Complete 32,000 ton/yr Sodium Cyanide (NaCN) Plant

with Super High Quality Liquor production

The Sodium Cyanide (NaCN) plant produces HCN from methane, ammonia and air. The HCN
is then reacted with caustic soda (50% NaOH) to produce a sodium cyanide liquor of
approximately 30 - 32% NaCN. The liquor is purified and diluted to 30% for sale.

The plant is capable of producing approximately 18,000 tonnes per annum of HCN which is
converted directly to 32,600 tonnes per annum of NaCN.

Process Chemistry

In the HCN converter stage a gaseous mixture of ammonia, natural gas and air is passed over
the noble metal catalyst where the ammonia and natural gas react exothermically to form HCN:

NH3 + CH4 ! HCN + 3H2

Approximately 60 – 65% of the reagent gasses react as above. Of the remaining ammonia,
approximately 50% passes through unreacted and the other 50% breaks down to nitrogen and
hydrogen.

Virtually all of the natural gas not converted to HCN is partially or completely combusted in
air to produce CO2, H2O and CO. All unreacted gasses, along with the side reaction products,
are sent to the main plant stack for flaring.

The HCN is removed from the gas stream by passing through NaCN liquor containing excess
NaOH. Some CO2 is absorbed at this stage producing sodium carbonate (Na2CO3).

HCN + NaOH ! NaCN + H20

C02 + 2NaOH ! Na2C03 + H20

At this point in the process some of the unlimed NaCN liquor is fed to the No.2,3 and 4 Stock
Tanks, this is known as standard grade liquor.

The liming process is used to convert soluble Na2CO3 to insoluble calcium carbonate (CaCO3).
This is removed by filtration.

Na2CO3 + Ca(OH)2 ! CaCO3 + 2NaOH

The filtered liquor is known a high quality liquor. A higher grade of sodium cyanide known as
Super High Quality Liquor (SHQL) is also produced in the sodium cyanide plant by reacting
liquid HCN from HCN6 with 50% sodium hydroxide solution.

Process Flow Diagram

A simplified flow diagram of the NaCN plant is shown in fig 2.3.1.

Process Inputs

Natural Gas

Natural gas is supplied to the NaCN plant by pipeline from site distribution system.

Hydrocyanic Acid (HCN)

HCN used for Super High Quality Liquor production is manufactured in the HCN6 plant. It is
imported to the NaCN plant by pipeline to the evaporator section via the ACH3 plant.

Note: The manufacture, import and central storage of HCN is covered in the HCN6 document
which forms part of this application.

Ammonia

Gaseous ammonia is imported by pipeline.

50% NaOH Solution

Caustic Soda is delivered by road tanker and is stored on the NaCN Plant.

Sodium Hypochlorite Solution

Sodium hypochlorite is delivered by road tanker and stored to the South side of the NaCN
plant.

Catalyst

The noble metal catalyst bed, for the conversion of natural gas and ammonia to HCN, is
replaced approximately every 6 months.

Lime

Lime (calcium hydroxide) is imported by road tanker and stored on the NaCN plant.
Water

There are several sources of water used on the NaCN plant:

Demineralised water is used for the dilution of NaCN liquor to the correct strength and to feed
the waster heat boiler.

Process Description

Overview (see fig. 2.3.1)

The plant produces HCN by the catalytic conversion of ammonia and natural gas in an air
stream. The HCN, combined with liquid HCN receipts by pipeline, is reacted with 50% sodium
hydroxide solution to produce sodium cyanide liquor of approximately 30% NaCN.

Conversion and Waste Heat Recovery

In the converter, the mixed gases react exothermically to produce HCN (and hydrogen) on a
platinum-rhodium gauze catalyst that operates at a pressure of 1.3 barg and a temperature of
950 –1050oC. Side reactions produce carbon monoxide and carbon dioxide. The hot gases
exit the converter and are used to generate steam at a pressure of 21.7 barg in a waste heat
boiler. Further cooling occurs with heat exchange with the boiler feed water in an economiser.
The process gas, containing about 8% by volume of HCN and 2% of unreacted ammonia is
passed to the HCN absorber at a temperature of at least 100oC and a pressure of about
70mbarg.

HCN Absorption

The HCN produced in the converter is absorbed in the HCN absorber, using 50% NaOH, to
produce NaCN liquor. An excess of NaOH in the liquor is necessary to prevent localised HCN
polymerisation. The absorption process also produces sodium carbonate (Na2CO3) by the
reaction of carbon dioxide by-product with NaOH. The Na2CO3 is removed in the liming and
filtration stage. The HCN absorber exit gases, now depleted in HCN, pass to the main plant
stack where they are burnt.

Liming and Filtration

The 30 % w/w sodium cyanide liquor made in the HCN absorber contains between 0.6 and
1.15% w/w sodium carbonate. This is removed from the liquor by the addition of 60-175 kg/h
calcium hydroxide (lime). The lime addition rate depends on the liquor rate and on the sodium
carbonate concentration. Calcium carbonate is precipitated and is removed from the liquor by
a rotary vacuum filter (Rovac). The sodium carbonate level is reduced to between 0.1 and
0.3% w/w. The filter cake is washed with water to remove the bulk of the cyanide liquor before
being discharged to the toxic effluent treatment section for neutralisation.

The vacuum driving force for the Rovac is applied to the metafilter feed tank using the Nash
Vacuum pump that exhausts directly to atmosphere. The liquor is then pumped to one of two
polishing filters (metafilters) in order to reduce colour and remove any fines that passed
through the Rovac. The sodium cyanide liquor, now substantially free of carbonate, is pumped
to cyanide liquor storage via a cooler to minimise hydrolysis of the cyanide to formate.
Evaporation

No.2 Evaporator, the smaller of the two at about 60te capacity, is used to produce Super High
Quality liquor, a purer sodium cyanide liquor using liquid HCN imported from the ACH3
HCN storage. This is a batch process using a vessel previously used to produce solid sodium
cyanide. Due to the high offtake of the recirculation loop on the vessel, it must be first filled
with demineralised water and a heel of caustic to establish a working level. HCN and 50%
caustic are then fed to form sodium cyanide liquor.

Steam is applied to the circulation loop to evaporate water purely to control the level in the
vessel.

Vacuum is applied to the vessel, using steam ejectors, to minimise hydrolysis of the cyanide to
formate and ammonia. The circulation loop must be maintained to ensure correct control over
the HCN/caustic reaction. Loss of vacuum, caustic flow, high level low level or recirculation
flow trips the HCN feed.

The evaporator overheads (water and a low levels of HCN) are condensed and fed straight to
the effluent treatment system.

The product liquor is pumped directly to stock tanks in the liquor storage area.

NaCN Liquor Storage

There are 9 storage tanks in this area, each one set aside for storage of a particular grade of
liquor. The maximum liquor storage capacity is 1615 tonnes. Each storage tank is fitted with
a level indicator and an independent high level alarm.

Tank No. Contents

2, 3 & 4 These tanks are used to store Standard grade liquor. (unlimed)

5 Used for the storage of limed, low carbonate liquor for recycle to
the HCN Absorber

6&7 Used for super high quality grade liquor storage.

8&9 Storage of high quality liquor. Like evaporator feed liquor. This
liquor has been passed through the liming section and contains
less impurities than standard liquor.

Shutdown Tank This tank is kept empty and is used to drop the contents of either
evaporator if a leak of NaCN develops. The tank is sized to take
the full contents of either evaporator.

From here all grades of liquor are loaded to road tankers at the NaCN liquor tanker filling
depot.
NaCN Liquor Tanker Filling

NaCN liquor is exported as a product in road tankers. Which are filled by selecting a tank and
pumping liquor into the top of the barrel. The total flow of liquor is automatically controlled by
means of a batchmeter. The area is continuously manned during tanker filling operations.

Effluent Treatment

The effluent treatment facility receives and treats the continuous purges referred to in previous
above, and any washings, leaks and spillages which may arise on the NaCN plant and liquor
storage and tanker loading area. Additionally, the facility also receives batches of effluent
arising from other process areas, these are

! ACH3 and ACH4 cubicle secondary containment sumps

! Purge from the HCN still at HCN6, if too high in HCN to be discharged to BB06

All effluent from the above areas remote from the sodium cyanide plant itself is pumped
slowly to the effluent treatment system. If there is a problem with the effluent treatment
system, e.g. due to increased load from the sodium cyanide plant, the transfers are stopped
immediately.

The alkaline cyanide effluent is treated with 10-15% sodium hypochlorite solution in four
stirred vessels in series. The sodium hypochlorite solution reacts with cyanide to form the less
toxic cyanate. The treated effluent, containing less than 10 ppm of cyanide, flows to drain
where, after mixing with other effluents, it is discharged via a consented outfall, BB03, to
Billingham Beck.

The hypochlorite storage consists of 3 tanks, with a total storage capacity of 250 tonnes, filled
from road tankers, from which sodium hypochlorite flows to the treatment vessels by gravity.
The flows are continuously measured, a high flow being indicative of an abnormally high loss
of cyanide.

If the treatment facility is in danger of being overwhelmed by a sudden large increase in

cyanide load or if the treatment process fails to function, then the operator may divert the
effluent leaving the fourth (final sump) into a large (300 m3) secondary containment pit whilst
the problem is being attended to. Later, the contents of the pit can be pumped back into the
effluent treatment system for re-treatment. As there are eH analysers in each sump, if there is a
spillage the operator will have many warnings before the effluent reaches BB03. The first
sump will have high cyanide and then the second, third and finally the fourth. When this
sequence starts to happen the operator will divert the effluent stream to the secondary
containment pit.

The secondary containment pit has sufficient capacity to contain all of the liquor released from
a catastrophic failure of the largest vessel on the sodium cyanide plant.

Caustic Storage and Dilution.

The 50% w/w sodium hydroxide solution used in the absorber and evaporators on the sodium
cyanide plant is stored in a series of tanks on the sodium cyanide plant.
The 50% w/w caustic is imported in road tankers and offloaded directly into 3 linked tanks
with a 225te capacity. From these tanks the 50% caustic is pumped into a 20te capacity
dilution tank located in the storage area where the caustic is diluted to give a 25% w/w solution
by the addition of softened water. This 25% caustic solution is used on the effluent treatment
sections of the Monomer 7 and Monomer 8 complexes.

An operator from the sodium cyanide plant is always present during off-loading operations.

Drainage Systems

All effluent from the sodium cyanide plant, liquor storage and tanker loading area passes first
through the effluent treatment system before being discharged via outfall BBO3. All
additional effluent streams which are pumped to the sodium cyanide plant effluent treatment
system will also discharge to BBO3

Any effluents arising from the caustic import depot will be discharged to BBO3 via the
effluent treatment system.
Process Outputs

NaCN Liquor

Liquor is exported as 30% NaCN in three forms, standard (unlimed), high quality and super
high quality which has a lower concentration of contaminants.

NaCN Plant Control Philosophy

The NaCN plant is operated on a continuous basis and controlled and monitored from a
Distributed Control System (DCS). Minimum operator intervention is required under normal
operation.

Absorption of HCN into caustic soda is the critical step which determines the efficiency of
HCN recovery and avoids HCN being burnt. Consequently it is essential that the HCN
absorber liquor is always circulating and is always alkaline. The flow of fresh caustic soda
solution to the Centre of the tower is ratioed to the converter load. pH control of the circulating
liquor adjusts the flow of trim caustic to the recirculation line. The recirculation flow is set at
200 m3/hr.

If either the absorber circulation pump or caustic feed pump fails, an alarm is generated and the
operator shuts the plant down immediately. If there is any delay in this action, the liquor inside
the vessel will turn black within 3 minutes from HCN polymerisation and the gases from he
converter will be burnt in the stack. A runaway HCN reaction could not occur as the solubility
of HCN in aqueous solutions containing ammonia is very low (<1% W/W) and the water
would remove the heat of reaction. Therefore, the loss of caustic supply to the HCN Absorber
is considered to be a product quality issue and not a safety issue.

Ancillaries

HCN Pipeline and Plant Cubicles

The HCN pipeline enables liquid HCN to be transferred from HCN storage at the ACH3 plant,
directly into the evaporation section for use in SHQL production. There is no HCN storage on
the NaCN plant. All flanges, joints, valves, etc. in this pipeline are located in HCN cubicles.

On shutdown, the pipework local to the evaporators is washed out by an automatic washing
system sequence using hot water. The hot water flushes the HCN flow control system through
to the evaporators. If the shutdown is prolonged then the entire pipeline from ACH3 to the
evaporators is flushed through.

An HCN cubicle comprises of an enclosure whose purpose is to confine any conceivable

spillage or leak. Any volatile material spilled or otherwise released within a cubicle is
extracted by a fan and discharged via a stack at height where its release into the atmosphere is
designed to avoid a significant hazard to individuals, either inside or outside the site
boundaries.

The cubicle vent fan is operated continuously and it is treated as local exhaust ventilation in
terms of operational checks. The cubicle vent stacks are continuously monitored for the
presence of HCN. The cubicles are provided with sumps to contain any liquid spillages.
Decontamination Area

The courtyard of the NaCN plant is used for decontaminating all materials/equipment that
leaves the works. All washings drain to the effluent treatment section.

2.3.1 Control of Point Source emissions to Air

To ensure that the emissions to air remain insignificant, besides applying the BAT for
Management Techniques, the following are specific to the plant:

1. The major emissions to air are to the plant stack, which is lit continuously to burn any
ammonia or HCN that may slip through the conversion and absorption process. The plant
flare has been demonstrated to have a combustion efficiency of 99.17%. If the flare cannot
be lit within an hour the plant is shutdown.

2. Monitoring and control of various temperatures in the main process equipment helps
minimise emissions, by ensuring the process operates efficiently. Key process efficiency
measurements are continually monitored.

3. Two cooling water condensers minimise discharges via the evaporator ejector vent.

4. The flanges and valves for the HCN pipeline are contained within ventilated cubicles
which discharge via vents at height, which reduces the ground level concentration of
components. The cubicle vents are constantly monitored for HCN and have high
concentration alarms and trips.

2.3.2 Abatement of Point Source emissions to surface water and sewer

All liquid flows and the slurry from the filtration section of the plant are channelled to the
cyanide effluent treatment section via a series of drains and gulleys on each floor of the plant.
Any cyanide present is destroyed by reaction with sodium hypochlorite to produce sodium
cyanate, in four stirred treatment pits in series.

The addition of sodium hypochlorite to each sump is automatically controlled using an

analyser that measures the extent of the cyanide destruction reaction by means of eH
measurement of the redox potential.

Emissions reaching the drain then flow to BB03 outfall. The Plant operation complies with its
permit to operate, and there are no emissions to public sewers. BB03 is the outfall route for the
cyanide effluent treatment plant as well as stormwater run-off from site roads, the site
laboratories and the site restaurant. In addition ‘scour water’ is added to ensure that there is
sufficient velocity in the drain to ensure that the suspended solids do not settle out, which
could ultimately lead to blockages. When the plant is not operational the ‘scour water’ is
isolated.

If the treatment facility is in danger of being overwhelmed by a sudden large increase in

cyanide load or if the treatment process fails to function the operator can divert the effluent.
The flow leaving the fourth (and final) sump can be directed into a large (300 m3) secondary
containment pit, whilst the problem is rectified. The contents of the pit can then be pumped
back into the effluent treatment system.
The effluent is diverted by means of a large valve, remotely operated from the sodium cyanide
control room, which when closed blocks the drain. The effluent then overflows via a weir into
the secondary containment pit. It takes three minutes for the diversion valve to move from fully
open to the fully closed position. If the diversion valve fails to close, identified from the valve
position indicator in the control room, the operator is required to operate the valve manually.
The operation of this valve is tested on a regular basis by the plant operating team.

The secondary containment pit has sufficient capacity to contain all the liquor released from
the catastrophic failure of the largest vessel on the sodium cyanide plant. Continuous
monitoring of the outfall for consented analytes and alarm values at warning limits ensures that
the diversion valve is closed soon enough to prevent consents being breached.

Improvement programme

To ensure that the emissions to water remain insignificant, besides applying the BAT for
Management Techniques, the following are specific to the plant

1. All storage tanks are located within bunds. The tanks are equipped with high level
alarms and independent high level trips which stop the feed into the tanks.

2. HCN liquor is not stored on the NaCN Plant but is imported as required from the HCN
Plants.

2.3.5 Odour Control

Ammonia, Nitrogen Dioxide and Chlorine are the components released from the process that
have the potential risk of an odour emission. Ammonia and NO2 are released from the main
plant stack which benefits from height and temperature to aid dispersion. Ammonia and
Chlorine are present in other intermittent process vents and in the storage tanks where they are
present in extremely low concentrations when compared with the odour threshold value. As the
compounds are part of a mixture the actual emission concentration should be converted to
odour units. This would require the emission to be captured and tested by an odour panel
however as the odour risk is believed to be low this characterisation is believed to be
unnecessary. The measures taken to limit the releases are described in section 2.3.1.