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Influence of LOI on Alumina Dissolution in Molten Aluminum Electrolyte

Chapter · May 2014

DOI: 10.1002/9781118448847.ch1h

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 Influence of LOI on Alumina Dissolution in Molten Aluminum Electrolyte

Youjian Yang, Bingliang Gao, Xianwei Hu, Zhaowen Wang, Zhongnin Shi

School of Materials & Metallurgy, Northeastern University, Shenyang (China)

Abstract: Alumina dissolution in molten aluminum electrolytes has

been a subject of intensive studies, and its relation to the alumina
physical properties had been attempted through various studies over
past decades. In this paper, influence of alumina LOI (loss on
ignition) on the dissolution behavior of alumina in cryolite-based
melts was investigated. The see-through cell approach was used to
observe dissolution behavior of alumina. It is concluded that higher
alumina LOI led to faster dissolution rate. The other factors, such as
crystal structures of alumina, grain size, were also considered and
discussed in this study.

Introduction
Today, aluminium fluoride, AlF3 is the most widely used bath additive in industrial cells. It
has several beneficial effects such as improving the current efficiency (CE) by reducing the
metal solubility in the bath and lowering the bath temperature [1]. During the past 110 years,
the AlF3 content in the molten bath of industrial cells has been gradually increased from
the slightly basic electrolyte (NaF/AlF3 molar ratio >3.0) to the strong acidic electrolyte
(NaF/AlF3 molar ratio approximately equal to 2.2). This reduces the bath temperature from
about 1000oC to 950oC [2-3]. However, the addition of AlF3 and the other additives (such as
LiF, MgF2, CaF2) decrease alumina solubility [1]. The alumina feeding strategy has to be
changed to keep the alumina concentration at a lower level. Therefore, the dissolution rate
of the alumina used in the electrolysis process becomes more and more important.
In this paper, influence of alumina LOI (loss on ignition) on the dissolution behavior of
alumina in cryolite-based melts was investigated. Besides bath temperature and bath
composition, dissolution rate of alumina depends on its physicochemical properties such as
particle size distribution, density, specific surface area, crystal structure, and LOI.

Experimental
Chemicals
Reagent chemicals, CaF2 (99%), LiF (99%), NaF (99%), Na3AlF6 (98%) were
commercially available and used after drying for 4 hours at 400oC.
AlF3 was prepared by following method: AlF3.3H2O mixed with NH4F (70:30, wt %) was
dried for 2h at 150oC, then 2h at 250oC, and finally kept for at least 3h at 500oC.
The preparation route for aluminas with different LOI was the dehydration of gibbsite for 1
hour at different temperatures.
All chemicals after dry treatment were stored in a dry box.
____________________
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1
Experimental method and apparatus for alumina dissolution rate measurement

With an established alumina refinning process, the particle size distribution of alumina is
stable in general. The average grain size of alumina samples is between 60 to 70um,
belonging to intermediate alumina.
The experimental apparatus of dissolution behavior is shown in Figure 1. A single-
chamber quartz crucible containing electrolyte is located in a resistance-heated furnace.
Quartz glass windows on sides of resistance furnace were used for observing the
experimental phenomena. After the electrolyte was melted, the dissolution process of the
sample in the electrolyte was recorded by a video recorder. A temperature controller
(DWT-702) with a Pt-PtRh10 type thermocouple was used for measuring and controlling
temperature of the furnace. The sample was added by a corundum tube with a funnel. The
solubility and dissolution rate of the sample in the aluminum electrolyte can be obtained by
recording charging weight, feeding time and dissolution time .

6 1
3
2
8
5

Figure 1. The experimental apparatus of the transparent cell.

1: resistance-heated furnace, 2: quartz glass window, 3: quartz
crucible, 4: charging pipe, 5: camera, 6: thermocouple,
7: temperature controller, 8: adjustable light source.

The composition of the electrolyte is shown in table I. 200 grams of electrolyte were added
into the quartz crucible. Temperature was controlled at 955±1oC during the experiment,
giving the electrolyte an initial superheat above liquidus of about 3oC. 2 grams of alumina
sample was charged into the transparent molten salt at one time. When the previous
alumina had been completely dissolved and the temperature returned to the constant 955oC,
another addation was done until newly added sample dissolved slowly or crucible was
seriously damaged by bath corrosion.

2
 Table I. Composition of the cryolite used.
Component Percentage（wt%）
Na3AlF6(CR=2.4) 91
LiF 5
CaF2 4
Theoretical Liquidus 1225K

Results And Discussion

LOI of aluminas prepared at different temperature

Figure 2 shows the LOI of aluminas prepared at different temperatures.
3.5

3.0

2.5

2.0
LOI /%

1.5

1.0

0.5

0.0

800 850 900 950 1000 1050 1100

o
Calcination temperature / C
Figure 2. LOI of alumina samples calcined at different temperatures.

Dissolution performance of γ-Al2O3(calcined at 800℃for 1h)

The structure of alumina obtained from dehydration at 800℃ is mainly γ-Al2O3 phase
according to XRD. As the alumina concentration in the cryolite rises, the dissolution time
of newly added sample gradually increases as is shown in Figure 3.

3
 20

18

16
Dissolution time / min

14

12

10

4
1 2 3 4 5 6 7
Alumina concentration in bath / %

Figure 3. Dissolution performance of alumina(calcined at 800℃ for 1h).

Dissolution rate of aluminas with different LOI

As is shown in the Figure 4, the higher LOI of the alumina, the faster it dissolves. This is
because of the high activity of low-temperature calcined alumina such as γ-
Al2O3(800℃,1h). With the increase of calcination temperature, the crystal form changes
fromγphase to α phase causing the activity of alumina decreases gradually. The structure
of sample prepared from calcination at 1373K is mainly α phase, therefore the sample
showed the lowest dissolution rate.

4
 40 LOI
0.154
35 0.461
1.01
30 1.91
Dissolution Time(min)

3.14
25

20

15

10

0 1 2 3 4 5 6 7 8 9 10
Alumina Concentration(wt%)

Figure 4. Comparison of 5 samples of alumina with different LOI.

Influence of specific surface area on dissolution rate of alumina

Besides crystal structure change, heating temperature for gibbsite dehydration also affects
the specific surface area of alumina. The BET surface area of alumina samples was tested
with a ASAP 2020 V3.01 H analyzer. The BET surface area of alumina is proportional to
LOI as is shown in Figure 5. The specific surface area of alumina works on the dissolution
process by affecting the contact area between alumina particle and molten cryolite.

90

80

70
BET Surface Area(m2/g)

60

50

40

30

20

10
0.0 0.5 1.0 1.5 2.0 2.5 3.0
LOI(wt%)

Figure 5. The relationship between BET surface area and LOI of alumina

5
LOI on average dissolution rate
Under low alumina concentration, the dissolved alumina have little affect on dissolution
rate of newly added alumina. The time interval between each addition is almost same,
indictated in figure 6(a). Ignoring the affects on newly added alumina caused by dissolved
alumina, the average dissolution rate of the alumina samples, which is the linear fitting
slopes of the curves in Figure 6 (a), is shown in Figure 6 (b).
9
a 1.91 1.01
8
3.14
7
0.461
6

5 0.154
W(Al2O3)%

-1
0 20 40 60 80 100 120 140 160
Total dissolution time for different alumina samples(min)
0.080
b
0.075
Average Dissolution Rate(Al2O3%/min)

0.070

0.065

0.060

0.055

0.050

0.045

0.040
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
LOI
Figure 6. Average dissolution rate of alumina samples with different LOI

The curve in Figure 6 (b) shows that alumina dissolves faster with higher LOI. When LOI
increase from 0 to 3(wt%), the average dissolution rate of alumina speed up. Although high
6
 LOI leads to high fluorine emission, the recovery efficiency of dry scrubbing system in
aluminum smelter will solve this problem. Alumina with higher LOI might be considered
as raw feeding materials for low temperature aluminum electrolysis.

Conclusions
Aluminas prepared at different calcination temperature have great difference in BET
surface area and LOI. The difference directly lead to the different dissolution rate of
alumina. The alumina dissolves faster with higher LOI, which means alumina with high
LOI is a more suitable raw feeding material for low temperature aluminum electrolysis.

Acknowlegement
The authors would like to acknowledge the financial support by “National Basic Research
Program of China (No.2007CB210305)” and “Nation Science & Technology Pillar
Program (No.2009BAE85B01)”.

REFERENCES

[1]. Qiu, Z., The Principle and Application of Aluminum Electrolysis, (The Press of
Chinese Mining University, Beijing, 1998).
[2]. Qiu, Z., “Development of bath acidity in aluminum electrolysis”, Aluminium, 74, 345-
348 (1998).
[3]. Cassayre, L., Palau, P., Chamelot, P., Massot, L., “Properties of Low-Temperature
Melting Electrolytes for the Aluminum Electrolysis Process: A Review”, Journel of
Chemical & Engineering Data, 55 (11), pp. 4549-4560 (2010).

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