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In the smelting of aluminium, HF fumes are produced that are subsequently trapped by absorption onto alumina.
The factors that affect the adsorption capacity of alumina have been studied previously and are weU established,
but the mechanism by which H F adsorbs onto the alumina surface is not well understood.
In this study, x-ray photoelectron spectroscopy (XPS)was used to investigate the nature of the surface adsorp
tion of HF on alumina. XPS is particularly weU suited to the study of this type of gas adsorption process.
Laboratory-prepared samples were studied with particular interest in evidence for AI-F bonding, or in fluoride
species formed by reaction with -OH or -0. Also of interest was the role of sodium, since it is segregated to the
surface of the alumina during calcination.
AI-F bonding was observed on only one sample type. An AI-F interaction was identified when the alumina had
been predried and dry HF was adsorbed. When moisture was present no AIF, formation was observed. This
suggests that under conventional conditions (i.e. moisture present) the adsorption of HF involves a weak inter-
action, probably hydrogen bonding, with intermediate layers of water. After heating the samples containing weakly
bound HF to 500 “C, no Al-F interaction was observed. Much of the HF was desorbed at 700 O C .
An Na-F interaction was observed in all fluoride-adsorbed samples; however, this can only account for a small
proportion of the total fluoride adsorbed.
adsorbed onto alumina. The efficiency of the scrubber H F is directly bound to the surface hydroxyl groups
will depend to a large extent on the fluoride adsorption since surface hydroxyl content (as determined by mois-
capacity of the alumina. ture on ignition) has a greater effect on HF capacity
Cochran et al.’ studied the adsorption of H F on than humidity. Coyne et al.’ found that the H F adsorp-
alumina. They found that the chemisorbed fluoride is tion capacity of alumina increased slightly with increas-
initially ‘amorphous’ but forms AIF, on heating. ing residual sodium content.
Cochran’ later postulated that the chemisorption of a One of the commercial processes for manufacturing
monolayer of H F on Al’O, takes place by the forma- AlF, is by the reaction of H F with Al(OH), at high
tion of F(O), tetrahedrons with H + as a central cation. temperatures (500-600 “C).’ In the HF adsorption
He suggested that at high temperatures this is converted studies referred to above,’-’ no direct evidence of the
into AlF, . He also commented on the role of sodium in formation of AIF, has been found at lower tem-
the adsorption and concluded that there was insufficient peratures (20-120 “C)comparable to those in dry scrub-
total sodium present to account for more than a small ber units. It appears that formation of AIF, by the
proportion of the fluoride to be adsorbed by reaction reaction of H F with alumina has not been identified
with sodium. except at elevated temperatures.
More recent studies on the mechanism of H F adsorp- This paper reports new studies using x-ray photoelec-
tion have generally concluded that water is involved in tron spectroscopy (XPS)to determine whether AlF, can
the adsorption process. be detected in samples prepared by the adsorption of
Lamb3 found that multilayers of HF are adsorbed H F on alumina under conditions of varying humidity.
and that water vapour has a large influence on the Evidence of an Na-F interaction was also sought. Al-F
amount of HF that can be held. Initial adsorption of interactions were identified only when the alumina had
HF on alumina takes place by reaction with surface been predried. When moisture was present, as in the
sodium and with surface hydroxyl groups, with the earlier studies, no AIF, formation was observed. Na-F
hydroxyl groups being substituted by fluoride. Further bonding was observed in all fluoride-adsorbed samples;
adsorption then takes place by another mechanism to however, this can only account for a small proportion
0142-2421/92/240139-06 $08.00
0 1992 by John Wilcy & Sons,Ltd.
140 R. G. HAVERKAMP ET AL.
of the total fluoride adsorbed. The work reported here allowed variable gas concentrations of hydrogen fluo-
deals only with adsorption of H F and H F / H 2 0 gas ride in nitrogen to be produced. Warming of the H F
mixtures but not with aluminium reduction pot off cylinder was required to maintain sufficient pressure of
gases, which also contain particulate sodium aluminium HF gas. The exhaust gas was bubbled into a solution of
fluorides. In an earlier paper9 we reported XPS studies TISAB with a fluoride electrode monitoring the pres-
on fluorinated alumina where Na-F bonding was iden- ence of dissolved fluoride.
tified and HF was shown to desorb on heating rather Two samples were prepared from a batch of
than form AIF, . commercial-grade aluminium-smelting-feed alumina.
For the first of these, DF1, the alumina was not
pretreated. This alumina had a weight loss due to
EXPERIMENTAL adsorbed water of 1.0% on heating to 300°C for 1 h.
For the second sample, DF2, the alumina was predried
for 12 h at 300°C before HF adsorption.
HF adsorption
Desorption of fluoride. The fluorinated aluminas were
Wet HF adsorption. A system for adsorbing fluoride onto subjected to heating in an electric furnace in air for 500,
alumina using aqueous hydrogen fluoride was set up 700 and lo00 "C for 1 h. The objective was to determine
based on the procedure of Coyne et aL6 The set-up is the effect of heating on the surface fluoride levels and on
illustrated in Fig. 1. A metered flow of preheated nitro- the fluoride bonding.
gen was mixed with 3.7% hydrofluoric acid solution
delivered by a calibrated syringe pump. This mixture X-ray photoelectron spectroscopy
then passed through a Teflon coil in a heated block
before passing through the heated alumina bed. The X-ray photoelectron spectra were collected using a
heated block was maintained at 120"C.The adsorption Kratos XSAM 800 spectrometer with an Mg Ka x-ray
behaviour was followed by monitoring the exhaust gas source. The presence in the analytical chamber was
fluoride content. The exhaust gas was bubbled into a typically in the 10-9-10-'0 Torr range during analysis.
solution of TISAB (total ionic strength adjustment Wide scans (0-1100 eV) of the alumina samples were
buffer) with a fluoride electrode monitoring the presence collected under analyser conditions that gave good
of dissolved fluoride. The alumina bed held up to 1 g of intensity but low-energy resolution. Narrow scans over
alumina, which was sufficient for XPS and XRD studies. the appropriate Na, F, 0, C and A1 peaks were subse-
Several samples were prepared by this method and quently collected under high-energy resolution condi-
the one referred to in this paper is labelled WF1. tions (20 eV pass energy). Binding energies (20.1 ev)
are quoted using the 2p peak of A1 and the 1s peak for
Dry HF adsorption. An apparatus for adsorbing hydro- 0. For Na and F, the Auger parameter (a')is reported.
gen fluoride gas, without added water, onto larger (80 g) This parameter is the difference between the kinetic
samples of alumina was developed. As illustrated in Fig. energy (KE) of the major Auger line and the binding
2, this consisted of a vertical bed of alumina fluidized by energy (BE) of the major photoelectron peak (the 1s
a nitrogen flow. Into this nitrogen flow, a small flow of level for both Na and F). It is more sensitive to changes
hydrogen fluoride gas was bled. This arrangement in the Na and F chemical environments than the BE of
(d)
/ \
ressure
1
'gauge
~ -- 1 (0-SOokPa)
1
alumina bed
flow teflon
meter tTbe
(0.2-2 Ilmin)
needle
valve
'teflon tee
TISAB solution
syringe pump
(HF solution)
(7 ressure
'gauge
'
i
\/'
i
,
alumina
p valves i 3 fluid bed
i
TlSAB solution
HF adsorption levels
/ \
wt.% F was obtained, corresponding to a surface F/Al
atomic ratio of 0.5: 1. For adsorption on alumina that
had been dried prior to adsorption (DF2), a very high
level of surface fluoride was achieved. The 44.8 wt.% F
corresponds to a surface F/Al atomic ratio of 2.2: 1.
Fluorination of the sample was stopped before equi-
librium was achieved. The reaction of HF with this 4f
/
.,-i "
I
,,
,
-
dried alumina was markedly exothermic, with a tem-
perature of 120 "Cbeing reached.
4
A1 2p binding energies
not a strong interaction between the H F and the surface From the width and shape of the 0 1s peak it is clear
A1 atoms. that this envelope is composed of several peaks. The
On the other hand, in sample DF2, which was dried peak at 531.8 eV is assigned to oxygen in Al,O, as well
-
prior to HF adsorption, there is a shift to higher BE of
the A1 2p peak of 1.4 eV from the unreacted alumina
value, This is clear evidence of A1-F bond formation.
as to adsorbed water, which also lies at -531.8 eV.
Another broad peak, which makes up 50% of the area,
is centred at 534.0 eV (Fig. 5). This second peak is con-
The A1 2p BE peak for the DF2 sample can be sistent with the compound 8-AIF, . 3H,O identified by
separated by computer curve-fitting into two unresolved x-ray diffraction in DF2, in which the oxygen contained
doublets, with 2p3,, peaks at 74.9 eV and 76.3 eV (Fig. in the lattice water is moved to higher BE by the adjac-
4). The area under each of these peaks is 49% and 51%, ent fluoride.
respectively. The intensity of the 76.3 eV peak is evi- For the HF-adsorbed samples where water was
dence that about half of the surface A1 atoms are present, i.e. WF1 and DF1, the 0 1s peak does not shift
involved in a strong interaction with F. from the value for pure alumina, indicating that there is
The x-ray diffraction patterns of the wet fluorinated no strong F-0 interaction (or F-OH).
alumina, WF1, and one dry fluorinated alumina, DF1, For compounds AlF, and Na,AlF,, which nominally
showed no peaks other than those due to alumina. This do not contain any oxygen, surface oxygen attributed to
indicates that the absorbed fluoride in these samples adsorbed water was detected. The 0 1s binding energies
does not form distinct crystalline compounds in SUE- for these compounds were, respectively, 533.0 and 531.8
cient quantity to be detected. It therefore supports the eV (Table 2). The approximate position for adsorbed
evidence from XPS that no AlF, is formed. The x-ray water is 531.8 eV. For AlF, the large shift in the 0 1s
diffraction pattern of the predried alumina that was peak suggests that water is structural rather than just
fluorinated (DF2) did show the presence of major surface adsorbed as with Na,AlF,.
quantities of 8-AlF, 3H20, with lesser amounts of The fluorine Auger parameters for the samples
a-AlF, 3H,O and possibly AlF,(OH). studied are listed in Table 2. There is little change in
The predried alumina may be able to react with the this parameter between the different standards, e.g. NaF
dry H F to form AlF, because the otherwise protective and AlF, , and between the samples.
layer of surface-adsorbed water has been removed.
When this layer of water is present, the fluoride is
hydrogen bonded to the water layer and is not able to Fluoride desorption
approach the aluminium or the oxygen atoms of the
alumina closely enough to enable reaction and the for- The desorption of fluoride from the fluorinated alu-
mation of AlF, . minas can be seen from the data in Table 1. Heating at
500°C for 1 h does not result in a reduction in the
surface fluoride levels. After heating at 700°C for 1 h a
0 Is binding energies significant removal of fluoride occurs, while at lo00 "C
essentially all the fluoride is removed. The desorption
The 0 1s peak position and the widths also provide behaviour is similar for all the samples.
information on changes taking place with fluorination For the WFl and DF1 samples there is no observ-
of alumina. For DF2 there is a shift in the 0 1s peak, able increase in the higher binding energy component of
relative to unreacted alumina, of +
1.2 to 532.7 eV the A1 2p peak with heating to 500"C, suggesting that
(Table 2). The peak width is 4.1 eV, which is consider- AlF, is not formed. With further heating this surface-
ably larger than the 2.8 eV of fresh, undried alumina. adsorbed HF is volatilized. For the DF2 sample, where
an Al-F interaction is already apparent, the average BE surface contains terminal hydroxyl groups (Al-OH),
of the A1 2p peak shifts to a higher value with heating, surface adsorbed water and surface segregated sodium.
indicating an increase in the proportion of aluminium X-ray photoelectron spectroscopy was used to look for
atoms involved in the A1-F interaction. The 0 1s peak an A1-F interaction in samples prepared by the adsorp-
also shifts to higher BE as the dehydration of P-AlF, . tion of H F on alumina under a variety of humidity con-
3H20 takes place to form AlF, . 2 H 2 0 and AlF, * ditions. Evidence of an Na-F interaction was also
H 2 0 , with a consequently stronger influence of fluoride sought.
on the oxygen orbitals. An Al-F interaction was observed in only one of the
sample types, i.e. the case of the alumina that had dry
HF adsorbed after being predried. When moisture was
Sodium fluoride interaction already present on the alumina, or water was present in
the H F gas stream, as in the earlier no AlF,
Sodium is involved with the bonding of some of the formation was observed. As the previous sample has
adsorbed fluoride. Coyne et aL7 found that the HF shown that when an Al-F interaction occurs we can
adsorption capacity of alumina increased slightly with detect this in the XPS spectrum, it can be confidently
increasing residual sodium content. In an earlier paperg said that there is no significant Al-F interaction in these
we reported XPS studies on fluorinated alumina where samples adsorbed with moisture present. This suggests
Na-F bonding was identified in fluorinated aluminas. that the adsorption of H F involves a weak interaction,
The sodium Auger parameters for the samples studied probably hydrogen bonding with layers of water, as
here are listed in Table 2. There is a progressive shift in proposed by other workers.,-'
the sodium Auger parameter in the order: unreacted On heating, no evidence of the formation of AlF, was
alumina > WF1 > DF1 > DF2. This shift in the Auger seen for the WF1 and DF1 samples up to 500"C, and
parameter is a result of the sodium present on the by 700°C the HF was being desorbed. For the DF2
surface of the alumina reacting with the adsorbed HF to sample, both the A1 2p and the 0 1s BEs increased with
form Na-F bonds. Despite the strong surface segrega- heating to 500 "C, indicating more Al-F interaction and
tion of sodium, even if all of the surface sodium is the dehydration of the P-AlF, 3H2O. The fluoride was
involved in HF bonding this can account for only a desorbed >700 "C for all these samples.
small proportion of the adsorbed fluoride. Na-F bonding was observed in all fluoride-
adsorbed samples; however, this can only account for a
small proportion of the total fluoride adsorbed.
CONCLUSIONS The work reported here deals only with the HF and
HF/H,O gas mixtures but not with aluminium
reduction pot off gases, which also contain particulate
We have investigated hydrogen fluoride adsorption pro- sodium aluminium fluorides.
cesses occurring at the surface of alumina. The alumina
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