An overview of chemical processes to manufacture

red mud construction products

Arun S. Wagh
Inorganic Polymer Solutions, Inc., 4 Helens Way Court, Naperville, IL, 60565, U.S.A.

Abstract
Major deposits of red mud are in highly populated emerging economic regions. Recycling
red mud as construction materials is important to these countries for economic as well as
environmental reasons. Room-temperature-setting chemical reactions to solidify red mud
into construction products may be one way to recycle red mud. We present two methods
developed by us, one in Jamaica and the other in U.S.A. The first method (Geopolymeric
method) takes advantage of the high alkalinity and high alumina content in red mud. Adding
sodium silicate, we developed sodium alumino-silicate binding phases in red mud. Using this
process, Jamaica Bauxite Institute constructed a demonstration sports pavilion with red mud
bricks. The second process is a byproduct of Ferro-Ceramicrete developed in Argonne
National Laboratory for immobilization of nuclear weapons legacy waste. In this process, we
took advantage of high content of iron oxide (hematite) in red mud, and partially reduced a
small portion of it to initiate activation reaction with an acid-phosphate. This process
produces rapid-setting alternative red mud cement that can be used to manufacture concrete,
bricks, and building blocks. Both processes have been proven and used in other fields. It is
hoped that red mud community will exploit these processes for recycling red mud.
Keywords : Red mud, Geopolymer, Ferro-Ceramicrete, Acid-phosphate, Construction
materials.
1. Introduction
Red mud, an industrial waste resulting from extraction of alumina from Bayer process, is a
mineral waste, containing iron in the form of hematite (Fe2O3), left-over aluminum oxide
(Al2O3), silica (SiO2), some titanium dioxide (TiO2), and other residual minerals. Because
the Bayer process uses dissolution of alumina in caustic soda for extraction of the same, the
waste also contains approximately 3wt.% sodium hydroxide that makes the mud highly
alkaline (pH in the range of 12 to 13).
At high pH, solubility of alumina and silica is much higher than at neutral pH. Thus, one can
take advantage of the dissolved minerals of these oxides and bind red mud particles to form
complexes of the dissolved substances. We evaluated the resulting products approximately
30 years back in an extensive study on Jamaican red mud [1]. The products are now known
as Geopolymers [2]. The work was conducted mainly in the University of the West Indies
and Jamaica Bauxite Institute in collaboration with McGill University in Montreal. Canadian
International Development and Research Centre (IDRC) funded this project.
Subsequently, we employed our minerals knowledge gained by the work in Jamaica to
radioactive waste stockpiled in the United States at U.S. Department of Energy sites since
years of weapons production in that country. While working on stabilization of a range of
nuclear waste streams, we also developed similar processes to bind minerals, but this time,
using phosphates. These processes again depended heavily on solubility characteristics of
236 TRAVAUX Vol. 36 (2011) No. 40

minerals in the waste. Realizing the similarity between the two processes, we returned to red
mud and conducted a limited study on red mud obtained this time from Alcoas operations in
Point Comfort, Texas (U.S.A.). This work was done approximately 12 years ago with a
generous funding from the U.S. Department of Energy at Argonne National Laboratory near
Chicago (U.S.A.). This paper gives an account of the two processes with an emphasis on the
role of solubility characteristics of minerals in binding red mud and how that could be
exploited to produce red mud products.
2. Typical red mud compositions
Table 1 provides a list of typical composition of red mud from two disposal areas in Jamaica.
Like any other red mud, Jamaican red mud is rich in hematite followed by alumina, calcium
oxide, and silica. Sodium oxide (in the form of sodium hydroxide) concentration is also high,
which makes the mud highly alkaline.
Table 1. Typical composition of red mud from two different operations in Jamaica
Alpart red mud Alcan red mud (Kirkvine)
Oxide
(From Boehmitic bauxite) (From Gibbsitic bauxite)
Al2O3 16.35 16.52
SiO2 7.99 3.05
CaO 9.06 5.68
MgO 0.45 0.34
Fe2O3 42.33 49.83
TiO2 5.99 6.8
Na2O 4.6 1.4
Loss on ignition 10.2 13.41

One may notice from Table 1 that almost half of the red mud consists of iron oxide. The
other significant components are alumina, silica, calcium oxide, titanium dioxide, and more
importantly, sodium oxide. Few other minor components also exist but are not listed in the
table, simply because they have no bearing on the solidification process or the product.
Sodium oxide, in the form of sodium hydroxide, is responsible for high alkalinity of red
mud. This alkalinity is very important for geo-polymerization of red mud. Red color of red
mud is due to iron oxide. As we will see later, alumina, silica, and calcium oxide are crucial
for solidification of red mud by the geopolymerization process, while iron oxide is important
for phosphate solidification.
3. Role of solubility in solidification of red mud
Solubility of the red mud components plays a crucial role in binding minerals. The principle
behind both geopolymer and phosphate processes is that the minerals should at least partially
dissolve and ionize so that their ions are available for reactions. Under right conditions, such
as suitable stoichiometry, these ions will react and form the most thermodynamically stable
binders. This principle is applied to both processes.
Figure 1 shows the solubility product constant (pKsp, a measure of solubility) of major red
Arun Wagh : An overview of chemical processes to manufacture red mud construction products 237

mud components as a function of pH. As one may notice from the figure, alumina, calcium
oxide, and silica have high solubility in the extreme alkaline region. Hematite (Fe2O3), on the
other hand, has high solubility in acidic region but its solubility is very low in alkaline
region. This is the reason alumina can be dissolved in highly alkaline Bayer liquor and
separated from the major components of bauxite such as iron oxide.

Fig 1. Log(pKsp) as a function of pH. The unlabeled solid curve is for SiO2.
In the geo-polymerization process, one exploits the high solubility of the minerals in the high
alkaline region. The process itself is dependent on extremely high solubility of silica and
alumina in the presence of sodium ions to form sodium alumino silicate as the binding phase.
Red mud has all three to form this binder. However, though the alumina and sodium content
is sufficient, silica content of 3 8wt.% is not good enough to form alumino silicate. Also
there is an issue of whether silica is in the right form to dissolve, because amorphous silica
dissolves easily at high pH but quartz does not. Due to some dissolved silica, red mud, when
dried, exhibits partial bonding. This attribute is called pozzalinic activity. Addition of silica
in soluble form can enhance this activity. This activity is responsible for solidification of red
mud. This is how red mud bricks were produced in Jamaica.
In the phosphate process, the bonding mechanism is entirely different. The process is based
on acid-base reaction, in which an acid-phosphate is added to an alkaline mineral. The acid
phosphate ions react with the ions of iron and form solids [3]. For example, at a pH between
2 7, phosphoric acid releases ions of dihydrogen phosphate (H2PO4-) by the dissolution
reaction,
H3PO4 = H+ + H2PO4-
At the same time, FeO, having high solubility in the acidic region, dissociates into its cation
and anion pairs according to
FeO = Fe2+(aq) + O2-.
The symbol (aq) indicates that it is an aqueous ion. Fe2+(aq) and H2PO4- react together to
eventually form FeHPO4. The total reaction may be written as
238 TRAVAUX Vol. 36 (2011) No. 40

FeO + H3PO4 = FeHPO4 + H2O.

FeHPO4 is the binder component that forms the solid product.
These reactions cannot occur, unless we have at least sparsely soluble species of iron oxide,
such as FeO. To convert some of the insoluble iron oxide to soluble ones, we used reduction
mechanism [4]. A very small amount (0.25 wt.%) of elemental iron was added and reacted it
with hematite. Elemental iron reduces iron oxide partially, the acid-base reaction occurs
immediately, and rapid-setting cement is formed. The reduction reaction is represented by
the Equation

Fe2O3 + Fe = FeO + Fe2O3-

The symbol in the above equation is the fraction of a mole of iron (Fe) that is added to red
mud. It is a very small amount, but its effect goes a long way. It produces a very small
amount of FeO, which is very highly soluble (see Fig. 1). It reacts with phosphates and forms
bonds. In addition, the reduced phase of hematite, viz., Fe2O3- is more soluble in acidic
conditions. So it forms its own phosphate bonds. Both together provide a good ceramic bond
in the reaction product, which is glassy. Details of this ceramic may be found in references
[3, 5].
These two totally different approaches depend on one concept. For a reaction to form bonds,
the components have to dissociate in solution. The first approach takes advantage of high
alkalinity of red mud, and the second one that of high iron oxide content in red mud.

4. Experimental demonstrations of the two processes

Geopolymers are alumino silicate binders [2]. As mentioned before, the silica content is not
sufficient in red mud to form geopolymers. Therefore, we used liquid sodium silicate
(Na2SiO3) as the activator in dry red mud. The reaction between sodium silicate and red mud
components was sufficient to cast bricks in a brick machine. Some of the properties of the
resulting product are presented in Figs. 2 and 3.

Fig 2. Compressive strength as a function of sodium silicate of red mud samples

Arun Wagh : An overview of chemical processes to manufacture red mud construction products 239

Fig 3. Modulus of rupture as a function of sodium silicate content

Figures 2 and 3 show the variation of mechanical properties of the set samples with the
silicate addition. As the silicate content increases, both compressive strength and modulus of
rupture increase linearly. Initially, red mud from gibbsitic bauxite (Alcan red mud) shows
higher strength values, but as the silicate content is increased, red mud from boehmitic
bauxite (Alpart red mud) shows much higher values. This may be because, red mud from
boehmitic bauxite contained higher amount of sodium. For a geopolymeric reaction,
sufficient amount of alkali metal is necessary. When sufficient amount was supplied through
sodium silicate, Alcan red mud samples showed higher strength.

Fig 4. Micro structure of the solid product formed by reaction with sodium silicate
240 TRAVAUX Vol. 36 (2011) No. 40

It is interesting to see the microscopic structure of the set product. Figure 4 shows the micro
structure of a fractured surface of one of the red mud samples bonded with silicate. The
surface is full of whiskers of size of only couple of microns. It is very difficult to
characterize these whiskers due to their small size. However, comparison of microstructure
of standard minerals provides some insight. They are crystals of alumino silicates or iron
silicates, or both [6]. Whatever be their actual composition, they provide better fracture
toughness and modulus of rupture to the product due to their acicular structure.
Using this process, Jamaica Bauxite Institute made sufficient bricks and constructed a
demonstration building during 1986. Figure 5 is a copy of an old photograph of that building.
Since bricks of visibly good compaction and compressive strength of 25 MPa are generally
acceptable for single storey structures, it was considered feasible to build this structure for
monitoring purposes. The floor area of the building was 48m2. It was built on concrete
foundation and consideration was given to the fact that Jamaica gets hurricanes, and often
there is seismic activity. Unfortunately, we have not followed up on the aging of the
building, but Jamaica Bauxite Institute, who took this initiative, may have more data on this.
Details of the construction and materials may be found in the article by McLeod et al. [7].
The demonstration of the phosphate binding process for red mud was limited compared to
the silicate process, though the phosphate process has been demonstrated on pure hematite,
magnetite, and metal swarfs. Details may be found in reference [8].
Red mud used in this process was obtained from Point Comfort operations of Alcoa in
Texas. Its composition is provided in Table 2.

Fig 5. Twenty five year old photograph of the red mud brick
building constructed by Jamaica Bauxite Institute.
Arun Wagh : An overview of chemical processes to manufacture red mud construction products 241

Table 2. Composition of Point Comfort red mud

Oxide Composition (wt.%)
Al2O3 18
Fe2O3 40
Na2O 2.7
CaO 7.6
SiO2 9.6
TiO2 8.5
Loss on ignition 10.3
This red mud, produced from Guinea bauxite had less iron oxide than Jamaican bauxite.
However, 40% of iron oxide is still more than what is needed to initiate a binding
mechanism.
The as received mud was sludge with 30% water. The pH was >13. To this mud we added
equal amount of sand and mixed for 10 min. To this mixture, we added 12.5 wt.%
phosphoric acid solution of 85% concentration and mixed it for 5 min. The acid-base
reaction between caustic soda and phosphoric acid occurred with some exothermic heat
evolution. To this, we added reagent grade iron and mixed. The amount of iron added was
0.2 wt.% of the mixture of red mud and sand. It formed a thick mass that was put in a brick
mold of size 20 cm x 10 cm x 6 cm and pressed at a pressure of 1000 psi. Again heat was
generated. The brick was hot but cooled within half hour in the mold. It had sufficient
strength so that it can be taken out of the mold. It set well after one day.
Unfortunately, we did not measure the strength of this brick, because this was only one
demonstration of the process with various iron oxide containing materials and there is
sufficient evidence that the brick would have a compressive strength of at least 20 MPa. Data
on pure iron oxide is presented extensively in the literature [5]. The important aspect of this
process, however, is that we did not use dry mud as in the case of Alpart red mud, and wet
mud itself was our starting material. Done in a large scale right at the source of the red mud
pond, this process may avoid dewatering step and can lead to significant cost reduction.

5. Discussion
The two processes discussed in this paper have still been mostly at the laboratory or pilot
scale, but they present novel chemical methods of binding red mud. They need to be tested at
a full scale. The demonstration at Jamaica Bauxite Institute is a good step towards this.
Both geopolymer and phosphate processes are in commercial use with similar other
materials in various applications. Mostly geopolymer process is used in Europe and the
phosphate process in the United States. Geopolymers are also known as Alkali-Activated
Cements. Chemistry and applications have been extensively covered in three books cited in
the reference [2,3, and 8]. These books provide sufficient insight into the processes by which
a researcher can develop his/her own methods of binding red mud. Our research is only the
beginning.
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6. References

[1] Wagh Arun S., A Study of Jamaican Bauxite Waste, Report 154 (vol. I III) to
International Development and Research Centre, Ottawa, Canada, University of the West
Indies, Kingston, Jamaica, 1986, pp.171.
[2] Davidovits, J., Geopolymers, Their Chemistry and Applications, Geopolymer Institute
pub. 2008, pp 584.
[3] Wagh, Arun S., Chemically Bonded Phosphate Ceramics, Elsevier pub. 2004, 300p.
[4] Pourbaix, Lance, Electrochemical Equilibria in Aqueous Solutions, NACE and Cebelcor
pub. 1974, pp 644.
[5] Wagh, Arun S., Jeong, S. Y., Chemically Bonded Phosphate Ceramics, III, Reduction
Mechanism and its Applications to Iron Phosphate Ceramics, J. Amer. Ceram. Soc., Vol.
86, No.11, (2003) pp1850-1855.
[6] Klein, Cornelis and Klein, Cornelius, Jr., Manual of Mineralogy (After J. D. Dana), 20th
ed., J. Wiley and Sons pub. 1985, pp 596.
[7] McLeod, D., Gordon, J., Rao, A.G.M., and Nyein, U. Kyew, Stabilised Building Material
Using Red Mud, in Bauxite Tailings, Proc. International Conf., Jamaica, 1986 pp 131-
137.
[8] Shi, Caijun, Krivenko, Pavel V., and Roy, Della, Alkali-Activated Cements and
Concretes, Taylor and Francis pub. (2006) 376 p.