METALURGIA

DE
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HISTORY AND USE.
Bentonite mining began on the Taylor ranch near Rock River, WY, in
1888. This bentonite reportedly was shipped crude to Philadelphia
where is sold for $25 a ton and was used in making cosmetic.
The value of bentonite as foundry sand bond was recognized in the
1920s, and the iron and steel foundries have since been major
consumers of bentonite.
Bentonite was first used as drilling mud in the late 1920s or early
1930s, and bentonite is still one of the most efficient materials for
drilling mud where the rocks penetrated contain only freshwater.
HISTORY AND USE.
In addition to the major uses, bentonite is used in many miscellaneos
products, and hundreds of parents for specialty uses have been issued
or applications filed. The specialty uses include:
Filtering agents (one of which is a high value product for clarifying
wine, and another is a less costly one for treating waste water),
Water impedance (preventing seepage loss from reservoirs,
irrigation ditches, and waste disposal ponds, and seepage through
basement walls, tunnel walls, and other structures)
Ingredients in cosmetics,
Animal feed,
Pharmaceuticals,
Colloidal filler for certain types of paints,
An additive to ceramic raw materials to increase plasticity,
Fire retarding materials,
And many other purposes.
Another use for bentonite is as a coating on some types of computer
paper and on no-carbon required copy paper.
PRODUCT SPECIFICATIONS.
Product specifications have been tentatively standardized for
bentonite and/or fullers earth sold for drilling mud, foundry sand
bond absorbent granules, and oil bleaching and will be outlined
briefly. Specifications for most of the many other products made from
these clays are prepared to meet the requirements of the individual
customer, and they commonly vary with each.
Drilling mud.
Suspension Properties.
Wet Screen Analysis
Moisture.
Foundry Sand Bond.
Iron Ore Pelletizing
Absorbent Granules
Bleaching Oils
PRODUCT SPECIFICATIONS.
DRILLING MUD.
The most critical specifications for bentonite for drilling mud are:
The suspension properties,
Wet screen analysis,
And moisture as shipped.
Suspension Properties: The test for suspension properties involves
the preparation of a suspension consisting of 22.5 g of bentonite in 350
cc of distilled water. The suspension is aged and the viscosity
determined and yield point calculated from dial readings at 300 and 600
rpm with a direct indicating viscometer, according to procedure and
equipment requirements outlined in American Petroleum Institute
specification API STD 13A
PRODUCT SPECIFICATIONS.
DRILLING MUD.
Another important suspension requirement is the filtrate test, which is a
measure of the volume of water lost from the prepared suspension
when tested in a pressurized filter press according to procedure outlined
in American Petroleum Institute specification API RP 13.
Wet Screen Analysis: Wet-screen analysis (grit test) is a measure of
the material in bentonite mud that is coarser than 200-mesh US
Series sieve.. The specified test is made by mixing 10 g bentonite in
350 cc water containing 0.2 g dispersing agent, aging, stirring, and
washing through a sieve with a specified spray system. The residue on
the sieve is then dried, weighed, and the percentage of the original
bentonite is determined. Bentonite to fulfill the specifications for
drilling mud must have no more than 2.5% residue (grit) and
palygorskite no more than 8% residue.
Moisture: The maximum moisture content of bentonite when shipped
from the plant where it is processed is 10% and that for palygorskite is
16%.
PRODUCT SPECIFICATIONS.
FOUNDRY SAND BOND.
Tentative specifications for Western bentonite for bonding foundry sand
are outlined in Steel Founders Society of America.
This specification requires the following characteristic and properties for
Western bentonite, as tested by methods described in the specification:
1) Water content shall not exceed 12% or be less than 6%,
2) pH value shall be equal to or greater than 8.2,
3) Calcium oxide content shall not exceed 0.70%,
4) And the liquid limit shall not be less than 600 or greater than 850.
Each foundry has its own green, dry, and hot strength
specifications for bentonite, which vary with the type of metal, size of
casting, and foundry production procedures.
PRODUCT SPECIFICATIONS.
IRON ORE PELLETIZING.
Specifications for bentonite used for pelletizing taconite-type iron ore
have not been standardized, and several tests are used.
As green pellets must be capable of withstanding handling,
compaction, and drying and the dry pellets must be even stronger,
mixtures of bentonite, iron ore, and water are commonly tested for wet-
drop stregth, wet compression strength, plastic deformation, and
dry compression stregth.
PRODUCT SPECIFICATIONS.
ABSORBENT GRANULES.
The size and absorbent characteristics required of granules as outlined
in the federal specification are listed in Table 1.
The specifications require that absorbent granules consist of a uniform
mixture of minerals of the silicate type. They also must be clean,
uniform, and free of lumps or foreing matter, and no more than 10% of
them can pass through an 80 mesh sieve in the attrition
resistance test. The attrition resistance test is made by shaking with
steel balls on a screen, according to a specified procedure.
PRODUCT SPECIFICATIONS.
PRODUCT SPECIFICATIONS.
BLEACHING OILS.
Test methods for evaluating bentonite and other types of fullers earths
for bleaching soybean and cottonseed oils are outlined in the American
Oil Chemists Society AOCS Ofificial Method Cc 8-52 (1958). These
specifications contain instructions on bench-type tests, including stirring
time, heating rates and temperatures; approved equipment; quantities
of raw oil and clay required; methods of color determinations; and so
forth. The color determination of the bleached oils and their comparison
with the oils bleached by the official earth in the same test are the basis
for purchase specifications.
PRODUCT SPECIFICATIONS.
GEOLOGY.
MINERALOGY.
Smectite: The major mineral constituent of bentonite, and the mineral
that gives bentonite its unique physicochemical properties, is smectite.
Smectite is the general term given to a group of clay minerals that
includes beidellite, montmorillonite, nontronite, saponite, and
hectorite (Table 2).
Each of these minerals shares a similar structure but each is
chemically distinct. Nontronite, for instance, is an iron-rich smectite
and hectorite is a lithium-rich smectite.
Structure: The most common smectite group mineral found in
economic bentonite deposits is montmrillonite. The calcium and
sodium varieties, named based on the predominant exchangeable
cation, are most abundant. Hectorite is also a major constituent of
important commercial deposits.
The smectite minerals are divided into two structural groups
depending on whether all three octahedral sites are occupied
(trioctahedral) or two out of three are occupied (dioctahedral).
GEOLOGY.
GEOLOGY.
GEOLOGY.
MINERALOGY.
The theorical structural formula for the dioctahedral smectite minerals
montmorillonite, beidellite, and nontronite is
[Al
x
Fe
y
Mg
z
)
2.00
(Si
4.00-(u+v)
Fe
v
Al
u
)O
10
(OH)
2
]M
+
u+v+z
where M
+
represents the exchangeable cations.
The trioctahedral smectites, hectorite and saponite, have the following
theoretical formula:
[Mg
3.00-Z
Li
Z
)(Si
4.00-u
Al
u
)O
10
(OH
2
]M
+
z + u
GEOLOGY.
MINERALOGY.
Other Minerals: Other minerals commonly found in bentonites fall into
three categories:
1) Those that are volcanic in origin,
2) Those that form in situ as secondary minerals in response to
diagenesis and weathering, and
3) Those that are detrital contaminants.
Tipical volcanic minerals include feldspars, biotite, quartz,
cristobalite, apatite, zircon, magnetite, amphiboles, and sometimes
unaltered volcanic glass.
Minerals of low temperature origin include various forms of poorly
ordered opaline silica, zeolites, calcite, selenite, other clay
minerals including kaolinite and illite, and various iron sulfate
minerals. Detrital minerals are the least abundant and include all of
the major rock forming minerals found in most sedimentary
environments. These minerals rarely constitute more than 10% of a
commercially viable deposit.
OCCURRENCE.
Bentonite is typically found as beds in marine and nonmarine strata
ranging in age from Jurassic to Pleistocene. These beds which tend to
be parallel to the overlying and underlying strata, range in thickness
from several centimeters to tens of meters and can be
geographically very extensive.
Bedded bentonite can also occur as small lens shaped bodies with a
limited lateral extent.
A less common occurrence of bentonite is as irregular shaped bodies
that grade into unaltered host rock..
Bentonite ranges in color from white to yellow to olive green to
brown to blue. It has a characteristic soapy texture and a waxy
appearance. Weathered sodium bentonite has a distinctive popcorn
texture.
Calcium bentonite weathers to an aligator skin texture.
ORIGIN.
Bentonite most commonly forms as a result of the in situ alteration of
volcanic ash or tuff. Another less common origin is as the
hydrothermal alteration of volcanic rocks.
The alteration of ash to smectite is a hydration reaction that requires
magnesium and produces excess silica as well as alkali ions. Because
of these requirements bentonite is most commonly found in marine
strata where the ash apparently altered in contact with seawater. In
some instances it also formed in contact with alkaline lake water and
groundwater.
The evidence for bentonite having altered from volcanic ash is:
1. Mineralogy--- bentonite beds often contain euhedral minerals
characteristic of volcaniclastic rocks,
2. Chemistry--- the major element and the rare earth element chemistry
of the smectite is consistent with a volcanic precursor,
3. Texture--- relict glass shards pseudomorphically replaced by smectite
have been observed both in thin section and under the scanning
electron microscope.
The most compelling evidence for a volcanic parent, however, is the
presence of unaltered glass shards in some deposits.
ORIGIN.
DISTRIBUTION OF DEPOSITS.
North America
Western Bentonite.
Southern Bentonite.
Fullers Earth
Hectorite.
Other Deposits.
Canada.
Mexico: Bentonite and fullers earth deposits are distributed
throughout central Mexico where volcanoclastic rocks are
pervasive. The majority of these bentonites contain calcium as the
dominant exchangeable cation and many of them occur in
marine rocks of Tertiary age.
Both calcium and sodium bentonites are mined in Mexico which
produced 136 kt of bentonite in 1986. The largest calcium
bentonite deposits are located in Tlaxcala and Morelos in
Hidalgo.
The principal sodium bentonite producing region is in Durango.
DISTRIBUTION OF DEPOSITS.
Other Deposits.
The sodium bentonite is marketed to the foundry industry and is also
used in detergents, pencil manufacture, and cosmetics.
Acid activated and sodium exchanged calcium bentonites are also
produced in plants in Durango and Puebla.
South America.
Brazil
Peru
Chile.
DISTRIBUTION OF DEPOSITS.
Europe.
United Kingdom
Germany
Sweden
France
Greece
Italy
Spain
Cyprus
Turkey.
Africa
Morocco
South Africa
DISTRIBUTION OF DEPOSITS.
Australia.
Asia
India
Pakistan
Japan
EVALUATION OF DEPOSITS.
EXPLORATION.
Exploration for bentonite and fuller s earth deposits consists of several
steps.
The first step in exploration is to identify areas that are likely to
contain bentonite deposits.
Once target areas have been identified, a field reconnaisance is
usually conducted to establish whether or not clay deposits are
present. If clay is found then the next step is to map the extent of
the deposits. In other areas drilling must be conducted to
accurately map the deposits. Usually both surface mapping and
drilling are utilized to determine the extent of available reserves.
After deposits has been located and mapped other factors must be
considered before capital is invested in evaluation and extensive
testing of the deposit. Factor such as amount of overburden,
distance to markets, available transportation, and amount of
reserves must be considered.
EVALUATION OF DEPOSITS.
MINERALOGICAL INVESTIGATIONS.
The mineralogy, and the chemistry of a clay are important properties
that must be considered when evaluating the economic use of a
deposit. A detailed understanding of the particle size and shape of the
clay fraction can also be essential to making the appropriate
determination for the end-use of a clay.
Simple physical testing is no longer sufficient for a number or reasons.
1. One reason is that these clays are being used in an increasing
number of specialty products that require very stringent
specifications, many of which are related to chemistry, particle
size, and shape.
2. Another is that reserves of the high quality clays, for which the
standard testing procedures and specifications were written, are
becoming depleted and different quality clays are being mined.
These clays often must be beneficiated to meet the traditional
specifications and this requires a detailed understanding of
mineralogy and chemistry.
EVALUATION OF DEPOSITS.
MINERALOGICAL INVESTIGATIONS.
3. A third reason for characterizing mineralogy and chemistry is
that there is an increasing interesting in the research and
development of these clays for use in more highly technical
industrial applications such as catalysis, non linear optics,
advanced ceramics, and polymer composites.
Analytical methods for studying clay minerals include X-ray
difraction, scanning electron microscopy, transmission electron
microscopy, infrared spectroscopy, differential thermal analysis,
and optical microscopy. These methods are used to study the
structure and chemistry of raw clays and clay based products. Other
methods used to investigate clays include various methods for
determining structural chemistry, surface chemistry, surface area, and
particle size distribution to name a few.
EVALUATION OF DEPOSITS.
APPRAISAL OF FIELD AND LABORATORY RESULTS.
Testing:
Mineralogy.
Appraisal of Field and Laboratory Results.
EVALUATION OF DEPOSITS.
PREPARATION FOR MARKETS.
Mining Methods: Bulldozers and scrapers or pans are most
commonly used in removing overburden. In gthe typical pit, the
overburden is removed in panels, the clay mined by loading trucks with
dragline or endloaders, and the overburden from an adjacent panel
shifted to the mined out area. Thicknesses of overburden removed vary
considerably. The overburden stripped from fuller s earth deposits
ranges from a few meters to more than 23 m.
The rocks overlying most bentonite deposits are soft and can be
loaded directly by self-propeller or pushed scrapers, but in places they
must be loosened by bulldozers and rippers before loading.
Most bentonite produced in other countries is also strip mined, but
underground methods are used in a few places.
Because of variable physical properties, most bentonite deposits are
selectively mined. Bentonite from a single pit or bed may by separated
into as many as three stockpiles at the plant, each with different
physical properties. Various grades of bentonite suitable for different
uses are then prepared from the separate piles and by blending clay
from more than one pile. Blending bentonite as it is dumped on
stockpiles, using earth-moving to obtain a unifom clay, is also common
practice.
EVALUATION OF DEPOSITS.
PREPARATION FOR MARKETS.
Beneficiation and Processing techniques: Bentonite is processed by
simple milling techniques that involve removal of water and in some
instances, other volatile matter, and grinding to suitable sizes. (Fig.
9).The high swelling bentonite, when delivered to the plant, contains
approximately 30% moisture; the free water in the calcium-type
bentonite is about 25%. Some fullers earth contains as much as
50% volatile matter and 10% undesirable impurities.
The processed bentonite ordinarily contains only 7 or 8% water, but
because it is hygroscopic, it may contain considerably more when used.
Moisture content of the fuller s earth is approximately the same as that
of bentonite. Most absorbent granules, however, are heated to a
temperature high enough to drive off interlayer and zeolitic water in the
minerals present. Any moisture in the granules has been absorbed after
processing.
In most plants, the raw clay is passed through some sort of a clay
slicer to break up the large chunks before drying. The temperature in
dryers varies with the intended use of the clay. The desirable
properties of bentonite is reduced greatly if the clay is heated too
much.
EVALUATION OF DEPOSITS.
PREPARATION FOR MARKETS.
Beneficiation and Processing techniques:
The temperature in dryers processing bentonite is likely to be
approximately 800C at the inlet, 100 to 200C at he outlet, and 400 to
500C in main drying zone. The bentonite itself is kept at temperatures
of less than 150 C.
The dried clay is ground and sized in several ways. In some plants,
rods in rotary dryers do much of the grinding, but most of the
powdered product is ground with roll and hammer mills or other
pulverizer, and screened. Most bentonite is ground to approximately
90% finer than 200 mesh.
Granular grades of bentonite are also sold, and the wide use of
absorbent granule-type fuller s earth requires the preparation of a
coarse product. The preparation of coarse absorbent granules is, in
effect, a beneficiation process, because much of the fine and medium
grained sand impurities in the fuller s earth are in the size fraction
discarded.
EVALUATION OF DEPOSITS.
PREPARATION FOR MARKETS.
Beneficiation and Processing techniques:
Hectorite and some Southern bentonite, in addition to being processed
like other bentonite, are beneficiated by a hydroclassification
process. In this process, the clay is dispersed in water and pumped
into a multistage concentrating circuit where nonclay and other
undesirable materials are separated and removed. The slurry is then
passed through drum or spray-type dryers, and the concentrated is
pulverized. A high value material is prepared in one plant by centrifuging
a dilute slurry.
EVALUATION OF DEPOSITS.
PREPARATION FOR MARKETS.
EVALUATION OF DEPOSITS.
SYNTHETIC AND ORGANIC-CLAD BENTONITE.
Synthetic hectorite is made in the United Kingdom. This material is
purer than naturally occurring varieties, as it contains no fluoride. It
presumably is suitable for some of the same uses that synthetic
bentonite was developed for in the Unites States.
For several decades an organic treated bentonite has been on the
market under the registered trade name Bentone. This product is
processed in such a way that the original inorganic exchangeable ion on
the bentonite is replaced by an alkyl amine organic cation. This reaction
produces a hydrophobic clay because the inorganic ions that can be
hydrated are removed, and a large part of the clay mineral surface
formely capable of absorbing water is coated by hydrocarbon chains.
Organic-clad bentonites are used in making paint, to gel organic
liquids, to produce greases having superior properties for adherence
to metal, ability to repel water, and resistance to high temperatures, and
in other products.
EVALUATION OF DEPOSITS.
FUTURE CONSIDERATIONS AND TRENDS.
The growth rate in fullers earth requirements will probably exceed
the rate forecast for bentonite.
Both bentonite and fuller s earth are used in so many different products
and in so many ways that there are many possible substitutes for
specific uses and both have lost markets to other materials in the past.
Bentonite is in some danger of a market loss which may be caused by a
breakthrough in the proportion of bentonite added in taconite bonding is
small, it is still a contaminant, and some type of bonding material that
will burn off completely or even add heat in the steel furnace will
continue to be sought.
The manufacture of synthetic hectorite and other montmorillonite-like
mineral products formerly in the United States and now in the United
Kingdom marks a technological breakthrough. World-wide markets for
organic-clad bentonite and washed or otherwise pufified white bentonite
for specialty products are also likely to increase with general
economic growth and the development of new uses and products.
Rising cost of transportation and fuel are two of the major
pressures on the bentonite and fuller s earth industries that are likely to
have a significant influence on future trends.