ABSTRACT

REVIEW OF LITERATURE
The environmental problem of Red Mud disposal is more acute in Japan, U.S.
and the European countries compared to Afro-Asian countries. In 1965, there
were public protests in France, which induced experts to give their decision for
a red mud dumping project in Bay of Cassis (Mediterranean Sea) (Dass et aL,
1995)
Red mud till today is mostly disposed off in two conventional ways. Firstly in
countries like Japan, Germany, France, etc it is directly disposed off into the
sea due to lack of land area available for dumping. In other countries however
where the dumping area is available it is disposed off in pools or lagoons made
for this purpose and the slurry is left open for sun drying, and overflowing
water taken back into the plant based on the conditions. The main reason for
implementing this method is low cost and easy implementation. It is widely
followed by nearly all the Indian plants except a few who have adopted dry
disposal only recently, (Thakur et al. 1995).
Whenever these wastes are disposed off, it causes harm to the surroundings.
The environmental chemistry and toxicity of aluminium in red mud is
significant under such alkaline conditions. This may create different impacts
under different environmental conditions. The conditions to consider are
annual rainfall, wind velocity, soil permeability, average temperature and so on
for land disposal while for sea disposal it depends upon length of inlet pipe,
depth at the point, variety of fish culture and under currents, if any.
Amelioration of red mud disposal sites is essential to use red mud as a soil
conditioner.
Halsband and Halsband(1971), Paffenhoefer(1971 and 1972), Cole(1973),
Blackman and wilson(1973), Rosenthal et al. (1971, 1972 and 1973) were the
firsts to study the physiological effects of red mud on marine organisms. In
northern sea, algae was getting affected at a lower rate compared to fishes.
However up to a concentration of 1g/l, it was not damaging either organism.
The iron hydroxide part of red mud was particularly responsible for inhibiting
growth in C. helgolendices cultured on phytoplakton. It was established in
general that waste was found harmful to fish or shell fish will similarly affect
other organisms also. Killing of fish and shell fish at any stage in their life cycle
contaminated them with persistent toxic substances so they became unsafe to
eat and were temporarily unsaleable. (Cole, 1973) Another impact is that
certain metals may accumulate in fish, which might not impact physiology of
fish but made fish quite unsafe for human consumption.
Williams and Hamdy (1982) introduced biological activities in red mud in order
to neutralize their extra alkali. In an envisaged programme, alfa alfa hey was
mixed up with red mud, which stimulated bacterial growth resulting in
production of organic acid within the system. This acid neutralized excess alkali
and made it amenable for earthworm and plant growth.
Koch and Bell (1983) used red mud along with lie and saw dust to make low pH
soils suitable for plant growth. Red mud at around 18% concentration was
found to be quite effective in reducing acidity and level of available aluminium
in the overburden spoils of coalmines. The red mud had some inherent fertility
especially in phosphorous but also had high adsorption capacities when
phosphate was added as fertilizer. However since its neutralization capacity
was less than that of CaCO3, it was found to be uneconomical under higher
concentrations.
Patel et al. (1986) studied the concentration of pollutant fluorides in effluents
and by product of alumina industry in India. Samples were obtained from
different alumina and smelter plants and collection was carried out also after
sufficient time gaps. It was a study of impact of micro pollutants in red mud on
soil and waters.
Mussels et al (1993) did a review to assess the feasibility of bioremediation of
bauxite residue by making estimates of the possible substrate and inoculums
required to achieve neutrality. Various possible avenues of microbial
neutralization were assessed in terms of the practicality of application of
bauxite residue. These involved the ability of an organism to survive and grow
in red mud and their production of neutralizing agent mainly organic acid and
carbon dioxide.
GLOBAL RESERVES
The top 5 countries, Guinea, Australia, Brazil, Vietnam and Jamaica, hold over
70% of the world's documented bauxite reserves.

Of these counties only Australia, Brazil and Jamaica have realised their
potential as bauxite mining or alumina producing nations. While still a major
bauxite producer sovereign risk has stunted development of the industry in
Guinea to a fraction of its full potential.

Strict nationalistic policies in Vietnam have resulted in the industry only just
beginning to emerge. Indonesia also possesses significant bauxite holdings and
has become a major exporter to China.

According to industry sources India, with total bauxite reserves of about 3

billion tonnes (or 4.87 billion tonnes), accounts for almost 9.76% of the world's
65 billion tonnes bauxite reserves and is ranked seventh among the countries
with highest bauxite reserves. Indian bauxite reserves are expected to last over
350 years with probable reserves estimated at ~1200 million tonnes. With over
7% growth per annum, one of the highest in the world, the Indian aluminium
market is booming. Total aluminium consumption in the country is around
1100 kt at present, which has grown significantly from 2002 level of 600 kt.
Though India's per capita consumption of aluminium is quite low (b1 kg)
compared to the per capita consumption of other countries like the US and
Europe (25 to 30 kg). Analysts say bauxite production in India should grow at
17.7% though 2020, with an estimated 8.2% contribution to the global output,
this year alone.

Bauxite production and relative proportion of main countries in 2008 (Saxena, Mohini., Gowari, V.S., Gupta, T.N).
World Bauxite Reserves – Key Counties

Brief details of the bauxite in key counties is provided below. More extensive
analysis if these countries is provided in sections at the end of this document.

 Guinea: High alumina content. Major concentration areas: Lower

Kindiaand Boke (around 5 billion), Central Labe (500 million), Gaoual
(500 million); and Upper Dabola (around 1.9 billion).
 Australia: Abundant reserves of easily mined surface deposits. Major
concentration areas include: 1) the Gulf of Carpentaria, 2) Darling
Ranges, 3) Mitchell Plateau and Cape Bougainville.
 Brazil: 90% of Brazil’s bauxite is distributed in Para State in northern
Brazil.
 Vietnam: Mainly distributed in DakLak, DakNong, Kon Tum and Lam
Dong provinces in central and southern Vietnam. Deposits are mainly
lateritic (Al2O3 36-39% or sedimentary (Al2O3 39-65%).
 India: Widely distributed, however 60% of all identified reserves are in
Orissa and Andhra Pradesh along East Coast.
  Indonesia: Mainly distributed in Bangka Island, Belitung Island, West
Kalimantan and Riau Province (Bintan Island).

TYPES OF BAUXITE
Bauxite deposits are commonly referred to by a number of different
terminologies relating to either their mineralogy or geological formation.

Alternately they may be described by likening them to other well-known

deposits elsewhere around the globe.

According the to their mineralogy:

1. Trihydrate or gibbsitic bauxite: consisting chiefly of gibbsite

2. Mixed bauxite: typically consisting of significant proportions of both
gibbsite and boehmite.
3. Monohydrate bauxite: consisting mainly of boehmite or diaspore.

According to their geological formation

1. Lateritic: formed in situ from weathering of aluminous parent rocks in

tropical and temperature regions. Consisting mostly of gibbsite or a
mixed gibbsite and boehmite content.
2. Karst: partially transformed or transformed bauxite materials washed
and accumulated in eroded limestone cavities where further
 transformation can occur. Commercially significant karst bauxites occur
in Europe, the Middle East, China and Jamaica.

According to other well-known deposits:

1. Suriname type: a pseudonym for trihydrateor gibbsitic bauxite

2. European type: composed mainly of boehmite
3. Jamaica type: applied to very fine grained high-iron gibbsitic bauxite
containing minor quantities of boehmite.
The Bayer Process:
Alumina is the main components of bauxite, so bauxite is refined in order to
produce Alumina. The Bayer process is the principal way for producing alumina
by refining Bauxite. Bayer process was invented by Austrian chemist, Carl Josef
Bayer in 1887, while working in Saint Petersburg, Russia for developing a
method to supply alumina to the textile industry. The Bayer process started
gaining importance after the invention of Hall-Heroult aluminium process. Till
today the process is unchanged and is used to produce nearly all the world’s
alumina supply

Bauxite other than with 30-60percentage of aluminium oxide contains mixture

of silica, iron oxides and titanium dioxide.

Bayer process of producing alumina can be divided into following four steps:

i. Digestion: A hot caustic soda (NaOH) solution is used to dissolve the

aluminium-bearing minerals in the bauxite (gibbsite, böhmite and diaspore) to
form a sodium aluminate supersaturated solution or “pregnant liquor”.

Gibbsite:
Al(OH)3 + Na+ + OH- → Al(OH)4- + Na+

Böhmite and Diaspore:

AlO(OH) + Na+ + OH- + H2O → Al(OH)4- + Na+

. Conditions within the digester (caustic concentration, temperature and

pressure) are set according to the properties of the bauxite ore. Ores with a
high gibbsite content can be processed at 140°C, while böhmitic bauxites
require temperatures between 200 and 280°C. The pressure is not important
for the process as such, but is defined by the steam saturation pressure of the
process. At 240°C the pressure is approximately 3.5 MPa.

The slurry is then cooled in a series of flash tanks to around 106°C at

atmospheric pressure and by flashing off steam. This steam is used to preheat
spent liquor. In some high temperature digestion refineries, higher quality
bauxite (trihydrate) is injected into the flash train to boost production.  This
"sweetening " process also reduces the energy usage per tonne of production.

Although higher temperatures are often theoretically advantageous, there are

several potential disadvantages, including the possibility of oxides other than
alumina dissolving into the caustic liquor.

ii. Filtration: In this step the mixture is clarified to remove impurities. Other
than alumina and silica, all other components present in Bauxite do not get
dissolved. The solids which are not dissolved get settled down at the bottom
forming red mud. This red mud is then discarded from the solution commonly
by using rotary sand trap.

The filtration process converts the aluminium oxide to soluble sodium

aluminates, 2NaAlO2, as per the equation:

Al2O3 + 2NaOH → 2NaAlO2 + H2O.

iii. Precipitation: The clear remaining mixture is added to precipitators by using

heat exchangers, which turns the mixture from heat to cool liquor. Silica is
precipitated from the mixture because heating. Crystals of aluminium
hydroxide are discovered in this step. Some amount of aluminium hydroxide
discovered in this step is used as a water treatment chemical

iv. Calcination: 90 percentage of the gibbsite manufactured is converted into

alumina by washing, drying, and then heating aluminium hydroxide in a rotary
klins or fluid flash calciners at temperature 1010-1260 degree Celsius.

2 Al (OH) 3 → Al2O3 + 3 H2O.

More than 90 percent of alumina manufactured is used to produce aluminium

by Hall-Heroult Process. Alumina, a white powder, is the product of this step
and the final product of the Bayer Process, ready for shipment to aluminium
smelters or the chemical industry.
NEUTRALISATION OF RED MUD

This alumina refinery waste is highly alkaline in nature with a pH of 10.5-12.5

and is conventionally disposed of in mostly clay-lined land-based
impoundments. The alkaline constituents in the red mud impose severe and
alarming environmental problems, such as soil and air pollution. Keeping in
view sustainable re-vegetation and residue management,
neutralization/treatment of red mud using different techniques is the only
alternative to make the bauxite residue environmentally benign.

Untreated or un-neutralized bauxite residue may have following adverse

effects (Power et al., 2009):

1) A highly alkaline, poorly compacted mud overlay is created;

2) It is highly lethal to natural ecosystems and hazardous to humans and
wildlife due to the contamination of surface and ground waters by leaching of
caustic liquor and associated toxic metals and alkaline dust;
3) Red mud ponds are difficult to close and rehabilitate because of the need to
remove a high amount of both supernatant and entrained caustic liquor;
4) Proper planning and engineering would be required to avoid catastrophic
failure of impoundments;
5) The high construction and maintenance cost of the pond. The treatment of
red mud is the only alternative and one of the most important ways of
reducing the environmental impacts of alumina industry (Cooling, 2007).
Towards this, a more sustainable method is neutralization of red mud and its
adequate treatment to allow its reuse, and this will certainly play an important
part in bauxite residue management due to increasing environmental
awareness and regulation (Brunori et al., 2005).
Neutralization will convert the highly alkaline state of red mud to a state that is
no longer highly alkaline and is less hazardous and safer to handle. The
neutralization of red mud to pH around 8.0 is optimum, because the chemically
adsorbed Na is released, alkaline buffer minerals are neutralized and toxic
metals are insoluble at this pH.
NEUTRALIZATION TECHNIQUES

1) Acid neutralization:

Neutralization using acids can be a cheaper option if sufficiently large

quantities of waste acid are available. Studies have been carried out for the
feasibility of treating bauxite refining residue with acid on Kwinana red mud
slurry (Hughes and Thornber, 1991). Carbonic acid (H2CO3) has also been used
for treating red mud. Besides, acidic industrial wastewater has also been
applied (Wong and Ho, 1994). Red mud has been treated with hydrochloric
acid to dissolve only the sodium content in red mud and make construction
bricks from the treated material after mixing it with kaolinitic clay

2) Neutralization using amenders:

The caustic properties of red mud can be ameliorated using low cost materials
having acidic properties (which may be called amenders). Neutralization with
low cost chemicals or amenders can ameliorate
red mud to develop vegetation cover on the surface of large disposal ponds
and abandoned bauxite mine pits. Vegetation cover will not only prevent
deterioration of soil erosion, but also act as a method of suppressing dust
generation due to the dried red mud. Neutralizing agents, such as coal dust,
superphosphate and gypsum, have the capacity to ameliorate the caustic
(alkaline) properties.

3) Neutralization using CO2

Atmospheric carbon dioxide or CO2 from industrial emissions can be a

significant source of acid for neutralizing red mud (Enick et al., 2001). Gas
phase CO2 or CO2-containing flue gas can be bubbled through
aqueous slurries to form carbonic acid in the aqueous phaseThe carbonic acid
would react with the basic components of red mud, lowering its pH. By mixing
carbon dioxide into the bauxite refining residue, the pH level is reduced
to levels normally found in alkaline soil.

4) Seawater neutralization
Seawater neutralization does not eliminate hydroxide from the system but
converts the readily soluble, strongly alkaline wastes into less soluble, weakly
alkaline solids. The carbonate and bicarbonate alkalinity of the waste is
removed mainly by reaction with calcium to form aragonite and calcite.
Seawater neutralization makes the red mud noncaustic but does not reduce its
acid-neutralizing capacity. This allows the red mud to be used without the
need for further chemical treatment. It has been established that reductions in
both pH and aluminium from the seawater neutralization process are due
to the formation of ‘Bayer’ hydrotalcite Mg7Al2OH18CO3/,
Mg7Al2OH18SO4·xH2O. This is the primary mechanism involved in the removal
of aluminium from solution.

5) Treatment of red mud through the sintering method

The neutralization or treatment of red mud using the sintering route is also
one feasible option .In the presence of an additive that provides silica, such as
fly ash, red mud can be sintered at a high temperature, which appreciably
lowers the pH value to an acceptable limit. The study on the neutralization of
red mud using the sintering route carried out by Rai et al. (2013d) showed that
temperature is the most important factor and a pH value of about 8.9 can be
obtained by mixing 25–50% of red mud with 50–75% of silicate material (i.e. fly
ash) at a temperature of 1100°C.
Bauxite amelioration of bauxite residue waste of industrial alumina
plants (Hamdy and Williams, 2001)
Six 10- l samples from Alcoa bauxite Residue Lake deposit at Mobile, AL were
collected in sterile laminated stainless steel containers. The first and second
samples were obtained from the bauxite residue lake deposit near the dike
and below the residue surface (0–5 and
5–20 cm, respectively), the third and fourth were 20 m away from the dike and
also below the surface (1–5 and 5–20 cm, respectively). The fifth sample was
fresh slurry, secured directly from the processing plant, and the sixth was lake
water from the impound bauxite residue lake.

This was followed by microbial analyses, repair of metabolically resting

bacteria and hay analyses and bioremediation of bauxite residue in columns.

Results –
Low levels of injured bacterial cells in the bauxite residue actively grew using
hay and/or various added nutrients. A lowering in pH from 13 to 7 occurred as
the organisms grew from less than 10 to more than 10 9 cells/g bauxite residue
and formed organic acid. A variety of bacterial cultures were isolated from
treated bauxite residue that included the species of Bacillus, Lactobacillus,
Leuconostoc, Micrococcus, Staphylococcus, Pseudomonas, Flavobacterium and
Enterobacter. Scanning electron micrographs demonstrated that untreated
particles of the bauxite residue were clumped together, and in treated bauxite
residue these particles were highly dispersed with micro colonial structures.
The treated residue supported growth of several earthworms and plants that
survived in it for almost over 300 days.
a) Effect of medium

b) Effect of added nutrients

 c) Effect of Bermuda grass hay and other added nutrients

An evaluation of successful reclamation of bauxite residue through

afforestation activities in south India (Suresh Chauhan and C. S.
Silori, 2011)

A pilot plant was implemented to improve the physio chemical characteristics

of bauxite residue (red mud) in order to make it more suitable for afforestation
activities. Prior to this, extensive experimentation on various reclamation trials
involving combinations of soil amenders along with bacteria and mycorrhizae
and selection of suitable tree and grass species was undertaken at the nursery
stage for one year. Five tree species and four grass species were finally
selected for the afforestation program. In the process, three out of five tree
species, Prosopis juliflora, Acacia nilotica and Pongamia pinnata responded
very well in combination with 55% red mud + 25% FYM + 15% gypsun + 5%
vegetative dry dust + bacteria + mycorrihzae, whie two species Melia
azedarach and Acacia tortilis did not survive and thus were replaced by Albizia
lebbek and Leucaena leucocephala during pilot implementation in 1.08 ha
research plot of red mud at Hindustan Aluminium Company Limited at
Belgaum, Karnataka, South India. Among the grass species, all the selected
species namely : Brachiaria mutica, Brachiaria becumbens, Stylosanthes scabra
and Sesbania sesvan responded well at the nursery stage and thus were
experimented at the research plot along with the tree plantation. Continuous
monitoring on growth pattern of tree and grass species, and soil characteristics
revealed remarkable changes in the physiochemical properties of red mud.
Apart from this, toxicity of the planted species and other naturally grown
herbaceous flora on the research plot of red mud was also tested for their
edibility properties and the results were found encouraging.

The reclamation of red mud pond was essentially based on experimentation of

the vegetative treatment at nursery stage and scaling it up at the red mud
pond site on pilot basis. The entire approach thus, included two major phases,
spanning over 5 years from 2002 to 2007. The first phase consisted of nursery
experiments with selected plant species grown under different set of
treatments and the second phase was to execute the nursery level results to
the pilot stage implementation.
Results-
Survival of tree species
Tree Height

Average density of plants and leguminous species

Average Height of grass and leguminous species

Changing Pattern in physical and chemical properties of the red mud

In order to analyse the change in properties of red mud three different

samples from different depths were taken for analysis (15 cm, 30 cm and 45
cm). The results indicated positive changes in both physical and chemical
properties of the red mud. pH values declined, micronutrients and total
bacterial population reported noticeable increase which ultimately made the
edaphic environment suitable to grow the vegetation and sustain it. Sand
contents increased while slit and clay contents decreased at all the three
depths.