The invention provides for a method of making isoalcohols using syngas-to-alcohol catalyst and method of making it. The catalyst is a highly dispersed, alkali promoted, La stabilized, microcrystalline Cu.sub.2 O having a particle size of .ltoreq.6 nm in the presence of an alumina structural promoter, wherein on a mole % alkali free metals-only basis Cu is present in from 45 to 55%, Zn from 10 to 20%, Al from 10 to 25%, La from 5 to 15%, and wherein the alkali is from 0.01 to 0.91% K and from 3 to 6.5% Cs. The method of making it involves coprecipitation at a constant pH from a solution of soluble metal salts of copper, zinc, lanthanum and aluminum with an alkali hydroxide, washing the coprecipitate in the essential absence of CO.sub.2, drying and calcining it, then contacting it with K and Cs to form the promoted catalyst. The promoted catalyst is dried and recalcining to produce a catalyst precursor with highly dispersed CuO crystallites. The catalyst is activated in flowing hydrogen.

FIELD OF THE INVENTION 
The present invention relates to the two stage synthesis of isobutanol and 
methyl butanols by passing synthesis gas over a novel first stage 
catalyst, then passing the product from that stage through a second stage 
containing novel noble metal loaded manganese, zinc, zirconium mixed oxide 
catalyst. Optionally, any ethanol and propanol produced are recycled to 
the second stage. 
BACKGROUND OF THE INVENTION 
Environmental and other concerns have increased the demand for oxygenated 
fuels components for internal combustion engines. For instance, methyl 
tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), as well as ethyl 
tert-butyl ether (ETBE), are some potential high octane oxygenates for 
gasoline engines. This increases the demand for isobutylene for MTBE and 
ETBE production and 2-methyl butylene for TAME production. These olefins 
can be derived by dehydrating isobutanol and methyl butanols, 
respectively. Similarly, alcohols like isobutanol or methyl butanols can 
be etherified with methanol or ethanol directly over solid acid catalysts 
to yield their respective methyl or ethyl ethers which are suitable for 
use as diesel fuel oxygenates. 
The lowest cost isobutylene is usually that recovered as a by-product 
during the catalytic cracking of heavy petroleum fractions. Another source 
of relatively low cost isobutylene is that produced by the dehydration of 
by-product tertiary butyl alcohol which arises from the oxidation of 
isobutane to a tertiary butyl hydroperoxide (TBHP), tertiary butyl alcohol 
(TBA) mixture, and the subsequent reaction of this mixture with propylene 
to produce propylene oxide. Once these supplies are used up, current 
technology requires that isobutylene be obtained by the on purpose 
isomerization and dehydrogenation of butanes. This technology yields 
relatively expensive isobutylene. Therefore, there is a need for a route 
to relatively inexpensive isobutylene. The conversion of synthesis gas to 
isobutanol and its subsequent dehydration is one such route, provide that: 
1) the synthesis gas is derived from low cost carbon sources such as 
remote natural gas or refinery waste streams; 2) the synthesis gas 
production technology is cost effective; and 3) the synthesis gas 
conversion process does not require excessively high pressures, that is, 
pressures above about 1500 psig (10,000 kPa). The cost is reduced if the 
process can be operated below 1000 prig (6900 kPa). Another important 
factor is that the process converts relatively little of the syngas to low 
value alkanes like methane and ethane. Syngas, as used here, is a mixture 
having a hydrogen to carbon monoxide ratio of from about 0.1 to about 4.0, 
preferably about 0.4 to about 2.5, and most preferably from about 0.5 to 
about 1.5. The synthesis gas may contain up to 50% or more carbon dioxide 
with less than 10% preferred, excluding the partial pressure of any inert 
components like nitrogen, argon or methane that may be present. 
Many different copper/zinc oxide based catalysts have been reported for the 
synthesis of methanol, ethanol, n-propanol, isobutanol mixtures, etc. from 
synthesis gas containing hydrogen and carbon monoxide. These catalysts 
usually produce primarily methanol but produce increasing amounts of 
higher alcohols as the reactor temperature is increased. However, as the 
temperature is increased to favor the production of higher alcohols, 
hydrocarbons like methane are also produced. The co-production of 
hydrocarbons limits the economically useful production of higher alcohols. 
Catalysts for the production of methanol are described in U.S. Pat. No. 
4,843,101. These catalysts contain 0.43 mole % CsOH, 29.97 mole % Cu and 
69.70 mole % ZnO and are prepared by precipitating the hydroxy carbonate 
material aurichalcite, Cu.sub.1.5 Zn.sub.3.5 (OH).sub.6 (CO.sub.3).sub.2, 
at pH 6.8 from a nitrate or acetate solution of copper and zinc with 
sodium carbonate. The precipitate is recovered by filtration and washing 
and calcined to 350.degree. C. which converts the hydroxycarbonate 
precursor to metal oxides. These are pelletized and then reduced at 
250.degree. C. at ambient pressure with a 2% H.sub.2 98% N.sub.2 gas 
mixture flowing at a rate of 1.0 to 1.5 liters per hour per gram of 
catalyst. The catalyst is removed under inert atmosphere and treated with 
an aqueous solution of CsOH under nitrogen at 50.degree. C. It is then 
dried under flowing nitrogen before use. At 75 atm pressure with 70% 
H.sub.2, 30% CO synthesis gas at 250.degree. C. flowing at a space 
velocity of 5000, this catalyst produced 455.6 g/kg of catalyst/hour 
methanol, 6.28 g/kg of catalyst/hour methyl formate and 1.61 g/kg of 
catalyst/hour ethanol. 
In other work Klier, et al. in "Direct Synthesis of 
2-Methyl-1-Propanol/Methanol Fuels and Feed Stocks," Final Technical 
Report, March 1988, DOE DE89 003390, reports that a catalyst that on a 
metals only atomic fraction basis was 0.291 Cu, 0.437 Zn, 0.243 Cr, 0.030 
Cs gave about 82 g/l catalyst/hour of a ethanol, n-propanol, isobutanol 
mixture under 0.45 H.sub.2 /CO syngas at 1100 psig (7600 kPa) 310.degree. 
C. and a 3,260 V/V-hr. gas hourly space velocity. 
J. C. Slaa, et al. reported in Catalysis Today 15 (1992) 129-143 the 
synthesis of higher alcohols over modified Cu/ZnO/Al.sub.2 O.sub.3 
catalysts. They state that the alkali dopants are effective for increasing 
the synthesis of higher alcohols in the order of Li&lt;Na&lt;K&lt;Rb&lt;Cs. They found 
at 40 atmospheres (4000 kPa) that the optimum doping of K.sub.2 CO.sub.3 
is between 0.5 and 1.0wt %. 
European Patent Application 0 034 338 A2 (1981) by C. E. Hofstadt, K. 
Kochloefl, and O. Bock discusses a series of potassium promoted 
copper-zinc oxide/alumina catalysts containing various other metal oxides: 
Cr.sub.2 O.sub.3, MnO, ThO.sub.2, Co.sub.2 O.sub.3 or La.sub.2 O.sub.3. 
These catalysts all produce methanol, ethanol, n-propanol, isobutanol, 
etc. but the catalysts described in the European's patent are prepared 
differently than the catalysts of our invention and have different metal 
ratios and lower surface areas than our catalysts. The catalysts described 
in European Patent Application 0 034 338 A2 (1981) are significantly less 
active than the catalysts of our invention. Significantly, their 
preparation does not involve a coprecipitation step involving copper, zinc 
and lanthanum soluble salts and an alkali hydroxide precipitating agent in 
the effective absence of CO.sub.2. 
For instance, in Example 3 of European Patent Application 0 034 338 A2, 
there is a catalyst that is 34.4% Cu, 32.9% ZnO, 16.4% Al.sub.2 O.sub.3, 
3.0% K and 3.4% La.sub.2 O.sub.3 (0.420 Cu, 0.314 Zn, 0.250 Al and 0.016 
La on a metals mole fraction basis as our catalysts are defined), that 
when operated at a space velocity of 2600 hr.sup.-1 at 350.degree. C. 
under 100 atm (about 1470 psi) of syngas containing 29.5% CO converted 
8.28 moles CO/l of catalyst/hour. In contrast, a lanthanum containing 
catalyst prepared according to our invention when operated at a space 
velocity of 12,220 hr.sup.-1 at 321.degree. C. under about 1000 psig 
syngas containing about 51% carbon monoxide converted about 50.9 moles % 
CO/l of catalyst/hour. 
There are a wide variety of other copper-based catalysts reported. For 
instance, Underwood, R. P.; Waller, F. J.; Weist, E. L.; "Development of 
Alternate Fuels From Coal-Derived Syngas," Liquefaction Contractors Review 
Meeting Proceedings, Sep. 3-5, 1991, pp. 65-85, report a promoted 
Cu-ZnO/Al.sub.2 O.sub.3, promoted with other elements, gave 97 g/l of 
catalyst/hour of C.sub.2.sup.+ liquids at 300.degree. C. from 0.45H.sub.2 
/l CO syngas at 1015 psig (about 7000 kPa) and a 10,000 V/V-hr. gas hourly 
space velocity. 
Catalysts based on zirconium oxide for the conversion of syngas to the 
isobutanol and methyl butanol have also been reported, (e.g., W. Keim and 
W. Falter, Catalysis Letters, Vol. 3, pp. 59-64, 1989 and M. Roper, W. 
Keim and J. Seibring, Federal Republic of Germany Patent Application No. 
3524317 A1 and W. Falter and W. Keim 3810421 A1 . However these zirconium 
oxide based catalysts only achieve reliably high productivities of higher 
alcohols at pressures well in excess of 1500 psig. Since the capital cost 
of syngas compressors and the energy cost of operating such compressors 
are major factors in cost of production, isobutanol processes that require 
pressures higher than about 1500 psig are not economically favorable. The 
above referenced works on the synthesis of isobutanol from synthesis gas 
do not disclose the coupling of methanol with ethanol or methanol with 
ethanol and propanol to produce isobutanol. 
Other catalysts, such as gamma alumina impregnated with inorganic base 
promoters such as a basic metal salt and a Group VIII metal, are 
disclosed, for example, in U.S. Pat. No. 3,972,952 for the vapor phase 
conversion of methanol and ethanol to higher linear primary alcohols (such 
as n-butanol and n-propanol) but no significant levels of isobutanol and 
2-methyl butanol. U.S. Pat. No. 4,681,868 and U.S. Pat. No. 4,935,538 
discloses that copper bismuth mixed metal oxide catalyst promoted with 
alkali couples n-propanol to C.sub.6 aldol products but does not disclose 
the conversion of methanol ethanol mixtures to isobutanol and 2-methyl 
butanol. U.S. Pat. No. 5,095,156 discloses that methanol and higher 
alcohols are coupled in the presence of magnesia, (MgO), and also 
discloses losses to methane, e.g., the wt. % selectivity of the water free 
products in Table 7 of the patent shows a selectivity to CO+CO.sub.2 
ranging from 35.8% to 67.7% and selectivity to methane ranging from 6.9% 
to 12.6% where methanol conversion ranged from 7.6% to 90.6% and ethanol 
conversion ranged from 20.4% to 99.1%. Such reactions are also discussed 
W. Ueda et al. in Catalysis Letters, Volume 12, pp. 97-104, 1992, although 
Ueda gives no information of losses to methane.

SUMMARY OF THE INVENTION 
The present invention provides for a method of using first and second stage 
catalysts to produce methyl branched alcohols, specifically isobutanol and 
methyl butanols, along with methanol from synthesis gas. The present 
invention may suitably comprise, consist or consist essentially of the 
elements disclosed herein and may be practiced in the absence of an 
element or limitation not disclosed as required. The present invention 
includes the products produced by the processes disclosed herein. 
DETAILED DESCRIPTION OF THE INVENTION 
Environmental and other concerns have increased the demand for oxygenated 
fuels components for internal combustion engines. For instance methyl 
tert-butyl ether (MTBE), tert-amyl methyl ether (TAME) as well as ethyl 
tert-butyl ether (ETBE), are some potential high octane oxygenates for 
gasoline engines. This increases the demand for isobutylene for MTBE and 
ETBE production and 2-methyl butylene for TAME production. These olefins 
can be derived by dehydrating the corresponding methyl branched alcohols, 
isobutanol and 2-methyl butanol, respectively. These alcohols in turn can 
be synthesized by reaction of methanol and ethanol in the presence of 
synthesis gas and a catalyst. Furthermore, if this reaction is carried out 
in the presence of synthesis gas and an olefin such as ethylene, the 
olefin becomes incorporated into the product isobutanol or 2-methyl 
butanol and other similar methyl branched alcohols. 
An embodiment of the invention provides for a first stage syngas to alcohol 
catalyst that consists of highly dispersed, alkali promoted lanthanum 
stabilized microcrystalline Cu.sub.2 O having a particle size of .ltoreq.6 
nm, interspersed with metallic copper crystallites having a particle size 
of .ltoreq.25 nm, and zinc oxide crystallites having a particle size of 
.ltoreq.6 nm in the presence of a structural promoter such as alumina or 
chromia. This catalyst is obtained by reduction of the mixed Cu, Zn, Al, 
La oxyhydroxides precipitated from solution at a constant pH by alkali 
hydroxide at a temperature between about 30.degree. C. and 100.degree. C. 
in the essential absence of carbon dioxide. The precipitation pH is 
between 7.0 and 11.0, preferably between 7.2 and 9.0, most preferably 
between 7.5 and 8.5, and ideally at 8.2. The alkali hydroxide used may be 
selected from LiOH, NaOH, KOH, CsOH or mixtures thereof. NaOH is 
preferred. While the precipitation temperature may be between 30.degree. 
C. and 100.degree. C., a temperature between about 50.degree. C. and about 
90.degree. C. is preferred and between 75.degree. C. and 85.degree. C. is 
most preferred. Ideally the precipitation is carried out with rapid 
effective mixing at a temperature between 79.degree. C. and 81.degree. C. 
After precipitation the precipitate may be optionally aged, that is, held 
in the essential absence of carbon dioxide in contact with the mother 
liquor (i.e., the solution from which it was precipitated) for 1 hour to 
more than 48 hours at a controlled temperature, typically the temperature 
of precipitation. The precipitate is washed in the essential absence of 
carbon dioxide with water until it is free of alkali, especially sodium. 
The washing may be done in a continuous manner or in a series of 
batch-wise steps. For instance, the precipitate may be recovered from the 
mother liquor by filtration, and the filter cake reslurried with high 
purity water and refiltered. This sequence may be repeated until the 
solids are sufficiently free of alkali. This unpromoted catalyst precursor 
should contain less than 1000 ppm alkali, preferably less than 100 ppm 
alkali and most preferably less than 20 ppm alkali. While we do not wish 
to be bound by any particular theory, we believe the presence of alkali 
during the drying and calcining of the unpromoted catalyst would interfere 
with the essential solid state chemistry that leads to the desired 
microstructure that is expressed after reduction. The washed precipitate 
is dried at up to 120.degree. C. and then calcined in air for more than 
three hours at a temperature from between 300.degree. C. to 700.degree. C. 
The calcined precipitate, after cooling, is then contacted with a solution 
of potassium, cesium, or potassium and cesium such that it contains after 
a second drying step from about 0.01 wt % to 0.91 wt % potassium and from 
about 3 wt % to about 6.5 wt % cesium. The carbonates are effective 
sources of potassium and cesium. The drying of the promoted catalyst is 
conducted in air at up to about 120.degree. C. After drying the promoted 
catalyst is recalcined at from 300.degree. C. to 700.degree. C. in air. 
The resulting catalyst precursor contains highly dispersed CuO 
crystallites of about up to 10 nm. The catalyst precursor is converted to 
an active catalyst by reducing inflowing gas containing hydrogen. The 
reduction step must be conducted in a manner which is conducive to the 
formation and preservation of the desired microstructure. Typically this 
entails a low temperature reduction step at about 140.degree. C. to about 
180.degree. C. and a higher temperature reduction step at about 
250.degree. C. to about 270.degree. C. The composition of this catalyst is 
about, on a metals only mole % basis, 45% to 55%, preferably 50% Cu; 10% 
to 20%, preferably 18% Zn; 10% to 25%, preferably 20% Al; and 5% to 15%, 
preferably 11% La. Promoted on a wt % basis between about 0% to 1%, 
preferably 0.91% K, and 3% to 6.5%, preferably 6.2% Cs usually from the 
carbonate. Rubidium may be substituted to some degree for the potassium 
and cesium, but it is usually not cost effective. 
A second embodiment is the use of this catalyst to convert synthesis gas to 
a mixture of C.sub.1 through C.sub.4 +isoalcohols. The C.sub.4 isoalcohol, 
and the isoalcohol produced in greatest abundance by this catalyst, is 
isobutanol also known as 2-methyl-1-propanol; and the C.sub.5 isoalcohol 
is 2-methyl-1-butanol which is sometimes called isoamyl alcohol. This 
catalytic reaction is governed by the synthesis of methanol which is 
equilibrium controlled and the thermodynamic constraints of which are 
well-known by those skilled in the art. The catalyst of this invention is 
exceptionally productive under economically attractive pressures of less 
than 1500 psig, especially under 1100 psig. 
A third embodiment of this invention is the use of this first stage 
catalyst to produce feed components for the two stage conversion of 
synthesis gas into C.sub.4 and C.sub.5 isoalcohols. The C.sub.4 isoalcohol 
and the isoalcohol produced in greatest abundance by this catalyst is 
isobutanol also known as 2-methyl-1-propanol, and the C.sub.5 isoalcohol 
is 2-methyl-1-butanol which is sometimes called isoamyl alcohol. This 
first stage catalyst produces mixtures of alcohols from methanol through 
ethanol, n-propanol to isobutanol and 2-methyl-1-propanol along with of 
course accompanying amounts of water and carbon dioxide. This total 
mixture can be fed without separation directly to the second stage 
catalyst. Typically, the first stage is operated under about 1000 psig 
(about 6900 kPa) syngas pressure. The first stage may have several 
substages with interstage cooling, but the final exit temperature is 
typically about 320.degree. C. to 330.degree. C. The effluent gas is then 
passed through a furnace and heated to between about 340.degree. C. and 
360.degree. C. before being fed to the second stage. The first stage 
catalyst of this invention is especially suited for this use because of 
its high productivity of C.sub.2 through C.sub.4 alcohols at temperatures 
and pressures close to that required for second stage operation. Its high 
productivity of C.sub.4 and C.sub.5 isoalcohols is a benefit since these 
alcohols pass through the second stage effectively unchanged. 
Although we do not wish to be bound by any specific theory, we believe that 
the second stage catalyst produces isoalcohols by converting an 
equilibrium fraction of the feed alcohols to their aldehydes or surface 
adsorbed equivalent thereof and then causes these species to undergo an 
"aldol"-like addition. This aldol addition is in effect the addition of 
one aldehydic carbon to the carbon alpha to the other aldehyde group. This 
results in a molecule that has a carbon bearing an alcohol group separated 
by one carbon atom from the carbon atom bearing the aldehyde group. Then 
in a key step this molecule effectively dehydrates to form a transient 
alpha beta unsaturated aldehyde before being rehydrogenated to the 
saturated alcohol. While preformed isoalcohols might dehydrogenate to the 
aldehyde and undergo an aldol type addition, they cannot dehydrate since 
the carbon atom alpha to the carbon bearing the newly formed hydroxyl 
group is quaternary; that is, does not bear a hydrogen atom, thus reaction 
reverses. 
This embodiment also provides for the use of a manganese, zinc, zirconium 
oxide containing alkali and noble metal containing second stage catalysts. 
The noble metal is selected from the group consisting of palladium and 
platinum with palladium preferred. Applicants have found that the 
composition and microstructure facilitate production of isobutanol and 
methyl butanols. The protocatalyst, on exposure to syngas at operating 
pressure and temperatures between about 360.degree. C. and 390.degree. C., 
undergoes a solid state reaction which rearranges its microstructure. This 
results in a more active and selective catalyst. Although the precursor 
(protocatalyst) has the overall global composition of the final catalyst, 
the microstructure of protocatalyst and final catalyst are different. 
These second stage catalysts are useful for converting methanol or ethanol 
alone or in combination with n-propanol to isobutanol and methyl butanols. 
The protocatalyst, upon treatment under synthesis gas between about 
360.degree. C. and 390.degree. C., preferably about 380.degree. C., 
results in the formation of a catalyst having at least three phases. The 
composition of each phase is given on an atomic percentage basis excluding 
oxygen and noble metals. The first phase, A' in FIG. 2, which is largest 
in volume and available surface area, is about 60 to about 74 atomic % (on 
a metals only basis) zirconium (preferably tetragonal, cubic or mixtures 
thereof), about 21 to about 31 atomic % manganese, about 5 to about 9 
atomic % zinc mixed oxide in the form of about &lt;40 .ANG. to about 100 
.ANG. crystallites with a ZrO.sub.2 -like structure that also contains a 
minor amount (&lt;1%) of alkali. The noble metal is principally associated 
with this phase. The noble metal may be in the form of a noble metal, a 
noble metal-containing alloy or mixed metal clusters. The noble metal is 
highly dispersed, typically 75% to 100% dispersion. The second phase, B' 
in FIG. 2, is comprised of larger crystallites (from about 200 .ANG. to 
about 1000 .ANG. crystallites), with a concomitantly lower surface area. 
This phase has the composition and structure of a Zr -doped hetaerolite, 
where the Mn/Zn ratio is approximately 2 to 1, that is, about 65 to about 
69 atomic % manganese, about 31 to about 35 atomic % zinc, and about 1 to 
about 5 atomic % zirconium in crystallites that may also contain a small 
amount (0.1 atomic %) of alkali metal. The third phase, C' in FIG. 2, 
which is present in an active catalyst, is zirconium doped manganese-zinc 
phase with a highly variable Mn-Zn ratio. These are relatively large Mn or 
Zn rich crystallites with a highly variable composition that can range 
from about 29 to about 55 atomic % manganese, about 13 to about 55 atomic 
% zinc and about 13 to about 35 atomic % zirconium and range in size from 
about approximately 1000 .ANG. to &gt;4000 .ANG.. 
While not wishing to be bound by any particular theory, Applicants believe 
that the overall efficiency of the catalyst in converting methanol with 
ethanol, n-propanol and light (C.sub.2 to C.sub.3) olefins to the 
corresponding higher (iso) alcohols depends primarily on the available 
surface area of the first phase, and that one of the roles of zinc in this 
phase is to maintain the noble metal highly dispersed thereon. The 
presence of the other phases are important insofar as they help stabilize 
the desired active phase. 
The protocatalyst is prepared by coprecipitating at an essentially constant 
pH of between 8 and 12, preferably between 8.5 and 10, a mixed manganese, 
zinc, zirconium oxyhydroxide with a base selected from the group of alkali 
hydroxides consisting of LiOH, NaOH, KOH, RbOH, CsOH and mixtures thereof 
at temperatures of about 0.degree. C. up to about 100.degree. C., with 
suitable regard given to the freezing and boiling points of the solutions 
used. Preferably, the temperature is between 50.degree. C. and 90.degree. 
C., most preferably between 60.degree. C. and 80.degree. C. The 
concentration, temperature and pH at which the co-precipitation is carried 
out may be varied within the disclosed ranges to produce the 
protocatalyst. Any soluble form of the transition metals manganese, zinc 
and zirconium, that are free of potential catalyst poisons, may be used. 
Manganese nitrate, zinc nitrate and zirconyl nitrate are the preferred 
starting materials. Constant effective stirring or blending of the 
solution is necessary during the precipitation. The precipitated solid is 
then preferably washed with water to remove the alkali salts and other 
soluble materials. If the conditions of catalyst usage require it, the 
solid then may be blended with a suitable binder such as "Cab-O-Si" or a 
silica or zirconia sol and extruded or formed in another suitable manner 
known to those skilled in the art. 
Preferably, the mole ratio of Zr to the sum of the moles of Mn plus Zr is 
between about 0.41 and about 0.50, more preferably between 0.425 and 0.49, 
while the mole ratio of Zn to the sum of the moles of Mn and Zr is 
preferably between 0.29 and 0.40, more preferably between 0.30 and 0.39. 
After an optional drying step, the precipitated solids are calcined, 
preferably in an oxygen containing gas such as air or oxygen, which is 
free of typical catalyst poisons, such as sulfur compounds. The solid is 
calcined at a temperature between about 360.degree. C. and about 
440.degree. C. for one to 24 hours, preferably between 360.degree. C. and 
425.degree. C. and most preferably between 370.degree. C. and 390.degree. 
C. After calcination, the solid is then cooled to room temperature and 
loaded with noble metal. Although the Applicants do not wish to be bound 
by any particular theory, it is believed that the catalyst is more 
effective if it does not contain strong acid sites which would result in 
the conversion of the methanol feed to dimethyl ether rather than to the 
desired higher alcohols by reaction with the corresponding reactants, 
e.g., ethanol, n-propanol. Hence, the noble metal compound or compounds 
used should not contain components which might engender acid sites. 
Materials such as ammonia or amine complexes of palladium or platinum, 
typically as the nitrate salts, are preferred. It is especially preferred 
if the amine complex of the noble metal is an ethanolamine complex. Such 
may be readily obtained by dissolving the noble metal salt (e.g. palladium 
nitrate) in water along with sufficient ethanolamine. A sufficient amount 
of ethanolamine is between about 9 to 36 times the molar amount of noble 
metal used. After noble metal loading, the material is dried either in air 
or under vacuum and is ready for activation. Depending on the noble metal 
precursor used, an optional air calcining step, as well as an optional 
pre-reduction or pre-reduction and passivation step as well-known by those 
skilled in the art, may be used. 
The protocatalyst, thus obtained by coprecipitation and washing will have 
at least two phases in addition to the noble metal or any added binder 
support. The first phase, Phase A in FIG. 1, is a continuous phase 
containing small and often poorly crystalline particles of a manganese and 
zinc doped zirconium oxide (preferably tetragonal, cubic or mixtures 
thereof) phase having about 71 to about 91 atomic % (on a metals only 
basis) zirconium, about 10 to about 16 atomic % manganese and about 4 to 
about 8 atomic % zinc and also containing the noble metal and alkali. 
Embedded in this extensive phase is a second, distinct phase, Phase B in 
FIG. 1, of zirconium doped hetaerolite (Mn.sub.2 ZnO.sub.4) or 
hetaerolite-like crystallites (e.g., crystals that give a electron or 
x-ray diffraction pattern similar to Mn.sub.2 ZnO.sub.4) containing about 
approximately about 65 to about 69 atomic % manganese, about 31 to about 
35 atomic % zinc and about 0 to about 5 atomic % zirconium. These 
hetaerolite phase crystallites range in size from approximately 500 .ANG. 
to about 2000 .ANG.. A few large (&gt;0.2 micron sized) particles of ZnO, 
sometimes containing some Mn and alkali metal, are occasionally found in 
less than optimum preparations that are believed to be indicative of 
insufficiently rapid mixing and pH control during the precipitation step 
or non-optimum starting metal ratios. 
The overall bulk composition of the protocatalyst or catalyst expressed as 
atomic ratios of the metallic elements a:Mn b:Zn c:Zr has values of 
between about 3 to about 5 for a, about 2 to about 3 for b, and about 3 to 
about 5 for c. On the same atomic ratio scale, the value for the alkali 
metal coefficient is typically less than 0.1. On this material 0.1 to 5 wt 
% palladium or about 0.2 to about 10 wt % platinum may be used with 0.2 to 
2 wt % preferred and palladium preferred. Higher noble metal 
concentrations unnecessarily add to the cost of the catalyst without a 
significant benefit. 
On reduction in hydrogen and exposure to synthesis gas at from about 
360.degree. C. to 390.degree., typically 380.degree. C., the protocatalyst 
is transformed into an active final catalyst phase (synthesis gas treated 
catalyst), the composition of which was discussed above. The reduction 
step is typically carried out in a manner that results in a highly 
dispersed noble metal phase. A typical reduction sequence would include 
establishing a flow of dry, poison-free inert gas at low pressure through 
the bed of the protocatalyst at about at least 30 SCCM/cm.sup.3 of 
catalyst volume and heating the reactor to 100.degree. C. at 8.degree. 
C./minute or less until 100.degree. C. is achieved and holding for at 
least 20 seconds per cm.sup.3 of catalyst volume. Thereafter, hydrogen is 
gradually introduced (to minimalize catalyst decomposition) into the inert 
gas until the hydrogen partial pressure is between about 60 and about 80 
kPa. The reactor temperature then is increased at about 8.degree. 
C./minute or less until 200.degree. C. is achieved, at which point the 
temperature is held for about 20 sec/cm.sup.3 of catalyst. The temperature 
is increased at 4.degree. C./min or less to 260.degree. C. and held while 
the partial pressure of hydrogen is increased up to about 1 atm. or 100 
kPa and the hydrogen flow rate increased to about 300 SCCM/cm.sup.3 of 
catalyst. The catalyst is held under these conditions for at least about 3 
min/cm.sup.3 of catalyst. This gentle reduction sweeps reaction products 
from the reactor The reactor temperature is then increased at a rate of 
3.degree. C./minute or less until up to about 380.degree. C. to 
400.degree. C. is achieved. The catalyst is typically held at that 
temperature for at least one hour before the introduction of synthesis gas 
and the increase in pressure to the operating range. It is often advisable 
to decrease the temperature to about 350.degree. C. before synthesis gas 
is introduced to avoid the occurrence of any destructive exotherms. If the 
temperature is decreased before the introduction of synthesis gas, it may 
be increased at a controllable rate back to about 380.degree. C. once the 
synthesis gas is introduced and flowing at operating pressure. 
The synthesis gas used may have a hydrogen to carbon monoxide ratio of from 
about 0.1 to 4.0, preferably 0.4 to 2.5, and most preferably from about 
0.5 to about 1.5. The synthesis gas may contain up to 50% or more carbon 
dioxide with less than 10% preferred. This synthesis gas may also contain 
light olefins, like ethylene or ethylene and propylene, during operation 
since the catalyst will incorporate a portion of these olefins into the 
higher alcohol product, but it is usually advisable to introduce these 
olefins to the catalyst after the catalyst has been operated under 
synthesis gas for several hours. Of course, the synthesis gas may also 
contain inert gases such as nitrogen, argon and relatively unreactive 
hydrocarbons like methane and ethane, etc. 
While the protocatalyst can be used directly after reduction in hydrogen, 
it tends to be more effective if treated or held under synthesis gas, 
typically from 24 to 96 hours at between 360.degree. C. and 390.degree. 
C., preferably 370.degree. C. to 390.degree. C., to allow the 
transformations (i.e., in microstructure to produce the final catalyst) to 
occur (see Example 23, Table 6 below). 
It is important that the combination of the overall elemental composition 
and microstructure of the catalysts fall within the requirements described 
herein. Desirably, the result will be a catalyst having high isobutanol 
selectivity and productivity at relatively low pressures for this type 
chemistry (pressure, up to about 1500 psig (10,350 kPa)). 
The operating pressures and temperatures in the process herein are a 
function of the methanol, hydrogen and carbon monoxide thermodynamics. If 
the temperature is too high relative to the synthesis gas pressure, 
methanol will be decomposed to synthesis gas. If the pressure is too high 
relative to the hydrogen partial pressure, too little dehydrogenation will 
occur and the rate of coupling will be slow. The ratio of methanol to 
ethanol, or methanol to ethanol and n-propanol can vary from 50:1 to 4:1, 
with a preferred range of 15:1 and 5:1, and a more preferred range of 12:1 
and 6:1. If the amount of ethanol, or ethanol and propanol is 
insufficient, the productivity will be low. If the amount of these higher 
alcohols is excessive, products such as n-butanol from ethanol-ethanol 
coupling, and 2-methyl pentanol from n-propanol to n-propanol coupling 
will become significant. Depending on the H.sub.2 and CO partial pressures 
and their ratio, methanol and ethanol, or methanol, ethanol and n-propanol 
will be smoothly converted to isobutanol with some methyl butanols at 
temperatures in the range of about 330.degree. C. to 355.degree. C., and 
above H.sub.2 to CO ratios of about 0.8 to about 1.2, with combined 
partial pressures of about 5600 kPa to about 6600 kPa. 
Conversion by this second stage catalyst is preferably greater than 50%, 
more preferably greater than 80%, most preferably greater than 90% of 
ethanol fed, and preferably above 70% more preferably above 80% of the 
n-propanol fed. Optionally any unconverted ethanol and n-propanol may be 
recycled. 
Table A below gives the composition of the various phases on a metals mole 
percent basis. 
TABLE A 
______________________________________ 
Phase Mn Zn Zr 
______________________________________ 
A 13 .+-. 3 6 .+-. 2 
81 .+-. 10 
B 67 .+-. 2 33 .+-. 2 
2.5 .+-. 2.5 
______________________________________ 
Phase A is composed of small, Mn doped crystallites of ZrO.sub.2 that are 
responsible for the majority of the protocatalyst surface area. These 
crystals also contain a small amount of Zn. Phase B consists of 
hetaerolite, Mn.sub.2 ZnO.sub.4, crystallites. 
Table B describes the catalyst after treatment for more than 80 hours under 
synthesis gas at 380.degree. C. 
TABLE B 
______________________________________ 
Phase Mn Zn Zr 
______________________________________ 
A' 26 .+-. 5 7 .+-. 2 
67 .+-. 7 
B' 67 .+-. 2 33 .+-. 2 
2.5 .+-. 2.5 
C' 42 .+-. 13 34 .+-. 21 
24 .+-. 11* 
______________________________________ 
*Dense agglomerates of the C' type are all relatively rich in Mn and Zn 
but exhibit a wide range of Mn to Zn ratios. 
Phase A' remains the high surface area phase composed of small (about 40 
.ANG. to about 100 .ANG.) Mn-doped ZrO.sub.2 that have become enriched in 
Mn while their Zn content hasn't significantly increased. These small 
crystallites exhibited a high concentration of stacking faults and other 
defects consistent with the presence of dopant atoms. The diffraction 
patterns, obtained from these small crystallites, were broad and poorly 
formed. They were most consistent with that expected for cubic ZrO.sub.2 
and differing only by the absence of the 102 reflection at 2.1 .ANG. from 
the pattern expected of tetragonal ZrO.sub.2. Monoclinic ZrO.sub.2 can be 
ruled out since many unique reflections expected for that structure were 
missing. Phase B' are hetaerolite crystallites as in the protocatalyst but 
are considerably fewer in number and smaller in size. As their diffraction 
pattern did not change, they gained little if any Zr during catalyst 
activation. The third phase, C', are dense crystallites, all relatively 
rich in Mn and Zn, which exhibit a wide range of Mn to Zn ratios. 
EXAMPLE 1 
This demonstrates the preparation and use of the first stage catalyst in a 
preferred embodiment. 
A "metals" solution was prepared by dissolving 32.41 g of 
Cu(NO.sub.3).sub.2.2.5 H.sub.2 O, 14.34 g of Zn(NO.sub.3).sub.3.6H.sub.2 
O, 21.67 g of Al(NO.sub.3).sub.3.9H.sub.2 O, and 13.86 g of La(CH.sub.3 
COO).sub.3.1.5H.sub.2 O in 300 ml of deionized water at 53.degree. C. to 
which sufficient concentrated HNO.sub.3 was added to adjust the pH to 1.6. 
A base solution was prepared by dissolving 30.0 g of NaOH in 300 ml of 
deionized water. A 300 ml. portion of deionized water was added to a 1 l 
beaker and preheated to 80.degree. C. To this the "metals" and base 
solution were added simultaneously over the course of about an hour in 
such a manner as the pH was controlled at 8.2 and the temperature of the 
slurry maintained at 80.degree. C. After the addition of the "metals" 
solution was complete, the mixture was aged for an hour at 80.degree. C. 
During the entire period of "metals" solution addition and aging, the 
reaction mixture was sparged with nitrogen to prevent the formation of 
carbonates by reaction with atmospheric CO.sub.2. After aging, the 
precipitate was filtered and washed in a continuous fashion with 2 l of 
deionized water. Then the precipitate was air dried at room temperature to 
yield 33.08 g of solids. 1.07 g of this material were retained for 
analysis and the remaining 32.01 g were oven dried at 120.degree. C. for 
12 hrs before being calcined in air for 3 hrs at 400.degree. C. The yield 
after drying and calcining was 23.33 g of solid. The powder x-ray 
diffraction pattern of both the air dried solid and the calcined material 
show only amorphous or very finely crystalline material present. The 
surface area of the calcined precipitate, as measured by argon BET, was 
98.9 m.sup.2 /g. The bulk density of the calcined material was 1.61 
g/cm.sup.3, thus the volumetric surface area of this material was 159 
m.sup.2 /cm.sup.3. The catalyst was then impregnated with an aqueous 
solution of K.sub.2 CO.sub.3 and Cs.sub.2 CO.sub.3 to give a material that 
after air drying contained 0.91 wt % K and 6.2 wt % Cs. 
2 cm.sup.3 of this material was then mixed with 4 cm3 of high purity low 
surface area alpha alumina and placed in a 0.4" (10.16 mm) internal 
diameter copper-lined reactor. After purging with inert gas to remove any 
traces of oxygen the catalyst was pressurized with flowing hydrogen to 
5175 kPa (750 psig) and reduced for 1 hr at 149.degree. C. then for an 
additional hour at 260.degree. C. During the reduction, the hydrogen 
hourly space velocity was 6,000. After reduction the hydrogen was replaced 
with 1 to 1 H.sub.2 /CO synthesis gas and the pressure increased to 6210 
kPa (900 psig) and the space velocity was increased to 12,000. Under these 
conditions of pressure and feed gas flow, the catalyst productivity was 
determined for three 4.5 hr periods at 260.degree. C., 288.degree. C., and 
321.degree. C. respectively. The catalyst productivity is given in Table 
1A. No activity decline was observed during this test. 
After use, the catalyst was examined by powder x-ray diffraction, electron 
microscopy and selected area electron diffraction. Powder x-ray 
diffraction revealed the presence of crystalline phases consistent with 
metallic copper and zinc oxide. Electron microscopy and selected area 
electron diffraction revealed that were also regions of microcrystalline 
Cu.sub.2 O. Since the used catalyst was subjected to exposure to air after 
use and before analysis and such exposure would be expected to oxidize any 
finely dispersed metallic copper or Cu.sub.2 O to CuO we believe that the 
presence of highly disperse microcrystalline Cu.sub.2 O is due to the 
stabilizing effect of lanthanum. This is supported by the finding that as 
determined by the ratio of emitted x-rays from representative 17,500 
nm.sup.2 regions of this used first stage catalyst the La/Cu ratio stayed 
more nearly the same than any other metal ratio. The presence of this 
highly disperse Cu.sub.2 O material is a unique feature of this catalyst 
that contributes to the high productivity and selectivity of this catalyst 
for the conversion of synthesis gas to C.sub.2 + alcohols. 
TABLE 1A 
______________________________________ 
Temperature .degree.C. 
260 288 321 
CO Conversion (%) 12.88 21.41 23.29 
Productivities (g/hr/l of catalyst) 
methane 1.59 5.00 15.18 
Other hydrocarbons 
1.78 13.44 38.47 
methanol 858.20 1132.68 715.35 
ethanol 28.72 62.31 47.40 
n-propanol 11.31 38.18 49.12 
isobutanol 2.71 24.10 77.25 
methyl butanols 2.80 13.40 29.66 
Other alcohols & oxygenates 
11.04 33.49 64.03 
______________________________________ 
EXAMPLE 2 
This example demonstrates the unexpected effect of the precipitating agent. 
The current art recognizes either sodium carbonate or sodium bicarbonate as 
typical precipitating agents for the preparation of alcohol synthesis 
catalysts. We have found, unexpectedly, that catalysts with superior 
activity for higher alcohol synthesis result when sodium hydroxide is used 
as the precipitating agent instead of the carbonate or bicarbonate. This 
effect is shown in the table below. The catalysts were prepared by 
continuous coprecipitation, followed by filtering and washing the 
precipitate, drying at 120.degree. C., and calcining in air at 400.degree. 
C. for 3 hrs. During co-precipitation the mixture was sparged with 
nitrogen to prevent reaction with atmospheric CO.sub.2. The catalysts were 
reduced in hydrogen at 177.degree. C. for 1 hr followed by reduction at 
260.degree. C. for 1 hr. The hydrogen space velocity was 6000/hr and the 
pressure was 750 psig (5,175 kPa). Testing followed reduction at 
approximately 13000/hr. space velocity, 925 psig (6383 kPa) pressure, and 
1/l H.sub.2 /CO ratio synthesis gas. 
TABLE 2 
______________________________________ 
Precipitation Agent Na.sub.2 CO.sub.3 
NaOH 
Metal Content Oxygen Free Mole Fraction 
Cu 0.67 0.68 
Zn 0.18 0.18 
Al 0.09 0.10 
Mg 0.05 0.03 
Precipitation pH 9 9 
Precipitation Temp (.degree.V) 
50 50 
Precipitation Sparge N.sub.2 N.sub.2 
Catalyst Surface Area (m.sup.2 /g) 
45.4 50.1 
Alkali 0.91 wt % K 
0.91 wt % K 
Performance at 321.degree. C. 
CO Conversion (%) 9.6 12.8 
Productivity (g/hr/l of catalyst) 
methane 3.4 4.5 
methanol 565.1 584.8 
ethanol 20.8 32.0 
n-propanol 9.6 22.1 
isobutanol 7.5 22.3 
n-butanol 2.5 5.3 
methyl butanols 0.5 0.8 
n-pentanol 1.6 3.4 
C.sub.2 through C.sub.5 alcohols 
42.5 85.9 
______________________________________ 
The powder x-ray diffraction patterns for the uncalcined precipitates shows 
significant differences between the sodium carbonate and sodium hydroxide 
precipitated materials. The sodium carbonate precipitated material shows a 
complex diffraction pattern indicative of a crystalline hydrotalcite-type 
material. On the other hand, the sodium hydroxide precipitated material 
has a pattern with diffuse peaks and also shows the presence of copper 
oxide. Copper oxide is absent from the sodium carbonate precipitated 
material. Both materials show similar patterns after calcination except 
that larger crystals of zinc oxide are present in the sodium hydroxide 
precipitated material than in the sodium carbonate precipitated material. 
EXAMPLE 3 
This example shows the effect of composition and preparation on catalyst 
selectivity toward the desired higher alcohols. It compares a commercially 
prepared "copper-zinc oxide" low pressure methanol synthesis catalyst with 
alcohol synthesis catalyst of this invention prepared by NaOH 
precipitation. 
TABLE 3 
______________________________________ 
Commercial 
Catalyst Methanol This Invention 
______________________________________ 
Added Alkali 3.1 wt % Cs 
3.1 wt % Cs 
Precipitation Agent -- NaOH 
Metal Content Oxygen free Mole Fraction 
Cu 0.65 0.50 
Zn 0.20 0.18 
Al 0.15 0.20 
La 0.00 0.11 
Precipitation pH 8.2 
Precipitation Temperature (.degree.C.) 
-- 80 
Precipitation Sparge 
-- N.sub.2 
Catalyst Surface Area (sq.m/g) 
90 99 
Performance at 610.degree. F. (321.degree. C.) 
GHSV 12580 12590 
Pressure (psig) 925 925 
H.sub.2 /CO 0.99 0.95 
CO conversion (%) 19.0 20.5 
Productivity (g/hr/l of catalyst) 
methane 10.9 13.2 
methanol 720.7 672.4 
ethanol 57.6 28.8 
n-propanol 39.4 25.5 
isobutanol 27.8 82.4 
n-butanol 11.9 5.4 
methyl butanols 18.3 23.6 
n-pentanol 6.6 3.3 
C.sub.2 OH-C.sub.5 OH 
161.6 169.0 
iROH/nROH 0.40 1.68 
______________________________________ 
The data above show the effect of optimization of the catalyst formulation 
and preparation on higher alcohol yields and selectivities. The comparison 
is with a commercial methanol catalyst alkalized with the same level of Cs 
(as Cs.sub.2 CO.sub.3). The isobutanol catalyst shows somewhat higher 
activity for higher alcohol synthesis and significantly higher selectivity 
to isoalcohols. The reduction and test procedures are the same as 
described under Example 1. 
EXAMPLE 4 
This example shows the effect of optimization on catalyst performance. 
Optimization of the catalyst formulation and preparation procedure had a 
very profound effect on the catalytic performance of these materials. The 
variables investigated were: metals content and composition, precipitant, 
precipitation temperature, precipitation pH, type of gas sparge used 
during precipitation and level and type of alkalizing agent. The catalyst 
preparation and formulation were optimized through the use of a neural net 
model. Data from several preparations were used to train the model. The 
model was then used to predict optimum formulations and preparation 
procedures. Data from these formulations were subsequently used to retrain 
the net and the cycle was repeated. The result can be seen below where an 
early formulation is compared with the optimum achieved through neural net 
modeling. 
TABLE 4 
______________________________________ 
Catalyst Early Example 
Optimized 
______________________________________ 
Precipitation Agent Na.sub.2 CO.sub.3 
NaOH 
Metal Content Oxygen Free Mole Fraction 
Cu 0.69 0.50 
Zn 0.19 0.18 
Al 0.09 0.20 
La 0.00 0.11 
Mg 0.02 0.0 
Precipitation pH 7.0 8.2 
Precipitation Temp (.degree.C.) 
50 80 
Precipitation Sparge 
CO.sub.2 N.sub.2 
Calcination Temperature (.degree.C.) 
400 400 
Alkali 
K, wt % 0.91 0.91 
Cs, wt % 0.0 6.2 
Catalyst Surface Area (sq.m/g) 
90 99 
Performance at 610.degree. F. 
GHSV 13210 12590 
Pressure (psig) 925 925 
H.sub.2 /CO 0.98 0.95 
CO Conversion (%) 9.0 23.3 
Productivity (g/hr/l of catalyst) 
methane 2.6 15.2 
methanol 443.4 715.4 
ethanol 15.7 47.4 
n-propanol 7.7 49.1 
isobutanol 6.5 77.3 
n-butanol 2.2 12.1 
methyl butanols 4.0 29.7 
n-pentanols 0.0 8.2 
C.sub.2 OH-C.sub.5 OH 
36.1 223.8 
iROH/nROH 0.43 0.92 
______________________________________ 
Despite the similarities of the two materials above, the effect of 
optimization was profound. The productivity of C.sub.2.sup.+ alcohols 
increased over six times and the selectivity to isoalcohols more than 
doubled. 
EXAMPLE 5 
This examples shows the effect of alkali. Alkalization of the catalysts is 
needed to increase selectivity to higher alcohols. 
TABLE 5 
______________________________________ 
Catalyst -- Optimized 
______________________________________ 
Precipitation Agent NaOH 
Metal Content 
Cu 0.50 
Zn 0.18 
Al 0.20 
La 0.11 
Mg 0.0 
Precipitation pH 8.2 
Precipitation Temp (.degree.C.) 
80 
Precipitation Sparge N.sub.2 
Calcination Temperature (.degree.C.) 
400 
Alkali 99 
K, wt % 0.0 0.0 0.91 
Cs, wt % 3.1 6.2 6.2 
Performance at 610.degree. F. (321.degree. C.) 
GHSV 12590 12729 12590 
Pressure (psig) 925 925 925 
H.sub.2 /CO 0.95 0.94 0.95 
CO Conversion (%) 
20.5 23.2 23.3 
Productivity (g/hr/lr of catalyst 
methane 13.2 14.8 15.2 
methanol 672.4 718.1 715.4 
ethanol 28.8 40.4 47.4 
n-propanol 25.5 39.0 49.1 
isobutanol 82.4 86.1 77.3 
n-butanol 5.4 9.4 12.1 
methyl butanols 23.6 29.3 29.7 
n-pentanols 3.3 6.3 8.2 
C.sub.2 OH-C.sub.5 OH 
169.0 210.5 223.8 
iROH/nROH 1.68 1.21 0.92 
______________________________________ 
Cesium improves activity and productivity of isoalcohols while potassium 
increases productivity of normal alcohols. Methane productivity increases 
with increasing alkali content. The higher levels of Cs and K are 
preferred due to the higher productivity of higher alcohols. 
EXAMPLE 6 
This example shows the unique effect of lanthanum. The addition of 
lanthanum improves the productivity of higher alcohols and the selectivity 
to isoalcohols. Overall CO conversion is increased, as is the catalyst 
surface area. 
TABLE 6 
______________________________________ 
Catalyst Without La 
With La 
______________________________________ 
Precipitation Agent 
NaOH NaOH 
Metal Content 
(Oxygen Free Mole Fraction) 
Cu 0.68 0.63 
Zn 0.18 0.17 
Al 0.10 0.09 
Mg 0.04 0.04 
La 0.00 0.06 
Precipitation pH 10.0 9.0 
Precipitation Temp (.degree.C.) 
50 50 
Precipitation Sparge 
N.sub.2 N.sub.2 
Calcination Temperature (.degree.C.) 
400 400 
Alkali 
K, wt % 0.91 0.91 
Cs, wt % 0.0 0.0 
Catalyst Surface Area (sq. m/g) 
40.1 71.9 
Performance at 610.degree. F. 
GHSV 12120 12250 
Pressure (psig) 925 925 
H.sub.2 /CO 0.96 0.95 
CO Conversion (%) 14.5 18.2 
Productivity (g/hr/l of catalyst) 
methane 5.0 10.7 
methanol 564.5 642.2 
ethanol 34.8 28.6 
n-propanol 28.1 21.5 
isobutanol 24.7 65.5 
n-butanol 6.9 4.7 
methyl butanols 11.6 21.0 
n-pentanol 4.4 3.2 
C.sub.2 OH--C.sub.5 OH 
110.5 144.5 
iROH/nROH 0.49 1.49 
______________________________________ 
EXAMPLE 7 
This examples compares lanthanum to other metals. The following table shows 
that lanthanum is superior to other metals in improving catalyst 
performance with regards to activity, productivity of higher alcohols, and 
selectivity to isoalcohols. Lanthanum is unique in that it simultaneously 
improves productivity to higher alcohols and improves selectivity to 
isoalcohols. All catalysts were precipitated with NaOH using a N.sub.2 
sparge and calcined at 400.degree. C. The alkali level was 0 wt % K and 
3.1 wt % Cs. The reactor pressure used to evaluate these catalysts was 925 
psig (.apprxeq.6383 kPa). The reactor temperature was 610.degree. F. 
(321.degree.). Precipitation is abbreviated as PPT. 
TABLE 7 
__________________________________________________________________________ 
Mn Cr V La Y Ce La 
Catalyst PPT @ 30.degree. C. and pH 9.0 
PPT @ 50.degree. C. pH 
__________________________________________________________________________ 
10.0 
Metal Content, 
Oxygen Free Mole Fraction 
Cu 0.60 0.60 0.76 0.62 0.62 0.62 0.63 
Zn 0.18 0.18 0.06 0.19 0.15 0.15 0.17 
Al 0.10 0.10 0.10 0.10 0.09 0.09 0.09 
Mg 0.04 0.03 00 0.04 0.05 0.05 0.04 
Mn 0.09 -- -- -- -- -- -- 
Cr -- 0.08 -- -- -- -- -- 
V -- -- 0.04 -- -- -- -- 
La -- -- -- 0.05 -- -- 0.06 
Y -- -- -- -- 0.08 -- -- 
Ce -- -- -- -- -- 0.08 -- 
PPT Ph 9.0 9.0 9.0 9.0 10.0 10.0 10.0 
PPT Temp. (.degree.C.) 
30 30 30 30 50 50 50 
Catalyst S.A. (m.sup.2 /gm) 
92.4 117.8 
54.8 84.4 41.2 54.1 71.9 
GHSV 12590 
12590 
12580 
12220 
12250 
12140 
12220 
H.sub.2 /CO 0.94 0.96 1.00 0.95 0.95 0.95 0.96 
Performance at 610.degree. F., (321.degree. C.) 
CO Conversion (%) 
17.0 17.0 12.3 18.3 14.0 14.0 18.4 
Productivities g/hr/l of catalyst 
methanol 734.7 
623.1 
471.2 
590.5 
529.2 
530.8 
611.0 
ethanol 32.5 57.6 15.6 40.7 37.0 34.6 32.2 
n-propanol 26.4 38.1 11.0 32.5 24.1 26.0 24.7 
i-butanol 43.0 21.7 4.5 48.2 21.6 27.6 55.7 
n-butanol 5.5 10.2 1.9 8.5 6.4 6.4 5.6 
methyl butanols 
15.5 13.3 2.3 25.5 9.9 11.0 18.9 
n-pentanol 3.2 5.8 0.9 5.9 4.2 3.8 3.6 
C.sub.2 OH--C.sub.5 OH 
126.1 
146.7 
26.1 161.3 
103.2 
109.4 
140.8 
iROH/nROH 0.87 0.31 0.18 0.84 0.44 0.55 1.13 
__________________________________________________________________________ 
EXAMPLE 8 
This example illustrates the use of a preferred first stage catalyst to 
provide a feed stream for the second stage catalyst. 
An 18 g portion of the solid prepared in Example 1 is charged to a 
stainless steel die with a diameter of 2.54 cm and compressed under about 
900 kg/cm.sub.2 (12,750 lb/in2) pressure in a hydraulic press. The 
resultant solid wafer is crushed and sieved to yield a granular material 
that is passed through a 60 mesh sieve (opening 250 .mu.m) and retained on 
a 100 mesh sieve (opening 150 .mu.m). 10 cm.sup.3 of this material were 
mixed with 20 cm.sup.3 of high purity acid washed and calcined crushed 
fused quartz. This inert diluent passed through a 40 mesh sieve (opening 
425 .mu.m) but was retained on a 60 mesh sieve (opening 250 .mu.m). This 
mixture is charged to a copper lined and copper jacketed 304 stainless 
steel reactor tube with and internal diameter of 0.41 inches (1.04 cm). 
The reactor tube is so configured that the highly purified, iron carbonyl 
free synthesis gas contacts no materials of construction other than copper 
at elevated temperatures. After purging the reactor with purified argon to 
remove any traces of air the argon is replaced with hydrogen flowing at 
6000 GHSV. The reactor is heated to 150.degree. C. and held there for an 
hour, then heated to 260.degree. C. and held for an hour. The hydrogen is 
then replaced with highly purified synthesis gas effectively free of 
sulfur compounds and metal carbonyls. The H.sub.2 /CO ratio in the 
synthesis gas is 1. The reactor inlet pressure is about 6400 kPa or about 
930 psig, and the synthesis gas space velocity is about 12,000. The 
reactor temperature is progressively increased at 5.degree. C./hr until it 
is stabilized at about 320.degree. C. Under these conditions, the CO 
conversion is about 23.3% and the reactor productivity is about as 
follows: 
TABLE 8 
______________________________________ 
Productivities (g/hr) 
______________________________________ 
methane 0.152 
Other hydrocarbons 0.385 
methanol 7.154 
ethanol 0.474 
n-propanol 0.491 
isobutanol 0.773 
methyl butanols 0.297 
Other alcohols & oxygenates 
0.640 
______________________________________ 
EXAMPLE 9 
Preparation of Second Stage Protocatalyst A with Ratio of Mn:Zn:Zr of 
0.38:0.26:0.30 
The protocatalyst was prepared by the constant pH precipitation of a mix 
oxyhydroxide of Mn, Zn and Zr by a 2 Molar LiOH solution. The Mn, Zn, Zr 
solution was prepared by dissolving in 500 ml of distilled water the 
following amounts of manganese, zinc and zirconyl nitrates that were 
obtained from Aldrich Chemical Company, Inc. of Milwaukee, Wis. 53233 USA. 
0.3 Moles, 43.06 g, Mn(NO.sub.3).sub.2.6H.sub.2 O, (F.W. 287.04), 0.2 
Moles, 29.70 g, Zn(NO.sub.3).sub.2.6H.sub.2 O (F.W. 297.47) and about 0.4 
Moles, 46.25 g, ZrO(NO.sub.3).sub.2..times.H.sub.2 O (F.W. 231.23). The 
resulting solution was 0.9 Molar in transition metals. This solution was 
added over the course of 30 minutes, with constant stirring, to 600 ml of 
water held at 70.degree. C. The pH of this 600 ml was initially adjusted 
to pH 9.0 with LiOH. Over the course of the addition, the addition rate of 
the transition metal solution and of 2.0 Molar LiOH was controlled to 
maintain a pH of 9.0. Five minutes after the addition was complete, the pH 
was observed to drift down to about pH 7 and additional 2.0 Molar LiOH was 
added to restore pH 9.0. Stirring was continued overnight at 70.degree. 
C., during which time the suspension was concentrated by water 
evaporation. The precipitate was isolated by filtration. The filtrate had 
a pH of 6.26. The solids were resuspended in one liter of distilled water 
and stirred vigorously for 30 minutes, then recovered by filtration. The 
pH of the filtrate was 7.07. This washing step was repeated and the pH of 
the final filtrate was 6.20. It was dried overnight at 130.degree. C. The 
dried material was ground to a fine powder and calcined in air in a tube 
furnace, the temperature of which was raised from room temperature to 
425.degree. C. over the course of two hours, held at 425.degree. C. for 
two hours, and allowed to cool to room temperature over the course of two 
hours. 13.79 g of dry material was recovered. 10 g of this material was 
treated with 10 ml of distilled water in which 0.0616 g of 
Pd(NO.sub.3).sub.2 was dissolved along with 15 drops of ethanolamine. 
After thorough mixing the slurry was dried in a vacuum oven for six hours. 
The Pd-loaded and dried catalyst was heated in air, with the temperature 
increased from ambient to 325.degree. C. over the course of one hour. The 
temperature was held at 325.degree. C. for three hours, then cooled over 
the course of one hour. 
The BET surface area was 74.1 m.sup.2 /g, and elemental analysis showed 
mole fractions of the Mn, Zn, Zr and Li to be respectively 0.3841, 0.2592, 
0.2954 and 0.0613. The wt % Pd was 0.24%. 
The calcined protocatalyst was crushed to a fine powder; a portion of this 
solid was then compressed under about 880 kg/cm.sup.2 pressure using a 
stainless steel die 2.56 cm in diameter to form wafers which were then 
crushed and sieved to obtain a granular material that was retained on an 
80 mesh sieve after passing through a 60 mesh sieve (that is, particles 
with an approximate size of about 180 .mu.m to about 250 .mu.m in 
diameter). 3.0 cm.sup.3 of this material, 3.9850 g, was mixed with 6 
cm.sup.3, 7.1860 g, of 40-60 mesh (that is, about 250 .mu.m to 425 .mu.m 
in diameter), crushed, high purity, acid washed and calcined quartz as a 
diluent. The resulting mixture was charged to a copper-jacketed, 
copper-lined stainless steel reactor tube (net I.D. 0.41 inch, 1.0414 cm) 
equipped with a copper-jacketed 0.125 inch (0.3040 cm) outside diameter 
thermowell. This reactor was attached to a flow system by means of "VCR" 
fittings. The catalyst bed was flushed with high purity argon, and then 
240 SCCM high purity hydrogen and 180 SCCM high purity argon under an exit 
pressure of 300 kPa were passed through the catalyst bed as it was heated 
to 240.degree. C. over the course of 120 minutes. After a one minute hold 
at 240.degree. C., the argon was turned off and the hydrogen flow rate was 
increased to 1200 SCCM. The catalyst bed was then heated to 260.degree. C. 
at 8.degree. C./min and held there for five minutes, then heated at 
2.degree. C./min. to 400.degree. C. and held there for one hour, after 
which time the reactor was cooled to 350.degree. C. at 8.degree. C./minute 
and held at 350.degree. C. while gas composition was changed to synthesis 
gas and the system pressurized to about 6540 kPa at the outlet of the 
catalyst bed. Once synthesis gas flow was established, the catalyst bed 
could then be heated back to 380.degree. C. at 3.degree. C./min without 
overheating. The synthesis gas mixture used contained 44.0% carbon 
monoxide, 39.4% hydrogen, 10.0% argon and 6.6% carbon dioxide. It was held 
at 380.degree. C. for 92 hours before the temperature was decreased to 
360.degree. C. and at 360.degree. C. for an additional 20 hours before the 
temperature was decreased to 340.degree. C. After 16 hours at 380.degree. 
C., a methanol ethanol water mixture was introduced and vaporized before 
the catalyst such that the gas composition entering the catalyst bed was 
approximately 44% CO, 39.4% H.sub.2, 6.6% CO.sub.2 and 10.0% Ar synthesis 
gas, into which was vaporized at a rate of 0.8 liquid hourly space 
velocity a mixture of 90.00 wt % methanol, 9.56 wt % ethanol and 0.44% 
water. The overall gas hourly space velocity was then about 8500 V/V/hr. 
Analytical transmission electron microscopy was used to characterize the 
composition and structure of phases in protocatalyst A, and in the same 
after activation, and used as an alcohol coupling catalyst. The 
composition (Zr, Mn, Zn) was determined for regions as small as 4 nm (40 
.ANG.) using a 200 kV accelerating voltage Philips CM20 field-emission 
transmission electron microscope equipped with energy-dispersive x-ray 
(EDX) analysis. Catalyst particles were embedded in an epoxy and then 
microtomed into about 500 .ANG.-thick slices in order to determine the 
morphologies of the large scale structures (about .ltoreq.1 .mu.m) while 
simultaneously making it possible to observe individual small Zr-rich and 
Mn-rich phases. Quantitative EDX analyses were carried out using 
macroscopic (about 5 .mu.m) sampling regions of the starting catalyst as 
standards for determining k-factors that were subsequently used for 
analysis of smaller regions in starting and treated catalysts. The small 
probe available in this field-emission instrument (about 2 nm diameter) 
made it possible to isolate the EDX signal from individual particles as 
small as 4 nm with efforts taken to minimize contributions from 
neighboring particles. Noble metals were located in Zr-rich regions using 
a Philips EM420ST TEM operated at 100 kV using large sampling regions in 
Zr-rich or Zr-depleted regions and energy-dispersive x-ray analysis. 
Protocatalyst A was found by transmission electron microscopy to have at 
least two phases in addition to palladium metal. The first phase is a 
continuous phase containing small (about 40 .ANG. to 50 .ANG.) and often 
poorly crystalline (as evidenced by the broad electron diffraction lines) 
particles of a manganese and zinc doped zirconium oxide phase containing 
about 71 to about 91 atomic % (on a metals only basis) zirconium, about 10 
to about 16 atomic % manganese and 4 to about 8 atomic % zinc on an metals 
only basis. On the basis of electron diffraction patterns, the zirconium 
dioxide is believed to have a cubic structure. Embedded in this extensive 
zirconium rich phase is a second, distinct phase of irregular hetaerolite 
(Mn.sub.2 ZnO.sub.4) or hetaerolite-like crystallites (e.g., crystals that 
give an electron or x-ray diffraction pattern similar to Mn.sub.2 
ZnO.sub.4) containing approximately about 65 to about 69 atomic % 
manganese, about 32 to about 35 atomic % zinc and about 0 to about 5 
atomic % zirconium. These range in size from about approximately 500 .ANG. 
to about approximately 2000 .ANG.. 
After activation and use the catalyst was found to have three phases in 
addition to palladium. The continuous, higher surface area, Zr rich phase 
had gained Mn and some Zn, while the hetaerolite-like crystallites had 
decreased considerably in size and number and a third phase of variable 
composition with variable Mn/Zn ratio had appeared. The first phase, which 
was largest in volume and available surface area, contained on a metals 
only basis about 60 to about 74 atomic % (on a metals only basis) 
zirconium, about 21 to about 31 atomic % manganese, about 5 to about 9 
atomic % zinc in the form of about 40 .ANG. to about 100 .ANG. 
crystallites. Compared to the protocatalyst, these are enriched in Mn, 
while their Zn content was not significantly increased. These small 
crystallites exhibited a high concentration of stacking faults and other 
defects consistent with the presence of dopant atoms. The diffraction 
patterns obtained from these small crystallites were broad and poorly 
formed. Their diffraction patterns were most consistent with that expected 
for cubic ZrO.sub.2 and differing only by the absence of the 102 
reflection at 2.1 .ANG. from the pattern expected of tetragonal ZrO.sub.2. 
Monoclinic ZrO.sub.2 can be ruled out since many unique reflections 
expected for that structure were missing. Embedded in this extensive 
zirconium rich phase are irregular hetaerolite (Mn.sub.2 ZnO.sub.4) or 
hetaerolite-like crystallites (e.g., crystals that give an electron or 
x-ray diffraction pattern similar to Mn.sub.2 ZnO.sub.4). These were 
smaller in size (200 .ANG. to approximately 1000 .ANG. across) and fewer 
in number than in the protocatalyst and contained approximately the same 
concentration of manganese, zinc and zirconium as in the protocatalyst, 
that is, about 65 to about 69 atomic % manganese, about 31 to about 35 
atomic % zinc and about 0 to about 5 atomic % zirconium, and gave the same 
diffraction pattern as in the protocatalyst. A significant increase in Zr 
would be expected to alter this pattern as the Zr atom is significantly 
larger in diameter than either Mn or Zn. Also embedded in the continuous 
Zr rich phase of the active catalyst was a new phase consisting of dense 
crystallites all relatively rich in Mn and Zn but which exhibit a wide 
range of Mn to Zn ratios. This latter phase varies in size as well as 
composition ranging from about approximately 1000 .ANG. to &gt;4000 .ANG. and 
from about 29 to about 55 atomic % manganese, about 13 to about 55 atomic 
% zinc and about 13 to about 35 atomic % zirconium. This phase is large 
enough to be clearly visible with a scanning electron microscope when a 
backscattered electron detector was used to obtain average atomic number 
images of the sample. 
EXAMPLE 10 
Preparation of Protocatalyst B with a Mn:Zn:Zr Ratio of 0.39:0.27:0.34 
This example illustrates the preparation and activation of Catalyst B, a 
catalyst within the preferred scope of this invention. 0.3 moles, 43.06 g, 
Mn(NO.sub.3).sub.2.6H.sub.2 O, (F.W. 287.04), 0.2 moles, 29.70 g, 
Zn(NO.sub.3).sub.2.6H.sub.2 O (F.W. 297.47) and about 0.4 moles, 46.25 g, 
ZrO(NO.sub.3).sub.2..times.H.sub.2 O (F.W. 231.23) were dissolved in 500 
ml distilled water to make solution TM. Similarly, 42 g of LiOH.H.sub.2 O 
were dissolved in one liter of distilled water to make a 1 Molar solution 
of LiOH designated solution B. At a relative rate of 2.7 for solution TM 
and 1 for solution B, these two solutions were added with rapid stirring 
to 600 ml of distilled water at 70.degree. C. such that the pH of the 
resultant slurry was maintained at 9.04.+-.0.2. The resultant light 
pinkish precipitate was allowed to cool to room temperature (ca 22.degree. 
C.) and settle overnight. On filtering off the supernatant, which had a pH 
of 8.59, a light brown solid was recovered. This was washed with three 
one-liter portions of distilled water. The pH of the filtrate from each 
washing was respectively 8.32, 8.15 and 7.56. 
After drying in a glass container at 130.degree. C. in air for an extended 
period of time, 36 g of the dry material were calcined to 380.degree. C. 
in air. 15 g of the calcined material was then palladium loaded as 
follows: 376 mg of Pd(NO.sub.3).sub.2..times.H.sub.2 O were dissolved in 
20 ml of distilled water along with 30 drops of ethanolamine. The solid 
and the solution were combined and mixed thoroughly and then dried in a 
vacuum oven for two hours prior to calcining. The dried solid was heated 
in air over the course of one hour to 380.degree. C., held at 380.degree. 
C. for one hour, and then cooled to room temperature over the course of 
one hour. 
The resulting material had a surface area of 75.1M.sup.2 /g and the atomic 
fractions of Mn, Zn, Zr and Li were respectively 0.3857, 0.2706, 0.3428 
and 0.0010. 
The material had a Pd concentration of 1.21 wt %. A portion of this solid 
was then compressed using a stainless steel die to form a wafer which was 
then crushed and sieved to obtain a granular material that was retained on 
an 80 mesh sieve after passing through a 60 mesh sieve, that is the 
granules had a size range of about 180 .mu.m to about 250 .mu.m. 3.0 
cm.sup.3 of this material, 3.3952 g, were mixed with 6 cm.sup.3, 8.0937 g, 
of 40-50 mesh crushed high purity, acid washed and calcined quartz as a 
diluent, that is, the irregular quartz chunks were from about 300 .mu.m to 
425 .mu.m in diameter. The resulting mixture of catalyst and quartz 
granules was charged to a copper-jacketed, copper-lined stainless steel 
reactor tube (net I.D. 0.41 inch, 1.0414 cm), equipped with a 
copper-jacketed 0.125 inch (0.3040 cm) outside diameter thermowell. This 
reactor was attached to a flow system by means of "VCR" fittings. The 
catalyst bed was flushed with high purity argon, and then 240 SCCM high 
purity hydrogen and 180 SCCM high purity argon under an exit pressure of 
300 kPa were passed through the catalyst bed as it was heated to 
200.degree. C. over the course of 15 minutes. After a one minute hold at 
200.degree. C., the catalyst bed was heated at 4.degree. C./min to 
260.degree. C. During a one minute hold at 260.degree. C., the argon was 
turned off and the hydrogen flow rate was increased to 1200 SCCM. Under 
this condition, the reactor bed temperature was increased at 3.degree. 
C./min to 377.degree. C. without overheating. After 60 minutes at 
377.degree. C., the temperature was decreased to 350.degree. C. and the 
gas composition changed to a carbon monoxide, hydrogen, argon, carbon 
dioxide, blend flowing at about 400 SCCM through the catalyst bed and the 
reactor pressure was slowly increased to 6500 kPa. The synthesis gas 
mixture used contained 44.0% carbon monoxide, 39.4% hydrogen, 10.0% argon 
and 6.6% carbon dioxide. Once this gas mixture was flowing through the 
system and the reactor pressure was stabilized at about 6550 kPa, the 
reactor temperature was increased to 377.degree. C. Under these conditions 
the temperature at the exit of the catalyst bed was about 380.degree. C. 
The resultant liquid produced from the synthesis gas was about 29.4% 
water, 67.3% identified organic compounds: methanol, methyl formate, 
ethanol, n-propanol, isobutanol, n-butanol, 3-methyl 2-butanol, 
3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 4-methyl pentanol, 
n-pentanol, 2,2-dimethyl 3-pentanone, 2-methyl-1-pentanol, and 2,4 
dimethyl-3-pentanol and about 3.3% trace, unidentified organic compounds. 
The identified organics were 73.6% methanol, 19.6% isobutanol, 1.8% 
n-propanol, 1.3% methyl butanols and 3.7% other materials on a carbon 
basis. 
EXAMPLE 11 
This example illustrates the performance of Catalyst B within the preferred 
scope of this invention with a methanol, ethanol, water feed. 
After the gas composition of Example 9 (at 380.degree. C.) was changed to 
47.1% carbon monoxide, 42.2% hydrogen and 10.7% argon, a 90 wt % methanol, 
9.56% ethanol and 0.44% water vapor was added to the gas mixture and fed 
to the catalyst. Under these conditions, 99.7% of the ethanol was 
converted to C.sub.3 + products through reaction with the methanol. Some 
methanol was also decomposed into hydrogen and carbon monoxide. In this 
case, the liquid produced was 11.4% water, 87.4% identifiable organic 
compounds: methanol, methyl formate, ethanol, n-propanol, isobutanol, 
n-butanol, 3-methyl-2-butanol, 3-pentanol, 3-methyl-1-butanol, 
2-methyl-1-butanol, 4-methyl-pentanol, n-pentanol, 
2,2-dimethyl-3-pentanone, 2-methyl-1-pentanol, and 2,4-dimethyl-3-pentanol 
and 1.2% trace materials. On a carbon basis, the produced liquid was 45.9% 
isobutanol, 35% methanol, 4.4% methyl butanols, 4.4% n-propanol, 1.7% 
2-methyl-1-pentanol with about 0.13% ethanol and 7.8% miscellaneous 
organic compounds. 
EXAMPLE 12 
This example illustrates that Catalyst B, a catalyst within the preferred 
scope of this invention, produces very little unwanted hydrocarbon and is 
effective in converting a methanol, ethanol, water and n-propanol feed. 
The reactor temperature in Example 11 was decreased from about 380.degree. 
C. to about 340.degree. C. and the liquid feed composition was changed to 
resemble the liquid produced without the methanol-ethanol vapor feed. 
Under these conditions, little, if any, methanol was decomposed into gas, 
and less than 0.1% of the carbon passing through the reactor was converted 
to hydrocarbon gas. The liquid composition was changed to about 87.2 wt % 
methanol, 7% ethanol and 5.8% n-propanol. Under these conditions, the 
ethanol conversion was 90.2% and the n-propanol conversion was 74.9%. The 
resultant liquid product contained 86.3% identified organic products: 
methanol, methyl formate, ethanol, n-propanol, isobutanol, n-butanol, 
3-methyl-2-butanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 
4-methyl-pentanol, n-pentanol, 2,2-dimethyl-3-pentanone, 
2-methyl-1-pentanol, and 2,4-dimethyl-3-pentanol, 8.9% unidentified 
organic products and 4.8% water. On a carbon basis, the liquid product 
contained about 67.7% methanol, 24.4% isobutanol, 2.6% methyl butanols 
along with 3.5% n-propanol and 1.4% ethanol. 
Increasing the temperature of the reactor in Example 11 from 340.degree. C. 
to 350.degree. C. increased the ethanol conversion to 97.8% and the 
n-propanol conversion to 88% after over 190 hours on-line. The liquid 
produced contained on a carbon basis 62.1% methanol, 30.8% isobutanol, 
2.1% methylbutanols, along with 0.4% ethanol and 1.9% n-propanol. 
EXAMPLE 13 
This example illustrates the incorporation of a light olefin, ethylene, 
into the alcohol product when ethylene is cofed to the second stage 
catalyst, along with methanol, ethanol, n-propanol and synthesis gas. 
Under the final conditions of Example 12 (350.degree. C. and about 6550 
kPa), the feed gas was changed to 44.0% carbon monoxide, 39.4% hydrogen, 
10.0% argon and 6.6% polymer grade ethylene. Under these conditions about 
25% of the ethylene fed was converted with 80% selectivity to liquids, 19% 
to ethane and 1% to higher hydrocarbons including n-butane and butenes. 
The liquid produced on a carbon basis was: 59.3% methanol, 32.4% 
isobutanol, 2.3% methyl butanols, 2.2% n-propanol, 1% 2-methyl-1-pentanol 
and 0.4% ethanol along with miscellaneous organic compounds. With an 
ethylene co-feed, the ethanol conversion was about 97.4% and the 
n-propanol conversion was about 86.2%. These values were comparable to, or 
slightly lower than, those without ethylene feed. With ethylene co-fed, 
the concentration of unidentified organic compounds in the liquid 
increased from 1.1% to 3.2%. Significantly, ethylene co-feed also 
increased the productivity of isobutanol by 7.8% and that of methyl 
butanols by 11%. 
EXAMPLE 14 
This example illustrates that this second stage catalyst within the scope 
of this invention converts very little of the carbon dioxide free 
synthesis gas and a methanol, ethanol, n-propanol liquid feed into 
undesirable byproducts. 
A second 3.0 cm.sup.3 (3.1215 g) sample of 60 to 80 mesh (180 .mu.m to 250 
.mu.m) granules of Protocatalyst B were blended with 6.0 cm.sup.3 (6.8880 
g) of acid washed and calcined high purity fused quartz crushed and sieved 
to 40 to 60 mesh (250 .mu.m to 425 .mu.m). This mixture was charged into a 
copper-jacketed, copper-lined stainless steel reactor tube (net I.D. 0.41 
inch, 1.0414 cm) equipped with a copper-jacketed 0.125 inch (0.3040 cm) 
outside diameter thermowell. This reactor was attached to a flow system by 
means of "VCR" fittings. The catalyst bed was flushed with high purity 
argon, and then 240 SCCM high purity hydrogen and 180 SCCM high purity 
argon under an exit pressure of 300 kPa were passed through the catalyst 
bed as it was heated to 200.degree. C. over the course of 30 minutes. 
Then, after a one minute hold at 200.degree. C., it was heated to 
260.degree. C. over the course of 30 minutes. After one minute at 
260.degree. C., the argon was turned off and the hydrogen flow rate was 
increased to 1200 SCCM. The catalyst bed was then heated to 377.degree. C. 
over the course of about 50 minutes, then held there for one hour, after 
which time the reactor was cooled to 350.degree. C. at 2.degree. C./min 
and held at 350.degree. C. while gas composition was changed to synthesis 
gas and the system pressurized to about 6540 kPa at the outlet of the 
catalyst bed. Once synthesis gas flow was established, the catalyst bed 
could then be heated back to 380.degree. C. in the catalyst bed at 
3.degree. C./min without overheating. Once the catalyst reached 
380.degree. C. under synthesis gas flowing at 400 SCCM, it was "on-line" 
and the run time clock was started. The synthesis gas mixture used 
contained 47.5% carbon monoxide, 42.5% hydrogen and 10.0% argon. After 41 
hours on-line, a mixture of 87.41% methanol, 6.42% ethanol, 5.85% 
n-propanol and 0.32 wt % water was vaporized into the synthesis gas above 
the catalyst bed at the rate of 2.4 cm.sup.3 of liquid at 0.degree. C. per 
hour. The catalyst bed was held at 380.degree. C. for 64 hours before the 
temperature was decreased to 350.degree. C. 
After 70 hours on-line at a catalyst bed temperature of 350.degree. C. and 
a feed synthesis gas composition of 47.10 mole % CO, 42.17 mole % H.sub.2 
and 10.73 mole % Ar as an internal standard, the carbon monoxide 
conversion was about 1.8%. This was determined using a gas chromatograph 
that alternately sampled feed and product gas streams. All the gas feeds 
to the experimental reactor are controlled with electronic mass flow 
controllers working with a constant feed and back pressure. Thus the flow 
of the individual gases and of the mixed gas feed to the reactor is 
effectively constant. Thus, the Molar ratio of carbon monoxide to argon in 
the feed and product should be constant in the absence of reaction. If a 
carbon monoxide-consuming reaction occurs over the catalyst, then the 
ratio of feed carbon monoxide, CO.sub.f, to feed argon Ar.sub.f must equal 
the ratio of product carbon monoxide, CO.sub.p, plus carbon monoxide 
consumed, CO.sub.c, to product argon, Ar.sub.p, that is: 
EQU CO.sub.f /Ar.sub.f =(CO.sub.p +CO.sub.c)/Ar.sub.p or CO.sub.c =(Ar.sub.p 
CO.sub.f --Ar.sub.f CO.sub.p)/Ar.sub.f 
A gas chromatograph was used to alternately sample feed and product gas. 
The carbon selectivity of this converted gas was found to be about 39.2% 
to carbon dioxide, 60.8% to hydrocarbon gases and effectively none to 
liquids using the carbon bookkeeping convention that carbon from converted 
carbon monoxide is first assigned to the observed net carbon dioxide 
(excess of CO.sub.2 in the exit gas over that fed), then to the observed 
hydrocarbon gases. The balance of the consumed carbon is then assigned to 
the liquid product, that is: 
Moles of CO converted-(moles CO.sub.2 produced+moles carbon as hydrocarbon 
gases)=moles CO converted to liquid. 
The carbon distribution of the hydrocarbon gases was: 28.8 C % ethylene, 
24.7 C % propylene, 18.8 C % isobutylene, 12.4 C % methane, 11.8 C % 
ethane, 2.3 C % propane and 1.2 C % isobutane. This composition suggests 
that most of these gases, with the exception of the methane, arose from 
the dehydration of the alcohols fed (or produced), forming olefins, with 
the subsequent hydrogenation of some of these olefins to form paraffins. 
These data also show that the losses to methane are on the order of 0.2% 
of the carbon passing through the reactor. The liquid product produced at 
the same time as above the gaseous products (that is, the liquid collected 
between 68.5 and 71 hours on-line) contained about 7 wt % water and 93 wt 
% organic products, of which 99% were identifiable. The breakdown of these 
organic products on a carbon percent basis is as follows: 62.41 C % 
methanol, 30.23 C % isobutanol, 2.08 C % n-propanol, 1.96 C % methyl 
butanols, 0.90 C % ethanol, 0.88 C % 2-methyl pentanol, 0.09 C % n-butanol 
and about 1.45 C % miscellaneous organic products. This represents about 
95.1% ethanol conversion, 88.7% n-propanol conversion. On a methanol, 
water free basis, the C.sub.2 + liquid products were about 80 wt % 
isobutanol, 6 wt % n-propanol, 5 wt % methyl butanols, 3.0 wt % ethanol 
and about 6 wt % other products. 
EXAMPLE 15 
This example demonstrates the performance of second stage catalyst within 
the scope of this invention for the incorporation of a light olefin, 
ethylene, into the liquid product produced from carbon monoxide and 
hydrogen. 
After 77 hours on-line, the gas composition over the catalyst in Example 14 
was changed to 43.7mole % CO, 39.1 mole % H.sub.2, 9.9 mole % Ar and 7.3 
mole % polymerization grade ethylene. After 89 hours, the liquid feed was 
turned off and the behavior of the thoroughly activated, lined-out 
catalyst under the ethylene containing synthesis gas was monitored by gas 
chromatography using argon as an internal gas standard as above. Using the 
carbon bookkeeping convention that ethylene could be converted to only 
ethane or liquid products and that CO could be converted to CO.sub.2, 
liquids or hydrocarbon gases except ethane and ethylene, the following 
results were obtained: Under these conditions 16.2% of the ethylene fed 
was converted to products. The carbon selectivity to ethane was 72.3 
carbon % and the selectivity to liquid products 27.7 carbon %. At the same 
time, the CO conversion averaged 4.3 mole %. Of this, 92.7% on a carbon 
basis was converted to liquid products, 2.7 C % to carbon dioxide and the 
balance, 7.3 C % to hydrocarbon gases (except for ethane and ethylene). 
The breakdown of the hydrocarbon gases on a carbon % basis was as follows: 
31.04 C % n-butane, 27.09 C % methane, 10.84C % propylene, 9.74C % 
isobutylene, 6.79C % isopentene, 6.25 C % propane, 3.79C % isopentane, 
2.53 C % n-butenes, 1.19C % n-pentane, and 0.11 C % isobutane, along with 
about 0.63 C % hexenes and hexanes. The liquid product was about 5% water 
and 95% organic products by weight. The organic products on a carbon % 
basis were derived 72.7% from the CO that was converted and 27.3% from the 
ethylene that was converted. It is believed that the carbon derived from 
the incorporated ethylene is in the C.sub.2 + products, especially in the 
C.sub.4 + products. The composition of the liquid products on a carbon 
basis was: 90.02 C % methanol, 5.81 C % isobutanol, 0.37 C % 
methyl-butanols, 0.35 C % n-propanol, 0.18 C % 2 methyl-1-pentanol, 0.08 C 
% ethanol and 0.07 C % n-butanol, with the balance of the carbon in other 
miscellaneous oxygen-containing organic products. 
EXAMPLE 16 
This example further illustrates the incorporation of an olefin, ethlyene, 
into the liquid product derived from synthesis gas and a methanol, 
ethanol, n-propanol liquid feed. 
After 165 hours on-line, the 87.41% methanol, 6.42% ethanol, 5.85% 
n-propanol and 0.32 wt % water liquid feed was once again vaporized into 
the synthesis gas (43.7 mole % CO, 39.1 mole % H.sub.2, 9.9 mole % Ar and 
7.3 mole % polymerization grade ethylene) above the catalyst bed at the 
rate of 2.4 cm.sup.3 of liquid (at 0.degree. C.) per hour. 
Under these conditions, 8.1% of the ethylene was converted with a carbon 
selectivity of 26.2% to ethane and 73.8% to "liquid products" with the 
same convention for carbon book keeping as above. Similarly, 2.5% of the 
carbon monoxide fed was consumed, being converted with a carbon 
selectivity of 72.5% to liquids, 21.4% to carbon dioxide and 6.1% to 
hydrocarbon gases except for ethane and ethylene. The breakdown of the 
hydrocarbon gases produced was on a carbon % basis as follows: methane 
24.58 C %, propylene 20.79C %, n-butane 19.63 C %, isobutylene 18.04 C %, 
propane 6.60 C %, isopentene 4.92 C %, isopentane 2.24 C %, n-butenes 2.07 
C %, n-pentane 0.82 C % and isobutane 0.31 C %. 
The liquid product was about 4% water and about 96% organic products. 66.2% 
of the carbon in these products was derived from the feed methanol, 13.6% 
from the feed ethanol and propanol, 10.6% from the feed ethylene and 9.6% 
from the feed carbon monoxide. These organic products contained on a 
carbon % basis: 63.24% methanol, 27.21% isobutanol, 3.96% n-propanol, 
1.96% methyl butanols, 1.00% ethanol, 0.83% 2-methyl pentanol and 0.16% 
n-butanol with about 1.64% miscellaneous products. 
EXAMPLE 17 
Preparation of Protocatalyst C with a Mn:Zn:Zr Ratio of 0.42:0.29:0.29 
In 500 ml of distilled water 21.53 g Mn(NO.sub.3).sub.2.6H.sub.2 O, 14.85 g 
Zn(NO.sub.3).sub.2.6H.sub.2 O(F.W. 297.47) and 23.12 g 
ZrO(NO.sub.3).sub.2..times.H.sub.2 O were dissolved. This solution was 
added over the course of 30 minutes, with constant stirring, to 600 ml of 
water held at 70.degree. C. The pH of this 600 ml was initially adjusted 
to pH 9.0 with LiOH. Over the course of the addition, the addition rate of 
the transition metal solution and of a 21.0 g/l solution of LiOH was 
controlled to maintain a pH of 9.0. On addition of the transition metal 
solution and lithium hydroxide, the precipitate slurry was brown from the 
outset. Stirring was continued for five hours at 70.degree. C. The 
suspension was allowed to settle overnight at room temperature without 
stirring. The precipitate was isolated by filtration, then washed three 
times by resuspension and stirring in a liter of distilled water for an 
hour at room temperature, followed by filtering to recover the solids for 
further resuspension. The washed solids were dried overnight at 
130.degree. C. The dried material was ground to a fine powder and calcined 
in air in a tube furnace, the temperature of which was raised from room 
temperature to 425.degree. C. over the course of two hours, held at 
425.degree. C. for two hours and allowed to cool to room temperature over 
the course of two hours. 16.35 g of dry material was recovered. 15.0 g of 
this material were treated with 15 ml of distilled water in which 0.0939 g 
of Pd(NO.sub.3).sub.2..times.H.sub.2 O (assay 39.95 wt % Pd) was dissolved 
along with 15-20 drops of ethanolamine. After thorough mixing, the slurry 
was dried in a vacuum oven at 80.degree. C. overnight. The Pd-loaded and 
dried catalyst was heated in air with the temperature increased from 
ambient to 325.degree. C. over the course of one hour. The temperature was 
held at 325.degree. C. for three hours, then cooled over the course of one 
hour. 
The BET surface area was 72.1 m.sup.2 /g, and elemental analysis showed 
mole fractions of the Mn, Zn, Zr and Li to be respectively 0.4202, 0.2914, 
0.2884 and 0.0613. The wt % Pd was 0.24%. 
EXAMPLE 18 
Preparation of Second Stage Protocatalyst D with a Mn:Zn:Zr Ratio of 
0.40:0.28:0.32 
In 500 ml of distilled water 21.53 g, Mn(NO.sub.3).sub.2.6H.sub.2 O, 14.85 
g, Zn(NO.sub.3).sub.2.6H.sub.2 O and 23.12 g, 
ZrO(NO.sub.3).sub.2..times.H.sub.2 O were dissolved. This solution was 
added over the course of 30 minutes, with constant stirring to 600 ml of 
water held at 70.degree. C. The pH of this 600 ml was initially adjusted 
to pH 9.0 with LiOH. Over the course of the addition, the addition rate of 
the transition metal solution and of a 21.0 g/500 ml solution of LiOH was 
controlled to maintain a pH of 9.0. On addition of the transition metal 
solution and lithium hydroxide, the precipitate slurry was lighter in 
color than similar precipitations conducted at 70.degree. C. Stirring was 
continued for five hours at 25.degree. C. The suspension was allowed to 
settle for about 60 hours at room temperature without stirring. The 
precipitate was isolated by filtration, then washed three times by 
resuspension and stirring in a liter of distilled water for an hour at 
room temperature, followed by filtering to recover the solids for further 
resuspension. The washed solids were dried overnight at 130.degree. C. The 
dried material was ground to a fine powder and calcined in air in a tube 
furnace, the temperature of which was raised from room temperature to 
425.degree. C. over the course of two hours, held at 425.degree. C. for 
two hours, and allowed to cool to room temperature over the course of two 
hours. 15.25 g of dry material were recovered. 15.0 g of this material 
were treated with 15 ml of distilled water in which 0.0940 g of 
Pd(NO.sub.3).sub.2..times.H.sub.2 O (assay 39.95 wt % Pd) was dissolved 
along with 15-20 drops of ethanolamine. After thorough mixing, the slurry 
was dried in a vacuum oven at 130.degree. C. for two hours. The Pd-loaded 
and dried catalyst was heated in air with the temperature increased from 
ambient to 325.degree. C. over the course of one hour. The temperature was 
held at 325.degree. C. for three hours; then cooled over the course of one 
hour. 
The BET surface area was 78.8 m.sup.2 /g, and elemental analysis showed 
mole fractions of the Mn, Zn and Zr to be respectively 0.4023, 0.2823, and 
0.3154. The wt % Pd was 0.25%. 
EXAMPLE 19 
(Comparative) 
Preparation of Catalyst E with a Mn:Zn:Zr Ratio of 0.54:0.29:0.17 that is 
outside the preferred range. 
In 500 ml of distilled water 0.10 moles, 28.70 g, 
Mn(NO.sub.3).sub.2.6H.sub.2 O, 0.05 moles, 11.56 g 
ZrO(NO.sub.3).sub.2..times.H.sub.2 O and 0.05 moles, 14.87 g, 
Zn(NO.sub.3).sub.2.6H.sub.2 O were dissolved, making a solution that was 
0.4 Molar in transition metals. A LiOH solution was prepared by dissolving 
21.0 g of LiOH in 500 ml distilled water. The transition metal solution 
was added over the course of 30 minutes, with constant stirring, to 600 ml 
of water held at 70.degree. C. The pH of this 600 ml was initially 
adjusted to pH 9.0 with LiOH. Over the course of the addition, the 
addition rate of the transition metal solution and of 1.0 Molar LiOH was 
controlled to maintain a pH of 9.04.+-.1.0. Five minutes after the 
transition metal solution addition was complete, the pH dropped to about 
7.0 and more LiOH solution was added to bring it back up to 9.0. The 
precipitate was a light tanish brown in color. Stirring was continued 
overnight at 70.degree. C., during which time the suspension was 
concentrated by water evaporation. The precipitate was isolated by 
filtration. The filtrate had a pH of 6.26. The solids were resuspended in 
one liter of distilled water and stirred vigorously for 30 minutes, then 
recovered by filtration. The pH of the filtrate was 7.07. This washing 
step was repeated and the pH of the final filtrate was 6.20. The solid 
appeared to get darker in color and more difficult to filter as the 
washing proceeded. The solid was dried overnight at 130.degree. C. and 
13.91 g of a black material were recovered. The dried material was ground 
to a fine powder and calcined in air in a tube furnace, the temperature of 
which was raised from room temperature to 425.degree. C. over the course 
of two hours, held at 425.degree. C. for two hours and allowed to cool to 
room temperature over the course of two hours. 13.79 g of dry material 
were recovered. 10 g of this material were treated with 10 ml of distilled 
water in which 0.0616 g of Pd(NO.sub.3).sub.2..times.H.sub.2 O (Johnson 
Matthey) were dissolved along with 15 drops of ethanolamine. After 
thorough mixing, the slurry was dried in a vacuum oven for 6 hours. The 
Pd-loaded and dried catalyst was heated in air with the temperature 
increased from ambient to 325.degree. C. over the course of one hour. The 
temperature was held at 325.degree. C. for three hours, then cooled over 
the course of one hour. 
The BET surface area was 59 m.sup.2 /g, and elemental analysis showed mole 
fractions of the Mn, Zn, Zr and Li to be respectively 0.5390, 0.2892, 
0.1674 and 0.0044. The wt % Pd was 0.24%. 
EXAMPLE 20 
(Camparative) 
Preparation of second stage Catalyst F with a Mn:Zn:Zr Ratio of 
0.27:0.22:0.51 that is outside the preferred range. 
In 500 ml of distilled water 28.42 g Mn(NO.sub.3).sub.2.6H.sub.2 O, 23.05 g 
Zn(NO.sub.3).sub.2.6H.sub.2 O and 74.79 g 
ZrO(NO.sub.3).sub.2..times.H.sub.2 O were dissolved. The LiOH solution 
used to precipitate this was prepared by dissolving 42.0 g of LiOH.H.sub.2 
O (F.W. 41.96) in a liter of distilled water. The transition metal nitrate 
solution, added over the course of 30 minutes, with constant stirring, to 
600 ml of water held at 70.degree. C. The pH of this 600 ml was initially 
adjusted to pH 9.0 with LiOH. Over the course of the addition, the 
addition rate of the transition metal solution and of 1.0 Molar LiOH was 
controlled to maintain a pH of 9.0. Stirring was continued for five hours 
at 70.degree. C. The suspension was then allowed to settle and cool 
overnight. The tan-brown gelatinous precipitate was isolated by 
filtration. The solid was washed three times by resuspension in one liter 
of distilled water and 30 minutes of vigorous stirring prior to 
filtration. The recovered solids were dried overnight at 130.degree. C., 
leading to the recovery of 45.5 g of material. The dried material was 
ground to a fine powder and 20.0 g was calcined in air in a tube furnace, 
the temperature of which was raised from room temperature to 425.degree. 
C. over the course of two hours, held at 425.degree. C. for two hours and 
allowed to cool to room temperature over the course of two hours. 13.46 g 
of cooled, calcined material were recovered. This material was treated 
with 10 ml of distilled water in which 0.0939 g of Pd(NO.sub.3).sub.2 was 
dissolved along with 15 drops of ethanolamine. After thorough mixing, the 
slurry was dried in a vacuum oven at 110.degree. C. for six hours. The 
dried material was then calcined in air as follows: the temperature was 
increased from room temperature to 325.degree. C. over the course of an 
hour, then held at 325.degree. C. for three hours before cooling to room 
temperature over the course of two hours. 
The BET surface area was 112.2 m.sup.2 /g, and elemental analysis showed 
mole fractions of the Mn, Zn, Zr and Li to be respectively 0.2663, 0.2184, 
0.5116 and 0.0037. The wt % Pd was 0.22%. 
EXAMPLE 21 
Preparation of Catalyst G with a Mn:Zn:Zr Ratio of 0.46:0.29:0.25 that is 
outside the preferred range. 
In 500 ml of distilled water 21.53 g Mn(NO.sub.3).sub.2.6H.sub.2 O, 17.94 g 
Zn(NO.sub.3).sub.2.6H.sub.2 O and 21.55 g 
ZrO(NO.sub.3).sub.2..times.H.sub.2 O were dissolved. This solution was 
added over the course of 30 minutes, with constant stirring, to 600 ml of 
water held at 70.degree. C. The pH of this 600 ml was initially adjusted 
to pH 9.0 with LiOH. Over the course of the addition, the addition rate of 
the transition metal solution and of 1.0 Molar LiOH was controlled to 
maintain a pH of 9.0. Stirring was continued for five hours at 70.degree. 
C. The suspension was then allowed to settle and cool overnight. The pale 
light gray-brown precipitate was isolated by filtration. The filtrate had 
a pH of 8.72. The solids were resuspended in one liter of distilled water 
and stirred vigorously for 30 minutes, then recovered by filtration. The 
pH of the filtrate was 8.04. This washing step was repeated three times 
and the pH of the filtrates were 7.58, 7.80 and 8.45, respectively. The 
recovered solids were dried overnight at 130.degree. C., leading to the 
recovery of 13.5 g of material. The dried material was ground to a fine 
powder and calcined in air in a tube furnace, the temperature of which was 
raised from room temperature to 425.degree. C. over the course of two 
hours, held at 425.degree. C. for two hours and allowed to cool to room 
temperature over the course of two hours. The material was treated with 20 
ml of distilled water in which 0.0814 g of Pd(NO.sub.3).sub.2 was 
dissolved along with 15 drops of ethanolamine. After thorough mixing, the 
slurry was dried in a vacuum oven for six hours. The dried material was 
then calcined in air as follows: the temperature was increased from room 
temperature to 325.degree. C. over the course of an hour, then held at 
325.degree. C. for three hours before cooling to room temperature over the 
course of two hours. 
The BET surface area was 100 m.sup.2 /g, and elemental analysis showed mole 
fractions of the Mn, Zn, Zr and Li to be respectively 0.4634, 0.2891, 
0.2475 and &gt;0.0001. The wt % Pd was 0.23%. 
EXAMPLE 22 
Preparation of Catalyst H with a Mn:Zn:Zr Ratio of 0.37:0.38:0.25 that is 
outside the preferred range. 
In 500 ml of distilled water 43.06 g Mn(NO.sub.3).sub.2.6H.sub.2 O , 44.55 
g Zn(NO.sub.3).sub.2.6H.sub.2 O and 34.69 g 
ZrO(NO.sub.3).sub.2..times.H.sub.2 O were dissolved, making a solution 
that was 0.90 Molar in transition metals. This solution added over the 
course of 30 minutes, with constant stirring to 600 ml of water held at 
70.degree. C. The pH of this 600 ml was initially adjusted to pH 9.0 with 
LiOH. Over the course of the addition, the addition rate of the transition 
metal solution and of 42.0 g LiOH.H.sub.2 O/liter was controlled to 
maintain a pH of 9.0. Stirring was continued for five hours at 70.degree. 
C. The suspension was allowed to cool and settle overnight. The 
precipitate was isolated by filtration. The filtrate had a pH of 9.43. The 
solids were resuspended in one liter of distilled water and stirred 
vigorously for 30 minutes, then recovered by filtration. The pH of the 
filtrate was 8.98. This washing step was repeated twice. The pH of the 
second filtrate was 8.61 and that of the final filtrate was 7.72. The 
solids were dried overnight at 130.degree. C. 35.63 g of dried, brownish 
black solid were recovered. This material was ground to a fine powder. A 
portion of this material was calcined in air in a tube furnace, the 
temperature of which was raised from room temperature to 425.degree. C. 
over the course of two hours, held at 425.degree. C. for two hours and 
allowed to cool to room temperature over the course of two hours. 20.16 g 
of cooled calcined solids were treated with 10 ml of distilled water in 
which 0.1263 g of Pd(NO.sub.3).sub.2 was dissolved along with 20 drops of 
ethanolamine. After through mixing, the slurry was dried in a vacuum oven 
for six hours. After drying, the Pd-loaded solids were calcined in air, 
the temperature of which was raised from room temperature to 425.degree. 
C. over the course of two hours, held at 425.degree. C. for two hours and 
allowed to cool to room temperature over the course of two hours. The 
resulting material had a bulk atomic ratio of Mn to Zn to Zr to Li of 
0.3675, 0.381, 0.2491 and 0.001476 respectively. 
EXAMPLE 23 
Preparation of Catalyst I with an Mn:Zn:Zr:Li ratio of 0.25:0.00:0.65:0.10 
that is without Zn and thus outside the preferred range. 
In 500 ml of distilled water 41.0 g of 50% Mn(NO.sub.3).sub.2.6H.sub.2 O 
solution and 58.0 g ZrO(NO.sub.3).sub.2..times.H.sub.2 O were dissolved. 
This solution was added at the rate of 200 drops/minute to 1000 mls of 
distilled water, the pH of which had previously been adjusted to 9.0 
through the drop-wise addition of 2.0 Molar LiOH solution. The pH of the 
mixture was maintained at 9.0 through the continuous addition of 2.0 Molar 
LiOH solution. The mixture temperature was maintained at about 70.degree. 
C. throughout the addition. The slurry containing the precipitate was aged 
overnight at 70.degree. C. The solids were then recovered by filtration 
and the filtrate had a pH of 6.98. The solids were resuspended in one 
liter of distilled water and stirred vigorously for 30 minutes before 
filtering. The filtrate had a pH of 6.36. The washing step was repeated 
and the final filtrate had a pH of 6.01. The gelatinous brownish maroon 
solid was dried overnight at 130.degree. C. 19.25 g of solids were 
recovered. These were finely ground and calcined at 425.degree. C. as in 
example above. 5 g of this solid were loaded with Pd as above. The 
Pd-loaded and dried catalyst was heated in air with the temperature 
increased from ambient to 325.degree. C. over the course of one hour. The 
temperature was held at 325.degree. C. for three hours, then cooled over 
the course of one hour. 
This material had a surface area of about 206 m.sup.2 /g, and the ratio of 
mole fraction of Mn, Zr and Li respectively was 0.2467, 0.6487 and 0.1041. 
The Pd loading was 0.23 wt %. 
EXAMPLE 24 
Preparation of Catalyst J with a Mn:Zn:Zr:Li ratio of 0.33:0.00:0.63:0.04 
that is without Zn and thus outside the preferred range. 
In 500 ml of distilled water 41.1 g Mn(NO.sub.3).sub.2.6H.sub.2 O, and 
115.6 g ZrO(NO.sub.3).sub.2..times.H.sub.2 O were dissolved and added 
drop-wise to 500 ml of water adjusted to pH 9.0 with LiOH. 42.0 g of 
LiOH.H.sub.2 O dissolved in 1000 ml of water was simultaneously added 
drop-wise (at about 1 drop per second) to the initial 500 ml so as to 
attempt to maintain a constant pH of 9.0. The temperature of the slurry 
was between about 60.degree. C. and about 65.degree. C. during the 
precipitation. The pinkish brown slurry was stirred overnight at 
65.degree. C. The recovered precipitate was washed three times with two 
liters of distilled water and air dried for about 60 hours before 
calcining. 
20 g of the solid were loaded with Pd as follows: 0.1240 g of 
Pd(NO.sub.3).sub.2.2H.sub.2 O were dissolved in 20 ml of water along with 
24 to 30 drops of ethanolamine. This was thoroughly mixed with 20.0 g of 
the calcined mixed oxide and dried in a 130.degree. C. vacuum oven for 
three hours prior to calcination. The Pd-loaded and dried catalyst was 
heated in air with the temperature increased from ambient to 325.degree. 
C. over the course of one hour. The temperature was held at 325.degree. C. 
for three hours, then cooled over the course of one hour. 
This material had a surface area of about 92 m.sup.2 /g, and the ratio of 
mole fraction of Mn, Zr and Li respectively was 0.3293, 0.6288 and 0.0418. 
The Pd loading was 0.24 wt %. 
EXAMPLE 25 
Preparation of Catalyst K, ZnMn.sub.2 O.sub.4, a composition outside the 
scope of this invention with a Mn:Zn:Zr Ratio of 0.68:0.32:0.00. 
In 500 ml of distilled water 57.41 g Mn(NO.sub.3).sub.2.6H.sub.2 O and 
29.70 g Zn(NO.sub.3).sub.2.6H.sub.2 O were dissolved, making a solution 
that was 0.6 Molar in transition metals with a pH of 2.32. This solution 
was added over the course of 30 minutes, with constant stirring to 600 ml 
of water held at 70.degree. C. along with a 2.0 Molar LiOH solution. The 
pH of this 600 ml was initially adjusted to pH 9.0 with LiOH. Over the 
course of the addition, the addition rate of the transition metal solution 
and of 2.0 Molar LiOH was controlled to maintain a pH of 9.0. Stirring was 
continued for five hours at 70.degree. C., then left unstirred to cool 
overnight. A creamy white gel resulted. The precipitate was isolated by 
filtration. The filtrate had a pH of 7.27. On resuspension the solid 
darkened to orange brown. The filtrate from this washing had a pH of 7.79. 
After the second washing the recovered air-dried orange brown powder was 
calcined directly, the temperature of which was raised from room 
temperature to 425.degree. C. over the course of two hours, held at 
425.degree. C. for two hours and allowed to cool to room temperature over 
the course of two hours. 13.79 g of dry material were recovered. 14.81 g 
of this material were treated with 10 ml of distilled water in which 
0.0927 g of Pd(NO.sub.3).sub.2 was dissolved along with 15 drops of 
ethanolamine. After thorough mixing, the slurry was dried in a vacuum oven 
for 1.25 hours, then calcined in air. Over the course of an hour, the 
temperature was increased from room temperature to 325.degree. C., then 
held at 325.degree. C. for three hours before cooling to room temperature 
over the course of two hours. 
The BET surface area was 35.7 m.sup.2 /g, and elemental analysis showed 
mole fractions of the Mn, Zn and Li to be respectively 0.6766, 0.3230 and 
0.0001. The wt % Pd was 0.21%. 
Table 9 shows the composition and surface area of catalysts. Composition is 
by relative atomic fraction of the metallic elements in the mixed metal 
oxide phase(s) of the catalyst analyzed in the protocatalyst. "MMF" means 
metal mold fraction. Preferred versions of our patent are designated A, B, 
and C. 
TABLE 9 
__________________________________________________________________________ 
Catalyst Composition Surface Area 
Mn Zn Zr Li Zr/ Zn/ BET 
MMF MMF MMF MMF (Mn + Zr) 
(Mn + Zr) 
m.sup.2 /g 
__________________________________________________________________________ 
A 0.3841 
0.2592 
0.2954 
0.061255 
0.4347 
0.3815 
74.1 
B 0.3857 
0.2706 
0.3428 
0.000963 
0.4706 
0.3714 
75.1 
C 0.4202 
0.2914 
0.2884 
-- 0.4288 
0.3838 
72.1 
D 0.4023 
0.2823 
0.3154 
-- 0.4395 
0.3933 
78.8 
E 0.5390 
0.2892 
0.1674 
0.004428 
0.2370 
0.4094 
59.0 
F 0.2663 
0.2184 
0.5116 
0.003681 
0.6577 
0.2808 
112.2 
G 0.4634 
0.2891 
0.2475 
-- 0.3482 
0.4067 
100.0 
H 0.3675 
0.3819 
0.2491 
0.001476 
0.4040 
0.6194 
-- 
I 0.2467 
0.0000 
0.6487 
0.104117 
0.7253 
0.0000 
206.2 
J 0.3293 
0.0000 
0.6288 
0.041848 
0.6563 
0.0000 
91.9 
K 0.6766 
0.3230 
0.0000 
0.0001 
0.0000 
0.4773 
35.7 
L 0.4165 
0.2925 
0.2910 
-- 0.5000 
0.5000 
67.9 
__________________________________________________________________________ 
EXAMPLE 26 
Table 10 is a comparison of the performance of second stage catalysts 
within the scope of this present invention with Catalyst E, a composition 
outside the scope of the present invention. Reaction conditions were 3.00 
cm.sup.3 of 60 to 80 mesh catalyst volume in the copper-lined reactor 
tube, about 6500 kPa, 44% CO, 39.4% H.sub.2, 6.6% CO.sub.2 and 10.0% Ar 
synthesis gas, into which was vaporized at a rate of 0.8 liquid hourly 
space velocity a mixture of 90.00 wt % methanol, 9.56 wt % ethanol and 
0.44 % water. Contact time is in seconds. Temperature is in .degree.C. 
iBuOH=isobutanol, MBuOH=methyl butanols, nPrOH=n-propanol, EtOH=ethanol. 
Others=other liquid products, including: n-butanol, n-pentanol, methyl 
pentanols, etc. CNV=ethanol conversion. 
TABLE 10 
__________________________________________________________________________ 
Catalyst C.sub.2 + Liquid Product 
Mn:Zn:Zr Reactor 
Contact 
CNV 
Composition, Weight % 
Atomic Fractions 
Temp. 
Time 
% iBuOH 
MBuOH 
nPrOH 
EtOH 
Others 
__________________________________________________________________________ 
A 380 9.5 
99.5 
75 4 10 0.3 
11 
0.384:0.259:0.295 
360 13.6 
98.0 
76 7 8 0.7 
9 
2M LiOH, 70.degree. C. ppt 
340 13.3 
94.6 
75 8 5 4 8 
320 13.2 
61.9 
36 5 20 30 9 
C 380 12.6 
99.5 
72 7 6 0.4 
15 
0.420:0.291:0.288 
340 13.5 
91.5 
66 12 11 6 5 
1M LiOH 70.degree. C. ppt 
D 380 12.6 
99.4 
72 7 8 0.4 
13 
0.402:0.282:0.315 
340 13.5 
86.4 
59 10 14 10 7 
1M LiOH 25.degree. C. ppt 
E 380 14.4 
98.8 
81 5 2 0.8 
10 
0.384:0.286:0.164 
360 13.1 
83.6 
67 7 7 12 8 
1M LiOH 70.degree. C. ppt 
340 13.5 
81.8 
56 7 16 13 7 
__________________________________________________________________________ 
EXAMPLE 27 
Table 11 is a further comparison of preferred second stage catalysts to 
other Pd loaded Mn:Zn:Zr mixed oxide catalysts. Reaction conditions were 
3.00 cm.sup.3 of 60 to 80 mesh catalyst volume in the copper lined reactor 
tube, about 6500 kPa, 44% CO, 39.4% H.sub.2, 6.6 % CO.sub.2 and 10.0% Ar 
synthesis gas, into which was vaporized at a rate of 0.8 liquid hourly 
space velocity a mixture of 90.00 wt % methanol, 9.56 wt % ethanol and 
0.44% water. Temperature is in .degree.C. iBuOH=isobutanol, MBuOH=methyl 
butanols, nPrOH=n-propanol, EtOH=ethanol. Others=other liquid products, 
including: n-butanol, n-pentanol, methyl pentanols, etc. CNV=ethanol 
conversion. 
TABLE 11 
__________________________________________________________________________ 
C.sub.2 + Liquid Product 
Composition, Weight % 
Catalyst T.degree. C. 
CNV iBuOH 
MBuOH 
nPrOH 
EtOH 
Others 
__________________________________________________________________________ 
A 380 
99.5 75 4 10 0.3 11 
0.384:0.259:0.295 
360 
98.0 76 7 8 0.7 9 
2M LiOH, 70.degree. C. ppt 
340 
94.6 75 8 5 4 8 
320 
61.9 36 5 20 30 9 
C 380 
99.5 72 7 6 0.4 15 
0.420:0.291:0.288 
340 
91.5 66 12 11 6 5 
1M LiOH 25.degree. C. ppt 
D 380 
99.4 72 7 8 0.4 13 
0.402:0.282:0.315 
340 
86.4 59 10 14 10 7 
1M LiOH 70.degree. C. ppt 
E 380 
98.8 81 5 2 0.8 10 
0.384:0.286:0.164 
360 
83.6 67 7 7 12 8 
1M LiOH 70.degree. C. ppt 
F 380 
99.6 74 7 5 &lt;1 13 
0.266:0.218:0.512 
340 
77.7 48 8 16 17 11 
G 380 
99.5 70 7 7 &lt;1 15 
0.463:0.289:0.247 
350 
72.0 41 9 19 22 8 
H 380 
95.7 72 6 7 &lt;1 14 
0.367:0.382:0.249 
340 
82.6 48 9 16 16 11 
__________________________________________________________________________ 
EXAMPLE 28 
Table 12 is a comparison of Mn:Zn:Zr catalysts to catalysts lacking either 
Zn or Zr. Reaction conditions were 3.00 cm.sup.3 of 60 to 80 mesh catalyst 
volume in the copper-lined reactor tube, about 6500 kPa, 44% CO, 39.4% 
H.sub.2, 6.6% CO.sub.2 and 10.0% Ar synthesis gas, into which is vaporized 
at a rate of 0.8 liquid hourly space velocity a mixture of 90.00 wt % 
methanol, 9.56 wt % ethanol and 0.44% water. Contact time is in seconds. 
Temperature is in .degree.C. iBuOH=isobutanol, MBuOH=methyl butanols, 
nPrOH=n-propanol, EtOH=ethanol. Others=other liquid products, including: 
n-butanol, n-pentanol, methyl pentanols, etc. CNV =ethanol conversion 
TABLE 12 
__________________________________________________________________________ 
C.sub.2 + Liquid Product 
Composition, Weight % 
Catalyst T.degree. C. 
CNV iBuOH 
MBuOH 
nPrOH 
EtOH 
Others 
__________________________________________________________________________ 
A 380 
99.5 75 4 10 0.3 11 
0.384:0.259:0.295 
360 
98.0 76 7 8 0.7 9 
2M LiOH, 70.degree. C. ppt 
340 
94.6 75 8 5 4 8 
320 
61.9 36 5 20 30 9 
I 380 
99.5 72 5 9 0.3 13 
0.247:0.000:0.649 
360 
94.5 73 6 6 4 1 
340 
59.8 36 6 21 32 4 
J 380 
97.4 74 6 6 2 12 
0.25% Pd 360 
86.0 63 6 11 10 9 
0.329:0.629 
340 
56.6 36 5 17 35 6 
K 380 
93.9 72 7 9 4 7 
ZnMn.sub.2 O.sub.4 
340 
28.7 17 0 20 63 0 
0.677:0.323:0.000 
__________________________________________________________________________ 
EXAMPLE 29 
Table 13 is a comparison of the preferred second stage catalysts of this 
invention, Pd on Mn:Zn:Zr mixed oxide catalysts, to literature catalysts. 
Reaction conditions were 3.00 cm.sup.3 of 60 to 80 mesh catalyst volume in 
the copper lined reactor tube, about 6500 kPa, 44% CO, 39.4% H.sub.2, 6.6% 
CO.sub.2 and 10.0% Ar synthesis gas, into which was vaporized at a rate of 
0.8 liquid hourly space velocity a mixture of 90.00 wt % methanol, 9.56 wt 
% ethanol and 0.44% water. Temperature is in .degree.C. iBuOH=isobutanol, 
MBuOH=methyl butanols, nPrOH=n-propanol, EtOH=ethanol. Others=other liquid 
products including n-butanol, n-pentanol, methyl pentanols etc. 
CNV=ethanol conversion. 
TABLE 13 
__________________________________________________________________________ 
C.sub.2 + Liquid Product 
Catalyst Hrs on Composition, Weight % 
MMF; Mn:Zn:Zr 
T.degree. C. 
Line 
CNV 
iBuOH 
MBuOH 
nPrOH 
EtOH 
Others 
__________________________________________________________________________ 
A 380 
87 99.5 
75 4 10 0.3 
11 
0.384:0.259:0.295 
360 
111 98.0 
76 7 8 0.7 
9 
2M LiOH, 70.degree. C. ppt 
340 
120 94.6 
75 8 5 4 8 
320 
135 61.9 
36 5 20 30 9 
CeC.sub.2 Alfa 
380 
119 82.1 
56 4 21 12 7 
360 
143 32.6 
16 3 19 59 3 
MgO 380 
2 88.1 
70 2 18 8 1 
380 
28 65.4 
40 2 30 27 12 
__________________________________________________________________________ 
EXAMPLE 30 
Table 14 shows the impact of time under syngas at about 380.degree. C. on 
the conversion of a second stage protocatalyst into a catalyst. Reaction 
conditions: 3.00 cm.sup.3 of 60 to 80 mesh catalyst volume in the copper 
lined reactor tube, about 6500 kPa, 44% CO, 39.4% H.sub.2, 6.6% CO.sub.2 
and 10.0% Ar synthesis gas, into which is vaporized at a rate of 0.8 
liquid hourly space velocity a mixture of 90.00 wt % methanol, 9.56 wt % 
ethanol and 0.44% water. Temperature is in .degree.C. Hours is hours at 
380.degree. C. under syngas. iBuOH=isobutanol, MBuOH=methyl butanols, 
nPrOH=n-propanol, EtOH=ethanol. Others=other liquid products, including: 
n-butanol, n-pentanol, methyl pentanols etc. CNV=ethanol conversion. 
TABLE 14 
__________________________________________________________________________ 
C.sub.2 + Liquid Product 
Catalyst Composition, Weight % 
MMF; Mn:Zn:Zr 
T.degree. C. 
Hrs 
CNV 
iBuOH 
MBuOH 
nPrOH 
EtOH 
Others 
__________________________________________________________________________ 
A 380 
87 
99.5 
75 4 10 0.3 
11 
0.384:0.259:0.295 
360 
111 
98.0 
76 7 8 0.7 
9 
2M LiOH, 70.degree. C. ppt 
340 
120 
94.6 
75 8 5 4 8 
320 
135 
61.9 
36 5 20 30 9 
C 380 
89 
99.5 
72 7 6 0.4 
15 
0.420:0.291:0.288 
340 
112 
91.5 
66 12 11 6 5 
C 340 
18 
85.4 
57 9 13 11 10 
0.420:0.291:0.288 
1M LiOH 70.degree. C. ppt 
__________________________________________________________________________ 
EXAMPLE 31 
This example illustrates the two step conversion of synthesis gas into 
isobutanol and methyl butanols using the novel first and second stage 
catalysts of this invention. Two reactors are arranged in series, 
connected by a steam jacketed copper-lined gas transfer tube. At the inlet 
of the second reactor there is a line leading to a pump and reservoir such 
that additional liquid can be added and vaporized. The second reactor tube 
is connected to a liquid product knockout section cooled to -10.degree. C. 
The first reactor is charged with 10 cm.sup.3 of catalyst and 20 cm.sup.3 
of inert high purity crushed fused quartz as in Example 8. It is brought 
on-line as in Example 8 with its product gas going to vent until the 
second reactor in the series as ready to receive it. Sufficient catalyst 
is prepared as in Example 9 to charge the copper-lined and jacked reactor 
tube with an I.D. of 1.04 cm (0.41 inches) with 10 cm.sub.3 of 
protocatalyst. The protocatalyst is reduced and activated under synthesis 
gas thus converting to the catalyst as in Example 9. After activation, its 
temperature is decreased to 350.degree. C. and the effluent stream from 
the first reactor, the composition of which is shown in Table 8 is allowed 
to flow over the catalyst in the second reactor such that its exit 
pressure was about 900 psig or about 6200 kPa. With the first reactor fed 
1 to 1 hydrogen/CO synthesis gas at a space velocity of 12,000, the liquid 
product from the second reactor produced at a rate of 995 grams/liter of 
catalyst volume/hour has the following composition in wt %: 70.0% 
methanol, 0.5% ethanol, 1.2% n-propanol, 17.5% isobutanol, 4.2% methyl 
butanols and 6.6% other compounds, primarily oxygenates including 
n-butanol and methyl pentanols. This liquid represents 94.8% of all the 
carbon containing products other than CO.sub.2, with the balance being 
1.5% methane and 3.7% C.sub.2 through C.sub.5 hydrocarbons. Of the C.sub.2 
+ liquids, the isobutanol methyl butanol fraction represents 72 wt %. 
EXAMPLE 32 
In this example, the two reactors are charged and operated as in Example 
29, but the liquid product is distilled into a methanol fraction, an 
ethanol, n-propanol fraction and an isobutanol, methyl pentanol and 
heavier fraction. The ethanol, n-propanol fraction is then fed via a feed 
pump into the second stage reactor such that it is vaporized and mixed 
with the effluent from the first stage reactor before contacting the 
second stage catalyst. In this example with ethanol and n-propanol 
recycled, the isobutanol productivity increased 10.3% from 174 g/l hour 
without recycle to 192 g/l hour recycle and similarly the productivity of 
methyl butanols increased 5.7% from 41.9 g/l hour without recycle to 44.9 
g/l/hour. The liquid product minus the recycled ethanol and n-propanol is 
produced at a rate of 998 g/l hour and contains in wt % 69.7% methanol, 
19.2% isobutanol, 4.4% methyl butanols and 6.7% others.