Zeolon 700 prepared in Preparation W and (2) H. 
LZY-82 prepared in Preparation O. Components 1 and 2 were employed in a 
volume ratio of 1:1 (9 ml each) and were randomly mixed in the reactor 
tube. 
EXAMPLE 10 
The catalyst system employed was a mixture of: (1) 4 percent Na on 
Cu.sub.1.5 Th O.sub.y /Na-Zeolon 700 prepared in Preparation V and (2) 
aluminum exchanged gallosilicate zeolite prepared in Preparation T. 
Components 1 and 2 were employed in a volume ratio of 1:1 (8.5 ml each) 
and were randomly mixed in the reactor tube. 
EXAMPLE 11 
The catalyst system employed was a mixture of: (1) 2.7 percent Na on 
Cu.sub.1.5 Th O.sub.y /Na-Zeolon 700 prepared in Preparation U and (2) 
SK-500 prepared in Preparation P. Components 1 and 2 were employed in a 
volume ratio of 1:3 (4.5 and 13.5 ml respectively) and were randomly mixed 
in the reactor tube. 
EXAMPLE 12 
The catalyst system employed was a mixture of: (1) 2.7 percent Na on 
Cu.sub.1.5 Th O.sub.y /Na-Zeolon 700 prepared in Preparation U and (2) 0.5 
percent Pd on H, ZSM-11 prepared in Preparation Q. Components 1 and 2 were 
employed in a volume ratio of 1:1 (9 ml each) and were randomly mixed in 
the reactor tube. The catalyst system was reduced as described in Example 
1. 
The results of Examples 8-12 are summarized in Table 4. 
The above described Examples 1-12 illustrate: 
(i) The ability of the catalyst system of the present invention to convert 
synthesis gas having a molar ratio of hydrogen to carbon monoxide of less 
than one to predominantly liquid hydrocarbons. 
(ii) The ability of the catalyst system of the present invention to convert 
synthesis gas to hydrocarbons in which the hydrocarbon product contains a 
low quantity of wax (hydrocarbon boiling over 340.degree. C.) and a low 
quantity of methane. 
(iii) As compared with prior references, U.S. Pat. Nos. 4,046,830 and 
4,279,830, the catalyst system of the present invention can be used in a 
single stage to convert synthesis gas to low wax content hydrocarbons. 
TABLE 4 
__________________________________________________________________________ 
Example 8 9 10 11 12 
__________________________________________________________________________ 
Alcohol Catalyst 
Cu O Al.sub.0.1 O.sub.x 
6.0 Wt. % Na on 
4.0 Wt. % Na on 
2.7 Wt. % Na on 
2.7 Wt. % Na on 
Cu.sub.0.1 Zr O.sub.x 
Cu.sub.1.5 Th Na.sub.0.1 O.sub.x 
Cu.sub.1.5 Th Na.sub.0.3 O.sub.x 
Cu.sub.1.5 Th Na.sub.0.3 
O.sub.x 
Iron Modifier Na-Zeolon 700 
Na-Zeolon 700 
Na-Zeolon 700 
Na-Zeolon 700 
Na-Zeolon 700 
Zeolite Waxcracking 
H,LZY-82 
H,LZY-82 0.1 Wt. Al on 
SK-500 0.5 Wt. Pd on 
Catalyst gallosilicate H,ZSM-11 
Vol. Ratio of Modified 
1:1 1:1 1:1 1:3 1:1 
Catalyst to Zeolite 
GHSV (Hr-1) 1267 1260 1263 2484 1212 
Feed H.sub.2 /CO 
0.36 0.38 0.43 0.35 0.40 
Molar Ratio 
Pressure (psig) 
750 750 750 750 750 
Set Temp. (.degree.C.) 
336 339 322 310 320 
Hot Spot 348 347 335 338 341 
Temp. (.degree.C.) 
Run Length (Hrs) 
24.0 48.4 41.5 47.0 30.9 
Synthesis Gas 
Conversion % 
H.sub.2 79.3 76.9 76.1 77.1 75.1 
CO (Total) 53.5 48.0 56.0 41.4 48.8 
CO to CO.sub.2 
24.3 21.6 24.4 19.5 23.3 
CO to Hydrocarbons 
22.8 24.3 24.3 17.7 21.7 
CO to Oxygenates 
trace trace trace trace trace 
H.sub.2 /CO Consumption 
0.54 0.61 0.58 0.66 0.61 
Ratio 
Hydrocarbon Product 
Distrib., Wt. % 
CH.sub.4 7.9 8.8 7.3 11.1 10.6 
C.sub.2 5.9 6.4 2.3 6.7 7.5 
C.sub.3 -C.sub.4 
17.8 19.7 27.6 18.2 23.7 
Gasoline 41.5 34.5 49.8 39.0 45.5 
(&lt;180.degree. C.) 
Diesel (&lt;340.degree. C.) 
17.9 16.1 10.3 14.5 5.2 
Higher (&gt;340.degree. C.) 
8.9 14.4 2.8 10.5 7.5 
Hydrocarbons in 
77.2 70.3 87.7 72.7 74.4 
the range C.sub.3 
to a boiling point of 340.degree. C. 
__________________________________________________________________________