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APCAT 2259
and
S. Hub
Centre de Recherches Rh&ze Alpes, ATOCHEM, 2, rue H. Moissan, BP 20,693lO Pierre Benite
(France)
(Received 9 December 1991, revised manuscript received 20 February 1992)
Abstract
The conversion of set-butylamine (BA) has been investigated over MFI, MOR, FAU, BEA and MAZ
zeolites. Faujasites were used in the H and Ce forms. The products of the reaction are l- and 2-butenes,
and di-set-butylamines (di-set-BA). Butene formation follows a zero order relative to the pressure of
butylamine, while dibutylamine formation follows a first order. The catalytic activity for deamination
to butenes is related to the total number of acid sites. An effect of the zeolite structure is observed: at
similar aluminium content, MFI and MOR appear more active than FAU and BEA for butene forma-
tion. The formation of dibutylamines is observed on large pore zeolites only, and results from two dif-
ferent pathways, di-set-butylamine appearing as a secondary product in the presence of non-dealumi-
nated H-form of Y zeolites, and as a primary product in the presence of Ce3+ exchanged and dealuminated
Y zeolites. This change is interpreted in terms of a classical consecutive reaction scheme in the former
case, through addition of set-butylamine to butene intermediates catalyzed by Brensted acids, and in
terms of a parallel reaction scheme in the latter case, through condensation of two set-butylamine mol-
ecules catalyzed by Lewis acids.
INTRODUCTION
Direct reaction of ammonia and alkenes is an attractive process for the man-
ufacture of amines. This reaction has been recently investigated in the pres-
ence of RE-Y zeolites, and alumina-, ferro- or boro-zeolites of the pentasil
group [l-6]. Deeba and co-workers [ 7-141 reported good yields using offretite
and dealuminated mordenites. They pointed out the problem of catalyst life
due to cokefaction of wide pore zeolites [ 121 and the limitations introduced by
unfavorable thermodynamics of the equilibrium. Amination is then difficult to
study because of these two factors, and presumably also because of possible
diffusional limitations at the high temperatures required for alkene activation.
For academic purposes it appears interesting to investigate the reverse re-
action of deamination, which has no thermodynamic limitations, in the tem-
perature range used for amination, and which is slow enough to permit a ki-
netic study in the absence of diffusional limitations.
The adsorption of butylamines has been investigated by many authors [ 15
211, using temperature-programmed desorption or infrared spectroscopy. A
strong adsorption of the amine occurs at temperatures < 473 K, with an initial
heat of adsorption of about 20 kcal/mol (1 cal= 4.1868 J) [ 161, and butylam-
ine forms a l/l adsorbed complex with each aluminium atom in H-ZSM-5
[ 211. Above 573 K the adsorption of butylamines is reversible, and the sub-
strate is partly decomposed into butenes and ammonia, part of the butenes
being transformed into hydrocarbons of higher molecular weight [ 19,211. The
rate of decomposition of butylamines has been reported to be limited by the
rate of desorption of ammonia [ 181.
Around 623 K, the conversion can be kept low, and the alkene should be
displaced by the amine, thus ensuring a good stability of the catalyst with time-
on-stream. Moreover, the dialkylamine is also formed in this reaction [ 171 and
the mechanism of this secondary reaction, which represents the main loss of
selectivity in amination can then be investigated more safely. The reaction of
alkylation of isobutene with arylamines has been reported to be useful as a
synthetic tool at high pressures [ 221.
The present work is devoted to the study of deamination of set-butylamine
on a series of zeolites in order to check the respective influence of the structure
and chemical composition of the catalyst.
EXPERIMENTAL
Catalysts preparation
Catalyst churacterizations
TABLE 1
Sample Suppliers Si/Al Vol. micro Vol. meso Acidity > 523 K
reference (ml g-‘) (ml g-‘) (me&)
nia. The catalyst was first activated in flowing nitrogen in situ, saturated with
ammonia at 373 K, then swept by a flow of dry nitrogen while the temperature
was raised by steps of 50 K. The amount of ammonia evolved by the solid was
monitored by conductometry. The chemical compositions, the textural and
acid properties of these catalysts are reported in Table 1.
Catalytic tests
RESULTS
Preliminary results
The reaction yields ammonia and l- and 2-butenes, with different amounts
of di-set-butylamine which vary with the type of catalyst used. On HY 2.5 the
selectivity to di-set-butylamine is about 6%, but reaches 87% on HY 15. There-
M. Lequitte et al. jApp1. Catal. A 84 (1992) 155-168 159
fore, two different kinetic studies were carried out on these catalysts to clarify
the mechanisms of the two reactions.
The rates of reaction as a function of the partial pressure of set-butylamine
are reported in Figs. 1 and 2 for HY 2.5 and HY 15, respectively. The rate of
the monomolecular reaction of deamination to butenes is zero order above 6.65
kPa at 613 K, as expected for the conversion of a strongly adsorbed substrate.
The kinetics follow a Langmuir Hinshelwood law, with a rate constant
I~=7*10-~ mol h-l g-l, and an adsorption coefficient 2=4.25 Pa-l. The ac-
tivation energy determined in the zero order range is 40 kcal/mol, and the
activation energy at low partial pressure, then in the first order range is 20
kcal/mol. The average heat of adsorption of set-butylamine on HY 2.5 can
then be calculated to be 20 kcal/mol, which appears reasonably consistent with
the calorimetric determination of the heat of adsorption of ammonia by Au-
roux [ 271 for zeolites (25-30 kcal/mol).
The rate of the reaction of see-butylamine to di-set-butylamine over HY 15
I
0 5 10 15 20 25
BA partial pressure (kPa)
Fig. 1. Influence of the partial pressure of set-butylamine on the rate of reaction at 613 K over HY
(LZ62).
s
._ 40
.
E
+?a .
z mm
0 0 L- I
0 10 20 30 40 50
BA partial pressure (Pa)
Fig. 2. Influence of the partial pressure of set-butylamine on the rate of reaction at 613 K over HY
dealuminated to a Si/Al ratio of 15.
is a first order fast reaction, with a low activation energy, about 11 kcal/mol.
Di-set-butylamine can be formed either by a parallel mechanism of reaction
of two amines leading to elimination of ammonia, or consecutive addition of
see-butylamine to the butenes produced by the reaction.
The selectivity of the reaction was determined at different conversions on
HY 2.5, H-MOR and CeY at the same temperature of 613 K. The results re-
ported in Figs. 3 and 4 show that on the two protonic zeolites di-see-butylamine
(di-set-BA) is a secondary product of the reaction.
However, on CeY, di-see-butylamine appears as a primary product. The se-
lectivity to di-set-butylamine obtained, at low conversion, on dealuminated Y
zeolites suggests that this is a primary product in that case too.
TABLE 2
TABLE 3
n-butyl (%) set-butyl (%) tert-butyl (%) n-butyl (%) see-butyl (%) tert-butyl (%)
All samples were compared in conditions in which the reaction is zero order,
at low conversion. The respective influences of structure and composition were
TABLE 4
Catalytic properties of a series of zeolites of different composition and structure for the conversion
of set-butylamine at 613 K
0 095 1 1,5 2
Acidity (meq.g-1)
TABLE 5
Sample Exchange Conversion Selectivity Reaction rates (mol s-’ g-l) E,(BA)
(W) BA C4 (kcal/mol)
(%) (mol-%) r(G) r(DBA) r(BA)
Catalyst deactivation
0
0 I 2 3 4 5
Fig. 6. Amount of carbon retained by the catalyst after reaction, as a function of its steady-state
activity.
Fig. 7. Amount of nitrogen retained by the catalyst after reaction as a function of ita aluminium
content.
164 M. Lquitte et al./Appl. Catal. A 84 (1992) 155-168
DISCUSSION
The formation of l- and 2-butenes can easily be accounted for by the well
known Hofmann degradation of amines represented in Scheme 1, as already
assumed in the literature for this kind of reaction performed over zeolites [ 201.
In the liquid phase this reaction is catalyzed by protonic acids, and the good
relationship observed between the rate of formation of butenes and the number
of acid sites is consistent with such an acid mechanism. As reported in Table
6, the butenes produced on HY, MFI and BEA are at thermodynamic equilib-
rium. By contrast MOR shows a high selectivity to cis-butene-2. These differ-
ences of selectivity are accounted for by consecutive reactions which are ap-
parently unfavored in the one directional channels or mordenite, as reported
earlier by Fajula and Dirringer from their results on butene-deuterium ex-
change [ 291.
The activity per protonic site follows the pattern: HMFI, HMOR > HBEA,
HFAU. It can be pointed out that diffusional limitations would lead to an
underestimation of the activity of small or medium pore zeolites, such as MFI
or MOR then the particular position of these zeolites merits a discussion.
For large Si/Al ratios, about 15, a critical examination of previous experi-
TABLE 6
But-l 25 30 34 4 37 8
&-But-2 38 39 29 70 23 69
trans-But-2 37 31 37 26 40 23
M. Lequitte et al./Appl. Catal. A 84 (1992) 155-168 165
ments, using high-resolution solid state NMR concluded that aluminium at-
oms are isolated in the lattice of faujasite [ 301, which has then the maximum
acidity permitted in this zeolite. The observation of higher activity for butene
formation on ZSM-5 (14) compared to HY15 could then be attributed to the
influence of the structure on the acid strength.
According to Rabo and Gajda [ 311, the rigidity of the lattice can affect the
acid strength since it is well known that acidity is controlled by the Si-O-Al
bond angle [ 321. Recent quantum chemical calculations demonstrate that de-
protonation of the zeolite lattice leads to large local changes in geometry that
change acidity [ 331. These calculations account for the modifications of the
infrared spectrum of NH,H and HY zeolites related to the relaxation of the
lattice when the proton is lost and then fur the higher acidity, at the same
aluminium content, of pentasil zeolites which possess a rigid lattice.
Some effect on the catalytic properties is then expected for those reactions
catalyzed by protons, and this effect should be larger for those reactions in-
volving strong bases which can completely displace the proton from the lattice,
and weaker for hydrocarbons, for the absorption of which Kazansky and Sen-
chenya [34] proposed the formation of a covalent bond. The present results
support this hypothesis, but also demonstrate that this influence of the struc-
ture is small and represents at most a factor of 3 on the activity at 613 K for
the deamination of set-butylamine.
The formation of di-set-butylamine is more complex, and can occur by two
different pathways:
(i) A consecutive alkylation of l- and/or 2-butenes by the non-reacted amine,
in agreement with the formation of di-set-butylamine as a secondary product
(Scheme 2). In addition, it should be noted that this consecutive reaction
scheme must lead to an isomerisation of the alkyl chain. This isomerisation is
indeed clearly observed in the conversion of n-butylamine with the high initial
selectivity to di-n,sec-butylamine.
CH3--HP-CH -CH,
I
\CH3-CH2-i; -CH, )
I
CH3-CH2-CH -CH3
CH3-CH H
-0 Al -
CONCLUSION
ACKNOWLEDGMENTS
We thank Mr. P. Espiau for the synthesis and characterization of the sam-
ples of zeolites BEA, the Service Central d’Analyses du CNRS (Solaize) for
the chemical analysis, and Dr. A. Germain for fruitful discussions.
REFERENCES
J. Peterson and H.S. FaIes, U.S. Patent 4 307 250 (April 8,198l).
J. Peterson and H.S. FaIes, U.S. Patent 4 375 002 (Feb. 22,1983).
J. Peterson andH.S. FaIes, European Patent 39 918 (Feb. 29,1984), assigned to Air Products.
M. Deeba, W.J. Ambs, Eur. Pat. 77016 (June 19,1985), assigned to Air Products.
V. Taglieber, W. Holderich, R. Kummer, W.D. Mross and G. Saladin, DBP 3 326 576 (Jan.
31,1985).
6 V. Taglieber, W. Holderich, R. Kummer, W.D. Mross and G. Saladin, DBP 3 327 000 (Feb.
7,1985), assigned to BASF AG.
7 M. Deeba, M.E. Ford and T.A. Johnson, in J.W. Ward (Editor), Catalysis 1987, Amsterdam,
1988, p. 221.
8 M. Deeba, M.E. Ford and T.A. Johnson, in D.W. Blackburn (Editor), Catalysis of Organic
Reactions, M. Dekker, New York, 1990, p. 241.
9 M. Deeba, Eur. Pat. 305 564 (March 8,1987) assigned to Air Products.
10 W.J. Ambs, M. Deeba and J.F. White, U.S. Pat. 403 889 (July 30,1982).
11 W.J. Ambs, M. Deeba and J.F. White, Eur. Pat. 101 921 (April 16, 1986), assigned to Air
Products.
12 M. Deeba and M.E. Ford, Zeolites, 10 (1990) 794.
13 M. Deeba, M.E. Ford and T.A. Johnson, J. Chem. Sot., Chem. Commun., (1987) 562.
14 M. Deeba and M.E. Ford, J. Org. Chem., 53 (1988) 4594.
15 P.A. Jacobs, B.K.G. Theng and J.B. Uytterhoeve, J. Catal., 26 (1972) 191.
16 J. Koubek, J. Volf and J. Pasek, J. Catal., 38 (1975) 385.
17 M. Takahashi, Y. Iwasawa and S. Ogawasara, J. Catal., 45 (1976) 15.
18 L.V. MaIysheva, E.A. Paukshitis and N.S. Kotsarenko, React. Kinet. Catal. Lett., 24 (1984)
97.
19 J.H. Zhu and Q.H. Xu, Chin. Sci. Bull., 34 (1989) 384.
20 C.G. Pope, Zeolites, 10 (1990) 28.
21 D.J. Parillo, A.T. Adamo, G.T. Kokotailo and R.J. Gorte, Appl. Catal., 67 (1990) 107.
22 D.D. Dixon and W.F. Burgoyne, Appl. Catal., 62 (1990) 161.
23 M.A. Nicolle, Ph.D. Thesis, University of Montpellier, France, 1991.
24 F. Fajula, F. Figueras and L. Moudafi, Eur. Pat. 118 382 (1987), assigned to CNRS.
168 M. Lequitte et al./Appl. Catal. A 84 (1992) 155-168