Selective Hydrometallurgical Extraction of Zn/Pb From Blast Furnace Sludge

Ludivine PIEZANOWSKI1, Samuel RAYNAL1, Jasmin HUGENTOBLER1, Michel HOUBART1

1
PAUL WURTH SA
32, Rue d’Alsace, Luxembourg, L-1122
Phone: +352 49 70 1
Email: ludivine.piezanowski@paulwurth.com

Keywords: Blast furnace, Sludge, Zinc, Lead, Iron, Carbon, Hydrometallurgy, Recycling, Sinter Plant.

INTRODUCTION
Blast furnace sludge is presently considered as an environmental burden, being classified as a hazardous waste due to the
presence of heavy metal compounds, particularly zinc and lead. Because of these elements, direct recycling in the blast
furnace process is difficult.
To date, the existing processes to treat blast furnace sludge only provide partial solutions and, generally speaking, are not
fully answering the real challenge of recovering the whole valuable iron and carbon content at low cost, in an
environmentally friendly way and using simple technology.
Paul Wurth’s long experience in providing the iron and steel industry with global solutions that are in compliance with the
industrial and environmental trends, and especially its know-how in the field of recycling technologies, using either pyro-
metallurgical or hydrometallurgical processes, or a combination of both, led to the development of a flexible technology.
The new robust, flexible and cost-effective hydrometallurgical process, developed by Paul Wurth, allows to recover the
valuable iron and carbon fraction, which represents more than 60% of the material, and to extract a zinc-lead by-product,
which can be valorized in other industries.
This innovative solution is a new milestone for the iron and steel industry, enabling a reduction of the operation costs while
addressing the specificities of each operator and securing its long-term environmental commitment.

DISCUSSION
1. Principle of the CIROVAL™ process
Combining its sound knowledge of the blast furnace process and proven expertise in non-ferrous applications, more precisely
in zinc hydrometallurgy, led Paul Wurth to develop a new technology called CIROVAL™ (Carbon Iron Valorization).
CIROVAL™ is a low temperature selective oxidizing leaching process for blast furnace sludge, in two steps:
• Step1: A selective leaching of zinc and lead in acidic and oxidizing conditions.
The sludge is mixed under acidic conditions with hydrochloric acid in order to dissolve zinc and lead in oxide form. The
addition of an oxidizing agent enables to:
o react with the zinc and lead when in metallic and sulfide form;
o limit the leaching of iron within the solution in order to maximize the global iron-carbon by-product recovery
yield.

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The process takes place in a series of reactors working at low temperature, around 55°C, and under pH control. After
reaction, the pulp is filtrated by means of a filter press. The resulting cake is washed in order to remove the impregnated salts
as the soluble Zn, Pb and Cl. The valuable fraction of the initial residue, the iron and the carbon, can be recycled back to the
blast furnace route via the agglomeration or coal injection processes.
• Step2: A neutralization step.
The filtrate coming from the filtration unit is recovered and treated in a second step. The soluble elements, like zinc, lead and
some iron, are in chloride form. The pH is increased to 8-9 in order to precipitate all the heavy metals in hydroxide form. The
neutralizing agent can be lime, burnt lime, milk of lime or caustic soda depending on the local market conditions.
The neutralization process takes place in a series of reactors working under pH control. The pulp is filtrated in order to
recover a zinc-lead cake which can be retreated in the non-ferrous industry, for example via a Waelz kiln process.
The figure hereunder gives an overview of the process principle:

2. Process status:
• From laboratory scale….
Paul Wurth started the development of the CIROVAL™ process in 2013 and has conducted around 70 tests with different
sludge types, coming from European blast furnaces, in a 5 liter reactor.
The laboratory equipment is shown in the figure below:

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At the beginning of the study, the objectives of the laboratory tests have been to:
o develop the process;
o define the main process parameters and their fluctuations regarding raw material composition;
o define the zinc and lead leaching rate.
Today, the laboratory tests are still used to pre-test the behavior of the sludge before going to the pilot plant unit.
• … to demonstration pilot unit
Further to successful laboratory results, a pilot plant unit has been designed for treating around 130 kg of blast furnace
sludge, wet basis, per batch. The objectives were to:
o define more precisely the operation costs of the process;
o operate as close as possible to an industrial plant unit;
o be able to size the industrial plant based on the raw material.
The pilot plant is composed as follows:
o one 1 m3 reactor made out of PVDF, equipped with an electrical heater and a mixer specially designed for
our reactions;
o one set of 10.8 m2 membrane filter press, composed of maximum 36 cakes;
o several storage tanks for hot water, filtrate and washing water.
All equipment has been installed in two containers, as shown in the pictures here below. One container is for the main
reactor; the second one dedicated to the filter press.

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The equipment in contact with the acidic fluid is built out of synthetic material or coated with material specifically designed
to work with concentrated hydrochloric acid.
The two truck containers can be sent as demonstration unit to steelmaking plants.

3. Test results
During the laboratory and pilot plant test campaigns, a large panel of blast furnace sludge coming from various European
steel making plants has been tested. Their compositions were in the following ranges:
Element Range%
Fe 16 - 34
C 34 - 60
Zn 1.0 - 5.3
Pb 0.1 - 1.0

The results obtained during the laboratory tests and with the pilot plant unit are very similar. They are summarized here
under:

At the leaching step:

• The leaching step has a total iron-carbon by-product recovery yield of around 85%.
• In the final iron carbon solid:
o the zinc can be decreased lower than 0.3% and the lead down to 0.1%;
o the carbon fraction is totally recovered;
o around 85% of the iron is remaining in the solid fraction;
o less than 0.8% of chlorine can be achieved depending on the water use during the cake washing;
o moisture content is around 30%.

At the neutralization step:

Depending on the initial zinc content of the blast furnace sludge, the final cake is mainly in hydroxide form and can contain
more than 20% of zinc and up to 5% of lead. The rest is mainly soluble iron, silica coming from step one and calcium
coming from the neutralizing agent. The quantity of zinc-lead cake recovered at the neutralization step depends mainly on
the initial zinc content and can vary from 50 to 80 kg/t of blast furnace sludge treated, dry basis.
The zinc and lead content of the produced salty effluent fits with the “BAT effluent level discharge for the blast furnace
production area, namely zinc and lead content lower than 0.5 mg/l. Thus, it can be discharged out of the plant with the other
plant effluents. The quantity of effluent produced is around 3.5 m3 per ton of blast furnace sludge treated, dry basis.

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 4. Economic benefits
CIROVAL™ offers multiple economic benefits, which can be valorized by each operator according to his site specificity:
• The proposed hydrometallurgical process uses proven and simple concepts, as already developed and operated by
non-ferrous industries since decades. The high flexibility of hydrometallurgical operations has been largely
demonstrated in different contexts and makes customizing by each operator possible.
• The technology uses simple and cheap equipment. The main equipment items are agitating reactors and filter
presses. Proven synthetic materials ensure long lifetime of the equipment in presence of hydrochloric acid solutions.
• The layout requires limited footprint and all equipment items are located on ground level, except the filter presses.
Only around 1000 m2 are required to install a plant treating 20 to 30 kty of blast furnace sludge, dry basis.
• The limited and simple control parameters allow to operate the treatment facility on full and reliable automatic
mode, requiring a limited number of operators.
• The zinc-lead fraction is separated and concentrated into a valuable by-product, which can be compared to a
secondary material feeding the non-ferrous and recycling industries.
• The iron and carbon fraction of the raw material, free of undesirable elements, can be easily re-introduced into the
iron and steel making route.

Such valorization of the by-products will limit, or ideally, eliminate any dumping costs.
Regarding the economic point of view, the figure hereunder gives an estimation of the sensibility of the technology regarding
the capacity of sludge treated:

The figure “total cost” includes the operation costs, the capital cost and the valorization of the by-products.
As an example, based on European prices, the treatment of at least 25.000 t/y [wet basis @ H 2 O ~ 40%] of blast furnace
sludge equivalent 15000 t/y [dry basis] with the CIROVAL™ technology leads to a total cost of around 50 ¬/t blast furnace
sludge [wet basis]. The cost has to be compared to the price for external landfilling which depends on local conditions.

5. Environmental benefit
Blast furnaces are producing 1.5 to 6.5 kg [dry] of sludge per ton of hot metal, depending on the gas cleaning system. Since
the seventies, this sludge has been most often stored on internal dumping sites and this landfilling solution is associated with
currently important space requirements, costs and environmental liabilities.

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In Europe, the internal storage areas are close to be saturated. Receiving new permits for building new areas or extending
existing ones is becoming more and more difficult. That’s why the treatment of blast furnace sludge gives many steel makers
the opportunity to reduce landfilling. At the same time, it promotes optimal recovery and recycling of by-products. In that
way, the CIROVAL™ solution reduces the ecological exposure and the environmental liabilities on a long-term basis.
Thus, by limiting the environmental impact, steel makers can promote a residue-free steel production.

CONCLUSIONS
Process-wise, CIROVAL™ is ready for a first industrial implementation. Several sites or groups of sites, geographically
close together, are under study.
Typically, any blast furnace plant generating more than 20-25 kty of sludge with at least 2-3% of zinc should be candidate,
mainly when landfilling is becoming difficult or expensive.
Through this recent development, Paul Wurth is focusing on real customer concerns and contributes to reducing the
environmental exposure of residual wastes generated by the iron and steel making industry. Blast furnace sludge will no
longer be seen as an issue to be solved, but rather as an economic opportunity to sustainably recover its valuable content in an
environmentally friendly way.

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