Mercury Production☆

Fathi Habashi, Laval University, Quebec, Canada

r 2017 Elsevier Inc. All rights reserved.

1 Occurrence 1
2 Recovery 1
2.1 Recovery From Mercury Ores 3
2.1.1 Thermal methods 3
2.1.1.1 Directly heated furnaces 3
2.1.1.2 Indirectly heated furnaces 3
2.1.2 Hydrometallurgical route 3
2.2 Recovery From Gold Ores 3
2.3 Recovery From Smelter Gases 3
2.3.1 Adsorption–filtration methods 4
2.3.2 Precipitation–filtration methods 4
3 Removal of Traces of Mercury From Sulfuric Acid 5
4 Amalgams 5
5 The Alkali-Chlorine Industry 6
6 Polarography 6
7 Toxicity of Mercury 6
Further Reading 6

Mercury is an ancient metal; its recovery from its principal mineral cinnabar, HgS, was already known to the Greeks and Romans
and its use in the recovery of gold was described by Pliny the Elder in AD 77. In Latin it is hydrargyrum, i.e., liquid silver, from
which the symbol Hg was derived. Although mercury deposits in northern Italy had been mined by the Etruscans, they were not
intensively worked by the Romans, to the benefit of the Spanish mines at Almaden. The toxicity of mercury was known to the
Romans. The alchemists called the metal mercury after the mythological Mercury, the messenger of the gods. Thomas Aquinas
(1225–74) studied solutions of metals in mercury and called them amalgams. Vanoccio Biringuccio mentioned the amalgamation
of gold and silver from their ores in his book De la Pirotechnia, published in 1540. Bartholomeo de Medina applied this process in
Pachuca in Mexico, on a large scale, in 1566. Mercury at that time had the importance of petroleum today. Amalgamation of ores
by mercury was the only means to obtain silver and gold from ores to mint coins.
During World War II some processes were developed in Germany for metal recovery by the amalgam route, for example, the
recovery of aluminum from shot-down airplanes. Most of these, however, have been abandoned. Production of mercury has
decreased drastically since the 1980s (Table 1). The most important data about mercury are given in Table 2.

1 Occurrence

Ores containing the mineral cinnabar (Fig. 1), the major mercury raw material, may be divided into two general types: (1)
disseminated ore, in which the mineral has impregnated fine-grained or highly brecciated gangue, or (2) ore deposited
in fissures or cracks of country rock as veins of pure cinnabar in which microscopic droplets of metallic mercury (Fig. 2) may
be found.
Prior to 1850, three mines dominated world production: the Almaden mine in Spain, the Idria mine in the former Yugoslavia,
and the Santa Barbara mine in Peru. In the second half of the 19th century, production began in the Monte Amiata district in Italy,
and output in the United States (California) became prominent. The early history of mercury in the United States is associated
with the development of gold mining in California. Since 1975, Nevada has become the leading mine producer with two gold
mining operations producing by-product mercury. Mines in Algeria, China, Czechoslovakia, Italy, Spain, Turkey, the former USSR,
and former Yugoslavia comprise about 75% of world capacity.
Sulfide concentrates contain on the average 100–300 ppm mercury. This amount is relatively small, but when the large tonnage
of concentrates treated annually is taken into consideration, the actual amount of mercury dealt with will be about the same as the
world consumption of the metal. These concentrates are either completely oxidized at high temperature to yield an oxide, as in the
case of lead and zinc concentrates, or partially oxidized to yield a matte, as in the case of copper and nickel concentrates. In both
cases mercury sulfide present in the concentrate is volatilized as mercury vapor in the sulfur dioxide gas phase, from which it can
be recovered.

☆
Change History: February 2017. Fathi Habashi added an Abstract, Keywords, and Figs. 1–3; updated text and references.

Reference Module in Materials Science and Materials Engineering doi:10.1016/B978-0-12-803581-8.10348-0 1

2 Mercury Production

Table 1 World production of mercury

Period Tonnes

1960–1969 19213a
1970–1979 18574a
1980–1989 7129a
1990 6060
1991 2540
1992 1920
1993 2270
1994 1800
1995 2820
1996 2800
1997 3000b
a
Yearly average.
b
Estimated.

Table 2 Pertinent data on mercury

Relative abundance in Earth’s crust (ppm) 4

Major mineral Cinnabar HgS

Atomic number 80
Atomic weight 200.61
Atomic radius (Å ) 1.6
Density at 201C 13.54616
Melting point (1C) –38.84
Boiling point (1C) 356.8
Crystal structure of solid Rhombohedral
Oxidation state þ 1, þ 2
Vapor pressure
at 201C 0.0013 mmHg
at 1001C 0.279 mmHg
Saturated vapor pressure of mercury in air at 201C 14 mg m3
Maximum allowable concentration in air 0.1 mg M–3, or about 0.01 ppm
Major uses Chlorine-alkali plants, electrical and electronic catalyst, dentistry, thermostates, switches

Fig. 1 Museum sample of the mineral cinnabar.

 Mercury Production 3

Fig. 2 Droplets of native mercury in cinnabar ore.

2 Recovery

Mercury is mainly recovered from its ores and also as a by-product of the gold and zinc industries.

2.1 Recovery From Mercury Ores

2.1.1 Thermal methods
The coarsely ground ore when heated with air forms mercury oxide, which breaks down at about 3501C to liberate mercury vapor:

HgS þ 3=2O2 -HgO þ SO2

HgO-Hg þ 1=2O2

Sometimes lime is added to bind SO2 in the form of CaSO4. Two methods of heating are used:

2.1.1.1 Directly heated furnaces

When mercury ores are oxidized in multiple hearth furnaces or in rotary kilns (Fig. 3), the mercury vapor formed will come into
contact with the dust generated in the reactors and will condense on it, necessitating a special treatment of the dust collected in the
cyclones and other dust recovery systems to recover the entrapped mercury, for example, by flotation.

2.1.1.2 Indirectly heated furnaces

This technology was introduced to avoid the problems associated with the treatment of ores in directly heated furnaces. In one
system, a rotary kiln constructed from two concentric tubes was developed. The ore passes continuously through a silicon carbide
inner tube while the outer tube is directly heated. Mercury is then recovered by condensation in water-sprayed towers.

2.1.2 Hydrometallurgical route

Although the method is not used at present, mercury can be leached from its ores and concentrates with a solution of sodium
sulfide and sodium hydroxide, and recovered as elemental mercury by precipitation with aluminum or by electrolysis. In another
process, also not in use, mercury in ores can be dissolved in a sodium hypochlorite solution, the mercury-laden solution passing
through activated carbon to adsorb the mercury, and the activated carbon heated to produce elemental mercury.

2.2 Recovery From Gold Ores

During the leaching of gold ores in Nevada, mercury in the ore is also solubilized in the cyanide solution and coprecipitated
together with gold by zinc. It is removed from the filter cake by distillation.

2.3 Recovery From Smelter Gases

Appreciable amounts of mercury are now recovered during the roasting of zinc sulfide concentrates. The concentration of mercury
in the SO2 gases generated ranges from 40 to 80 ppm. When the SO2 gas is converted to acid, nearly half of the mercury in the gas
will enter the acid. Since a great part of this acid is consumed in the fertilizer industry, there exists the hazard that mercury in the
acid may enter the food chain. As a result the zinc industry has devised methods for removing and collecting this mercury. Two
routes are presently used:
4 Mercury Production

Fig. 3 Recovery of mercury in a rotary kiln.

2.3.1 Adsorption–filtration methods

These methods are suitable only for low mercury concentrations, about 1 mg m3, and can remove about 90% of the mercury.

• Carbon filter. This process is based on adsorption on activated carbon, which can normally adsorb 10–12% of its own weight of
mercury. For efficient adsorption, the temperature in the adsorption tower should not exceed 501C. Activation of the carbon is
accomplished by passage of 100% SO2 gas.
• Selenium filter. In this method a porous inert material is soaked with selenious acid, then dried and used as filter for the gases.
Red amorphous selenium is precipitated when the gases are passed through, according to the reaction:

H2 SeO3 þ H2 O þ 2SO2 -Se þ 2H2 SO4

• The selenium precipitated on the pores of the carrier reacts with mercury in the gas at 251C forming HgSe. The filter element
continues to absorb mercury until its mercury content reaches 10–15%. When this is reached, it is treated by standard methods
to recover the mercury and regenerate the filter for reuse.

2.3.2 Precipitation–filtration methods

These methods are suitable for the removal of large amounts of mercury in the gas stream (800 mg m3). They are based on the
formation of an insoluble mercury compound, which can be removed as a slurry in scrubbers. The slurry can then be filtered to
recover the mercury compound and recycle the solution (Fig. 4).

• Sulfuric acid method. In this method the gas is cooled in waste heat boilers and its dust content is removed in cyclones and
electrostatic precipitators. The gas at 3501C is cooled in heat exchangers to about 2001C using concentrated H2SO4 as a heat
exchange medium. It is then scrubbed with the same acid, which is now at 150–2001C, to convert elemental mercury into a
sulfate according to:

2Hg þ H2 SO4 þ 1=2O2 -Hg2 SO4 þ H2 O

The acid is recycled to become saturated in Hg2SO4. As a result, crystals of Hg2SO4 precipitate and can be separated in
thickeners. Since the smelter gases contain moisture, which would dilute the acid and render it ineffective as a sulfating agent,
an optimum temperature of 150–2001C and acid concentration of 85–90% H2SO4 must be used.
 Mercury Production 5

Fig. 4 Recovery of mercury as a by-product from smelter gases by precipitation and filtration.

• Selenium scrubbers. This process is based on the fact that if a certain level of amorphous elemental selenium is maintained in the
circulating wash liquid in the gas scrubbing circuit, mercury is effectively removed from the gas as mercury selenide, HgSe.
• Mercuric chloride method. This is the most widely used method and is based on the oxidation of mercury vapor by mercuric
chloride solution at 30–401C and its precipitation as mercurous chloride according to:

HgCl2 þ Hg-Hg2 Cl2

• Hydrogen sulfide method. In this process HgS is precipitated from the gas stream by injecting a controlled amount of hydrogen
sulfide, whereby the following reactions take place:
2H2 S þ SO2 -3S þ 2H2 O

S þ Hg-HgS

Mercury sulfide is then removed in the gas filtration system.

3 Removal of Traces of Mercury From Sulfuric Acid

Removal of mercury from H2SO4 is based on its precipitation as a sulfide and iodide. A product containing less than 1 ppm of
mercury can be obtained.

• Sulfide method. In this method, colloidal sulfur is generated in the acid by injecting a solution of sodium thiosulfate, whereby
the following reaction takes place:
2Hþ þ S2 O3 2 -S þ SO2 þ H2 O

Colloidal sulfur then reacts with mercury to form mercuric sulfide, which is filtered off. The concentration of acid must be
below 85%, because at higher concentration elemental sulfur is oxidized to SO2. This process is therefore suitable for acid to be
used in fertilizer manufacture.
• Iodide method. In this method potassium iodide is added to precipitate mercuric iodide:
Hg2þ þ 2I -HgI2

The precipitation is favored by high acid concentration (93%) and low temperature (01C). Mercuric iodide is then separated
by filtration.

4 Amalgams

The solubility of metals in mercury at room temperature varies greatly; the highest is that of indium (57%), and the lowest is that
of chromium (4  107%). Solubility increases with increased temperature. The following types of solubilities can be identified:

1. Metals dissolve with formation of compounds at room temperature, for example, the alkali and alkaline earth metals. The
reaction is exothermic.
2. Metals with low solubilities that do not form compounds, for example, aluminum, chromium, cobalt, and iron.
3. Metals with low solubilities that do form compounds, for example, uranium.
6 Mercury Production

Due to its high surface tension, mercury has the ability to wet metals. When the solubility limit of a metal is exceeded, mercury
still can wet the metal, forming a thick amalgam paste. Strictly speaking, an amalgam is a solution of a metal in mercury and a
quasi-amalgam is a metal wetted by mercury after the solubility limit has been exceeded.

5 The Alkali-Chlorine Industry

The manufacture of sodium hydroxide and chlorine by the electrolysis of aqueous sodium chloride solution using a mercury
cathode resulted in the large-scale use of expensive and poisonous mercury in the chemical industry. The reactions taking place are:
At the anode : 2Cl -Cl2 þ 2e

At the cathode : Naþ þ xHg þ e -NaHgx

The amalgam is then decomposed by water to form NaOH and liberating mercury for recycle:
NaHgx þ H2 O-NaOH þ 1=2H2 þ xHg

6 Polarography

This is a method of chemical analysis using the dropping mercury electrode, from which the current–voltage curves yielded
important information on the behavior of amalgams and the reactions occurring at the phase boundaries of amalgams in aqueous
solution.

7 Toxicity of Mercury

While mercury sulfide is nonpoisonous and can be stored and transported without any problem, metallic mercury and its other
compounds are hazardous substances and various regulations have been issued to control their emission into the environment.
Mercury thermometers are no longer used. Most biocide uses for mercury have been canceled, and the use of alkyl and nonalkyl
fugicides containing mercury for use on rice and in laundry products and as marine antifouling paint have been suspended.
Cosmetic use of mercury has been prohibited, except in special cases, as was dumping of wastes containing more than trace
amounts of mercury. Emission of mercury from the incineration or drying of waste water sludges has been limited to 0.1 mg m3.
The maximum amount of mercury in public drinking water was recommended to be 2 mg L1.
Because of the considerable vapor pressure of mercury even at room temperature and the toxicity of its vapors, particularly safe
and reliable methods must be used in the extraction of mercury to avoid releasing traces of the metal into the environment. In
spite of that, about 10 million skilled workers are currently involved directly and indirectly in amalgamation of gold in mining
world-wide. Their annual production is about 200 t of gold with a corresponding 200 t of mercury emitted in the environment
every year. From the beginning of the new gold boom in these tropical countries at the end of the 1970s up to 1997, around 5000 t
of mercury have been discharged into the forests and urban areas.
The majority of mercury emitted is deposited near the emission source. The high content of organic acids in sediments and
waters favors oxidation of the deposited metallic mercury. Soluble organic mercury complexes are transformed by micro-
organisms into methylmercury, CH3Hg þ , which is soluble in water and is rapidly taken up by species in aquatic environments.
Symptoms of mercury poisoning are detected in miners, gold dealers, and people living near the emission sources. Communities
who have fish as the main diet have shown high levels of mercury in blood. Deaths were reported in Minamata, Japan due to this
cause. Artisanal amalgamation of gold is also associated with forest destruction, incorrect tailing disposal that silts up streams, and
numerous social problems.

Further Reading
Goldwater, L.J., 1972. Mercury, A History of Quick-Silver. Baltimore, MD: York Press.
Habashi, F., 1978. Mercury Pollution Abatement in Metallurgical Plants. Environmental Science & Technology 12 (13), 1372–1376.
Habashi, F., 1996. Pollution Problems in the Minerals and Metallurgical Industries. Sainte Foy, QC: Métallurgie Extractive Québec, (distributed by Laval University Bookstore).
Habashi, F., 1999. Handbook of Extractive Metallurgy, vol. 2. Weinheim, Germany: Wiley-VCH.
Habashi, F., 1999. Principles of Extractive Metallurgy, volume 4 – Amalgam and Electrometallurgy. Québec: Métallurgie Extractive Québec, (distributed by Laval University
Bookstore, www.zone.ul.ca).
Habashi, F., 1999. Textbook of Pyrometallurgy. Québec: Métallurgie Extractive Québec, (distributed by Laval University Bookstore, www.zone.ul.ca).
Pennington, J.W., 1959. Mercury. A Materials Survey. Washington, DC: US Bureau of Mines.