JOURNAL OF CATALYSIS .

%, 88-91 (1972)

Mechanism of Ether Formation from Alcohols

over Alumina Catalyst
V. R. PADMANABHAN” AND F. J. EASTBURN
Chemical Engineering Department, University of Louisville,
Louisville, Kentucky 40208

Received March 19, 1971

The kinetics of vapor-phase dehydration of methanol and ethanol over alumina

catalyst has been explained by proposing a reaction mechanism wherein the surface
reaction between an adsorbed ROH molecuIe on an acidic site and an adsorbed
alkoxide anion on a basic site is assumedto be the rate-controlling step.

INTRODUCTION Jain and Pillai (6) proposed a reaction

The mechanism of vapor-phase dehy- mechanism for the dehydration of methanol
dration of ethanol over alumina catalyst and ethanol to ethers over alumina catalyst
to yield ethylene as proposed by many has by studying the effect of different diluents
been discussed by Emmett (I), whereas on the rate of ether formation. Their pro-
the mechanism of ether formation from posed mechanism calls for dual-site ad-
alcohols has been reported by only a few sorption of alcohols as anticipated by
(1). Balaceanu and Jungers (2) studied Knoezinger and co-workers (5, 4) while
the kinetics of dehydration of methanol proposing Eq. (1). The present authors
over alumina. They concluded that a have extended this mechanism in this arti-
second-order reaction mechanism between cle and have derived a kinetic-rate expres-
two adsorbed methanol molecules explained sion for the dehydration of methanol over
their experimental data with the least dis- alumina catalyst.
crepancy, but did not present a suitable
correlating equation. Knoezinger and co- MECHANISM OF DEHYDRATION REACTION
workers (3, 4) fitted kinetic data on meth-
anol and ethanol dehydration to corre- Jain and Pillai (6) concluded that ether
sponding ethers over alumina catalyst with is formed by a nucleophilic-displacement
an “empirical” equation of the following reaction caused by an adsorbed ROH mole-
form : cule on another ROH molecule adsorbed
re = o”od~a)/(dpa + @eJ). on a different kind of active site shown
(1)
on page 89, where A and B represent an
They explained that the dependence of acidic and a basic site, respectively.
the rate of ether formation upon the square Chemisorption of alcohol on a basic site
root of partial pressure of alcohol was due represented as a hydrogen bonding to the
to possible dual-site adsorption of alcohols surface, increases the nuc,leophilicity of
on the alumina surface. The present au- the oxygen of that molecule resulting in an
thors (5) found that Balaceanu and Jun- incipient alkoxide anion. Jain and Pillai
gers’ (2) kinetic data can best be explained (6) have pointed out that the type of hy-
by Eq. (1). drogen bonding explained above finds
*Taken from the Ph.D. thesis of V. R. parallel in the proposed nature of chemi-
Padmanabhan, University of Louisville, Louisville, sorption of water on alumina by de Boer
KY, 1970. Present Address: B. F. Goodrich et al. (7) and the spectroscopic evidence
Chemical Co., Calvert City, KY 42029. for the adsorption of formic acid to form
88
@ 1972 by Academic Press, Inc.
 ETHER FORMATION FROM ALCOHOLS OVER ALUMINA

R-y: -R-q--H R-Y-R 9-H

(i + + +

_... 6 _... .__.b . . . b _... ._ & . .

formate ions (8) and the adsorption of
acetylene through the acidic hydrogen (9).
The reaction mechanism proposed in this
article for ether formation is shown by Eqs.
(2)-(7) below.
CHsOH + .s.t,+ CHIOH
CHHOH + SB 5 CHzOH . SB
CHsOH . sg + SB ti CHIO- SB + Hf.
CHzOH + 2sB$
CH,O- . 8B +
CH,OH . 8A + CHaO- . SB S
CHsOCHs 8~ + OH-.
H+~sB+OH-~SA~H~O.SB+SA
CH,OCH, . .ss = CH,OCH,
HtO . SB ti Hz0 + SB
Equation (3c), which is obtained by
summing the Eqs. (3a) and (3b), repre-
sent,s B-type adsorption of methanol
molecule accompanied by dissociation into
alkoxide anion and a proton. Summation of
Eqs. (2)-(7) [not including (3a) and (3b)]
gives the overall reaction in the hetero-
geneous phase [Eq. (8) 1.
2CHsOH e CH,OCHa
DERIVATION OF KINETIC-RATE
The following assumptions will be made
in the derivation of a kinetic-rate equation
for the dehydration of methanol and ethanol
over silica-alumina catalyst:
1. There are two types of active sites upon
which methanol can be adsorbed and
they are as follows:
a. an acidic site, referred to as So,
saturated with methanol.
b. a basic site, referred to as sR, not
saturated with methanol.
2. The methanol adsorbed on basic site is
weakly dissociated, the proton being
transferred to another basic site as
shown in Eq. (3b).
3. The adsorbed water molecule on sg is
more weakly dissociated than the ad-
sorbed methanol molecule on .sn, so that
the source of proton is only provided by
Eq. (3b).
4. A nucleophilic-displacement reaction
caused by an adsorbed alkoxide anion
[Eq. (4) ] occurs on the positively
polarized carbon atom of the methanol
. SA (2) adsorbed on the acidic site. This reaction
(3a) of an adsorbed alkoxide anion (basic
SB (3b) site) with an adsorbed methanol mole-
cule (acidic site) is assumed to be the
H+ * SB (3~) rate-controlling step. Hence adsorption
of methanol, desorption of products, and
SA (4) the formation of water from H+ and OH-
(5) ions [Eq. (5) ] are at equilibrium, and
+ SB (6) external and internal diffusional resist-
(7) ances are negligible.
5. The alumina surface is saturated with
A-type adsorption, so that the dehydra-
tion reaction does not appreciably
change the surface concentration of
methanol adsorbed on A sites.
6. The concentration of vacant basic sites
on the catalyst surface is negligible
compared to the total concentration of
adsorbed molecules.
+ H,O (8)
Th le net. adsorption rate of methanol mole-
EQGATION cule on a basic site with subsequent dis-
sociation of the methanol molecule can be
expressed as follows.
(T,d)n = (fCnd)oPaCv2,B
- [(kad)a/KalCnlk.BCp.B, (9)
where the subscript B on Calk and C, terms
indicates that nlkoxide anions and protons
are adsorbed on B-type sites. Since Eq.
(3~) is at equilibrium (r&a = 0, and
noting that C,,n = Calk,B as per assumption
number 3, the above equation gives
c P,B -C
- alk,B = 4mcw.B. (10)
The rate-controlling step, Eq. (4) gives
rs = @&a,ACalk,B/Ct), (11)
where Ca,A = concentration of adsorbed
alcohol on A site. According to assumption
90 PADMANABHAN AND EASTBURN

number 5, Ca.* is approximately constant and Jungers (%), and the data of Pad-
(similar to pseudo first-order reaction). manabha,n (5) :
rs = ~‘&k,B, w rc = m@i/h% + W,), (1)
where k’, = (lc,C,,,/C,).
where r0 and b can be obt.ained from Eq.
Combining Eqs. (10) and (12) we get, (20) as follows:
r, = umiEC,,B. (13) r, = Ic’,(C, - C,,*)/4 = constant
Equation (6) at equilibrium gives and
Ce,B = K,P,Cu,u. (14)
b = (K, + Kw)/(hhL).
Equation (7) at equilibrium gives
It is interesting to note here that Knoe-
Cw,~ = K,PwCv,u. (19 zinger and co-workers (3, 4) suggested that
the constant b involved the ratio of Kw
Now,
and a
Ct = &.A + Cv,B + Ca,A

+ Calk,R + Cp.B + c,,B + CW,B. (16)

Since C,,, is approximately constant (as-

sumption number 5)) CV,nis negligible (as-
sumption number 6) and C2.,A= 0 (as-
sumption number la), Eq. (16) reduces to
Eq. (17) below.
Ct - C~,A = Cnik.H + c,,u
Combining Eq. (17)) (lo), (14), and (15),
and noting that P, = P,,
c __ ct
“” = 2x&J’, + (Ke + KtJPta
Equations (13) and (18) can be combined
to get
k’,(C,
__~ - ca,*hmT . (19)
” = 2dK,P, + (Ke + Kw)Pw
Rearranging Eq. (19) to group the con-
stants, we get
k’,(C, - ca,*>dE
dz+ [We + KtJl(2~W'w
Noting that re = rs/2, Eq. (20) can be
reduced to Eq. (l), the kinetic-rate equa-
tion, which fits the data of Knoezinger and
co-workers (3, 4), the data of Balaceanu
Subscripts denot,ing acidic and basic
sites, respectively.
Subscripts denoting alkoxide anion,
proton, alcohol, ether, and water mole-
+ C&B + Cw,B rules, respectively.
= constant’. (17) Const,ant, (atm)-‘/2.
Molal concentration of adsorbed com-
ponent j, moles per unit mass of cata-
lyst. Subscript i indicates the type of
site on which the component j is
adsorbed.
- &.A
. (18)
Molal concentration of tot)al active
sites per unit mass of catalyst.
Molal concentration of vacant adsorp-
t.ion sites per unit mass of catalyst.
Subscript i indicates the type of active
sites.
Adsorption equilibrium constant for
component j, atm-‘.
Forward reaction-rate constant for the
nucleophilic-displacement surface re-
action 4.
Adsorption velocity constant, time-’
atm-‘.
>' Partial pressure of component j, atm.
c-w Net adsorption rate, moles per unit
time per unit mass of catalyst.
Rate of ether formation, moles per
unit time per unit mass of catalyst.
Initial reaction-rate constant, molea
per unit time per unit mass of catalyst.
Net surface reaction rate, moles per
unit time per unit mass of catalyst.
Acidic and basic active sites.
 ETHER FORMATION FROM ALCOHOLS OVER ALUUINA 91

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