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Journal of Molecular Catalysis 93 ( 1994) 337-355
Abstract
Kmetlc studies were performed over slhca-alumma and acldlc zeohtes to determme the effects of
temperature (from 600 to 700 K) and reactant pressures ( < 80 Torr) on the rates of methylamme
synthesis from methanol and ammonia Related kmehc studies were conducted of methylamme
dlsproportlonahon reactions, methanol dehydration, and reactions of methanol and dlmethyl ether
with methylammes The results suggest that the reactive species for methylamme synthesis are
adsorbed nitrogenous bases, while methoxy groups are reactive species for dlmethyl ether production
Dlsproportlonahon reactions may be important pathways for the production of the higher-substituted
ammes durmg methylamme synthesis The combination of rmcrocalonmetnc measurements, reported
elsewhere, and kmetlc studies suggests that acid sites are required m these reactions for the strong
adsorption of ammoma and methylammes, and weak adsorption sites are required to facilitate desorp-
tlon of adsorbed amme species from the acid sites
Keywords Acid catalysts, Alumna, Kmetlcs, Methylamme, Slhca, Sohd acid, Zeolttes
1. Introduction
The synthesis of methylammes from methanol and ammoma over acid catalysts
IS an important mdustnal process This reaction may also be a useful probe of
catalyst acldlty For example, m contrast to reactions such as hydrocarbon crackmg,
the products of methylamme synthesis are limited to three substituted methyl-
ammes, water, and dlmethyl ether Furthermore, the small number of reactants and
products allows for detailed studies of adsorption processes [ l] Methylamme
* Correspondmg author
’ Current address 3M Corporation, St Paul, MN 55144. USA
synthesis also proceeds without catalyst deacttvatton over a variety of sohd actd
catalysts
Most of the literature on methylamme synthesis relates to the goal of achieving
high selectivity towards the lower-substituted ammes, dimethylamme (DMA) m
particular Mochida, et al studied a variety of metal oxide and zeohte catalysts and
found that Lewis acid sites alone are not active for the reaction [ 21 They suggested
that the highest selectivity to DMA was achieved over acid sites of medium strength
In contrast, Weigert found that Bronsted acid sites associated with H-mordemte
were not selective for the lower substituted ammes and that Na-mordemte was more
selective, though less active [ 31 Shannon, et al [ 41 proposed that a combmation
of strong and weak sues is necessary for high activity and selectivity, with weaker
sites allowing for weaker adsorption of the methylammes and more facile methanol
adsorption. These researchers suggested that Lewis acid sites may be associated
with low DMA selectivity, and they performed studies directed towards the for-
mulation of shape-selective catalysts for production of DMA [ 5-101 Small-pore
catalysts such as ZK-5 [ 61, rho [ 51, and enomte and chabazite [ 81 were found to
have low selectivity towards trrmethylamme ( <20%), while the rho and ZK-5
exhibited high DMA selectivity ( > 50%) Similar work was conducted by Herr-
mann [ 1 l] and Segawa and Tachibana [ 121 The latter workers formulated a
dealummated H-mordemte catalyst with high DMA selectivity
The primary focus of the aforementioned literature has been the development of
highly selective catalysts, and the correspondmg kmetic data were collected at high
conversions The present study was undertaken to probe the surface chemistry by
collectmg kinetic data at low conversions, m the form of turnover frequencies,
activation energies, and kmettc reaction orders In addition, we report catalytic
activities for the followmg related reactions methylamme disproportronation reac-
tions, reactions of methanol and dimethyl ether with arnmes, and methanol dehy-
dration Finally, we suggest catalytic cycles that are consistent with adsorption,
spectroscopic, and kmetic data For our work we have chosen to study acidic
silicon-alummum oxides, which have proven to be effective catalysts for methyl-
amme synthesis and which are used commercially It is important to note that we
have specifically avoided the study of shape-selective, small-pore zeohtes to msure
that our kmetic data are not influenced by transport hmttattons In this respect, we
have limited our studies to silica-alumma and the relatively large-pore zeohtes Y,
mordemte, and ZSM-5
2. Experimental
Table 1
Catalyst acldx propemes
NaH-Y-33 360
NaH-Y-65 1000
NaH-Y-82 1450
H-mordemte 710
H-ZSM5-13 670
H-ZSM5-35 360
H-ZSM5-225 74 a
sihca-alumma 90 Brensted/200 total
He and 7 cm3/mm for NH,. Methanol was fed to the system with a syrmge pump
(Harvard Apparatus Model 11) , typically at 0 4 cm3 /h For methylamme synthesis
reactlon studies, methanol inlet pressures were typically held between 1 5 and 3
Torr, while ammonia feed pressures were typically m the range of 4 to 6 Torr Feed
pressures were vaned as necessary to measure reaction orders or to conduct kmetlc
studies of related reactlons (I e , methanol dehydration, methylamme dlspropor-
tlonatlon reactions, and reactions of methanol and dlmethyl ether with methyla-
mines) For these latter studies, methylammes were fed to the system through a
Nupro needle valve The entire system was made of stainless steel and heated to
423 IS
Analyses of the feed and reactor effluent streams were performed using a gas
chromatograph (Hewlett-Packard 5890A) with a packed column of 0 05 M/8%
KOH washed Carbowax on Carbopack B Samples (20-75 mg) were first treated
under vacuum for 1 h at 300,473,573, and 723 K, followed by calcmatlon under
flowing oxygen (100 cm3/mm) at 723 K
The catalysts used m these kinetic studies are listed m Table 1 Three catalysts
were prepared from NaH-Y zeohte (Lmde), with 33, 65, and 82% of the Na
exchange cations replaced by protons, and these catalysts are designated as NaH-
Y-33, NaH-Y-65, and NaH-Y-82, respectively H-mordemte was obtamed from
Conteka Corporation. Two H-ZSM-5 catalysts were obtamed from T Degnan of
Mob11 Corporation (Paulsboro) with &/Al ratios of 13 and 225, and these samples
are designated as H-ZSM5-13 and H-ZSM5-225, respectively Another H-ZSM-5
catalyst, designated as H-ZSM5-35, had a G/Al ratio of 35 and was provided by
W Haag of Mob11 Corporation (Prmceton) . The amorphous srhca-alummacatalyst
was obtamed from Davison Corporation and had an alummum loading of 13 wt%
The slhca catalyst was a fumed slllca obtamed from Cabot Corporation (grade EH-
5)
The acidities of the catalysts were assessed by infrared spectroscopic and mlcro-
calonmetnc measurements of pyndme adsorption The detads of these measure-
ments for the NaH-Y zeohtes [ 131, H-mordemte [ 13,141, and silica-alumina [ 151
340 D T Chen et al / Joumal of Molecular Catalysts 93 (1994) 337-3S5
Table 2
Average enthalpy changes of adsorptlon on H-ZSM5-35 and H-mordemte (all values are m kJ/mol)
have been described elsewhere We report m Table 1 the number of Bronsted acid
sites and the total number of acid sites for those catalysts that also display Lewis
acidity Further mlcrocalonmetnc measurements of the adsorptlon of ammonia,
methylammes, methanol, dlmethyl ether, and water on H-ZSM-5 and H-mordemte
catalysts [l] have been previously reported We summmze the latter data m
Table 2
3. Results
0’0013 I
0 0014
I . ..I 0 0015.
I ..I 00016
I . . 00017
. .
I . . 00016
.
Rg 1 Arrhemus plots for total methylamme production on NaH-Y-33 CO), NaH-Y-65 (V). H-ZSM5-35 ( A ),
H-ZSM5-225 ( n ), and sdlca-alumma (+ )
Table 3
Apparent activation energtes The total amme actwahon energy IS the apparent activation energy for total meth-
ylamme formation
a For both of these catalysts, DMA was produced only at the lughest temperature studled, I e ,723 K Therefore,
an apparent activation energy for DMA productlon could not be calculated, and the acttvatron energy for productlon
of total ammes IS thus larger than for MMA
2
d 5000;...:...:...:...:...:...;
Rg 3 Dependence of methylammes production rate on ammonia partial pressure at 603 K for NaH-Y-65 (V),
H-ZSM5-13 (0). and H-mordemte (0)
D T Chen et al /Journal of Molecular Catalysts 93 (1994) 337-355 343
900 . . . : . . . : . . . : . . . : . . .
Q) 800~-,
G,
CTi;j 700-- ‘I\
r
0 20 80 100
NH, F?~ssur:~(Torr)
Rg 4 Dependence of dlmethyl ether producbon rate on ammonia partial pressure at 673 K for H-ZSM5-35 (A)
and at 603 K for NaH-Y-65 (V), and H-mordemte (0)
methanol for all catalysts For example, Fig 7 shows DME production rate versus
methanol partial pressure for NaH-Y-65, H-mordemte, H-ZSM5-13, and slhca-
alumma
Turnover frequencies for total methylamme formation durmg methylamme syn-
thesis were calculated at methanol and ammoma inlet pressures of 1 8 and 5 4 Ton-,
respectively These results are shown m Table 4 The turnover frequencies appear
to vary by a factor of - 50 between zeohtes, while slhca-alumma shows slightly
higher activity.
3 2 Methylamne dmproportlonatlon reactions
Kinetic studies were made of methylamme dlsproportlonatlon reactions over H-
ZSM5-35, because these reactions may be important durmg methylamme synthesis
350 . . . . ; . . . . 1 _ . . I
300--
0
200
250:; /
150 !-
. :j;+/--
:d
100 .‘“;“.” . . . . I . . . . -
0 5 10 15 20
CH,OH Pressure (Torr)
Rg 5 Dependence of methylammes production rate on methanol patt~al pressure at 603 K for H-mordemte (0)
and at 623 K for slhca-ahunma (+ )
344 D T Chen et al /Journal of Molecular Caralysls 93 (1994) 337-355
g!
d
2oo-
150
t
A
,,. L_
0 “‘:‘“:“‘:‘“:“‘:..‘:...:...-
0 2 4 6 6 10 12 14 16
CH,OH Pressure (Torr)
Fig 6 Dependence of methylammes productlon rate on methanol partml pressure at 603 K for H-ZSM5-13 (0)
and H-ZSM5-35 ( A )
from methanol and ammonia When monomethylamme (MMA) was passed over
the catalyst at a pressure of 2 8 Torr, the pnmary products were NH3 and DMA
The results also showed that DMA can dlsproportlonate further to tnmethylamme
(TMA) and MMA at higher temperatures For example, 8% of the methylammes
produced were TMA at 592 K, and the TMA selectlvlty increased to 17% at 700
K The apparent activation energy for dlsproportlonatlon 1s low, equal to 9 4 kcal/
mol for MMA consumption Importantly, the dlsproportlonatlon of MMA 1s rapid
compared to the reaction between ammonia and methanol to form methylammes
For example, the turnover frequency of dlsproportlonatlon 1s 2 3 and 7 1 ks- ’ at
temperatures of 592 and 699 K, respectively, and these rates are faster than the
0 15 20
&,OH Pr&ure (Torr)
Fig 7 Dependence of DME production rate on methanol partial pressure at 603 K for NaH-Y-65 (0). H-
mordemte (0). H-ZSM5-13 (O), and sdlca-alurmnaat 623 K ( 4)
D T Chen et al /Journal of Molecular Catalysis 93 (1994) 337-355 345
Table 4
Methylamme synthesis reactton rates at 667 K Inlet pressures of ammoma and methanol are 5 4 and 1 8 Torr,
respectively
NaH-Y-33 0 089 32 0
NaH-Y-65 049 490
NaH-Y-82 0 022 32
H-mordemte 12 850
H-ZSM5-13 0 66 440
H-ZSM5-35 061 220
H-ZSM5-225 0 040 29
slhca-alumma 56 500
Reactions of methanol with MMA and DMA were studied to evaluate the relative
rates of dlsproportlonatlon and senes methylatlon processes Reaction condltlons
were identical to those used for methylamme dlsproportlonatlon studies, except for
the addition of 2 9 Torr of methanol for the MMA reaction and 3 2 Torr of methanol
for the DMA reaction
It can be seen m Fig 8 that the addition of methanol to DMA over H-ZSM5-35
leads to a decrease m the amount of MMA formed from DMA, most hkely due to
reaction between MMA and CH,OH to form DMA The rate of TMA production
remains essentially unchanged with methanol addition
Slmllar behavior was observed for the addition of methanol to MMA Speclfi-
tally, addition of methanol decreased the rate of NH, formation, the rate of DMA
production remained essentially unchanged, and there was a slight increase m the
rate of TMA formation
The reactlvltles of DME with NH3, MMA, and DMA were measured over H-
ZSM5-35 for comparison with the correspondmg reactlvltles of methanol Ammo-
346 D T Chen et al /Journal of Molecular Catalysrs 93 (1994) 337-355
Q) = 2000--
zo”
K 9
c :x00-- 0
00
‘3 u) %
gS lOOO-- 0
U= * l 4
,OE . 0
C
ns 500--
0
0
- 0 0
0 “‘:“‘:“‘:‘“:“‘:“’
580 800 820 840 880 880 700
Temperature (K)
Fig 8 Influence of methanol on DMA disproportlonation (0) MMA and ( 0) TMA produced Sohd characters
represent DMA dlsproportlonatlon results m the absence of methanol
looo’.........:.........:.........:.........;
OS
32
K m 100-r
=o
OQ,
‘3 ttj
SE \ !
mz 10-r
2E k-my
a&
-
.
rMeOH
4-r MMA + hA
0’00140 0 00145
~~.-......:......“.:.... 0 00150 ““:‘“’
0 00155 . 0 00160
l/T (K-l)
Fig 9 Arrhemus plots for the production of (0) methanol, ( A ) MMA, and ( + ) DMA from the reactlon of
ammoma and dlmethyl ether over the H-ZSM5-35 catalyst
Chen et al /Journal of Molecular Catalysts 93 (1994) 337-355 341
0
o-
500 ..~:...?...:...:...:...
560 600 620 640 660 660 700
Temperature (K)
Rg 10 Influence of dlmethyl ether on DMA dlsproportlonatlon (0) MMA and (0) TMA produced Sohd
characters represent DMA dlsproportlonatlon results m the absence of DME
0 15
CH,& Pressure Eorr)
Fig 11 Dependence of DME production rate on methanol partial pressure, m the absence of ammes, at 603 K for
H-ZSM5-35
3 5 Methanol dehydration
4. Discussion
rP 1s the radms of the particle, C, 1s the reactant concentration at the surface of the
particle, and D, 1s the effective dlffuslvlty [ 161 Mass-transport hmltatlons are
negligible when the value of the Damkohler number IS less than unity Under
methylammes synthesis condltlons, the value of this dlmenslonless group 1s approx-
imately 0 06, suggestmg that the reaction kmetlcs observed m this study are con-
trolled pnmardy by the surface chemistry
Kinetic studies of methylamme synthesis show that the methylamme formation
rate 1s first order with respect to ammoma pressure for reaction temperatures from
603 to 723 K This result indicates that the surface coverage by ammonia 1s low
under methylamme synthesis condltlons This behavior 1s consistent with the results
of m situ IR studies that show the surface to be predommantly covered with
methylammes under methylamme synthesis condltlons The ongm for this behavior
1s that methylammes adsorb more strongly than ammoma [ 1] (see Table 2) For
example, the pressure of methylammes at the reactor outlet 1s typically on the order
of 0 2 Torr, about 500 times lower than that of ammoma at the highest pressures
studied However, the heat of adsorptlon of MMA 1s approximately 55 kJ/mol
higher than that of ammonia, and the surface coverage of ammonia 1s expected to
be 1% of the surface coverage of MMA at 623 K
A result of this study 1s the understanding that the dependence of the methylamme
synthesis rate on methanol pressure 1s rather complex H-ZSMJ and NaH-Y-65
catalysts show negative orders with respect to methanol, while H-mordemte and
slhca-alumma show zero and posltlve methanol orders This kmetlc behavior 1s
surpnsmg because methanol adsorption 1s relatively weak compared to the adsorp-
tion of ammonia and methylammes [ 11 (see Table 2)) and the surface coverage
of adsorbed methanol on the acid sites 1s expected to be low compared to the
strongly basic methylammes
The observed kmetlc behavior can be explamed m the followmg manner When
methanol reacts with adsorbed ammonia to form methylammes, a first-order
dependence on methanol pressure would be expected d the acid sites are covered
pnmardy by ammoma, this behavior 1s observed for several catalysts at low meth-
anol pressures As the methanol pressure 1s mcreased and the rate of formation of
methylammes increases, the reactlon products displace ammonia from the active
sites (because methylammes adsorb more strongly than ammonia) The rate of
methylamme synthesis decreases and approaches zero order m methanol The ongm
for the negative reactlon orders with respect to methanol 1s not clear at present We
suggest that this behavior may be related to the mhlbltlon by weakly adsorbed
methanol of methylamme desorptlon from the acid sites, as dlscussed later m this
paper
be seen m Table 2 that the heats of adsorption of the ammes on acid sites increase
m the order NH, < MMA < DMA, m accord with the proton affinities of these
molecules The heat of adsorption of TMA on acid sites 1s similar to that of NI-&,
despite the fact that TMA has the highest gas-phase proton affinity; this behavior
may be due to stenc factors Methanol adsorbs on acid sites with a heat of adsorption
lower than that of any of the ammes Thus, as noted above, ammonia and methyl-
amme coverages should be much higher than that of methanol The mlcrocalon-
metnc studies also show that all catalysts possess sites on which the reactants and
products of methylamme synthesis weakly adsorb with strengths ranging from
about 50-140 kJ/mol These sites may be associated with hydrogen bonding or
van der Waals mteractxons wlthm the catalyst mrcropores
A cntlcal aspect m the formulation of catalytic cycles for methylamme synthesis
reactions mvolves the possible role of surface methoxy species As noted above,
we suggest that methoxy species are reactive mtermedlates m the dehydration of
methanol to DME It IS less clear whether these species are mvolved m the synthesis
of methylammes from methanol and ammonia
We now present a general sequence of steps that descrrbes the essential aspects
of methylamme synthesis and related catalytic processes The first steps m the
sequence are adsorptlon and desorptlon of all reactants and products onto the weak,
non-acidic sites of the catalyst, represented by # These steps are followed by
migration of weakly adsorbed species to acid sites, represented as Bronsted acid
sites, H *, where * represents the zeohtlc lattice oxygen
The dehydration of methanol to DME can be represented by the followmg two
reaction steps mvolvmg methoxy species (CH; ) .
CH3 OH# + H * +CH; +H,O# (1)
CH,OH#+CH; +H* +DME# (2)
The catalytic cycle for methanol dehydration thus consists of Steps 1 and 2. This
reaction can exhibit first-order kinetics with respect to methanol pressure If the
surface 1s saturated with methoxy species Also, this reaction will be suppressed m
the presence of ammonia or ammes, because these bases Interact more strongly
with acid sites than do methoxy species
Under methylamme synthesis reaction condltlons, the surface ~111be saturated
with DMA and MMA, and only a small fraction of the acid sites ~111 contam
ammoma and methanol molecules Accordmgly, the probablllty of havmg adjacent
adsorbed methanol and ammonia molecules 1s low, and, the rate of methylamme
synthesis vta reaction between these adsorbed species would be negligible There-
fore, we suggest that methylamme synthesis takes place by reaction of a strongly
adsorbed species on an acid site with a second species that 1s weakly adsorbed on
the catalyst
Methylamme synthesis and dlsproportlonatlon reactions can be wntten with or
without partlclpatlon of methoxy species Consider, for example, the following
steps
D T Chen et al /Journal of Molecular Catalysrs 93 (1994) 337-355 351
DMA are directly proportional to pressure, and the reactlon scheme represented by
Steps 4-7 gives the proper dependence of the dlsproportlonatlon rate on pressure
The reaction steps leading to methylamme synthesis and to the effects of adding
methanol to MMA and DMA may be wntten as follows
DME# MeOH#
Rg 12 Catalytrc cycles for methylamme synthesis and related reactlons Each box represents a reactive surface
mtermedlate Verhcal hnes represent rcactlon paths, and mtersectmg honzontal bars separate reactants and prod-
ucts Arrows and shading refer to reaction rates under typical methylamme synthesis reactlon condmons dark,
sohd lines refer to pnmary production pathways, hght, solid lines refer to a secondary pathways, and light, dashed
lines refer to mmor pathways under reaction condltlons Arrows associated with honzontai bars indicate reversi-
blhtles of the steps
kJ/mol) than the range for heats of adsorption on the acid sites (ca 170 kJ/mol),
the surface coverage of these weak sites by CH30H# species can become slgmficant
at high methanol pressures [ l] Accordingly, these species can suppress amme
desorptlon
A direct effect of methanol on methylamme synthesis kmetlcs IS the formation
of methoxy species m the presence of methanol For example, DME formation
under methylamme synthesis reaction condltlons IS not mhlblted by methanol, and
this observed behavior IS consistent with the suggestlon that methoxy species are
reactive intermediates for this reaction However, while these species are involved
m DME formation from methanol, surface methoxy species are not apparently
involved m methylamme synthesis or dlsproportlonatlon steps Therefore, higher
surface coverages by methoxy species lead to lower coverages by reactive amme
species on the acid sites and to lower rates of methylamme synthesis
354 D T Chen et al /Journal of Molecular Catalysts 93 (1994) 337-355
5. Conclusions
Acknowledgements
This work was supported by the Office of Basic Energy Sciences of the Depart-
ment of Energy and through a Joint China-US Cooperative Research Grant admm-
lstered by the National Science Foundation Two of us (DTC and JMK) would
like to thank the National Science Foundation for graduate fellowships We also
wish to thank Randy Cortrrght at the Umverslty of Wlsconsm for valuable insight
durmg the latter stages of this proJect
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