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We have been asked by quite a number of students preparing
research papers to provide some basic information on the
properties, manufacture and uses of magnesium oxide. In response
to these requests we are pleased to provide the following summary
which we hope will not only be educational but interesting as
well.
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Everything You Ever Wanted to Know About Magnesium Oxide
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Mineral deposit of magnesite
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The majority of magnesium oxide produced today is obtained from
the processing of naturally occurring minerals such as magnesite
(magnesium carbonate), magnesium chloride rich brine, and
seawater.
Large mineral deposits of
magnesite are located in Austria, Brazil, Canada, China, the
Commonwealth of Independent States (CIS), former Czechoslovakia,
Greece, Turkey, North Korea, former Yugoslavia, and the U.S.
When heated from 700°C to 1000°C, magnesium carbonate
thermally decomposes to produce magnesium oxide and carbon
dioxide:
MgCO3 --heat-->MgO
+ CO 2(gas)
While mining is one source, another important
source of magnesium oxide is obtained from processing seawater and
underground deposits of brine which contain magnesium chloride.
The remainder of this summary will follow the extraction and
processing of magnesium oxide from a typical brine source. The
process for extraction from seawater would follow basically the
same route, differing only in the concentration of magnesium in
seawater.
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Deposits of brine, located
approximately 2,500 feet below ground, are used in Martin
Marietta's process as one source of magnesium.
Brine is essentially a saturated salt solution
which, in this case, contains magnesium chloride, calcium chloride
and water. Since the concentration of magnesium in this brine
source is around 9%, it takes about 2.5 gallons of brine to
produce just one pound of magnesium oxide.
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Dolomitic Limestone quarry
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In order to extract magnesium from brine,
another ingredient is needed. Typically this ingredient is lime
or calcium oxide (CaO) which is obtained from a mineral source
such as dolomitic limestone (CaMg(CO3) 2 ).
When heated to high temperatures the carbon dioxide is driven off
leaving calcined dolime:
CaMg(CO 3) 2
--heat--> (CaO·MgO) + 2CO 2(gas)
Calcined dolime also provides another source of
magnesium.
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First, naturally occurring brine is mixed with
both calcined dolime and water to produce an aqueous suspension
containing magnesium hydroxide and calcium chloride:
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CaCl2+MgCl2+H2O
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+
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(CaO·MgO)
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+
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2H2O
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--->
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2Mg(OH)2
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+
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2CaCl2
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+
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H2O
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brine
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calcined dolime
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water
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magnesium
hydroxide
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calcium chloride
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water
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The magnesium hydroxide and calcium chloride
produced from this reaction exist together but in two distinct
physical states: magnesium hydroxide is formed as solid particles
while the calcium chloride is dissolved in the liquid or watery
phase. An aqueous suspension containing solid particles is also
referred to as a slurry.
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Gravity is used to separate the solids from the
liquid in the aqueous suspension since magnesium hydroxide is
heavier than water. If you look at a bottle of milk of magnesia,
which you probably have in your bathroom medicine chest, you'll
see this separation clearly.
Milk of magnesia is another name for magnesium hydroxide. In
the photo at left, the freshly made magnesium hydroxide slurry
(white) is pumped over to another holding tank and allowed to
settle.
The blue color indicates the watery layer
containing dissolved magnesium chloride that has formed above the
settled magnesium hydroxide particles.
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The bottom solids are then filtered to remove
any remaining water and given a series of water washes to remove
chlorides from the material. This results in a damp filter cake
which can be seen dropping off the lower roller of the press (at
left) about waist high to the operator. The washed filter cake is
finally directed to a source of heat, such as a rotary kiln shown
in the photo below, where it is thermally decomposed (calcined) to
produce magnesium oxide:
2Mg(OH) 2 --heat-->
2MgO + 2H2O(steam)
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Rotary kiln pictured in foreground
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Several types of kilns can be used in the
calcination step. Calcination not only converts magnesium hydroxide
to magnesium oxide, but is also the most important step for
determining how the final product will be used.
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Three basic types or grades of "burned" magnesium
oxide can be obtained from the calcination step with the
differences between each grade related to the degree of reactivity
remaining after being exposed to a range of extremely high
temperatures.
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Different Grades of Magnesium Oxide:
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The original or "parent" magnesium hydroxide particle
is usually a large and loosely bonded particle. Exposure to
thermal degradation causes this particle to alter its structure so
that the surface pores are slowly filled in while the particle
edges become more rounded.
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Thermal alteration dramatically affects the reactivity of
magnesium oxide since less surface area and pores are available
for reaction with other compounds. This change in particle
structure is demonstrated in the photographs below.
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Dead
burned magnesium oxide
Temperatures used when calcining to produce
refractory grade magnesia will range between 1500°C - 2000°C and
the magnesium oxide is referred to as "dead-burned"
since most, if not all, of the reactivity has been eliminated. Refractory
grade MgO is used extensively in steel production to serve as both
protective and replaceable linings for equipment used to handle
molten steel.
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10,000 X (surface area:
<0.1 m 2 /gr)
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Hard burned magnesium oxide
A second type of magnesium oxide produced from calcining at
temperatures ranging from 1000°C - 1500°C is termed
"hard-burned".
Due to it's narrow range of reactivity, this grade is typically
used in applications where slow degradation or chemical reactivity
is required such as with animal feeds and fertilizers.
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5,000 X (surface area:
0.1 - 1.0 m 2 /gr)
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Light
burned magnesium oxide
The third grade of MgO is produced by calcining at temperatures
ranging from 700°C - 1000°C and is termed "light-burn"
or "caustic" magnesia. Due to the material's wide
reactivity range, industrial applications are quite varied and
include plastics, rubber, paper and pulp processing, steel boiler
additives, adhesives, and acid neutralization to name just a few.
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5,000 X (surface area:
1.0 - 250 m 2 /gr)
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High
purity magnesium oxide
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Due to increases of significantly cheaper
foreign sources of magnesium oxide and a widely fluctuating steel
market (the biggest user of refractory grade MgO), the focus of
major magnesium oxide producers in the United States has turned to
improved quality rather than supplying commodity quantities. In
order to meet the specialized needs of customers, magnesium oxide
is further refined and purified. Usually the magnesium oxide is
rehydrated (mixed back with water) to form magnesium hydroxide:
2MgO + 2H 2O ----> 2Mg(OH) 2
(slurry)
The slurry form of magnesium hydroxide allows
for easier addition of other elements or compounds (in either
gaseous or liquid form) to remove contaminants such as calcium,
sulfur, and any excess chlorides that may have remained in the
original reaction and thereby increases the purity of the product.
Using relatively simple chemistry it is also
possible to add certain ingredients to magnesium oxide to generate
a broad range of new
magnesium based compounds. As in the high purity magnesium
oxide process, magnesium hydroxide slurry is a convenient medium
for these additions. Examples of typical reactions include:
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slurry reactants
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slurry
+ additive --->
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end
product + water
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2MgO + 2H2O --->
(mag oxide + water)
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2Mg(OH)2 + 4HNO3
--->
(mag hydroxide + nitric acid)
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2Mg(NO3)2
+ 4H2O
(mag nitrate + water)
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2MgO + 2H2O --->
(mag oxide + water)
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2Mg(OH)2 + 2H2SO4
--->
(mag hydroxide + sulfuric
acid)
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2MgSO4 + 4H2O
(mag sulfate + water)
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2MgO + 2H2O --->
(mag oxide + water)
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2Mg(OH)2 + 2CO2(gas)
--->
(mag hydroxide + carbon
dioxide)
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2MgCO3 + 2H2O
(mag carbonate + water)
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Abrasives
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As a binder in grinding wheels
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Animal feed supplement
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Source of magnesium ions for chickens,
cattle and other animals
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Boiler (oil-fired) additives
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Raises melting point of ash generated to
produce a friable material that is easily removed; reduced
corrosion of steel pipes holding steam as well as sulfur
emissions into the environment
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Boiler feedwater treatment
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Reduces iron, silica and solids
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Chemicals
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Starting point for the production of
other magnesium salts such as sulfate and nitrate
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Coatings
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Pigment extender in paint and varnish
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Construction
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Basic ingredient of oxychloride cements
used for flooring, wallboard, fiber board, and tile
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Electrical
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Semi-conductors; heating elements
insulating filler between wire and outer sheath
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Fertilizers
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Source of essential magnesium for plant
nutrition
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Foundries
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Catalyst and water acceptor in shell
molding
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Glass manufacture
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Ingredient for specialty, scientific and
decorative glassware and fiberglass
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Insulation
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Light, flexible mats for insulating
pipes
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Lubricating oils
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Additive to neutralize acids
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Pharmaceuticals
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Special grades of magnesium hydroxide,
oxide and carbonate are used in antacids, cosmetics,
toothpaste, and ointments
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Plastics manufacture
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Filler, acid acceptor, thickener
catalyst and pigment extender
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Refractory and ceramics
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Basic ingredient in product formulations
for the steel industry
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Rubber compounding
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Filler, acid acceptor, anti-scorch
ingredient, curing aid, pigment
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Steel industry
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Annealing process; coating for
grain-oriented silicon steel used in electrical
transformers
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Sugar refining
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Reduces scale build-up when used in
juice clarification and precipitation
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Sulfite wood pulping
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Source of base for cooking liquors
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Uranium, gallium and boron processing
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Precipitation initiator by acid
neutralization
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Wastewater treatment
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Acid stream neutralizer; precipitates
heavy metals
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While there are many factors to be considered in the production
of magnesium oxide, this summary presents just a general overview
of the entire process. To obtain more information concerning the
production of magnesium oxide, please visit the U.S.
Geological Survey - Minerals Information page. Another
excellent resource can be found on the National
Toxicology Program's website. Hopefully, this
overview helps demonstrate the versatility and value of
magnesium oxide in the world of industry today.
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