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Graham-Fridjonsson

NaCN Production
Feasibility Study
Literature Review, Process Selection,
Mass and Energy Balances

Presented to The School of Mechanical and Chemical


Engineering:
Dr. Einar Fridjonsson, PhD

Prepared by
Design Group 2
Chanel Bernardo 21131417
Callum Biggs 20498066
Wei Cui 21250612

Pauline Ho 21108549
Vincent Lim 20859448

Graham-Fridjonsson NaCN Production Feasibility Study

Table of Contents
Table of Contents................................................................................................... 1
List of figures......................................................................................................... 1
List of tables.......................................................................................................... 2
1. Introduction...................................................................................................... 3
2. Literature Review............................................................................................. 4
2.1 Literature Sources........................................................................................ 4
2.2 Gas Treatment.............................................................................................. 4
2.3 Primary Reaction Pathway............................................................................4
2.3.1 Andrussow Process................................................................................ 4
2.3.2 BMA Process (Degussa or Blausare-Methan-Ammoniak Process)...........4
2.3.3 Shawinigan Process (or Flouhmic Process).............................................5
2.3.4 Formamide Process................................................................................ 5
2.4 Quenching.................................................................................................... 5
2.5 Ammonia Recovery...................................................................................... 6
2.5.1 Fertiliser Production...............................................................................6
2.5.2 Ion Exchange......................................................................................... 6
2.6 HCN-NaCN Conversion................................................................................. 7
2.6.1 Articles................................................................................................... 7
2.7 Storage......................................................................................................... 8
2.8 Waste Management...................................................................................... 8
2.8.1 Cyanide Waste....................................................................................... 8
2.8.2 HCN Absorber Off-Gas............................................................................9
3. Process Selection........................................................................................... 10
3.1 Selection Method........................................................................................ 10
3.2 Batch versus Continuous............................................................................11
3.3 Ammonia Recovery.................................................................................... 12
3.4 Waste Management.................................................................................... 13
3.5 Quencher.................................................................................................... 13
4. Mass & Energy Balance..................................................................................16
5. Project Management...................................................................................... 17
5.1 Team Allocation.......................................................................................... 17
5.2 Gantt Chart................................................................................................ 17
5.3 Timeline...................................................................................................... 17
5.4 Resource Graph.......................................................................................... 17
5.5 Network Diagram....................................................................................... 17
5.6 Critical Path Assessment............................................................................17
6. Conclusion..................................................................................................... 18
7. Appendices.................................................................................................... 19
Appendix A Literature Review Data................................................................19
7.1
Primary Reaction Pathway....................................................................19
7.2
Quenching............................................................................................ 22
7.3
Recycle & Waste Treatment.................................................................27
7.4
HCN-NaCN Conversion.........................................................................33
7.5
Storage................................................................................................ 43
8. References....................................................................................................... 49

List of Figures
Figure 1 Internal and external constraints placed on the design space (Sinnott
2005)................................................................................................................... 10
Figure 2 Iterative design process (Sinnott 2005).................................................10

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Graham-Fridjonsson NaCN Production Feasibility Study


Figure 3 The onion model for process design. The inner layers must be designed
before the outer layers can be determined (Smith 2005)....................................11
Figure 4 BMA (left) and Andrussow (right) reactor geometries (Brennan 2012). .22
Figure 5 Temperature decay curves at typical quenching conditions (Pylilo 2012)
............................................................................................................................ 22
Figure 6 Typical quenching processes (top) (Pylilo 2012)and heat exchanger
transfer line (bottom) (Moulijn et al. 2013)..........................................................23
Figure 7 PFD for Andrussow Process (IntratecSolutions)......................................25
Figure 8 Hydrogen cyanide processes global distribution (Evonik)......................26
Figure 9 Evolution of accumulated number of ammonia separation patents
(Mendivil et al. 2005)........................................................................................... 28
Figure 10 Median lethal dose toxicity measurement guideline based on European
Union (Towler and Sinnott 2008)..........................................................................28
Figure 11 Selected international quality guidelines for cyanide in groundwater
(Dzombak et al. 2006)......................................................................................... 30
Figure 12 Cyanide treatment technology summary (reference?).........................31
Figure 13 NaCN/NaOH solubility chart (Aigueperse and Guerin 1966).................37
Figure 14 NaCN-NaOH-H2O 25C system.............................................................37
Figure 15 NaCN-NaOH-H2O 35C system.............................................................38
Figure 16 NaCN-NaOH-H2O 55C system.............................................................38

List of Tables
Table 1 Design factors for batch and continuous processes................................11
Table 2 Ammonia recovery considerations..........................................................12
Table 3 Achievable cyanide treatment level (Dzombak et al. 2006)....................13
Table 4 Quencher considerations.........................................................................13
Table 5 Typical reactor off-gas compositions (Maxwell 2007)..............................19
Table 6 Reactor summary.................................................................................... 19
Table 7 Comparison of methods to produce hydrogen cyanide...........................20
Table 8 Summary and selection of quencher unit (Cross and Hesketh 1995,
BCS_Inc 2008, Brennan and Hoadley 2003).........................................................24
Table 9 Quench water requirements (Brennan and Hoadley 2003)......................25
Table 10 Summary of various ammonia recoveries from inventors.....................27
Table 11 Comparison of hydrogen gas separation methods (Shenoy 1980,
Nguyen 2012, Phair and Badwal 2006)................................................................28
Table 12 Toxicity data for selected chemicals (Towler and Sinnott 2008).............29
Table 13 Selected international quality guidelines for cyanides in soil (Dzombak
et al. 2006).......................................................................................................... 32
Table 14 HCN liquid least-squares parameters to fit Ln(P(torr))=A+B/T+CT 2
(Appleton and Van Hook 1982)............................................................................ 33
Table 15 Vapour pressure of HCN Ln P=C1+C2+C3LnT+C4T C5 in Pa (Green and
Perry 2007).......................................................................................................... 33
Table 16 Single temperature or unspecified temperature values for K H for HCN
(Ma et al. 2010)................................................................................................... 33
Table 17 Temperature dependence of KH values of HCN as reported in literature
(Ma et al. 2010)................................................................................................... 34
Table 18 Flammability limits, important temperatures and heats of phase change
for hydrogen cyanide (Green and Perry 2007).....................................................35
Table 19 Physical properties of NaCN..................................................................36
Table 20 Summary of existing patent literature of ?............................................39

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Introduction

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Graham-Fridjonsson NaCN Production Feasibility Study

Literature Review

2.1 Literature Sources


Whilst a patent does not have to have commercial viability in order to be granted
(Heines, 2008), they can still be considered to be a viable source of information
given that the experimental conditions match the proposed process conditions
(Towler and Sinnott, 2008b) and the processes in question are relatively well
established (Sinnott, 2005). However, even if a patent is to be applied in a
design, it cannot be assumed to work without checking or testing (Horsley and
Engineers, 1998).

2.2 Gas Treatment

The feed of natural gas pipeline to the proposed plant location in Kwinana
originates in Dampier (Kimber, 2006). The mole fraction of the feed stream is
listed in Appendix #. Appendix # lists the maximum fraction of impurities that
coming into the reactor, data which was taken from the work of Caton et al.
(2015).
Analysis of the feed stream in Appendix # in light of these maximum allowed
impurities identifies the necessity of gas pre-treatment for the proposed NaCN
production facility. Failure to do so could lead to yields reducing, equipment
damage, and costing increasing (Trusov, 2001, Shimekit and Mukhtar, 2012).

2.2.1 Nitrogen Treatment

In order to avoid carbon dioxide generation and reduce ammonia decomposition


(Delagrange and Schuurman, 2007), the ratio of NH 3/CH4 should between 1.08
and 1.085 (reference).
Keeping nitrogen in the reactor feed has several benefits. The selectivity and
yields of hydrogen cyanide can be improved as nitrogen will inhibit the
decomposition of ammonia (Delagrange & Schuurman 2007). Furthermore,
nitrogen is an inert gas so that no side reaction will occur in the system. For
these reasons, nitrogen will not be removed as long as satisfy the pipeline
composition specification of natural gas (Shimekit & Mukhtar 2012).

2.2.2 Ethane Treatment

Ethane will exert negative effect on the content of hydrogen cyanide in the
production gas (Trusov 2001). Moreover, carbon black, the by-product from the
hydrogen cyanide synthesis, do occur disturbances when using types of natural
gas which contains only a few percentage of ethane (Voigt et al., 1981). Thus,
ethane has to be removed before reaction.
There are four methods to remove ethane from natural gas (Mokhatab et al.,
2006, Tobin et al., 2006).
2.2.2.1 Refrigeration Process
Refrigeration is the simplest and most direct process for NGL recovery (Mokhatab
et al. 2006). When natural gas was cooled or pressurised, the ethane will become
liquid so that it can be separated (1914). It can separate ethane efficiently, while
the energy consuming is extremely high (Ikoku, 1992).

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2.2.2.2 Leon Oil Absorption
Lean oil absorption is the oldest and least efficient process to recover NGLs
(Mokhatab et al. 2006). It is a mature technology but this method can only
absorb from C3-C7+. In other words, this method cannot separate methane and
ethane effectively (Kohl & Nielsen 1997).
2.2.2.3 Membrane Separation
Gas permeation membranes are usually made with vitreous polymers that
exhibit good diffusional selectivity (Mokhatab et al. 2006). In order to separate
effectively, the membrane must be very permeable with respect to the
contamination to be separated and it also must be relatively impermeable to
methane (Katz, 1959).
2.2.2.4 Adsorption
This process is generally reverted by applying heat to the adsorbent and adsorb
phase. If the heat applied is sufficient, the ethane will leave the adsorbent
internal surface and pores. To complete regeneration, the adsorbent is once
again cooled to its initial temperature (Triebe et al., 1996). Suitable adsorbent

materials include materials based on silica, silica gel, alumina or silicaalumina. Among them, silica gel is declining in favor of continuous process
such as cryogenic condensation and absorption (Kohl & Nielsen 1997).
Furthermore, Zeolite type adsorbents are preferred (Dolan and Wyatt,
2013).
2.2.3 Carbon Dioxide Treatment
An important gas purification technology is removing carbon dioxide (Shimekit &
Mukhtar 2012). The process of CO 2 may cause operational problems, pipeline
and equipment corrosion and effect the purity of HCN and NaCN (Allison et al.,
2010, Nagelvoort and Robertson, 1999).
Five methods for removing CO2 are applied in industry (Halim, 2015), which can
be listed:
1. Membrane
2. Adsorption
3. Cryogenic separation
4. Physical absorption
5. Chemical absorption
2.2.3.1 Membrane
Some gas molecules permeate faster through a membrane because of the
differences in physical or chemical properties of gas. For producing an impure
CO2 product, membranes suffer from both the cost of compression and heat
exchange. No commercial applications of membranes, however, for recovery
CO2 from flue gases (Mofarahi, 2008).
2.2.3.2 Adsorption
CO2 can be separated from natural gas based on physical attraction between the
gas components and active sites on the solid (Mofarahi et al. 2008). Suitable

adsorbent materials include materials based on silica, silica gel, alumina

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or silica-alumina (Kohl & Nielsen 1997). Furthermore, Furthermore, Zeolite


type adsorbents are preferred (Dolan & Wyatt 2013).
2.2.3.3 Cryogenic Separation
Through condensing CO2 at cryogenic temperature (56.61, 5.18 bar), it can be
separated from other gases. It is normally used for purification of high
concentrations of CO2 while amount of energy is needed if the concentration is
low (Mofarahi et al. 2008).
2.2.3.4 Physical Separation
Due to Henrys Law, CO2 can be physically absorbed in a solvent, but no chemical
reaction will occur during the process. This technology is favoured for the gases
which contain low concentration of inert gases or under high pressure (Mofarahi
et al. 2008).
2.2.3.5 Chemical Absorption
Unlike previous one, chemical reaction will occur during the absorption. Chemical
solvents are likely to be preferred for gases with low concentrations of CO 2 in the
flue gas (Halim et al. 2015). Furthermore, amine solvents are good choice for
capturing CO2.

2.3 Primary Reaction Pathway

The reactor for which hydrogen cyanide is synthesised is dependent on the


reaction that is taking place. The following reactions are presented by (Maxwell,
2005):
1. Andrussow Process
2. BMA Process
3. Shawinigan Process
4. Formamide Process
5. Methanol Process
6. SOHIO Process
The SOHIO and Methanol processes will not be discussed here, due to the
commercial unviability and technological immaturity of the processes (Stanford
Research Institute International, 2000, Maxwell, 2005). Supplementary
information on the advantages, disadvantages, reaction information and current
operating plants for all of the processes are presented in Appendix #, # and #.

2.3.1 Andrussow Process

The Andrussow Process consists of the exothermic reaction between methane


and ammonia in the presence of oxygen (Evonik Industries AG, 2014), conducted
over a platinum-rhodium catalyst gauze (Hickman et al., 1993):

C H 4 + N H 3 +1.5 O2 HCN +3 H 2 O H=474 kJ /mol

The reactor off-gas must be immediately quenched after the reaction to reduce
the probability of HCN decomposition (Brennan, 2012a). Due to the exothermic
nature of the reaction, the reaction becomes self-sustaining, and costs
associated with the reactor are low in comparison to other processes, thus
making this process dominant in industry (Ponton, 1998). However, the presence
of multiple side reactions reduces the selectivity for hydrogen cyanide, thus
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reducing the yield, and increases the need for further separation units
downstream (Hazair et al., 1999). As with reactions that will be discussed below,
the risk also exists that hydrogen cyanide will behave explosively in the reactor if
in contact with excess ammonia, and not quenched sufficiently (Ponton, 1998),
making this process potential dangerous.

2.3.2 BMA Process (Degussa or Blausare-Methan-Ammoniak Process)


Another common production method of hydrogen cyanide is the BMA Process
(Owen and Parekh, 1998). This synthesis is similar to the Andrussow, however,
the reaction occurs in the absence of air, and is highly endothermic (Mendivil,
2003):

C H 4 + N H 3 HCN +3 H 2 H=+252 kJ /mol

The literature states that the catalyst for this reaction is platinum with a rhodium
supporter (Maxwell, 2005), that is lined within the tubular reactor (Brennan and
Hoadley, 2003). There is also some suggestion for the use of an Al 2O3-ThO2
catalyst, with a promoter of H2S or CS2, by Kotake et al. (1958). However, this
catalyst system may be ineffective, as methane is required to be in large excess,
which may result in coke formation and deactivation of the catalyst (Kotake et
al., 1958).
There are three reactor types that may be used for the BMA reaction tubular,
monolithic membrane and dual membrane (Hazair et al., 1999). The tubular
configuration will be discussed here, as there is limited literature pertaining to
the alternative reactors for industrial use. The tubular reactor consists of a series
of tubes mounted in a furnace chamber, which provides the heating required to
counteract the endothermic nature of the reaction (Brennan and Hoadley, 2003).
Multiple reactor units are required for this reaction, thus making the design
complex and expensive (Maxwell, 2005). However, the reaction produces
hydrogen cyanide in high yield, as well as hydrogen gas, which can be used in
the furnace (Maxwell, 2005).

2.3.3 Shawinigan Process (or Flouhmic Process)


The Shawinigan method forms hydrogen cyanide from hydrocarbon gases
(methane, propane or butane) and ammonia, with no catalyst (Maxwell, 2005,
Mendivil, 2003) and in the absence of oxygen (The Lummus Company, 1961).
The reaction using propane is stated below (Maxwell, 2005):

3 N H 3 +C 3 H 8 3 HCN + 7 H 2 H =+ 632 kJ /mol

At present, there is a plant in Australia that operates with this method (Maxwell,
2005), and the process appears desirable due to the many advantages
(Appendix #). However, in comparison to BMA and Andrussow, this synthesis is
not as commercially dominant, and attracts higher operating costs if the cost of
electricity in the plant location is high (Maxwell, 2005).

2.3.4 Formamide Process


The Formamide Process was conceived in 2001 and follows three reaction steps
to obtain hydrogen cyanide (Maxwell, 2005, Weissermel and Arpe, 2008):
1. Methyl Formate synthesis

CO+C H 3 OH HC O2 C H 3

2. Formamide synthesis

HC O 2 C H 3 + N H 3 C H 3 NO +C H 3 OH

3. HCN formation

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C H 3 NO HCN + H 2 O H=+75 kJ /mol


The reaction occurs in a tubular reactor that is packed with an appropriate
catalyst (Maxwell, 2005) (Appendix # for catalyst systems). Although the
selectivity for HCN is high and the operating conditions are less energy intensive
than the dominant processes (Maxwell, 2005), the reactor configuration for this
synthesis is still being optimised, and this method has limited used in industry
(Maxwell, 2005).

2.4 Quenching

The quench unit operation is implemented to rapidly cool the reactor gas. The
heat must be removed to prevent fouling and subsequent reactions taking place
(Pylilo, 2012). Literature shows, the type of quencher employed is not dictated
by production process. The auto ignition temperature for HCN is 538 oC (Orica,
2014) while NH3 becomes unstable at 426oC (AirProducts, 1999). Quenching to
300oC (Gail et al., 2011) in less than a second (Chatelain, 1955) inhibits
decomposition and avoids ignition of NH 3 resulting in cleaner products with
reduced environmental impact (Lior, 2004). Sundstrom and DeMichiell (1971)
investigated plasma chemical processes and found no quenching method is
superior as all exhibited similar cooling rates (10 6 oR/second).
Predominantly, industrial quenching is done directly with water spray towers or
indirectly in waste heat boilers (WHB) for heat recovery (Santoleri et al., 2000,
Brennan, 2012a, Caton et al., 2015). Pylilo (2012) investigates chemical
quenching with light hydrocarbons. Cooling takes place through dilution of
product streams and hydrocarbon cracking. A valuable hydrocarbon product is
produced as a form of heat recovery. Hunt and Steinmeyer (2000) suggests using
waste streams from the absorber, cooled product gas or reactants as quench
fluid to minimise waste (Pylilo, 2012), however using product gas encourages
HCN and NH3 decomposition.
Direct quenching through contacting the process stream with air (Danielson,
1973), acidic solution to neutralise NH 3 (Hunt and Steinmeyer, 2000), a cold
surface (Santoleri et al., 2000) with high heat capacity such as ceramic elements
(Santoleri et al., 2000, Pylilo, 2012) or a heat pipe coated in alumina where
pressure differential drives cooling (Slaten, 2010, Reay et al., 2013) is
alternatives. A venturi scrubber, reverse heat scrubber (Hunt and Steinmeyer,
2000), a packed or plate tower, draft cooling, shell and tube exchanger
(Danielson, 1973, Coulson and Richardson, 2005), and a submerged tank is
infrequently seen as operational (Santoleri et al., 2000) but can be used (see
Appendix 3.1 further discussion and schematics).
Industrially, a WHB is followed by an economiser with BFW (Mtetwa, 2014),
second WHB or a water tower ensuring the stream leaves at 90 oC (Caton et al.,
2015). It is possible to quench with an aqueous solution directly from 1100 oC to
the desired temperature (Kent, 2013) or use externally cooled water recirculation
in the tower (Hunt and Steinmeyer, 2000). Industry also uses liquid spray towers
with water or oil and a transfer-line-exchanger (figure 3.1.3) to generate high
pressure steam (Moulijn et al., 2013). Quartz, alumina or carbon steel is the
materials proposed as high temperatures can be tolerated, steel is preferred as
its cheaper (Pylilo, 2012, Gail et al., 2011). Green and Perry (2007) states the
performance of a quencher is governed by flash temperature; stability and
appropriate heat transfer characteristics and needs to be considered in the
design phase.

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2.5 Ammonia Recovery

The presences of NH3 in the process after quenching can result in either
explosive interactions with produced HCN (Ponton, 1998), or due to its alkaline
nature, self-polymerisation and decomposition of HCN (Ullmann, 2007). If the
latter self-polymerization was allowed to occur, the exothermic nature of the
reaction could result in a runway process, resulting in explosive pressure
production (Flynn and Theodore, 2002, Gause and Montgomery, 1960). Hoffmann
et al. (2001) states that unit operations are only required to prevent the
aforementioned interactions at ammonia levels above several hundred ppm,
below this simple small scale scrubbing or absorbing/adsorbing operations could
suffice.
Table # details the multitude of patents regarding the elimination of the
ammonia that was reviewed. Of these technologies, both Sulphuric Acid and
Ammonium Phosphate treatment are of particular relevance to the production of
NaCN and as seen in Figure # are the most intensively studied and documented.

2.5.1 Fertiliser Production

Sulphuric Acid, H2SO4 could be introduced to react with the unreacted NH 3 to


form Ammonium Sulphate, (NH4)2SO4, the fertiliser. The by-product fertiliser could
be sold, yet expensive crystallisation process is needed (EPA, 2000, Mendivil,
2003):

2 NH 3 ( g )+ H 2 SO 4 ( aq ) ( NH 4 )2 SO 4 (s)
This method does not allow the recycle of the unreacted ammonia, as the
chemical process is expensive to employ (Radke and Kotheimer, 1955). In
addition, dilute H2SO4 is recommended in the literature (typically <15wt%) as
concentrated acid could cause rapid decomposition of HCN (Flynn and Theodore,
2002). This process has been utilised traditionally yet the selling price of the
fertiliser is less than its production cost (Miller, 1978).

2.5.2 Ion Exchange

A second alternative is the use of a monoammonium phosphate, NH 4H2PO4


solution, in which the ammonia reacts to form diammonium phosphate
(NH4)2HPO4 is presented in the works of Hoffmann et al. (2001) and acts as
follows:

NH
( 4 )2 HPO4 ( s ) NH 3 ( g )+ NH 4 H 2 PO 4 (s)

To recover the ammonia the absorption solution is boiled in a stripper by steam


injection and the released ammonia is condensed and recycle back to the
reactor, while the NH4H2PO4 solution is regenerated and reused (Gail et al.,
2011). Alternative is licensed by Dupont and is widely used in the Andrussow
process where quantities of un-reacted ammonia are higher (Mendivil et al.,
2005).

2.6 HCN-NaCN Conversion

However, even if a patent is to be applied in a design, it cannot be assumed to


work without checking or testing (Horsley and Engineers, 1998). Appendix #
tabulates the reviewed literature, the findings of which conclude there exists 3
methods for converting HCN to NaCN.
Direct Neutralisation

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Ion Exchange
o Resin Adsorption
o Activated Carbon Adsorption
Solvent Extraction (Limited interest in cyanide production industry)
In the following sections, both Direct Neutralisation and Ion Exchange methods
will be discussed in light of current academic literature.

1.1.1. Neutralisation
From the patent literature reviewed, it is apparent that direct neutralization is the
most established process for the conversion of HCN to NaCN. In this process,
HCN is directly contacted with NaOH in either gaseous or aqueous form, to
produce NaCN, as per HCN + NaOH

NaCN + H2O (Or see appendix?). This

concept has developed into two primary modern processes, the AVR process
(Botz and Stevenson, 1995, Silva et al., 2003, Dai et al., 2012, Estay et al., 2014)
and the Cyanisorb process (Demopoulos and Cheng, 2004, Kuyucak and Akcil,
2013).
The vast majority of commercially produced NaCN is produced by wet
neutralization (Pesce, 2000), (Pesce, 2000), in which purified HCN is contacted
with purified 50%w/w NaOH, to obtain 99% pure process. It is essential to
removal all CO2 to prevent the formation of Na 2CO3. If HCN gas is produced by
the BMA process, it can be directly contacted and still obtain a 98% pure produce
NaCN (Pesce, 2000). Contacting can take place in a contacting column setup
(See Appendix #), or if there is a concern with impurities, a CSTR reactor setup
(in which a shorter residence time will increase purity), a concept that exist both
in patent literature and in Gail et al. (2011). It is recommended by Demopoulos
and Cheng (2004) that the neutralization occurs at a negative pressure to ensure
hazardous HCN does not escape. In order to maintain product purity and prevent
polymerization of NaCN, it is essential at all stages to maintain a slight excess of
NaOH of 0.2-0.3% (Gail et al., 2011).

1.1.2. IX

An IX process would involve one the adsorption of aqueous or gaseous HCN onto
an exchanging media, and then eluted in such a way that NaCN is formed. The
advantage of this method compared to directly contacting the relatively pure
HCN stream (Pesce, 2000) would be the use of NaCl or Ca(OH)2 as a reagent over
NaOH (Ray and Rajchel, 2003), a cheaper (Alibaba, 2015) and safer (Gail et al.,
2011) alternative. An anion resin would be ideal, due to a stronger preference for
CNthan H+ over present ions (Inglezakis and Poulopoulos, 2006), this
assumption is confirmed by the vast majority of present literature only discussing
anion exchanging technology. IX processes could also be combined with
membrane technology (Lee et al., 1998) to reduce OPEX consideration, at a cost
of increased contacting time.
Whilst there is a large amount of data existent for the use of IX to produce NaCN
(See Appendix # - Ion Exchange Resins), the majority focuses on the treatment
of hydrometallurgical wastes, and the metal cyanide complexes present in them,
not on the treatment of free cyanide. This presents an issue in both quantity of
cyanide to be treated, and the selectivity of reviewed resins towards free cyanide
(Zagorodni, 2006).
The works presented by both (Green et al., 2002) and (Fernando et al., 2002)
conclude that in the application of CN- treatment in the gold industry, despite
being a topic of interest for the last 50 years, IX for CN - removal is yet to prove
commercially viable, likely due to process complexity and economic constraints.
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Significant literature exists on the application of impregnated activated carbon
(Adhoum and Monser, 2002) in the removal of CN- from wastewater, from bench
scale tests of capacities to investigations on optimum plant conditions
(Stavropoulos et al., 2015). Whilst relatively cheap to source (Alibaba, 2015), the
activated carbon regeneration poses significant technical difficulties compared to
traditional polymer resins in regeneration of adsorbed CN - species (Han et al.,
2005).

2.7 Storage

Storage should be considered for catalysts, utilities, fuels, reactants and products
(Woods, 2007) with sufficient capacity to ensure continuous operations (Towler
and Sinnott, 2008a) while adhering API or ASME codes. The industry standard for
gas storage is with wet or dry seals (undesirable for flammable gases) or
underground strata as it is cheap (Peters and Timmerhaus, 1991). Gas tanks are
made out of carbon steel primarily or aluminium if temperatures are very low.
Alternative storage options are;
Bottles, for small volumes and portability (Perry and Green, 1997)

Pressure vessels (cylindrical or spherical) (Perry and Green, 1997)

Low temperature storage tanks which requires some form of insulation


(Perry and Green, 1997) due to the gas liquefaction hence less storage
requirements (Towler and Sinnott, 2008a).

Liquid storage general entails subcooling (Lieberman and Lieberman, 2008) and
pumping into vertical cylindrical atmospheric tanks that are open or with fixed or
floating roofs (Brennan, 2012b). These tanks are either constructed of steel (if
the fluid is flammable (Towler and Sinnott, 2008a)), wood, fibre reinforced plastic
or prestressed concrete (if its water (Perry and Green, 1997, Peters and
Timmerhaus, 1991)). Design should consider wall thickness, location and size,
pressure and temperature controls and the corrosive action of contents
Smaller capacity tanks can be in cylindrical or rectangular shapes (Towler and
Sinnott, 2008a) and due to the relative scale of such tanks, the use of cheaper,
corrosion resistant materials such as plastics or glass reinforced plastics is
warranted(Perry and Green, 1997).
The following issues should also be considered in the storage of liquids
If the stored liquid exerts vapour pressures above atmospheric then
vapour tight tanks should be used (Peters and Timmerhaus, 1991).

If venting of flammable vapours is required, then flame arresters are


required in compliance with AS4603

Tanks are built on concrete foundation, saddled or legs (small capacity


usually) (State_of_Michigan, 2003)

If a fire risk is present a porous base for drainage should be considered


(Perry and Green, 1997).

In the case of the proposed NaCN plant, table 3.3x outlines storage
considerations for selected fluids. Majority of the tanks on the plant will be
vertical atmospheric tanks as its cost effective. If needed it is efficient to store
natural gas in liquid form however it can be stored underground or taken directly
from pipeline. For transportation iso tanks are generally used, noting that storage

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should be located close to distribution facilities and away from populated areas
(CSBP, 2014)

2.8 Waste Management


2.8.1 Cyanide Waste

Based on the European Union (EU) guideline, HCN is considered to be a very


toxic chemical as indicated as a very small LD50 value (about 3.7mg/kg) based
on the Table # and Table # given, whereas toxicity for NaCN is about 6.4mg/kg
(Towler and Sinnott, 2008b, CSBPLimited, 2008). The permissible limit for
cyanide in effluent is 0.2mg/L, according to US Health Service (Balomajumder,
n.d.) together with various sources of quality guideline attached in Table # and
Table # for references (Dzombak et al., 2006). Table # gives an overview on the
current technology specifically on cyanide waste management in the industry.
Mainly due to the technology maturity, 2 methods will be further discussed.
2.8.1.1 Chemical Treatment
Basically, this method involves the injection of NaOH, chlorine (Cl2) or
hypochlorite (ClO-) solution. (Taylor and Fransen, 2006, Dash et al., 2009) This
measure recognised as the alkaline chlorination process will largely be devoid of
free cyanide and will be turned into less toxic cyanate (CNO-) provided sufficient
reaction time has been allowed (Taylor and Fransen, 2006, Dzombak et al., 2006)
Specifically in the BMA process, possible cyanide wastes which are the HCN and
NaCN (readily dissociate to CN- or HCN at neutral pH) which are considered as
Weak Acid Dissociation Cyanides (WAD CN), regardless the fact that it could not
remove the complexed metal cyanide-containing waste. (Dash et al., 2009)
2.8.1.2 Thermal Treatment
This high energy-intensive process which is also known as the incineration
method, is employed widely in the industry to thermally decompose cyanide by
mixing and heating in the combustion tank or chamber, which could promote
high level of cyanide destruction (>99.9%). (Dzombak et al., 2006) In fact, EPA
(1990) claimed that CSBP managed to reduce the CN- concentration to 50ppm
by heating the combustion tank up to 100C on the existing NaCN plant, after
the treated effluent pass through a cooling tower airstream. (EPA, 1990)

2.8.2 HCN Absorber Off-Gas

H2, N2 and minor unreacted CH 4 gas will present in the off-gas streamline after
HCN absorption occurs (Caton et al., 2015). There are 3 common methods
employed to separate the gases (Seader and Henley, 2006):
Pressure Swing Adsorption (PSA) - in which the selective gas will be
adsorbed by the molecular adsorbing bed,
Cryogenic distillation (Phair and Badwal, 2006) by utilising the difference
in gas boiling point and freezing gas mixture as well as
Membrane separation (Phair and Badwal, 2006)
The pros and cons for each process are detailed in Table #. Since the recovered
H2 gas is highly purified, it could be used either as a feed for other processes
(Caton et al., 2015) or to use for energy source through combustion (Ballard,
2011). Brennan (2003) stated that due to BMA process produce more H 2 as a
byproduct than is consumed as H 2 within ammonia in cyanide production

14

Mass & Energy Balance

Graham-Fridjonsson NaCN Production Feasibility Study


compared to Andrussow, its possible to produce sufficient NH 3 to self-supply the
reactant. The off-gas stream which contains about 95wt% of N 2 can then be vent
out via the flue gas stream for flare emission. (EPA, 1990)

15

Mass & Energy Balance

Graham-Fridjonsson NaCN Production Feasibility Study

3 Process Selection
3.1 Selection Method
In the design of any chemical process, the variety of possible operations at each
stage create a large solution space of all possible solutions (Hoffmann et al.,
2001). The subspace of plausible designs is exists within the inflexible external
constraints and flexible internal constraints placed on the design (Sinnott, 2005).

Figure 1 Internal and external constraints placed on the design space


(Sinnott, 2005)

Figure 2 Iterative design process (Sinnott,


2005)
The creation of a plausible design involves an iterative process, detailed in Error:
Reference source not found, where a possible design is generated from the

16

Mass & Energy Balance

Graham-Fridjonsson NaCN Production Feasibility Study


collection of data, physical properties and methods, and then compared to the
original objective. This objective, is the requirement placed on the design in
order to produce a satisfied customer (Towler and Sinnott, 2008b). This method,
presented by Sinnott (2005) has been combined with the onion model (depicted
in Error: Reference source not found) of process design, as presented by Smith
(2005) to create structure method in which a viable NaCN production facility can
be designed. Not depicted in the hybrid process is the determination of Batch vs.
Continuous process utilization.
Figure 3 The onion model for process design. The inner layers must be

designed before the outer layers can be determined (Smith, 2005).


It is stressed by Sinnott (2005) that a wise engineer will prefer tried and true
technology (i.e. matured technology), over new, novel untested technology. This
is particularly applicable to the proposed production of NaCN, given that is falls
into the second category of process designs presented by Sinnott (2005), one in
which a new production capacity to meet growing demand is required. It is
suggest in this case that repetition of existing design with only minor design
changes is the best course of action.

3.2 Batch versus Continuous

There exists an overabundance of literature guiding the utilization of batch or


continuous processes in the context of process synthesis, in the following table
are the aspects to be considered in the decision of batch or continuous process.
Table 1 Design factors for batch and continuous processes
Batch
Production rate is greater than 5 x 106 kg/h
(Sinnott,
A range of products or product specifications
2005, Towler Severe fouling
and Sinnott,
Short catalyst life
2008b,
New product
Albright,
Uncertain design
2008)
Processes with difficulty in scale up
Integrity of the product is paramount
Production rate can be very flexible and suffers no turn down
issues when operating at low output
Continuous
(Sinnott,
2005)
17

Production rate is greater than 5 x 106 kg/h


Single product

Mass & Energy Balance

Graham-Fridjonsson NaCN Production Feasibility Study

No severe fouling
Good catalyst life
Proven processes design
Established market

3.3 Gas Treatment


3.3.1 Ethane treatment
Table 2 Ethane treatment considerations
Aspects
Choices
Economy
Lean oil absorption

Energy Efficiency

Solid bed adsorption

Safety

Solid bed adsorption

Product Quality

Solid bed adsorption

Maturity

Lean oil absorption

Environmental
Sustainability

Membrane

Reasons
Cheap raw material, doog
for mass production
(Mokhatab et al. 2006)
The operation
temperature and
pressure of natural gas is
similar with feed natural
gas
High degree of
automation (Tobin et al.
2006)
Separate efficiently
Easy to start up
(Tobin et al. 2006)
The oldest
process(Mokhatab et al.
2006)
Less environment impact
(Mokhatab et al. 2006)

According to Table 3, solid bed adsorption is the best method to remove C 2H6
from natural gas because of energy efficiency, safety and product quality.
Furthermore, Zeolite 13X can be selected because it is one of the preferred
adsorbents (Dolan & Wyatt 2013).

3.3.2 Carbon dioxide treatment


Table 3 Carbon dioxide treatment consdierations
Aspects
Choices
Reasons
Economy
Chemical absorption
Show the greatest
promise of
implementation for
thermal power
plants(Mokhatab et al.
2006)
Energy Efficiency
Adsorption
Low energy
requirements(Shimekit &
Mukhtar 2012)

18

Mass & Energy Balance

Graham-Fridjonsson NaCN Production Feasibility Study

Safety

Adsorption

Product Quality

Adsorption

Maturity

Chemical absorption

Environmental
Sustainability

Membrane

Highly energy intensive


for regeneration of
cryogenic separation (Ali
et al. 2014)
Relative moderate
conditions, no high
pressure or low
temperature (Cavenati et
al. 2005; Mofarahi et al.
2008; Shimekit &
Mukhtar 2012; Medeiros
et al. 2013; Alias et al.
2014)
Nearly all the carbon
dioxide can be
captured(Cavenati et al.
2005)
Widely used technology
for efficient (50-100%)
removal of carbon
dioxide (Medeiros et al.
2013)
Less environment
impact(Mokhatab et al.
2006)
No physical or chemical
solvents

From table 2 and table 4, because of the high quality of CO 2 specification in


purified natural gas, adsorption is the best method for CO 2 capture. A bunch of

adsorbents have been applied in industries widely (Rufford, 2012). Among


the adsorbents, activated carbon and zeolites are the commercially
available adsorbents mostly studied for CO2 capture (Liu, 2011). Whats
more, Zeolite 13X performs good results in separating CO 2 and CH4 as the
CO2 was removed completely in the zeolite layer (Cavenati et al., 2005).
Thus, Zeolite 13X can be used in removing CO2.

3.4 Primary Reaction Pathway


The literature review has identified many methods of hydrogen cyanide synthesis
and their reactors. However, as the alternative processes has a lack of industrial
application, the BMA and Andrussow Processes will be considered for process
selection.
Table 4 Primary reaction pathway considerations
Aspects
Choice
Reason
Economy

Andrussow

19

Mass & Energy Balance

The Andrussow Process has a lower


CAPEX then the BMA Process, as the
reactor design is less complicated
(Maxwell, 2007)
Additional heating is required for the

Graham-Fridjonsson NaCN Production Feasibility Study

Energy
Efficiency

Andrussow

Safety

BMA

Product
Quality

BMA

Maturity

Andrussow

Environment
al
Sustainabilit
y

BMA

BMA process, increasing the OPEX for


this reaction (Brennan and Hoadley,
2003)
The Andrussow Process becomes selfsustaining
at
high
temperatures
(Ponton, 1998)
There is a requirement for heating for
the BMA reaction (Maxwell, 2007) to
counteract the endothermic nature of
the reaction
More side reactions exist in the
Andrussow Process (Brennan, 2012a)
However, the safety for each reaction is
comparable
The BMA Process has reactor off gas
composition higher in HCN (Appendix
7.1.1)
The BMA Process produces high purity
hydrogen gas, which can be sold or used
for heating purposes (Maxwell, 2007).
The Andrussow Process was established
in the 1933 (Maxwell, 2007)
The BMA process was established in
1949, with improvements being made in
the mid 1990s (Maxwell, 2007)
The majority of hydrogen cyanide
production occurs via the Andrussow
Process (Appendix 7.2.6)
High purity hydrogen gas in the BMA
reactor off gas, can be sold or used for
heating other unit operations (Maxwell,
2007)
Andrussow off-gas produces carbon
dioxide and carbon monoxide, which are
environmentally undesirable (appendix
7.1.1)

The above table shows that BMA and Andrussow both excel in certain aspects;
however, as the client has specified the BMA Process, this will be the final choice
for the reaction pathway.

3.5 Quencher

The literature review has identified several of methods of quenching; due to the
lack of industrial application the selection process will focus on WHB and spray
towers (ST). From the literature review Table 3.1 and Table 3.2 was constructed.
For elaboration on the content see Appendix 3.2.
Table 5 Quencher considerations
Aspects
Choice
Economy
ST
-

20

Mass & Energy Balance

Reasons
ST has a lower CAPEX and OPEX
BMA process produces less gas hence
steam generation not viable.
ST less area hence lower footprint than

Graham-Fridjonsson NaCN Production Feasibility Study


WHB
ST does not require BFW which is
expensive
60-70% heat recovery

Energy
Efficiency
Safety

WHB

ST

Product
Quality

ST

Maturity

Environmental

ST

Sustainability

WHB

Decomposition and auto ignition of HCN


and NH3 needs to be considered.
- ST cooling is more efficient hence less
chance of runaway reactions
- BMA process needs water addition, hence
product quality not adversely affected
- Excessive dilution results in difficult
separation
- WHB does not affect product quality
Both options are most commonly used in
tandem and hence will have the same
technical maturity score.
- BFW is not required as in a WHB
- Lower quality water is requires less
processing
- Less CAPEX/OPEX required for utilising
generated steam
-

If feed has impurities plugging occur in ST


and impurities in quench water can
increase fouling. Shut down is required
every 6 months for maintenance.
WHB can operate 2 years before shut down
is required
Dilution in ST causes 10% of water
removed from the quench feed

Table 3.2 shows the spray tower is preferred for our process primarily due to the
low production rate of our plant making steam generation uneconomical.
(Brennan and Hoadley, 2003) confirmed for a plant of 18,000 ton/yr. the WHB
was an economic burden. It was decided the ammonia removal will further cool
the product stream during the neutralisation to 90 oC (McKetta, 1987).

3.6 Ammonia Recovery

Thorough considerations have been taken and decision is chose to add H 2SO4 to
separate ammonia from the product stream for fertiliser production, mainly due
to more cost-effective, more energy efficient, safer to operate, and more
importantly the industry maturity as clarified in table 1.
Table 6 Ammonia recovery considerations
Aspects
Choices
Economy

Fertiliser
Production

21

Mass & Energy Balance

Reason

Cheaper to design a production for


fertiliser production
Elimination of solid impurities due to the
polymerisation of HCN present in recycle

Graham-Fridjonsson NaCN Production Feasibility Study

Energy
Efficiency

Fertiliser
Production

Safety

Fertiliser
Production

Product
Quality

Ion Exchange

Maturity

Fertiliser
Production

Environment
al
Sustainabilit
y

Ion Exchange

stream would increase the operating


cost. (Benderly, 2002)
Ion Exchange Method is Licensed by
Dupont which means increased cost
(Mendivil, 2003)
Ion Exchange would not be as effective
in BMA Process as less unreacted NH 3
could be recycled back to the reactor
due to high yield compared relatively to
Andrussow Process (see yield table)
(Mendivil et al., 2005)
NH4H2PO4
considered
to
be
poor
adsorbent for NH3 (Miller, 1978)
Unreacted HCN will present in the
ammonia ion exchange method stream
which would cause polymerisation and
might
Block the pipeline due to the formation
of
tarry
and
gummy
materials.
(Kotheimer, 1955)
Recycled ammonia would have more
recovery value than fertiliser as fertiliser
is cheap and not in demand (Miller,
1978)
Degussa Plants in the United State is
has been using fertiliser production
method (EPA, 2000)
NH3 is not recovered at any of the 3
centralised
NaCN
plants
in
Australia(Brennan and Hoadley, 2003)
Fertiliser production could consider as
waste generation (Mendivil, 2003)

When it comes to cost analysis, burning the separated ammonia together with
other gases in the flaring stream can be considered as it greatly reduce the
process cost and unwanted waste fertiliser could be avoided. However, the
primary drawback of this cost-effective measure is the generation of oxides of N2
which are extremely toxic, and one of the primary anthropogenic sources for air
pollutants (Flagan and Seinfeld, 1988).

3.7 HCN-NaCN Conversion

A significant factor which influences the choice of HCN to NANC conversion is the
lack of CO2 in the feed stream, due to the implementation of the BMA reactor
(Pesce, 2000), in a 96-97% pure product can be obtained by direct contacting of
BMA product gases with a 50 w/w% solution of NaOH (Pesce, 2000)
Aspects
Choices
Reason

22

Mass & Energy Balance

Graham-Fridjonsson NaCN Production Feasibility Study


CAPEX

Direct NaOH
Contacting

OPEX

Ion Exchange

Energy
Efficiency

Direct NaOH
Contacting

Safety

Ion Exchange

Product
Quality

Direct Contacting

Maturity

Direct Contacting

Environment
al
Sustainabilit
y

Ion Exchange

Direct contacting could occur in a simple


absorption
column
(Pesce,
2000),
compared to either r a simulated
moving bed setup or merry-go-round
setup of multiple columns required for
an ion exchange process (Zagorodni,
2006)
Exchange resins can be reused with
minimal degradation (Say et al., 2004)
Cost of Ca(OH)2 is 1/10 of NaOH (Ray
and Rajchel, 2001)
Direct contacting would only require
energy to pump and contact the liquid
and vapour streams, as opposed to the
energy to create a counter current
simulated moving bed or an automated
merry-go-round
system
(Zagorodni,
2006)
Ion exchange could theoretically only
involve the use of NaCl as a reagent,
compared to NaOH, which is far more
toxic (Green and Perry, 2007)
By ensuring that the final solution is
alkaline (via NaOH in solution), the
product will be more stable (Gail et al.,
2011)
Refer to Appendice
The reduced used of caustic reagents
would reduce the possible impact on the
environment

From the above table, the clear choice is the use of a direct NaOH contacting
tower. This choice was primarily influenced by the choice of reactor
implemented, which was determined initially by the hybrid onion model used.

3.8 Storage
3.9 Waste Management

There are 3 selections needed to be justified in the waste management, as


follow:
3.9.1 Cyanide Waste Treatment
Both chemical and thermal treatment could effectively lower the cyanide
concentration, where chemical chlorination would be much cheaper to install
than the incineration method (Dzombak et al., 2006).
Even though the chemical method makes it more cost-effective in term of CAPEX,
however consideration of expensive chemicals injection should not be forgotten
as it will contribute to OPEX, include the SO2 injection to perform de-chlorination
to protect aquatic life from toxic effect of chlorine (EPA, 2000). Moreover,

23

Mass & Energy Balance

Graham-Fridjonsson NaCN Production Feasibility Study


another major environmental consideration should be included for selection
judgement, by the fact that thermal treatment is much more effective when it
comes to reduce the cyanide concentration. Furthermore, technology maturity
for this method is verified by the CSBP Kwinana NaCN plant (EPA, 1990).
Table 7 Achievable cyanide treatment level (Dzombak et al., 2006)
Chemical Treatment
Thermal Treatment
0.2mg/L (roughly 200ppm after density
<1ppm
conversion)
3.9.2 Gas Separation
According to Mody and Strong (n.d.), simple elimination method could be used to
remove the non-optimal solution with as little effort cost as possible. Hence,
the cryogenic distillation method should be eliminated with ease due to the
extremely high energy requirement, and high CAPEX is required (Shenoy, 1980).
Due to the technology maturity, as well as the product quality, Pressure Swing
Adsorption is chosen to be the resolution to separate H 2 from unreacted CH4 and
N2.
Table in content or appendix?

3.9.3 Hydrogen Usage


Caton et al. (2015) stated that the by-product H 2 gas is highly purified in
recovered stream and would be more valuable to sell it as raw material than
treating it as fuel for the reactor. Besides, the global demands for H2 is expected
to increase to 5% (ref below) One of the major usages of H2 would be for the
production for NH3 (IHS, 2013) and as the NaCN plant will be built at the selected
location in Kwinana, H2 gas could be sold back to the ammonia plant as the feed
gas which owned by CSBP (EPA, 1990, Brennan and Hoadley, 2003).

3.10 Economic Considerations


3.11 Environmental and Safety Considerations

24

Mass & Energy Balance

3.12 Final Process Selection


Table 8 Process selection using weighted score system
Ammonia
HCN-NaCN
Reactor
Separatio
Conversio
Assessment
Weighti
n
n
Criteria
ng
Andruss
BMA
ow

Gas
Separati
on

Recovery

Quenchin
g
Tow
er

WH
B

Energy &
Operating Costs

Separation Ease

1.5

1.5

Waste Disposal
& Environment

Safety

0.5

Technical
Maturity

CAPEX

1.5

1.5

0.5

Feed
Insensitivity
Reaction
Efficiency
OPEX
Selectivity
Total Weighted
Score

Stora
ge

Waste
Managem
ent

4 Mass & Energy Balance


1.2. Water Removal!
1.3. Software Choice
1.3.1. Fluid Package Utilized
1.3.2. Reaction Simulation
1.3.3. Use of Logical Operations

1.4. Process Conditions Chosen


Given Streams
(Feed, Ammonia, Output)
Conditions
Unit
Ethane Adsorption
Operation Feed
Op
Post
Temperature 30oC
30oC
1
Pressure 1
8MPa
Other 1
Temperature 150oC
2
Pressure 2
5.8MPa

8MPa

CO2 Removal
Feed
Op
24.85o
C
1MPa

BMA Reactor
Post
Feed
Op
24.85o
C
1MPa

150oC 100oC

100oC

5.8MP 1MPa
a

1MPa

Post

Other 2

Unit
Operation

Quencher
Feed Op
Temperature 1300oC
Pressure
1 bar
Other
Temperature 25oC
2
Pressure 2
1 bar
Other 2
Liquid

Unit
Operation
Temperature
Pressure
Other
Temperature
2
Pressure 2

Fertilizer Removal
Post
Feed Op
Post
300oC
1 bar
Gaseou
s
100oC

HCN Neutralization
Feed Op
Post
60
90
90
90
Gaseo
us
60
30

1 bar
Gaseou
s

90

Post Gas treatment?

90

90
Liquid

Other 2

5 Project Management
5.1 Team Allocation
5.2 Gantt Chart
5.3 Timeline
5.4 Resource Graph
5.5 Network Diagram
5.6 Critical Path Assessment

6 Conclusion

7 Appendices
Appendix A Literature Review Data
7.1 Gas Treatment
7.1.1 Gas compositions
Table 9 Mole fraction compositions of typical pipeline gas (reference?)
Temperature
30
Pressure
8MPa
Component
Methane
Ethane
Propane
Iso-Butane
N-Butane
Iso-Pentane
N-Pentane
Hexane
Heptane
Octane
Nitrogen
Carbon dioxide
Total
Table 10 Preferable
(reference?)
Component
Carbon dioxide
Ethane
Water

Mole fraction
87.850
5.755
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
2.394
4.000
100.000
mole

fractions

of

impurities

Maximum mole fraction


0.03
0.5
4

2.5 10

in

natural

gas

7.1.2 Natural gas pipeline

Figure 4 Natura gas pipeline of DBP (Kimber, 2006)

7.2 Primary Reaction Pathway


7.2.1 Reactor Off-Gas Compositions
Table 11 Typical reactor off-gas compositions (Maxwell, 2007)
Mole % composition
Product
Andrusso
BMA
Shawiniga Formamide Methanol SOHIO
w
n
HCN
6-12
20-23
25
(No reputable literature data
was found for these processes)
NH3
1.5-3
2-3
0.25
H2
7-11
70-72
72
H 2O
20-25
CO
3-4
CO2
0.3

CH4
N2
O2

0.1
50-55

1-2.4
0.5-1

7.2.2 Summary of reactor conditions, catalyst and reactor configurations for


hydrogen cyanide synthesis
Table 12 Reactor summary
Process
Reactor
conditions
Andrussow 1000 1300C, <
2 bar2

BMA

1200 1300C,
atmospheric
pressure2, 13

Shawiniga
n

>
1500C5,
atmospheric
pressure10
380

430C,
reduced
pressures2

Formamide

Methanol

350 500C, 1
bar8

SOHIO

400

510C,
0.35 2.07 bar7

Catalyst

Reactor configuration

Platinumrhodium
catalyst gauze1

Reactor vessel with at least


one gaseous inlet and outlet,
and a solid phase metallic
catalyst section within the
reactor3, 4
Furnace tubular reactor12, 2

Pt with Rh or Al
supporter2;
Al2O3-ThO2
catalyst, with a
promoter of H2S
or CS211
No
catalyst
required2, 5
Phosphate of Fe
or
Al,
with
promoter of Mg,
Ca, Zn or Mn2
Oxide catalyst
containing Fe,
Sb, P, V2
Mixed
metal
oxides6

Fluidised bed reactor, heated


by carbon electrodes2
Tubular2or
reactor9

fluidised

bed

Vapour phase, fluidised bed


reactor2
Fluidised
reactor2

bed

catalytic

1. (Hickman et al., 1993), 2. (Maxwell, 2007) 3. (Koch et al., 2000) 4. (Brennan, 2012a) 5. (Mendivil, 2003) 6.
(Cespi et al., 2014) 7. (Midwest Research Institute, 1993) 8. (Sasaki et al., 1998) 9. (Mattmann et al., 2002) 10.
(The Lummus Company, 1961) 11. (Kotake et al., 1958) 12. (Brennan and Hoadley, 2003) 13. (Gail et al., 2011)

7.2.3 Comparison of hydrogen cyanide production processes


Table 13 Comparison of methods to produce hydrogen cyanide
Process and reaction/s
Advantages
Andrussow
Low reactor costs
C H 4 + N H 3 +1.5 O2 HCN +3 H 2 O
(maintenance and
procurement)1
H=474 kJ /mol
Dominant method for HCN
production, large knowledge
base1
Medium to high purity
product2
Long catalyst life2
Self-sustaining at
temperatures about 1000C4
due to combustion reactions9

Disadvantages
Many side reactions
reduce efficiency3
(side reactions are
oxidation of CH4 and
NH3)11

BMA

C H 4 +N H 3 HCN +3 H 2
H=+252 kJ /mol

Higher HCN yields in


comparison with Andrussow1
High purity hydrogen byproduct can be used in other
operating units5

Shawinigan

3 N H 3 +C 3 H 8 3 HCN +7 H 2

H=+ 632kJ /mol

Formamide
Methyl Formate synthesis

CO+C H 3 OH HC O2 C H 3

Formamide synthesis

HC O 2 C H 3 + N H 3 C H 3 NO +C H 3 OH

Complex reactor
design1
High costs associate
with reactor design
and maintanence1
High heating needed
to counteract
endothermic reactio
Not suited for
locations with high
electricity costs1

No catalyst needed6
Low concentration of
ammonia in off gas reduces
recovery units required1
Able to process reactants of
varying purity, as there is no
catalyst to deactivate10
High HCN concentration in
off gas12
Useful if cost carbon
monoxide low1
If fluidised bed reactor use,
less equipment damage and
more economical7
High selectivity for HCN1

Limited use in indus


Reactor configuratio
still being optimised

HCN formation

C H 3 NO HCN +H 2 O
H=+75 kJ /mol

Methanol

Lower operating
temperatures in comparison
to Andrussow and BMA

Limited use in indus


High costs of obtaini
carbon source1

SOHIO

Lower operating

to Andrussow and BMA

Synthesis aim is not


HCN (by-product)
Low yield of HCN1
Multiple reaction ste
required
Technically immatur

N H 3+C H 3 OH + O2 HCN +3 H 2 O

C H 2 CHC H 3+ N H 3 +1.5 O2 C H 2 CHCN +temperatures


3 H2 O
in comparison
C H 2 CHC H 3+ 1.5 N H 3 +1.5 O2 1.5C H 3 CN +3 H 2 O

C H 2 CHC H 3+ 3 N H 3 +3 O2 3 HCN +6 H 2 O
1. (Maxwell, 2007) 2. (Gail et al., 2011) 3. (Brennan, 2012a) 4. (Pirie, 1958) 5. (Owen and Parekh, 1998) 6.
(Mendivil, 2003) 7. (Mattmann et al., 2002) 8. (Stanford Research Institute International, 2000) 9. (Midwest
Research Institute, 1993) 10. (McKetta, 1987) 11. (Ponton, 1998) 12. (The Lummus Company, 1961)

7.2.4 Typical reactor configurations for BMA and Andrussow Processes

Figure 5 BMA (left) and


(Brennan, 2012a)

Andrussow

(right) reactor geometries

7.3 Quenching

Figure 6 Temperature decay curves at typical


quenching conditions (Pylilo, 2012)
7.3.1 Temperature decay correlations for typical quenching

7.3.2 Quencher diagrams

Figure 7 Typical quenching processes (top) (Pylilo, 2012)and heat


exchanger transfer line (bottom) (Moulijn et al., 2013)

7.3.3 Further explanations on quenching


Quenching is essentially a type of heat exchanger under the category of direct
contact. The difference between a normal heat exchanger and a quencher comes
down to the time in which cooling is done. Cooling mechanisms looked at can be
shell and tube, double, pipe, plate , agitated vessels and fired heaters (Coulson
and Richardson, 2005). However, majority of the usual heat exchanger types is
not considered for the range of cooling the HCN requires (Zoldak, 1989). The only
possible option is a shell and tube heat exchanger which in industry is referred to
as a waste heat boiler for the purposes of rapid cooling and heat recovery. Direct
contact is usually done through spray chambers or spray, plate and packed
columns and when the fluids are compatible and heavy fouling (Coulson and
Richardson, 2005). The design of the quencher is analogous to that for gas
absorption (Coulson and Richardson, 2005). Heat pipes is an emerging form of
quenching but lacks industrial application (Reay et al., 2013)
7.3.4 Further explanations on types of quenching
Direct water cooling can be advantageous over indirect boilers such as bayonet
heat exchangers or a WHB because of the lower capital costs, operational costs
and maintenance requirements (Mular et al., 2002, Sundstrom and DeMichiell,
1971, Cross and Hesketh, 1995). Direct contact requires lower quality water feed
hence can be cheaper (Brennan and Hoadley, 2003). The offset from steam
generation is what makes WHB viable in most situations (Brennan, 2012a),
however BMA has a lower volume product gas hence makes this benefit less
attractive (Seddon, 2006).
WHB recover 60-70%(Santoleri et al., 2000) of heat and H 2 can be burned to
provide heating for feed streams. If excessive dilution takes place separation will
be more difficult than the WHB (Pylilo, 2012), however this dilution might be
beneficial downstream as the BMA process produce a more concentrated product
stream (Brennan, 2012a). Dilution results in 10% top up required as some of the
water saturates the product stream gas (Santoleri et al., 2000, Brennan and
Hoadley, 2003) See table 3.2.2.
Spray towers can handle fouling fluids however needs replacing every 6 months
due to water impurities while a WHB can potentially operate for 2 years before

needing to be shut down (Caton et al., 2015) are prone to fouling since impurities
might cause plugging however it is better suited to handle heavy fouling fluids.
Direct Quenching is more efficient at cooling than WHB (Coulson and Richardson,
2005), runaway reactions are a risk in the quench operation (Green and Perry,
2007) hence the faster the temperature is reduced below 300 (Gail et al., 2011)
the safer the process.
Weightings were made on the basis of the above discussion. For clarification,
waste disposal and environment had the same scores because a spray tower
needs regular shutdowns but this can be avoided if the construction material can
handle fouling. A waste heat boiler needs BFW which requires extensive
processing to be of high quality so both options have drawbacks.
7.3.5 Quencher unit specifications
Table 14 Summary and selection of quencher unit (Cross and Hesketh,
1995, BCS_Inc, 2008, Brennan and Hoadley, 2003)
Type
Mass
Corrosi
Develo
Installati
Heat
Operation
Operat
Relative
transf
ve
ps a
on
Recove
and
or
Capital
er
Potenti
wet
Space
ry
Maintenance training
cost
al
plume
required
WHB
No
No*
No
Small
Yes
Moderate to
High
High2
high
HEX
No
No*
No
Moderate Minimal Moderate to
Low
Moderat
high
e
Quenc
Yes
Yes**
Yes1
Small
No
Moderate to
Low to
Moderat
her
high
modera
e
te
* minimum corrosion if temperatures are kept above dew point ** can be handled by design and
material of construction
1
can be handled by reheat 2 offset by payback from steam produced.

Table 15 Quench water requirements (Brennan and Hoadley, 2003)

NOTE:

Heat Required=252kJ /mol


Rough estimate:

MW of NaCN =49 g/mol

Moles=
Heat

1000
=20.41 moles of NaCN 1 kg
49

required
MJ
=25220.41=5143 kJ =5.1
NaCN required
kg
kg

7.3.6 Miscellaneous quencher data

Figure 8 PFD for Andrussow Process (IntratecSolutions)

Figure 9 Hydrogen cyanide processes global distribution


(Evonik)

7.4 Recycle & Waste Treatment


7.4.1 Ammonia Recovery Inventions
Table 16 Summary of various
Patent Topics &
Industry
Inventors
Technology
Process for the
Ion
separation of NH3
Exchange
from a gaseous
mixture
containing HCN
and NH3 (Miller,
1978)
Improved Process
Ammonia
Recovery
(Benderly, 2002)

Adsorption

ammonia recoveries from inventors


Process
Description
HNO3
use
of
ammonium nitrate,
NH4NO3 solution

ASD
system
is
introduced
(Adsorption,
Stripping
and
Dissociation)

It can effectively
separate ammonia from
HCN solution due to the
fact that nitric acid, HNH3
is volatile as to ensure
HCN is in acidic
environment to prevent
the formation of Azulmic
acid.
It is basically a process
of monitoring the Nickel
concentration as
polymerisation of HCN
could occur due to the

Process for the


production of
Hydrogen
Cyanide (Voigt et
al., 1982)

Ion
Exchange

Absorption
zeolite

by

Production of
Hydrogen
Cyanide
(Radke and
Kotheimer, 1955)

Adsorption

Silica
Gel
adsorbent

as

Method of
recovering
Ammonia
(Amakawa et al.,
2008)

Distillation

Distillation
Apparatus
made
with different alloys
content

Process for
Recovering
Ammonia
from a gaseous
mixture
containing
NH3 and HCN

Ion
Exchange

Absorption
Ammonium
Hydrogen
Phosphate

by

formation of NickelCyano complexes


through corrosion of
process equipment.
NH3 can be selectively
absorbed onto zeolites
through ion exchange,
and then flushed off with
reactor gases.
Some HCN would be
adsorbed initially but
ammonia would
preferred to be adsorbed
as reaction time goes
Desorption of ammonia
is quite rapid by passing
air through the heated
column
Distillation comes in
contact with solution
made with alloys of
molybdenum, nickel and
chromium
Production of nitrile as
side reaction
Formation of
Diammonium Hydrogen
Phosphate through the
ion exchange between
ammonia and
ammonium phosphate

Figure 10 Evolution of accumulated number of ammonia separation


patents (Mendivil et al., 2005)
7.4.2 Hydrogen Separation

Table 17 Comparison of hydrogen gas separation methods (Shenoy, 1980,


Nguyen, 2012, Phair and Badwal, 2006)
Technolog
y

Description

Advantages

Disadvantages

PSA

Molecular
adsorbing beds
adsorb non
hydrogen gas in
high pressure
condition
Utilise difference in
gas boiling point by
freezing gas
mixture
Supply enriched
gas mixture to one
side of membrane
to create potential
gradient for mass
transfer

High Purity of gas


Produced
Mature Technology
hence widely used

High Energy
Requirement for adsorbent
regeneration

Very high purity gases


can be achieved
Efficient for large gas
production
More cost-effective
Less energy needed

Very High Energy


Requirement for Refrigeration
High cost

Cryogenic
Distillatio
n
Membran
e

Cannot achieve high degree


of separation
Multiple stages are needed
Not very widely used as not
as developed

7.3.3 Toxicity Data

Figure 11 Median lethal dose toxicity measurement guideline based


on European Union (Towler and Sinnott, 2008b)

Table 18 Toxicity data for selected chemicals (Towler and Sinnott, 2008b)

Figure 12 Selected international


groundwater (Dzombak et al., 2006)

quality

guidelines

for

cyanide

in

Figure 13 Cyanide treatment technology summary (reference?)

Table 19 Selected international quality guidelines for cyanides in soil


(Dzombak et al., 2006)

7.4 HCN-NaCN Conversion


7.4.1 Hydrogen cyanide physiochemical data
7.4.1.1

Vapour pressure data

Table
20
HCN
liquid
least-squares
parameters
to
fit
Ln(P(torr))=A+B/T+CT 2 (Appleton and Van Hook, 1982)
No.
Temperat
b
of
Ref
ure range (RMS
A
B
C
point
K
Error)
s
17.9932
7 x 10-3389.16
2
7
259-294
0.063
3
17.3
20.1987
3 x 10-3687.25
-4.1067 x 10-3
3c
10
260-299
0.109
4
15.2
(0.19 x 10-3)
Prese
19.7777
-3624.28
-3.4169 x 10-3
1.1 x
nt
40
260-297

0.239
10-3
33.1
(0.43 x 10-3)
Work
Table 21 Vapour pressure of HCN Ln P=C1+C2+C3LnT+C4T C5 in Pa (Green
and Perry, 2007)
CAS
C1
C2
C3
C4
C5 Temperatur
Pressure at
No.
e range
temperature
K
range
Pa
74-90- 36.7 38948 x 10- 6
259.83
2.95E+4
8
5
3927.
2.1245 17
456.65
5.35E+6
1
7.4.1.2

Henrys Law Constants

Table 22 Single temperature or unspecified temperature values for K H for


HCN (Ma et al., 2010)
KH,
t, oC
pHCN, ppmv
Reference
Comments
M/atm
13.3
18
138 000
8
Based
on
the
lowest
concentration data in this
tabulation
9.3
25
197 000
9
Value
extrapolated
from
above data
8.8-9.6
10
Secondary compilation, no
sources are cited
7.5
11
Stated
to
be
effective
constant at pH 4, no sources
cited
8.7
25
100
12
Value
given
in
atm/mol
fraction,
extrapolated
to
infinite dilution
8.2-8.8
25
100
12,13
As for previous entry, data
from (12), interpreted by

8.8

150

13

8.4-9.8

2190-4150

13

10.511.6

2020-3030

13

13.7

12

25

15

12.2

20

2-40

16

12.8
9.4

25
-

318-376
-

17
18

11.9
7.6

30
25

825
21

19
20

authors of (13)
As for previous entry, this
paper has different values in a
table than in text, tabulated
values are given here; this
result is for a pure cyanide
solution
As for previous entry, results
for
a
cyanide
bearing
synthetic leaching solution
As for previous entry, results
for a cyanide based actual
zinc leaching solution
Ref1 cites this as from ref14,
we were unable to locate this
in ref 14.
Secondary
source,
cites
Edwards et al. (1978) that
contains no primary data
Electronically published MS
thesis
Review, primary source not
given
As interpreted in (16)
Static
measurement
of
headspace by GC. Author
suggests
that
static
techniques produce lower KH
values

Table 23 Temperature dependence of KH values of HCN as reported in


literature (Ma et al., 2010)
KH, M/atm
t, oC
pHCN,
Referenc
Comments
ppmv
e
7.5
64
19 750
21
Most
previous
treatments assume that
ref
21
has
also
measured results at
18C. In fact, these
authors merely take
that datum from the
International
Critical
Tables8, based on their
three
experimental
temperatures we derive
the following linear eq:
ln(KH(M/atm))= (6023.6

(682.9)/T-15.817

(1.922,
3.0

85.5

49 380

21

r2 =0.9873
r2 drops to 0.8362 if KH
value of 13.3 at 18 oC is

added to these three


points
1.3

ln ( K H ( M/atm ) )

100
20-95

113 960
8400-64
600

21
22

7.7897 ) 0.11
( 2931.0
T

ln ( K H ( M/atm ) )

10-70
10-140

25

49068.8
1446.005
T

Primary data not given


t=20-95
range
was
studied for C=0.01-0.5
M to estimate range of
gas concentration
Conservatively
assumed 0.5 M at 20 oC
and 0.01 M at 95 oC
No primary data, cited
as
peronal
communication

+241.82 ln (T )0.315014 T
ln ( K H ( M/atm ) )

14.38

0.8-36

(Ma et 24 Measurements used


al., 2010) in triplicate

8205.7 341.9
T

( 25.323 1.144 )
2

r =0.9914

7.4.1.3
Dissociation constant of HCN and CN- (Ma et al., 2010)
Dissociation constant allows for the concentration of undissociated HCN to be
computed.

109.24

K D=
exp

1
(( HR )( T1 298.15
))
r 298

H r 298 =135.1 kJ/mol

C N

10 pH C N

+ K
pH
10 C N

[ HCN ] =

, mM
CN

pH =0.125

CN =

1.5

1.83 10 ( DT )

I2
1

0.5

1+50.3 ( DT )

a I2

log
T Absolute Temp

DDielectric constant of water at

I Ionic Strength

aMean distanceangstroms=3.5 A
7.4.1.4

Hydrogen cyanide flammability data and important temperatures

Table 24 Flammability limits, important temperatures and heats of phase


change for hydrogen cyanide (Green and Perry, 2007)
LFL
LFL UFL
UFL
Flash point Flash point Auto ignition
Auto
o
ratin
rating
C
rating
Temperature
ignition
o
g
C
rating
6.00
11 41.00
11
-18.00
6
537.85
11
Melting point Heat of fusion Boiling point at 1 atm
Heat of vaporisation
C
cal/mol
C
cal/mol
-13.2
2009
25.7
6027
7.4.2 Hydrogen cyanide physiochemical data
7.4.2.1
Chemical reactions (Pesce, 2000)
Thermal Decomposition occurs from 600-1050oC in He and from 10501225oC in N2
The pH of a solution of NaCN should maintained above 9 to avoid
formation of nitrogen trichloride
At lower pH aqueous solutions react with chlorine to form cyanogen
chloride
Solutions are slightly hydrolysed at room temperature according to the
following
NaCN + H2O

NaOH + HCN

Above 50oC an aqueous solution of NaCN will undergo irreversible


hydrolysis,
NaCN + 2H2O
o

NH + HCOONa
3

If heat of reaction is not removed the increased temperature


accelerates the decomposition and can create high pressure in a
closed vessel (reference the other stuff)

In presence of a trace of iron or nickel oxide, rapid oxidation occurs when


cyanide is heated in air,
2NaCN + O2

+ 2NaCNO

2NaCNO + 1.5 O2
7.4.2.2

Na CO + N2 + CO
2
3
2

Sodium cyanide physical data

Table 25 Physical properties of NaCN


Property
Value
Molecular Weight (g/Mol)
49.015
562
Melting Point (oC)
561.7 (98 wt %)
563.7
1530
Boiling Point (oC)
1500 10oC
1496
10% NaCN 1.047
20% NaCN 1098
Density of Solutions (g/mL)
30% NaCN 1.15
at 25oC
Vapour Pressure (kPa)
Heat Capacity, (J/gK)

800oC 0.1013
1360oC 41.8
298.15-345.15K 1.4
273.1K 1.667
288K 1.7950
298.6K 1.402
179

Heat of Fusion J/g


Heat of Formation (J/mol)
Hform
Heat of Vaporization (J/g)
Hvap,
Heat of Solution (J/mol)
200 mol H2O, Hsoln,
Hydrolysis Constant
Kh, 25oC
Appearance
Odour
Odour Threshold
Reaction with H2O
Viscosity
Index of Refraction
Solubility
Specific Heat Capacity

314
-89.9 x 103
3041

References
(Pesce, 2000)
(Pesce, 2000, Gail et
al., 2011, Green and
Perry, 2007)

(Pesce, 2000)

(Pesce, 2000, Gail et


al., 2011)

(Pesce, 2000, Gail et


al., 2011)
(Pesce, 2000)
(Pesce, 2000, Gail et
al., 2011)

3185
-1547
2.51 x 10-5
White, Granular or
crystalline Solid
Faint, almond-like odor
0.2-5 ppm as HCN
Sinks and mixes
4 cP
1.452
10oC 480000 ppm
35oC 820000 ppm

(Pesce, 2000)

(Fingas, 2001)

7.4.2.3

NaCN/NaOH solubility chart

Figure 14 NaCN/NaOH solubility chart (Aigueperse and


Guerin, 1966)
7.4.2.4

NaCN/NaOH/H2O isotherms (Oliver and Johnsen, 1954)

Figure 15 NaCN-NaOH-H 2 O 25C system

Figure 16 NaCN-NaOH-H 2 O 35C system

Figure 17 NaCN-NaOH-H 2 O 55C system

7.4.3 Existing patent literature


Table 26 Summary of existing patent literature of ?
Inventor, Year
Relevant Industry
Absorber
Technology

Notes

Fareid (2012)

Cyanide Production

Direct

Neutralization
Absorption Column

Allison et al.
(2014)

Deckers et al.
(2006)

Cyanide Production

Cyanide Production

Rogers and
Green (2005)

Cyanide Production

Thorpe and

Hydrometallurgical

Direct
Neutralization
CSTR Reactor

Direct
Neutralisation

Absorption Column

Direct
Neutralisation

Absorption Column
Ion
Exchange

HCN is passed through cold water absorber initially, with free


off gases being used for fuel
CO present in HCN feed is managed by catalytic conversion of
NH3 + H2 into HNCO, to prevent Na2CO3 formation in
neutralization
HCN gas is directly contacted
Contacting impure HCN gas with NaOH
Management of polymerization due to CO2 content by
controlling residence time in CSTR reactor
Ideal contacting times, temperatures and pressures discussed
Expected feed conditions also discussed
Flowsheet detailed
Bench scale tests detailed
Treatment of HCN gas from dehydration of formamide
Production of up to 98% pure cyanide salts
Details of NaOH concentration and the feed stream conditions
are given
Regular monitoring of hydroxide levels during absorption is
considered ideal
Comparison to existing methods for treatment of HCN from
dehydration of formamide is given
Bench scale tests detailed
NaOH should be kept in excess to prevent polymerisation and
decomposition of NaCN and HCN
Bench scale tests detailed
IX applied to CN-


Fleming (2005)

waste CN- recovery

Strong Base Anion

Dreisinger
(2001)

Hydrometallurgical
waste CN- recovery

Solvent Extraction

Ray and
Rajchel (2001)

Cyanide Production

Ion
Exchange

Anion and Cation

Simulated Moving

Bed

Day et al.
(2000)

Cyanide Production

Direct
Neutralization

Absorber Column

Patent is for the production of Ca(CN)2, which occurs via


contacting with Ca(OH)2
Provides detailed information on the IX behaviour of multiple
resins and elution solutions with CN- in various states
Bench scale tests detailed
PFDs given
Cyanide recovery in gold industry can occur through the AVR,
SART and MNR process
Requires the use of NaOH solution for the strip
List of possible commercial solvents given, mostly
organophosphorous compounds
Issue of effect of ammonia in feed not addressed
Bench scale tests detailed
PFDs detailed
Discusses the use of both Anion or Cation Ion Exchangers, in a
one or two step process
NaCl is used as eluant
Can result in the production of CuCl 2 as a useful by product
Anion Exchangers are the preferred IX technology
Expected feed conditions not detailed, leaves many things
broad
Bench scale testing is detailed
PFDs detailed
Market share of NaCN production
o DuPont: 25% of NaCN
o Degussa: 20% of NaCN
o ICI: 15% NaCN
Most producers contact pure HCN with pure NaOH, important
to ensure the purity of both
Transportation of NaCN in concentrated solution form reduces
crystallization expense and but increases transportation costs
Bench scale testing is detailed

Hecht et al.
(1990)

Cyanide Production

Direct
Neutralization
Absorber Column

Coltrinari
(1987)

Hydrometallurgical
waste CN- recovery

Crits (1981)

Hydrometallurgical
waste CN- recovery

Fries (1976)

Hydrometallurgical
waste CN- recovery

Friedrich et al.
(1971)

Cyanide Production

Ion
Exchange

Weak Base Anion


Packed Bed

Ion
Exchange

Anion
Packed Bed

Ion
Exchange

Anion and Cation

Packed Bed

Direct

Neutralization

Absorber Column

PFDs detailed
Gaseous HCN contacted with fine droplets of NaOH
Aim is to enhance crystallization of final product
Details ideal feed conditions, including the ideal feed ratios of
NaOH and HCN
Crystallization is enhanced by the injection of HCN into the
vessel via fluidized nozzles
Treatment of solution containing 10-2500 mg/L CN- in free or
complexed form
Ion Exchanging of complexed cyanide, not free cyanide
Elution with Ca(OH)2
Regeneration with H2SO4
Proposed feed conditions and resins are given
Contains proposed simplistic PFD
Flowsheet detailed
PFDs given
IX of weak CN- solutions, both complexed and free
Elution with NaCl
Details possible resins to be used
Resins can be regenerated by a weak alkaline solution, which
would be required anyway to prevent polymerization of the
final NaCN product
Minimal CN- in waste
Academic references supplied
Bench scale experiments detailed
CN- must be complexed with Cu before contacting
Bench scale tests are discussed
Suitable resins are detailed
Alkaline regeneration is required
Contacting of pure HCN gases with aqueous NaOH or KOH
Details feed stream conditions

Aigueperse and
Guerin (1966)

Cyanide Production

Direct
Neutralisation

Absorption Column

Byron (1959)

Cyanide Production

Oliver (1955)

Mcminn (1955)

Cyanide Production

Cyanide Production

Direct

Neutralisation

Absorption Column

Direct

Neutralisation

Absorption Column

Provides PFD
Reacting with 30-35% NaOH until free OH has been lowered to
0.3-0.1% to prevent polymerization
NaCN solution of 28-33% produced
NaCN solubility table is provided
Production of 96% NaCN
HCN solution undergoes quick intermitant contacting with
solution of NaOH/NaCN, with NaOH being the minor proportion
NaCN, NaOH solution should remain between 50 oC and 35 oC
as to prevent the polymerization and hydration of NaCN
respectively
NACN solution should contain at least 0.2 % w/w NaOH so that
it remains stable
Neutralisation can occur in multiple steps, 2 is considered
ideal
Contact between NaOH and polymerized HCN will result in a
violent reaction and a large increase in gas volume
PFD detailed
Contains several ternary phase diagrams for NaOH-NaCN-H 2O
Simplistic PFD
Production of anhydrous alkali metal cyanides
Feed flowrates and conditions discussed for neutralisation
States the neutralization reaction is slightly exothermic
Simplistic PFD

7.4.4 Ion Exchange Resins


Author
Goldblatt (1956)
Ning et al. (2013)
Silva et al. (2003)

Resin
Amberlite IRA-400
Metal Loaded Zeolites
Imac HP555s

Capacity

Adsorbed Ions

Eluate
1% H2SO4

CN

0.05 M H2SO4

Silva et al. (2003)


Say et al. (2004)

Amberlite IRA-420
Molecular Recognition

5.41 mg/L

CN
CN-

0.05 M H2SO4
NaOH

7.5 Storage

(I STOPPED EDITING HERE PAULINE)


Storage selection for specific fluids
Fluid
Temperature
Pressure
NH3
(liquid)

1 ] -33oC

1.1 bar

2] ambient

16-18bar

3] 0oC

3-5 bar

Material

Type

Comments

References

High strength steel

Double wall full containment is


preferred in a cylindrical insulated
tank with flat bottom and domed roof,
50,000t [1]

All

Brennan, lele, appl

Semi-refrigerated
sphere
or
cylindrical, 1500t [2] and 2500t [3]

insulated to avoid
radiated heating. Inert
gases
for
pressure
control.
Horizontal
pressurised tank is a
safety
hazard
if
leakages
occur.
Alternatives are difficult
to construct and more
expensive.

Stress corrosion cracking is


a problem in tanks,
0.2%
water
added
during transportation to
avoid it
HCN

5oC

atm

Steel
Monel
Hastelloy

Liquid phase and not corrosive

Would not usually store as it


goes straight to absorption.

Gail, peters

Recirculation is required
Water content < 3%

Steel is cheaper so
preferred

NaCN

ambient

atm

304/ 316 stainless


steel
Carbon steel if the
flow rate is below
1.2-1.5m/s

Prevent decomposition and


polymerization by addition
of
<0.5%
sulphuric/phosphoric acid
Liquid phase
Install a cooling coil and outside
insulation to avoid temperature
increases

Stable at ambient conditions


of use and storage. Avoid
contact with acids, CO2,
water and oxidising agents
e.g. aluminium
Avoid temperatures higher

Csbp ltd, taek

Ensure HCN detectors are available

than 38oC.
pH close to 12 to ensure
HCN is low
Add 0.4% free NaOH to
stabilise solution

NaOH

ambient

ambient

Stainless
steel.
Mild
and
soft
carbon steel and if
iron
content
important
need
epoxy or vinyl ester
liners
Plastics
specifications
followed

if
are

Liquid phase
Cylindrical tank is often used
Must be built on reinforced concrete
and placed in a bund or double
walled, note
NaOH corrodes concrete

Avoid moisture in the tank


and
NaOH
does
not
decompose or polymerise.
Below 45oC to avoid caustic
corrosion cracking
Avoid
contact
with
amphoteric metals (copper,
tin, brass), sugars, acid,
phosphorus, explosives as it
reacts hazardously
If stored outside must be
insulated,
the
freezing
temperature depends on the
concentration
i.e.
50%
freezes at 12oC electrical
tracing can be used

Csbp 2011, solvay

Section 3.3.1 Summary of NaCN Hazard Identification (CSBP_Ltd, 2014)


Sodium cyanide solution is specified as dangerous in the Australian Code for the Transport of
Dangerous Goods by Road and Rail (ADG Code), 7th Edition. Factors to consider:
NaCN solution is an asphyxiant, very toxic if inhaled, swallowed or contacted with
skin causing severe burns, drowsiness, dizziness, damage to eyes and respiratory
system. Death from central nervous system failure.

If contacted with acid toxic gas is liberated

Vapour pressure, check. Cooler temps crystalize

Fire or explosion event, never use CO2, fumes should not be breathed and water spray,
chemical powder, dry sand or foam should be used to extinguish it.

People should wear safety gear when handling NaCN, protective clothing covering
the face needs to be worn. First aid professionals needs to be available in case of
emergencies.

Accidental spill procedures need to be in place to avoid human and environmental


exposure.

Ensure absorbent stock material is on hand for emergencies, in spill situations sodium
or calcium hypochlorite is used, ensuring the free cyanide is less than 1ppm.

The solution itself is not considered combustible or at fire risk, however it generates
toxic flammable, corrosive and explosive HCN gas.

Cyanide impact on environment:


Fish and aquatic invertebrates are very sensitive to cyanide exposure, concentrations
of 30 to 200mg/L is fatal.

Birds and mammals exhibits the symptoms associated with human exposure. Birds
recover rapidly due to the conversion of cyanide to thiocyanate. It is not stored or
accumulated in any animal studied.

Aerobic conditions the microbial activity degrades cyanide ions in concentrations up


to 200ppm.

Migrated to ground water if exposed to water/soil. There is a lack of sunlight ad


oxygen to degrade it.

Storage requirements:
Tank needs to be sealed and situated in a well-ventilated area.

Away from populated areas such as control rooms.

Smoking is not allowed near the storage and handling of NaCN or any associated
equipment.

Storage must follow Australian Standard AS 4452 The storage and handling of toxic
substances and Dangerous Goods Safety Act 2004

Prolonged contact with air leads to HCN production resulting in an explosive mixture.
Its flammable between 5.4 to 46.6v/v%. The HCN concentration above the liquid
increases as the pH of solution decreases and the ambient temperature rises. At 30oC
HCN is 100-150ppm and at 40oC is 150-200ppm.

Stabilised by 0.4 wt/wt% of free NaOH in the solution to avoid acidification.

Store away from acids as toxic flammable HCN is released. Keep away from
chlorinating agents and note the NaCN is incompatible with oxidising agents such as
copper, zinc and aluminium

Should be handled within closed systems and the national exposure standard is
5mg/m3 as cyanide dust and 10ppm as HCN (ES-TWA exposure standard time
weighted average)

Extract 3.3.1a

Extract

3.3.1b

Extract 3.3.1c

3.3.1 Summary of NaOH 32% solution Hazard Identification (CSBP, 2011)


Sodium hydroxide is listed as dangerous in the Australian Code for the Transport of
Dangerous Goods by Road and Rail (ADG Code), 7th Edition, (FORS, 2007). Information
and factors to consider:
- Its corrosive, causes burns and is harmful to swallow
- Wear suitable clothing when handling

NaOH is not combustible but may produce explosive H2 when in contact with aluminium,
copper etc.
In fire hazards, dont use mono ammonium phosphate (fire extinguishers) as this liberates
NH3. Rather use foam or a dry agent, note that water can be used but a violent reaction
might occur.
Leaks can be managed with sand, or neutralisation with NaHCO3.
Instantaneous degradation in air, produces salts when neutralised in soil and will
contaminate groundwater if its raining.
Can be harmful to fish and plankton at 10-100mg/L mainly due to the shift in pH
Boils at 120oC 1 atmosphere, and crystallises at 2oC.

Storage:
- Smoking should not be permitted.
- Dilution, always add NaOH to water with agitation.
- National exposure standards is 2mg/m3 as NaOH (ES-TWA)
- Adequate ventilation is required when used and stored.
Figure X: Storage tanks and pollution reduction (Shonnard, 1999)

http://www.epa.gov/oppt/greenengineering/pubs/module_4_master.pdf
Table 3.3.x:
2007)
Substance

Technical information on dangerous goods (Government_of_WA,

AMMONIA,
ANHYDROUS
HYDROCHLORIC ACID
NATURAL
GAS,
COMPRESSED
with
high
methane
content
NATURAL
GAS,

UN No.
1005

Class
division
2.3

or

Sub risk

Packing Group

1789
1971

8
2.1

II/III
-

1972

2.1

REFRIGERATED
LIQUID
with
high
methane
content
(LNG)
SODIUM CYANIDE
1689
6.1
I
SODIUM HYDROXIDE, 1823
4.2
II
SOLID
SULFURIC ACID (with 1830
8
II
more than 51% acid)
Table 3.3.y : Quantities relating to classes of fluids from table
(Government_of_WA, 2007)

3.3.x

Division
Placarding quanityt
Manifest Quantity
2.1
500L
5000L
2.3
50L
500L
4.2
1000kg/L
10000 kg/L
Packing(
II)
6.1
50kg/L
500kg/L
Packing
(I)
8
1000 kg/L
10000 kg/L
Packing
(II/III)
Storage on plant must follow the Australian standards such as AS3780 for
corrosive substances, AS1940 for flammable and combustible liquids,
AS2022 for ammonia, AS 4332 fir gases in cylinders, AS4452 for toxic
substances (NaCN) and more research will be done during the design
phase of the project.

Licensing would need to be looked at if the plant stores more than the
manifest quantity on site.

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