Hydrometallurgy 187 (2019) 195–202

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Clean and efficient utilization of low-grade high‑iron sedimentary bauxite T

via calcification‑carbonation method
⁎
Guozhi Lu, Tingan Zhang , Fangfang Guo, Xuhua Zhang, Yanxiu Wang, Weiguang Zhang,
Long Wang, Zimu Zhang
Key Laboratory of Ecological Metallurgy of Multi-Metal Intergrown Ores of Ministry of Education, School of Metallurgy, Northeastern University, Shenyang 110819, China

A R T I C LE I N FO A B S T R A C T

Keywords: With the rapid development of China's aluminum industry and the depletion of high-quality bauxite resources,
Low-grade high-iron bauxite technology for the clean and efficient utilization of non-traditional bauxite resources has become the focus in
Calcification-carbonation method related fields.
Isomorphic replacement transformation The alumina-to-silica mass ratio of low-grade high-iron sedimentary bauxite from Yunnan, China is 2.65;
Fe reduction
diaspore and goethite coexist in this bauxite. To enhance the utilization efficiency of bauxite, the hydro-
metallurgy process of the “calcification-carbonation method” (CCM) had been proposed, and the research results
indicated that the addition of lime promoted the transformation of the goethite phase significantly, and the
replacement ratio of Al in goethite decreased from 16.02% to 12.15% for a calcification temperature of 200 °C.
The Gibbs free energy for the generation of Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4 decreases gradually with an in-
crease in the reaction temperature, and an excessive decomposition temperature in the carbonization process is
not conducive to the decomposition of the garnet phase. The calcification reaction is controlled by diffusion and
chemical reaction, and the activation energy in the temperature range from 220 to 260 °C (determined using a
high-pressure DSC) is 38.4 kJ/mol; it is 19.6 kJ/mol in the temperature range from 260,276.8 °C. Fe completely
dissociates from hydrogarnet upon carbonization, and the main silica-containing phases in the digested slag are
unreacted hydrogrossular and calcium silicate. The CCM enhanced the recovery ratios of Al2O3 and Fe from
high-iron diasporic bauxite by ~20% and 10%, respectively, compared with those in the Bayer process, and the
Na content decreased to lower than 0.1% in the CCM slag; this can be used as cement raw material directly. Thus,
the clean and efficient utilization of low-grade high-iron sedimentary bauxite was achieved using the CCM.

1. Introduction et al., 2013).

In 2017, the global alumina yield exceeded 115 million tons, over
50% of which originated from mainland China. Currently, > 90% of
global alumina is produced via the Bayer process (Wang et al., 2017;
Zhang et al., 2014; Liu et al., 2018a).
The rapid development of China's aluminum industry has led to the
swift depletion of high-quality aluminum resources (Lu et al., 2014).
The traditional bauxite resource of China is diaspore, which has a main
phase with high alumina and silica contents, low iron content, and a
low alumina to silica mass ratio (A/S) (Yang, 1998; Chen and Peng,
1998). However, with an increase in mining depth, the iron content in
bauxite gradually increases. Therefore, technology for the comprehen-
sive utilization of high-iron diasporic bauxite (Fe2O3 mass ratio >
15%) has caused widespread concerns due to the depletion of tradi-
tional bauxite resources (Liu et al., 2012; Zhang et al., 2016a; Zhao
Iron in diasporic bauxite can be regarded as a harmful element in
the Bayer process because: (1) Iron in bauxite mainly exists in the form
of goethite, which belongs to the orthorhombic system; similar to dia-
spore, iron and aluminum are generally isomorphic in bauxite
(Neumann et al., 2014). Therefore, alumina in diasporic bauxite with
high iron content is difficult to digest in the Bayer process due to this
isomorphic phenomenon. (2) Iron exists in the form of
Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4 (Fe hydrogarnet) in Bayer red mud
due to the addition of lime (Liu et al., 2018b), and is difficult to recover
using magnetic or other separation technologies.
Moreover, the existence of Fe increases the emission of red mud
from the Bayer process. Red mud is the insoluble solid residue left after
the digestion of bauxite ores with caustic soda during alumina pro-
duction, as in the Bayer process. The production of 1 ton of alumina
generates 1–1.5 tons of red mud; 2.5 tons may be generated during the

⁎
Corresponding author.
E-mail address: zta2000@163.net (T. Zhang).

https://doi.org/10.1016/j.hydromet.2019.04.027
Received 12 December 2018; Received in revised form 3 March 2019; Accepted 21 April 2019
Available online 29 April 2019
0304-386X/ © 2019 Published by Elsevier B.V.
G. Lu, et al. Hydrometallurgy 187 (2019) 195–202

treatment of low-grade or high-iron bauxite ores (You et al., 2014; Bauxite Alkaline solution Lime
Borges et al., 2011; Brunori et al., 2005; Ghosh et al., 2011; Liu et al.,
2009; Poulin et al., 2008; Liu et al., 2015). It is estimated that the global
Calcification
red mud stockpile has exceeded 2.7 billion tons, and over 120 million
tons of red mud is generated annually throughout the world (Power
et al., 2011; Zhang et al., 2018). Due to its high alkalinity (pH 9–12.5),
Calcified liquor Solid phase
red mud is classified as a corrosive hazardous material in some coun-
NaOH and NaAl(OH)4 as main contents Hydrogarnet as main content
tries (Zhang et al., 2018; Xuan et al., 2016; Kumar and Kumar, 2013).
To precipitation for Al2O3
The NaOH- and metallic-oxide-bearing impurities precipitate out from
CO2 Carbonation
red mud and contaminate surface and underground water resources
(Chandra et al., 2010). Inadequate disposal of red mud leads to po-
tential direct contact with fauna and flora, and eventually threatens
human health and the environment (Hajjaji et al., 2013). In the red mud Solid phase Liquid phase
accident of October 4, 2010 in Ajka (Hungary), 10 persons lost their
lives (Liu et al., 2012; Gelencser et al., 2011) and 800 ha of agricultural Digestion
Digested residue Liquid phase
land was estimated to have been inundated.
CaSiO3, CaCO3 and Fe2O3 NaOH and NaAl(OH)4 as
To minimize the damage to the environment and the waste of sec-
as main contents main contents
ondary aluminum resources, great efforts have been made to recover
New-structure red mud To Bayer process
the alkali and alumina from red mud or the other low-grade alumina
Iron reduction CaSiO3 and CaCO3 as main
containing resources, and to utilize other materials (Liu et al., 2004;
Cresswell et al., 1987; Hrishikesan, 1977; Meher et al., 2011; Xu and contents

Smith, 2012; Zhang et al., 2011; Carneiro et al., 2018; Liu and Naidu, Iron Utilization for cement or
2014). However, the recovery of a significant quantity of valuable soil
components from red mud is difficult, as they are locked up in complex
Fig. 1. Process flowchart of CCM for comprehensive utilization of high-iron
mineral phases that are very fine-grained and quite alkaline (Liu et al., bauxite.
2012). The main composition of red mud includes mineral phases such
as sodalite, cancrinite, garnet, and hematite (Liu et al., 2012; Lu et al.,
2017). Sodium in red mud mainly exists in the stable phases such as 2. Experimental
sodalite or cancrinite, with m(Al2O3)/m(SiO2) ≈ 1 (the value is
usually > 1 in factory production), which leads to the loss of alumina; 2.1. Materials and characterizations
the consumption of caustic in production processes always increases
with the silica content in the mineral. Therefore, the Bayer process has The diasporic bauxite used in this research was from Wenshan,
two problems: one is that the alumina yield and economic benefit is low Yunnan province (China), and had Al2O3, SiO2, Fe2O3, and TiO2 mass
for bauxite with a low A/S, and the other is that the large amount of red contents of 46.25%, 17.43%, 17.86%, and 3.42% respectively; the XRD
mud generated with high alkali content (sodium oxide content is > 4%, results are shown in Fig. 2. Analysis showed that the A/S was relatively
and samples can have up to 15%) cannot be reused directly and widely low (A/S = 2.65), clearly identifying it as low-grade diasporic bauxite
(Lu et al., 2017). Moreover, the transformation and recovery char- with high Fe and Ti contents, and the main phases in the bauxite sample
acteristics of iron in alumina production process have also attracted were diaspore, goethite, and kaolinite. Bauxite is a typical low-grade
extensive attention in recent years. (Li et al., 2015, 2017, 2018; Li, sedimentary mineral with high iron content, and has not been applied
2001). to actual production due to its low A/S and a lack of comprehensive
The hydrometallurgy process of the “calcification-carbonation utilization technology.
method” (CCM; process flowchart shown in Fig. 1) was proposed The SEM and EDS analysis results shown in Fig. 3 illustrate that
(Zhang et al., 2017; Zhang et al., 2013; Lu et al., 2014; Lu et al., 2017) diaspore and goethite coexist in the bauxite; they are difficult to se-
to convert the hydrated sodium aluminosilicate phase in Bayer red mud parate directly using magnetic separation or flotation technology.
to CaO·SiO2 and CaCO3. During the calcification process, silicon-con-
taining phases (such as kaolinite in bauxite) are transformed into hy-
drogarnet, which subsequently changes into Al(OH)3, CaO·SiO2, and
CaCO3 during the pressure carbonation process with CO2. Since Al
(OH)3 is digested by the alkali when the digestion temperature is below
100 °C, the remaining residues constitute modified red mud with a
primary composition of CaO·SiO2 and CaCO3 (Zhang et al., 2013).
The new-structure red mud generated in the CCM can be used as
cement raw material or plant soil directly, and the clean production of
alumina is achieved. Earlier research illustrated that the Fe reduction
performance is enhanced by CCM treatment (Zhang et al., 2016b).
However, the phase transformation mechanism of the iron-containing
phase in the CCM should be further investigated. Therefore, the iso-
morphic transformation of the iron- and aluminum-containing phases in
the calcification transformation process was investigated, the thermo-
dynamics of the iron-containing phase in the CCM transformation
process was analyzed, the decomposition performance of Fe hydro-
garnet in the carbonation treatment was determined, and the extraction
performance of alumina and iron from high-iron bauxite was tested in
this research.

Fig. 2. X-ray diffraction pattern of the bauxite sample.

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G. Lu, et al.
Fig. 3. SEM and EDS analysis results of the bauxite sample.
2.2. Experimental methods
The raw materials used in the bauxite phase transformation research
were an alkaline solution (with initial NaOH concentration of 240 g/L
and Al2O3 concentration of 120), bauxite (100% of the particles were
finer than 250 μm and 70% of the particles were finer than 74 μm), and
CaO. The pure reagents used for the transformation mechanism re-
search on iron-bearing phases included the alkaline solution, Fe(OH)3,
and Na2SiO3·9H2O. All the reagents used in this research were of ana-
lytical reagent grade.
The calcification and carbonation experiments were performed in a
WHFS-1 autoclave (Weihai, China). The raw materials were placed in
the autoclave together. The temperature of the autoclave was increased
to a predetermined value, and then held for a certain time period for
each process. All the experiments were performed with a rotary speed
of 300 r/min. After the reaction, the autoclave was cooled to below
100 °C. The digested slurry was separated into solid and liquid parts via
filtration.
The carbonation experiments were carried out in the autoclave,
with a of temperature 120 °C, CO2 partial pressure of 1.2 MPa, liquid to
solid ratio of 5 mL to 1 g, reaction time of 60 min, and rotary speed of
300 r/min. CO2 was injected into the autoclave when the temperature
reached 120 °C. Deionized water was used as the liquid phase in the
carbonation experiments.
The digestion experiments on carbonated slag were performed in a
HH-501 constant-temperature water bath. The NaOH (100 g/L) solution
was placed in the water bath and the temperature was increased to
60 °C; then, the carbonated slag was added to the system for 60 min.
The reduction experiment was carried out in a muffle furnace, using
coal powder as the reducing agent with a molar ratio of [C]/[Fe] = 3:4.
The red mud (both the Bayer red mud and the CCM slag) was mixed
with coal powder firstly; after pellet preparation, the mixture pellets of
about 10 mm diameter were placed in the muffle furnace under a re-
duction temperature of 1050 °C for a certain holding time. Moreover,
the reduction performance of iron in the Bayer red mud and CCM red
mud was comparatively tested in this research.
2.3. Analysis and calculation methods
XRD analysis was carried out using a D8 Advance (Bruker,
Germany), with a Cu target and step size of 0.0095° for a scanning
spectrum between 10° to 90°. SEM and EDS analyses were conducted
using an SU9000 scanning electron microscope (Hitachi, Japan). DSC
analysis of the calcification process was carried out using a HP-204
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Hydrometallurgy 187 (2019) 195–202
high-pressure DSC (Netzsch, Germany). Chemical analysis was done
using an ICP prodigy XP (Leeman, USA).
The isomorphic replacement phenomenon of aluminum in goethite
is ubiquitous in high-iron bauxite due to the similar chemical properties
of Al and Fe, and the similar ionic radii of Al3+ and Fe3+. Al3+ occupies
the position of Fe3+ in the goethite phase, and the mineral lattice has a
stabilizing effect. Therefore, the Al3+ in goethite is difficult to digest
until goethite is transformed into hematite or other mineral phases.
Lime addition in the Bayer process enhances the phase transformation
rate of goethite and the digestion performance of alumina in high-iron
bauxite (Chen and Peng, 1998; Peter, 2017). However, there is no re-
port on the promotion scale, especially for the high-calcium medium
system. There is a certain limitation on the replacement of Fe3+ in
goethite by Al3+, and the replacement ratio of Al3+ is generally
0–32 mol%. The molecular formula after replacement is (AlxFe1-x)OOH.
Such aluminized goethite is called aluminum goethite. When Al3+ en-
ters goethite by replacement, the unit cell dimensions of goethite de-
crease. For the same diffraction peak, the d value shifts and tends to
decrease. Its deviation is linearly related to the replacement rate of
Al3+. The isomorphic replacement calculation equation (Eq. (1)) used
in this research was Thiel's equation (Fitzpatrick and Schwertmann,
1982), and the replacement ratio of the raw ore was 23.98%.
AlOOH mol% = [4.18 − d (110) ]/0.0019 (1)
3. Results and discussion
3.1. Effect of lime addition on isomorphic replacement of Al in goethite
The results in Fig. 4 indicate that the addition of lime promotes the
transformation of the goethite phase significantly. The replacement
ratio of aluminum in the goethite phase of the reacted slag (no lime
addition) at 120 °C is almost the same as that in the raw ore (22.25%);
however, it decreases to 16.93% under the action of lime. For the
sample with no lime addition at 220 °C of reaction temperature, the
replacement ratio is 16.02%; it decreases to 12.15% upon lime addition
at 200 °C. The goethite phase disappears from the sample after lime
addition at 220 °C; it can be estimated that there is a phase transfor-
mation of goethite, and the product is assumed to be
Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4 or hematite.
3.2. Thermodynamic analysis
Earlier research demonstrated the change in the Gibbs free energy
G. Lu, et al. Hydrometallurgy 187 (2019) 195–202

react with the most acidic oxides firstly, and then with the less acidic
oxides. In most cases, water exists in the form of hydrated salt, and
sometimes participates in the reaction as structural water. Therefore,
the Gibbs free energy of a complex silicate mineral can be regarded as
the sum of the Gibbs free energy of each oxide and the reaction free
energy between the reductants. Based on this, the Gibbs free energy of
Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4 can be calculated using Eq. (4); the
changes in the Gibbs free energy for the generation and decomposition
of the iron-containing garnet phase in the CCM are shown in Fig. 5.

Ca3 (Fe0.87 Al 0.13)2 (SiO4 )1.65 (OH)5.4 → 1.65CaO·SiO2 + 0.13CaO·Al2O3

+ 0.87CaO·Fe2 O3 + 0.35Ca(OH)2
+ 2.35H2 O (4)

The calculation results in Fig. 5a illustrate that the Gibbs free energy
for the generation of Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4 decreases gra-
dually with an increase in the reaction temperature. In Fig. 5b, the
calculated Gibbs free energy for Reaction (3) at a CO2 partial pressure
of 1.0 MPa demonstrates that an excessive decomposition temperature
of the carbonization process is not conducive to the decomposition of
the garnet phase. Moreover, a high decomposition temperature also
Fig. 4. Effect of lime addition on isomorphic replacement of Al in goethite.
leads to a decrease in CO2 solubility in the water phase, which affects
(Reaction time of 60 min, liquid to solid ratio of 4 mL to 1 g, calcium to silica
the decomposition performance of Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4
mass ratio of 4.68:1)
as well.

for the generation and carbonation decomposition reaction of hydro-

garnet/grossularite in a CCM system without Fe content (Lu et al.,
2014; Lu et al., 2017). The main reactions of iron present in the CCM
are:
Calcification process:
0.26Al(OH)4− + 1.65SiO32 − + 3CaO + 1.74Fe(OH)3 + 1.35H2 O
= Ca3 (Fe0.87 Al 0.13)2 (SiO4 )1.65 (OH)5.4 + 3.56OH−
Carbonation process:
Ca3 (Fe0.87 Al 0.13)2 (SiO4 )1.65 (OH)5.4 + 1.35CO2 = 1.65CaO·SiO2
+ 1.35CaCO3 + 0.26Al(OH)3 + 0.87Fe2 O3
+ 2.31H2 O
There is no report on the Gibbs free energy of the iron-containing
garnet phase of Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4. This research as-
sumed that any complex silicate mineral is the compound of various
acidic and alkaline oxides. When combined, the most alkaline oxides
3.3. High-pressure DSC analysis
There is an exothermic peak in the DSC curve of high-iron bauxite in
the calcification process with a 10 K/min heating rate, as shown in
Fig. 6a. The temperature range of the ascending section is 220–260 °C,
and that of the descending section is 260–276.8 °C.
The Freeman-Carroll method was used to analyze the kinetics of the
(2)
calcification reaction. The ascending and descending segments of the
curve of the △log intensity/△log S″ vs △ (1/T)/△log S″ were fitted
accordingly. For the ascending section (shown in Fig. 6b), the reaction
order of calcification is n1 = 2.40 and the activation energy is
E1 = 38.4 kJ/mol. Therefore, in the temperature range from 220 to
260 °C, the calcification reaction is controlled by diffusion and chemical
(3)
reaction. Furthermore, the reaction order of calcification is n2 = 1.02
and the activation energy is E1 = 19.6 kJ/mol in the temperature range
from 260 to 276.8 °C. Since diasporic bauxite usually dissolves at
temperatures above 260 °C (Peter, 2017), it can be considered that
diaspore dissolution mainly restricts the transformation process at

-300 0

-310 -20

-320 -40

-330 -60

-340 -80
G0T/kJ mol-1

G/kJ mol-1

-350 -100

-360 -120

-370 -140

-380 -160

-390 -180

-400 -200
300 350 400 450 500 550 600 300 350 400 450 500 550 600
T/K T/K
(a) (b)
Fig. 5. Gibbs free energy change for Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4 in the CCM.
(a-generation, b-decomposition)

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G. Lu, et al. Hydrometallurgy 187 (2019) 195–202

30

25

20
DSC/uV mg-1
15

10

-5
0 50 100 150 200 250 300
T/ C
(a)

(b) (c)
Fig. 6. High-pressure DSC analysis results of calcification process using high-iron bauxite
(a-DSC curve; b-△log intensity/△log S″ vs △ (1/T)/△log S″ results at 220–260 °C; c- △log intensity/△log S″ vs △ (1/T)/△log S″ results at 260–276.8 °C).

temperatures below 260 °C. When the temperature is higher than
260 °C, the chemical reaction is no longer the limiting link of the pro-
cess. The DSC analysis results demonstrate that the activation energy of
the calcification reaction decreases with an increase in the temperature,
and the calcification reaction can be more easily carried out at high
temperatures.
3.4. Generation and decomposition performance of hydrogarnet in the CCM
The XRD analysis results for a CaO to silica mass ratio of 4.68:1 and
solid to liquid ratio of 4:1, shown in Fig. 7, indicate that the main
phases of the calcification product using pure reagents as raw materials
are sodium aluminosilicate hydrate and hydrogrossular; some un-
reacted calcium oxide and ferric oxide phases are also present in the
product. The Fe hydrogarnet appears in the 200 °C product, but the
characteristic peak is weak. It is indicated that the formation tem-
perature of iron garnet is above 200 °C in this system.
The Fe hydrogarnet is the main phase in the calcification product in
the temperature range 210–280 °C (shown in Fig. 8). In the Bayer
process, hydrogarnet is the main product in the digestion residue due to
the addition of lime (McCormick et al., 2002). The general chemical
formula for silicate hydrogarnet is {A}3[B]2(SiO4)x(O4H4)3-x, where A
and B are cations (Zhang et al., 2011; Mercury et al., 2007; Lager et al.,
1998). A, B, and Si exhibit dodecahedral, octahedral, and tetrahedral
coordinations relative to O, respectively (Ballaran and Woodland,
2006). The structure is of the space group Ia3d and all the cation po-
sitions are fixed by symmetry (Hawthorne, 1981). This structure has
been described as one of a considerable number of chemical con-
formations that can accommodate a wide variety of elements. These site
occupancies involve Na, Mg, Ca, etc. in the A-site; Al, Fe, Mg, Ti, etc. in
the B-site (Locock, 2008); and the mutual substitution of (SiO4)4− and
(O4H4)4− (Marin and O'Keefee, 1990). Consequently, many species of
silicate hydrogarnet with isomorphic substitution always exhibit ex-
tensive solid solutions.
Another substitution in the Bayer residue is that of Fe and Al; it
always takes place under high-temperature conditions, and the Fe

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G. Lu, et al. Hydrometallurgy 187 (2019) 195–202

1--Ca3Al2(SiO4)(OH)8 2--Fe2O3
4 3 3--Ca2SiO4 4--CaCO3
3 3 24
4 4
3 32 13 1 12 13 41 4 1 342 2 1
4 280

270
260

250
240

230
220
210

20 30 40 50 60 70
2/
Fig. 7. XRD analysis of the calcification product in the temperature range (a)
120–200 °C
(1-Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4; 2-3CaO·Al2O3·xSiO2·(6-2×)H2O; 3- 1--Ca3Al2(SiO4)(OH)8 2--Fe2O3
Fe2O3; 4-Fe3O4; 5-CaO; 6-Na8Si6Al6O24(OH)2(H2O)2; 7-Na8(Al6Si6O24) 4 3--Ca2(SiO4) 4--CaCO3
(OH)2.04(H2O)2.66; 8–0.99Na2O·Al2O3·4.07SiO2·5.7H2O). 3 24 4
1 13 34 1 3 4
13 41 2 1 342 3
2 11 2 1 2 12 1 4 22 280
1--Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4 3--Fe2O3
2--3CaO· Al2O3· xSiO2· (6-2x)H2O 4--Ca(OH)2 270
2 2 2 2 23 2 2 2 22 260
1 1 3 1 2 13 1 1 1 1 11 280
4 4 250
3 4 34 3 33 270 240
260 230
250 220

240
210
230
220 20 30 40 50 60 70
2/
210 (b)
Fig. 9. XRD analysis of the (a) carbonized and (b) digested slag.
20 30 40 50 60 70
/
Table 1
Fig. 8. XRD analysis of the calcification product in the temperature range
Chemical analysis of Bayer red mud and CCM slag (wt%).
210–280 °C.
Composition Al2O3 SiO2 Fe2O3 TiO2 CaO Na2O LOI

hydrogarnet is the stable phase in the residue as well (Qian et al., 2002; Bayer red mud 19.15 17.01 16.97 3.26 12.96 8.44 22.03
Dilnesa et al., 2014). Moreover, 3CaO·Al2O3·6H2O and 3CaO·- CCM slag 7.30 14.27 8.36 1.99 39.73 0.07 27.50
Fe2O3·6H2O have similar cubic structures with lattice parameters
a = 12.58 Å and a = 12.72 Å, respectively. This similarity in crystal Bayer process conditions: digestion temperature of 260 °C for 60 min, initial
structure enables these two components to form solid solutions. Fig. 8 Na2O to Al2O3 molar ratio in alkaline solution of 3.1, rotary speed 300 r/min;
Calcification conditions: calcification temperature of 240 °C for 30 min, initial
shows that the characteristic peaks of Fe hydrogarnet are similar to
Na2O to Al2O3 molar ratio in alkaline solution of 3.1, rotary speed 300 r/min;
those of hydrogrossular due to their similar crystal structures.
Carbonation conditions: carbonation temperature of 120 °C for 60 min, CO2
The calcified slag produced using the pure reagents as the raw partial pressure of 1.2 MPa, liquid to solid ratio of 5 mL to 1 g, rotary speed of
materials was carbonized with CO2, followed by digestion with a low- 300 r/min;
concentration alkaline solution. Fig. 9a demonstrates that the main Digestion conditions: initial NaOH concentration of 100 g/L, digestion tem-
phases in the carbonized slag are iron oxide, calcium silicate, calcium perature of 60 °C for 60 min, liquid to solid ratio of 10 mL to 1 g, rotary speed of
carbonate, and hydrogarnet, and there is no Fe hydrogarnet phase, 300 r/min.
which proves that Fe completely dissociates from hydrogarnet upon
carbonization. Moreover, the main silica-containing phases in the

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G. Lu, et al.
Fig. 10. XRD analysis of the (a) Bayer red mud and (b) CCM slag.
Fig. 11. Fe reduction performance of the Bayer red mud and CCM slag.
digested slag (shown in Fig. 9b) are unreacted hydrogrossular and
calcium silicate.
3.5. Na, Al, and Fe recovery performance through CCM treatment
In the CCM, the recovery of Na and Al was carried out in the cal-
cification process and digestion process, respectively. The comparison
results (shown in Table 1) for high-iron bauxite as the raw ore indicate
that the Na2O content in the CCM slag is 0.07%, which meets the re-
quirement of cement raw material (Na wt% < 0.8%). Moreover, the
CCM can reduce alkali consumption by > 90% relative to that in the
alumina production process. The A/S of the CCM slag is 0.51 and the
alumina recovery ratio is 80.75%; it is 57.50% in the Bayer process.
Moreover, the optimal calcification temperature is 240 °C, which is
20 °C lower than that for the Bayer process due to the lime addition and
the transformation of goethite.
Na and Fe exist in the Bayer red mud in the form of Na8(Al6Si6O24)
(OH)2.04(H2O2)2.66 and Fe hydrogarnet, respectively (shown in
Fig. 10a), when high-iron bauxite is used as the raw ore. However, Fe in
Fe hydrogarnet completely dissociates upon CCM treatment into the
form Fe2O3, and the other phases in the CCM slag are unreacted hy-
drogrossular, calcium silicate, and calcium carbonate (shown in
Fig. 10b).
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Hydrometallurgy 187 (2019) 195–202
The reduction results of Fe shown in Fig. 11 indicate that the CCM
slag exhibits a better Fe reduction performance due to the dissociation
of Fe. The iron reduction ratio of the 60-min product is higher than
80%, which is about 10% higher than that of the Bayer red mud.
In summary, the recovery ratios of Al2O3 and Fe from high-iron
diasporic bauxite in the calcification-carbonation treatment are about
20% and 10% higher than those in the Bayer process. Moreover, the Na
content decreases to lower than 0.1% and the CCM slag can be used as
cement raw material. Furthermore, for 1 ton of alumina product, ap-
proximately 80 kg of Na2O, > 100 kg of alumina, and 10 kg Fe can be
recycled in addition to those in the Bayer process, with an economic
benefit of 30–150 CNY. The land occupied by the red mud can be re-
used as well. Therefore, the clean and efficient utilization of low-grade
high-iron sedimentary bauxite can be achieved using the CCM.
4. Conclusions
The A/S of high-iron sedimentary bauxite from Wenshan, Yunnan
province is 2.65; diaspore and goethite coexist in this bauxite, and are
difficult to separate directly using magnetic separation or flotation
technology. The replacement ratio of Al in goethite is 23.98%.
The addition of lime promotes the transformation of the goethite
phase significantly. The replacement ratio of aluminum in the goethite
phase is almost the same as that in the raw ore (22.25%) at 120 °C, but
decreases to 16.93% under the action of lime. The transformation
temperature of goethite with lime addition is between 200 and 220 °C.
The Gibbs free energy for the generation of
Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4 decreases gradually with an increase
in the reaction temperature, and an excessive decomposition tempera-
ture in the carbonization process is not conducive to the decomposition
of the garnet phase.
The reaction order of the calcification reaction using high-iron
bauxite as the raw ore is n1 = 2.40, and the activation energy is
E1 = 38.4 kJ/mol. Therefore, in the temperature range 220–260 °C, the
calcification reaction is controlled by diffusion and chemical reaction.
Furthermore, the reaction order of calcification is n2 = 1.02 and the
activation energy is E1 = 19.6 kJ/mol in the temperature range
260–276.8 °C.
The formation temperature of iron garnet is above 200 °C in the
calcification process using pure reagents, and there is no Fe
G. Lu, et al.
hydrogarnet phase in the carbonized product. Fe completely dissociates
from hydrogarnet upon carbonization. The main silica-containing
phases in the digested slag are unreacted hydrogrossular and calcium
silicate.
The recovery ratios of Al2O3 and Fe from high-iron diasporic bauxite
in the calcification-carbonation treatment are about 20% and 10%
higher than those in the Bayer process. The Na content decreases to
lower than 0.1% and the CCM slag can be used as cement raw material.
Therefore, the clean and efficient utilization of low-grade high-iron
sedimentary bauxite can be achieved using the CCM.
Acknowledgements
We acknowledge the National Natural Science Foundation of China
(Nos. 51874078, U1710257, U1202274, 51874094), State Key
Laboratory of Pressure Hydrometallurgical Technology of Associated
Nonferrous Metal Resources (YY2016006), Fundamental Research
Funds for the Central Universities (N182505038), and Shenyang
Science and Technology Project (17-500-8-01, Z18-5-022).
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