LABORATORY RESEARCH AND INDUSTRIALISATION TEST ON

TWO-STAGE CONTINUOUS CARBONISATION PRECIPITATION TECHNOLOGY

FOR PRODUCING HIGH GRADE SANDY ALUMINA
Li G*, Ma D, Zhang Z, Zhang L and Fan J
Shanxi Branch of China Aluminium Corporation, China
Abstract
In order to solve the problem of the poor quality of alumina product by the traditional carbonisation precipitation and
the high loss of alumina by the deep desilication for the sintering liquor, the authors put forward Two-Stage Continuous
Carbonisation Precipitation technology (TSCCP). Both laboratory and industrialisation test results have proved that this
process has ingeniously solved the problem.
In the First Stage of Continuous Carbonisation Precipitation (FSCCP), high-grade sandy alumina is produced. In the Second
Stage of Continuous Carbonisation Precipitation (SSCCP), the alumina is charged into the slurry flash tank (130–140°C)
of the high-pressure digestion unit during the Bayer process of the Combination process. In this way, the shortcoming
of low A/C of the high-pressure digestion liquor from diasporic bauxite can be overcome, and will produce high-grade
sandy alumina. Furthermore, the process has other advantages such as increasing productivity of two-stage carbonisation
precipitation, improving the evaporation performance of spent liquor of the SSCCP (deep precipitation), reducing gallium
content in product alumina during the first stage, etc. So it is proposed that this process can be applied to alumina
refineries with a Sintering process.

1. Introduction alumina. The -45 μm particle size of product alumina by FSCCP

is reduced from the previous 20–44.7% to 9.92% and A.I. from
Because of the characteristics of diasporic bauxite (high alumina,
36% to 10.5%. Figure 3 shows the -45 μm particle size and A.I.
high silica and low ratio of A/S) in Chinese alumina bauxite
of product alumina in the pilot test, while Table 1 presents the
resources, either a Combination process or a Sintering process
main performance parameters of the product alumina. The
is mostly used in traditional alumina production in China. The
physical performance of alumina reached a level of high-grade
carbonisation precipitation process is an important part of
metallurgical quality alumina, thus demonstrating the ability of
alumina production process in both Combination and Sintering
FSCCP to produce sandy alumina in an industrial application.
processes. In the Shandong Alumina Refinery, the traditional
carbonisation precipitation process, a kind of batch carbonisation
precipitation technology that produces floury alumina, has been
successfully upgraded to continuous carbonisation precipitation
technology to produce medium-sized alumina (Xingliang, Liu,
et al., 1998, p. 185). Based on the study of the technological
characteristics of the Combination process, the author put
forward the original model of TSCCP in 1998. The process solves
a number of problems. As precipitation of seed at high A/C ratio is
difficult to achieve from the hard-to-digest diasporic bauxite in the
Bayer process, the strength of alumina product can be affected
(Dai, Chen, 1996, p. 21). To achieve product with good chemical
performance, sintering of green liquor from deep desilication and
a lowered carbonisation precipitation rate are needed.

2. Research course of main technology of TSCCP

Laboratory research, pilot and industrialisation testing for FSCCP
were completed during 2001 to 2003. Laboratory research, Figure 1. SEM of hydrate by carbonisation precipitation (radiation-shaped
pilot and industrialisation testing for SSCCP and its product branch crystal growth)
sweetening digestion were completed during 2002 to 2006.

3. Laboratory research and pilot test for producing

sandy alumina by FSCCP
Through a series of laboratory and pilot tests, a technical
breakthrough has been made for the transformation of the hydrate
structure. Traditional carbonisation precipitation produces a
branched crystal growth mode, while this new process produces
crystals with an agglomeration filling growth mode (Figures 1
and 2). This has provided the key technique of FSCCP to produce
sandy alumina. The industrialisation test results of the process Figure 2. SEM of sandy alumina by FSCCP (agglomeration filling growth)
are as follows: average 6.39% for -45 μm particle size of hydrate
to calciner; max. 11.64%, min. 5.44% and average 9.46% for
-45 μm particle size of product alumina from calciner; max.
14.5%, min. 7.6% and average 10.5% for Attrition Index (A.I.) of

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 16
14
12
10
8
6
4
2 "-45μm (% ) A .I.(% )

0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41

Figure 3. -45 μm particle size and A.I. of product alumina by industrialisation

test of FSCCP

Table 1. Main performance parameters of product alumina by

industrialisation test of FSCCP
Figure 6. SEM of product by SSCCP after technical breakthrough
45 μm A.I. B.E.T. α-Al2O3 Bulk Angle of
Surface (%) Density Repose
(%) (%) Area
Note: SEM energy spectrum analysis showed that when products
(m2/g) (g/cm3) (°) are fine dawsonite crystal appearing as irregular thread-like
9. 64 10. 5 71. 5 6.2 0. 92 31–33
shapes (Figure 5), which independently exist or adhere to the
surface of hydrate particle. These make settling, filtration and
4. Laboratory research and industrialisation test of separation difficult.
SSCCP
SSCCP at a precipitation rate of 76.12% produced a stick-shaped
Through laboratory research and pilot tests (Figure 4), a technical hydrate that settles, filtrates and separates easily (Figure 6).
breakthrough was achieved for the stable production of hydrate Product over-precipitated by SSCCP at a precipitation rate of
precipitated by the first-stage spent liquor in SSCCP. This has about 90.33% allows fine dawsonite to adhere to the surface of
shown to be helpful in the settling, filtration and separation of the product (Figure 7).
hydrate. In precipitated product, there is almost no unexpected
dawsonite (Na2O·Al2O3·2CO2·nH2O). Dawsonite is easily produced Testing proved that the technology and the product control in
using the earlier technology, and causes difficulties in settling, SSCCP of spent liquor directly affect the chemical composition of
filtration and separation. In the successful industrialisation precipitated product. Improper technology produces thread-like
test of SSCCP, the remaining Al2O3 content in spent liquor was dawsonite that is difficult for solid/liquid separation (Figure 5),
lowered to an average of 2–3g/L. The SSCCP-precipitated while the precipitated hydrate is not suitable for use because of
product is gibbsite almost without crystal impurity, while settling, the high Na2CO3 content. After being washed and filtered by hot
filtration and separation processes occurred without difficulty. water, the main physical phase Al(OH)3, when controlled by the
The industrialisation test for sweetening digestion of hydrate by refined technology, still contains trace CO32- mainly in the form of
SSCCP was also successful. dawsonite (Na2O·Al2O3·2CO2·nH2O).

4.1 Key technical breakthrough of SSCCP

Spent liquor of the FSCCP CO2 gas

Tank

Thickener

Filter Evaporation

The SSCCP production to sweetening processing

Figure 4. Illustration of pilot test of SSCCP

Figure 7. SEM of over-precipitated product by SSCCP

4.2 Industrialisation test of SSCCP

Industrialisation testing of SSCCP followed the successful
laboratory and pilot tests. From XRD the product of SSCCP is
gibbsite without crystal impurity (Figure 8). The particle size
distribution and SEM of shape of SSCCP product from this testing
are shown in Figures 9 and 11. Figure 10 graphs Al2O3 remaining
in spent liquor of SSCCP in industrialisation testing.

Figure 5. SEM of product by SSCCP before technical breakthrough

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 4.3 Sweetening digestion industrialisation test of hydrate by
SSCCP
Testing shows that gibbsite does not remain in sweetening red
mud with the same physical phase as is common in the Bayer
process. This sweetening process resulted in total digestion,
and A/C values increased 0.029–0.058 in the Bayer process
pregnant liquor. The operating conditions in the industrialisation
sweetening test are shown in Table 2.
Figure 8. Physical phase of product by SSCCP
Table 2. Operating index in industrialisation sweetening test
80 Parameter Operating Index
70
Digestion slurry flow rate (m3/h) 755
60
Sweetening temperature (°C) 138
50
˘-10μm(% ) Slurry solid content (g/L) 221
40
˘-20μm(% ) Transporting flow rate (m /h)3
17
30
˘-45μm(% )
20 The physical phase of red mud during the sweetening test consists
10 of sodium aluminosilicate, garnet hydrate, calcite, perovskite and
0 hematite.
1 2 3 4 5 6 7 8 9 10 11 12 13
4.4 The influence on evaporation process by TSCCP spent
Figure 9. Main particle size distribution of product by SSCCP in industrialisation liquor
test
Relational study results (Xiancui, Lv, et al., 2002, p. 50) indicated
a number of significant gains following the implementation of
16
14 TSCCP. Concentrations of Al2O3 and SiO2 (which are harmful
12 for evaporation) are considerably reduced, while the solubility
10
of Na2CO3 in spent liquor of SSCCP and the concentration of
Al 2 O 3 g/L

8
6 Na2CO3 in evaporation are raised. Scaling of silica slag in the
4
2
heat exchanging pipe bundle of the evaporator decreases from
0 source, thus improving evaporation efficiency and reducing
0 20 40 60 80 100 120 140 160 180 200 220 energy consumption during evaporation.
Oprating tim e,hour

Figure 10. Al2O3 (g/L) remaining in spent liquor of SSCCP in industrialisation

test
During industrialisation testing, SSCCP produced dissolvable
gibbsite, whose crystals mainly exist in the disperse form of a
single stick-shaped crystal. It has characteristics such as large
porosity, fine particle size and high activity, without thread-like
dawsonite.
The filtration testing results of SSCCP product in industrialisation
testing are as follows: average 25% for moisture of filtered cake;
average 0.7% for Na2O; and average 0.93 g/L for suspension
in filtration liquor. These results demonstrate that the filtration
4.5 Setting of dividing point for TSCCP
To determine the defining point for TSCCP, and the selection and
setting of the precipitation rate of FSCCP, the following two points
should be considered: the silica index of pregnant liquor in FSCCP,
and the customer’s required chemical composition for FSCCP
product. Testing proved that SiO2 content in product obtained
by continuous carbonisation precipitation and seed charging is
much lower than that by traditional technology (Table 3).
Table 3. Corresponding relationship between silica index in
pregnant liquor and precipitation rate
Silica Index (Al2O3/ SiO2 ) Precipitation Rate (%)

performance of SSCCP product is able to meet commercial > 500 88-90

production requirements.
451-500 87-89

401-450 86-88

376-400 84-86

351-375 83-85

326-350 80-82

301-325 79-81

251-300 77-79

In addition, the customer’s requirement on the limit of gallium

Figure 11. SEM of product by SSCCP in industrialisation test
content in FSCCP product can be considered. The research of
gallium behaviour during carbonisation precipitation (Xiaowei,
Liang, et al., 2005, p. 28) has proved that in the carbonisation
precipitation of sodium aluminate solution, the decreasing range
of gallium in solution starts to rise slightly after a precipitation
rate over 60%, and to rise further at a precipitation rate over
80%. The decreasing range of gallium content in liquor starts to
be considerably raised when the precipitation rate is controlled
over about 88%.

Thus, the dividing point can be set at about 80% in order to

produce alumina with the same chemical composition as

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 that of Bayer process product at a silica index of 370–400 in 6. Conclusions
pregnant liquor of FSCCP, but at 84% – 86% to produce common
TSCCP has good application prospects in improving product quality
alumina.
of the Combination process and the Sintering process, cutting
CO2 gas Or CO2 gas from Kiln
down energy consumption and raising yield. The technology can
Pregnant liquid
Spent liquid to be optimised by combining the flow sheet characteristics of the
evaporation
from sinter
processing
Combination process and the Sintering process to produce sandy
 alumina. This is of momentous significance in the technical
upgrading of the traditional Combination and Sintering processes
used in China.
The FSCCP The SSCCP
production to bake sand production to Acknowledgements
alumina sweetening
processing
The authors are grateful to many people who have contributed
to the work reported in this paper; particular thanks to Shanxi
Figure 12. TSCCP flow sheet
Branch, Zhengzhou Research Institute and Scientific &
5.0 Advantages of TSCCP Technological department of CHALCO and the Ministry of Science
& Technology of China.
The main advantages of TSCCP, as demonstrated during
laboratory research and industrialisation testing, are:

First of all, about 80% of TSCCP product is sandy alumina with

good chemical and physical performance, which is characterised
by low SiO2 and Ga content, coarse particle size and high
strength. Secondly, about 18% TSCCP product has high activity
and is very suitable for sweetening digestion. In a Combination
process, if sweetening digestion can be carried out in the self-
evaporation system of high-pressure digestion of the Bayer
process, TSCCP can effectively raise A/C. The over-saturation of
seed precipitation in pregnant liquor is increased and the seed
precipitation rate improved. This will create favourable conditions
for the Bayer process to produce high-grade sandy alumina. In
a Sintering process, if sweetening digestion can be carried out
by adding a medium-pressure desilication section, TSCCP will
produce high-grade sandy alumina. The high impurity content in
SSCCP product hydrate can be purified through re-decomposition
by sweetening digestion.

In comparison with the traditional Sintering process, more

Al2O3 remaining (normally 8–12 g/L) in spent liquor following
carbonisation precipitation can be recovered. This allows lower
circulation of alumina remaining in spent liquor of SSCCP,
and increased circulation efficiency for the spent liquor of
carbonisation precipitation. Thus, the alumina production
capacity in the Sintering process can be improved, while energy
consumption during clinker sintering can be reduced.

With this technology, the concentration of Al2O3 and SiO2 in the

spent liquor of SSCCP can be considerably lowered, the solubility
of Na2CO3 in liquor increased, and the scaling of silica and Na2CO
in the spent liquor evaporator noticeably reduced, which provides
material conditions for effective energy saving in evaporation.

The requirement for the silica index (Al2O3 / SiO2) of pregnant

liquor of carbonisation precipitation in the Sintering process
can be lowered, and even the deep desilication section can
be eliminated. This can decrease the circulation of alumina
remaining in silica slag (product of deep desilication), as well
as energy consumption during sintering. Correspondingly, it can
lower the water content added to the system by deep desilication
agents, and reduce the relevant energy consumption.

References
1. Guangzhu, Li, N 1998, ’Proposal of improving alumina productivity and product quality by Combination Process’, Paper Volume of 9th Chinese alumina
academic meeting & 10th alumina technical information exchange, pp. 21-31.
2. Xingliang, Liu and Changren, Yao, N 1998, ‘Implementation of alumina quality creating project to realize leap of alumina quality’, Paper Volume of 9th
Chinese alumina academic meeting & 10th alumina technical information exchange, pp. 180-185.
3. Dai, Chen, N 1996, ’Requirement on the quality of metallurgical-grade alumina by international aluminum industry and its developing trend’, The
Chinese Journal of Light Metals, No.3, pp. 10-25.
4. Xiancui, Lv, Weibing, Jing, Tianmei, Bo, N 2002, ’The way of aggrandizement sintering process’, The Chinese Journal of Nonferrous Metallurgy, No.6, pp.
49-50.
5. Xiaowei, Liang, Kun, Quan, Qiusheng, Zhou, N 2005, ‘Behavior study of Gallium in the alumina production process by sinter method’, The Chinese
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