HG Extraction 2

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Extraction

of Mercury
Prof. Dr. Eng.
Mohamed Sayed Ahmed
Physical properties of Mercury:
 Name: mercury
 Group of mercury in periodic table: metal
 Symbol of mercury: Hg
 Atomic number of mercury: 80
 Atomic weight of mercury: 200.59
 Appearance of mercury: silver-white liquid at room temperature
 Melting point of mercury: −38.89◦C under atmospheric pressure
 Boiling point of mercury: 357.25◦C under atmospheric pressure
 As compared to other metals, mercury is a poor conductor of heat, but a
fair conductor of electricity
 Mercury and its compounds are very toxic

Crystal Structure of β‐Hg


The crystal structure of β‐Hg, which is the stable form below 79°K, is found
to be a body‐centered tetragonal with a =3.995 A, and b =2.825 A at 77°K.
Metallic mercury uses:
 As a liquid switch in electrical appliances
 Mercury-vapor lamps
 Mercury-vapor rectifiers
 Thermometers, and barometers,
tachometers, ‫ أجهزة قياس سرعة الدوران‬، ‫ البارومترات‬، ‫موازين الحرارة‬
The Ores of Mercury
The most important mineral of the mercury ores is
Cinnabar, which is a composition of mercury and
sulfur (HgS), with a mercury content of 86.2 %.
Secondary minerals include metacinnabarite (β-
sulfide of mercury), native mercury (Hg), livingstonite
(HgSb4S7), corderoite (Hg3S2Cl2), and the mercury-
containing sulfosalts of Cu, Sb, and As. Distinctions
are made between high-grade mercury ores (approx.
1% Hg), medium-grade ores (0.2–0.3% Hg), low-grade
ores (0.06–0.12% Hg), and very low-grade ores (0.02–
0.06% Hg). Complex mercury ores contain Sb, Cu-Pb-
Zn, W, Au-Ag, and the harmful admixture As.
.
Compared to other elements, Mercury ores found in the
earth crust is low but it is not a rare element. The red
ore called cinnabar available abundantly on the earth.

CINNABAR IN ITS MASSIVE FORM

The main areas for cinnabar mining are in Italy and


Spain which provide 50% of the worlds mercury
Cinnabar is usually found in a massive or granular
form but can also occur as small crystals shown
below. This ore is bright red in colour and small
droplets of mercury metal can sometimes be found
within the ore itself.

CINNABAR IN ITS CRYSTAL FORM


Production of Hg from its Ores
Mercury (Hg) is considered as a noble metal which is
easy to produce.
Hg is mostly obtained by reduction from the mineral
cinnabar (HgS) in two steps, as follow:
 Roasting: The first step is the oxidation of mercury
in the presence of oxygen inside the ore.
 Extraction: Since, it has a low boiling point; it can
easily be extracted via vacuum distillation. The
extracted mercury may contain impurities like
copper, bismuth, lead, zinc etc. which can later be
extracted as per the requirement.
Thermodynamic of Hg Production

Thermodynamically HgO is easily decomposed by heating to above 450


oC, since this temperature is higher than the boiling point of Hg (356.6 oC):

T > 450 oC
2 HgO(s) 2 Hg(g) + O2 (1)
Since the most common ore of Hg is cinnabar (HgS),
Thus, HgS (cinnabar) is decomposed by oxidizing roasting:

T > 450 oC
HgS(s) + O2 oC)
Hg(g) + SO2 (2)
(500 - 600

Reactions (1) and (2) shift to the left on cooling, thus the reactions would
reverse completely during condensation of the product. Fortunately, the
back-reaction is very slow at cooling temperature. This makes the
extracting of Hg is very simple process, which is one operation produces
the metal and separates it from the gangue and from other non-volatile
metal.
The decomposition of HgS may be also carried out by
means of other reactants, such as:
T > 450 oC
HgS(s) + Fe Hg(g) + FeS (3)
(500-600 oC)

T > 450 oC
4 HgS(s) + 4 CaO oC)
4 Hg(g) + 3 CaS + CaSO4 (4)
(500-600

For these cases, reactions (3) and (4), the vapor


contains only Hg(g), and there is no danger of back-
reaction during condensation.
Industrial Hg Processes
The Manufacturing Process:
The process for extracting mercury from its ores has
not changed much since Aristotle first described it
over 2,300 years ago. Cinnabar ore is crushed and
heated to release the mercury as a vapor. The
mercury vapor is then cooled, condensed, and
collected. Almost 95% of the mercury content of
cinnabar ore can be recovered using this process.
Here is a typical sequence (process flow diagram) of
operations used for the modern extraction and
refining of mercury.
Mercury extraction flow diagram (the metallurgy of Hg).
Mining :
Cinnabar ore occurs in concentrated deposits
located at or near the surface. About 90% of these
deposits are deep enough to require underground
mining with tunnels. The remaining 10% can be
excavated from open pits.
1) Cinnabar is dislodged from the surrounding
rocks by drilling and blasting with explosives or by
the use of power equipment. The ore is brought
out of the mine on conveyor belts or in trucks or
trains.
Roasting:
Because cinnabar ore is relatively concentrated, it can be processed
directly without any intermediate steps to remove waste material.

2) The ore is first crushed in one or more cone crushers. A cone crusher
consists of an interior grinding cone that rotates on an eccentric vertical
axis inside a fixed outer cone. As the ore is fed into the top of the crusher,
it is squeezed between the two cones and broken into smaller pieces.
3) The crushed ore is then ground even smaller by a series of mills. Each
mill consists of a large cylindrical container laying on its side and rotating
on its horizontal axis. The mill may be filled with short lengths of steel rods
or with steel balls to provide the grinding action.
4) The finely powdered ore is fed into a furnace or kiln to be heated. Some
operations use a multiple-hearth furnace, in which the ore is mechanically
moved down a vertical shaft from one ledge, or hearth, to the next by
slowly rotating rakes. Other operations use a rotary kiln, in which the ore is
tumbled down the length of a long, rotating cylinder that is inclined a few
degrees off horizontal. In either case, heat is provided by combusting
natural gas or some other fuel in the lower portion of the furnace or kiln.
The heated cinnabar (HgS) reacts with the oxygen (O2) in the air to produce
sulfur dioxide (SO2 ), allowing the mercury to rise as a vapor. This process
is called roasting.
Condensing :
5) The mercury vapor rises up and out of the furnace or kiln along
with the sulfur dioxide, water vapor, and other products of
combustion. A considerable amount of fine dust from the powdered
ore is also carried along and must be separated and captured.
6) The hot furnace exhaust passes through a water-cooled
condenser. As the exhaust cools, the mercury, which has a boiling
point of 675° F (357° C), is the first to condense into a liquid, leaving
the other gases and vapors to be vented or to be processed further to
reduce air pollution.
7) The liquid mercury is collected. Because mercury has a very high
specific gravity, any impurities tend to rise to the surface and form a
dark film or scum. These impurities are removed by filtration, leaving
a liquid mercury that is about 99.9% pure. The impurities are treated
with lime to In order to extract mercury from its ores, cinnabar ore is
crushed and heated to release the mercury as a vapor. The mercury
vapor is then cooled, condensed, and collected.
Refining :
Most commercial-grade mercury is 99.9% pure and can be used
directly from the roasting and condensing process. Higher purity
mercury is needed for some limited applications and must be
refined further. This ultrapure mercury commands a premium
price.
8) Higher purity can be obtained through several refining
methods. The mercury may be mechanically filtered again, and
certain impurities may be removed through oxidation with
chemicals or air. In some cases the mercury is refined through an
electrolytic process, in which an electric current is passed through
a tank of liquid mercury to remove the impurities. The most
common refining method is triple distillation, in which the
temperature of the liquid mercury is carefully raised until the
impurities either evaporate or the mercury itself evaporates,
leaving the impurities behind. This distillation process is
performed three times, with the purity increasing each time.
Shipping :
9) Commercial-grade mercury is poured into
wrought-iron or steel flasks and sealed.
Each flask contains 76 lb (34.5 kg) of
mercury. Higher purity mercury is usually
sealed in smaller glass or plastic containers
for shipment.
Quality Control
Commercial-grade mercury with 99.9% purity is called prime virgin-
grade mercury. Ultrapure mercury is usually produced by the triple-
distillation method and is called triple-distilled mercury.

Quality control inspections of the roasting and condensing process


consist of spot checking the condensed liquid mercury for the presence
of foreign metals, since those are the most common contaminants. The
presence of gold, silver, and base metals is detected using various
chemical-testing methods.

Triple-distilled mercury is tested by evaporation or spectrographic


analysis. In the evaporation method, a sample of mercury is evaporated,
and the residue is weighed. In the spectrographic analysis method, a
sample of mercury is evaporated, and the residue is mixed with
graphite. Light coming from the resulting mixture is viewed with a
spectrometer, which separates the light into different color bands
depending on the chemical elements present.
Health and Environmental Effects
 Mercury is highly toxic to humans. Exposure may come from
inhalation, ingestion, or absorption through the skin. Of the three,
inhalation of mercury vapor is the most dangerous. Short-term
exposure to mercury vapor can produce weakness, chills, nausea,
vomiting, diarrhea, and other symptoms within a few hours.
Recovery is usually complete once the victim is removed from the
source. Long-term exposure to mercury vapor produces shaking,
irritability, insomnia, confusion, excessive salivation, and other
debilitating effects.

 In normal situations, most exposure to mercury comes from the


ingestion of certain foods, such as fish, in which the mercury has
accumulated at high levels. Although mercury is not absorbed in
great quantities when passing through the human digestive system,
ingestion over a long period of time has been shown to have
cumulative effects.
 In industrial situations, mercury exposure is a far more serious hazard.
Mining and processing mercury ore can expose workers to mercury
vapor as well as to direct contact with the skin. The production of
chlorine and caustic soda can also cause significant mercury exposure
hazards. Dentists and dental assistants can be exposed to mercury
while preparing and placing mercury amalgam fillings.

 Because mercury poses a serious health hazard, its use and release to
the environment has come under increasingly tight restrictions. In 1988,
it was estimated that 24 million lb/yr (11 million kglyr) of mercury were
released into the air, land, and water worldwide as the result of human
activities. This included mercury released by mercury mining and
refining, various manufacturing operations, the combustion of coal, the
discarding of municipal refuse and sewage sludge, and other sources.

 In the United States, the Environmental Protection Agency (EPA) has


banned the use of mercury for many applications. The EPA has set a
goal of reducing the level of mercury found in municipal refuse from 1.4
million Ib/yr (0.64 million kg/yr) in 1989 to 0.35 million lb/yr (0.16 million
kg/yr) by 2000. This is to be accomplished by decreasing the use of
mercury in products and increasing the diversion of mercury from
municipal refuse through recycling.

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