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Sulphuric Acid on the WebTM Technical Manual DKL Engineering, Inc.

Knowledge for the Gas Cleaning System - Mercury Removal

Sulphuric Acid November 16, 2016

Industry
Introduction Associated Links
Gas Phase Removal Methods
Outokumpu Process Analytical Procedures for Mercury
Sulphuric Acid on the Bolkem Process
Web Selenium Filter Norzink Reference List
Selenium Scrubber
Introduction Boliden Norzink Process
General Carbon Filter
Equipment Suppliers
Sulphide Precipitation - Gas
Contractor
Instrumentation
Phase
Industry News Sumitomo Process
Maintenance Liquid Phase Removal Methods
Acid Traders Sulphide Precipitation - Liquid
Organizations
Phase
Fabricators
Conferences
Molecular Recognition
Used Plants Technology (MRT)
Intellectual Propoerty Toho Process
Acid Plant Database
Market Information
Library Introduction

Technical Manual Copper, zinc, pyrite and lead ores often contain mercury as a trace
contaminant. When these ores are treated in thermal processes, the mercury is
Introduction volatilized as mercury vapour and exit with the off-gases. Without any special
General treatment approximately half of the mercury will report to the product acid.
Definitions
Instrumentation
Plant Safety When the ore contains selenium it will also be liberated in the roasting/smelting
Metallurgial Processes process along with the mercury. The selenium will be in the amorphous state
Metallurgical which will readily combine with mercury to form HgSe. Mercury in this form will
Sulphur Burning be easily removed from the gas in the scrubbing and wet electrostatic
Acid Regeneration precipitation stages.
Lead Chamber
Technology
Gas Cleaning Mercury will also react with the sulphur dioxide and oxygen in the gas to form
Contact mercury sulphate according to the reaction:
Strong Acid
Acid Storage Hg(g) + SO2(g) + O2(g) --> HgSO4(s)
Loading/Unloading
Transportation
Sulphur Systems
Mercury sulphate will be removed from the gas in the subsequent scrubbing and
Liquid SO2 wet electrostatic precipitation stages.
Boiler Feed Water
Steam Systems The mercury that remains uncaptured will proceed towards the drying tower as
Cooling Water mercury vapour. If left untreated the mercury will enter the strong acid system
Effluent Treatment and contaminate the product acid.
Utilities
Construction
Maintenance The mercury contaminated acid cannot be used in any industry or products
Inspection where there is the potential for the mercury to enter the food chain. Therefore, it
Analytical Procedures is desirable to remove the mercury from the acid to produce a more saleable
Materials of Construction product.
Corrosion
Properties
Vendor Data
Many different processes have been developed specifically to deal with the
mercury problem. The mercury can be treated while it is in the off-gases or after
it has entered the product acid.
DKL Engineering, Inc.

Handbook of Sulphuric Acid

Gas Phase Removal Methods
Manufacturing
Order Form The removal of mercury as far upstream in the process is desirable in order to
Preface minimizes the chance of it entering the final product acid. This involves treating
Contents the entire gas volume passing through the gas cleaning section of an acid
Feedback
plant. Various methods have been developed for removing mercury from the
gas before it enters the drying tower.
Sulphuric Acid Decolourization
Order Form
Preface Outokumpu Process
Table of Contents
The Outokumpu process is based on converting the elemental
Process Engineering Data mercury in the gas into a sulfate according to the reaction:
Sheets - PEDS
Order Form
Hg + H2SO4 --> 1/2 O2 + HgSO4 + H2O

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Table of Contents
The smelter gas is scrubbed with 80-90% H2SO4 at a temperature
Introduction
of 150-180°C. The acid is recirculated until the solution becomes
saturated with HgSO4 and precipitation begins. The crystals of
Bibliography of Sulphuric Acid
HgSO4 are then separated in a thickener. In addition to removing
Technology mercury, other contaminants in the gas will be removed in the
Order Form scrubber. The solids collected in the thickener will also contain
Preface iron, zinc, copper, selenium, etc.
Contents

Mercury can be recovered by mixing the solids with calcium oxide,

Sulphuric Acid Plant
and then heating to distill away the mercury. Selenium remains
Specifications
behind in the form of calcium selenite.

Bolkem Process
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Mercury is captured in a two drying towers operating in series.

The first drying tower operates at an acid concentration of 80%
H2SO4 and a temperature below 50°C. The second drying tower
is a conventional tower operating at 93% H2SO4. Mercury reacts
with the mercury dissolved in the acid to form mercurous sulphate.

HgSO4 + Hg --> Hg2SO4

The mercurous sulphate is then oxidized to mercuric sulphate by

the strong acid and oxygen in the gas. A bleed of acid is taken
from the drying system to control the concentration of mercuric
sulphate in the circulating acid. The acid is treated with sodium
thiosulphate to precipitate the mercury as mercuric sulphide. See
Sulphide Precipitation - Liquid Phase

Selenium Filter

This process developed by

Boliden is especially suited
for low mercury
concentrations in the gas.
The selenium filter consists
of a porous inert material
soaked with selenious acid
which is then dried to
precipitate red amorphous
selenium.

H2SeO3 + H2O + 2 SO2 -

-> Se + 2 H2SO4

The red amorphous selenium reacts

with the mercury in the gas to form
HgSe. The contact time in the filter is
about 1 to 2 seconds. The filter
continues to be effective until the level
of mercury in the filter reached 10-
15%. The filter is then treated to
recover the mercury and regenerate
the selenium. The filter will remove
approximately 90% of the incoming
mercury.

Selenium Scrubber

Like the selenium filter, this removal process relies on the

presence of amorphous elemental selenium to react with the
elemental mercury in the gas. Sulphuric acid containing selenium
is circulated over a packed tower . The acid concentration is
maintained between 20 and 40%. At lower concentrations
selenium will form highly soluble selenium-sulphur compounds
making it ineffective in reacting with the mercury in the gas. At
higher acid concentrations, the oxidizing power of the acid will
result in selenium dioxide or selenite being formed.

If the gas being treated contains sufficient selenium, there may not
be a requirement to add selenium to the scrubber solution.

The selenium scrubber is suitable for removing relative large

quantities of mercury in the gas and has an efficiency of
approximately 90%.

Boliden Norzink Process

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The

Boliden Norzink process was developed in 1972 and is the most

popular method for removing mercury from the process gas. The
process is based on the oxidation of mercury vapour by mercuric
chloride to form mercurous chloride (calomel).

HgCl2 + Hg --> Hg2Cl2

A solution of mercuric chloride containing xx mg/l HgCl2 is

circulated over a packed tower. The process gas containing
mercury passes through the packing where the mercury reacts
with mercuric chloride to form mercurous chloride. Mercurous
chloride is insoluble and precipitates out of the solution.

A side stream from the main tower circulating stream is directed to

the primary settler where the mercurous chloride settles to the
bottom of a conical tank. The clarified solution overflows back to
the scrubbing tower pump tank. The collected solids from the
bottom of the primary settler flows to the secondary settler where
further concentration of the mercurous chloride. In the secondary
settler, zinc dust can be added to further aid in the precipitation of
mercury from the solution. The solids from the secondary settler
are discharged to storage drums for sale or further processing.

The scrubbing process removes mercuric chloride from the

scrubbing solution. If the concentration of mercuric chloride is not
maintained it will become ineffective as a scrubbing solution. To
regenerate the scrubbing solution, a portion of the mercurous
chloride collected is chlorinated to regenerate the scrubbing
solution. A separate tank and circulating system is used to
regenerate the scrubbing solution. Chlorine is injected into a
circulating stream which reacts with mercurous chloride to form
mercuric chloride.

Hg2Cl2 + Cl2 --> 2 HgCl2

When the solution is completely regenerated it is pumped into a

storage tank. As the concentration of mercuric chloride in the
main scrubbing circuit is depleted, make-up solution is taken from
the storage tank to maintain the concentration of mercuric chloride
in the solution.

This method is very effective in removing mercury from the gas. A

product acid containing less than 0.5 ppm mercury can be
produced from a gas containing 150 ppm mercury.

The mercury absorption tower is a fibreglass reinforced vertical

cylindrical vessel. The tower is packed with polypropylene
packing, generally saddles. The scrubbing solution is sprayed
onto the top of the packing through a series of nozzles. A chevron
and mesh pad mist eliminator at the top of the tower prevents the
carryover of scrubbing solution out of the scrubber.

Elemental mercury can be recovered by electrowinning. All the

mercurous chloride formed is reacted with chlorine to form a
solution of mercuric chloride. Electrowinning the solution of
mercuric chloride in a specially design cell using metallic mercury
as the cathode will produce elemental mercury and chlorine gas at
the anode.

Overall Reaction
HgCl2 + e = Hg + Cl2

Cathode Reaction
Hg2+ + 2e = Hg

Anode Reaction 2
Cl- = Cl2 + 2e

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Under unfavourable conditions hydrogen gas can be formed at the
cathode. At the anode the formation of oxygen is a competing
reaction.

The chlorine that is produced can be reused in the chlorination

reaction that converts mercurous chloride to mercuric chloride. If
no chlorine is loss in the process there will be no requirement for
fresh chlorine gas since the overall process generates as mush
chlorine as it consumes.

The electrolyte solution is continuously recirculated over the cell to

avoid the formation of concentration gradient in the cell. The cell
is kept at a slight vacuum in order to prevent the leakage of
chlorine gas out to the environment.

The technology developed by Boliden Norzink was purchased by

Outokumpu in 200x and is now part of Outotec which was spun off
from Outokumpu Technology.

Carbon Filter

Activated carbon is well known for its adsorption properties. For

the adsorption of mercury, activated carbon can normally adsorb
10-12% of its own weight. The operating temperature of the
carbon filter is limited to 50°C. The method is especially suitable
for low mercury concentrations in the gas. A 90% removal
efficiency is normally achievable.

Sulphide Precipitation - Gas Phase

A controlled amount of hydrogen sulphide gas is injected into the

gas phase which reacts with mercury to form mercury sulphide
(HgS).

2 H2S + SO2 --> 3 S + 2 H2O

S + Hg --> HgS

H2S + Hg --> HgS + H2

The mercury sulphide that is produce is scrubbed out of the gas in

downstream gas cleaning equipment and reports to the weak acid
effluent stream. The consumption of hydrogen sulphide is
approximately 1.5-2.0 times the stoichiometric amount.
Approximately 90% of the mercury in the gas is removed.

This process has successfully been used by St. Joe Minerals

Corporation at their zinc smelter in Monaca, Pennsylvania, USA.

Sumitomo Process

Sumitomo Metal Mining Engineering Co., Ltd. (SMMEC) process

is based on the absorption of mercury onto coke and a metal
sulphide material like copper concentrate. Mercury laden gas
passes through a bed of coke and copper concentrate where it is
removed from the gas by absorption.

A 1500 mm thick bed can give a 95% removal efficiency at a bed

velocity of 0.2 m/s. The bed has a low pressure drop of 0.2 kPa/m
at a gas velocity of 0.2 m/s.

The mercury absorber would be located after the wet ESP and
before the Drying Tower.

Liquid Phase Removal Methods

If mercury is not removed from the gas stream before entering the drying tower
it will report to the product acid. Treating the product acid will generally involve
smaller process equipment since you are dealing with a liquid stream instead of
extremely large gas volumes. The disadvantage is that it is generally desirable
to remove contaminants as far upstream in the process as possible.

Sulphide Precipitation - Liquid Phase

Colloidal sulphur can be created in the acid by the addition of

sodium thiosulphate. The reaction to form colloidal sulphur is as
follows:

H2SO4 + Na2S2O3 -> S + Na2SO4 + H2O

The sulphur will react with the mercury to form crystalline mercury
sulphide (HgS). Other metal contaminants in the acid will also
react with the sulphur to form insoluble metal sapphires.

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The method is restricted to acid concentrations less than 85%
H2SO4. At higher acid concentrations the sulphur is oxidized to
sulphur dioxide (SO2). As well, the product acid will also contain
sodium sulphate which may be undesirable in the product acid.
The proper dosage of sodium thiosulphate is also required
otherwise a very fine mercury sulphide is produced which is
difficult to filter. This method is capable of reducing the mercury
levels from 15 ppm to 0.5 ppm after a holding time of 1 hour.

Hydrogen sulphide could also use as the source of sulphide for

precipitation of mercury and other metals. This method is
preferable is the presence of sodium sulphate is undesirable in the
final product.

Molecular Recognition Technology (MRT)

MRT consists of highly selective, often non ion exchange systems

using specifically design ligands or macrocycles. These ligands
can be chemically bonded to solid supports such as silica gel or
polymers or used free in solution to complex with selected ions.
The solid phase system consists of the bound ligand material,
called SuperLig packed into fixed bed columns or filter cartridge
elements.

The MRT process is able to effectively and selectively separate

specific individual metal species. MRT exhibits high selectivity and
binding factors for the specific ionic species of interest, efficiency
of separation, rapid kinetics and simple elution chemistry.

The MRT process can be used as the primary method of mercury

removal or it can be used as a polishing stage where the plant has
an existing mercury removal system.

For mercury in concentrated sulphuric acid, IBC Advanced

Technologies, Inc. have developed a ligand capable of reducing
the concentration of mercury to less than 0.1 ppm. The mercury
must be in the +2 oxidation state to be removed. This is done by
adjusting the oxidation-reduction potential (ORP) to 600-900 mV
vs. Ag/AgCl using SO2 or 30% hydrogen peroxide (H2O2).
Prefiltration of the acid may also be required in order to remove
solids that would otherwise plug the bed of SuperLig®.

The ligand is generally packed into a number of columns arranged

in series. Acid enters the first or lead column where the bulk of the
mercury is removed. The acid then passes through the remaining
'trail' columns where the remainder of the mercury is captured.
When the first column is fully loaded and has no mercury removal
capacity remaining, it is taken out of service and the second
column becomes the lead column. A standby column containing
fresh ligand is placed in service as the final column. This method
of operation ensures that each column is fully utilized and that the
maximum polishing capacity is available to achieve the lowest
possible mercury concentration.

When the ligand is fully loaded it can be regenerated using a

thiourea eluent. The eluent containing the captured mercury can
be further treated to recover the mercury. The regenerated
column is then placed back in service as the standby column.

Alternatively, the ligand can also be disposed of rather than

regenerated. This method is most effective where the MRT
Process is used as a polishing operation. The ligand can be
disposed of in the upstream smelter where the mercury will be
captured by the primary mercury removal system or disposed of
under environmentally sound conditions.

Toho Process

This process is based on the addition of potassium iodide and

precipitating mercury as mercuric iodide. The chemistry very
complex as shown in the following reactions:

Hg2+ + 2 I- --> HgI2

2 KI + 2 H2SO4 --> I2 + 2 KHSO4 + SO2 +

2 H2 O

I2 + I --> I3-

Hg2+ + 2 I3- --> HgI2 + 2 I2

The addition of cuprous iodide in addition to potassium iodide will form a more
stable precipitate Cu2HgI4. The precipitated mercury is separated by filtration.

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Air is used to strip sulphur dioxide and iodine from the acid.

Under the right conditions, the mercury levels can be reduced from 60 ppm to
less than 1 ppm. The reaction is favoured by high acid concentration and low
temperature. Good performance is obtained with 93% H2SO4 at 0°C but poor
performance is obtained at 98% H2SO4 at 75°C.

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