You are on page 1of 17

ELSEVIER Applied Catalysis A: General I18 (1994) 33-49

Vapour-phase reaction of methanol with acetone


over alkali containing zeolites
M. Huang, P.A. Zielinski, J. Moulod, S. Kaliaguine *
Dgpartement de GEnie Chimique et CERPIC, Universite L.aval, Quibec GIK 7P4. Canada,
Tel. (+ I-418)6562708, fax.
(+418)6567763, E-mail kaliagui@gch.ulaval.ca

Received 17 January 1994; revised 10 May 1994; accepted 10 May 1994

Abstract

Three types of reactions were observed on alkali exchanged A, X and Y zeolites during the vapour
phase reaction of methanol with acetone: the methylation of acetone followed by dehydrogenation to
form methyl vinyl ketone (MVK) ; the Meerwein-Ponndorf-Verley (MPV) reaction between acetone
and methanol, coupled with the further dehydration to form propene and formaldehyde; and the
condensation of acetone followed by further decomposition to form isobutene. The last two kinds of
reactions are the main reactions on LiX and NaX, which possess a relatively strong Lewis acidity.
When Lewis basicity increases and Lewis acidity decreases, these two reactions are dramatically
depressed, which results in an increase in selectivity to MVK. After high energy milling the zeolite
becomes amorphous with no change in chemical composition. The catalytic results over these materials
also revealed an increase in the production of MVK and the depressing of the other two reactions.
This change is attributed to the crush of the zeolite pore structure, which is another factor affecting
the product distribution.

Keywords: Acetone; Acidity (Lewis); Alkali zeolites; Basicity (Lewis); Milling; Methanol

1. Introduction

The methanol to gasoline process based on ZSM-5 is a milestone of applied


catalysis research, since methanol is conveniently derived from methane or coal,
and therefore this reaction is significant for the utilization of the huge C1 sources
in the world. Many other reactions involving methanol have been also investigated
in past decades. For example, the reaction of methanol with acetone has been
reported on both acidic and basic catalysts. The results on H-ZSM-5 [ 1 ] revealed

* Corresponding author.

0926-860X/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved


.SSDIO926-860X(94)00116-9
34 M. Huang et al./Applied Catalysis A: General l l S (1994) 33-49

that the main products are propene and isobutene accompanied by some dimethyl
ether and aromatics. An investigation performed over Cs-impregnated X zeolites
[2] reported the majority of products to be from acetone aldol condensations with
a minor formation of methy I viny I ketone. No detail about the conversion, selectivity
and the possible reaction mechanism have however been reported. It is noticed that
the methyl vinyl ketone is effectively formed from the reaction of methanol with
acetone over MgO [3], which is a representative basic catalyst. Vinyl ketones are
becoming increasingly important [4] as polymeric photosensitizers and electro-
conducting polymers. In view of the importance of both MVK and the utilization
of methanol, the reaction of acetone with methanol was performed over a series of
alkali exchanged and also some modified alkali exchanged zeolites. Our previous
studies [5-7] confirmed that these alkali exchanged zeolites contain both Lewis
basic and Lewis acid centres, which are the framework oxygens and the neigh-
bouring extraframework alkali cations, respectively. The base strength of zeolites
decreases with an increase in Si/Al ratio ofthe framework, and increases when the
electropositivity of the counter alkali cation is raised, whereas the Lewis acid
strength of counter cations increases with the Si/Al ratio and decreases with elec-
tropositivity. However, the basic strengths of alkali exchanged zeolites are close to
that of MgO [5] and still relatively low compared with some other basic oxides,
particularly those oxides designated as superbases [S]. On the other hand, the
Lewis acidity of some alkali cations, such as Li + , is relatively strong and causes
undesirable reactions in some cases. An attempt to further adjust both the Lewis
acidity and basicity of these materials was then performed by two different tech-
niques, namely high energy ball milling [9] and the further impregnation with
basic compound. The initial characterization and catalytic tests of these modified
materials are also reported here.

2. Experimental

NaA, NaX, NaY and MgO samples were used as received (Strem Chemicals,
Inc.). Alkali-cation exchanged X zeolites were prepared from the sodium forms
contacted with the corresponding chloride solution. The exchange temperature was
maintained at 7o-S0C and the time for a single exchange was around 24 h. Up to
three successive exchanges were performed in order to obtain high exchange levels.
After exchange the slurry was filtered, washed with distilled water, and dried in air
at 120C. Sample X-AC was prepared in the following manner: S g of NaX was
placed in a beaker containing 40 ml of 2 M sodium acetate solution, the solution
was stirred at room temperature for two hours followed by filtration but no rinse
with distilled water. The slurry was then dried at 120C, and calcined at 500C for
5 h. A-30 and A-l20, X-30 and Y-30 samples were prepared by the high energy
ball milling of NaA, NaX and NaY zeolites, respectively. For each preparation a
2.7 g zeolite sample was put in a hardened steel vial under air and then milled using
M. Huang et al. /Applied Catalysis A: General 1 I8 (I 994) 3349 35

three hardened steel balls (d= 6116 in.) in a SPEX 8000 laboratory ball mill (1010
rpm) . Each milled sample is designated by its milling time expressed in minutes.
Thus for example X-30 is a sodium X sample milled for 30 minutes. Samples X-
30-1 and X-30-2 were prepared by impregnation of X-30 using 4 M and 8 M Na
acetate solutions, respectively. The impregnated samples were also dried and cal-
cined at 500C for 5 h. The bulk composition of all zeolite materials was established
by atomic absorption using a Perkin-Elmer (Model 11OOB)spectrometer. Table 1
lists the unit-cell composition of the zeolite samples used in this work. The crys-
tallinity of the milled samples was monitored by X-ray diffraction using a Philips
spectrometer with a Cu K, radiation source. The BET surface area and pore volume
of Na-zeolite samples were measured using a computer-controlled sorption ana-
lyzer (Omnisorp 100). The catalytic reaction was carried out in a continuous flow
reactor operated at atmospheric pressure. Usually 0.1 g of catalyst was packed in a
tubular reactor placed in a vertical furnace, and then heated under an Ar stream up
to 400C. The temperature was then decreased to 350C and the vapour mixture of
methanol and acetone (133.8 Torr of methanol and 6.8 Torr of acetone) was
introduced using Ar as the vector gas with a W/F of 5.3 g h mol- . In some cases
pure acetone vaporized at room temperature (224.5 Torr) , pure methyl ethyl ketone
vaporized at room temperature ( 105.0 Torr) and the vapour mixture of formalde-
hyde (from 37% of formaldehyde aqueous solution) and acetone ( 196.1 Torr of
formaldehyde, 2.0 Torr of acetone and 17.4 Torr of water) were used as the reactant
feeds. The effluent gas was analyzed using a Perkin-Elmer Sigma 115 gas chro-
matographic system, and a 4 m OV- 17 column. The catalytic results are expressed
in terms of conversion and product distribution, which were expressed on the carbon
Table 1
Unit-cell composition of zeolite samples

NaA
LiX

Nti
Kx
RbX
csx

NaY

X-AC Na99.,(A19)ss.4(SiOz)loa.6
x-30- 1 Na12,.s(A10~)s5.4(Si4)106.6
X-30-2 Na169.s(A14)85.4(Si4)~~.6

The chemical compositions of A-30 and A-120, X-30, and Y-30 are the same as NaA, NaX and Nay, respectively,
and then not shown.
36 M. Huang et al. /Applied Catalysis A: General 118 (1994) 3349

number basis. The conversion was based on the amount of acetone which had
reacted. As will be shown in the discussion, most of the reactions involving acetone
are of the form: A + B + C + D, which does not cause a change in volume after
reactions. Moreover, since the reactions were carried out at atmospheric pressure
and the molar flow of Ar was much larger than that of the acetone feed, the effect
of the change in density of the gaseous reaction mixture due to reaction can be
neglected in the calculation of conversions.
Samples used in infrared experiments were pressed into self-supported wafers
of 10 mg. These wafers were mounted in an infrared Pyrex vacuum cell with calcium
fluoride windows and designed to accommodate four different samples. The cell
was then connected to a vacuum line and the samples were degassed at 400C
overnight (p = 10m5 Torr). After cooling to room temperature, the samples were
exposed to the vapour of methanol and/or acetone. The temperature was then raised
to the desired experimental value and kept for a period of time, followed by
decreasing to room temperature and evacuation. To avoid the complexity in illus-
tration of IR spectra caused by coke formation, the time employed in the above
procedure is usually around 10 min, which is less than that used in catalytic reaction.
Thus the IR results may mainly reflect the situation of initial reaction. The FIlR
spectra were recorded after every step of the treatment using a Digilab FTS-60
spectrometer with a 2 cm- resolution.

3. Results

3.1. Catalytic results

Table 2 lists the catalytic results observed after one and a half hour of reaction
with a constant W/F of 5.3 g h mol- over all the zeolite samples. As reference,
MgO was also examined under the same reaction conditions. In consistence with
literature [ 31, MgO showed activity to produce methyl vinyl ketone (MVK)
accompanied by some amount of methyl ethyl ketone (MEK) at 350C. However,
the fraction of &-ketones (including both saturated and unsaturated) is relatively
high and even &-ketones (including both saturated and unsaturated) are formed
in our reaction conditions. Moreover, no isopropyl alcohol is detected during reac-
tion, whereas propene and formaldehyde appear instead of this compound. Com-
pared with MgO, all the alkali exchanged X zeolites display lower selectivity to
MVK and MEK. The main products over these samples are isobutene, propene and
formaldehyde. Another apparent feature over these alkali exchanged X zeolites is
the failure to detect the presence of C,-ketones. It is noticed that the milling and
impregnation with sodium acetate dramatically reduce the fractions of isobutene,
propene and formaldehyde. In fact the production of propene and formaldehyde is
completely depressed over X-30, X-30- 1 and X-30-2 samples, while a small amount
of &-ketones also appears on X-30-2 sample, which was impregnated with a larger
hf. Huang et al. /Applied Catalysis A: General 118 (1994) 33-49 31

Table 2
Conversion and product yield in reaction of methanol with acetone a

Sample Conv. of acetone (%) Product distribution (46)

FM C3 C, MEK MVK C5K CsK others

MgO 32.6 4.9 2.0 0 14.1 30.9 37.2 8.3 2.6


LiX 29.4 19.7 33.6 32.8 4.2 4.5 0.8 0.07 4.4
NaX 51.3 22.0 26.6 33.9 6.2 6.0 0.0 0.0 5.3
KX 30.2 29.9 19.0 15.4 0.0 10.1 21.1 0.0 4.5
RbX 25.9 11.9 16.9 23.4 0.0 13.9 29.4 0.0 4.5
C.?+X 23.5 2.8 13.3 30.0 0.0 12.2 37.8 0.0 3.9
X-AC 64.4 22.4 15.8 19.7 0.0 13.2 0.0 0.0 28.9
x-30 39.6 0.0 0.0 24.3 0.0 27.0 0.0 0.0 48.7
x-30- 1 38.8 0.0 0.0 2.5 0.0 62.5 0.0 0.0 35.0
X-30-2 34.9 0.0 0.0 2.6 0.0 59.0 0.0 10.3 28.1
NaA 39.5 10.9 0.0 17.2 0.0 43.8 7.8 9.4 10.9
A-30 29.7 0.0 0.0 2.7 0.0 70.7 8.0 8.0 10.6
A-120 22.8 0.0 0.0 0.7 0.0 63.8 4.7 16.6 14.2
NaY 20.0 42.9 11.9 33.3 0.0 0.0 0.0 0.0 11.9
Y-30 0

a WIF=5.3 g h mol., after reaction at 350C for one and a half hour. Conversion and product distribution are
calculated on carbon bases. FM: formaldehyde; Cs: propene; C.,: isobutene; MSK: methyl ethyl ketone; MVK:
methyl vinyl ketone; CsK: Cs ketones; CsK: C, ketones; Others: other unidentified compounds with high molecular
weight, which are most likely to be the polymerization products or coke from reactions.

amount of sodium acetate (Table 1) . The behaviour of NaA and modified NaA
samples is similar to that of modified NaX samples, namely a decrease in formation
of isobutene, propene and formaldehyde, and an increase of MVK in the products.
Particularly, the MVK product fraction on A-30 sample reaches as much as 70.7%.
Moreover, both C5- and &-ketones are detected over these samples. NaY has no
activity to produce MVK and MEK, however, &-ketones and also isobutene,
propene and formaldehyde are formed on this sample, whereas the milled NaY
sample completely lost its activity in the reaction of methanol with acetone.
For comparison, the NaX zeolite was also examined at the same temperature
using pure acetone or a vapour mixture of formaldehyde and acetone as the feed-
stock (Table 3). In the case of pure acetone the yield of isobutene is so large that
the fraction of all other compounds can be nearly omitted. In contrast, in the case
of the formaldehyde and acetone vapour mixture, the main products are some heavy
molecules denoted as others in Table 3, which are most likely to be the polym-
erization products or coke from formaldehyde.
The vapour of the pure methyl ethyl ketone at room temperature was also intro-
duced into the reactor at 350C over a series of catalysts. Table 4 summarizes the
results. Clearly, the results indicate the production of MVK for all those catalysts
examined. The fraction of MVK in the products was as high as 76% over the milled
sample A-30. Other compounds with heavier molecular weight were also detected
in this reaction.
38 M. Huang et al. /Applied Catalysis A: General 118 (1994) 3349

Table 3
Conversion and product yield over NaX sample 0

Reactant Conv. of acetone Product distribution

PM C3 C., MEK MVK CSK CBK Others

MeOH + Acetone 51.3 22.0 26.6 33.9 6.2 6.0 0.0 0.0 5.3
HCHO + Acetone 55.9 I 20.4 11.3 22.6 0.0 0.5 6.8 38.4
Acetone 21.5 0.0 2.0 73.0 1.5 0.3 0.1 2.9 20.2

W/F= 5.3 g h mol.I, after reaction at 350C for one and half hour. Conversion and product distribution are
calculated on carbon bases. PM: formaldehyde; Ca: propene; C,: isobutene; MRK: methyl ethyl ketone; MVK:
methyl vinyl ketone; CSK: C, ketones; C,K: C, ketones; Others: other unidentified compounds with high molecular
weight, which are most likely to be the polymerization products or coke from reactions.

Table 4
Conversion and product yield in reaction of methyl ethyl ketone

Sample A-30 NaA X-30-2 x-30 NaX

Conversion of MEK (8) 39.5 40.2 54.7 39.6 30.2


Product distribution (a) MVK 76.7 49.8 36.9 59.8 9.0
Others 23.3 50.2 63.1 40.2 91.0

W/F= 3.2 g h mol, after reaction at 350C for one hour. Conversion and product distribution are calculated on
carbon bases. MEK: methyl ethyl ketone; MVK: methyl vinyl ketone; Others: other compounds with heavier
molecular weight.

3.2. Infrared results

Fig. 1 shows infrared spectra observed on reference sample MgO. After adsorp-
tion of methanol at room temperature bands appeared at 3605 (broad), 2940,287O
(weak), 2807, 2794 (shoulder), 1465 (broad) and 1410 cm- (Fig. la). The
weak 3750 cm- band is due to the OH groups on MgO surface, which is also
detected before adsorption of methanol. All these bands are also found in the
standard spectrum [lo] of liquid methanol with slight shifts in wavenumbers. The
further introduction of acetone vapour at room temperature, followed by heating at
350C produced a new band at 1605 cm- and some changes in both OH and CH
stretching regions (Fig. lb). These changes can be seen more clearly in Fig. lc,
where the spectrum was obtained after simultaneous introduction of a vapour
mixture of methanol and acetone ( 133.8 Torr of methanol plus 6.8 Torr of acetone)
at 350C. Besides the new band at 1605 cm-, a band appeared at 3480 cm- in
the OH stretching region and a band appeared at 2920 cm- in the CH stretching
region, while the band around 2870 cm- became more pronounced. Moreover, a
band at 1645 cm- (shoulder) was detected. The original bands due to adsorbed
methanol also appeared with weakened intensities. The 2920 cm- band represents
the strong asymmetric CH2 stretching vibrations [ 111, while the relatively weak
symmetric CH2 stretching vibration should consist in the band around 2870 cm- ,
since the difference in wavenumber of symmetric CH2 and CH, stretching vibration
M. Huang et al. /Applied Catalysis A: General 118 (1994) 3349 39

cm -1
Fig. 1. Infrared spectra of MgO. (a) After dehydration at 400C overnight, the sample was exposed to methanol
vapour at room temperature for 10 min followed by evacuation at room temperature for 20 nun. (b) After step a,
the sample was exposed to acetone vapour for 5 min at room temperature, followed by evacuation at room
temperature for 20 min, increasing temperature to 350C and keeping it at this temperature for one hour, cooling
to room temperature and evacuation again. (c) After dehydration at 400C overnight, the sample was exposed to
vapour mixture of methanol and acetone ( 133.8 Torr of methanol and 6.8 Torr of acetone) at 350C for 5 min.
followed by cooling to room temperature and evacuation.

is usually less than 20 cm- and both are located between 2860-2880 cm-
[ 11,121. Combined with the fact that methyl vinyl ketone and also other unsaturated
ketones were detected on MgO samples, the new band at 1605 cm- is assigned to
the C=O stretching vibration of adsorbed unsaturated ketones, mainly MVK. The
lower GO stretching frequency observed here must be due to conjugation of C=O
bond with C=C bond [ 131 in adsorbed MVK molecule. For example, the C=O
frequency in cr- p unsaturated hydroxylated ketones is in the region of 1540-l 640
cm- [ 131. Since the a! hydrogen in ketones possesses partial positive charge and
is easily abstracted by basic sites, the adsorbed MVK could have a similar structure
as that in (Y-P unsaturated hydroxylated ketones. For example, bonding can exist
between (Yhydrogen and the basic oxygen of a catalyst, and this could be the
intermediate form for the further methylation to produce C5+ ketones ( see Discus-
sion below). The band around 1645 cm- could be due to the C=O stretching
vibration of adsorbed saturated ketones [ 121, however, this band is usually an
indication of C=C bond [ 121. In our cases, since this band also appeared in the
case of NaX (see below), combined with some broad bands between 1450-1400
cm- , this could be due to the formation of carbonaceous materials [ 12,131. The
new OH stretching band at 3480 cm- suggests the presence of new OH groups.
Its assignment will be discussed together with a similar band observed on NaX
(below).
Fig. 2 gives the infrared spectra of NaX sample. The fresh sample after dehydra-
tion showed only a very weak band around 1590 cm- , which may be attributed
to a tiny amount of carbonaceous material on the surface. New bands appeared
after adsorption of methanol at room temperature (Fig. 2a). The adsorption of
acetone also produced some bands (Fig. 2b) which had been described in detail in
40 M. Huang et al. /Applied Catalysis A: General 118 (1994) 3349

the literature [ 14,151. Mainly, after adsorption of acetone and further evacuation
at 18OC,a strong band at 1705 (C=O stretching) accompanied by bands at 3470
(broad, hydrogen bonded OH stretching), 2995, 2920 ( v, of CH2 group), 1423
(CH&O bending) and 1372 cm- appeared, which indicate condensation of
adsorbed acetone to form diacetone alcohol. Another weak band around 1670 cm-
(C=O stretching) was due to adsorbed acetone. After adsorption of methanol
followed by introduction of acetone and heating at 35OC,the new spectrum (Fig.
2c) was obtained. In the OH stretching region the main band shifted to 3430 cm- ;
in CH stretching region the same band as in the case of acetone adsorption appeared
at 2920 cm- , accompanied by the original bands at 2950 and 2834 cm- observed
after methanol adsorption; in the C=O stretching region, instead of the bands at
1705 and 1670 cm-, a new band located at 1690 cm - appeared. A band was also
detected at 1645 cm- while other bands previously attributed to adsorbed diace-
tone alcohol were also found at 1423 and 1372 cm-. Since nearly all the bands
due to adsorbed diacetone alcohol are detected here except for the C=O frequency
(which shifted to a lower position), a reasonable assignment for these bands is the
mesityl oxide formed from the dehydration of diacetone alcohol. The shift of C=O
vibration to lower frequency is then attributed to the conjugation with the y
neighbouring C=C bond in mesityl oxide, this influence should be weaker than the
direct conjugation effect of C=C bond observed in MVK molecule. This is also
consistent with the general properties of hydroxylated ketones with high molecular
weight, which are not stable and easy to dehydrate to form unsaturated ketones
upon heating [ 161. However, no mesityl oxide is detected in the gas phase during

cm -1
Fig. 2. Infrared spectra of NaX. (a) After dehydration at 4OWCovernight, the sample was exposed to methanol
vapour at room temperature for 10 min followed by evacuation at room temperature for 20 min. (b) After acetone
adsorption followed by heating at 180C for one hour and further evacuation. (c) After step a, the sample was
exposed to acetone vapour for 5 min at room temperattne, followed by evacuation at room temperahue for 20
min, increasing temperature to 350C and keeping it at this temperature for one hour, cooling to room te.mperature
and evacuating again. (d) After dehydration at 400C overnight, the sample was exposed to a vapour mixture of
methanol and acetone (133.8 Torr of methanol and 6.8 Torr of acetone) at 350C for 5 min, followed by cooling
to room temperature and evacuation.
M. Huang et al. /Applied Catalysis A: General 118 (I 994) 33-49 41

catalytic reaction. This could be due to the strong adsorption of mesityl oxide.
Another possible reason would be the low acetone pressure employed in the cata-
lytic reaction test (6.8 Torr, compared with 224 Torr of acetone vapour introduced
to obtain spectrum in Fig. 2c), and thus the condensation of acetone and the further
dehydration could not compete with other reactions. In fact all above bands assigned
to mesityl oxide became very weak or disappeared in the spectrum of Fig. 2d,
where the reaction vapour consisted of 133.8 Torr of methanol and 6.8 Torr of
acetone. In this case the band at 1605 cm- appeared again whereas the band at
2920 cm- can still be detected (shoulder). Following the argument issued in the
case of MgO, these bands are also attributed to adsorbed MVK. The main OH band
after the introduction of acetone is located at 3430 cm-, which suggests the
presence of new OH groups. A similar band also appeared in the case of MgO with
a relatively weak intensity and located at 3480 cm- (Fig. lc, Id). Ueda et al. [ 31
reported the formation of isopropyl alcohol in the reaction of methanol with acetone
over MgO. In our case no isopropyl alcohol but propene was detected. In particular
the amounts of propene formed over Li and Na exchanged X zeolites are dramati-
cally large (Table 2). Therefore a reasonable assignment for the new OH group is
still the adsorbed isopropyl alcohol, which is easily decomposed to form propene
due to the presence of acid sites. In our cases these effects should be due to the
presence of Lewis acid sites. In fact, the LiX and NaX possess stronger Lewis
acidity than the other alkali exchanged X zeolites. In consistence with the discussion
of IR spectra of MgO, another band around 1645 cm- is also attributed to the
formation of carbonaceous materials.
The spectra observed after exposure to the vapour mixture of methanol and
acetone are also shown for sample NaX, Nay, NaA and A-30 (Fig. 3). Before
exposure, as in the case of NaX, all these samples did not show any features except
for a weak band around 1600 cm- after dehydration at 400C overnight. It is
interesting to note that the C=O stretching bands previously observed [ 14,15 ] after

cm -1
Fig. 3. Infrared spectm of (a) Nay; (b) NaX; (c) NaA aad (d) A-30. After dehydration at 400C overnight, the
sample was exposed to vapour mixture of methanol and acetone ( 133.8 Torr of methanol and 6.8 Torr of acetone)
at 350C for 5 min. followed by cooling to room temperature and evacuation.
42 M. Huang et al. /Applied Catalysis A: General 118 (i994) 3349

adsorption of acetone on NaY and NaA samples, located at 1713 and 1666 cm- ,
respectively, also appeared with weaker intensities. The new C=O band at 1605
cm- was also detected in the case of NaA but not for sample Nay. This is consistent
with the catalytic observation, where MVK was formed over NaA but not on NaY
sample. The situation of A-30 is quite different. After reaction nearly the same
spectrum as that of fresh sample was obtained (Fig. 3d), except for a minor feature
in the C-H stretching region. The only bands observed in fresh A-30 sample are
located at 1581 and 1379 cm-, which were also observed with reduced intensity
in fresh NaA sample.

3.3. XRD results and surface area

X-ray powder diffraction patterns were recorded for NaA, NaX, NaY and the
corresponding milled samples (Fig. 4). Clearly, the intensities of diffraction peaks
of all milled samples were seriously reduced, which means a significant loss in
zeolite crystallinity. Comparing the height of the strong diffraction peaks of milled
samples with that of parent zeolites, it was found that more than 90% crystallinity
was lost after 30 min of milling for A and X zeolites, while about 70% crystallinity
was lost for Y zeolite. This is reasonable, since Y zeolite possesses higher Si to Al
ratio among these zeolites and therefore has more mechanical strength [9]. In
relation with the lower Si/Al ratio of NaA a nearly complete loss in crystallinity
was discovered from the diffraction pattern of A-30 and A- 120 indicating that these
samples are actually amorphous. In accord with the loss of crystallinity, the BET
surface area and micropore volume ( r < 10 A) are also reduced after milling (Table
5). Surprisingly, it is noticed that not only the total surface area, but also the
external surface area is reduced after milling in the cases of NaA and NaX.

10 20 30 40

28
Fig. 4. X-ray diffraction patterns. The number on the line is the milling time expressed in minutes.
M. Huang et al. /Applied Caralysis A: General 118 (1994) 33-49 43

Table 5
Surface area and pore volume

Sample Surface area (m/g) Pore volume (cm3/g)

Total External Micro ( < 10 A) Meso+Macro(>lOA)

NaY 835.6 43.3 0.303 0.127


Y-30 407.7 43.2 0.140 0.138

NilX 777.4 41.7 0.280 0.111


x-30 142.8 22.6 0.046 0.112

NEIA (1 10.8 () 0.054


A-30 a
A-120 a

Cannot be measured.

4. Discussion

Scheme 1 lists possible reaction routes in the presence of both methanol and
acetone over basic catalysts. No methane nor acetol were detected by GC, thus
route 5 can be ruled out. Both catalytic and infrared results revealed the formation
of MVK, which can be formed at least through three routes in Scheme 1. Route 1
is actually the aldol condensation between acetone and formaldehyde. The latter is
supposed to be produced from dehydrogenation of methanol. However, the alkali

15 CH,-LH,
+ CHzO 2% CH,-fLCH=CH,
tl_ CH,-LH,-CH,OH
-H,O CH,-LCH=CH,
0
CH,-!-CH,-CH,

6 CH,-~-WC% 1 + CH,OH _H,O,


+ CH,OH -H,O
C,K ______) C,K

7 CH, - p - CH=CH, 1
Scheme 1.
44 hf. Hung et al. /Applied Catalysis A: General II8 (1994) 3349

CHyC-CH, - - - - - CH,
H -. --.(jH

Scheme 2.

exchanged zeolites were examined using pure methanol vapour as the reactant feed,
and the yield in formaldehyde can be nearly neglected. For example, a result over
NaA at 400C shows that the conversion of methanol is about 50%, but only 3.8%
appeared as formaldehyde and less than 0.2% as other compound, while the remain-
der of converted methanol was retained on catalyst as coke. Argument can be raised
because the formation of HCHO may not be observable due largely to its rapid
reaction with acetone along route 1. Then the direct aldol condensation between
acetone and formaldehyde (contain water vapour, see Experimental) was also
tested over several X zeolite samples, the results obtained over NaX are listed in
Table 3. They reveal that no MVK but MEK was detected. This is certainly an
unexpected result since route 1 is the known way to synthesize MVK over metal
oxides (a series -of works about this topic has been reported by Ai. [ 17,181) . The
appearance of MEK in the reaction of formaldehyde (containing water vapour)
with acetone could be explained by the reaction of acetone with other reactant, such
as the molecular fragments due to the cracking of polymer&d formaldehyde, or
still the methanol formed from formaldehyde and water. However, the absence of
MVK suggests that the alkali exchanged zeolites are completely different from
metal oxides in the reaction of formaldehyde with acetone. Therefore route 1 is not
responsible for the formation of MVK in the case of alkali containing zeolites.
Route 2 is different from route 1. According to this route, not only the (Yhydrogen
in acetone is first abstracted on basic sites, but also an hydrogen atom in the methyl
group of methanol must be abstracted simultaneously. Unlike the a! hydrogen in
ketones, the C-H bond in methyl groups possesses less polarity and is difficult to
split. Besides, the activation of a C-H bond is usually basicity dependent [ 81 while
dehydration is acidity dependent [ 81. An increase in basicity should then result in
a large yield in MEK and slightly in MVK if route 2 is an effective mechanism.
This deduction is not confirmed by catalytic results. As can be seen in Table 2, the
more strongly basic samples, such as CsX, NaA and impregnated X zeolites [ 5,6],
do not produce MEK but MVK. Therefore the main route responsible for the
formation of MVK is also not route 2 but route 3, the direct methylation of acetone
by methanol. An activation model for the first step in this route is drawn in Scheme
2, where, instead of a stronger C-H bond (98.8 kcal/mol) in methyl group, a
weaker C-O bond (84.0 kcal/mol) is required to be broken.
The direct methylation mechanism also illustrated the formation of CSK + C6K
ketones (routes 6 and 7). In fact a large portion of CSK ketones was observed over
X zeolites with large cation size. This is completely different from the observation
of Ai [ 17,181 over metal oxides in reaction of formaldehyde with acetone and also
hard to be explained by route 1. Clearly, the model in Scheme 2 suggests a reaction
M. Huang et al. /Applied Catalysis A: General 118 (1994) 3349 45

which is both Lewis basicity and acidity dependent. This is consistent with the
conclusion of Ai [ 171 about MVK formation from acetone and formaldehyde on
metal oxides. For example, the yield of MVK on Fe203, NiO, TiOz and ZnO
increased by adding P205 and decreased by adding of I&O, while the yield of MVK
on W03 and Moo3 decreased by adding PZ05 and increased by adding of KzO. The
different effects of adding P,O, and KzO upon different oxides are explained by an
adjustment of both acidic and basic strength on the surface. In our case of zeolite
samples, the largest yield in MEK was observed over LiX and NaX samples, which
possess the strongest Lewis acidity among our zeolite samples [ 5-71. When the
Lewis acidity was reduced and basicity increased, MEK disappears from the prod-
ucts and the yield in MVK is, while the yield in CSK ketones is also increased
(mainly 3pentanone: CzHSCOCzHS). The increase in basic@ should favour the
dehydrogenation of MEK to form MVK. However, the increase in formation of
C&Kketones with increasing cation size in X zeolites is hardly explained by only
the increase in basicity. Factors other than acidity and basicity should be operating
in the direct methylation of ketones in the case of zeolite, and this will be discussed
latter.
Another piece of evidence to support route 3 is the direct detection of MVK after
introduction of MEK over a series of catalysts (Table 4). The results revealed that
the dehydrogenation of MEK to form MVK has indeed occurred at 350C over
several catalysts, particularly the samples modified by milling and further impreg-
nation. Moreover, the yield in MVK over the NaX sample is very small, which is
consistent with the results in Table 2, where the yield in MVK is also small over X
zeolites.
It has to be emphasized that isobutene and formaldehyde are also major products
over X zeolites, particularly in the case of LiX and NaX. Route 4 is therefore
regarded as a parallel reaction route responsible for the formation of formaldehyde
and propene. The first step of route 4 is a kind of MPV (Meerwein-Ponndorf-
Verley) reaction [ 191. The MPV reaction is a hydrogen transfer between an alcohol
and a ketone (or an aldehyde) . It was reported [ 191 that the alkali exchanged X
zeolites are active at 100C for the MPV reaction between n-C&, alkanals and
isopropanal. In the acetone-methanol system the formation of isopropanol was
reported over MgO by Ueda et al. [ 31, but not observed in this work. This can be
explained by the further dehydration of isopropanol (second step, route 4). As
mentioned above, however, the dehydrogenation of methanol is actually very dif-
ficult over alkali zeolites. Nevertheless, two reasons make route 4 still possible.
One is the high temperature employed here (35OC), another more important reason
could be the coupled dehydration of isopropanol, which will favour the shift of the
MPV reaction to the right side due to the immediate removal of isopropanol. The
possibility that the hydrogenation of acetone was using the hydrogen issued from
route 3 cannot be ruled out, but this mechanism cannot explain the formation of
formaldehyde, which constitutes much of the products observed over LiX and NaX
46 hf. Huang et al. /Applied Catalysis A: General 118 (1994) 3349

\ FH3
9 CH,COOH + CHI-C=CH2
Scheme3.

samples. Therefore, route 4 should be the main route responsible for the production
of propene and formaldehyde over X zeolites.
The formation of isobutene is related to the acetone condensation. This is con-
firmed by the reaction using pure acetone at the same temperature (Table 3)) where
the fraction of isobutene in the products is as high as 73%. The secondary reaction
products of acetone condensation were analyzed in detail by Lippert et al. [ 201 for
the basic oxides and Reichle [ 211 for MgO-A1203 catalyst. According to Lippert
et al. [ 201, the isobutene formation mainly comes through the routes depicted in
Scheme 3.
The infrared results suggest the formation of mesityl oxide after introduction of
224 Torr acetone into the cell (Fig. 2~). However, when the partial pressure of
acetone is low, no C6 ketones are formed. Thus route 9 should be the main route to
produce isobutene. The formation of acetic acid cannot be detected at all, this is
consistent with most of the observations [20] by other authors in the acetone
condensation experiments. The reason is generally attributed to the strong adsorp-
tion of acetic acid, its further decomposition to form methane and carbon dioxide,
or to the ketonization of acetic acid with ketene (produced in route 8) to give back
acetone and COZ. Since no methane was detected in this work, the possible reason
here could be the strong adsorption of acetic acid and/or its polymerization prod-
ucts.
In conclusion of this part of the discussion, mainly three types of reactions are
occurring on alkali exchanged A, X and Y zeolites in the vapour phase reaction of
methanol with acetone: Type 1, the methylation of acetone followed by dehydro-
genation to form MVK. Type 2, the MPV reaction between acetone and methanol,
coupled by the further dehydration to form propene and formaldehyde. Type 3, the
condensation of acetone followed by further decomposition to form isobutene. The
MPV reaction is the main reaction over LiX and NaX, which possess relatively
strong Lewis acidity. When Lewis basicity increases and Lewis acidity decreases
by exchange with K, Rb and Cs, this reaction is dramatically depressed. Aldol
condensation of acetone at 180C over alkali exchanged zeolites has been reported
in our previous work [ 14,151. It is both Lewis acidity and Lewis basicity dependent
and the highest activity was found on NaX zeolite. The results at high temperature
observed here is consistent with this conclusion, however, the high temperature
caused dehydration of diacetone alcohol and final decomposition to form isobutene.
A low partial pressure of acetone, an increased basic strength and reduced acid
M. Huang et al. /Applied Catalysis A: General 118 (1994) 33-49 41

strength will effectively suppress this reaction. The methylation of acetone is also
suggested to be both Lewis acidity and Lewis basicity dependent. In the range of
alkali exchanged X zeolites the increased basicity and reduced acidity depressed
type 2 and type 3 reactions and then increased selectivity to MVK. However, the
further methylation of MEK overcomes its dehydrogenation under our reaction
conditions, which resulted in the formation of C5K ketones, mainly 3pentanone.
The modified samples can be roughly divided into two groups. First, X-AC, X-
30-1 and X-30-2 samples contain more Na than required to balance the zeolite
framework charge (Table 1) . The presence of extraframework Na species usually
involves the existence of extra basic sites [ 221. The catalytic results over these
samples are also consistent with an increased basicity compared with their parent
samples (NaX and X-30). Type 2 and 3 reactions are indeed depressed and the
MVK selectivity is increased. The second group of modified samples was prepared
only by high energy milling, namely A-30, A-120, X-30 and Y-30. The catalytic
results over these samples also revealed a dramatic increase in MVK yield while
type 2 and 3 reactions were depressed. For example, milled NaA (A-30) shows a
yield in MVK as high as 70.7%. The chemical composition is not changed after
milling for these samples. Moreover, pyrrole adsorption over these samples showed
nearly the same shift in NH stretching band compared with that of corresponding
parent samples, which suggests that milling does not affect base strength. Another
reason could be the reduced surface area which should result in a reduced catalytic
activity, but, cannot explain however the dramatic change in products distribution.
Therefore a third possibility is the change in zeolite structure. The XRD and
BET results reveal the formation of amorphous material after milling. Combined
with the fact that the yield in C5 ketones increases dramatically with the cation size
in X zeolites, the channel structure of zeolites must be another factor which deter-
mines the product distribution in reaction. First, the pore structure of zeolite would
create a configurational diffusion effect for certain products [ 231, particularly when
the alkali cations occupy the sites near the window of the zeolite cage. For example,
in the cases of K, Rb, Cs-X samples, the diffusion of the MEK and MVK may be
hindered by the presence of the large cation that tends to block or narrow the pores
of the zeolite. The MEK and MVK will therefore have time to undergo further
methylation before they leave the zeolite. In the case of MEK reaction (Table 4))
the same reason can be used to explain the higher production of heavier compounds
over normal zeolite samples than those over milled samples. The same diffusion
limitation of zeolite would also favour the acetone condensation, which requires
the combination of two acetone molecules. Vice versa, the collapse of the zeolite
pore structure will depress these reactions, provided that the distribution of basic
and acidic sites remains the same. Another role of zeolite pore structure may be to
stabilize certain intermediates via hydrogen bonding on the pore walls. This could
be the reason for the depression of type 2 reaction (MPV reaction) on the milled
samples. In fact, the MPV reaction between alkanals and isopropanol was only
reported in the case of X zeolites [ 191.
48 M. Huang et al. /Applied Catalysis A: General 118 (1994) 3349

5. Conclusion

As discussed in several previous papers from our laboratory, alkali-ion


exchanged zeolites provide the ability to vary in an almost continuous manner the
strength of well defined Lewis acid (the cations) and Lewis base (the lattice
oxygens) sites. It was however observed in the present work that the extent to
which the changes of these two variables affects the product distribution in the
reactions of methanol with acetone for the solids studied (NaA, NaX, NaY and
alkali exchanged X), is not very important compared to the effect of milling. The
product distribution indicates that milling depresses very effectively type 2 (MPV
reaction with secondary dehydration to propene) and type 3 (aldol condensation
of acetone with secondary decomposition yielding isobutene) reactions. Both types
involve the participation of a surface Lewis acid site. Milling however increases
dramatically the selectivity of the formation of MVK through type 1 reaction
(methylation of acetone by methanol followed by dehydrogenation) , This result
added to the fact that IR of chemisorbed pyrrole indicates no change in basic strength
upon milling, suggests that the pore structure of zeolites is another important factor
affecting the product distribution. The collapse of zeolite crystals upon milling is
evidenced by both XRD and BET experimental results. Therefore, in the Discussion
of this paper, the role of the pore structure was mainly attributed to a configurational
diffusion effect, which should favour the secondary reactions in the case of non-
ground zeolite samples. However, it has to be pointed out that another possible
effect of the zeolite pore structure may be to allow for a high strength of Lewis acid
sites. In other words, the collapse of the pore structure would result in a weaker
Lewis acidity and then depress some acidity dependent reactions. Further exami-
nation of the change in Lewis acidity upon milling is currently being performed in
this laboratory.

References

[I 1 J. Novakova, V. Bosacek, Z. Dole&k and L. Kubelkova, J. Mol. Catal., 78 ( 1993) 43.


121 P.B. Hathaway and ME. Davis, J. Catal., 119 (1989) 497.
131 W. Ueda, T. Yokoyama, Y. More-Oka and T. Ikawa. J. Chem. Sot., Chem. Commun., ( 1984) 39.
[4] T. Ogawa, R. Cedeno and M. Inoue, Polym. Bull., 2 (1980) 275.
[5] M. Huang and S. Kaliaguine, J. Chem. Sot., Faraday Trans., 88(5) (1992) 751.
161 M. Huang, A. Adnot and S. Kaliaguine, J. Catal., 137 (1992) 322.
171 M. Huang and S. Kaliaguine, in K.J. Smith and E.C. Sanford (Editors), Progress in Catalysis, Studies in
Surface Science and Catalysis, Vol. 73, Elsevier, Amsterdam, 1992, p. 291.
181 K. Tanabe, M. Misono. Y. Ono and H. Hattori, New Solid Acids and Bases, Studies in Surface Science and
Catalysis, Vol. 51, Elsevier, Amsterdam, 1989.
191 P.A. Zielinski, R. Schulz, S. Kaliaguine and A. Van Neste, J. Mater. Res., 8( 11) (1993) 2985.
[ 101 Sadtler Standard Intinred Vapor Phase Indexes, Sadtler Reseach Laboratories, Philadelphia, PA, 1980.
[ 11I L.H. Little, Infrared Spectra of Adsorbed Species, Academic Press, London, 1966.
1121 H.A. Szymanski, Infrared Band Handbook, Plenum Press, New York, 1963.
[ 131 L.J. Bellamy, Infrared Spectra of Complex Molecules, Wiley, New York, 1964.
M. Huang et al. /Applied Catalysis A: General 118 (1994) 33-49 49

[ 141 M. Huang and S. Kaliaguine, Catal. Lett., 18 (1993) 373.


[ 15] M. Huangand S. Kaliaguine, in M. Guisnet, J. Banault, C. Bouchoule, D. Duprez, G. Perotand C. Montassier
(Editors), Heterogeneous Catalysis and Fine Chemicals, Studies in Surface Science and Catalysis, Vol. 78,
Elsevier, Amsterdam, 1993. p. 559.
[ 161 I.D. Roberts, M.C. Caserio, Chimie Organique Mcnieme, Ediscience, Paris, 1968.
[17]M.Ai,J.CataL.106(1987)273.
[ 181 M. Ai, in L. Guczi, F. Solymosi and P. T&&tyi (Editors) New Frontiers in Catalysis, Studies in Surface
Science and Catalysis, Vol. 75, Elsevier, Amsterdam, 1993, Part B, p. 1199.
[ 191 J. Shabtai, J. Catal., 27 (1984) 35.
[20] S. Lippert, W. Baumann, K. Thomke, J. Mol. Catal., 69 ( 1991) 199.
1211 W.T. Reichle, J. Catal., 63 (1980) 295.
[22] H. Tsuji, F. Yagi, H. Hattori, Chem. I_&., (1991) 1881.
[23] E.G. Derouane, in B. Imelik, C. Naccache, Y. Ben Taarit, J.C. Vedrine, G. Coudurier, H. Praliaud, (Editors)
Catalysis by Zeolites, Studies in Surface Science and Catalysis, Vol. 5, Elsevier, Amsterdam, 1980, p. 5.