Debre Berhan University Food & Beverage

Institute of Technology Industry R&D

Chemical Engineering Center

Beneficiation and Industrial application of Indigenous Bentonite Clay:

pharmaceutical sector, Oil Bleaching, Brewery, water and wastewater
treatment

Team Members Profession Role

1) Sishu H/Mariam (Msc) Environmental Engineering PI
2) Tsiye T/Yohannes Process Engineering Member
3) Befkadu Ayalkie Environmental Engineering Member
4) Dr. Neway Belachew Chemistry Member
5) Gebeyanesh Endalkachew Food Engineering Member
6) TA Pharmacy Member

Contacts:
Email: sishu39@gmail. com
Phone: 0912925954

Debre Berhan, Ethiopia

September,2022
Contents
1. Introduction ................................................................................................................... 3
1.1. Problem Statement ...................................................................................................... 4

1.2. Objectives .................................................................................................................... 5

1.2.1. General Objectives ................................................................................................... 5

1.2.2. Specific Objectives ................................................................................................... 5

1.3. Scope of the study ....................................................................................................... 6

1.4. Significance of the Study ............................................................................................ 6

2. Literature Review ........................................................................................................ 7

2.1. Clay and Clay Minerals ............................................................................................... 7

2.2. Bentonite Clay ............................................................................................................. 7

2.3. Industrially Attractive Properties of Bentonite ........................................................... 8

2.4. Uses of Bentonite ...................................................................................................... 10

2.4.1. Pharmaceutical Uses of Bentonite .......................................................................... 11

3. Materials and Methods .............................................................................. 15

3.1. Collection of Samples ............................................................................................... 15

3.1.1. Sample Preparation ................................................................................................. 15

3.2. Purification of Raw Bentonite ................................................................................... 15

3.2.1 Method-I: Simple Sedimentation............................................................................. 15

3.2.2. Method-II: Classical NaCl Treatment .................................................................... 16

3.2.3 Method-III: Soda Activation Followed by Sedimentation ...................................... 16

4. Budget ............................................................................................................................ 16

5. Schedule ........................................................................................................................ 18

6. Reference ........................................................................................................................ 18
 1. Introduction
Clay is the most important, plentiful, and low cost naturally occurring material, widely used in
diverse fields that are agriculture, engineering, construction, process industries and
environmental application [1]. Clay composed primarily of fine-grained minerals, which
generally show plastic behavior at appropriate water contents and hardness upon drying or
firing [2]. Clays are studied by, and used in many disciplines for fundamental, applied research
and in industry. The multidisciplinary approach is at the border between material science and
colloidal science [3].The rapid development in the use of clays and clay minerals in the
production of enhanced materials and the need for optimization of clays for hundreds of uses,
including the area of health, is the consequence of endeavor of clay science which combining
chemistry, colloid science, material science, environmental science, physics, soil science, civil
engineering , geotechnical engineering and biological science [3, 4]. The term bentonite, which
is very frequent in the business world is used to designate any plastic, colloidal, swelling clay
dominated by one of the largest groups of clay minerals called smectite (such as
montmorillonite, nontronite, beidellite, saponite and hectorites) with no regards for its origin
[1, 5-6]. The member of clay mineral group called mica‖ is often found in bentonite as a minor
clay mineral impurity. Non-clay mineral found in bentonite are zeolites, feldspars, carbonates,
gypsum, and crystalline silica (quartz and opals) [7-9] Commercial bentonite contains either
calcium montmorillonite (Ca2+ -montmorillonite) or sodium montmorillonite (Na+ -
montmorillonite) and lower amount of other minerals [6]. Bentonite are extensively used in
foundry sand as a binder, in paper industry, drilling mud, catalysis, barrier for water and nuclear
waste, iron ore pellets, ceramics and refectories, rubber, cement, soil stabilization, cat litter,
perfume, cosmetic, plastic, paint, food and pharmaceutical [1]. In pharmaceutical industry
bentonite is commonly used as medicinal product as an excipient and active ingredient in the
forms of liquid (suspensions, emulsions), semisolid (creams, ointments) and solid (capsules,
tablets and powders) either for topical or oral administration [10-15]. The usefulness of the
bentonite due to which it is considered as a suitable pharmaceutical raw material are high
surface area, small particle size, porous nature, high swell potential, gel formation, alkaline
nature, high cation exchange capacity low or null toxicity for the patient and low price [16-19].

The worldwide raw material, bentonite, also occurs in Ethiopia (Afar, Oromia, Amhara and
other regions) in a large scale. Though bentonites found abundantly in Ethiopia but none of
them have yet been properly characterized or investigated for pharmaceutical, food, cosmetics,
water and wastewater treatment, oil bleaching application. Therefore prior to its use, it is crucial
importance for indigenous bentonite to be evaluated and/or purified, modified by different
chemical and physical treatments to comply with the requirements set forth by major
pharmacopeias to achieve the status of pharmaceutical raw material as suitability study of any
bentonite before its use in manufacturing medicinal products is unavoidable [18,21].And also
, the need to enhance its properties for other industrial application.

Keeping in view that, the basic requirements for bentonite to be used as pharmaceutical raw
material are: mineralogical, microbiological and chemical inertness. The properties such as
swelling power, gel formation, CEC, surface area and pore distribution, and particle size
analysis are also important for particular uses.

1.1. Problem Statement

The clay type, bentonite, is extensively used in Pharmaceutical industry both as an excipient
and active principle in the forms of liquid, semisolid and solid either for topical or oral
administration [10-15,29-31]. As natural material bentonites may vary in composition, and
texture i.e. varies in toxic elements, non-clay minerals (crystalline silica) and microbial
contents particularly Escherichia Coli, these all are harmful to the human health. Therefore,
Prior to bentonite application in pharmaceutical sector as a adsorbent, opacifying agent,
anticacking agent, binder, therapeutic agent, suspending agent, tablet and capsule diluents or
disintgrant agent etc it is imperative that they must comply with some general features as high
mineral, chemical and microbial purity. The physicochemical properties such as gel formation,
swelling capacity, CEC, Surface area and porosity and particle size analysis are also important
to be tested to investigate its specific use.

Before usage, the clay often has to be processed to increase the purity of the main phase, to
improve the properties related to pharmaceutical application and to remove grit and non-
swelling phases, such as quartz, feldspars etc. It is also important to mention that no bentonite
can be equally well in the manufacturing of different medicinal product. Moreover, their
specific function in any particular formulation depends on both their physical properties and
chemical features. For example, its use as a suspending and tablet disintegrate agent mostly
depend upon swelling and gelling properties while as a drug adsorbent and drug carrier in
control drug release system depends upon its specific surface area, porous structure and cation
exchange capacity value.

In Ethiopia bentonite are found in abundance but none of them have neither been properly
characterized nor investigated for pharmaceutical application. Therefore, the feasibility studies
on the basis of major pharmacopeia’s, oil bleaching, purification, water and wastewater
treatments are necessary and important to investigate its suitability for particular use. To
achieve this goal the knowledge of characteristics properties of bentonite related to
pharmaceutical use, oil bleaching, water and wastewater treatment, and impurities from the
characterization study of the raw material is first needed to adopt proper purification
process/chemical treatments to make it suitable for use with improved properties. As expected,
clay from all of Ethiopia sites may have different composition, properties and may require
different processing technique for its pharmaceutical, oil bleaching, water and wastewater
treatments suitability, which is a wide range subject required huge fund and cannot be done in
a single lab and human resources.

In this study, the bentonite from Afar, Amhara and Oromia regions mines sites will be collected
and studied, characterized i.e. mineralogical, geochemical, microbiological and
pharmacopeia’s suspension tests and then necessary processing technique will be developed to
purify the material for pharmaceutical use, oil bleaching, water and wastewater treatment will
be carried out. These laboratories testing will be essential to assess the potential application
before suggestion can be made for further processing to make them suitable for pharmaceutical
industry and other applications. This study will also provide the road map for processing using
local bentonite in pharmaceutical industry and other processing units. No doubt the suitability
study on local bentonite will generate an alternate income and the processing will convert the
raw material into value added product for export and local use.

1.2.Objectives
1.2.1. General Objectives
The general objective of the research is production and characterization of local bentonite for
industrial Application

1.2.2. Specific Objectives

❖ To select the bentonite samples from different site locations for appropriate uses
❖ To characterize the physiochemical, surface and crystalline property of raw and
activated bentonite
❖ To activate the local bentonites for enhancing its performance
❖ To determine the specific surface area and cation exchange capacity
❖ To study the adsorption performance of activated bentonite for water and
wastewater treatments
❖ To examine the process parameters
 ❖ To determine the optimum process models and parameters
❖ To study the adsorption isotherm and kinetics
❖ To study the suitability of local bentonite for use as a pharmaceutical product,
Brewery industries, Oil Bleaching, water and wastewater treatments.
❖ to develop the research technique in order to produce particular quality bentonite
for its subjective use.
❖ To conduct comparative study of local bentonites with commercial bentonite

1.3. Scope of the study

In this research, modification, characterization and performance evaluation of local bentonite
will be performed on pharmaceuticals, oil bleaching, purification, water and wastewater
treatments. Batch and continuous studies will be conducted. The influence of process
parameters will be addressed to optimize the conditions for maximum performance. The
process model will be developed. Bentonite samples from three different districts in raw form
will be collected for this study.

Prior to the purification process, the raw samples will be characterized using XRD, XRF, ICP-
AES, SEM, Particle Size Analyzer, Surface Area Analyzer, CEC, Pharmacopeias Suspension
Tests. This is important because to know that whether the local bentonites are suitable (i.e.
fulfilling the basic requirement of pharmacopeia and having contents of crystalline silica within
the permitted amount) or they failed to comply with required specification.

After characterization and knowing the impurities in raw form further processing for
purification, conversions and activations will be adopted.

1.4. Significance of the Study

The significance of this study is to prove that the local bentonite can be used for water and
waste water treatment, oil bleaching, pharmaceutical use and beverage industries industrial
application. From this study, the potential of the local bentonite resource will be studied. Once
the potential of bentonite resource is proven, it can be used for water and wastewater treatment,
oil bleaching, pharmaceutical production, cosmetics and beverage industries. Due to high cost
of conventional treatment methods of heavy metals removal; this study concerns to look back
into the environment and searching the available, low cost and efficient method of heavy metal
removal. It also contributes a lot for environmental pollution control since commercial
adsorbents are costly and generate secondary pollutants. Localities are beneficial from this
research output, keep them living in healthy environment. Industrialist also highly beneficial
because they can reduce the cost for importing commercial adsorbent and reduction of sludge
production which was a headache for disposal and treatment. Therefore, it has great role in
reduction of foreign currency by import substitution of local resources. Generally, it has great
significance in terms of showing directions of pollution prevention and resource utilization. In
addition to this, the research can be used as an input for future studies to explore more about
bentonite for other purpose and application.

2. Literature Review
2.1. Clay and Clay Minerals
The use of clay and clay minerals in pharmaceuticals and cosmetics are very ancient. Clays
are versatile and low cost naturally occurring material, which has been used since antiquity,
characterized by a primitive economy, going through all historical eras of human civilization
to our contemporary time. In present time we can find clay in natural, modified or synthetic
form, as well as mixtures of clays with different origins and colors which may be used for
various therapeutic purposes. The clay in raw form is inexpensive and abundant material
worldwide. Though Clay is important, inexpensive and widely used industrial raw material
but still there is some confusion in the meaning of clay and clay mineral.

2.2. Bentonite Clay

Bentonite is a rock composed essentially of a crystalline clay-like mineral, usually the mineral
montmorillonite, but less often, beidellite, formed by the devitrification and the accompanying
chemical alteration of a glassy igneous material, usually a tuff or volcanic ash‖ The above
definition for bentonite is origin based and is restricted to volcanic ash, tuff, or glass parent
material. Therefore, deposit consisting of smectite having uncertain origin or parent material
cannot properly be called bentonite. Perhaps the best definition of bentonite is one proposed
by Grim and Guven [6] which differentiates the geological and industrial usage of the term and
overcome the difficulty in assigning a name to smectite that formed from igneous rock other
than volcanic or sedimentary or other uncertain origin. According to their definition bentonite
is any clay which dominantly comprised of smectite mineral (montmorillonite group in some
usage) regardless of the mode of origin and occurrence.

A rock which contains Ca2+ -montmorillonite or Na+ -montmorillonite as major clay minerals
is called calcium bentonite or sodium bentonite respectively [6]. Commercial Bentonite
contains either Ca2+ -montmorillonite or Na+ -montmorillonite and lower amount of other
minerals [6, 33].
2.3. Industrially Attractive Properties of Bentonite
Bentonite is a natural material varies in composition and texture. Hence, they are not performed
equally well for specific industry. Bentonites are mainly composed of a Montmorillonite with
minor contents of impurities that give it a unique fingerprint. The more montmorillonite in the
bentonite ore, the better it will perform as an industrial raw material [1]. The other clay, non-
clay mineral, heavy and trace element, and pathogenic microorganism that might be present in
bentonite, reduce its net drawing power. For example, the mineral kaolinite, mica, gypsum,
calcite, crystalline silica (quartz and cristobolite), the toxic element especially arsenic and lead,
the photogenic bacteria i.e. Escherichia Coli and salmonella species and other organic
compound might be present in bentonite [1,6,18] which dilutes its potential use in industries
especially in pharmaceutical sector [1,3,18,22]. Apart from its purity, bentonite ability to
industrial use comes from several properties but the most important are described below: i.
Cation Exchange Capacity The cation exchange capacity (CEC) is one of the basic properties
of clay minerals. Cations are attracted and held in between the sheets and on the edges of
particles in order to maintain the electro-neutrality of particle charges. CEC is defined as ―the
quantity of cations reversibly adsorbed by clay particles‖, expressed as milliequivalents per 100
grams (meq/100g) of dry clay [34]. The total CEC consists of two parts namely the exchange
capacity of the interlayer and that of the edges. The interlayer exchange capacity comes from
isomorphic substitutions of aluminium by magnesium at octahedral and /or silicon by
aluminium at tetrahedral leads to the net negative charge, the cations then balances this ionic
deficiency. This part is independent of pH value, so gives almost constant value. The CEC
results from the edge are strongly pH dependent. At pH 7 about 20% of the CEC of smectite is
located at the edges [35-36]. In the acid pH range, the edges are positively charged; thus, the
edges do not contribute to the measured CEC. While in the basic pH range, the edges are
negatively charged; therefore, in this pH range all edges contribute to the CEC. The CEC values
are expressed in unit recommended by IUPAC known as centimole of positive charge per
kilogram of dry clay sample (cmol(+)/kg), which is numerically equal to the traditional unit
called milliequivalents per hundred grams of clay (meq/100g). Smectite have high CEC, which
is in the range of 40-150 meq/100g. This high CEC of smectite is due to the high isomorphic
substitution occurring within the octahedral and tetrahedral layers [1]. Sodium montmorillonite
has a CEC which is generally between 80 and 130 meq/100g. On the other hand, Ca2+ -
montmorillonite has a CEC normally ranges from 40-70 meq/100g. Among the clay minerals,
the bentonites enjoy wide applications in the pharmaceutical industry because of their high
swelling and high CEC [12, 30, 37]. It is due to their high CEC that smectite can interact with
certain drugs affecting their bioavailability. Nevertheless, this interaction could be
advantageous in the formulation of controlled release systems, which is one of the most
attention-grabbing fields of clay applications at present [14,31]. The variation in
montmorillonite interlayer cations and CEC are resulting changes in drug loading ability or
adsorption capacity [38]. ii. Swelling The most important property of smectite and
corresponding bentonite is the uptake of water in the interlayer space and the resulting swelling
of the mineral. Swelling is defined as the change in physical state of clay from an anhydrous
solid to gel [39-40]. It is due to this property that bentonite can be used as a disintegrate agent
for tablets formulation, for preparation of oral and topical suspension [18, 33]. There are two
stages of swelling: one is the crystalline and the other is osmotic swelling. In former case the
smectite can take water gradually from one to four layers [34-5], controlled by balancing
between strong electrostatic and hydration repulsive forces [46, 51-54]. While in osmotic
swelling complete dissociation of the smectite layers occur [50, 55], which is generally based
on Defuse Double Layer Theory [56- 59]. The increase in basal spacing by swelling depends
on the bentonite mineralogy, types of exchangeable cation, magnitude of the layer charge and
hydration of exchangeable cations [55,60]. Usually sodium bentonite develops higher swelling
than calcium ones, therefore for specific purposes the purification and conversion techniques
are applied to improve the properties especially swelling of poor bentonite [32]. According to
Japanese pharmacopoeia [61] the required swelling property of bentonite for pharmaceutical
use is 20ml, while specified by European pharmacopeia [27] and US pharmacopeia [25] are
22 ml and 24ml respectively. iii. Surface Area and Porosity Bentonites are porous in nature.
The high contents of montmorillonite contained in the bentonite are the main source of
porosity. In a solid, the voids located among and within particles are known as pore. The pores
can be cylindrical, parallel-sided silt, cavity and ink-bottle of different sizes [60]. The IUPAC
classified the pores by their internal pore width [62]. The diameter of cylindrical pore and the
distance between opposite walls in case of silt pore can be taken as the internal width. The
pores with internal widths greater than 50 nm, between 2 nm and 50 nm and smaller than 2 nm
are called macropores, mesopores and micropores respectively [62-64]. The macropores lie
among the particle while mesopores and micropores lie within the particle [9]. These three
types of pores are often found in bentonite. The physicochemical properties of bentonite
especially adsorption depends extensively on mesopores and micropores [9]. The pores area of
the inner and outer walls in one gram of solid is defined as specific surface area [65]. Surface
area approximately corresponds to the walls of micropores and mesopores. The contribution of
the macropore surface to the total surface area is negligible [65]. The pores volume in one gram
of solid is taken as specific pore volume. A number of methods have been investigated to
determine pore-size distribution, surface area and pore volume. They include mercury
porosimetry, N2 adsorption-desorption and thermoporometry [62, 66].

2.4. Uses of Bentonite

Bentonite is the most important industrially applied clay because of its main montmorillonite
component which gives it a very high sorbent ability and swelling capacity [1, 67-68]. Sodium
Bentonite clay is particularly of great interest due to its formation of a gel like structure at
relatively low clay concentration and high swelling capacity [69]. For specific industrial use
the bentonite properties can be controlled and the conversion of bentonite from one form to
another can be possibly obtained by chemical treatment and purification process [70]. The uses
of bentonite in pharmaceutical industry are discussed in detail in the subsection, other uses are
briefly mentioned below. Bentonite are used extensively as a bonding material in the
preparation of molding sand (mixture of sand and bentonite) for the production of shaping
metals in the casting process [1,3,71-72]. Bentonite provides the plasticity to sand- clay mixture
so that it can be moulded around the pattern. The important properties of bentonite yield sand
moulds with good compact-ability, flow-ability, and thermal stability for the production of
high-quality casting. Another important and conventional use of bentonite is as a mud
constituent for oil well drilling [1]. The role of the bentonite in drilling is mainly to seal the
borehole walls, to lubricate the cutting head and to remove cutting from the drill hole. High
viscosity and gel formation properties are required in order to prevent the cutting from the
settling to the bottom and remove it from the drill hole. Mostly sodium bentonites are used in
drilling fluid because of its high viscosity, high swelling and gelling properties. Bentonites are
used as a binding agent in the production of iron ore pellets [70]. Finely pulverized iron ore
concentrates are converted into spherical pellet of about 2.5cm in diameter for easiness of
handling and shipping and to produce a superior furnace feed. Sodium bentonite is preferably
used for pelletizing because of its best dry strength and its low percentage is enough to bind
the pellet. Sodium bentonites are also important to paper making where it is used to prevent
agglomeration of pitches, waxes and resinous material so that it will not stick to machine, wires,
screen and press roll etc. Hence not causes any defect and holes in the paper but improve the
quality [1, 3, 6]. Bentonite is also useful in the deinking process for paper recycling [1]. In the
deinking process the ink pigment is first released by heating the recycled paper in a caustic
soda solution and then added sodium bentonite to absorb the ink pigment. The bentonite are
then removed by washing procedure. In addition, acid activated bentonite is used as the active
component in the manufacturing of carbonless copy paper. Bentonite is used as constituent in
cat litter because of its high absorbent quality and swelling power [6, 73-74]. In this case when
the feline waste hits the granular product of bentonites, they swell and form a hard clump which
can easily be removed from the litter box and leaving the remaining product safe for further
use. Sodium bentonites are also famous for water impedance for their high swelling power.
Bentonites swell and fill the voids and pores in the material into which they are incorporated,
preventing liquid from moving through the barrier. Bentonites are commonly used in dams,
ponds and impound to prevent seepage of water. They are also used to prevent water from
entering basements of homes. In landfills and toxic waste dumps sodium bentonite are used to
prevent liquid from entering and exiting [97]. Bentonite in acid activated form are used to refine
and bleach palm oil, sunflowers, rapeseeds, animal fat, soybean, corn oils because of its high
adsorptive property [75-76]. In drinks such as wine, bear, mineral water and in products like
honey or sugar bentonites are used as clarifying agent. The more refining uses of bentonite are
as carrier for pesticides and fertilizers, purification of waste water and animal feed binder [1,
6, 32]. Bentonite is also used in Portland cement and mortars due to its viscosity and plasticity.
The additions of small amount of sodium bentonite in cement improve the workability and
impermeability. It has also been reported that bentonite is acceptable pozzolan in cement [77].
In ceramic industry Bentonite is not used as a major component but to improve the plasticity
and dry strength small percentage of sodium or calcium bentonite is added [78]. Sometime
bentonite is added to porcelain to lower the firing temperature and as a suspending agent.
sodium bentonite in small amount can also be added to glazes as a suspending agent [1].
Bentonites with sodium montmorillonite are also playing an important role in paints where they
function as a thickening, emulsifying and suspending agent. The adsorption properties of
bentonite are appreciated for dying cloths and lacquers for paints and wallpapers. Bentonites
are extensively used in cosmetic and pharmaceutical industry as an excipient and active
ingredients [14,18], as described in more detail in the following section.

2.4.1. Pharmaceutical Uses of Bentonite

A medicinal product is a substance or combination of substances administered to humans in
order to treat or prevent illness, carry out a diagnosis or restore, correct or modify disturbed
physiological functions. Bentonite is used as medicinal product in industry as both excipients
and active principle in the forms of liquid (suspensions, emulsions), semisolid (creams,
ointments) and solid (capsules, tablets and powders) either Pharmaceutical for topical or oral
administration [10-15]. The usefulness of the clay minerals in pharmaceutical application are
due to different properties such as high adsorption ability, interlayer reactions, high surface
area, chemical inertness, high cation exchange capacity, low or null toxicity for the patient and
low price [17,37].

2.4.1.1 Use as an Active Substance

i. Oral Administration: Bentonite administered orally to the patient may act as antacids,
gastrointestinal protectors, antidiarrhoeics, and osmotic oral laxatives.
ii. Antidiarrheal Uses: Diarrhoea is either an acute or chronic pathological condition,
may be caused by defective intestinal absorption, bacterial infection, allergy,
intoxication etc. In Diarrheal the fluidity and frequency of evacuation of the feces
increased. Clays including bentonite are widely used as anti-diarrhoeaics for its high
specific surface, sorption capacity, and non-toxic to patient. Smectite and the
corresponding bentonite are used in the treatment of infectious diarrhea as they reduce
the fluidity and frequency of evacuation of the feces by mechanisms including
absorption of water and electrolytes in the intestine, protection of the luminal surface
against pathogenic bacteria and decrease of mucolysis caused by bacteria [79-80]. In
addition, some authors have described the use of bentonite in the cure of acute
diarrhoea, although no experimental evidence supports this statement [81-83]. Prior to
its usage, smectite are commonly ―activated‖ by acid or heating in order to enhance
their antidiarrhoeaic efficiency [8, 84-85]. The long-term use of clay minerals is not
recommended as antidiarrheas because of the risk of renal silica calculi (kidney stone)
formation [86-87].
iii. Gastrointestinal Protectors: In patients suffering from peptic ulcer, the thickness of
the mucus layer formed on the gastro-duodenal mucous membrane [88], act as a
physical barrier preventing direct contact between the gastric enzymes and the cells of
the mucous membrane [89], decreases while the mucolytic activity of the gastric
enzyme levels increase [90-91]. Clay (e.g. bentonite) used as effective gastrointestinal
protectors because of its high sorption capacity, large specific surface and non-toxic to
organisms [92-93]. These clay minerals reduce irritation and gastric secretion; take up
gases, bacteria, toxins, and even viruses while adhering to the gastric and intestinal
mucous membrane [94]. The mode of action of clay mineral involves stability of the
gastric mucus, increasing the viscosity and decreasing the degradation of glycoprotein
 in the mucus [14,94]. The use of sodium smectite as osmotic laxative was also
illustrated by Carretero [12], though no experimental evidence support this statement.
iv. Antacids: Antacids are drugs which are administrated orally to the patient in the form
of tablets, suspensions, or powders to reduce the gastric acidity arising from the excess
production of hydrochloric acid in the stomach [30]. The clay minerals can act as
antacids by reducing the gastric acidity through the adsorption mechanism of H+ ions
(protons) to the surface. The main reaction products are silica gel, and interlayer cations
in the case of smectite [30]. The continual use of clay minerals is not recommended as
antacids, because of the formation of renal silica calculi [86-87]. The mixture of
different antacids has the extra advantage of prolonging the therapeutic effect of the
pharmaceutical preparation.
v. Topical Administration: Because of high sorption capacity, smectite can also be
administered to the patient topically (to the exterior or on a limited portion of the body)
as dermatological protectors to protect the skin against external agents and,
occasionally, taking up agents exuded by the skin itself [30,95]. They are generally in
the form of ointment, creams and powders. Smectites are applied as dermatological
protectors to adhere to skin, forming a film to mechanically protect the skin against
external physical or chemical substances and recommended for inflammatory process
such as acne, boils, ulcers [14, 17, 30]. Bentonites are also used in antiseptic purposes
[14]. The amalgamation of Bentonite with some other clay mineral can be employed as
dressing for the treatment of skin injuries [14, 96].
vi. Use as Excipients: Bentonites with higher amount of smectite are widely used as
excipients in pharmaceutical formulation. The word excipient means, an agent to
facilitate the pharmaceutical formulation and to improve the organoleptic properties i.e.
smell, taste and colour, physical and chemical properties (e.g. viscosity), facilitate
liberation of the active ingredient within the organism (carrier-releasers, disintegrates),
and their elaboration (lubricants, binders, diluents agents). The different roles of
bentonite as excipients in pharmaceutical formulation are summarized below.
vii. Disintegrants, Binders and Diluents: Bentonite serves as diluents, tablet disintegrants
and binder agent. The using of bentonite as disintegrant agent play an important role in
liberating the active ingredients administered to the patient in the form of tablets,
because of its high swelling capacity and readily decomposition in the acidic medium
of stomach. It is investigated that bentonite disintegrate efficiency is more effective
comparable to other topical disintgrants such as cellulose derivative [97]. In addition,
 smectite also facilitates the compaction of tablets. The uses of bentonite as tablet and
capsule disintegrant, and tablet binder have been studied by several authors [98-100].
Bentonites can also be used as diluents in pharmaceutical preparations because of their
plastic nature at moisture content and are non-toxic to the patient. Smectite are also
useful diluents for cosmetics. Bentonites with high contents of smectite are very useful
as stabilizers for their thixotropic properties [104].
viii. Suspending, Emulsifying, Anticaking Agents and Flavour Correctors: The
pharmaceutical preparations in the form of liquid for oral or topical administration,
there is a need of an agents to prevent segregation of the components, and avoid
formation of sediment that may be not easy to re-suspend suspensions, syrups and gels
etc. Bentonites are widely used as suspending, emulsifying, anticaking and stabilizing
agents in the formulation of suspension, ointment, cream and gel because of their
thixotropic and colloidal characteristics [14, 69,105-106].In the case of smectite, the
particles can interact in an ‗face-to face‘ and ‗edge-to-face‘ fashion to form a rigid
system [107-108].Bentonites are also wildly used as flavour correctors in
pharmaceutical preparations to fix the unpleasant test of orally administrated active
ingredient [14, 30].
ix. Carriers and Releasers of Active Ingredients: Smectite and the corresponding
bentonite are well suited to act as drug carriers and releasers, because of their large
specific surface area and high cation exchange capacity [109]. McGinity and Lach have
been examined the Amphetamine sulfate montmorillonite complexes as a method of
controlling the drug release [110]. The drug concentrations were tracked by urinary
recovery studies and found montmorillonite effective in prolong drug release system.
Shrivastava et al showed that at acidic pH, the Metronidazola- montmorillonite
complex and their corresponding physical mixture were effective in inhabiting drug
release [111]. In order to obtain continual action in the administration of oral
antihistamines, the interaction between montmorillonite and chlorpheniramine maleate
was studied [112]. Lin et al. have reported the use of montmorillonite as a slow release
vehicle of a 5-fluorouracil drug against colon cancer suitable for oral administration
[37]. Some authors have also reported that acid activated bentonites are more effective
than natural ones in extended drug release formulation [110- 112]. Pharmaceutical
preparations, using bentonites as a carrier and releasers of active ingredients, can
generally be administered orally to the patient.
x. Bentonite in Cosmetic Products: Cosmetic products such as Creams, powders,
emulsions are applied to external parts of the body in order to beautify or change
physical appearance, or care for the physicochemical conditions of skin. The opaque
material, bentonite with a high sorption capacity are commonly used as active principles
in cosmetic formulations as creams, powders, emulsions in order to remove shine, give
opacity, and cover blemishes [12, 30]. In addition, adhering to skin and forming a
protective film, bentonite can absorb grease and toxins.

3. Materials and Methods

3.1. Collection of Samples
The raw bentonite Samples used in this study will be obtained from three different sites in Afar
and Amhara province.

3.1.1. Sample Preparation

The samples in rock form were collected from the above-mentioned sites and prepared powder
bentonite for characterization study. The wet sieving method will be adopted by dispersed each
sample in distilled water for 48h, stirred occasionally by mechanical stirrer and will be sieved
by using mesh No-325 sieve (ASTM). The sieved clay suspension will be then dried at 60°C.
The dried samples will be further ground, sieved through mesh No-120 and placed in a dry
controlled environment for experimental use and designated as raw bentonites.

3.2. Purification of Raw Bentonite

In order to separate the main clay particles (particle size-fractions  2 μm) from associated
minerals such as crystalline Silica (quartz, cristobolite), feldspar etc, and to improve its related
properties to pharmaceutical application, three different purification methods (i.e. Simple
Sedimentation using Sodium hexametaphosphate (Na (PO3)6) as a dispersing agent, Classical
NaCl Treatment Method and Soda Activation Method followed by sedimentation process) will
be applied on the raw bentonites previously leached for 48 hours.

3.2.1 Method-I: Simple Sedimentation

Five grams of each raw bentonite sample will be suspended in one litre (1 L) of deionized water
with about 0.25 g of dispersant agent (Na (PO3))6 and stirred magnetically for 1hr. By letting
the suspension stand at constant temperature and decant the supernatant of clay suspension
above certain depth after the specific time at 25°C estimated from the following relation, based
on stoke law, assuming the spherical shape of the solid particle.

𝑡 = 18𝜂ℎ /(𝜌 − 𝜎 )𝑔𝑑 2

Where : density of the spherical material = 2.65(106) g/m3 : density of liquid = 0.997 (106)
g/m3 η: viscosity of the fluid= 0.89 g/ms h: depth from the surface of suspension in cylinder=
0.1m g: Gravitational acceleration = 9.8m/s2 d: diameter of the particle= 2(10-6 ) m The
separated supernatant was washed at least two times with distilled water to remove the traces
of dispersant. The previously described sedimentation process was applied at least three times
successively on each clay fraction until the mass ratio of the dispersed particle collected in the
solution was found negligible with respect to the total amount of pristine material (i.e. 5 g).

3.2.2. Method-II: Classical NaCl Treatment

This classical treatment is well described in the Handbook of Clay Science [3]. In this method
30 g of raw bentonite will be dispersed in 500 ml of 1M NaCl solution, stirred for overnight
and centrifuged. The above procedure was repeated three times. Finally, the slurry was washed
with de-ionized water until chloride free slurry was obtained as tested by AgNO3 solution. The
treated sample will be dried at 60 °C and the clay particle less than 2µm will be separated by
sedimentation technique according to the Stokes law of sedimentation. The purified clay will
be obtained by dispersing 5 g of dried treated bentonite in 1L de-ionized water and collecting
the supernatant dispersion of particles less than two micron.

3.2.3 Method-III: Soda Activation Followed by Sedimentation

To obtain pure sodium montmorillonite, the soda activation procedure will be applied as
described by Yildiz and Calimli [113] and further to separate the main clay particles from
associated minerals, especially quartz, the simple sedimentation technique will be used.

4. Budget
Table 1: Budget

Research Theme Budget Total cost, birr

category
Pharmaceutical sector Material Cost 100,000
Chemical Cost 250,000
Lab Cost 250,000
Per diem and 250,000
transportation
 Experts 80,000
payment/lab
technician
Sub Total 950,000
Water and wastewater Material Cost 100,000
Chemical Cost 250,000
Lab Cost 250,000
Per diem and 250,000
transportation
Experts 100,000
payment/lab
technician
Sub Total 950,000

Oil Bleaching Material Cost 100,000

Chemical Cost 250,000
Lab Cost 250,000
Per diem and 250,000
transportation
Experts 100,000
payment/lab
technician
Sub Total 950,000
Brewery Industries Material Cost 100,000
Chemical Cost 250,000
Lab Cost 250,000
Per diem and 250,000
transportation
Experts 100,000
payment/lab
technician
Sub Total 950,000
Total budget 3,800,000 birr
Remarks: Details will be provided in request
 5. Schedule
The research scheduled to be completed in two years. But For some instances and obstacles it
will be extended for additional half or one year.

Table 2: work plan

N Activities

May

May
Nov

Aug

Nov

Aug

Nov
Mar

Mar
Dec

Dec
Apr

Apr
Feb

Sep

Feb

Sep
o
Oct

Oct

Oct
Jun

Jun
Jan

Jan
Jul

Jul
1 Literature survey
2 Data collection
3 Data analysis and
Experimental
work
4 Progress report
compilation
5 Draft report
submission
6 Final report
compiling and
binding
7 Final report
submission

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