Applied Clay Science, 8 (1994) 321-330 321

Elsevier Science B.V., Amsterdam

NMR and acidity studies of dealuminated

metakaolin and their correlation with cumene
cracking

Josd Carlos D. Macedo ~, Claudio J.A. Mota ~, S6nia M.C. de Menezes b

and Vera Camorim ~
aPETROBP~S Research Centre (CENPES), Catalyst Division. llha do Fund~o, Q- 7, Cid. Univers.,
Rio de Janeiro, CEP 21949-900, Brazil
bpETROBRAS Research Centre (CENPES), Chemical Division. llha do Fund~o, Q- 7, Cid. Univers.,
Rio de Janeiro, CEP 21949-900, Brazil
(Received March 24, 1993; accepted after revision September 16, 1993 )

ABSTRACT

Metakaolin is obtained by dehydroxylation of kaolin; its dealumination is carried out with sulfuric
acid. 29Si MAS NMR studies show that a three-dimensional framework of SiO4 is formed with an
increase in kaolin calcination temperature. On the other hand, 27A1MAS NMR shows that calcination
temperatures up to 850 °C bring on a decrease of the bexa-coordinated aluminum nuclei, while tetra-
and penta-coordinated aluminum nuclei are being formed. In the range of temperatures studied, the
amount of Br~nsted sites are not constant and decrease up to 850 °C, probably because the metakaolin
structure undergoes less collapse during acid attack. A synergism between Lewis and BrSnsted sites is
suspected. Thus, it is suggested that penta-coordinated aluminum nuclei, which are strong Lewis sites,
increase the strength of Br6nsted sites. Consequently, cumene cracking activity increases.

INTRODUCTION

In 1936, the first catalyst to be used with Houdry packed beds were clay-
based. With the development of the process and use of fluid beds, clay-based
catalysts were used until the end of World War II. At that time these catalysts
were replaced by synthetic (silica-alumina) catalysts, and later by zeolitic
ones. At present a revival of research on kaolinite and halloysite clays as cat-
alysts for oil cracking is taking place (Macedo, 1990, 1992).
Upon dehydroxylation of kaolinite a water molecule is lost and a vacancy
in the lattice is created. The process results in an irregular phase named me-
takaolin. According to Rocha and Klinowski (1990), metakaolin contains a
main crystalline lattice with Q4 (n A1) units, containing one or two tetra-
coordinated aluminum atoms, probably with a residual number of OH groups
associated with them, and penta-coordinated aluminum sites, which consti-

0169-1317/94/$07.00 © 1994 Elsevier Science B.V. All rights reserved.

SSDI 0159-1 3 1 7 ( 9 3 ) E 0 0 3 2 - 7
322 J.C.D. MACEDO ET AL.

tute structural defects, with a significant number of associated residual OH

groups.
This study is an attempt to correlate cumene cracking activity with differ-
ent physicochemical parameters such as aluminum coordination state, acid-
ity and textural modifications of metakaolins, acid-leached metakaolins and
calcined acid-leached metakaolins.

EXPERIMENTALMETHODS

Kaolin was obtained from Caulim da Amazrnia S.A. (CADAM), grade

AMAZON-88. It is a material of high mineralogical purity (kaolinite content
> 97 wt%) and of narrow particle size distribution, i.e., 100% particles have
an equivalent diameter below 2 #m. X-ray diffraction patterns of this kaolin,
recorded with a Jeol JDX-8030 diffractometer at 1 ° ( 2 0 ) / m i n with Ni-fil-
tered C u K a radiation, show its layer stacking disorder. The sequence of 02•,
1 ll reflections in the range 20°-33 ° ( 2 0 ) is blurred, and in the range 35 °-
40 ° ( 2 0 ) , reflections with indices 13l, 201 occur together with the 003 basal
reflection. According to Murray and Lyons (1956), kaolin AMAZON-88 is
the tenth in a thirteen-sample diagrammatic representation of a well- to poorly-
crystallized kaolin. Chemical analysis was performed with model 975 Jarrel-
Ash equipment, by plasma emission spectroscopy technique. It is composed
of 50.4 wt% SiO2, 43.5 wt% A1203, 2.27 wt% Fe203, 1.52 wt% TiO2, 0.82 wt%
Na20, 0.70 wt% K20, 0.27 wt% P205, and 0.13 wt% CaO, after calcining at
1000°C for one hour.
Metakaolin was prepared by calcining of kaolin at temperatures ranging
from 550°C to 925 °C, generating samples M-550, M-700, M-800, M-850, M-
875, M-900 and M-925, where the figures indicate the calcination tempera-
ture. Calcining time was two hours, and calcination was carried out in atmos-
pheric air. The calcination rate was 10 ° C/min.
Metakaolin dealumination was done using a 25 wt% sulfuric acid solution
at 98°C for one hour; acid solution to metakaolin mass ratio was 3. Under
such conditions, an excess of 70% of stoichiometric quantity is used to re-
move the aluminum. At the end of the reaction, the product is filtered and
washed with sufficient water to remove aluminum sulfate and leachable im-
purities. The product is then dried in an oven at 115 ° C, generating samples
DM-550, DM-700, DM-800, DM-850, DM-875, DM-900 and DM-925, and
finally it is calcined at 550°C for 3 hours, generating samples CDM-550,
CDM-700, CDM-800, CDM-850, CDM-875, CDM-900 and CDM-925.
Chemical analysis reveals that there is no significant difference among the
acid dealuminated samples; acid leaching removes mostly iron impurities.
The dealumination yield is shown in Table 1.
Surface areas were calculated according to BET equation from data ob-
tained with ASAP 2400-Micromeritics equipment. The samples were pre-
NMR AND ACIDITYSTUDIES OF DEALUMINATEDMETAKAOLIN 323

TABLE 1

Dealumination yields and surface areas of dealuminated metakaolin samples calcined at 550 °C for 3
hours

Dealumination Surface area

yield (wt%) (m2/g)

CDM-550 60 94
CDM-700 57 85
CDM-800 59 114
CDM-850 62 243
CDM-875 65 272
CDM-900 57 237
CDM-925 47 54

treated at 200°C for 2 hours. They are shown in Table 1.27A1 MAS N M R
were taken on a Varian VXR-300 at 78.1 MHz with a 0.7 gs ( ~ ~r/12) pulse
width, 0.2 S relaxation delay, and about 12,000 scans. Impregnation of the
samples with acetylacetonate (ACAC) was tried to verify the presence of con-
densed hexa-coordinated aluminum atoms, invisible to NMR. 29Si MAS N M R
were taken on the same apparatus at 59.6 MHz with a 8.2 #s (~t/2) pulse
width, 20.0 s relaxation delay, and about 500 scans. Finally, after pyridine
chemisorption, the calcined acid-leached samples were submitted to infrared
spectroscopy. Pyridine chemisorption was carded out on self-supported waf-
ers previously treated at 500°C, in vacuum of 10 -5 torr. The chemisorption
temperature was 150 °C and after one hour the wafer was degassed by a 10-5
torr vacuum at 150°C. Intensities of peaks at 1540 cm -~ and 1450 cm -1,
related to Br6nsted and Lewis acidities, respectively (Parry, 1963 ), were ob-
tained, using a FT-IR Nicolet model 60 SXR spectrometer.
Catalytic activity was determined by cumene cracking. The calcined deal-
uminated metakaolin samples were dried overnight at 120 ° C, and were pre-
treated in a glass U-type flow reactor at 500°C for 30 minutes with 38 m l /
rain of nitrogen flow. The temperature was decreased to 370 °C and the nitro-
gen flow was driven into a saturator, kept at 30°C, containing cumene (iso-
propylbenzene). The products, basically propene and benzene, were analysed
by on-line capillary gas chromatography using a Hewlett-Packard model 5890
A apparatus, and activity was taken after 5 minutes on stream. The activity
was calculated assuming differential reactor kinetics as a = x'Fc~m/w'S, where
a is the activity ( g m o l / m 2- rain ), x is the conversion (wt%), Fcum is the molar
flow of cumene ( # m o l / m i n ) , w is the weight of calcined dealuminated me-
takaolin dried overnight at 120°C (g), and S is the surface area (mE/g).
324 J.C.D. M A C E D O E T AL.

RESULTS A N D DISCUSSION

MAS-NMR studies

Figures 1 and 2 show the spectra for metakaolin obtained at 700°C and
925°C, respectively. For kaolin, 29Si MAS N M R shows an unique peak at
- 91.5 ppm, corresponding to Q3 (Rocha and Klinowski, 1990). This peak
shifts towards more negative values upon calcination. Also peak broadening,
as a direct consequence of structural disorder, can be observed. Such shifts
are known for various silicates (Plee et al., 1985) and depend on several
structural parameters. In short, it reflects the formation of Q4 environment
which predominates into the silica phase already built up at 925 ° C.
After acid leaching, the structure becomes more ordered; this is evidenced
by the narrowing of the band related to 29Si. The extent of the effect depends
on the temperature at which metakaolin was obtained, as shown in Figs. 1A
and 1B. One might state that the higher the calcination temperature of kaolin,
the less pronounced is the effect.
M-700 - M-925
- - - - - -

.......... DI~-700
- CDM-700/550
A ..... DM-925
-- CDM-925/550_
B

/i?J \\h]
.-' / / /,/\
j
•
,)y x ~;'X
'\ ,,
//(i --\
f
ITIIIIIIHIIIIIIIIIIIIIIIIIIITITIIIIIItt 1HI IlIIIIIII[I[tlIrlH ItI[IFIIItIll[IIIIH 111111~1111
90 -lOOppM-llO -!20 -80 -gO -100 110 120
PPM

Fig. 1. 298i MAS N M R for the series obtained from kaolin calcined at 700°C (A), and at 925 °C
(B).

El
,T
-'~

[]

%
/
/-
®f---®..

k/

~J
J
/

N~. --E]J N
fi3"--..~.~3 j E ]"
A/ ......... ®
m

550 625 7(~3 775 8,~) 9~5 "r(oc)

Figs. 2 and 3. Populations of 4- ( © ) , 5- ( & ) and 6-coordinated AI nuclei ( [] ) versus temper-

ature for metakaolin samples and acid-leached metakaolin samples, respectively.
NMR AND ACIDITY STUDIES OF DEALUMINATEDMETAKAOLIN 325

Calcined acid-treated samples showed the same general trend. Calcination

of the acid-treated metakaolins still determines the increase of the SiO4 tet-
rahedra three-dimensional network formation up to 800°C, although to a
smaller extent.
27A1 MAS N M R spectra show that kaolin contains only hexa-coordinated
aluminum nuclei with one well-defined peak at 0 ppm, while metakaolin and
acid-leached metakaolin contain hexa-coordinated aluminum atoms as well
as tetra-coordinated (50-60 ppm), and penta-coordinated ones (30-50 ppm).
Lippmaa et al. ( 1986 ) described the occurence of a peak for andalusite at 32
ppm related to penta-coordinated aluminum nuclei.
Kaolin calcined at temperatures ranging from 550 to 850°C shows a signif-
icant decrease of the signal related to hexa-coordinated aluminum. Simulta-
neously, a great increment of intensity took place on peaks related to nuclei
of tetra- and penta-coordinated aluminum. Over 850 ° C up to 925 ° C, the peaks
for tetra- and penta-coordinated aluminum decreased, as can be seen in Fig. 2.
Spectra of acid-leached samples (Fig. 4) indicate that leaching of penta-
coordinated aluminum was prefered. Figure 3 shows a very low penta-coor-
dinated aluminum nuclei content for different kaolin calcination tempera-
tures. Additionally, trends for both tetra- and hexa-coordinated aluminum
nuclei were the same before. In fact, DM-925 sample was already displaying
a very low population of tetra-coordinated aluminum nuclei; consequently,
the amount of hexa-coordinated aluminum nuclei was very high, emphasiz-
ing the segregation of a new alumina-rich phase. Acid attack supports the ap-
pearance of an amorphous silica phase, which propably encouraged the reor-
ganization of such an alumina-rich phase.
Finally, calcined acid-leached samples showed a somewhat distinct trend,
as shown in Fig. 5. There, well-defined maximum and minimum amounts of
aluminum atoms of different coordination states were detected. Also, penta-
coordinated aluminum nuclei were formed as well. At 800 ° C, the sum of tetra-
and penta-coordinated aluminum nuclei is highest and the amount of hexa-
coordinated aluminum nuclei is lowest. In spite of the different shape of such
a plot when compared with Figs. 2 and 3, it is suspected that calcination of
acid-leached metakaolins favors the rearrangement of their framework, in
trying to regenerate the former metakaolin structure.
To verify if all the aluminum was N M R active, and, therefore, visible in
the spectra, samples were impregnated with ACAC. The percentage of hexa-
coordinated aluminum nuclei thus obtained was much higher than that the-
oreticaUy possible. Due to the previous acid treatment, the metakaolin struc-
ture might become weak enough to undergo reaction with ACAC, which would
be removing tetra-coordinated aluminum atoms from the framework. Since
dealumination of metakaolin samples was carded out under severe condi-
tions, it was not expected that aluminum species other than those belonging
326 J.C.D. MACEDO E T AL.

A C

i,

Itlt]llrpllllllrlrilrllllllll irll ~pll i i i i i I ii i ii i,,111 llllll l

100 0 -100 100 0 -100
PPM PPM

D F

I llill I1~ I~1 I plwnr!vl yl n i I p f ~ I [ v T I ] r rw~,'~'r'v ~

1!:x) 0 ! -100 foo 100 0 - 100
PPM PPM PPM

Fig. 4. 27A1MAS NMR for acid-leached metakaolins obtained at 550°C (A), 700°C (B), 800°C
(C), 850°C (D), 875°C (E) and 925°C (F).

B
iA

s~o r~s 75o ~ ~ 9~5 ¥("c) s~o ~s ~ 7-~ e~o 9~5 ~¢ocl

Fig. 5. Populations of aluminum atoms of different coordination states for acid-leached metak-
aolin samples calcined at 550°C for 3 hours. (A) 4-coordinated A1 nuclei ( O ) , 5-coordinated
A1 nuclei (ZX), and 6-coordinated Al nuclei ( [ ] ) . (B) Sum of 4- and 5-coordinated A1 nuclei
( O ), and 6-coordinated A1 nuclei ( [] ).
NMR AND ACIDITY STUDIES OF DEALUMINATED METAKAOLIN 327

to the crystalline structure be present. Thus, all the aluminum is believed to

bc N M R active, rendering support to our discussion.

Infrared spectroscopy

Acid-leached metakaolin samples calcined at 550°C for 3 hours were spec-

troscopically analysed after saturation with pyridinc. BrSnstcd and Lewis
acidic siteswcrc observed. Figure 6 shows that the percentage of BrSnstcd
acidity decreases with the increase of the calcination temperature of kaolin
up to 850°C.
BrSnsted acidic sites may be originated from broken bonds on edges of the
lattice or even from dehydration of the grid which may become hydrated,
providing the formation of acidic sites by deprotonation (Hanna and Soma-
sundaran, 1979 ). Upon greater stability of the structure, denoted by the de-
crease of hexa-coordinatcd aluminum nuclei ariscd from the increase in ka-
olin calcination temperature, it is expected that collapse will be less so that
BrSnsted acidity will become smaller. Such structural collapse was also ob-
served by Aglictti et al. (1988) whose studies were based on infrared spec-
troscopy upon dealuminated samples obtained at 170 °C with 1N sulfuric acid
solution.
Above 850°C, however, the percentage of BrSnsted acidity increases. The
lattice rearrangement to form a new silica-alumina phase probably reduces
the homogeneity of the crystalline strucutre. Thus, acid attack favors its col-
lapse to a greater extent, consequently increasing BrSnsted acidity.
Nevertheless, for the whole range of calcination temperatures studied, Lewis
acidity is stronger than BrSnsted acidity, determining the shape of Fig. 7 where
the total acidity is shown. Since the crystalline lattice for metakaolin is mainly
formed by Q4 (n A1) units, containing one or two tetra-coordinated alumi-
num atoms (Rocha and Klinowski, 1990), a partial removal of such atoms
from that grid imparts a negative charge to the lattice, forming Lewis acidic

"~4
T

Fig. 6. Relativeamount of BrSnstedacidicsites versustemperaturefor acid-leachedmetakaolin

samples calcinedat 550°C for 3 hours.
328 J.C.D. MACEDO ET AL.

"o

iio
..J ®

Fig. 7. Total acidity versus temperature for acid-leached metakaolin samples calcined at 550 °C
for 3 hours.

"~0.7I
. o.d
~o.54

o:1

Fig. 8. Cumene cracking activity versus temperature for acid- leached metakaolin samples cal-
cined at 550°C for 3 hours.

sites in the fraction of the remaining aluminum atoms. Van Olphen ( 1977 )
ascertained a similar effect with kaolin. Consequently, the same trend ob-
served for the sum of tetra- and penta-coordinated aluminum nuclei applies
to the total acidity of the samples. The acid-leached metakaolin which was
obtained at 800 °C presents the highest acidity while its amount of hexa-co-
ordinated aluminum atoms is the lowest.

Cumene cracking activity

Figure 8 shows activity in terms of calcination temperature of kaolin for

acid-leached metakaolin samples calcined at 550 °C for 3 hours.
Activity is seen to be fairly correlated with total acidity but not linearly. It
has been extensively reported that cumene cracking is dependent on Br/Snsted
acidity (Corma and Wojciechowski, 1982; Guisnet, 1985). However, a plot
of Br6nsted acidity versus activity did not show a good linear correlation
either, although the activity increases with the increase of Br/Snsted acidity.
On the other hand, BrSnsted acidity correlates well with the amount of tetra-
NMRANDACIDITYSTUDIESOFDEALUMINATEDMETAKAOLIN 329

o
Q6-
c
E
0,5-

o
~0.4-

> 0.3-

0.2- /
4 - plus 5-coordinated aluminium
( arbitrary unlts)

Fig. 9. Sum of 4- and 5-coordinated aluminum nuclei versus activity for acid-leached metaka-
olins calcined at 550°C for 3 hours.

coordinated aluminum nuclei. The sum of tetra- and penta-coordinated alu-

minum atoms is highest for the sample obtained from kaolin calcined at 800 oC
(CDM-800). That sample also displays maximum activity under cumene
cracking.
Young et al. (1992) proposed that penta-coordinated aluminum atoms are
strong Lewis acidic sites and confer an increase of activity for butene isomer-
ization on alumina catalysts. On the other hand, Carvajal et al. (1990) and
Nock and Rudham (1987) ascertained that superacidity caused by the syn-
ergism between BrSnsted and Lewis acidic sites can explain the differences in
activity for n-hexane and cumene cracking on Y-zeolite. Thus, one might as-
sume that such a synergism is believed to occur with acid-leached metakaolin
samples. Furthermore, there is a fairly good correlation (Fig. 9) between ac-
tivity and the sum of tetra- and penta-coordinated aluminum nuclei of cal-
cined acid-leached metakaolin samples, where the coeficient is 0.978. We thus
suggest that penta-coordinated aluminum nuclei as strong Lewis acidic sites
might increase the strength of the Br6nsted acidic sites mainly associated with
tetra-coordinated aluminum atoms. Accordingly, cumene cracking activity on
calcined acid-leached metakaolin samples is expected to increase.

CONCLUSION

Both acid treatment and calcination of the acid-leached samples support

segregation of a silica-rich phase. Acid treatment removes predominantly
penta-coordinated aluminum atoms while calcination of the dealuminated
330 J.C.D. MACEDO El" AL.

samples tries to regenerate the former metakaolin structure; calcined acid-

leached samples once again present penta-coordinated aluminum nuclei.
There is a generation of Lewis and BrSnsted acidic sites with the removal
of aluminum atoms from the metakaolin structure. However, the activity of
cumene cracking on dealuminated samples is not solely determined by their
acidity. This is more likely correlated to the sum of tetra- and penta-coordi-
nated aluminum nuclei. We may thus suggest that penta-coordinated alumi-
num atoms increase the strength of the BrSnsted acidic sites mainly associ-
ated with tetra-coordinated aluminum atoms. Accordingly, the activity for
cumene cracking on calcined acid-leached metakaolins increases.

REFERENCES

Aglietti, E.F., Lopes, J.M.P. and Pereira, E., 1988. Structural alterations in kaolinite by acid
treatment. Appl. Clay Sci., 3: 155-163.
Carvajal, R., Po-Jen, C. and Lunsford, J.H., 1990. The role of polyvalent cations in developing
strong acidity. A study of lanthanum-exchanged zeolites. J. Catal., 125:123-131.
Corma, A. and Wojciechowski, B.W., 1982. The catalytic cracking of cumene. Catal. Rev. Sci.
Eng., 24( 1 ): 1-65.
Guisnet, M., 1985. Characterization of acid catalysts by use model reactions. In: B. Imelik (Ed-
itor), Catalysis by Acids and Bases. Elsevier, Amsterdam, pp. 283-296.
Hanna, H.S. and Somasundaran, P., 1979. Equilibration of kaolinite in aqueous inorganic and
surfactant solutions. J. Colloid Interface Sci., 70 ( 1 ): 181-191.
Lippmaa, E., Samoson, A. and Magi, M., 1986. High-resolution 27A1NMR of aluminosilicates.
J. Am. Chem. Soc., 108: 1730-1735.
Nock, A. and Rudham, R., 1987. Enhanced cracking activity of dealuminated Y zeolites. Zeo-
lites, 7: 481-484.
Macedo, J.C.D., 1990. Kaolin-containing fluid cracking catalyst. EP-358261, 10 pp.
Macedo, J.C.D., 1992. Avalia~o de catalisadores de craqueamento contendo fosfato de alumi-
nio sintetizado a partir de caulim. In: Actas, XIII Simp6sio Iberoamericano de Catalisis.
Sociedad Iberoamericana. Segovia, 2:1141-1144.
Murray, H.H. and Lyons, S.C., 1956. Correlation of paper-coating quality with degree of crystal
perfection of kaolinite. Clays Clay Miner., 5:31-40.
Parry, E.P., 1963. An infrared study of pyridine adsorbed on acidic solids. Characterization of
surface acidity. J. Catal., 2: 371-379.
Plee, D., Borg, F., Gatineau, L. and Fripiat, J.J., 1985, High- resolution solid-state 27A1and 295i
nuclear magnetic resonance study of piltared clays. J. Am. Chem. Soc., 107: 2362-2369.
Rocha, J. and Klinowski, J., 1990. Solid-state NMR studies of the structure and reactivity of
metakaolin. Angew. Chem. Int. Ed. Engl., 29 (5): 553-565.
Van Olphen, H., 1977. Clay Colloid Chemistry. Wiley, New York, 218 pp.
Young, H., Coster, D., Chert, F.R., Davis, J.G. and Fripiat, J.J., 1992. Aluminum coordination
and Lewis acidity in aluminas and steamed zeolites. Preprint 10th Int. Congr. on Catalysis,
Budapest, pp. 189-191.