Scat Porn
Scat Porn
Scat Porn
NaCN Production
Feasibility Study
Literature Review, Process Selection,
Mass and Energy Balances
Prepared by
Design Group 2
Chanel Bernardo 21131417
Callum Biggs 20498066
Wei Cui 21250612
Pauline Ho 21108549
Vincent Lim 20859448
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
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
Introduction
Literature Review
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).
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).
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
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
8
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).
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).
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
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.
10
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 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).
NH
( 4 )2 HPO4 ( s ) NH 3 ( g )+ NH 4 H 2 PO 4 (s)
11
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
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.
12
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)
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).
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
13
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
15
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).
16
No severe fouling
Good catalyst life
Proven processes design
Established market
Energy Efficiency
Safety
Product Quality
Maturity
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).
18
Safety
Adsorption
Product Quality
Adsorption
Maturity
Chemical absorption
Environmental
Sustainability
Membrane
Andrussow
19
Energy
Efficiency
Andrussow
Safety
BMA
Product
Quality
BMA
Maturity
Andrussow
Environment
al
Sustainabilit
y
BMA
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
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
Energy
Efficiency
Safety
WHB
ST
Product
Quality
ST
Maturity
Environmental
ST
Sustainability
WHB
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).
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
Reason
Energy
Efficiency
Fertiliser
Production
Safety
Fertiliser
Production
Product
Quality
Ion Exchange
Maturity
Fertiliser
Production
Environment
al
Sustainabilit
y
Ion Exchange
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).
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
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
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
23
24
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
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
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
2.5 10
in
natural
gas
CH4
N2
O2
0.1
50-55
1-2.4
0.5-1
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
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
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)
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
Shawinigan
3 N H 3 +C 3 H 8 3 HCN +7 H 2
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
HCN formation
C H 3 NO HCN +H 2 O
H=+75 kJ /mol
Methanol
Lower operating
temperatures in comparison
to Andrussow and BMA
SOHIO
Lower operating
N H 3+C H 3 OH + O2 HCN +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)
Andrussow
7.3 Quenching
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.
NOTE:
Moles=
Heat
1000
=20.41 moles of NaCN 1 kg
49
required
MJ
=25220.41=5143 kJ =5.1
NaCN required
kg
kg
Adsorption
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
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
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 Energy
Requirement for adsorbent
regeneration
Cryogenic
Distillatio
n
Membran
e
Table 18 Toxicity data for selected chemicals (Towler and Sinnott, 2008b)
quality
guidelines
for
cyanide
in
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
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
(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
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
+241.82 ln (T )0.315014 T
ln ( K H ( M/atm ) )
14.38
0.8-36
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
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
I Ionic Strength
aMean distanceangstroms=3.5 A
7.4.1.4
NaOH + HCN
NH + HCOONa
3
+ 2NaCNO
2NaCNO + 1.5 O2
7.4.2.2
Na CO + N2 + CO
2
3
2
800oC 0.1013
1360oC 41.8
298.15-345.15K 1.4
273.1K 1.667
288K 1.7950
298.6K 1.402
179
314
-89.9 x 103
3041
References
(Pesce, 2000)
(Pesce, 2000, Gail et
al., 2011, Green and
Perry, 2007)
(Pesce, 2000)
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
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
Fleming (2005)
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
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
Ion
Exchange
Anion
Packed Bed
Ion
Exchange
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
Resin
Amberlite IRA-400
Metal Loaded Zeolites
Imac HP555s
Capacity
Adsorbed Ions
Eluate
1% H2SO4
CN
0.05 M H2SO4
Amberlite IRA-420
Molecular Recognition
5.41 mg/L
CN
CN-
0.05 M H2SO4
NaOH
7.5 Storage
1 ] -33oC
1.1 bar
2] ambient
16-18bar
3] 0oC
3-5 bar
Material
Type
Comments
References
All
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.
5oC
atm
Steel
Monel
Hastelloy
Gail, peters
Recirculation is required
Water content < 3%
Steel is cheaper so
preferred
NaCN
ambient
atm
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
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.
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.
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.
Storage requirements:
Tank needs to be sealed and situated in a well-ventilated area.
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.
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
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
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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