REPORT ON THE USE OF SODIUM CYANIDE IN MINING

INTRODUCTION: Sodium Cyanide was first discovered in 1775 by Swedish scientist Scheele. It was produced by the interaction of coke with soda ash in a nitrogen atmosphere. The reaction can be represented as: Na2CO3 + N2 + 4C 2NaCN + 3CO

In the following years, another method of producing Sodium Cyanide was developed. It comprised heating a mixture of soda ash, coal and 20% ammonia solution, as represented by the following chemical formula: Na2CO3 + C + 2NH3 NaCN + 3H2O

Sodium Cyanide is a deadly poison which is widely used in the mining industry. It is used as the leaching agent (lixiviant) in the recovery of gold and silver from mined ore. It is a white powder which is readily soluble in water. It is this solution which in the strength of between 100 and 500 mgl-1 (or gt-1) readily dissolves gold and silver from ores to allow them to be separated using activated charcoal, or less frequently, zinc dust. The reaction takes place according to Elsners equation, represented thus: 4Auo + 8NaCN + O2+ 2H2O USES: The bulk of Sodium Cyanide produced in the world is used for this purpose. A smaller amount is used as a depressant of a selection of sulphide minerals to produce a cleaner product. Common sulphide minerals depressed are mainly Galena (PbS), Pyrite (FeS2), Pyrrhotite (FeS) and Arsenopyrite (FeAsS2). The combination of these two uses of Sodium Cyanide accounts for 93% of the entire commodity produced globally. Minor industrial uses include: To add surface hardness, wear resistance and fatigue strength to steel products For soldering and liquid hardening of metals, and As an insecticide for pest control SAFETY: Sodium Cyanide is highly toxic. It causes suffocation due to paralysis of respiratory tissue (asphyxiation), and ultimately, heart failure. The lethal dose for humans is 0.1g. Poisoning can occur through inhalation of dust, swallowing or absorption through the skin, especially if there is a wound.
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4Na[Au(CN)2] + 4NaOH

For these reasons, most of the Sodium Cyanide produced is in the form of pressed briquettes. To minimise dust inhalation hazard, a wind sock is always mounted on top of the cyanide handling area and personnel are instructed to work up-wind of the toxic material. To minimise inhalation and skin absorption, all personnel handling Sodium Cyanide must wear the following Personal Protective Equipment (PPE): Masks Waterproof overalls Gum boots Gauntlets, and A portable cyanide meter

After handling Sodium Cyanide, fully clothed showering is a prerequisite. During the handling of Sodium Cyanide, a paramedic with full resuscitating equipment must be present. At a pH value below 10.5, Sodium Cyanide dissociates to the highly toxic Hydrogen Cyanide gas. To prevent this, protective alkalinity, using lime, or caustic soda, is always provided. MANUFACTURING: The main method of producing Sodium Cyanide today is by the neutralisation of hydrocyanic acid with caustic soda, followed by evaporation of the aqueous solution and drying, as represented by: HCN + NaOH Specific industrial processes are as follows: 1. The Shawinigan Process: 3NH3 + C3H8 2. The Andrussaw Process: CH4 + NH3 + 1.5O2 HCN + 3H2O 3HCN + 7H2 NaCN + H2O

This is the most popular manufacturing process. This is the most popular method of manufacturing. Approximately 60% of global manufacturing is by this method. 3. The BMA Process: (Patented by Degussa of Germany. BMA stands for Blausaure, Methane, Ammoniak CH4 + NH3
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HCN + 3H2

A platinum/rhodium catalyst, which is replaced every six months, is essential for these reactions. Methods 1 and 3 can market hydrogen as a by-product, after thorough scrubbing to ensure that it is free of HCN gas. A typical manufacturing plant is shown schematically in Figure 1. The production and use of Sodium Cyanide is monitored and regulated by the world governing body called the International Cyanide Management Code (ICMC). Checks, audits and guidance are offered to all members. As a result, signatories to the ICMC produce Sodium Cyanide at about $200/tonne higher than non-members.

Figure 1: Schematic diagram of a typical Sodium Cyanide manufacturing plant The courtyard of a Sodium Cyanide plant is used for decontamination of all materials/equipment that leaves the works. All washings drain to the effluent treatment section, Figure 2. A typical plant is operated from a Distributed Control System (DCS). This facilitates minimum operator intervention.

Figure 2: Monitoring and effluent treatment in a typical Sodium Cyanide manufacturing plant MONITORING: Monitoring is in the form of Weak Acid Dissociable (WAD) cyanide. In practice at mine sites, some common measures taken to reduce the hazards of Sodium Cyanide are: Reduced ponding on heaps by agglomeration of the ore prior to building the heap Installing WAD measuring meters in the agitation leaching tanks
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Covering of ponds by mesh and nets to prevent birds and animals from drinking the cyanide solution

CYANIDE DESTRUCTION: The cost of treating tailings and plant effluent can be a significant percentage of total operating costs, and unlike other operating costs, yields no economic return. It is very important, for both regulatory and economic reasons, that the correct method is selected. It is the prerequisite of all responsible mining operations to neutralise the cyanide from the processing plants before disposal of the effluent in the Tailings Storage Facility (TSF). Cyanide destruction is achieved by the following methods: 1. ALKALINE CHLORINATION: Cl2 + 2NaOH NaOCl + NaCl + H2O CNO- + NaCl

NaOCl + CN-WAD Advantages:

Simple to operate Fast kinetics Strong oxidant Can oxidise thiocyanate Can oxidise CN-WAD efficiently Disadvantages: Non-selective, leading to high reagent consumption Requires high pH (pH 11) to ensure rapid and complete hydrolysis of highly toxic cyanogen chloride gas May leave residual chlorine in solution. This might entail the construction of a polishing pond Ferrocyanide is not destroyed but oxidised to ferricyanide 2. HYDROGEN PEROXIDE: H2O2 + CN-WAD CNO- + H+ + H2O CNO- + H2O CO2 + NH3

Advantages: Simple to operate No production of toxic gases Ferrocyanide is precipitated as a base metal/ferrocyanide complex Can oxidise CN-WAD efficiently
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Disadvantages: Requires copper in solution as a catalyst (20mgl-1 or higher) Tends to leave some residual copper in solution High unit cost of the regent Can react with sulphides in the solid phase, leading to high reagent consumption Ferrocyanide is not destroyed, but precipitated as a base metal/ferrocyanide complex. The precipitate can redissolve at pH>9. Cyanate hydrolyses to undesirable ammonia CNO- + H+ + H2O CO2 + NH3 3. SO2/AIR: SO2 + O2 + H2O + CN-WAD CNO- + H2SO4 CNO- + H+ + H2O CO2 + NH3 Advantages: Low reagent cost More selective than chlorination and hydrogen peroxide towards CN-WAD Can oxidise CN-WAD efficiently Sulphite salts such as sodium metabisulphite or sodium sulphite can be used 2CNO- + 2NaHSO4 Na2S2O5 + 2O2 + H2O + 2CN-WAD Disadvantages: Quite difficult to operate Requires copper in solution as a catalyst ( >30mgl-1 Cu) Requires longer retention time than chlorination or hydrogen peroxide Requires efficient dispersion of SO2 gas and air, vigorous mixing Cyanate hydrolyses to undesirable ammonia 4. OZONATION: 7CN-WAD + O3 CNO- + H+ + H2O CNO- + O2 CO2 + H3

Advantages: Strong oxidant, fast kinetics Does not require copper catalyst Can oxidise thiocyanate Can oxidise CN-WAD efficiently Disadvantages: Non selective, reacts readily with sulphides in solids leading to high reagent consumption, (when compared to SO2/air or hydrogen peroxide)

May react with solid phase and release undesirable species such as arsenide in solution High reagent cost Requires O3 resistant equipment Can release toxic O3 gas, necessitating scrubbing Cyanate hydrolyses to undesirable ammonia Ferrocyanide is not destroyed, but may be precipitated as base metal iron cyanide complex Tends to leave some residual copper in solution

5. CARO ACID: H2SO5 + CN-WAD CNO- + H+ + H2O H2SO4 + CONCO2 +NH3

Advantages: Strong oxidant, fast kinetics Does not require copper catalyst No production of toxic gas Can oxidise part of the thiocyanate Can oxidise CN-WAD efficiently Can remove ferrocyanide as base metal iron cyanide precipitate Disadvantages: High reagent cost More difficult to handle because of the heat generated Less selective than alternative processes, reacts readily with sulphides in solids leading to high reagent consumption, (when compared to SO2/air or hydrogen peroxide) May need to add copper, iron or zinc salts to precipitate iron cyanide Cyanate hydrolyses to undesirable ammonia Ferrocyanide is not destroyed, but may be precipitated as base metal iron cyanide complex Copper and/or zinc may redissolve in high chloride environment 6. FERROUS SULPHATE COMPLEXATION: Fe2+ + 6CN-WAD Fe(CN)642Fe2+ + Fe(CN)64- Fe2Fe(CN)6 4Fe3+ + 3Fe(CN)64Fe4(Fe(CN)6)3

Advantages: Low reagent cost Relatively simple to operate Can sequester CN-WAD efficiently Does not oxidise cyanide to Cyanate and, therefore, does not produce ammonia CN-WAD is converted to ferrocyanide which is precipitated as ferro ferrocyanide at neutral pH Disadvantages: Requires longer retention time than chemical oxidation methods May require aeration to convert Fe2+ to Fe3+ Does not oxidise thiocyanate Cyanide is not destroyed, but precipitated as mixed iron ferrocyanides. The precipitate can redissolve at basic pH (pH>9) Difficult to achieve <5mgl-1 CNT because of residual, soluble ferrocyanide PACKAGING: Sodium cyanide is either packaged in lockable 50 kgs steel drums (Figure 3), or 750 kgs 850 kgs bulk boxes. Figure 3: A 50 kgs lockable steel drum used for packing Sodium Cyanide Bulk packaging has an outer woven polypropylene bag, to which lifting straps are sewn. The inner liner is waterproof polyethylene material. The bag is then placed in a 16mm plywood box with reinforced internal corner bracings. Each box is then bound and strengthened with steel strapping.

Kenneth R Seecharran
Consultant