GOLD EXTRACTION WITH HALOGENS

J.-M. Lalancette, B. Dubreuil, D. Lemieux and C. Chouinard

10/31/07

Nichromet Oxide Process Presentation

Introduction
Nichromet process has been developed over the last decade by Nichromet Extraction Inc., a private Canadian company controlled by Dundee Corporation of Toronto.

The approach has been conceived as a way to avoid problems, both operational and environmental, encountered with classical treatments of polymetallic ores in view of gold extraction. It is based on the use of halogens (Cl2, Br2) as extractive reagents with a closed loop approach.
10/31/07 2

State of the art

After an eclipse of more than a century by cyanide, halogens, particularly chlorine, reappear in approaches for gold extraction.
Moyes and Houllis report the use of an oxydo-reduction approach with
halides of iron or copper to attack sulfides and collect precious and base metals. U.S. Patent 7,858,056 assigned to Intec Ltd. Harris et al describes the use of a chloride, an oxidant and hydrochloric acid, in such a way that sulfur in sulfide ores is released as H2S and base and precious metals are further collected. U.S. Patent 7,968,065 B2. Pressure leaching in the presence of chlorides (Platsol process) for the recovery of base and precious metals. C.J. Ferron et al, The South African Institute of Mining and Metallurgy Colloquium, Nov. 14th-16th 2001, Rustenburg.

Nichromet Process. Gold and silver recovery with halogens. U.S. Patent 7,537,741 issued to Lalancette, 26th, 2009. 10/31/07 NichrometMay Oxide Process Presentation

Flowsheet of the Nichromet Process

Ore Sodium Hypochlorite Vat Leaching Sulfuric Acid

Rinsing Water

Filtration Electrolysis

Barren Solid

Pregnant Brine Na2CO3

Diluted Brine

Recycled Brine

Polishing

Carbon In Column

Reverse Osmosis

CaCO3/Fe(OH)3

Au/Ag Recovery

Au/Ag

Characteristics of the Nichromet Appoach

The active reagents for the collection of gold and silver are chlorine accompanied by a minor amount of bromine. The leaching of precious metals is achieved at atmospheric pressure in a vat at 40-50oC, and the ore is slurried at the level of 30-40 % solid in a brine at 5-15 % salts (NaCl, NaBr). This operation is conducted on a substrate previously treated for sulfur and base metal removal. By reverse osmosis, the water used for rinsing of the barren solids and gas scrubbing is recycled so as to reconstitute the initial brine at proper salt concentration. The barren solid after gold/silver extraction is essentially sulfur-free, inert and stable.
10/31/07 5

 The halogens involved are recycled after gold/silver recovery by

reoxidation in an electrolytic cell. The regeneration of halogens is done by the electrolysis of the recycled brine in a cell without membrane or diaphragm, and the resulting solution is fed back to the vat leaching as sodium hypohalites. The vat leaching proceeds under acidic conditions (pH 0.5-3.0), where the hypohalites reverse to elemental halogens. The leaching is operated at an ORP in the range of 0.75 to 0.85 volts (Ag/AgCl reference). The water consumption is limited to the moisture in rejected cakes.

10/31/07

Pretreatment of the ore

The starting ore can be a typical polymetallic flotation concentrate incorporating base and precious metals, sulfides, arsenic, along with tellurides, carbonates and traces of other main group elements. The objectives of this pretreatment is the recovery of base metals of value and the removal of elements with high chlorine consumption

Oxidation
The first step in this pretreatment calls for a controlled oxidation
of the ore so as to remove most of the sulfur, down to less than 0.5 % . This controlled oxidation at 650-800oC is accompanied by several important reactions. A significant part of the sulfides is oxidized to the corresponding sulfate, almost 50 % in the case of copper sulfides. Arsenic can be volatilized, up to 90 %, as arsenious oxide, the remaining being combined to iron in situ as ferric arsenate. The sulfur dioxide stream is then washed, arsenious oxide stabilized as scorodite and the cleaned SO2 is available for the production of sulphuric acid.

Collection of base metals

The oxidized solid is first washed with water to remove sulfates

of base metals formed during the controlled oxidation. These metals are separated and recovered by standard methods. The base metals present as oxides are then leached out with acid, such as the sulphuric acid obtained from the SO2 stream. Remaining copper, zinc, nickel, cobalt and lead can then be reclaimed.
The residual solid will still contain some iron not collected by the

acid washing. But this iron shows a low reactivity with halogens, as indicated later.

The chemistry involved

Chlorine, along with a small amount of bromine, has been selected as oxidizing agent because of the particularly fast reaction of bromine with gold. The capability of chlorine to oxidize bromides to bromine, thus regenerating this last element, explains the low concentration of bromide required in the brine. 2 NaBr + Cl2 2 NaCl + Br2
2 Au + 3 Br2 2 AuBr3 + 3 Cl2 2 AuBr3 2 AuCl3 + 3 Br2

2 HOCl + 2 HCl 2 Cl2 + H2O

The active elements, chlorine/bromine, are generated in an electrolytic cell without separated compartments.

Cathode:

2 Cl-

Cl2 + 2e2 Na 2 NaOH + H2 NaOCl + NaCl

Anode: 2 Na+ + 2e- 2 Na + 2H2O Mixing : 2 NaOH + Cl2

Results
The process has been studied with a large variety of materials, either
fresh ore, flotation concentrates or tailings, these experiments being done at lab scale (200-500 g) or pilot scale (0.2-0.4 T). For materials showing more than 0.5 % S, the pretreatment by controlled oxidation was applied before chlorination. The results were very generally a gold extraction of the order of 90 to 95%, while silver recovery was in the range of 80 to 85 %. The arsenic, if present, was fixed as scorodite in the case of the volatilized arsenious oxide, while the non-volatilized As2O3 was fixed as ferric arsenate during the oxidation.

It was noted that by using the hypohalite approach for the recycling of
the halogen, the iron left in the pretreated ore was solubilized to a level not exceeding 20 %. This led to a low consumption of halogens, no more than 2 % of the weight of the treated ore.

Environment
The Nichromet approach is based on the recycling of reagents and water. Therefore, no brine is lost via rejected cake. The barren solids are rinsed with water and this diluted solution of salts is brought up to proper brine concentration by reverse osmosis. The halogens in the circuit exist either as halides (sodium chloride or sodium bromide), or as diluted (less than 1 %) hypohalites. Therefore, all apprehensions that could be associated with a significant inventory of halogens (chlorine or bromine) on site can be forgotten. The solids discarded at the end of the operation are the barren ore and the precipitate resulting from the purification of the recycled brine. These solids are essentially sulfide-free, inert and stable. Arsenic is disposed of as scorodite.

The water consumption by the operation corresponds to the water of hydration of the rejected solids.

Economics

From several tests at pilot scale with ores or concentrates from four different sources, it has been estimates that within a few percent, the operating costs per ton for the implementation of the chlorination process at the level of 500 T/day are the same.

$ / Ton Labor
Hypochlorite Energy Chemicals

Details

11.00 25 persons 2.20

2.80
1-2% of ore weight Mechanical

10.00 Salts,
acids, etc.

TOTAL

26.00

Operating cost per ounce of gold produced :

Initial Au (g/T)
3.0 5.0 10.00

Process cost ($ / oz Au)

269.00 161.00 80.00

31.00

26.00

From these figures, it is obvious that a concentration step, such as flotation or gravimetric, prior to chlorination is very attractive.

View of the pilot installation

Pannevis Filter Cap. : 300 kg/h

Chlorination Reactor Cap. : 300 kg/h