208 Ind. Eng. Chem. Prod. Res. Dev., Vol. 17, No.
3, 1978
High Surface Area Molybdenum Catalysts: Preparation,
Characterization, and Activity
George A. Tsigdinos” and Wllbur W. Swanson
climax Molybdenum company of Michigan, Research Laboratory, A Subsidiary of AMAX INC., Ann Arbor, Michigan 48105
Methods for preparing high surface area Mo/MoO,, Moo2, and Co-Mo and Ni-Mo bimetallic compositions are
described. Methods for preparing metal molybdates, such as Fe,(MoO,),,
moderately high surface area are also described. All of the materials prepared were characterized by chemical
analysis, X-ray, and surface area. Passivation and regeneration procedures were also devised for the pyrophoric
materials. The Mo/Mo02 composition was found to be active in the isomerization of n-hexane.
Introduction
Over a period of years, molybdenum-containing ma-
terials have found uses as catalysts in several industrial
applications. For example, iron molybdate is one of the
standard catalysts for the oxidation of methanol to
formaldehyde, cobalt and nickel molybdates are catalysts
in the hydrotreating of petroleum, and bismuth molyb-
dates reportedly are active in the ammoxidation of pro-
pylene to acrylonitrile.
Although molybdenum trioxide and its reduction
products have been extensively investigated as catalysts
on carriers, relatively little work has appeared on the
preparation and characterization of high surface area
molybdenum trioxide and the lower oxides of molybde-
num. It is known that established industrial processes
(Climax Molybdenum Co.) produce molybdenum trioxide
of low bulk density by carrier gas sublimation; however,
the surface area of the sublimed material is in the vicinity
of 8 to 10 m2/g. In an investigation of the sublimation
process for molybdenum trioxide (Dietz and Klostermann,
19661, materials having a bulk density from 0.2 to 1.2 g/mL
were produced, but the surface areas were not given. A
technique for producing ultrafine powders by arc va-
porization has been reported to yield platelike MooB
particles having surface areas of 20 m2/g with equivalent
sphere diameters of 700 A (Holmgren et al., 1964). More
recently, molybdenum trioxide with surface areas up to
130 m2/g was produced from dispersions of condensed
aerosols (Sutugin and Fuks, 1970). Finally, molybdenum
trioxide of surface area 17 m2/g was obtained by the
decomposition in air at 300 “C of anhydrous ammonium
heptamolybdate (Fransen et al., 1976).
Several methods for preparing metal oxides or com-
pounds from highly dispersed mixtures of oxides that
contain high surface areas have been described (Delmon
et al., 1969; Courty et al., 1973). Such materials include
refractory oxides like TiOz and Al2O3,spinels like MgA1204,
or perovskite-type structures like LaCr03 They have been
prepared by pyrolysis of precursors of the oxide(s) obtained
from solutions containing all the required ions and an
organic polyfunctional acid possessing at least one hydroxy
and one carboxylic group such as citric, malic, tartaric,
glycollic, or lactic acid (Delmon, 1968, 1969, 1970; Courty,
1973; Szabo and Paris, 1969; Paris and Paris, 1965). Of
the metal molybdates, iron molybdate and the bismuth
molybdates have been the most extensively investigated
because of their use in selective hydrocarbon oxidation
catalysis. Iron(II1) molybdate gels, stoichiometric or
promoted by other metals, have been prepared by mixing
Fe(N03)3.9H20 and (NH4)6M07024-4H20 (AHM) and
0019-7890/78/1217-0208$01.00/0
CoMoO,, NiMoO,, and MnMoO, of
kneading at room temperature to give a very viscous so-
lution that transforms to an elastic, transparent gel within
30 min. Gels prepared in this manner have surface areas
of 0.5 to 50 m2/g. However, when these were used as
catalysts in the oxidation of methanol to formaldehyde,
the best selectivity was obtained with surface areas of 10
to 12 m2/g (Courty et al., 1970; Courty, 1971, 1973).
As reported in the literature, methods for preparing high
surface area molybdenum metal include primarily the
reduction of molybdenum dioxide and molybdenum
pentachloride by hydrogen. The reduction of molybdenum
dioxide by hydrogen at 450 O C yielded molybdenum
“metal” having a maximum surface area of 50 m2/g;
however, the source of the starting material or the extent
of its reduction was not given (Hillis et al., 1966). Nev-
ertheless, the reduced materials prepared by this method
have been found to have catalytic activity for the hy-
drogenation of absorbed nitrogen to ammonia (Hillis et al.,
1966) and for the hydrogenolysis of ethane (Sinfelt and
Yates, 1971). Molybdenum metal powder of 0.01 to 0.1
pm average particle diameter has been prepared via the
reduction of MoC15 by hydrogen in an argon atmosphere
at 800 “C. The pyrophoric metal contained 0.15% 0 and
had a surface area of 11m2/g (Lamprey and Ripley, 1962).
Aside from the work thus far cited, no other information
on high surface area molybdenum-containing materials is
available. Consequently, this study has centered on de-
vising methods for preparing high surface area materials
such as molybdenum oxides, metal molybdate gels, and
mono- and bimetallic molybdenum-containing composi-
tions. The procedures devised for preparing moderately
high surface area metal molybdates depended on the use
of hydrogen peroxide solutions of ammonium hepta-
molybdate, whereas the preparation of high surface area
mono- and bimetallic molybdenum-containing composi-
tions was based on procedures involving the use of mo-
lybdenum oxalate (Tsigdinos et al., 1975) or metal mol-
ybdate prepared from AHM/H202. These products were
examined for surface area and sintering properties.
Passivation and regeneration procedures were also devised
for the pyrophoric materials. The activity of Mo/Mo02
toward the isomerization of n-hexane was also evaluated
by others (Burch and Mitchell, 1976, 1977).
Experimental Section
Materials. All chemicals used were reagent grade
unless otherwise specified. The aquaoxalatomolybdic(V1)
acid (molybdenum oxalate), H2[Mo03C204.H20]-H~0, used
was prepared as described in the literature (Killeffer and
Linz, 1952). All air-sensitive materials were handled in a
0 1978 American Chemical Society
 Ind. Eng. Chem. Prod. Res. Dev., Vol. 17, No. 3, 1978 209

Table I. Analysis of Metal Molybdates Table 111. Data on Supported Mo/MoO,

~-
~~

found calcd reduc-

metal tion at molyb- total sur-
molybdate %metal % MO %metal % MO 500 'C, denum, carbon, face area,
Fe,(MoO,), 19.0 46.2 18.9 48.6 support h wt% wt% m'/g
MnMoO, 25.3 44.1 25.5 44.6 Catapal SB A1,0, 48 9.49 <0.038 260
CoMoO, 28.5 41.9 26.9 43.8 Harshaw Al-4104 24' 9.98 214
NiMoO, 25.6 41.7 26.8 43.9 extrudate
Bi,(MoO,), 41.7 31.5 46.5 32.0 Silica Gel 59 24a 9.12 293
(W. R. Grace)
Table 11. Surface Areas of Metal Molybdates as a Y-Type Zeolite 48 8.09 <0.038 782
Function of Temperaturea SMR-54-806
(W. R. Grace)
surface area at indicated temp, Ludox A M b (223 48 7.5 0.11 174
metal m'k m'/g surface
molybdate 450 C 550 a C 650 "C area)
Fe2(Mo04 13 8.1 7.42 3.Sb a Produced in 2-kg quantities. Products are not pyro-
MnMoO, 20.7 11.0 3.0 phoric, but warm to approximately 60 "C upon exposure
CoMoO, 24.4 18.3 11.3 to atmosphere. Pure Ludox solid was obtained by gela-
NiMoO, (27.8)' 25.2d 19.7 tion with tert-butyl alcohol. However, gelation of Ludox
Bi2(Mo04)3 3.2 solution in the presence of molybdenum oxalate was ob-
tained by addition of 5% NH,.
Calcination at temperature was for 2 h unless other-
wise indicated. Refers to green form of iron molyb-
date. ' Impure phase (contains NiO). Calcined for 24 temperature. The experiments employing larger charges
h to eliminate oxides. were carried out in a 1-L stirred-bed reactor. In all ex-
periments the reactor was freed of air by purging with
drybox with an antechamber that could be evacuated and argon prior to reduction. At the end of each run, the
refilled with dry nitrogen and with a circulating 96% hydrogen gas was flushed with argon at the temperature
Nz-4% H2 atmosphere for removing traces of oxygen. A of the reaction, and the reactor was cooled in argon. Care
25-W light bulb, with the shroud removed, served as an was exercised to prevent restriction of the hydrogen flow
indicator for traces of oxygen and moisture. by the anhydrous oxalic acid that formed during the initial
Preparation of Compounds. (a) Metal Molybdates. stages of the decomposition.
The cobalt, nickel, and manganese metal molybdates were In a typical run, 500 g of powdered molybdenum oxalate
prepared by the addition of powdered metal acetate to a (-10 to +30 mesh) was reduced in flowing hydrogen, with
highly concentrated (37 w t % Mo) ammonium hepta- stirring, according to the following sequence: heat-up time
molybdate/ hydrogen peroxide solution. Iron nitrate was to 300 "C, 2.3 h; heat at 300 "C, 16 h; heat-up time to 400
used for preparing ferric molybdate. In a typical example, "C, 1 h; and reduction at 400 "C, 24 h. The flow rate was
CoMo04 was prepared by adding 87.5 mL of 30% HzOz 5 L/min. The black pyrophoric powder, 213 g, was purged
t o 350 mL of water followed by the addition of 805 g of and cooled in argon.
(NH4)6M07024-4H20 (AHM). When all the AHM was (d) The Mo/Mo02 Product. Powdered molybdenum
dissolved, 1136.1 g of C O ( C H , C O O ) ~ . ~ Hin
~ Opowdered
, oxalate (-10 to +30 mesh), 500 g, was reduced in the
form, was added while the solution was stirred vigorously. stirred-bed reactor in flowing hydrogen, with stirring, by
After a 10-min period a gray unstirrable mass formed, heating to 300 "C in 2.5 h, heating at 300 "C for 16 h,
which had the odor of acetic acid. The mass was heated heating to 500 "C for 1.5 h, and finally heating at 500 "C
in a vacuum oven at 120 "C for approximately 2 h, and the for 48 h. The flow rate was 7.6 L/min. The black product
dried material which crumbles readily was then ground to obtained, 176 g, was purged and cooled in argon. The
a fine powder and calcined in air at 450 "C for 2 h. A 1-kg following compounds were also reduced under the same
yield was obtained. The analyses of the metal molybdates conditions: ammonium formatomolybdate, (NH4)3-
prepared are given in Table I. The surface areas of the [CHCOO)Mo2O7].Hz0(see Brauer, 1965, for preparation),
products as a function of temperature are given in Table (NH4)2M0207, air-micronized Mooz and undensified grade
11. MOO, (Climax Molybdenum Co., surface area of 8 m2/g).
(b) Molybdenum Trioxide and Blue Oxides. For this The porous precursor to Mo/MoOz was prepared as fol-
preparation, 487 g of molybdenum oxalate (-30 mesh) was lows: a 500 g charge of molybdenum oxalate was treated
heated a t 300 "C for 1 h with vigorous stirring in a stir- in flowing hydrogen, as indicated above, by heating up to
red-bed reactor having an air flow of 2 L/min. The 300 "C for 2 h and heating at 300 "C for 24 h. The black
heat-up time was 1.5 h. The yield of the slightly gray-blue nonpyrophoric powder, 225 g, was purged with argon.
powder obtained was 212 g. Supported Mo/Mo02 was produced by dissolving the
When the decomposition of molybdenum oxalate was required amount of molybdenum oxalate in water and
carried out in nitrogen at 300 "C with vigrous stirring, impregnating the support. The reduction cycle was similar
bright blue solids were obtained. Decomposition under to that used for unsupported material. The preparation
vacuum (300 "C, vigorous stirring) produced blue-black of the catalyst by the gelation of colloidal silica was
products. A sample of molybdenum oxalate was also prepared as follows: 28 g of H2[Mo03C204H20]~H20 was
decomposed under vacuum, with no stirring provided, to dissolved in 300 g of Ludox AM Colloidal Silica (30%
yield a blue powder. SiOz), and the solution was converted into a thick gel by
( c ) Molybdenum Dioxide. All small-scale runs (em- the addition of 64 mL of 5.2% NH, solution. The gel was
ploying 30 g or less of molybdenum oxalate charge) were then dried overnight at 70 "C and ground to -10 to +30
carried out in a vertical Vycor tube, 3.8-cm i.d., provided mesh prior to reduction, as indicated above. Analyses and
with a coarse-porosity frit at the lower part so that the surface areas of the products are given in Table 111.
charge could be fluidized. A thermocouple imbedded in (e) Bimetallic Compositions (Ni-Mo and Co-Mo).
the center of the charge was used to record the internal The starting materials for preparing high surface area
210 Ind. Eng. Chem. Prod. Res. Dev., Vol. 17, No. 3, 1978

Table IV. Passivation and Regeneration Data for Mo/MoO,, Ni-Mo, and Co-Mo Compositions'
regeneration datab
max temp surface area, m'/g surface
starting quantity reached in area, restoration,
material used, g passivation, a C initial passivated m'/g %
MO/MOO,~ 15 35 52 41 49 94
MO/MOO,~ 25 49 124 103 115 93
M~/M~o,c~ 25 57 124 99 111 90
Ni-Mo 20 31 198 177 191 96
CO-MO 20 31 71 49 52 73
All regenerated samples were pyrophoric, Regenerated in hydrogen at 500 "C for 1 6 h. For activity testing, the
materials could be regenerated for 2 h at the temperature of preparation. Different preparations. Duplicate experi-
ment.
Table V. Sintering of Mo/MoO,, Co-Mo, and Ni-Mo
STIRRER
Compositions in Argon (17 h )
decrease
teomp, surface in surface
R TIGHT SEAL material C area, m'/g area, %
I 400 90 26.2
Mo/MoO, 500 75 38.5
600 35 71.3
400 38 7
CO-MO 500 35 15
600 28 32
400 137
Ni-Mo 500 125 9
600 60 56

Table VI, Data from Nitrogen Adsorption Isotherm",

of Mo/MoO, (90.9%Total Mo)
Figure 1. Apparatus for passivation of large samples (-250 g) of
pyrophoric materials. BET surface area 123.7 m'/g
average pore radius 21.2 nm
Cc-Mo and Ni-Mo bimetallic compositions were produced total pore volume 0.13 cm3/g
as indicated below; however, they were not further ex- pore volume distribution
amined in the untreated form. For this preparation, 270 pore radius,
g of H2[Mo03C204H20].H20 and 290 g of cobalt or nickel nm vol, % area, %
nitrate hexahydrate were dissolved in 400 mL of water, and 7-10 15.4 38.7
the solutions obtained were air-evaporated at room 10-15 19.9 36.8
temperature to produce solids that were dried at 35 "C. 15-20 7.2 9.4
The reductions were carried out by placing 25-g samples 20-30 5.3 4.8
30-50 5.3 3.0
(-30 mesh) of NiMo04 and CoMoO,, prepared as shown 50-100 7.7 2.6
above, in a 2.5-cm diameter coarse-frit Vycor furnace tube 100-300 39.1 4.8
and heating in a hinge-type furnace in a vertical position.
The samples were first purged with argon, then exposed Isotherm is mixture of Type I and Type 11. Work
performed by Analytical Services of Gulf Research and
to a 0.25 L/min flow of hydrogen, nearly fluidizing the Development Co.
sample, and finally cooled in argon after the appropriate
reduction time. The CoMoO, gel was heated directly to Sintering Studies. All sintering studies were carried
500 "C and maintained for 40 h. The product was a out in a Vycor tube reactor equipped with an internal
pyrophoric powder. The reduction of NiMoO, was sim- thermocouple. Heating was carried out in a minimal argon
ilarly carried out, but at 400 "C for 60 h. This powder was stream for 17 h. The sintering data obtained for Mo/
also pyrophoric. Moo2, Co-Mo, and Ni-Mo compositions at 400,500, and
Passivation and Regeneration of Materials. All 600 "C are given in Table V.
pyrophoric high surface area materials were passivated Surface Studies. All surface areas (single point), BET
using a mixture of 2% O2 in carbon dioxide that was nitrogen, were obtained with a Micromeritics High Speed
further diluted with argon or carbon dioxide during the Surface Analyzer Model 2200. Data from a nitrogen
initial stages of the passivation. In all cases the oxy- adsorption isotherm of Mo/Mo02 (containing 25% free
gen-containing gas was slowly added to the diluting gas molybdenum) are given in Table VI.
through a manifold containing a flow meter for each gas.
The rate of passivation was controlled by not allowing the Results and Discussion
temperature, monitored internally, to exceed 40 to 50 "C. (a) Metal Molybdates. The metal molybdates pre-
Small samples (10 to 25 g) were passivated in the Vycor pared and shown in Table I, namely Fe2(Mo04)3,MnMo04,
apparatus used for reductions, as described above. CoMo04, NiMoO,, and B ~ * ( M O Oall ~ ) have
~ , moderately
Samples, each containing several hundred grams, were high surface areas with the exception of the bismuth
passivated in a 500-mL round-bottom flask fitted with a molybdate. Formation of such high surface area materials
mechanical stirrer, a thermocouple, and the appropriate cannot be obtained from ammonium heptamolybdate
gas connections, as shown in Figure 1. The passivated solutions in the absence of hydrogen peroxide because
samples were regenerated in flowing hydrogen at 500 "C precipitation occurs readily, leading to low surface ma-
for 16 h. Passivation and regeneration data for Mo/Mo02, terials. It was found that gel (molybdate) formation was
Ni-Mo, and Co-Mo compositions are given in Table IV. pH dependent; that is, an addition of acid prevented such

formation. Such procedures have also been used in this
work to prepare other metal molybdates, such as those of
magnesium (17 m2/g), zinc (8 m2/g), lanthanum (15 m2/g),
etc. In most cases, not all of the metal nitrate or acetate
dissolved in the AHM/H20, solutions before thickening;
consequently, after mixing, these mixtures had to be dried
a t 120 "C and then ground to obtain homogeneity prior
to calcination. Although the required stoichiometric
quantities of the starting materials were employed in
preparing these gels, the analytical data obtained and
shown in Table I deviate somewhat from the calculated
values. This may be attributed to some lack of homo-
geneity and to analytical (atomic absorption) accuracy.
The variation of surface area with calcination tem-
perature of the metal molybdates prepared is shown in
Table 11. The decrease in surface area was studied by
maintaining the samples at the specified temperature for
2 h. In general, the surface areas decreased with increasing
temperature, but both CoMoO, and NiMoO, retained
appreciable surface areas a t 650 "C, 11.3 and 19.7 m2/g,
respectively. The phase purity of the metal molybdates
was ascertained via X-ray by calcining the gels for the
minimum amount of time to yield an X-ray pure material
at the lowest temperature possible. Thus, Fe2(Mo04),was
obtained pure in the tan form after calcining at 450 and
550 "C for 2 h in accordance with published X-ray data
(Plyasova and Kefeli, 1967). However, the green form was
obtained after calcination at 650 "C. The manganous
molybdate, MnMo04, obtained after calcination at 450 "C
was identical with the low-pressure monoclinic modifi-
cation reported (Abrams and Reddy, 1965). Cobalt
molybdate, CoMo04, was obtained in X-ray pure form
after calcination a t 450, 550, and 650 "C, and the color
remained purple at these temperatures. Its X-ray powder
patterns are the same as the /3 form, which is monoclinic
(Courty, 1968). However, the peaks become better defined
with increasing calcination temperature, consistent with
the decrease in surface area, and hence, increase in
crystallinity with an increase in temperature. All cobalt
molybdate samples that had been calcined a t the tem-
peratures specified became green when ground. The X-ray
powder patterns of the green powders showed the in-
creasing presence of y-CoMoO, with increasing amount
of grinding, indicating that the green form that is produced
with pressure grinding is identical with the y-CoMoO,
obtained at elevated temperatures (Spretnak and Speiser,
1955).
The nickel molybdenum produced was shown to be free
of NiO and MOO, only after calcination at 550 "C for 24
h, but at 650 "C only 2 h of heating was necessary to yield
such material; however, it had a lower surface area (Table
11). The NiMoO, products thus produced were found by
X-ray to be identical with the high-temperature /3 form
(Spretnak and Speiser, 1955; Wetzlar, 1964). The calci-
nation of NiMoO, at 550 "C for periods considerably less
than 24 h showed, in addition to 0-NiMoO,, the presence
of nonstoichiometric nickel molybdate (Corbet et al., 19581,
also identified in phase studies of the NiO-Moo, system
(Pilipenko et al., 1973). Stoichiometric bismuth molyb-
date, Bi2(Mo04),, was obtained by calcination of the
precursor gel at 450 "C and was shown by X-ray to be
similar to that reported in the literature (Erman et al.,
1964; Aykan, 1968). Calcination of the precursor gel
(containing 1:l Bi to Mo atomic ratio) for formation of
Bi2M0209at 450 "C gave a product with the X-ray pattern
of Bi2(Mo04),. The Bi2M0209,containing only a very small
amount of B~,(MoO,)~, resulted only after calcination of
the gel at 650 "C for 2 h and was identical, by X-ray, with
Ind. Eng. Chem. Prod. Res. Dev., Vol. 17, No. 3, 1978 211
1
IO0 200 300 400 500 600
TEMPERATUi7C.C
Figure 2. Thermal behavior of H2[MoO3C2O4H2O]~H20
in nitrogen
(sample wt, 0.6552 g; heating rate, 10 OC/min).
that reported in the literature (Erman et al., 1964).
(b) Molybdenum Trioxide and Blue Oxides. The
preparation of high surface area molybdenum oxides is of
importance as hydrogen reduction of such oxides at low
temperatures would be expected to lead to lower oxides
of increased surface are due to pore formation by oxygen
removal. Thw, molybdenum trioxide having a surface area
of 24.3 m2/g was produced by air oxidation of molybdenum
oxalate. The product was identified by X-ray. Heating
was carried out up to 300 "C since thermogravimetric data
obtained in air for this material show a continuous weight
loss up to apptoximately 240 "C. Similar data obtained
by TGA in nitrogen are shown in Figure 2. However, this
material demonstrated appreciable sintering when heated
at 400 and 500 "C for 5 h; the surface areas obtained were
13 and 5.2 ma/g, respectively. No further reduction in
surface area was noted after heating at 400 "C for 48 h;
however, the surface area showed a slow decrease upon
heating at 500 "C. It was found that decomposition of the
oxalate in nitrogen at 300 "C (see Figure 2) yielded blue
oxides with surface areas from 31 to 65 m2/g, but upon
analysis these materials were found to contain from 39 to
45% reduced molybdenum (expressed as Mo5+),deter-
mined cerimetricdy. The carbon content was <0.170. An
X-ray oE the products showed the presence of MOO, and
MOO,. However, when such decomposition was carried out
under vacuum, in the absence of stirring, the blue product
obtained had a surface area of 8 m2/g, and X-ray showed
the presence of Moo3. Thus, high surface area MOO,
produced under reducing conditions from molybdenum
oxalate a t 300 "C serves as the precursor of such inter-
mediates and end products that are obtained by hydrogen
reduction, as will be explained later.
(c) Molybdenum Dioxide. No report for very high
surface area MOO, has appeared in the literature. The high
surface area Mooz prepared in this study had a surface
area of 192 m2/g, and contained 77% Mo. The material
was black and pyrdphoric although purged of hydrogen
with argon, a t the redtxtion temperature indicative of
possible hydrogen chemisorption, to form Mo-OH
bonding. To obtain this material with high surface area
it was necessary to produce a high surface area porous
intermediate, by reduction at 300 "C for 16 h of molyb-
denum oxalate, identified by X-ray as a mixture of MOO,
and M04O11 (158 m2/g surface area). When formation of
this intermediate was avoided by bypassing the reduction
step at 300 "C, the surface area of the MOO, obtained was
only 58 m2/g. Similar observations were also made during
the reduction of molybdenum oxalate to produce high
surface area Mo/MoO,, ELS shown later. Whenever the high
surface area intermediate was not observed, the final
products had low surface areas. Fluidization of the oxalate
during the heating period from 25 to 300 "C was found
212 Ind. Eng. Chem. Prod. Res. Dev., Vol. 17, No. 3, 1978
necessary to yield such intermediates. No high surface area
products could be produced when fluidization was avoided;
fluidization allows for the rapid purging of the off-gas
(Brauer, 1965) during the initial stages of the heating
process. It was found that oxalic acid, which evolved in
considerable quantity during the early stages of the re-
duction, could accumulate in the outlet of the reactor thus
causing clogging and restriction of the flow of hydrogen.
Although oxalic acid sublimes above 100 "C and decom-
poses at 190 "C, the exits of the reactors had to be
maintained sufficiently above this temperature so that the
hydrogen flow rate would not be restricted. It was also
found that a flow rate of 0.25 (L/min)/50-g charge of
molybdenum oxalate was sufficient to produce reduced
products of high surface area, but flow rates of 0.5 (L/
min)/50-g charge are preferable. Lower flow rates resulted
in products of low surface area. The final Mool product
thus obtained was X-ray pure but contained 91% Mooz
(based on molybdenum analysis), indicating some over
reduction. Thus, some care should be taken in the
preparation of this material by the method indicated, i.e.,
prevention of over or under reduction by controlling the
time of heating under the conditions of reaction.
(a) Mo/Mo02. The preparation of high surface area
Mo/Mo02 is carried out in a manner identical with that
for preparing molybdenum dioxide except that the final
reduction is performed a t 500 "C instead of 400 "C
(Tsigdinos et al., 1975). The extent of reduction and, thus,
the percent free molybdenum present in the final com-
position depends on the length of reduction at 500 "C and
also on the efficiency of the reactor. Thus, reduction times
could range from 24 to 48 h. Batches of 2 kg prepared in
a stirred-bed reactor produced pyrophoric materials
containing, for example, 81.3% total Mo corresponding to
25.2% free Mo-the extent of reduction being similar to
that obtained in processing 50-g samples as shown in the
Experimental Section. Furthermore, the molybdenum
oxalate can be predried in air a t 80 "C for 3 h prior to
reduction, thus facilitating more adequate fluidization.
The surface areas of the products thus obtained are similar
(100 to 170 m2/g) to those obtained from the undried
material.
A multiple point nitrogen adsorption isotherm of an
Mo/Mo02 sample (124 m2/g) surface area (90.9% total
Mo) is shown in Table VI. This material contains a
substantial micropore structure and the isotherm is a
mixture of Type I and Type 11. It is possible that most
of the high surface area materials prepared in this study
may contain similar pore size distribution so that the single
point surface area measurements presented should be
considered only approximate, as shown by Gregg and Sing
(1976). Efforts to elucidate this point and to determine
the contribution to the surface area by the Mo and MOO,
components via chemisorption will constitute another
study.
Several compounds other than molybdenum oxalate
were also investigated for producing high surface area
Mo/Mo02 but none of these yielded products of the same
surface areas as those obtained from the oxalate. Am-
monium formatomolybdate yielded a pyrophoric product
having a surface area of 28 m2/g and containing 81.170Mo.
The carbon content was 0.035%. Ammonium dicitrato-
molybdate yielded a tar a t 170 "C and consequently the
reduction was not pursued further. Ammonium di-
molybdate gave a product containing 83.8% Mo with a
surface area of 77.5 m2/g. The reduction of air-micronized
Moo2 and undensified grade MOO, (Climax Molybdenum
Co.) yielded Mo/Mo02 products having surface areas of
10.5 and 43.5 m2/g, respectively.
The high solubility of Hl[Mo03C204Hz0]-H20has af-
forded the preparation of Mo/MoOl on various supports,
as shown in Table 111. The carbon content of the final
products is very low (0.1%). However, high loadings of
molybdenum must be used in employing hydroxylated
supports to allow for the reduction of Moo2 to free mo-
lybdenum so that Mo/Mo02 compositions can be formed
on such supports. It is known that Mooz is not readily
reduced to the metal on hydroxylated aluminas (Massoth,
1973). Although the supported Mo/MoOz materials
containing approximately 10% Mo loadings are not py-
rophoric, they were found upon atmospheric exposure to
warm from 25 to 50 "C.
In producing high surface area Mo/MoOz compositions,
reduction temperatures above 500 "C were not employed
although higher rates of reduction of Moo2 could be thus
attained. As will be shown later, considerable sintering
occurs at 600 "C, but the hydrogen reduction of Mooz to
the metal is slow (von Destinon-Forstmann, 1965) even at
that temperature.
( e ) Bimetallic Compositions. As indicated in the
Experimental Section, Co-Mo and Ni-Mo bimetallic
compositions were produced by hydrogen reduction of
metal molybdate gels. Because molybdenum oxalate
yielded Mo/Mo02 products with high surface areas (100
to 120 m2/g) upon hydrogen reduction, compositions of
1:l molar nickel nitrate/molybdenum oxalate and cobalt
nitrate/ molybdenum oxalate, obtained by air evaporation
at room temperature, were also reduced in hydrogen. In
general, it was found that high surface area materials
containing nickel or cobalt could be obtained from the
metal molybdate gels or the oxalates with reduction
temperature lower than that used for molybdenum oxalate.
This ease of reduction can be attributed to the nickel and
cobalt that are more easily reduced to the metallic state
than molybdenum and they can serve as catalysts for the
reduction of molybdenum by chemisorption. For example,
the hydrogen reduction of Moo3 mixed with palladium on
silica and alumina has been shown to be catalyzed by the
noble metal (Bond and Tripathi, 1974). The mechanism
of palladium-catalyzed reduction of molybdenum trioxide
was investigated by thermogravimetric analysis (Lavrenko
et al., 1975). The addition of 0.1% Pd lowered the re-
duction temperature to about 200 "C. The reduction was
also found to be autocatalytic since there was an increase
in the rate of reduction after an induction period. The
preparation of nickel-catalyzed, hydrogen-reduced mo-
lybdenum and tungsten materials with surface areas of 20
to 50 m2/g from metal oxides has been reported (Kehl et
al., 1972). It was indicated (Zabala et al., 1974) that cobalt
does indeed catalyze the reduction of Moo3-the reduction
rate of trioxide to the metal being doubled in the presence
of cobalt. Thermodynamic data for the reduction of
several metal oxides at 400 "C have been reported (An-
derson, 1975). The P H 2 0 / P H 2 equilibrium constants for the
reduction of NiO, COO, and Moo3 by hydrogen are 500,
50, and 40, respectively, at that temperature. In general,
it was found that Ni-Mo materials prepared either from
gel or from molybdenum oxalate are more easily reduced
and have a higher surface area than the corresponding
Co-Mo compositions. In particular, the reduction of
CoMoOl and NiMo04 at 500 "C for 40 h gave a 40%
reduction for a Co-Mo sample and a surface area of 71
m2/g compared with 45 and 65% reduction for Ni-Mo
compositions with surface areas of 142 to 200 m2/g. The
Co-Mo products prepared by the reduction of oxalate
precursors were shown by X-ray to consist of Co + MOO:,
 Ind. Eng. Chem. Prod. Res. Dev., Vol. 17, No. 3, 1978 213

Table V1I.g Isomerization of n-Hexane by Mo/MoOza

Mo/MoO,
Pd-zeolite
products pyrophoricb passivatedC MO/Mo~ ,d Pt-F/Al,O,e SK120f
methane + ethane 0.09 0.1 0.04 0.4 0.20
propane 0.27 0.5 0.36 0.8 1.27
is0 bu tane 0.06 0.08 0.11 0.03 1.10
n-butane 0.08 0.15 0.08 0.5 0.5
isopentane 0.10 0.14 0.10 0.1 0.9
n-pentane 0.09 0.2 0.06 0.5 0.4
2,2-dimethylbutane 1.03 1.0 1.27 1.2 1.7
2-meth ylpentane 27.34 25.4 22.10 15.0 27.2
3-methylpentane 13.85 14.2 11.39 9.4 14.6
me thylcyclopentane 2.1
benzene 1.0
n-hexane 57.11 57.7 64.50 69.0 52.3
total activity, % 42.9 41.5 35.5 31.0 47.7
selectivity (for C6), % 98.4 97.8 97.9 92.5 91.2
a Reaction conditions: 330 '(2, 1.0 LHSV, after 2 h, 1 atm. Pyrophoric Mo/MoO, (90.9% total Mo) having a surface
area of 1 2 4 mz/g (see Table VI). Same sample as pyrophoric Mo/MoO, but passivated t o a surface area of 103 m'/g (see
Table VI). Pyrophoric Mo/MoO, (83.9% total Mo)having a surface area of 1 2 1 mz/g. e Contains 0.54% Pt and 0.52% F.
f Union Carbide isomerization catalyst SK-120 containing 0.5% Pd and 10.7% rare earth oxides on Y-type zeolite support.
All Mo-containing catalysts were prepared in this work and supplied for testing t o Burch and Mitchell (1976, 1977).

gas contact. The passivated samples suffer an approximate

20% reduction in surface area (see Table V), but can be
8 4
t
\- \ regenerated prior to activity testing by reduction with
hydrogen (2 h) at the temperature at which they were
originally reduced. Restoration of the surface area by
hydrogen regeneration a t 500 "C for 16 h is usually over
90% effective, as shown in Table V. The regenerated
"
Y 7 DAYS (168 HOURS) =25rn2/g samples are pyrophoric. Although the passivated samples
5 -
13DAYS(312HOURS)=16m2/g
40 DAYS (960HOURS) = 12 m2/g can be handled in air for short periods of time, continuous
exposure of Mo/Mo02, Co-Mo, and Ni-Mo to the air leads
to slow diminution of the surface area as shown in Figure
3. The surface area of a Mo/Mo02 sample that was
passivated (100 m2/g) was reduced to approximately 90
m2/g after 2 h; thereafter the surface area slowly decreased
to 50 m2/g following a 30-h period. It is therefore rec-
ommended that the passivated materials be stored under
nitrogen.
Isomerization Activity of Mo/Mo02. High surface
area Mo/Mo02 prepared in this study was evaluated for
n-hexane isomerization activity (Burch and Mitchell, 1976,
1977). The data obtained (Table VII) indicate that both
pyrophoric and passivated Mo/Mo02 yield conversions per
pass (42.9 and 41.5%, respectively) comparable to those
obtained for commercially available isomerization catalysts
under the conditions employed. The selectivities to iso-
hexanes are over 98%. The data were obtained at 330 "C,
1.0 LHSV, and 1 atm for a 2-h period. Further work is
presently being carried out to fully evaluate the activity
of this promising catalyst.
Acknowledgment
The authors are indebted to the analytical staff of this
laboratory for the analyses, to R. W. McConnell and A. K.
Mallock for experimental assistance, and to K. S.W. Sing
of Brunel University for helpful comments on the surface
area studies.
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Academic Press, New York, N.Y., 1965.
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Receiued for review November 22, 1977
Accepted May 8, 1978

Oligomerization of C3-C4 Olefins Using a Navel

Nickel-Aluminosilicate Catalyst

Paul G. Berclk, Kirk J. Metrger, and Harold E. Swift"

Gulf Research & Development Company, Pittsburgh, Pennsylvania 15230

By proper sulfiding it has now been found that nickel-substituted synthetic mica-montmorillonite (Ni-SMM) is a very
active catalyst for oligomerizing C3and C4 olefins to desirable products. For example, from a mixed C4 stream
isobutene can be selectively converted to a high octane dimer while 1-butene is concurrently isomerized to 2-butene.
This could be of interest as a processing scheme to complement HF and H,SO,-catalyzed isobutane alkylation
processes. Isobutylene dimer gasoline has a high clear, RON blending value of about 117 and could be used as
a "trim" agent in lead-free gasoline blending. Also, propylene can be converted to a dimer-trimer mixture which
offers a route to a high octane product without requiring expensive isobutane for alkylate production. This catalyst
can also convert propylene to C12-C18and C2,+ isoparaffinic fractions (after hydrogenation) for use in such applications
as jet fuel and low pour hydraulic and transformer oils. Ni-SMM is a noncorrosive catalyst, which can give long
cycle lives and can be used to process feedstocks containing relatively high levels of sulfur impurities.

Introduction Table I. Composition of Feedstocks

An earlier paper reported that synthetic nickel lay- feedstock
ered-lattice clays are highly active for catalyzing light
component A B C E D
hydrocarbon hydroisomerization and hydrocracking re-
actions (Swift and Black, 1974). The layered-lattice butadiene 0.2 0.2 0.3
dioctahedral clay, without incorporated nickel, is known 1-butene 0.0 11.4 12.0 7.5 9.9
as synthetic mica-montmorillonite (SMM) which can be cis- 2-butene 0.1 10.4 10.3 6.4 26.6
ethane 0.1 0.1
represented as ethylene 0.0
isobutane 24.3 33.6 32.3 22.3 51.1
isobutylene 0.0 11.1 11.7 7.5 10.6
where each layer group is separated by cation-exchange isopentane 3.4 3.5 0.5
2-methyl-1-butene 1.0 1.0
sites to maintain charge neutrality (Capell and Granquist, 2-methyl-2-butene 0.1 0.0
1966). The aluminum ion is in tetrahedral (tetra) coor- n-butane 24.0 10.4 10.5 7.5 1.8
dination in the silica-alumina layers and in octahedral (oct) n-pentane 0.1 0.1
configuration in the alumina layers. Incorporation of 2-pentene 0.2 0.3
nickel in the SMM structure occurs mainly by substitution propane 12.1 1.6 1.6 9.4
for octahedral aluminum and results in some rather propylene 39.3 1.5 1.5 29.0
trans-2-butene 0.0 14.9 15.0 9.4
striking changes. For example, the surface area increases
as does surface acidity, as evidenced by large increases in as platelet-like particles having an average diameter of lo00
catalytic activities for hydroisomerization and hydro- A. The average number of layers per platelet is five,
cracking C5-Cs hydrocarbons. corresponding to an average platelet thickness of 50 A.
It has been suggested that the catalytic activity of SMM Exactly how nickel incorporation enhances catalytic ac-
is due to particle edges and faces (Wright et al., 1972). tivity is not known. Besides having a much higher surface
Electron micrograph studies have shown that SMM exists area, it may be that nickel-substituted material crystallizes
0019-7890/78/1217-0214$01.00/0 0 1978 American Chemical Society