Odeste, Adel Y.

Pet E-5201

SODIUM CYANIDE PRODUCTION BY ANDRUSSOW PROCESS OF AMMONIA AND

METHANE

As the global economy and technology progresses and the function of things are getting
more attention from the industry, demand for materials which are truly useful and has several
functions are in need. One of these materials is the Sodium Cyanide (NaCN).

Sodium cyanide (NaCN) is a water soluble inorganic salt that is a white crystalline solid
at ambient temperature and pressure. It has a high toxicity, and thus can be deadly to humans
through ingestion, dust inhalation, and skin absorption through open wounds. It is a highly basic
substance, and when wet,small amounts will revert back into hydrogen cyanide (HCN) gas
though hydrolysis, a key intermediate in the production of sodium cyanides.

Sodium cyanide is used throughout the world, primarily as a reagent in the mining
industry for the isolation of precious ores. Approximately 90% of sodium cyanide is used for
gold and silver processing in markets and around 78% is used for this purpose worldwide. Aside
from its use in the mining industry, sodium cyanide is also used as feedstock to produce
compounds including cyanuric chloride, cyanogen chloride, and various types of nitriles.
Another major market for cyanides is the electroplating segment which constitutes
approximately 9% of worldwide demand, where sodium cyanide is used to improve the
durability and reduce corrosion in automotive parts. As the global technology progresses and the
function of things are getting more attention from the industry, demand for sodium cyanide
which are truly useful and has several functions are in need.

Process Flow Diagram

In this design, the feed will pass through the reactor to undergo Andrussow reaction. In
this process, the physical and chemical properties will separate before it transported to the
Caustic Absorber. The caustic absorber neutralizes the hydrogen cyanide. This is used to clean
up hazardous chemicals then transported to the Hot Surface Precipitator. The precipitator
removes the fine grains component such us sand and dust that became waste or the sodium
carbonate. After removal of sodium carbonate it will pass through the Evaporative Crystallizer
that separate the liquid phase to the gas phase then transport again to the Centrifuge. A pusher
centrifuge will dewater, this excess water will go back to the Crystallizer to reuse in the process
cycle and the sodium cyanide before it being molded into briquettes.

Process Description

A spherical anhydrous ammonia storage tank is employed to hold approximately 2 days

worth of production requirement at 85% vessel volume capacity. Ammonia is fed into the
process at a rate of 766.10 kg/hr. Natural gas located on-site is fed into the process. Ambient air
is fed into the system via a centrifugal turbo blower. The vapor stream mixture is preheated via a
process stream heat exchanger. This process heat exchanger was employed to lower heating and
cooling utility requirements.
The first step in the process involves the production of HCN gas in reactor via the
Andrussow process. The mixed inlet stream contains methane, ammonia, and air, with molar
ratios of methane to ammonia to oxygen at 1:1:1.3. The stream is fed into the reactor operating at
2058°F and 17.7 psig and flows downward through a pad of woven mesh screens lined with
catalyst of 90% Platinum and 10% Rhodium with a cumulative thickness of 3 mm. The reaction
gas flowing out is comprised of the hydrogen cyanide product (about 7% by volume),
unconverted ammonia and methane, by-products of carbon monoxide, hydrogen gas, water
vapor, carbon dioxide, and a large proportion of nitrogen. To avoid decomposition of the
hydrogen cyanide, the gas is quickly cooled from 1125.56 °C to 315.56 °C via a waste heat
boiler of high pressure steam. Further cooling occurs via a process stream heat exchanger to
bring the vapor stream down to 162.22 °C. An additional heat exchanger employing cooling
water as the heat transfer fluid is utilized to bring the process stream to the caustic absorber
conditions at 70 °C.
The steam coming is fed into an absorber operating at atmospheric pressure and 70 °C.
Keeping the temperature low reduces the tendency for HCN to polymerize and minimizes
decomposition of ammonia, which can result in a loss of yield as well as contamination of the
NaCN product. It is comprised of a 50 wt% of aqueous sodium hydroxide, is fed from storage
tank into the column. An excess of NaOH, about 5% greater than stoichiometric requirements, is
fed to prevent localized HCN polymerization and to account for the production on undesired by-
products like sodium bicarbonate and sodium carbonate. The caustic solution flows counter-
current to the vapor stream. Here a neutralization reaction occurs between the hydrogen cyanide
and sodium hydroxide, forming aqueous sodium cyanide and water. The reaction is assumed to
be fast and proceed to nearly 100% conversion within the column. The vapor stream exiting the
absorption column is then sent to a series of absorption and stripping columns to recover the
unreacted ammonia and recycle it back the feed of HCN reactor. The stream flows through a
heat exchanger which has a surface temperature of between 104.44 °C and 121.11°C. The
principal purpose of this unit is to provide a surface for which to selectively crystallize out the
sodium carbonate impurity since its solubility is inversely to temperature. A film of sodium
carbonate is formed on the surface and is measured via pressure or temperature differential to
determine when the efficiency of the surface has been decreased to the point of adversely
affecting the process.
Based on surface area of 13,000 ft2 and input from industrial consultants, the exchanger is
assumed to remove approximately 80% of the incoming sodium carbonate and takes
approximately 24 hours before the fouling compromises its efficiency and has to be switched out
with its spare and washed using a high pressure water stream. The steam leaves the hot surface
exchanger at 91.11 °C and is mixed with recycle stream before entering a forced circulation
evaporative crystallizer. The crystallizer unit operates at 60 °C and -13.8 psig. Hydrolysis and
decomposition of sodium cyanide begins to occur at around 70°C so greater temperatures are not
advised.
It is pumped to 0.2 psig via a centrifugal pump and fed into a pusher centrifuge at 60 °C.
The centrifuge operates continuously and dewaters the crystal slurry to about 5% moisture
content as per the manufacturer's specifications. The mother liquor saturated with NaCN ions is
recycled back into the crystallizer. The wet cake is then transported to a briquetter unit producing
the desired solid sodium cyanide in the form of a briquette.