BONTONITE DEFINITIONS

Bentonite is the commercial name of a whole range of natural clays with a high water
absorption capacity causing it to expand and swell. Bentonite predominantly consists
of montmorillonite: a clay mineral belonging to a class of phyllosilicates called
smectites. The term Bentonite was first used for a clay found in about 1890 in upper
cretaceous tuff near Fort Benton, Wyoming. The main constituent, which is the
determinant factor in the clay's properties, is the clay mineral montmorillonite. This in
turn, derives its name from a deposit at Montmorillon, in Southern France.
Bentonites may contain a variety of accessory minerals in addition to
montmorillonite. These may include lesser amounts of other clay minerals such as
kaolin, mica, illite, as well as non-clay minerals like quartz, feldspar, calcite, and
gypsum. The presence of these minerals can impact the industrial value of a deposit,
reducing or increasing its value depending on the application. Bentonite presents
strong colloidal properties and its volume increases several times when coming into
contact with water, creating a gelatinous and viscous fluid. The special properties of
bentonite (hydration, swelling, water absorption, viscosity, thixotropy) make it a
valuable material for a wide range of uses and applications.
Bentonite is a clay generated frequently from the alteration of volcanic ash, consisting
predominantly of smectite minerals, usually montmorillonite. Other smectite group
minerals include hectorite, saponite, beidelite and nontronite. Smectites are clay
minerals, i.e. they consist of individual crystallites the majority of which are <2µm in
largest dimension. Smectite crystallites themselves are three-layer clay minerals.
They consist of two tetrahedral layers and one octahedral layer.
In montmorillonite tetrahedral layers consisting of [SiO4] - tetrahedrons enclose the
[M(O5,OH)]-octahedron layer (M = and mainly Al, Mg, but Fe is also often found).
The silicate layers have a slight negative charge that is compensated by exchangeable
ions in the intercrystallite region. The charge is so weak that the cations (in natural
form, predominantly Ca2+, Mg2+ or Na+ ions) can be adsorbed in this region with their
hydrate shell. The extent of hydration produces intercrystalline swelling.
Bentonite deposits are normally exploited by quarrying. Extracted bentonite is
distinctly solid, even with a moisture content of approximately 30%. The material is
initially crushed and, if necessary, activated with the addition of soda ash (Na 2CO3).
Bentonite is subsequently dried (air and/or forced drying) to reach a moisture content
of approximately 15%. According to the final application, bentonite is either sieved
(granular form) or milled (into powder and super fine powder form). For special
applications, bentonite is purified by removing the associated gangue minerals, or
treated with acids to produce acid-activated bentonite (bleaching earths), or treated
with organics to produce organoclays.

While sharing a common elementary

structure, the various types of bentonite are
very different with regard to their chemical
composition, as well as to the physical state
of their constituents, which account for
bentonite different properties and determine
its various technological applications.
Montmorillonite is an aggregate of lamellar
platelets, packed together by electrochemical
forces and containing interposition water.
Each platelet consists of three sandwich-
arranged layers: a central octahedral alumina
(Al2O3) layer, and two tetrahedral silica (SiO2) layers. The silicon ion and the
aluminium ion often undergo isomorphous substitutions by lower valence metals,
such as magnesium and iron. In turn, these substitutions lead to a charge imbalance,
compensated by exchangeable cations, in particular calcium (Ca2+), magnesium
(Mg2+) and sodium (Na+) ions, together with water molecules bonded together by ion-
dipole forces. These ions, with no more place inside the reticular structure, migrate to
the external silica layers and are the main cause of hydration in the crystal lattice.
Therefore, each platelet can be assumed to have the following general formulation:

[ (Si Al)4 (Al Fe . Mg)2 O10 (OH)2 ]2 ∙ Mn ∙ mH2O

where the first member in brackets refers to isomorphic constitutions in the tetrahedral
layers, the second member refers to isomorphic constitutions in the octahedral layer;
and M and mH2O symbols refer to exchangeable cations and interposition water,
respectively.
Every clay has a constant, maximum amount of exchangeable cations, as indicated by
its Cation Exchange Capacity (CEC), measured in milliequivalents per gram (meq/g)
or, more frequently, per 100 grams (meq/100g). Bentonite CEC varies depending on
the level of isomorphous substitutions occurred within the lattice. From a chemical
point of view, bentonites can be distinguished depending on the quantity and quality
of exchangeable bases: in particular, we have calcium bentonites and sodium
bentonites, when the prevailing exchangeable cation is calcium or sodium,
respectively. The largest deposits on earth contain calcium bentonites, which,
however, have less hydration and swelling capacity than sodium bentonites.

Owing to its unique valuable properties,

bentonite is employed in a great number of
different applications, as illustrated below:

Foundry

Bentonite is used as a bonding material in the preparation of moulding sand for the
production of cast iron, steel, and non-ferrous casting. The unique properties of
bentonite yield green sand moulds with good flowability, compactability, and thermal
stability for the production of high quality castings.

Drilling

Owing to its rheological properties and thixotropy of aqueous suspensions, bentonite

is used as a mud constituent for oil and water well drilling. Its functions are mainly to
stabilise the borehole, seal the borehole walls, and remove drill cuttings. Bentonite
muds are thus employed for oil and water well drilling, tunnel, and microtunnel
drilling.

Civil engineering

Bentonite slurries are used in the construction of special foundations for digging
diaphragm walls and bored piles. In geothecnical engineering, bentonite is used for
self-hardening mixtures employed to build cut off walls, grouting mortars, and
grouting. Finally, bentonite waterproofing properties are best exploited in
environmental engineering, to seal off soil infiltrations, and line the base of landfills.

Feedstuff

Bentonite is used as an animal feed supplement. Under European regulations, it is

classified as a food additive, with E number E558. Bentonite is used as a pelletizing
aid in the production of animal feed pellets. Due to its high adsorption power, it is
particularly effective against micotoxins.

Water treatment

Due to its ion exchange, flocculation, and sedimentation properties, bentonite is used
in environmental protection for water clarification, and as an aid to polyelectrolites
and inorganic flocculants.

Agriculture

Bentonite is used as an ion exchanger for soil improvement and conditioning. It is

also used for gardening in soil compounds and mixtures to absorb humidity, and as a
carrier for various herbicides and pesticides.

Ceramics

Bentonite is used to enhance ceramic paste plasticity and as an anti-settling agent in

ceramic enamels.

Paper
Bentonite is used to improve the efficiency of conversion of pulp into paper, as well
as for paper quality improvement by preventing rubber particle agglomeration. Due to
its absorbing property, bentonite also offers useful de-inking properties for paper
recycling.

Wine making

In winemaking, bentonite is used to enhance clarification and protein stabilization.

Cat litter

Owing to its swelling property, bentonite is used for cat litter, due to its advantage of
absorbing refuse by forming clumps.

Pelletizing of iron ore

Due to its water absorption capacity and colloidal property, bentonite is used as a
binding additive to convert iron ore fines into pellets.

Pharmaceuticals, cosmetics, and spa mud therapy

Bentonite is used as a filler in pharmaceuticals, and for its absorption/adsorption

functions. It is also employed in creams, face-powders, and spa mud preparations.

Detergent additive

Bentonite is used in detergents to soften the fabrics. Liquid cleansers/soaps rely on the
inclusion of bentonite as a suspension agent and viscosity enhancer.

Food industry (wine, edible oils and fats)

Bentonite is utilized in the removal of impurities in oils where its absorptive

properties are crucial in the processing of edible oils and fats. In drinks, bentonite is
used as a clarification agent.

Paints and varnishes

Bentonite functions as a thickening and/or suspension agent.

WATER TREATMENT

Understand Industrial Wastewater Treatment

A variety of techniques play roles in removing contamination

By Amin Almasi, mechanical consultant, Apr 13, 2018

Process plants generally try to minimize the amount of wastewater they generate.
However, operations invariably result in production of some wastewater. Proper
treatment of this wastewater is crucial for both environmental and economic reasons.

Industrial wastewaters usually contain organic and inorganic matter in varying

degrees of concentration. They may include toxic and other harmful materials as well
as components that are non-biodegradable or that can reduce the efficiency of many
wastewater-treatment operations.

Thus, treatment of industrial wastewaters typically is a very difficult task — far more
complicated than municipal wastewater treatment —that requires special methods and
sophisticated technologies. These options fall into three categories: physical, chemical
and biological. Physical treatment methods include sedimentation, flotation, filtering,
stripping, ion exchange, adsorption and other processes that remove dissolved and
non-dissolved substances without necessarily changing their chemical structures.
Chemical methods include chemical precipitation, chemical oxidation or reduction,
formation of an insoluble gas followed by stripping, and other chemical reactions that
involve exchanging or sharing electrons between atoms. Biological methods rely upon
living organisms using organic or, in some instances, inorganic substances for food.

Reverse Osmosis

Figure 1. Use of such a unit for tertiary treatment of wastewater is becoming popular.

Biological treatment is more widely used than any other option where reasonably
complete treatment is required. It most often serves as the secondary treatment stage
to remove major portions of contamination. Other processes handle primary and
tertiary treatment to complete the removal of solids and other pollutants.

The Challenge

Some industrial wastewaters are rich in organics and easily biodegradable while
others are nutrient deficient, inhibiting or preventing biodegradability. Total dissolved
solids and contamination may exceed by many times the levels found in domestic
sewage. Industrial wastewaters often also have pHs well beyond the range of 6–9 and
may contain high concentrations of dissolved metal salts. To further complicate
matters, wastewater flows and characteristics within a plant also can vary with time
because of campaign manufacturing or slug discharges on top of the usual discharges.
In addition, spillages and dumping that occasionally may occur very adversely can
impact the performance of the plant’s wastewater treatment plant. Consequently, it’s
always prudent to carefully assess current wastewater and its treatment requirements
rather than relying on the past situation. An understanding of the nature of the plant’s
operations is vital.

One key parameter for wastewater is its biochemical (or biological) oxygen demand
(BOD). This is the amount of dissolved oxygen needed by aerobic biological
organisms to break down organic material present in a given wastewater sample at a
certain temperature over a specific time period. Therefore, BOD indicates indirectly
the amount of organic compounds in wastewater. The BOD most commonly is
expressed in milligrams of oxygen consumed per liter of sample during 5 days of
incubation at 20°C.

Another key parameter is chemical oxygen demand (COD), which indirectly specifies
the amount of organic compounds in the wastewater. It indicates oxygen consumption
and also is given in mg/L.

Both BOD and COD measure the amount of organic compounds in wastewater.
However, COD is less specific because it measures everything that can be chemically
oxidized rather than just levels of biodegradable organic matter. You can estimate the
biodegradability of wastewater by considering its COD and corresponding BOD.

Primary Treatment

Removing large, suspended and floating solids is the focus of the first stage of
wastewater treatment. However, before such treatment takes place, the plant
wastewaters usually first go to an equalization tank or system, which acts as a buffer
and normalizes varying flow and contamination loads. It’s always best to use a single
large concrete tank to which an appropriate coating has been applied. This tank most
often is sized based on the difference between expected peak and average flows, with
a capacity of 4–8 hours’ worth of difference common.

From the equalization tank, the raw wastewater goes for primary treatment. This
usually includes screening to trap solid objects, sedimentation by gravity to remove
suspended solids and some adjustments. Primary treatment sometimes is referred to as
“mechanical treatment” because it relies on mechanical methods, although chemicals
often are used to accelerate the sedimentation process. The design for a primary
treatment facility most often includes neutralization (i.e., pH adjustment), coagulation,
flocculation and dissolved air flotation (DAF).

The main purpose of primary treatment is to remove colloidal solids, emulsified oil
and a small portion of BOD and COD. Primary treatment can reduce BOD of the
incoming industrial wastewater by around 20–30 % and the total suspended solids by
some 50–65%.

Neutralization. Usually, wastewater must have its pH adjusted so that subsequent

operations such as downstream biological treatment can take place at optimum pH.
Therefore, the wastewater passes to a neutralization system that corrects its pH. This
system generally involves multiple neutralization tanks; common configurations are
“3+1” (3 operating + 1 standby), “5+1” (5 operating + 1 standby) and “7+1” (7
operating + 1 standby). Injection of chemicals such as a caustic soda or sulfuric acid
solution adjusts the pH to the desired level.
Sensors installed at the inlet and outlet of the neutralization tank (a minimum of one
sensor in each location) measure the pH of the wastewater. A controller uses these
readings to automatically adjust a dosing pump to achieve the desired final pH
(typically, 6.7–8.3 with an optimum of 6.9–7.4).

The neutralization-chemical system consists of storage and mixing tanks and other
equipment such as agitators necessary to reduce the concentration of the chemical and
prepare it for injection. Dosing pumps are deployed in a “1+1” arrangement (1
operating +1 standby) for each chemical. Often positive displacement pumps handle
these services. However, these sometimes can pose maintenance and reliability issues.
A variable-speed-drive centrifugal pump often offers an attractive alternative that
provides reliability and high performance.

Coagulation and flocculation. Wastewater from the neutralization tank usually flows
by gravity into coagulation tanks for removal of colloidal solids. Coagulation is a
quick process, requiring a relatively low retention time of 2–5 min. There commonly
are multiple rectangular coagulation tanks made of reinforced concrete with proper
coating; each contains a few agitators that provide high-energy mixing. Large plants
often use configurations such as “7+1” (7 operating + 1 standby) or “9+1” (9
operating + 1 standby) or similar. For instance, a treatment plant of 3,000-m3/hr total
capacity employed“7+1” tanks, each of 16 m3 capacity, to achieve retention time of
more than 2.2 minutes. Some large plants have used retention times as low as 1.5 min
and certain radical designs propose times as low as 1 min. However, low retention
times can pose risks. Generally, it’s wise to keep retention times above 2 min.

A coagulant solution (typically polymer based) usually is injected automatically by

dosing pumps (“1+1” configuration); most often stroke variation adjusts injection.
Modern plants automatically control injection rate according to incoming flow rate
based on a more or less fixed chemical concentration, preliminarily defined through
site experimental tests and adjustable during normal plant operation. Coagulant aid
can be added to the wastewater stream to facilitate separation of solids.

Wastewater from coagulation tanks most often flows by gravity into the flocculation
system (tanks) where agglomeration of flocculent formed during coagulation process
takes place. Anionic polymer usually serves as flocculent. Flocculation is a process of
slow mixing with retention times of 12–40 min. Some designs for large plants have
used lower retention times, say, 9–10 minutes, but typically times of 11, 12 or 15 min.
are recommended. It is a process that requires less energy for agitation than
coagulation.

Dissolved air flotation. Wastewater from flocculation passes by gravity into a DAF
clarifier system. Its main purpose is to remove the suspended solids, emulsified oil,
grease and some portions of BOD and COD from the wastewater. Elimination occurs
through the action of micron-sized air bubbles. These are created by dissolving air in
wastewater under pressure and then reverting to atmospheric pressure in DAF
clarifiers. The millions of micron-size air bubbles released attach to the contaminants,
decreasing their effective density and thus causing them to float on the surface to form
a concentrated sludge blanket. A skimming device removes the floating sludge, which
then go to sludge treatment units for processing. A common design uses a separate
pressure vessel for compressed air introduction. DAF clarifiers operate effectively
over a wide range of hydraulic and contamination loading.

Secondary Treatment

Often considered the heart of the treatment plant, its major purpose is to remove
biodegradable organics (expressed as BOD, COD, etc.) and ammonia. Secondary (or
biological) treatment uses microbes to consume dissolved organic matter that escapes
primary treatment, converting it to carbon dioxide, water and energy for microbe
growth and reproduction. After this biological process, the stream goes to additional
settling tanks (“secondary” clarifiers or sedimentation vessels) to eliminate more of
the suspended solids. Well designed and functioning secondary treatment can remove
about 85–90% of the suspended solids and BOD. Technologies employed include the
activated sludge process, which is the most commonly used method, as well as
variants of pond and constructed wetland systems, trickling filters and other forms of
treatment that rely on biological activity to break down organic matter.

An activated-sludge train usually is divided into an aeration section for BOD removal
and nitrification, and an anoxic section for denitrification. In the aeration section,
compressed air passes through the wastewater. Dissolved oxygen from the
compressed air acts as a respiratory source for aerobic bacteria present in wastewater
that decompose the organic load (expressed as BOD and COD) and ammonia to
carbon dioxide and nitrates, respectively.In the anoxic section, bacteria use the
oxygen in nitrates as a respiratory source, thus converting the nitrates to nitrogen gas.

In practice, denitrified wastewater from the anoxic tank flows downstream to the
aeration (or BOD-removal) tank where aerobic bacteria decompose the organic load
and ammonia present using dissolved oxygen supplied by air blower(s). The treated
effluent from the aeration tank usually flows by gravity to a secondary clarifier, which
most often is a gravity clarifier. Here, sludge is removed from the treated effluent,
which then passes to tertiary treatment. A portion of the sludge gets recycled to the
anoxic section to provide nitrates for denitrification. This recirculation keeps effluent
nitrates’ concentration below the required limits. The remaining portion of sludge
goes to sludge treatment facilities.

Biological treatment usually consists of multiple streams, say, 4, 6 or 8 trains, with a

proper safety factor (for instance, 1.5 or more) to ensure the biological treatment can
handle the incoming design flow even if one train is taken out of operation. Selection
of the hydraulic retention time for the anoxic zone requires great care. Considering
different operational and process factors, as a rough indication, this time usually is 5–
8 hr. Some designs for large plants have used 5.5 hr, 6 hr and 6.5 hr as optimum
values. Hydraulic retention time for the aeration tank is longer, somewhere between
19 and 24 hr. Some large plants have found a retention time of 20 hr to be optimum.

Tertiary Treatment

This ensures removal of remaining contamination and solids in the wastewater. Such
tertiary treatment usually involves filtration systems such as disc filters, reverse
osmosis (RO) units (Figure 1), etc. You usually should direct filter reject from
backwash or RO unit rejects to the flow distribution chamber upstream of the
equalization system; most often, these rejects require a dedicated pumping system. To
eliminate specific contaminations to meet regulatory requirements, many plants must
resort to special treatment, e.g., the Fenton process to remove non-biodegradable
COD. While other technology options are available, the Fenton process most often is
selected because of its reliability, initial cost, operational cost and footprint.
The Fenton section usually consists of dosing systems for hydrogen peroxide and
ferrous sulfate. After dosing with chemical in an oxidation tank, the wastewater goes
to tube settlers to settle out the contaminants. During regular operation plants
generally don’t need to put wastewater through such treatment. However, having a
Fenton section can ensure treatment adequacy when facing sustained peak COD in the
wastewater.

Many units in tertiary treatment such as that for the Fenton process or fine filtration
should consist of multiple parallel streams to provide flexibility during operation.
Commonly used arrangements are “n+1” and “n+2” — for example, “2+2” “3+1”
“4+2” and “5+1”.