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John Karlstrm
Department of Chemical Engineering II, Lund University, P.O. Box 124, SE- 221 00 Lund, Sweden
A reactor model was developed to simulate the production of aluminum fluoride from
fluosilicic acid and aluminum hydroxide in a semibatch reactor. The reaction
mechanism was determined and a kinetic model was combined with the material and
energy balances to create a reactor model. The reactor model was used to study the
effects of the preheating temperature of fluosilicic acid and aluminum hydroxide, the
concentration of fluosilicic acid as well as the grain size of aluminum hydroxide.
Introduction
Aluminum fluoride is used in many industrial
processes. It is one of the minor constituents added
to the electrolytic cells during the production of
metallic aluminum. It is also used in the preparation
of white enamels, as an anti-reflection coating in
complex optical systems, as a constituent in welding
fluxes, and in the preparation of fluorine containing
glasses, (Gernes, 1962).
The present study was carried out with the aim to
investigate the reaction between fluosilicic acid and
aluminum hydroxide under the production of
aluminum fluoride and silica. The process for
production of aluminum fluoride and silica is
schematically depicted in Figure 1.
The total process of fluosilicic acid interaction
with aluminum hydroxide can be described by the
following overall reaction:
H2SiF6 + 2 Al(OH)3 2 AlF3 + SiO2 + 4 H2O
(I)
(II)
Al(OH)3
Reactor
Filter
(IV)
Crystallization
AlF3
H2SiF6
SiO2
(1)
(2)
r3 = k3 * CB * CD
(3)
k1 = k01 * exp(-E1/(R*T))
(4)
100
k2 = k02 * exp(-E2/(R*T))
(5)
k3 = k03 * exp(-E3/(R*T))
(6)
)
C
(
e
r
u
t
a
r
e
p
m
e
t
simulation
95
90
85
80
75
70
65
60
100
200
300
400
500
600
reaction time(s)
700
800
900
1000
(II)
C + 6 G 2 F + 3 E + 12 D
(III)
12 D + 4 B 4 F + 12 G
(IV)
(1)
r2 = k2 * CC * CG
(2)
r3 = k3 * CB * CD
(3)
(7)
Material balances
The reaction cycle of the model has been the
basis of the whole investigation. In this model
fluosilicic acid is pumped into the reactor initially, at
the time t0, with a constant flow. At the time t1 the
start of pumping aluminum hydroxide into the
reactor with a certain flow takes place. The flow of
aluminum hydroxide is decreased at t2, the so called
fine feeding is started. At the times t3 and t4 the feed
of aluminum hydroxide and fluosilicic acid,
respectively, are stopped. At the latter time the
double amount of aluminum hydroxide in relation to
fluosilicic acid has been pumped into the reactor. In
other words the reaction is performed
stoichiometrically. After the time t4 the reaction
proceeds until emptying of the reactor takes place at
t5. In Table 1 all the time points of the different
moments are presented.
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
Operation
Start of acid filling, t0
Start of hydrate filling, t1
Start of fine feeding of hydrate, t2
Stop of fine feeding of hydrate, t3
Stop of acid filling, t4
Emptying of reactor
Time
0s
37 s
78 s
90 s
128 s
700-800 s
Thermodynamic data
In the model H f-values of the components are
used to calculate the heat of reaction of the three
reactions. Although the temperature increases during
the reaction the H f-values at 25C will be used.
The Hf- and Cp-values of the components are
presented in Table 2.
Component
H2SiF6 (aq)
Al(OH)3 (s)
Al2(SiF6)3 (aq)
HF(aq)
SiO2 (s)
AlF3 (aq)
H2O (aq)
Hf (J/mol)
-2331300, HA
-1276000, HB
-8066300, HC
-333000, HD
-847300, HE
-1510000, HF
-286000, HG
Cp (J/(K*mol))
94, Cp1
93, Cp2
-107
44
75
75
estimated value
(24)
(25)
(26)
(28)
H = Cpmix*
ni * T
A
(29)
Time (s)
2200
2000
1800
1600
1400
1200
1000
800
600
400
200
0
50% conversion
95% conversion
45
50
55
60
65
70
75
80
85
90
0
0
100
200
300
400
500
600
reaction time(s)
700
800
900
1000
)
l
/
l
o
m
(
n
o
i
t
a
r
t
n
e
c
n
o
c
1000
50% conversion
800
95% conversion
600
400
200
0
15
20
25
30
35
40
)
l
/
l
o
m
(
n
o
i
t
a
r
t
n
e
c
n
o
c
0
0
100
200
300
400
500
600
reaction time(s)
700
800
900
1000
Literature cited
1. Donald C. Gernes, Producing aluminum fluoride, patent
US 3,057,681, Oakland, California, 1962.
2. Arankathu Skaria, Felix Hartmann, Process for
producing aluminum fluoride, patent GB 2,049,647,
London, England, 1980.
3. L. D. Skrylev, Kinetics and mechanism of interaction of
fluosilicic acid with aluminum hydroxide, Zh. Prikl.
Khim, 1966 , 39(1), 58-64. Journal written in Russian.
4. G. E. Dmitrevskij, E. B. Semenova, Kinetics of
fluosilicic acid interaction with aluminum hydroxide,
Odess. Gos. Univ. im. Mechnikova, Odessa, USSR.
Izv. Vyssh. Ucheb. Zaved., Khim. Khim Tekhnol,
1970, 13(7), 960-962. Journal written in Russian.