Applied Catalysis, 7 (1983) 159-168

Elsevier Science Publishers B.V., Amsterdam -Printed in The Netherlands

159
ACI D- BASE PROPERTI ES OF ALUMI NI UM OXI DE
Z. Vf T, J . VALA and J . MALEK
I nsti tute of Chemi cal Process Fundamental s, Czechosl ovak Academy of Sci ences,
165 02 Prague 6 - Suchdol , Czechosl ovaki a.
(Recei ved 22 December 1982, accepted 30 March 1983)
ABSTRACT
The ef f ect of the acti vati on temperature on aci d- base properti es of al umi na
catal ysts was studi ed. The aci di ty and basi ci ty of catal ysts were characteri sed
by usi ng the dynami c sorpti on method and by testi ng the catal yst acti vi ty i n the
depol ymeri sati on of paral dehyde and decomposi ti on of di acetone al cohol . For al l
catal ysts, i t was f ound that the aci di ty i ncreases si gni f i cantl y wi th i ncreasi ng
acti vati on temperature up to 55O"C, whereas the basi ci ty goes through a maxi mum
at 140C. The aci di ty of al umi na i ncreases wi th i ncreasi ng surf ace dehydrati on.
Maxi mum basi ci ty corresponds to a surf ace covered compl etel y wi th hydroxyl groups.
I NTRODUCTI ON
Al umi na i s a bi f uncti onal catal yst whose aci d and base si tes catal yse a number
of reacti ons. Whereas the surf ace aci di ty has been attri buted unambi guousl y to
al umi ni um cati ons and the surf ace basi ci ty to oxygen ani ons, the hydroxyl groups
can have aci di c as wel l as basi c character [1, 2]. Surf ace concentrati ons of al l
these si tes depend on the degree of surf ace dehydrati on whi ch i s i nf l uenced by
the acti vati on temperature [l ]. Thus, accordi ng to i deas on the al umi na surf ace
the aci di ty of hydroxyl group hydrogens shoul d decrease and that of al umi ni um
cati ons shoul d i ncrease wi th the gradual surf ace dehydrati on. At the same ti me,
the basi ci ty shoul d change as a resul t of i ncreased number of oxygen ani ons and
decreased number of hydroxyl group oxygens on the catal yst surf ace.
As has been f ound experi mental l y, the surf ace aci di ty of al umi na i ncreases
markedl y wi th i ncreasi ng acti vati on temperature [3- 61, i n accordance wi th the
f ormati on of strongl y aci di c A13+ si tes.
Onl y a f ew data are avai l abl e i n the l i terature concerni ng the ef f ect of hyd-
rati on on the surf ace basi ci ty. Usi ng the ti trati on method, Yamadaya and co-
workers [7] have f ound that the basi ci ty of al umi na i ncreases wi th i ncreasi ng
hydrati on and that i t reaches a constant val ue when the amount of sorbed water
corresponds to three mol ecul ar l ayers. From an IR study of adsorpti on of carbon
di oxi de on a- al umi na i t f ol l ows that the rel ati vel y hi ghest basi ci ty i s shown
by oxygen ani ons occurri ng i n the nei ghbourhood of a hydroxyl group; the surf ace
basi ci ty decreases wi th i ncreasi ng dehydroxyl ati on [8]. Mochi da and coworkers [9
have studi ed dehydrochl ori nati on of hal oal kanes on al umi nosi l i cate, Si 02/ KOH
0166- 9834/ 83/ $03. 00 0 1983 Elsevier Science Publishers B.V.
160
catal yst, on al umi na acti vated at 500C and al umi na doped wi th water, whereas
the product composi ti on obtai ned on acti vated al umi na was si mi l ar to that obtai ned
on al umi nosi l i cate, the product composi ti on resul ti ng f rom the reacti on on doped
al umi na was comparabl e to that f ound wi th the Si 02/ KOH catal yst. Resul ts of these
experi ments i ndi cate that the aci di c properti es predomi nate on the surf ace of
dehydrated al umi na, basi c properti es are predomi nati ng on the surf ace of hydrated
al umi na and the surf ace basi ci ty i s i ncreased by the sorbed water rather than by
the presence of oxygen ani ons.
EXPERI MENTAL
Chemi cal s
Di acetone al cohol [I O], 1, 3, 5_tri ni trobenzene [I l l and di methyl zi nc tetrahydro-
f uranate [I 23 were prepared accordi ng to known methods. Except n- butyl ami ne (pure,
Koch- Li ght, UK), p- xyl ene, paral dehyde (both pure compounds, Soj uzchi mexport, USSR)
and 1, 3, 5_tri methyl benzene (pure, Al dri ch, Bel gi um), the other compounds used
(Lachema, Czechosl ovaki a) were reagent grade chemi cal s. Li qui d compounds were
dri ed over mol ecul ar si eve Nal si t A5 or sodi um wi re and di sti l l ed under ni trogen
bef ore use.
Catal ysts
A Cherox 3300 al umi na produced f rom sodi um al umi nate (CHZ CSSP Li tvf nov, Czecho-
sl ovaki a), a Pural S al umi na produced by hydrol ysi s of al umi ni um al cohol ate (Condea
Chemi e, FRG) and an al umi na prepared i n thi s l aboratory were used. 4 sampl e of
the l atter (Al prep) was obtai ned by preci pi tati ng an al umi ni um ni trate sol uti on
wi th aqueous ammoni a at 20C and by cal ci nati onof thegel i nai rat 550C f or 4 h.
Al l catal ysts (f racti on 0. 07- 0. 125 mm i n di ameter) were cal ci ned i n oxygen at
550C f or 3. 5 h, cool ed to room temperature, rehydrated i n di sti l l ed water f or
16 h and dri ed at 20C. Pri or to sorpti on measurements as wel l as catal yti c tests,
al l catal ysts were acti vated by dryi ng i n ni trogen (35 ml mi n- ' ) at the desi red
temperature f or 1 h. The surf ace area of catal ysts was measured by Nel sen- Eggert-
sen method [13]. The l oss of water duri ng acti vati on was determi ned gravi metri -
tal l y. The surf ace concentrati ons of resi dual hydroxyl groups on catal ysts, acti -
vated at temperatures z 14O"C, were determi ned by a pul se method [14] based on
the reacti on of gaseous di methyl zi nc tetrahydrof uranate wi th acti ve hydrogen.
Sorpti on measurements
The surf ace concentrati ons of aci di c (c, ) and basi c (c, ) si tes of catal ysts were
determi ned by the dynami c sorpti on method descri bed earl i er [15, 16]. A sampl e of
catal yst (about 0. 4 g) was acti vated by dryi ng at the desi red temperature i n a
stai nl ess steel col umn (50 mmx4 mm i . d. ) and cool ed "i n si tu" to room temperature.
A 0. 0025 M sol uti on of the sorbate (pyri di ne i n cycl ohexane f or the determi nati on
161
of CA or benzoi c aci d i n methanol f or the determi nati on of CD) was passed over
the catal yst unti l surf ace saturati on was reached, whi ch was i ndi cated by a steady
sorbate concentrati on i n the col umn output. The catal yst sampl e was washed by
200 ml of sol vent to remove the weakl y bound sorbate and the remai ni ng sorbate was
quanti tati vel y desorbed by a 0. 05 M sol uti on of n- butyl ami ne i n cycl ohexane
(measurement of CA) or by a 0. 05 M sol uti on of aceti c aci d i n methanol (measurement
of ~8). Sorbate concentrati ons i n the col umn output were conti nuousl y measured
by means of a UV detector 254 nm (Devel opment Workshops, Czechosl ovak Academy of
Sci ences, Prague) whi ch was connected to a l i near recorder. The overal l amounts
of the adsorbed and di spl aced sorbate were determi ned f rom the mass- bal ance of
the sorbate. The overal l amount of the adsorbed sorbate corresponded to the
overal l si tes concentrati on A
PY
and ABa and the amount of the di spl aced sorbate
to the f racti on of strong si tes cA and ~6.
Catal yti c tests
Depol ymeri sati on of paral dehyde (1, 3, 5- tri methyl - 2, 4, 6- tri oxane) to acetal dehyde,
a typi cal l y aci d catal ysed reacti on [17], was chosen f or testi ng the aci di ty of
catal ysts. Decomposi ti on of di acetone al cohol to acetone, whi ch i s known to be
an excl usi vel y base catal ysed reacti on [18], was used f or testi ng the basi ci ty
of catal ysts.
Depol ymeri sati on of paral dehyde was carri ed out under pressure i n the l i qui d
phase by usi ng a stai nl ess steel batch mi cro- reactor [19]. The reactor contai ni ng
the acti vated catal yst s 0. 16 g and 7. 1 ml of benzene was heated to reacti on
temperature 105C and 1 ml of a benzene sol uti on contai ni ng 0. 25 ml of paral dehyde
and 0. 12 ml of p- xyl ene (i nternal standard) was added through a septum. Sampl es
of the reacti on mi xtures were anal ysed at 93C by GLC usi ng f l ame- i oni zati on de-
tector and a col umn packed wi th 15% Carbowax 20M on Chromaton N (carri er gas
ni trogen). The reacti on l ed to a deacti vati on of catal ysts; f ormati on of smal l
amount of crotonal dehyde < 3%was observed.
Decomposi ti on of di acetone al cohol i n the l i qui d phase was perf ormed i n a
magneti cal l y sti rred 50 ml gl ass reactor. The reactor contai ni ng 34 ml of benzene
and about 0. 23 g of acti vated al umi na was heated to reacti on temperature 70C
and a mi xture of 4 ml of di acetone al cohol and 3 ml of 1, 3, 5_tri methyl benzene
(i nternal standard) was added through a septum. Sampl es of the reacti on mi xture
were anal ysed at 76C by GLC usi ng catharometer and a col umn packed wi th 3%
Si l i cone OV- 17 on Gas Chrom Q (carri er gas hydrogen). The reacti on proceeded wi th
hi gh conversi ons and wi thout deacti vati on of catal ysts. Mesi tyl oxi de < 4% was
f ormed as by- product.
In both reacti ons the catal ysts were pl aced i n the reactors wi thout contact wi th
ai r moi sture. Conversi ons of reactants were determi ned f rom thei r decrease i n con-
centrati ons wi th respect to i nternal standards. The course of reacti ons was
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163
characterised by initial reaction rates at conversions up to 20%. Thermal decom-
position of reactants did not occur in reactions under study.
RESULTS AND DISCUSSION
The effect of the activation temperature (Tact) on the properties of catalysts
is documented by the data in Table 1. The amount of water released from the cata-
lysts increases with increasing Tact and this leads to a continuous increase in
the surface areas. Only the Cherox 3300 exhibits a maximum at 140C due to the
structure changes at higher temperatures. The concentrations of residual hyd-
roxyl groups c
OH
decrease with increasing Tact' The values of c
OH
are near to
those reviewed for y-alumina by Hendriksen et al. [20].
From Table 1, it also follows for all catalysts that the increase of Tact en-
hances the overall adsorption of pyridine A
py
approximately within one order of
magnitude, whereas the amount of displaced pyridine c
A
is increased by more than
two orders of magnitude. The proportion of strong sites therefore increases, in
accordance with the literature data [3-5]. The concentrations of basic sites ex-
hibit a completely different tendency. Whereas the overall adsorption of benzoic
0,15
r
pA
mol g11i
1
.
0,10
0,05
o
o 200 400 600
Tact c
FIGURE 1 The effect of the activation temperature (T
acs)
on the catalytic activity
of alumina in the decomposition of diacetone alcohol (r
DAA,
circle points) and
in the depolymerisation of paraldehyde r ~ A square points). () [] Cherox 3300,
Pural S, () [J Al
prep
164
acid ABa does not change too much, the amount of displaced benzoic acid c
B
slowly
decreases (except for the Cherox 3300). It is noteworthy that also unactivated
catalysts show high concentration of basic sites. Similar result has been obtain-
ed by titration with bromthymol blue (pK
a
= 7.2) by Yamadaya and coworkers [7J.
Apresence of strongly basic sites is qualitatively evidenced by adsorption of
1,3,5-trinitrobenzene (pK
a
= 14.4) from a benzene solution. The intensity of
alumina colouration decreases for all catalysts in the order of Tact:
55020C. Strongly basic sites are therefore present in a significant amount on
the catalysts activated at 140-550C.
The different effect of Tact on the rate of acid catalysed depolymerisation
of paraldehyde and base catalysed decomposition of diacetone alcohol (rg
AA)
is presented in Figure 1. Whereas increases markedly for all alumina samples
with increasing Tact' maximum value of rg
AA
is exhibited by alumina samples acti-
vated at 140C. In the depolymerisation of paraldehyde on all catalysts the values
of can be correlated with concentrations c
A
(Figure 2). The concentrations of
these active sites, which are expressed by the number of pyridine molecules dis-
placed per 1 m
2,
correspond for T
act
=500C to 6-8 x 10
17
m-
2,
a value which is
near to concentration of sites found by Knozinger [21J for the isomerisation of
mol 11' ni
2
4
2
a
FIGURE 2 The dependence of catalytic activity of alumina in the depolymerisation
of paraldehyde on the concentration of acid sites (c
A).
[] Cherox 3300,
.. Pural S, DI Al
prep'
The numbers denote the activation temperatures of catalysts.
165
2
IO3 r&
mol Ii ti2
1
0
140
140
5
. 300
300
9550
550
082 014 086
cB pmol mB2
FI GURE 3 The dependence of catal yti c acti vi ty of al umi na i n the decomposi ti on
of di acetone al cohol (r: AA) on the concentrati on of basi c si tes (c, ). l Pural S,
@ *' prep.
The numbers denote the acti vati on temperatures of catal ysts.
' 2, 3- di methyl - I - butene. Al though the aci d si tes concentrati ons obtai ned f or i n-
di vi dual Tact do not di f f er very much, the catal ysts di spl ay consi derabl e di f f er-
ences i n the acti vi ty. That may be caused by vari ous trace i mpuri ti es such as
cati ons of other metal s ori gi nati ng f rom the preparati on of catal ysts. The val ues
Of +A*
correl ate l i nearl y wi th the concentrati ons c5 onl y f or Pural S and Al
prep
catal ysts acti vated at 140- 550C (Fi gure 3).
Taki ng i nto consi derati on that the dependence of ri AA on c5 does not pass through
the zero val ue, we can not excl ude the possi bi l i ty that the measurement of basi ci ty
by the sorpti on method i nvol ves a certai n proporti on of catal yti cal l y i nacti ve
si tes.
Fi gures 4 and 5 show the dependences of t- E* and ri AA on the concentrati ons of
resi dual hydroxyl groups co, , of the catal ysts, demonstrati ng cl earl y the ef f ect
of hydrati on on aci d- base properti es of al umi na. As i t can be seen, the i ncreasi ng
dehydrati on of al umi na surf ace l eads to a rapi d i ncrease i n the rate of the aci d
catal ysed depol ymeri sati on of paral dehyde (Fi gure 4). In agreement wi th sorpti on
measurements, thi s evi denced that aci di ty of al umi na i s connected wi th the de-
hydrated part of the surf ace and that chemi sorbed water i n thi s range of surf ace
coverage behaves as a catal yti c poi son of aci d si tes. I n thi s range of surf ace
166
mo I t-i n-i2
4-
2-
0_
0
4 8 12
- 18
cOH number m2 10
FI GURE 4 The dependence of catal yti c acti vi ty of al umi na i n the depol ymeri sati on
of paral dehyde (' ; A) on the concentrati on of resi dual hydroxyl groups (CO, ).
Cl Cherox 3300,m Put- al S, m Al prep. The numbers denote the acti vati on tem-
peratures of catal ysts.
coverage, the hydroxyl groups act as basi c si tes f or decomposi ti on of di acetone
al cohol at the same ti me. The rate of thi s reacti on i ncreases wi th surf ace con-
centrati on of hydroxyl groups (Fi gure 5). The hi ghest acti vi ti es are possessed
by catal ysts acti vated at 14O"C, thei r surf ace coverage by hydroxyl groups i s
about of a monol ayer capaci ty. Thi s capaci ty i s assumed f or y- al umi na to be about
12. 5 x 10180H mW2 [ZO]. The hi gher content of sorbed water excessi ng thi s capaci ty
decreases the concentrati on of strong si tes and theref ore the catal yti c acti vi ty
owi ng to the occupati on of hydroxyl groups. Thi s i s the reason of negl i gi bl e
retroal dol i sati on acti vi ty of unacti vated Cherox 3300 and Pural S catal ysts whi ch
contai n over 20% water, i n contrast to unacti vated Al
prep
catal yst wi th smal l er
water content (Tabl e 1). Thi s l owwatercontentdoesnot suf f i ce to occupy al l
basi c OH groups and theref ore thi s catal yst posses rel ati vel y hi gh acti vi ty
(Fi gure 1). However, the concentrati ons of basi c si tes cB obtai ned by the sorpti on
method do not exceed 10% of the number of present hydroxyl groups. I t i s possi bl e,
that the real number of strong basi c hydroxyl groups i s represented by a smal l
f racti on, whi ch i s proporti onal to the overal l concentrati on of hydroxyl groups.
167
2
1
Ololll:::::.. I-- I-- ---'
o 4 8 12
- 2 -18
C
OH
number m 10
FIGURE 5 The dependence of catalytic activity of alumina in the decomposition
of diacetone alcohol (rg
AA)
on the concentration of residual hydroxyl groups
(c
OH)'
() Cherox 3300, tt Pural S, at Al
prep'
The numbers denote the activation
temperatures of catalysts.
It follows from the above results, that acid-base properties of alumina depend
markedly on the degree of surface hydration and they can be influenced by acti-
vation temperature in a broad range. For all studied catalysts, independently
of their different origins, it was found that acidity of alumina increases with
increasing surface dehydration whereas maximum basicity is reached when alumina
surface is completely hydroxylated.
ACKNOWLEDGEMENTS
The authors express their thanks to Dr. L. Beranek for providing samples of
commercial catalysts and to Dr. D. Tomanova for determination of surface areas
of catalysts.
REFERENCES
1 J.B. Peri, J. Phys. Chem., 69 (1965) 220.
2 H. Knozinger and P. Ratnasamy, Catal. Rev.-Sci.Eng., 17 (1978) 31.
3 J. Medema, J.J.G.M. Van Bokhoven and A.E.T. Kuiper, J. Catal., 25 (1972) 238.
4 D.S. MacIver, H.H. Tobin and R.T. Barth, J. Catal., 2 (1963) 485.
168
5 C. Morterra, A. Chi ori no, G. Chi otti and E.
Trans. , 1 (1979) 271.
6 D. S. MacI ver, W. H. Wi l mot and J . M. Bri dges,
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72 (1969) 1050.
Garrone, J . Chem. Sot. , Faraday
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H. Uchi da, Kogyo Kagaku Zasshi ,
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