Research Article

Waste Management & Research

29(10) 1053–1063

Utilization of red mud in cement ! The Author(s) 2011

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production: a review DOI: 10.1177/0734242X11407653
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Xiaoming Liu1 and Na Zhang2

Abstract
Red mud is a solid waste residue of the digestion of bauxite ores with caustic soda for alumina production. Its disposal
remains a worldwide issue in terms of environmental concerns. During the past decades, extensive work has been done by a lot
of researchers to develop various economic ways for the utilization of red mud. One of the economic ways is using red mud in
cement production, which is also an efficient method for large-scale recycling of red mud. This paper provides a review on the
utilization of red mud in cement production, and it clearly points out three directions for the use of red mud in cement
production, namely the preparation of cement clinkers, production of composite cements as well as alkali-activated cements.
In the present paper, the chemical and mineralogical characteristics of red mud are summarized, and the current progresses on
these three directions are reviewed in detail.

Keywords
Red mud, composition, utilization, cement, properties
Date received: 11 August 2010; accepted: 26 March 2011

disposal is expensive, accounting for about 2% of the alumina

Introduction price (Tsakiridis et al., 2004). For example, the alumina price
Red mud is the solid waste residue of the digestion of bauxite is about US$439 per ton in China, so the disposal cost of red
ores with caustic soda for alumina (Al2O3) production. mud would be nearly US$9 per ton of alumina production.
Approximately 35–40% of the processed bauxite ore goes Over the years, extensive work has been done by research-
into the waste as an alkaline red mud slurry which consists ers worldwide to develop various economic ways for the uti-
of 15–40% solids (Kalkan, 2006; Yang and Xiao, 2008), and lization of red mud. The various applications that have been
0.8–1.5 tons of red mud is generated per ton of alumina pro- investigated include: (i) as a stabilization material for the prep-
duced. It is estimated that annually 70 million tons of red mud aration of liners (Coruh and Ergun, 2010; Kalkan, 2006);
is produced all over the world, with 0.7 million tons in Greece (ii) as adsorbents for the removal of heavy metals, dyes,
(Vangelatos et al., 2009), 2 million tons in India (Agrawal phosphate, nitrate and fluoride (Altundogan et al., 2002;
et al., 2004), 30 million tons in Australia (Wang et al., Apak et al., 1998; Coruh, 2008; Li et al., 2006; Huang et al.,
2008), and nearly 30 million tons in China. As a solid waste, 2008; Pradhan et al., 1999; Santona et al., 2006; Wang et al.,
red mud is usually disposed in mud lakes in the form of slurry 2005, 2008; Yue et al., 2010); (iii) preparation of catalysts
impoundment or stack in ponds as dry mud near alumina
plants, or directly discharged through a pipeline into a 1
Key Laboratory of Ecological and Recycle Metallurgy of Chinese
nearby sea. Due to the characteristics of fine particles, high Ministry of Education, School of Metallurgical and Ecological
alkalinity (pH 10–12.5) and trace metal content, the disposal Engineering, University of Science and Technology Beijing, Beijing,
of large quantities of red mud has caused serious environmen- China.
2
State Key Laboratory of New Ceramics and Fine Processing,
tal problems including soil contamination, groundwater pol-
Department of Materials Science and Engineering, Tsinghua
lution and fine particles’ suspension in the sea. Moreover, the University, Beijing, China.
storage of red mud in lakes or ponds occupies huge areas of
land, and the storage of dry red mud can also lead to dust Corresponding author:
Xiaoming Liu, Yejin Shengtai Building, University of Science and
pollution which is a serious health problem for the people Technology Beijing, Beijing 100083, China
living near the red mud storage ponds. The cost of red mud Email: [email protected]
1054 Waste Management & Research 29(10)

(Wang et al., 2008); (iv) recovery of iron, aluminium, titanium (http://www.redmud.org/Industrial_Uses.html). Utilization
and other trace metals (Cengeloglu et al., 2003; Kumar et al., of red mud for the production of cements generates many
2006; Liu et al., 2009; Paramguru et al., 2005; Zhong et al., benefits in terms of the environment and economy such as
2009); (v) production of radiopaque materials (Amritphale reducing contamination of soil and groundwater, relieving
et al., 2007); (vi) preparation of ceramics (Pontikes et al., dust pollution, saving natural resources for the cement clinker
2007; Sglavo et al., 2000; Yalcin and Sevinc, 2000; Yang and finally decreasing the production cost of cement.
et al., 2008); (vii) production of construction bricks The aim of this paper is to summarize the chemical and
(Amritphale and Patel, 1987; Liu et al., 2009; Yang and mineralogical characteristics of red mud and present a
Xiao 2008); (viii) development of pigments and paints (Pera detailed review of the current progress on the utilization of
et al., 1997); and (ix) preparation of cements (Singh et al., red mud in cement production, and clearly point out three
1996, 1997; Tsakiridis et al., 2004, Vangelatos et al., 2009). directions for using red mud in cement production, namely
Since the use of red mud for producing construction and the preparation of cement clinkers, production of composite
building materials has the potential to consume the waste in cements as well as alkali-activated cements.
large quantities, more and more attention has been paid to the
utilization of red mud for cement production. Utilizing red
Chemical and mineralogical
mud in the cement industry has been put into practice gradu-
ally all over the world. For instance, it was reported that
characteristics of red mud
in India, 2.5 million tons of red mud was consumed by The general characteristics of red mud have been described in
the cement industry during 1998–1999 (http://www.redmud. a review paper in relation to the applications of red mud as
org/Industrial_Uses.html). In Japan, plant scale tests were coagulant, adsorbent and catalyst (Wang et al., 2008). Here
initiated in 2003 to confirm the feasibility of using dry red more emphasis is put on the chemical and mineralogical com-
mud as a raw material blended with other materials such position of red mud, as they are two of major factors that
as lime, clay, silica and iron source to produce cement. relates to its cementitious properties.
It has been demonstrated that the prepared red mud-based Red mud is a complex material whose chemical and min-
cement, including mortar and concrete made from this eralogical composition varies widely in terms of the source of
type of cement, can meet the Japanese Industrial Standards bauxite and the production process. Figure 1 shows a

Bauxite ores Crushing

Alkali treatment
with
Evaporation NaOH or Na2CO3

Sodium aluminate
slurry
Mother solution

Decomposition Sodium
aluminate Filtration Red mud
Precipitation
solution

Rotary kiln
calcination

Alumina

Figure 1. Production process of alumina.

Liu and Zhang 1055

schematic diagram for the production process of alumina. also used in some of the Chinese alumina plants with
Generally, the Bayer process is used for refining bauxite to large productions such as Zhengzhou Aluminum Plant,
produce alumina in most countries. The process was devel- Guizhou Aluminum Plant and Shanxi Aluminum Plant.
oped by Karl Josef Bayer in 1888. In the Bayer process, the The combination process is used for refining bauxite ores
crushed bauxite ores are digested in a concentrated sodium with A/S >4.5.
hydroxide solution at temperatures between 150 and 230 C No matter what the production process is, the chemical
under pressure (Newson et al., 2006), and subsequently, the composition of red mud contains six major constituents,
majority of aluminium oxide is dissolved in the solution namely Fe2O3, Al2O3, SiO2, TiO2, Na2O and CaO. It con-
including insoluble substances such as sodium aluminate tains small quantities of minor/trace elements such as V, Ga,
slurry. The slurry is then filtered, leaving the insoluble residue Cr, P, Mn, Cu, Cd, Ni, Zn, Pb, Mg, Zr, Hf, Nb, U, Th, Y, K,
which is red mud. The Bayer process is suitable for refining Ba, Sr, and trace amounts of rare earth elements (Kalkan,
high-grade bauxite ore which has composite properties of 2006; Singh et al., 1996, 1997; Tsakiridis et al., 2004). The
high Al2O3/SiO2 (A/S) (>7–10). However, most of the local major chemical composition of red mud all over the world is
bauxite ore in China is low grade with average A/S value of presented in Table 1. It can be seen that iron oxide and alu-
5–6 (Yang and Xiao, 2008), which determines that the sin- mina are the major components in red mud from the Bayer
tering process is widely used in the Chinese alumina refining process, whereas calcium oxide and silica are the most major
plants. In the sintering process, the crushed bauxite ores are constituents for red mud from the sintering process.
usually mixed with limestone and caustic soda, and the mix- Generally, the major mineralogical phases of red mud
ture is sintered at a high temperature of about 1200 C to from the Bayer process are gibbsite (Al(OH)3), boehmite
form soluble sodium aluminate upon addition of water or (g-AlOOH), hematite (Fe2O3), goethite (FeO(OH)), quartz
diluted alkaline solution. The sintering process is suitable (SiO2), anatase (TiO2), rutile (TiO2) and calcite (CaCO3),
for refining bauxite ore with A/S values of 3–6. In addition, and the principal mineralogical constituents of red mud
the combination of Bayer process and sintering process is from the sintering process are -2CaO.SiO2, calcite

Table 1. Major chemical composition of red mud generated in alumina plants in various countries

Country Plant Reference Major composition (wt.%)

Fe2O3 Al2O3 TiO2 SiO2 Na2O CaO

India HINDALCO Singh et al. (1997) 33.1 18.2 19.6 8.8 5.8 2.7
Italy Eurallumina Sglavo et al. (2000) 35.2 20.0 9.2 11.6 7.5 6.7
Turkey Seydisehir Altundogan et al. (2002) 36.94 20.39 4.98 15.74 10.10 2.23
UK ALCAN Srikanth et al. (2005) 46.0 20.0 6.0 5.0 8.0 1.0
Greece Tsakiridis et al. (2004 40.8 19.95 5.8 6.8 2.7 12.6
France Aluminium Pechiney Pera et al. (1997) 26.62 15.00 15.76 4.98 1.02 22.21
Canda ALCAN Vachon et al. (1994) 31.60 20.61 6.23 8.89 10.26 1.66
Jamaicaa Gordon et al. (1996) 42.3 16.4 6.0 8.0 4.6 9.1
Jamaicab Gordon et al. (1996) 49.5 16.5 7.0 3.0 2.3 5.5
Chinac Liu et al. (2009) 27.93 22.00 2.3 20.98 10.5 6.23
Chinad Zhang et al. (2009) 12.32 6.27 3.27 17.78 2.75 37.52
Australia AWAAK Snars and Gilkes (2009) 28.5 24.0 3.11 18.8 3.4 5.26
Australia AWAAP Snars and Gilkes (2009) 31.7 18.8 3.17 20.2 4.2 4.44
Australia AWAAW Snars and Gilkes (2009) 29.6 17.3 2.65 30.0 3.2 3.64
Australia WAPL Snars and Gilkes (2009) 56.9 15.6 4.46 3.0 2.2 2.39
Australia Nabalco Snars and Gilkes (2009) 34.8 23.2 8.03 9.2 7.1 2.25
Australia QAL Snars and Gilkes (2009) 30.7 18.6 7.01 16.0 8.6 2.51
Brazil Alunorte Snars and Gilkes (2009) 45.6 15.1 4.29 15.6 7.5 1.16
Germany AOSG Snars and Gilkes (2009) 44.8 16.2 12.33 5.4 4.0 5.22
Spain Alcoa Snars and Gilkes (2009) 37.5 21.2 11.45 4.4 3.6 5.51
USA RMC Snars and Gilkes (2009) 35.5 18.4 6.31 8.5 6.1 7.73
a
Represents red mud derived from the processing of a typically boehmitic bauxite.
b
Represents red mud from the processing of gibbsitic bauxite.
c
Represents the Bayer-process red mud from an alumina plant in Chiping of Shandong Province, China.
d
Represents the Sintering-process red mud from Shandong Aluminium Plant.
1056 Waste Management & Research 29(10)

(CaCO3), aragonite (CaCO3), hematite (Fe2O3), gibbsite development of cements made from lime þ red mud þ baux-
(Al(OH)3) and perovskite (CaTiO3). ite. It is interesting to notice that the highest strength value
obtained for the raw mix containing 50% lime, 25% red mud
and 25% bauxite was consistent with the maximum forma-
Use of red mud as raw meal for the
tion of C4AF in the corresponding cement. The produced
production of cement clinker cements had a regular increase in strength with firing tem-
According to the chemical composition of red mud as shown peratures from 1150 to 1300 C, and the cements fired at
in Table 1, red mud from the Bayer process is mainly com- 1300 C had much higher strength than that of OPC, which
posed of Fe2O3 and Al2O3 as well as some silica, and thus it was due to the maximum formation of C4AF phase at
should be suitable as a raw material for the preparation of 1300 C. Firing time (0.5–2.0 h) had significant influence on
cement clinkers. the strength of the cements produced from lime þ red
mud þ bauxite. The strength of the produced cements exhib-
ited an increase trend up to 1.5 h and a decrease thereafter,
Preparation of special cements
corresponding to the increasing formation of C4AF with the
from red mud increase in firing time up to 1.5 h and thereafter the dissoci-
Singh et al. (1996, 1997) conducted investigations on prepa- ation of C4AF back to C2F. Therefore, it was concluded that
ration of special cements using lime, red mud, fly ash, bauxite red mud addition of 25–40% in the raw mixes and a firing
and gypsum. Three varieties of special cements were pro- temperature of 1250 C for 1.0–1.5 h presented the best results
duced: (a) aluminoferrite (C4AF)–belite (-C2S) using lime- for the preparation of special cement using lime þ red
þ red mud þ fly ash; (b) C4AF–ferrite (C2F)–aluminates (C3A mud þ bauxite.
and C12A7) using lime þ red mud þ bauxite; and (c) sulfoalu-
minate (C4 A3 S)–C4AF–C2F using lime þ red mud þ baux- Cements made from lime þ gypsum þ red
ite þ gypsum. The effects of different process parameters mud þ bauxite: Singh et al. (1997) performed a detailed
such as compositions of raw meals, firing temperature and investigation for the preparation of sulfoaluminoferrite
firing time on the 28-day compressive strength of special (C4 ðA, FÞ3 S)–C4AF-based cements using lime þ gyp-
cements were studied. The results indicated that special sum þ red mud þ bauxite. They prepared two sets of raw
cements prepared using lime þ red mud þ bauxite or lime- mixes, namely, Series A (lime ¼ 47.5%, gypsum ¼ 7.5%, red
þ red mud þ bauxite þ gypsum possessed 28-day strength mud ¼ 0–45% and bauxite ¼ 45–0%) and Series B
that was comparable with that of ordinary Portland cement (lime ¼ 32.5%, gypsum ¼ 12.5%, red mud ¼ 5–50% and
(OPC). However, the cements made from lime þ red mud þ fly bauxite ¼ 50–5%) to determine the effect of raw meal com-
ash or lime þ red mud þ gypsum þ fly ash did not exhibit suf- positions. It was found that the cements made from Series A
ficient strength. Even a partial replacement (5%) of bauxite by composition were soft and friable with a light brown colour.
fly ash played a deleterious effect on the strength of cements
made from lime þ red mud þ gypsum þ bauxite þ fly ash
mainly due to the increased formation of non-hydraulic
2C2S.CS and C2AS phases. Therefore, here emphasis is
placed on the two varieties of cements produced using lime-
þ red mud þ bauxite and lime þ gypsum þ red mud þ bauxite,
respectively, and the main findings by Singh et al. (1996, 1997)
are summarized in the following sections.

Cements made from lime þ red

mud þ bauxite: The cements produced using lime þ red
mud þ bauxite (lime ¼ 50%, red mud ¼ 5–50% and baux-
ite ¼ 45–0%) were hard with a dark brown colour. It was
found that their hardness, intensification of colour, glassy
nature and relative density increased with the red mud addi-
tion. Figure 2 displays the effect of red mud addition on the
28-day compressive strength of special cements made from
lime þ red mud þ bauxite. It can be seen that peak strength
values were obtained for the raw mixes containing 25–40%
red mud. This variety of special cement was primarily com- Figure 2. Effect of red mud content on the 28-days strength
posed of C3A, C12A7, C4AF and C2F phases. It could be the of cements made from lime þ red mud þ bauxite (Singh et al.,
former three phases that contributed to the strength 1996. Reproduced with permission from Elsevier).
Liu and Zhang 1057

Their density increased and colour intensified with the mud þ bauxite. It was reported that sulfate content in the pres-
increasing red mud addition, and the strength increased ence of titania had a critical influence on the phase formed in
with increasing red mud content as seen from Figure 3. the produced cements. It was also found that the strengths of
The major phases of cements produced from series A com- cements produced from both series A and B were strongly
position were C4 ðA, FÞ3 S, C4AF and C2F. Although there dependent on the firing temperature (1150–1300 C) but not so
were 5.2–11.4% TiO2 contained in the raw mixes of Series much on the firing time (0.5–2 h). From a comprehensive view-
A, no formation of titanate phases were detected in the pro- point, a firing duration of 1–1.5 h at 1250 C were optimum con-
duced cements. It was thought that all of the TiO2 which was ditions for the preparation of special cements from
obtained from red mud, got doped in the C2F and C4 ðA, FÞ3 S lime þ gypsum þ red mud þ bauxite. In addition, as the red
phases. The increasing strength shown in Figure 3 could be mud used contained a significant amount of TiO2, the effect of
explained by the increasing formation of C4AF phase with TiO2 doping in pure phase of C4 A3 S was studied. The results
the increase in red mud content. showed that TiO2 doping in C4 A3 S was helpful by increasing the
The clinkers made from series B composition were hard compressive strength of cement pastes, and it could affect the
with brownish-black colours. Similar to the special cements thermal behaviour of hydrates by lowering the dehydration tem-
made from lime þ red mud þ bauxite, their hardness, glassy perature of monosulfate hydrate.
nature and relative density increased with the increase in red
mud content. However, it is interesting to notice that their
Production of Portland cement clinker
strength decreased with the increasing content of red mud as
shown in Figure 4. When the red mud content increased to
from red mud
35–50%, excessive expansion occurred resulting in significant Tsakiridis et al. (2004) assessed the feasibility of producing
cracking and deformation. Unlike the previous cements Portland cement clinkers by addition of red mud into the raw
made from series A composition, C4 ðA, FÞ3 S, calcium tita- meals. They used 3.5% Bayer-process red mud blended with
nate (CT) and gehlenite (C2AS) were found to be the major 74.8% limestone, 11.4% schist, 3% bauxite and 7.3% Milos
phases formed in the cements produced from series B com- sand as a raw mix composition to prepare Portland cement
position, and no phases of C2F and C4AF was formed in clinkers which were sintered from the raw meal at 1450 C.
these cements. The trend of decreasing strength shown in They studied chemical and mineralogical compositions and
Figure 4 was attributed to the decrease in C4 ðA, FÞ3 S with microstructure of the produced clinkers, and mixed the clin-
corresponding increased formation of CT and C2AS. kers produced with gypsum (5%) to form final cement. It was
Therefore, the raw mix composition has a significant effect found that the addition of red mud in the raw mix resulted in
on the properties of cements made from lime þ gypsum þ red a well-burnt clinker with a free lime content of 1.94% at

Figure 3. Effect of red mud content on the 28-days strength Figure 4. Effect of red mud content on the 28-days strength
of cements made from series A (Singh et al., 1997. of cements made from series B (Singh et al., 1997.
Reproduced with permission from Elsevier). Reproduced with permission from Elsevier).
1058 Waste Management & Research 29(10)

Table 2. Chemical and mineralogical composition of the red temperature of 1450 C to achieve free lime content less
mud-containing cement clinker and the reference OPC clinker than 1%, while the raw meal with 1% FA addition required
(Tsakiridis et al., 2004. Reproduced with permission from
a higher firing temperature of 1550 C. The chemical and
Elsevier.)
mineralogical composition of the produced FA-containing
3.5% Red Reference clinkers is presented in Table 3. Although the produced clin-
mud addition clinker kers had variations in their chemical and mineralogical com-
Oxides (%) position, FA addition up to 5% did not negatively affect the
SiO2 20.80 21.24 mineralogical phases formed in the produced clinkers.
Al2O3 4.87 4.61 Subsequently, the FA-containing OPC were produced
Fe2O3 3.87 3.23 through co-grinding the produced clinkers with 5%
CaO 65.78 66.52 gypsum for 10 min. Tests on physical properties showed
MgO 2.40 2.27 that the produced OPC with FA addition had good physical
K2O 0.43 0.42 properties including specific surface area, setting time and
Na2O 0.36 0.35 water demand, which can be comparable to those for the
SO3 0.35 0.30 reference OPC. With extremely high early-age strength
TiO2 0.54 0.28 (26.5–30.8 MPa at 2 days and 57.5–62.9 MPa at 28 days),
LOI 0.23 0.22 the produced FA-containing cements can be ranked into
Mineralogical CEM I52.5 N category, and the compressive strength at
phases (%) 360 days was around 70 MPa, which was significantly
C3S 61.91 63.50 higher than that of the reference OPC. Considering that
C2S 13.02 13.08 the FA may contain up to 0.2% chromium, the change in
C3A 6.37 6.76 water-soluble Cr of the produced cements was evaluated.
C4AF 11.76 9.82 The results indicated that the addition of FA increased the
amount of water-soluble Cr6þ proportionally to the amount
of total chromium of the raw meal, but the conversion of
1450 C which was even lower than that of the reference OPC total Cr to water-soluble Cr6þ remained at similar levels
clinker. As shown in Table 2, the chemical composition of within the range of 32–35% in the produced cements con-
the produced clinker was close to that of OPC clinker, and taining 1–3% FA. The content of water-soluble Cr in the
the incorporation of red mud residue at 3.5% did not affect produced FA-containing cements exceeded the limit of
the mineralogical composition of the Portland cement clin- 0.0002% according to the directive 2003/53/EC of the EU
ker. The produced clinker contained 62% C3S, 13% C2S, Parliament. However, this excess of the limit can be relieved
6.4% C3A and 12% C4AF. Figure 5 displays microstructures by adding a reducing agent such as ferrous sulfate
of the produced red mud-containing cement clinker. Through (FeSO4.7H2O) during clinker-gypsum co-grinding (Bensted,
the observation, it was found that: (1) C3S phase appeared as 1996; Hills & Johansen, 2007).
small well-formed crystals; (2) C2S crystals were few and From the above investigations conducted by Tsakiridis
evenly distributed in relation to C3S crystals, suggesting a et al. (2004) and Vangelatos et al. (2009), it was found that
homogenous raw mix in which the addition of red mud res- small additions (3–5%) of red mud residue into the raw meals
idue by 3.5% is helpful to proceed the clinkering reaction will result in a well-burnt clinker with low free lime content,
extensively in the direction of C3S; and (3) the liquid phase and this low range addition of red mud is apparently bene-
was uniformly distributed as fine crystals. They also found ficial to OPC production. The small addition of red mud will
that the physical properties of the produced cement, includ- not affect the formation of the mineralogical phases of the
ing grindability, setting time, water content for standard con- produced clinkers, but it will lead to small changes for some
sistency and expansibility were similar to those obtained for physical properties of the produced OPC, such as greater
OPC. The red mud addition of 3.5% did not negatively affect specific surface and more water demand compared to those
the compressive strength of the produced cement (about of the reference OPC (Table 4). However, these differences
55 MPa at 90 days). on the specific surface and water requirement are negligible.
Another interesting investigation of producing OPC by More importantly, the small addition of red mud is beneficial
the addition of red mud has been reported (Vangelatos to improve the compressive strength of OPC.
et al. 2009). Red mud was firstly dewatered by a filter
press. The filtrand with water content of 26–28%, named
Use of red mud as raw material for the
ferroalumina (FA), was added at 1, 3 and 5%, respectively,
into the raw meals composed of limestone and sandstone to
production of composite cements
produce OPC clinker. The results of burnability tests showed The use of pozzolanic materials as constituents of cement
that the raw meals with 3 and 5% FA required a firing (as mineral additive) is an interesting direction for the
Liu and Zhang 1059

Figure 5. Microstructure of Portland cement clinker containing 3.5% red mud: (a) well-formed C3S crystals (500), (b) C2S
crystals scattering among alite (100), (c) high percentage of C4AF (500), (d) CaOf scattering among alite (500) (Tsakiridis
et al., 2004. Reproduced with permission from Elsevier).

Table 3. Chemical and mineralogical composition of the Pozzolanic activity of red mud
produced FA-containing clinkers (Vangelatos et al., 2009.
Reproduced with permission from Elsevier.) Pera et al. (1997) evaluated the possibility of using Bayer-
process red mud to develop a new admixture for concrete.
Reference 1% FA 3% FA 5% FA
clinker They investigated the pozzolanic activity of calcined red mud
(600–800 C, at a step of 50 C) by monitoring Ca(OH)2 con-
Oxides (%) sumption of pastes composed of 50% calcined red mud and
SiO2 22.05 23.61 22.64 21.53
50% Ca(OH)2. The results showed that the calcined red mud
Al2O3 5.66 4.17 4.52 4.89
was pozzolanic, and the red mud calcined at 700 and 800 C
Fe2O3 3.38 1.94 3.17 4.40
seemed to have greater activity than those calcined at other
CaO 67.12 67.45 66.93 66.07
temperatures. It was found that amorphous alumina was
MgO 1.60 0.83 0.82 0.81
formed during the calcination probably due to the decompo-
K2O 0.54 0.24 0.32 0.38
sition of boehmite and gibbsite. Part of the calcite in the red
Na2O 0.23 0.17 0.27 0.38
mud decarbonated yielding quick lime (CaO) from 750 C,
SO3 0.22 0.08 0.13 0.16
having negative effects on the reactivity and resulting in a
Mineralogical
drastic decrease in early-age strength of the blended cements
phases (%)
C3S 62 64 65 66 containing 20% (or more) red mud calcined at 750 or 800 C.
C2S 16 19 16 12 To increase the pozzolanic activity, the calcined red mud at
C3A 9 8 7 6 these temperatures required to be prehydrated with 25% of
C4AF 10 6 10 13 water to completely transform the quick lime into Ca(OH)2.
It was reported that a replacement of 20% OPC by the pre-
hydrated red mud calcined at 800 C gave good mechanical
development in the cement industry. Some attempts have properties with 90-day compressive strength of 59.9 MPa.
been made to use red mud as a raw material for the produc- Moreover, they found that the hydration products formed
tion of composite cements. in these blended cements were primarily C–S–H, ettringite
1060 Waste Management & Research 29(10)

Table 4. Specific surface and water of normal consistency for the red mud-containing OPC

(Tsakiridis et al., 2004) (Vangelatos et al., 2009)

Physical properties
OPCRef 3.5% RM OPCRef 3% FA 5% FA

Specific surface (cm2/g) 3950 3960 3730 4010 3870

Water of normal consistency (%) 23.3 24.1 21.6 22.6 22.2
OPCRef represents the reference OPC in the corresponding literature; 3.5% RM means addition of red mud residue by 3.5%; 3% FA and 5% FA
represent addition of red mud filtrand by 3 and 5%, respectively.

(AFt), portlandite, and mono-carboaluminate (C4 ACH11 ), in as a construction material without applying Portland cement
which the C4 ACH11 was a reaction product between portlan- as binder. They reported that the red mud composite exhib-
dite, calcite and the amorphous alumina obtained from the ited compressive strength in the range of 15–18 MPa at 28
calcined red mud. days and 18–22 MPa at 122 days. The strength development
could be attributed to the formation of stratlingite
(C2ASH8), and also possibly due to the formation of complex
Properties and hydration of red mud-based
carbonates such as hydrogrossular (Ca3Al2(SiO4,CO3,OH)3).
composite cements Although the compressive strength of the red mud compos-
Regarding the preparation of red mud-OPC blended ites cannot be comparable with that of OPC, it helps in the
cements, one main concern is the strong alkalinity of red understanding of the strength-giving processes operating in
mud which is detrimental to the life of cement and concrete. these composites, and provides a fundamental point for the
Kumar et al. (1989) conducted a neutralization treatment to investigation of red mud-based composite cements.
red mud by using hydrochloric acid, and performed an inves- Zhang et al. (2009) used sintering-process red mud and
tigation on partly replacing OPC by the neutralized red mud coal gangue as main raw materials with proportion of 50%
in different proportions of 0, 5, 10 and 15% to prepare incorporating 24% blast-furnace slag, 20% clinker and 6%
blended cements, and subsequently studied the effects of par- gypsum to prepare composite cement. In this investigation,
tial replacement of OPC by the neutralized red mud on the the red mud and coal gangue were firstly mixed together at a
strength characteristics of concrete made from the blended ratio of 3 : 2, and shaped in small spheres with a water to
cements. They found that the settling rate of solid particles solid ratio of 0.30 and then calcined at 600 C for 2 h to
increased after the neutralization of red mud. Tests on the improve their cementitious activity. They found that the pri-
physical properties of the OPC–red mud blended cements mary chemical compositions of the produced composite
showed that the water demand for the produced blended cement were silica, alumina and calcium oxide, and the
cements became greater gradually with the increase of red amount of silica þ alumina was larger than that of calcium
mud content, probably due to the increase of finer particles oxide. This was significantly different from the chemical com-
and absorbing characteristic of red mud; all of the blended position of OPC containing a higher amount of CaO. Due to
cements had similar initial and final setting times except for water absorption by the fine particles of red mud, the water
the one with 10% red mud exhibiting lower initial setting demand for standard consistency of the produced composite
time; replacement of OPC with the neutralized red mud cement was higher than that of Portland cement. However,
had an adverse effect on the soundness of the blended this did not affect the good fluidity of the produced cement.
cements, however, the expansion measured was well below Furthermore, the produced composite cement still had excel-
the maximum accepted value of 10 mm (EN 196-3). The com- lent physical properties such as setting time and soundness
pressive strength of concrete made from the produced and exhibited mechanical properties that compared well with
blended cement with the red mud content of 5 or 10% those of 32.5 OPC. The hydration products of the produced
were comparable to or ever higher than that of the OPC composite cement were mostly ettringite, C–S–H gel and cal-
concrete. This may be partly due to the proper content of cium hydroxide. The former two phases were principally
neutralized red mud around 5 to 10% increasing the finer responsible for the strength development of composite
particles in the concrete mix so as to fill the voids during cement in early hydration process. The content of calcium
the hydration process, and hence increasing its compacted hydroxide initially increased up to 21 days but later
structure. Another reason could be due to the increase of decreased, being depleted by the pozzolanic reaction of red
alumina in the blended cement with red mud. mud and coal gangue. It was found that the composition of
Gordon et al. (1996) conducted a preliminary investiga- C–S–H gel shifted towards higher Si, Al and Na contents
tion on strength development of Jamaican red mud compos- with the increase of hydration time, whereas that of Ca
ites incorporating hydrated lime, condensed silica fume and shifted towards a lower content. It seemed that Naþ from
limestone. The red mud composite was attempted to be used the initial red mud could be solidified by the C–S–H gel
Liu and Zhang 1061

during the hydration process of the produced composite However, only a small amount of red mud is actually
cement. being used in the cement industry, and large quantities of
red mud are still piled up in the large ponds. One of the
main factors limiting the utilization of red mud in the
Use of red mud as raw material for the
cement industry is transport cost, since the location of alu-
production of alkali-activated cement mina plants is relatively concentrated whereas the cement
Beyond applications of red mud in the production of clinker plants are dispersed. As the red mud is generally acquired
and composite cements, another interesting direction for the for free and the countable transportation cost is currently
utilization of red mud in the cement industry is the prepara- RMB 0.5 km1 t1 in China, it is feasible to decrease the
tion of alkali-activated cement. Pan et al. (2002, 2003) con- cost of cement production if the saved cost for using red
ducted an investigation of using sintering-process red mud, mud as the raw meal is greater than the transportation
blast-furnace slag and solid alkali activator such as solid cost. Another main constraint to a large utilization of red
water glass and sodium aluminate clinkers to produce mud in OPC production is the high alkalinity (pH 10–12.5)
alkali-activated cement. This kind of alkali-activated characteristic of red mud. From Table 1, it can be seen that
cement belongs to clinker-free cementitious material. They the content of Na2O in the worldwide red mud ranges from 1
reported that the alkali-activated red mud–slag cement pos- to 10%. Currently in China, the entire utilization ratio of red
sessed high compressive strength (56 MPa at 28 days and mud is only 4% with even lower utilization ratio in cement
65 MPa at 90 days) and excellent resistance against chemical and concrete. As a successful example of applying red mud in
attacks and freezing–thawing cycles, mainly due to the denser the cement industry, Shandong Alumina Company owned a
microstructure and lower total porosity in the hydrated paste cement plant which was built in 1958. In this cement plant,
in comparison with those of the reference OPC paste. It was wet processing was adopted for the production of OPC clin-
found that the hydration products of the produced alkali- ker. The washed red mud was first filtered and then trans-
activated cement were primarily amorphous C–S–H gel ported into the cement plant through a slurry pump.
with low Ca/Si ratio in the range of 0.8–1.2 without any Subsequently, the red mud was used instead of clay and
detection of crystallized Ca(OH)2, ettringite and zeolite-like incorporated with other materials such as limestone and
phases. sandstone, etc. to prepare cement clinker. Under the wet
processing technique, the total output of cement was 30 Mt
with consumption of red mud over 8 Mt in Shandong
Utilization potential of red mud in the
Alumina Cement Plant. In recent years, with the implemen-
cement industry tation of Chinese new cement standards in which the alkali
In Greece, 0.7 Mt of red mud is produced annually. content (Na2O þ 0.658K2O) in cement is strictly limited to no
Considering that 22 Mt of raw materials are used every more than 0.6%, the wet processing production line of
year in Greece for cement production (about 15 Mt year1) Shandong Alumina Cement Plant has been closed down. In
(http://www.hcia.gr), addition up to 3 wt.% will basically order to push ahead with the red mud utilization, Shandong
allow all the produced red mud to be accepted by the Alumina Company built a new cement clinker production
cement industry. In China, nearly 30 Mt of red mud is pro- line (dry processing) in 2003. Currently, the capacity of
duced each year, and the output of cement in 2009 was 1.6 Bt. cement produced from this dry processing line is
Considering that 2.4 Bt of raw materials are needed for 3 Mt year1. However, because of the constraint of alkali
cement production (1.6 Bt year1) in China, additions up to content required by the cement standard, the addition of
1–2 wt.% will result in the consumption of all the produced red mud into the raw meals of clinker production has largely
red mud by the cement industry. The world total production decreased. High alkali content in cement is a main factor to
of cement in 2009 was 2.8 Bt, and the worldwide alumina generate alkali-aggregate reaction and this reaction can cause
industry produces 70 Mt of red mud annually. Considering expansion of the altered aggregate, leading to spalling and
that 4.1 Bt of raw materials are used for the cement output of loss of strength of the concrete. Considering the high content
2.8 Bt year1, the addition of up to 2 wt.% will make all the of Na2O occurring in the red mud, solidification of Naþ in
produced red mud to be accepted by the cement industry red mud-containing cement to avoid alkali-aggregate reac-
globally. As reviewed in the section entitled ‘Production of tion of concrete could be an effective method to improve
Portland cement clinker from red mud’ above, small addi- the utilization ratio of red mud in cement production, and
tions of red mud (3–5 wt%) in the raw meals for producing deep research into the solidification mechanics of Naþ in red
Portland cement clinker does not negatively affect the prop- mud-containing cement is also required. Additionally, the
erties of the final OPC. In ideal circumstances, additions of red colour of red mud has also to be considered as a potential
2–3 wt.% red mud into the raw meals could allow all the constraint during the red mud utilization in cement produc-
produced red mud to be accepted by the OPC manufacturing tion, especially when red mud is added in a large percentage.
annually. However, since the current mixed content of red mud in
1062 Waste Management & Research 29(10)

cement production is relatively low (2–3 wt.%), it is thought suggestions to improve the quality of this review paper, and
that the issue of dark colour for the red mud utilization in kind permission to publish this paper.
cements can be negligible.
References
Agrawal A, Sahu KK and Pandy BD (2004) Solid waste management in
Conclusion non-ferrous industries in India. Resources, Conservation and
Recycling 42: 99–120.
Utilization of red mud for the production of cement is an Altundogan HS, Altundogan S, Tümen F and Bildik M (2002) Arsenic
efficient method of large-scale recycling for this bauxite res- adsorption from aqueous solutions by activated red mud. Waste
Management 22: 357–363.
idue. This review clearly points out three directions for the
Amritphale SS and Patel M (1987) Utilization of red mud, fly ash for
use of red mud in cement production, namely the preparation manufacturing bricks with pyrophyllite. Silicates Industriels 52: 31.
of cement clinkers, the production of composite cements as Amritphale SS, Anshul A, Chandra N and Ramakrishnan N (2007)
A novel process for making radiopaque materials using bauxite-
well as alkali-activated cements. The studies conducted on
Red mud. Journal of the European Ceramic Society 27: 1945–1951.
these three aspects are overviewed in detail. Due to the super- Apak R, Tütem E, Hügül M and Jülide H (1998) Heavy metal cation
fine particle characteristics of red mud, the produced cement retention by unconventional sorbents (red muds and fly ashes).
containing red mud generally exhibits slightly high normal Water Research 32: 430–440.
Bensted J (1996) A discussion of the paper ‘Determination and quanti-
consistency, but this does not affect the good fluidity of red fication of total chromium and water soluble chromium contents in
mud-containing cement. Tests demonstrate that good physi- commercial cements’’’ by M Frias and MI Sánchez Rojas. Cement
cal properties and excellent mechanical properties can be and Concrete Research 26: 329–330.
Cengeloglu Y, Kir E, Ersoz M, Buyukerkek T and Gezgin S (2003)
obtained for those products with proper proportion design,
Recovery and concentration of metals from red mud by Donnan
and they are also safe to the environment. However, from dialysis. Colloids and Surfaces A: Physicochemical and Engineering
this overview, it is found that, in most cases, the investiga- Aspects 223: 95–101.
tions conducted in this area have been on a laboratory scale, Coruh S (2008) Immobilization of copper flotation water using red
mud and clinoptilolite. Waste Management and Research 26:
and most of them were focused on the physical properties 409–418.
and mechanical properties of the red mud-containing Coruh S and Ergun ON (2010) Use of fly ash, phosphogypsum and red
cements, and hence further investigation on the durability mud as a liner material for the disposal of hazardous zinc leach res-
idue waste. Journal of Hazardous Materials 173: 468–473.
of the red mud-containing cements and their development Gordon JN, Pinnock WR and Moore MM (1996) A preliminary inves-
into industrial scale are still necessary to proceed. tigation of strength development in Jamaican red mud composites.
Utilization of red mud in cement production produces Cement and Concrete Research 18: 371–379.
Hills L and Johansen VC (2007) Hexavalent Chromium in Cement
significant environmental and economic benefits such as con-
Manufacturing: Literature Review. Portland Cement Association,
suming large quantities of red mud, lowering contamination Skokie, Illinois, USA, PCA R&D serial no. 2983.
of soil and groundwater, reducing landfill volume, cutting Huang W, Wang S, Zhu Z, Li L, Yao X, Rudolph V, et al. (2008)
Phosphate removal from wastewater using red mud. Journal of
waste disposal costs, saving natural resources for cement
Hazardous Materials 158: 35–42.
clinker, and decreasing the production cost of cement. http#http://www.hcia.gr (accessed 4 January 2011).
However, only a small amount of red mud is actually being http#http://www.redmud.org/Industrial_Uses.html (accessed 3 January
used in the cement industry currently. It is thought that two 2011).
Kalkan E (2006) Utilization of red mud as a stabilization material for
main factors constrain the large utilization of red mud in the preparation of clay liners. Engineering Geology 87: 220–229.
cement manufacturing. One factor is transport cost, and Kumar S, Kumar R and Bandopadhyay A (2006) Innovative method-
the other factor is the high alkalinity characteristic of red ologies for the utilization of wastes from metallurgical and allied
industries. Resources, Conservation and Recycling 48: 301–314.
mud. Considering that high content of Na2O occurring in
Kumar V, Nautiyal BD and Jha AK (1989) Use of neutralized red mud
the red mud, solidification of Naþ in red mud-containing in concrete. Indian Concrete Journal 63: 505–507.
cement to avoid alkali-aggregate reaction of concrete could Li Y, Liu C, Luan Z, Peng X, Zhu C, Chen Z, et al. (2006) Phosphate
be an effective method to improve the utilization of red mud removal from aqueous solutions using raw and activated red mud
and fly ash. Journal of Hazardous Materials B137: 374–383.
in cement production, and of course more investigations in Liu W, Yang J and Xiao B (2009) Application of Bayer red mud for iron
this area are required. recovery and building material production from alumosilicate resi-
dues. Journal of Hazardous Materials 161: 474–478.
Funding Newson T, Dyer T, Adam C and Sharp S (2006) Effect of structure on the
geotechnical properties of bauxite residue. Journal of Geotechnical and
This work has been financially supported by the National Geoenvironmental Engineering 132: 143–151.
Natural Science Foundation of China (project No. 51034008) Pan Z, Cheng L, Lu Y and Yang N (2002) Hydration products of alkali-
and China Postdoctoral Science Foundation (project No. activated slag–red mud cementitious material. Cement and Concrete
20100480202). Research 32: 357–362.
Pan Z, Li D, Yu J and Yang N (2003) Properties and microstructure of
Acknowledgements the hardened alkali-activated red mud–slag cementitious material.
Cement and Concrete Research 33: 1437–1441.
The authors are grateful to Professor H. Sun (University of the Paramguru RK, Rath PC and Misra VN (2005) Trends in red mud
Pacific, Stockton, USA) and Professor L. Li (Tsinghua utilization – a review. Mineral Processing and Extractive Metallurgy
University, Beijing, China) for their valuable comments and Review 26: 1–29.
Liu and Zhang 1063

Pera J, Boumaza R and Ambroise J (1997) Development of a pozzolanic Tsakiridis PE, Agatzini-Leonardou S and Oustadakis P (2004) Red mud
pigment from red mud. Cement and Concrete Research 27: addition in the raw meal for the production of Portland cement clin-
1513–1522. ker. Journal of Hazardous Materials B116: 103–110.
Pontikes Y, Nikolopoulos P and Angelopoulos GN (2007) Thermal Vachon P, Tyagi RD, Auclair JC and Wilkinson KJ (1994) Chemical
behavior of clay mixtures with bauxite residue for the production and biological leaching of aluminum from red mud. Environmental
of heavy-clay ceramics. Journal of the European Ceramic Society Science and Technology 28: 26–30.
27: 1645–1649. Vangelatos I, Angelopoulos GN and Boufounos D (2009) Utilization of
Pradhan J, Das SN and Thakur RS (1999) Adsorption of hexavalent ferroalumina as raw material in the production of Ordinary Portland
chromium from aqueous solution by using active red mud. Journal of Cement. Journal of Hazardous Materials 168: 473–478.
Colloid and Interface Science 217: 137–141. Wang S, Boyjoo Y, Choueib A and Zhu ZH (2005) Removal of dyes
Santona L, Castaldi P and Melis P (2006) Evaluation of the interaction from aqueous solution using fly ash and red mud. Water Research
mechanisms between red muds and heavy metals. Journal of 39: 129–138.
Hazardous Materials 136: 324–329. Wang S, Ang HM and Tadé MO (2008) Novel application of red mud as
Sglavo VM, Campostrini R, Maurina S, Carturan G, Monagheddu M, coagulant, adsorbent and catalyst for environmentally benign pro-
Budroni G and Cocco G (2000) Bauxite ‘red mud’ in the ceramic cesses. Chemosphere 72: 1621–1635.
industry. Part 1: thermal behavior. Journal of the European Ceramic Yalcin N and Sevinc V (2000) Utilization of bauxite waste in ceramic
Society 20: 235–244. glazes. Ceramics International 26: 485–493.
Sglavo VM, Maurina S, Conci A, Salviati A, Carturan G and Cocco G Yang J and Xiao B (2008) Development of unsintered construction
(2000) Bauxite ‘red mud’ in the ceramic industry. Part 2: production materials from red mud wastes produced in the sintering alumina
of clay-based ceramics. Journal of the European Ceramic Society 20: process. Construction and Building Materials 22: 2299–2307.
245–252. Yang J, Zhang D, Hou J, He B and Xiao B (2008) Preparation of glass-
Singh M, Upadhayay SN and Prasad PM (1996) Preparation of special ceramics from red mud in the aluminium industries. Ceramics
cements from red mud. Waste Management 8: 665–670. International 34: 125–130.
Singh M, Upadhayay SN and Prasad PM (1997) Preparation of iron rich Yue Q, Zhao Y, Li Q, Li W, Gao B, Han S, et al. (2010) Research on the
cements using red mud. Cement and Concrete Research 27: characteristics of red mud granular adsorbents (RMGA) for phos-
1037–1046. phate removal. Journal of Hazardous Materials 176: 741–748.
Snars K and Gilkes RJ (2009) Evaluation of bauxite residues (red muds) Zhang N, Sun H, Liu X and Zhang J (2009) Early-age characteristics of
of different origins for environmental applications. Applied Clay red mud-coal gangue cementitious material. Journal of Hazardous
Science 46: 13–20. Materials 167: 927–932.
Srikanth S, Ray AK, Bandopadhyay A and Ravikumar B (2005) Phase Zhong L, Zhang YF and Zhang Y (2009) Extraction of alumina and
constitution during sintering of red mud and red mud-fly ash mix- sodium oxide from red mud by a mild hydro-chemical process.
tures. Journal of the American Ceramic Society 88: 2396–2401. Journal of Hazardous Materials 172: 1629–1634.