Escolar Documentos
Profissional Documentos
Cultura Documentos
Sodium Chloride
Analysis of a full experimental cycle
Exam committee:
Dr. L Hartmann
K. Yasadi
Contents
Acknowledgement ........................................................................................................................................ 6
Abstract ......................................................................................................................................................... 7
Table of figures ............................................................................................................................................. 9
Nomenclature ............................................................................................................................................. 11
1.
2.
3.
4.
5.
Introduction ........................................................................................................................................ 13
1.1.
1.2.
1.3.
1.4.
1.5.
1.6.
2.2.
2.3.
2.4.
2.5.
3.2.
3.3.
Conclusion ................................................................................................................................... 37
4.2.
4.3.
4.4.
Conclusion ................................................................................................................................... 45
5.2.
5.3.
Mass balance............................................................................................................................... 49
4
5.4.
5.5.
5.6.
5.7.
5.8.
Conclusion ................................................................................................................................... 60
6.
6.2.
6.3.
6.4.
6.5.
6.6.
6.7.
Conclusion ................................................................................................................................... 72
7.
7.2.
7.3.
Conclusion ................................................................................................................................... 78
8.
Conclusion ........................................................................................................................................... 79
9.
Recommendations .............................................................................................................................. 81
Appendices.................................................................................................................................................. 82
A.
B.
C.
Bibliography ................................................................................................................................................ 87
Acknowledgement
The final project for obtaining a Master degree has fascinated me over the past 8 months ; it offered me
a wonderful opportunity to finalize my studies in Mechanical Engineering on a subject in Process and
Energy in Delft.
There are a number of people whose support I would like to acknowledge. First of all I have to thank
prof. dr. GJ Witkamp for giving me the opportunity to work on the subject of eutectic freezing. It was a
pleasure to work in his motivating department doing interesting research on this innovative subject.
Two post-doc researchers of the department kept constantly track of me and pushed me in the right
direction. Jaap van Spronsen helped me especially with the experiments and it was a pleasure to work
with him. He is really motivating and a passionate researcher who is always willing to help. Always
curious to the outcome and having an interesting view on not only the process industry but on live in
general. Furthermore, I want to thank Elif for the motivating meetings we had and her critical view on
my work. When I was struggling with the equipment in the skid Hans Evers was always willing to help
and his practical knowledge of all the equipment was valuable. I wish the EFC BV and researchers
involved good luck and wish all the best for the future of EFC becoming a commercial technology. Finally
I want to thank Dr. L Hartmann and K. Yasadi to contribute to my examination committee.
I would like to thank my family for all the support during my studies and their patience, despite it might
have taken a little longer than they had expected. Their support and especially some earnest but really
motivating speeches of my parents made me able to push myself step by step towards the end. When
subjects were not the way I wished they were and I started to throw my laptop out of the window, so I
couldnt study anymore, there was always a warm home with an abundance of distraction. This holds for
my house at the Oude Delft and my current living at the West. I want to thank all my friends for having
such a wonderful time and experiences together.
Abstract
The full experimental cycle of Eutectic Freeze Crystallization (EFC) for sodium chloride has been
investigated. EFC separates the solution into pure water and pure salt by cooling to the eutectic
temperature at which both ice and salt crystals are formed. By gravitational forces the salt and ice are
separated and after filtration and washing the pure products are obtained.
The aim of the research is to investigate the potential of EFC for sodium chloride solutions and to
develop an EFC process from lab scale to industrial scale. The following aspects are addressed in this
report:
Experiments were performed in the cooled disk column crystallizer (CDCC), a small scale crystallizer of
10 liter volume, as described in Chapter 3. Furthermore a large scale set-up built in a skid is used for the
experiments, which are described in Chapter 4 & 5. The most important components of the skid are a
200 liter volume scraped cooled wall crystallizer (SCWC), a settler to separate the ice and salt crystals
and two belt filters to filtrate and wash the products.
The following conclusions were made on the heat transfer on the scraped wall of the CDCC for a pure
solution and for a solution containing 1 wt% magnesium:
The eutectic temperature for a pure NaCl solution in the experiments is found to be -21.1 C
which corresponds to the theoretical value.
High temperature difference between coolant and solution (TLM) resulted in scaling on the heat
exchanger wall, which took place in a larger extent for a pure solution. This was observed by
increasing scraper noise, increasing scraper torque and a decreasing heat transfer coefficient at
increasing TLM.
The presence of magnesium resulted in up to 24% higher heat transfer at a TLM of 7C, which is
found to be 5.5 kW/m2. The same heat transfer was achieved for the pure NaCl solution at a
much higher TLM of 10C.
The same experiments were also performed with the CDCC for a pure solution and for a solution
containing 0.5 wt% magnesium.
The heat transfer coefficient in the absence of scaling is approximately 0.8 for the lower heat
exchanger and 0.6 kW/m2/K for the upper heat exchanger. The difference is caused by the flow
regime in the crystallizer.
The theoretical heat transfer coefficient calculated in Chapter 2 is 0.71 kW/m2/K. So the
average heat transfer measured in the upper and lower heat exchanger corresponds well with
the theoretical value.
A maximum heat transfer of 8 kW/m2 has been attained at a temperature difference of 12C for
a solution containing magnesium.
At a TLM of 8C the heat transfer in the presence of Magnesium is 30% higher than for the pure
solution.
7
During five hours of continuous operation of the skid 70 kg of filtrated ice and 18 kg of the anhydrate of
sodium chloride have been produced. These products have been washed on experimental scale and all
contaminants are perfectly washed from the crystals, so no contaminants are encapsulated in the
crystals. Considering mass- and energy balances resulted in the following conclusions:
The efficiency of the crystallizer and settler together is 59%, the remaining is heat loss.
42% of the ice produced was melted on the belt filter.
For continuous operation without washing 395 kWh per m3 feed was extracted in the crystallizer
by the coolant. Using a 2-step refrigeration cycle to extract this heat 132 kWh/m3 feed would be
required.
A number of possible improvements for continuous operation of the skid have been proposed in
Chapter 6, i.e. improved process for filtration and washing, CO2 as refrigerant and the use of different
materials for the heat exchanger surface. Based on an optimized process without heat losses and
ignoring energy requirements for pumps, the salt belt filter and scraper motor 51 kWh per m 3 of feed
solution is required. Highly optimized multi stage evaporative crystallizers typically operate with an
energy consumption of 40-50 kWh per m3 of feed solution. Optimization of the EFC process might result
in a similar or even lower energy requirement than evaporative techniques require, depending on
process specifications.
Table of figures
Figure 1-1; Eutectic phase diagram of salt in water ................................................................................... 14
Figure 1-2; Phase diagram NaCl solution .................................................................................................... 16
Figure 1-3; Separation method as a function of amount of total dissolved solids, courtesy Shell ............ 17
Figure 1-4; Photo of the CDCC .................................................................................................................... 18
Figure 1-5; P&I diagram CDCC..................................................................................................................... 19
Figure 1-6; Photo of the skid mounted unit................................................................................................ 20
Figure 1-7; Process flow diagram skid mounted unit ................................................................................. 21
Figure 1-8; 200L crystallizer in skid ............................................................................................................. 22
Figure 1-9; Heat exchangers in the 200 liter crystallizer in 3d view and top view ..................................... 22
Figure 2-1; Schematic representation of heat transfer in HEX ................................................................... 25
Figure 2-2; Top view of the flow channels in outer HEX of 200L unit......................................................... 27
Figure 3-1; Scaling in CDCC by Rodriguez ................................................................................................... 33
Figure 3-2; Results CDCC pure NaCl experiment ........................................................................................ 34
Figure 3-3; Torque vs heat transfer coefficient at constant TLM............................................................... 35
Figure 3-4; Torque increase over time vs temperature difference (values calculated in Table) ................ 35
Figure 3-5; Power vs TLM for two different solutions................................................................................ 36
Figure 4-1; Heat transfer pure NaCl in SCWC ............................................................................................. 39
Figure 4-2; Heat transfer NaCl + Mg in SCWC ............................................................................................. 40
Figure 4-3; Heat transfer in the SCWC for a pure solution and for Magnesium added ............................. 41
Figure 4-4; Effect of solid particles on the heat transfer ............................................................................ 42
Figure 4-5; Heat transfer coefficient under static conditions ..................................................................... 43
Figure 4-6; Heat transfer coefficient under stirring conditions .................................................................. 43
Figure 4-7; Corrosion in 200L crystallizer .................................................................................................... 44
Figure 5-1; Simplified flow diagram skid ..................................................................................................... 46
Figure 5-2; Experimental filtration & washing set-up................................................................................. 48
Figure 5-3; Microscopic photo's of salt- (left) and ice crystals (right) ........................................................ 49
Figure 5-4; Production of filtrated ice and salt vs time .............................................................................. 50
Figure 5-5; Mass balance continuous operation ........................................................................................ 50
Figure 5-7; Flow scheme settler (ideal situation) ....................................................................................... 51
Figure 5-6; Top view in the settler (non ideal situation)............................................................................. 51
Figure 5-8; Heat losses from crystallizer to surroundings .......................................................................... 52
Figure 5-9; Mass balance ice filtration ........................................................................................................ 53
Figure 5-10; Contaminant concentration in ice after washing ................................................................... 54
Figure 5-12; Mass balance salt filtration..................................................................................................... 55
Figure 5-11; Photo of the salt belt filter ..................................................................................................... 55
Figure 5-13; Contaminant concentration in salt after washing .................................................................. 56
Figure 5-14; Energy balance crystallizer and settler: In formula and schematically .................................. 57
Figure 5-15; Pie of the energy flows in the crystallizer and settler ............................................................ 57
Figure 5-16; Overview mass- & energy flows continuous operation.......................................................... 58
Figure 6-1; Heat recovery in EFC by means of a 2-step refrigeration unit ................................................. 61
9
Figure 6-2; COP for 2-step refrigeration cooling according to van Ham [VI] .............................................. 62
Figure 6-3; Heat transfer coefficient vs vapor fraction for evaporative CO2 refrigeration......................... 65
Figure 6-4; Conceptual filtration, recrystallization & washing of the salt .................................................. 67
Figure 6-5; Scheme countercurrent washing of ice .................................................................................... 69
Figure 6-6; Wash column to purify ice ........................................................................................................ 70
Figure 6-7; Flow scheme of a theoretical ideal operation .......................................................................... 71
Figure 7-1; Visualization of the water supply system ................................................................................. 74
Figure 7-2; Electricity consumption different water treatment processes ................................................ 74
Figure 7-3; Schematic representation of evaporative crystallizer by GE .................................................... 77
Figure 7-4; Schematics of evaporative crystallization ................................................................................ 78
10
Nomenclature
List of symbols
11
List of subscripts
List of abbreviations
12
1. Introduction
In many parts of the world fresh water has become a product, which is available in large amounts at a
low price and for that reason a lot of water is wasted. In other parts of the world water is a scarce
resource particularly in desert areas leading to poverty and conflict. In the next decades, increased
water consumption and a decreasing amount of fresh water resources will result in a water scarcity
problem. In 2025, approximately one third of the world population will suffer from a water stress
situation according to Unesco [XIX]. This expected scarcity can be prevented by people awareness and
technological innovation.
Access to fresh water is crucial for industry, agriculture and for domestic use. The characteristic
properties of water makes it a unique substance, e.g. fresh water is crucial for life, for the chemical
industry since it dissolves many chemical components, for cooling/heating using its relatively high heat
capacity. The demand for water differs in quality and quantity for every specific application. Therefore
fit-for-purpose technology solutions will need to be developed in order to re-use/recycle water or to
generate it from external waste streams providing the right quality and quantity.
Sodium chloride (NaCl) is a valuable product which is found in many water streams. The ocean contains
approximately 4%; it is often dissolved in ground waters, it is present in many industrial water streams,
from which it is separated or disposed. The product finds its purpose in food (table salt is mainly NaCl),
de-icing of roads, manufacturing processes (e.g. paper industry) and chemical industry.
The NaCl can easily and at relatively low cost be removed from water by reverse osmosis (RO). RO only
works for low concentration streams. The high concentrates (brines) are often disposed in the
environment or more costly methods, such as evaporative techniques, are used to obtain the pure
products (water and NaCl) from the brine. Eutectic Freeze crystallization might be a good alternative for
disposing the brine or treating with evaporative crystallization techniques. EFC is being considered now
in horticulture, treatment of water from oil production (Kuwait) and from shale gas.
13
In 1983 Swenne studied Eutectic Freeze Crystallization on Sodium Chloride. Direct cooling was used by
injecting R-114 direct in the crystallizer, or using butane as a refrigerant. Direct injection cooling was
considered to be more economic, but involves contaminants in the product which are difficult to
separate. In the late 1990s vd Ham and Witkamp started their research for EFC by means of indirect
cooling. Applicability was proven for a couple of solutions of waste water streams or other industrial
process streams. In 1998 Vaessen developed two EFC crystallizers with a volume of 100 liters. These
were the continuous disk column crystallizer (CDCC) and the scraped cooled wall crystallizer (SCWC).
Next to indirect cooling, Vaessen also researched direct cooling by using CO2 clathrates, which involves a
higher eutectic temperature. Himawan (2002) studied and modeled EFC based on magnesium sulphate
14
solutions. Elif Genceli (2008) studied up scaling of EFC and did further studies on the crystallization of a
MgSO4 solution. Jaap van Spronsen (2010) showed that EFC can be used as a method to separate a
waste stream into pure water, a concentrated Molybdate solution and soda.
Indirect cooling prevents contact of the refrigerant to the solution, but uses a heat exchanger surface
instead. The disadvantage of a cooled wall heat exchanger is the scaling of both ice and salt crystals on
the wall. These scaling can be removed by scrapers over the surface. Besides the removal of the scaling,
the scrapers also prevent scaling by creating a turbulent flow and improving heat transfer from the wall.
Van Der Ham and Witkamp developed an EFC process using indirect cooling.
A start-up company initialized by the TU Delft is commercializing EFC technology. In cooperation with
several companies in horticultural, oil- and other (process) industries the technique is being adapted for
industrial use.
15
Table salt is refined salt, which contains about 97% to 99% sodium chloride. Furthermore some anti
caking agents are added and sometimes rice to absorb residual water and water vapour. It is expected
that successful EFC can produce table salt quality. This quality has a high market price.
Figure 1-2 shows the phase diagram of NaCl in water. The eutectic point is reached at a temperature of 21.1 C and a salt concentration of 23.3%. Compared to other salts, the eutectic temperature is low. This
is a disadvantage, because an increased cooling power is required for the operation. Another important
property is that the crystal formed at the eutectic point is a dihydrate, which is a crystal with the
chemical formulae NaCl.2H2O. As shown in the diagram the recrystallization to the anhydrate (NaCl
without H2O molecules) takes place at 0.1C. For this reason the produced salt has to be heated and
dried to obtain the pure NaCl. Another important property from the diagram is the steepness of the
solubility line, which means that the saturation concentration is almost independent of the
temperature. This property might involve difficulties in filtration and washing of the produced ice.
Reverse osmosis (RO) is the most commonly used method for desalination of water; a typical example is
seawater desalination. By pressurizing the feed through a membrane clean water is obtained at
16
relatively low energy requirements (overcome the osmotic pressure of NaCl). A residual highly
concentrated stream is a byproduct and usually disposed. RO only works effectively for low
concentrated brine solutions, because high concentrates involves scaling on the membrane. Figure 1-3
shows common separation techniques as a function of the amount of total dissolved solids. EFC is
shown at the right for treating highly concentrated solutions, for example the residual from RO.
Evaporative and crystallization techniques are shown for the same concentrations and are the main
competitors for EFC.
Figure 1-3; Separation method as a function of amount of total dissolved solids, courtesy Shell
17
kinematic viscosity
1.36kg / dm3
0.45W / (m.K )
density
thermal conductivity
Figure 1-5 shows the P&I diagram of the CDCC. The unit can be used for both continuous as batch
operation. In this thesis only batch experiments have been performed with the unit. For that reason the
instruments used for continuous operation are grey in the figure. All the tubes and the cold components
are insulated. The insulation was removed for the photo of Figure 1-4.
18
The temperatures of the coolant at the inlet and the outlet of the heat exchanger and the temperature
at different places in the crystallizer are continuously measured and saved every 30 seconds using
labview software. The thermometer is an ASL F250 precision unit connected to PT-100 temperature
sensors with an accuracy of +/- .01C. The flow rate of the coolant is measured with a Rosemount Eseries magnetic flow meter with an accuracy of +/- 1 liters/hour.
M
Pi-001
Pt-001
Tqt001
Tqi001
Ft-002
Fi-002
Ti-010
Ti-001
Tt-001
Ti-002
Tt-002
Tt-010
Coolant cycle
Tt-009
Ft-003
Ti-009
Ti-005
Tt-005
Fi-001
Ft-001
Pt-003
Pt-002
Pi-002
Tt-004
Tt-003
Ti-004
Ti-003
Pi-003
Fi-003
19
A simplified representation of the equipment is shown in Figure 1-7. All pumps, measurement
equipment and components that were not used in the experiments are excluded for simplification. A
storage tank in the left is used as a buffer for the feed solution. A pre-cooler is installed to cool the feed
towards the eutectic temperature before entering the crystallizer. Due to high capacity of the precooler, part of the pre cooled solution is sent back to storage tank. Two heat exchangers are installed on
top of each other through which freezium (as described in paragraph 1.3) flows as represented by the
blue lines. A rotating scraper is driven by an electrical motor on top of the crystallizer. Due to the
turbulent flow in the crystallizer, a slurry containing both ice and salt crystals, leaves on top towards the
settler. In the (almost stagnant) settler, the ice crystals are floating and leave the settler on top towards
the belt filter.
On the belt filter, the ice is filtrated and dry ice is produced. From the bottom of the crystallizer and the
settler, salt slurry is directed towards the belt filter for the filtration and recrystallization of the NaCl. A
vacuum pump creates a low pressure under the belt and sucks the liquid through it. The size of the
pores in the belt has to be chosen such that the crystals are unable to penetrate nor obstruct passage of
liquid. The mother liquid is captured and circulated to the crystallization process. After filtration, the
crystals can be washed in a couple of steps on the belt filter. This thesis did not study the washing on the
belt filters, but only researched small scale washing on experimental scale.
20
Watson-Marlow Peristaltic pumps are used for controlled transport. These pumps are chosen, because
they are able to pump the slurries with solid content. All flow speeds and temperatures are measured
and every 125 seconds saved and monitored by Labview software. This also holds for the torque on the
scraper motor as well as the rotational speed.
Filtrate
M
Ice
slurry
Ice
Settler
Brine storage Pre-Cooler
Cooling machine
NaCl
Salt slurry
Filtrate
The flow rates are measured by magnetic flow transmitters manufactured by Rosemount Fisher with an
accuracy of +/-0.25. The temperatures are measured by PT-100 probes connected to a controlled ASL
F250 precisions thermometer with an accuracy of +/-0.02 and a resolution of +/- 0.001 C. Control of the
pumps and acquisition of the data was done with a computer running on Labview.
The skid mounted unit has a crystallizer with a 200 liter volume, which is also known as the scraped
cooled wall crystallizer (SCWC). In the CDCC, described in section 1.3, the bottom of the crystallizer is
cooled and extracts heat from the solution. In the 200 liter SCWC the heat exchangers are mounted
vertically in the crystallizer as shown in Figure 1-8, two heat exchangers are mounted on top of each
other on the left drawing. The picture in the right bottom shows the heat exchanger surface with the
white scraper clearly visible. The drawing in the top right shows the geometry of the scraper blades. The
heat exchanger surface is a steady / non rotating part. The scraper motor drives a shaft through the
center of the column. The scrapers are mounted to the shaft and rotate over the heat exchanger
surface. Each heat exchanger has two sides which both exchange heat and are both scraped. In the left
of Figure 1-9 the mounted scrapers over the surface are clearly shown. As visible, inside of the heat
exchanger surface another heat exchanger is installed. So a total of four heat exchangers are mounted
21
inside the column. The two inner heat exchangers were not used during the experiments, because the
accompanying flow meters were malfunctioning.
The column is insulated, which is not shown in the figures. An observation window is kept open to keep
vision on the solution. On a couple of locations at different heights in the crystallizer the temperature is
measured. Also flow rates and temperatures of the coolant are constantly measured and each 25
seconds saved by Labview.
The dimensions of the heat exchangers are important for determining the performance. The total heat
exchanger area for the outer heat exchangers is calculated by Eq. 1-1.
A h *( D 0.5* t )* h *( D 0.5* t )*
A 0.105*(0.45 0.5*0.030)* 0.105*(0.45 0.5*0.030)* 0.297m2
Figure 1-9; Heat exchangers in the 200 liter crystallizer in 3d view and top view
22
Eq. 1-1
1.5.EFRO project
One of the motivations of this study is the research of treating a waste stream from horticulture with
EFC. This Paragraph describes the problem in horticulture dealing with brines and in Chapter 8 it will be
concluded whether EFC is a possible solution.
Since a couple of years a cooperation between EFC BV and EFRO is investigating the treatment of a
waste stream from horticulture. EFRO (Europees Fonds voor Regionale Ontwikkeling) is a European fund
for regional development which supports EFC to find a solution for treating brine streams. Horticulture
companies from the Westland in the Netherlands obtain water from ground waters. This contaminated
water is treated with reverse osmosis to obtain fresh water for the irrigation of plants. A concentrated
brine is the by product, which is generally discharged into the environment, thereby also valuable
components are lost. Environmental issues make the disposal of the brine undesirable. The aim of the
EFRO project is to investigate the possibility to treat the brine and extract the valuable components,
resulting in a zero liquid discharge.
Table 1-2; Sample of EFRO solution from Tunk [XXI]
The waste product of the horticulture is shown in Table 1-2. The salt percentage is still very low and can
be further treated by reverse osmosis (RO). RO is a filtration method in which the large molecules are
filtrated when a solution is pressurized through the membrane. A relatively cheap separation technique,
but limited by the concentration of the solution. A too high concentration results in scaling of the solid
particles on the membrane. For that reason high recovery reverse osmosis will be combined with EFC,
resulting in a zero liquid discharge solution. The RO unit will separate the solution of Table 1-2 into a
pure water stream and more concentrated brine as presented by Table 1-3, which are the
concentrations of Table 1-2 multiplied with 4.34 to obtain a 5 wt% NaCl solution. The brine will be
further treated with EFC. This research will answer whether this brine stream can be treated with EFC
and an energy evaluation is given of EFC treatment of the brine.
Table 1-3; EFRO solution concentrated by reverse osmosis
23
Heat transfer in the heat exchangers of the crystallizer and the influence of contaminants. This is
theoretically evaluated in Chapter 2, small scale experiments are described in Chapter 3 and
large scale experiments in Chapter 4.
Washing and filtration of the products (Chapter 5).
Continuous industrial operation with the skid and evaluation of the energy and mass balances
(Chapter 5).
Optimization of the process for full scale industrial operation (Chapter 6).
Comparison with evaporative crystallization and an environmental analysis (Chapter 7).
24
Q
UOVERALL * TLM
A
TLM
kstainless steel
twall
solution
coolant
UCOOL
Eq. 2-1
TLM
TCOOL OUT
T(C)
TEUT
TCOOL
T
TCOOL. IN
COOL.OUT
T T
ln( SOL COOL. IN )
TSOL TCOOL.OUT
Eq. 2-2
TCOOL IN
The heat transfer is divided in three parts as schematically represented
in Figure 2-1. In the coolant and in the solution the heat transfer is Figure 2-1; Schematic representation of
heat transfer in HEX
convective, while in the stainless steel of the heat exchanger
conductive heat transfer occurs. The overall heat transfer resistance is the sum of the heat transfer
resistances of the three parts as defined by Eq. 2-3. In the next paragraph the three components will be
determined theoretically.
1
U OVERALL
1
U SOL
t WALL
kSTAINLESS STEEL
1
Eq. 2-3
U COOL
25
1
U OVERALL
1
U OVERALL
UWALL
1
U SOL
1
U SOL
W
mK
Eq. 2-4
4E -3
1
)
0.0139kW / (m * K ) U COOLANT
1
U COOLANT
0.288
Eq. 2-5
1
kW
3.5 2
0.288
m K
DHYD
u
4 A 4 (20 20) 3
E 0.02m
WP
4 20
Eq. 2-6
V
12
0.5m / s
A 1000 60 0.022
Re
u DHYD
Eq. 2-7
0.5 0.02
909
11E 6
Eq. 2-8
26
Figure 2-2; Top view of the flow channels in outer HEX of 200L unit
With a Reynolds number of 909 the flow regime is fully laminar. This has a negative influence on the
heat transfer. The flow can be made turbulent by changing the HEX dimensions or increasing the
freezium volume flow. Low Reynolds number involves a laminar boundary layer with heat transfer
dominated by conduction rather than convection. The Nusselt number relates the conductive to the
convective heat transfer. A Nusselt number close to one is characteristic for laminar flow, resulting in
heat transfer dominated by conduction. A larger Nusselt number corresponds to more active
convection, with turbulent flow typically in the 1001000 range. Despite of the small Reynolds number,
heat transfer is promoted by the small tube lengths, they are 180 turned every 8 cm. This means that
the laminar boundary layer is redeveloped every 8 cm which improves heat transfer. Hausen developed
a correlation to define the Nusselt number, as a function of the tube geometry, the Reynolds and the
Prandtl number (Eq. 2-9). This results in a theoretical heat transfer coefficient in the coolant of 1.05
kW/(m2.K).
UCOOL
Pr
DHYD
Nu
DHYD
[3.65
0.0668 Re Pr DH / Lltube
kW
] 1.05 2
2/3
1 0.04(Re Pr DH / Ltube )
m K
Eq. 2-9
v cp
Eq. 2-10
27
Penetration theory
Scraped heat transfer from a plate to a solution is commonly described by the penetration theory [VII].
Flow phenomena and viscosity of the solution have no influence in this theory; the conductive heat
transfer from the plate to the surface is described in very small time steps. Each time step is the period
between scraper blade passes. Due to a scraper pass the laminar boundary layer of the solution is
removed from the surface, which mixes completely and instantaneously with the bulk. A new laminar
boundary layer comes in place, which has the temperature of the bulk. This theory is valid for a
rotational speed of at least Nmin, which is calculated in Eq. 2-11. The turbulent heat transfer coefficient is
used here.
N min
U turbulent 2
n Cp
Eq. 2-11
A minimum scraper rotational speed of 52 rpm is required for the penetration theory to be valid. During
the experiments the rotational speed was 50 rpm, so that is only 4% too low for the penetration theory
to be valid. If the rotational speed is lower, the heat transfer is ruled by a combination of heat
penetration and heat transfer in a turbulent flowing medium. For now the penetration theory will be
used keeping in mind that the actual heat transfer might be a little lower.
The Fourier equation (Eq. 2-12) describes heat transfer for conductive heat transfer in y-direction, which
the penetration theory is based on.
2T
t
Cp y 2
y 0, T Twall ; y ; T Tbulk
Eq. 2-12
t 0, T Tbulk
Solving Fourier for the boundary conditions and substituting into the relation for heat transfer results in
the time dependence heat transfer equation (Eq. 2-13), which is rewritten in a heat transfer coefficient
of Eq. 2-14. By integration, this time dependent heat transfer coefficient results in an average heat
transfer coefficient between scraper passages as shown in Eq. 2-15.
28
Q(t )
T
Cp
(Tbulk Twall )
y
t
Eq. 2-13
Cp
t
U SOL (t ) 2
s
1 s
Cp
Cp n N
U (t ) dt n N
dt 2
ts 0
t
U SOL. AVERAGE
Eq. 2-14
Eq. 2-15
SOL l [
2l s 2 ws (l s )
]
2l s ws (l s )
Eq. 2-16
The thermal conductivity for the sodium chloride solution (mother liquor) is described by Ramires [XI].
The temperature dependence of the conductivity is described by the second degree polynomial of Eq.
2-17.
l A B T ( C ) C T ( C )2
Eq. 2-17
In this formula the constants are dependent on the sodium chloride concentration. Ramires [XI]
obtained the constants for a number of concentrations, of which the second and the third column of
Table 2-1. From the given constants, interpolation resulted in the constants in the right column of the
table.
Table 2-1; Constants for the temperature dependency of the conductivity of a NaCl solution
For the eutectic concentration of 4.02 mol/kg and a temperature of -21.1C the thermal conductivity in
the liquid solution is 0.49 W/(m*K) according to Eq. 2-17.
29
The solution consists of both ice and salt crystals. Depending on the concentration of the feed, the
relation between the amount of ice- and salt crystals can be determined. Assuming a eutectic
concentration of the feed, more than 75 wt% of the solid particles is ice. For this reason the ice
conductivity has been used to approach the conductivity of the solid particles in the solution. The
conductivity of the solution containing solid particles is 0.679 W/m/K based on Eq. 2-16.
U SOL 2
Cp n N
kW
5.9 2
m K
Eq. 2-18
Re STIRRED.VESSEL
ND 2
Eq. 2-19
Thomas equations [XVII] describes the viscosity of the slurry as a function of the solid content.
Eq. 2-20
The Reynolds number for a rotational speed of 50 rpm is 60.000 at the outer heat exchanger, assuming
effective stirring. Scrapers are not designed for stirring however and have a small frontal area with the
solution. It is expected that the real Reynolds number is lower and might be close to the laminar regime.
The Reynolds number is also influenced by the heat exchangers, tube ends and other equipment
30
installed in the crystallizer, so the Reynolds number is only an estimated value. Computational Fluid
Dynamics or accurate measurements in the crystallizers might result in a better estimate.
1
U OVERALL
1
U OVERALL
t WALL
kSTAINLESS STEEL
1
U COOL
1
U SOL
U OVERALL 0.71
Eq. 2-21
kW
m2 K
The largest heat transfer resistance is in the coolant. This is caused by the low Reynolds number in the
tubes. The overall heat transfer coefficient will be compared with the experimental heat transfer of the
SCWC derived in Chapter 4.
31
3.1.Experimental procedure
To verify the content of a solution or a solid, or to determine the content of certain flows during the
process, samples of all flows and solutions were taken and analyzed. Inductively Coupled Plasma Atomic
Emission Spectrometry (ICP-AES) was used to determine contents of the solutions or solids with an
accuracy of 2.5%. The result of those analyses is shown in Appendix B.
The first experiment was performed with a pure NaCl solution. The sodium chloride used for all
experiments in this report is supplied by Roth and has a purity of more than 99.5%. The water used is
demi water, which is purified water clean from minerals. All the experiments have been done with a
NaCl concentration of 23.3 wt%, which is the eutectic concentration. The contents have been weighed
accurately to make sure the mixture was at the desired concentrations.
Secondly, for determining the influence of contamination in the solution, magnesium chloride was
added to the mixture, which is supplied as flakes by NedMag. The flakes consist of the six hydrate form
(MgCl2.6H2O) with a MgCl2 content of 47% and a Mg content of 12%. To obtain a Mg content of 1% in
the mixture, 8.3 wt% of the flakes was added to the solution. All the mixtures were created by mixing of
the solid content under stirring until completely dissolved.
For determining the power per square meter and the heat transfer coefficient, the mass flow and the
temperatures of the freezium in Eq. 3-1 are measured as described in Paragraph 1.3. Furthermore the
density and the specific heat are required, which are provided by the supplier. Also the torque on the
scraper is continuously measured. This is an important variable for evaluating scraper behavior.
UOVERALL
P
A TLOG. MEAN
Eq. 3-1
To obtain accurate measurement, cooling with a constant coolant temperature is performed. After
operating at a constant temperature for approximately 10 minutes a higher temperature difference will
be set. This was realized by turning off the mass flow of the freezium, while the cooling machine was
working to decrease the temperature.
32
33
During the experiments scraper noise was present. This indicates that scaling takes place at the heat
exchanger surface. During continuous cooling the torque keeps increasing, which might be caused by a
continuous increase of scaling on the surface, which is not scraped off. If this is the case, it is expected
that the heat transfer coefficient decreases while the torque increases.
To find out whether this phenomena of scale build-up is happening the situation of the third cooling
step is focused on. In the time interval [8307;9327] the temperature of the coolant is very constant, so a
good analysis can be made. When no scaling occurs, the scraper torque is approximately 0.9 Nm. For
this reason the variable Tq* has been introduced as the torque caused by scaling effects. Tq* is defined
as the torque minus 0.9 Nm. In Figure 3-3 the relation between Tq* and U has been shown at constant
temperature difference. There is a strong relation and it is concluded that scaling build-up increases the
torque of the scraper and decreases the heat transfer on the wall, which are very logical correlations.
34
During constant cooling a scaling layer builds up on the surface. A higher temperature difference results
in a faster build up of solid particles on the surface. The faster build up results in a faster torque increase
over time, which is the derivative of the torque (blue line in the bottom of Figure 3-2). So the time
derivative of the torque is a measure for the amount of scaling. For the four time intervals of continuous
cooling the time derivative of the torque has been calculated as shown in Figure 3-4. It is concluded that
an increase in temperature difference results in a faster growth of solid particles on the surface,
resulting in a larger time derivative of the torque and a lower heat transfer coefficient.
Figure 3-4; Torque increase over time vs temperature difference (values calculated in Table)
For the time intervals of Figure 3-4 the average power per square meter has been calculated. Also the
average temperature difference has been calculated for the time intervals. The results are plotted in the
blue line of Figure 3-5. The power per square meter is a common measure for the performance of a heat
exchanger. At a temperature difference of 10C between coolant and solution the maximum power of
35
5.5 kW/m2 was attained. At his point, a lot of noise, increasing torque and a decrease in heat transfer
coefficient indicated that scaling limited the process. It is expected that the scaling effect is large due to
the purity of the solution. All components in the mixture crystallize and can scale on the surface. The
presence of contaminants influences local mass transfer close to the wall. These elements do not
crystallize and are expected to promote heat transfer away from the wall on microscopic scale.
For that reason magnesium chloride has been added to the mixture, and the whole experiment has
been repeated. The red line of Figure 3-5 shows the result of a 1 wt% Mg mixture in the eutectic NaCl
solution (as described in the experimental procedure). The eutectic point for NaCl and H2O is lower for
this mixture (-23C), causing a limitation of the temperature difference, because the maximum cooling
capacity was achieved. Less noise and much better heat transfer indicated that less scaling occurred in
the presence of Magnesium. It is noted that at a temperature difference of 7 C the heat transfer for the
solution with magnesium is 24% higher than the pure solution.
The reason of the better heat transfer in the presence of magnesium is the absence of scaling. The local
super saturation close to the heat exchanger is the driving force for the nucleation and growth of the
crystals. Magnesium is the only substance in the solution that does not crystallize. On a microscopic
scale this has large effects on mass transfer on the heat exchanger surface. The presence of magnesium
might also influence the crystal growth rate, crystal shapes etcetera. Further studies are required to fully
understand the role of magnesium or other contaminants on the scaling intensity. For now it can be
concluded that adding magnesium to the solution has a very positive effect on the heat transfer. In
Paragraph 6.5 it will be determined whether magnesium is found in the water product during
continuous operation. If it remains in the mother liquor the magnesium only has to be added to the
system once during continuous operation. If small amounts are found back in the produced ice or salt
there is no big problem, because magnesium is a non toxic substance (e.g. present in vitamin pills at 10
wt%).
Figure 3-2 and Figure 3-3 show a large variation of the measured data. Part of it is scatter caused by the
inaccuracy of the measurements, but the main variation is caused by physical phenomena. Looking at
36
the heat transfer per square meter (green line in Figure 3-2) there is a peak at the beginning of each step
change (for example at 9800 seconds). This is due to the fact that the flow rate was stopped and the
freezium close to the thermometer was static for a while and heated up. For this reason the heat
transfer appears very large for a while. Another physical phenomenon causing scatter is the local scaling.
For example a small ice particle might stick to the heat exchanger or next to the heat exchanger for a
while before the scrapers manage to remove it. This has a direct influence on the torque and the heat
transfer locally. The experiments have been performed a second time and the phenomena repeat itself,
with similar scattering effects, but the trends were the same. For that reason the conclusions in the next
paragraph can be made, despite the scattering of the results.
3.3.Conclusion
The first experiments with the CDCC for EFC with a pure NaCl solution have been performed
successfully. The following conclusions can be drawn:
The eutectic temperature for the solution in the experiments is found to be -21.1 C which
corresponds to its theoretical value.
High temperature difference between coolant and solution (TLM) resulted in scaling on the heat
exchanger wall. This was confirmed by increasing scraper noise, increasing scraper torque and a
decreasing heat transfer coefficient at increasing TLM.
Scaling is reduced by impurities in the solution. Adding 1.0 wt% magnesium to the solution resulted in:
Decreased amount of scaling, based on lower torques of the scraper motor, less noise from the
scraper and an increased heat transfer coefficient.
The presence of magnesium resulted in up to 24% higher heat transfer at a TLM of 7C, which is
found to be 5.5 kW/m2. The same heat transfer was achieved for the pure NaCl solution at a
much higher TLM of 10C.
37
4.1.Experimental procedure
The crystallizer in the skid consists of four heat exchangers. In two layers above each other an inner and
an outer heat exchanger can operate at the same time. Due to technical malfunctions of the flow meters
of the inner heat exchangers, only the outer heat exchangers have been used.
The first experiment was performed with a pure NaCl solution. Secondly the experiments were done
with magnesium added to the system. The supplier and specification of the contents of the solution has
been described in the previous chapter. To obtain a mass percentage of 0.5 wt% in the solution,
0.5/0.12 = 4 wt% of the flakes have to be added, because only 12% of the flakes is magnesium.
Re STIRRED.VESSEL
ND 2
Eq. 4-1
38
Because the flows in the inner heat exchanger are unknown and because of the large torque on the
inner plates, the experiments have been carried out on the outer heat exchangers only. The flow was
shut down on the inner ones, so only the two outer plates extract heat from the solution. Due to single
driving of the scraper, the inner scrapers could not be turned off. But no temperature difference is
present here, so there will only be a small contribution to the torque.
The first experiment was done with a pure NaCl solution, of which the heat transfer of both plates is
plotted in Figure 4-1. It is remarkable that the heat transfer in the lower plate is much better than in the
upper plate. An explanation will be given later in this paragraph. For the same experiment in the 10 liter
CDCC the power at a temperature difference of 7C is 4 kW/m2. Comparing this with the experiment in
the SCWC it is concluded that the lower heat exchanger of the skid performs better than the CDCC and
the upper one performs worse. It must be noted that heat transfer is also influenced by heat exchanger
design and not only by scraper performance. Just like in the CDCC, also in the SCWC a lot of scaling was
present. This is concluded from very high torque (up to 70Nm) and lots of scraping noise. This resulted in
break-down of the scraper motor, so the planned experiments were cancelled.
The experiment was repeated with magnesium-chloride added to the solution to obtain a 0.5 wt%
magnesium in a eutectic NaCl solution (see ICP of the solution in Attachment B). The same difference in
the upper and lower heat exchanger occurred as shown in Figure 4-2. For the lower heat exchanger a
much higher temperature difference is shown. Due to limitations in the cooling capacity of the skid
these large temperature difference can only be obtained for one heat exchanger at a time.
A maximum power of 8 kW/m2 was extracted from the solution by the lower HEX, which is a good
performance for scraped wall heat exchangers. The cooling capacity limited the maximum achievable
temperature difference, but when looking at the steepness of the curve at 13C, increasing the
temperature difference does not increase the power per square meter a lot anymore.
39
Figure 4-3 shows the heat transfer in the 200 liter SCWC in the lower heat exchanger. The blue line is in
the presence with magnesium and the red line is in the absence of Magnesium. Just as shown in the 10
liter CDCC the presence of Magnesium involves less scaling and higher heat transfer. At low TLM the
heat transfer is the same, because the effect of scaling is very small in this region. At a TLM of 8C the
heat transfer in the presence of Magnesium is 30% higher than for the pure solution. The maximum
attained heat transfer is 8 kW/m2.
40
Figure 4-3; Heat transfer in the SCWC for a pure solution and for Magnesium added
The steepness of the curves of Figure 4-3 is defined as the heat transfer coefficient. At a low
temperature difference the steepness of both curves is almost the same. The heat transfer coefficient in
the absence of scaling is approximately 0.8 kW/m2/K for the lower heat exchanger and 0.6 kW/m2/K
for the upper heat exchanger. The theoretical heat transfer coefficient calculated in Chapter 2 is 0.71
kW/m2/K. It is concluded that the average heat transfer measured from the upper and lower heat
exchanger is very well corresponding with the theoretical value.
41
Assuming that the heat transfer resistance through the steel plates is identical for both heat exchangers,
the difference can be in the resistance on both fluid sides. To get more understanding on the heat
transfer on the side of the solution, the behavior under static conditions has been investigated. At a
solution temperature above the eutectic, constant cooling at low temperature difference has been
performed. At this low temperature difference no scaling occurs, so the scrapers were turned off. No
flow in the crystallizer is present and during 25 minutes of continuous cooling the heat transfer
coefficient is calculated and plotted as shown in Figure 4-5.
42
The heat transfer is almost the same for upper and lower heat exchangers with an average deviation of
2% (Eq. 4-2). The same experiments have been done for the same parameters except for a scraper
velocity of 50 rpm. The result is plotted in Figure 4-6 and shows a remarkable difference in heat transfer
coefficient of 44% (Eq. 4-3).
0.218 0.214
1.9%
0.214
43
Eq. 4-2
0.82 0.57
44%
0.57
Eq. 4-3
Under static conditions the heat transfer is the same for both plates, but under dynamic conditions
there is a large (44%) difference. It can be concluded that the difference is caused by the flow in the
crystallizer. There is little knowledge of the flow through the crystallizer. Equipment, such as tube ends,
thermometers etcetera influence the flow regime locally. It is possible that the Reynolds number in the
upper part is much lower than in the lower part of the crystallizer. A detailed study in the flow regime
and the influence on the heat transfer is recommended for further studies.
44
4.4.Conclusion
Experiments were performed successfully in the SCWC. Experiments were performed on a pure NaCl
solution and 0.5 wt% magnesium added to the solution.
During the experiments in the 10 liter CDCC it was concluded that a lot of scaling was present for a pure
NaCl solution and that magnesium in the solution results in decreased scaling and increased heat
transfer. This conclusion can also be made for the 200 liter SCWC. Furthermore, the following
conclusions can be drawn:
The heat transfer coefficient in the absence of scaling is approximately 0.8 kW/m2/K for the
lower heat exchanger and 0.6 kW/m2/K for the upper heat exchanger.
A maximum heat transfer of 8 kW/m2 has been attained at a temperature difference of 12C for
a solution containing magnesium.
At a TLM of 8C the heat transfer in the presence of magnesium is 30% higher than for the pure
solution.
The theoretical heat transfer coefficient calculated in Chapter 2 is 0.71 kW/m2/K. So the average heat
transfer measured in the upper and lower heat exchanger is very well corresponding with the
theoretical value. Furthermore the difference in heat transfer between the upper and lower heat
exchanger has been investigated. The influence of the presence of solid particles was found to have a
limited influence on the heat transfer. From an experiment that looked into the effects of stirring it was
concluded that the heat transfer difference between upper and lower HEX has to do with the flow
regime in the crystallizer.
45
5.1.Experimental procedure
Here a brief description is given on the set-up and how it is used in this experiment. The skid itself is
described in Paragraph 1.4. Figure 5-1 shows a simplified flow scheme. Pumps and sensors are not
displayed, but all flows are measured and can be controlled with valves and pumps. Also the
temperatures of all streams are measured continuously.
Filtrate
M
Ice
Ice
slurry
Settler
Cooling machine
Salt slurry
46
NaCl
In the crystallizer the two outer heat exchanger plates are used to extract heat from the solution. Due to
the high torque accompanied by the two inner plates and the malfunction of the flow meters of the
inner plates they were shut down. It must be noted that this might limit the capacity of the set-up.
The cooling machine was also used to pre-cool the brine before entering the crystallizer as shown by the
blue lines in Figure 5-1. Due to the high capacity of the pre-cooler, part of the pre-cooled brine is
pumped back to the brine storage. By use of the overflow, ice and salt slurry are directed to the settler.
Salt is leaving the crystallizer both on top as on bottom of the crystallizer due to the turbulent flow. In
the stagnant settler, there is time for the ice to settle to the top and the salt to settle to the bottom by
gravitational forces. The ice slurry is directed to the belt filter and ice separated from mother liquor is
produced on top of Figure 5-1. Despite turbulent flow in the crystallizer, salt is accumulated in the
bottom, so it is pumped from here directly to the bottom belt filter. Together with the salt slurry from
the bottom of the settler, the slurry is filtrated and dry sodium chloride (after recrystallization) is being
produced. The filtrate from both belt filters is pumped back to the brine storage. The settler is equipped
with a cooling system as well. This is not shown in the figure, because the cooling was not used due to a
technical malfunction. More details about the process later in this Chapter.
The experiment has been performed on a sodium chloride solution at the eutectic concentration with a
magnesium content of approximately 0.5%. The method to produce this initial solution is described in
the experimental procedure of Chapter 2. For ICP of the solution see Appendix B.
The washing of the products has been performed on small scale in the cold room. The cold room was
used to prevent melting of the ice and recrystallization of the salt. The room was also used to make
microscopic pictures of the crystals. The filtration & washing set-up is shown in Figure 5-2. A slurry is fed
on top of the glass filter. By turning on the vacuum pump a low pressure is created underneath the glass
filter. Pores in the filter allow the liquid to penetrate and the crystals remain on top. Solid liquid
separation is attained. Mixing the crystals with washing liquor cleans the crystals and by turning on the
vacuum pump a more pure solid is attained. These washing steps can be done a couple of times after
each other.
As a washing liquid for the ice demi water has been treated with the PURELAB Ultra, a water purifying
system designed for the most critical biological and analytical laboratory techniques that guarantees
water purity to 18.2 M-cm. The cold room was set at -7.5C and the washing water cooled to 1C. For
50 gram pure dried ice another 50 gram of water was used for each washing step. The water was added
to the ice, a little bit stirred and after 20 seconds the filtration process was started.
The washing of the salt has been performed with a saturated sodium chloride solution of -1.5C. The
temperature of the cold room was -7C and the slurry temperature was -19C. On an initial salt cake of
157 gram, 50 gram of washing solution was used at each washing step. The solution was evenly
distributed over the cake and after 15 seconds the filtration process was started.
During the continuous operation at some points in the process the solid fraction in the solution was
determined. This was done by tapping of the solid / liquid mixture and directly bringing it to the cold
room of -15C. After weighing the mixture is filtrated and the solid particles remain on the glass filter.
47
Dividing the mass of the dry solid by the mass of the initial solution, the solid fraction (m solids/msolution) is
determined.
5.2.General results
The aim of the experiment was to seek for the highest possible production rates of clean salt and water.
The reference time in the crystallizer is influenced by the feed flow rate as indicated by Eq. 5-1. For that
reason the residence time in the crystallizer is kept as short as possible to increase production rate.
Figure 5-3 shows photographs of the formed crystals taken in the cold room. The salt crystals (in the left)
have very sharp edges and have an average size of 300 m for a residence time of 1.6 hour. The ice
crystals (right) are approximately three times smaller with an average size of 100 m.
tresidence.crystallizer
SOLVCRYSTALLIZER
mFEED
1200 0.180
5800s 1.6hour
0.037
48
Eq. 5-1
Figure 5-3; Microscopic photo's of salt- (left) and ice crystals (right)
5.3.Mass balance
The mass flow of the feed stream has large influence on the operation of the crystallizer under constant
cooling power. The feed flow directly influences the residence time and therewith the amount of solids
in the crystallizer and finally in the slurries to the belt filters. Increasing feed stream results in large flows
to the belt filters, with low solid content. Salt and ice are produced, but more heat is lost due to the
large mass flows of for example the filtrates in this case. More ice is molten on the belt filter. A small
feed stream will result in thick slurries with a lot of solid particles. Less ice is melted and less heat is lost
to the environment. The disadvantage is that the thick slurries can hardly be pumped and the pumps
may get stuck. For that reason an optimization must be made for the feed stream to the crystallizer.
Trial and error was applied to keep the feed stream small and the pumps not to get stuck. The optimum
mass flow of the feed was found to be 37 gr/sec, which was continuously fed for five hours.
Figure 5-4 shows the amount of ice and salt being produced. The flows are very constant, except after
one hour when the steepness of both curves are deviating. At this point in time there was a problem
with the salt belt filter, so it had to be stopped. At the same feed rate, 20% more ice was going to the ice
belt filter and the steepness of the ice line increases. Salt accumulated in the settler and crystallizer;
when the salt belt filter was operational again (at t=1.5 hour), this accumulated salt is produced as
shown by the increased steepness of the red line in Figure 5-4. In the overall mass balance average
values for the flows are used, thus eliminating the malfunction of the salt belt filter.
49
Figure 5-5 shows the mass balance of all the flows in the system. These values are the averaged values
while steady state operation was approached. The settler has not been shown here but is included in
the crystallizer, because it is irrelevant for this consideration. In the real case the ice slurry and part of
the salt slurry comes from the settler. The feed stream of 37 gram/s is divided in 28.2 gram/s ice slurry
and 8.5 gram/s salt slurry. The ice slurry mass flow is 3.3 times larger than the salt mass slurry due to the
higher concentration of water than salt in the initial brine. The mass balances on both belt filters are
separately evaluated in Paragraph 5.5 & 5.6.
50
The residence time in the settler is approximately 1.4 hours. Whether this time is enough for the crystals
to completely settle to the top or bottom of the vessel can be determined by Stokes law (Eq. 5-2). Due
to density difference between the solid particle and the solution a force is acting on the solid particle.
Depending on the viscosity of the solution this force results in a velocity of the particle. The velocity of
both the ice and salt crystals has been calculated resulting in 8.5E-3 and -4.5E-4 m/s, respectively, using
the sizes estimated from the microscopic photos of Figure 5-2. The largest travel distance (1 meter) for
the slowest particle (salt) results in a minimum required residence time of 0.6 hours. The residence time
of 1.4 hours, which has been realized during operation, must suffice based on this calculation.
u particle
2
( crystal solution ) g Dcrystal
18solution
Eq. 5-2
The ice produced on the belt filter still contains 9 wt% of sodium chloride. In Paragraph 5.5 the washing
of the ice is considered. The large amount of salt in the ice is partly caused by the way the settler
operates. Based on the design of the skid, the slurry should be pumped from the crystallizer to the
settler. The slurry (containing both ice and salt) is than somewhere halfway pumped into the settler as
shown in Figure 5-7. The solid particles have enough time to settle to the bottom or the top of the
settler and the ice and salt are well separated. During operation, the pump to feed the settler got stuck
by the solid particles many times. For that reason the overflow from the crystallizer was used. Instead of
pumping the slurry to the middle of the settler, it flows by gravity to the top of the settler, as shown in
the picture of Figure 5-6. The slurry that contains salt crystals contaminates the top ice layer in the
settler. These salt crystals do not have enough time to descend and directly leave the settler towards
the ice belt filter. It is recommended that a solution for this pumping problem is developed. For example
an ice crusher can be installed to prevent the pump getting stuck.
51
Ploss
dQ
dT
m Cp
0.51kW
dt
dt
Eq. 5-3
This heat loss is assumed linear as a function of temperature difference between solution and
environment. Eq. 5-4 is used to evaluate heat losses as a function of crystallizer and environmental
temperatures.
Ploss
0.51
kW
14.2 E 3
Tenvironment Tcrystallizer 20 16
C
52
Eq. 5-4
During five hours of continuous operation, the mass flows were measured. In Figure 5-9 the mass and
energy flows are schematically pictured during continuous operation. From the left of the belt filter 28.2
gram/sec ice slurry is fed. By filtration of this ice slurry in the cold room at -17C 19.4% appeared to be
solid. Continuous filtration of the product results in a product stream of 3.2 gr/s dry ice, while 5.5 gr/s
(28.20.194) was fed to the belt filter. The remaining ice crystals were melted on the belt filter (42%), as
shown by the leaving flow on the top right in Figure 5-9. The melted ice and the filtrate together leave
the system and are circulated to the crystallizer system. In the experiment, the melt and the filtrate are
one single stream, but in Figure 5-9 they are schematically shown separately, to indicate the amount of
53
ice melting. The filtrate leaves the filtration system at a temperature of -9.8 C so it is heated
significantly. It was calculated that in the melting process 0.77kW of cold is lost and in the temperature
increase of the mother liquor and the molten ice 1.3kW is lost. In total more than 2kW of cold is
exchanged to the surrounding.
Filtered ice leaving the belt filter still contains some sodium chloride as indicated in Figure 5-10 (at 0
washing steps). In the feed 23 mass percent of salt is present and in the dry ice, the sum of sodium and
chloride is 9 mass percent. Due to the 1.5 times larger molar mass of chlorine than sodium, it was
expected that the relation between those compounds is the same in the product streams. The amount
of chlorine is much higher however, which is impossible, because it would indicate that the produced ice
is negatively charged. This difference in ICP has also been shown in other experiments, for that reason it
is concluded that there is an error in the ICP results.
In the solution in the crystallizer 5000 ppm (0.5%) of magnesium is present. As shown in Figure 5-10 half
of it is still present in the ice before washing. After one washing step already more than 80% of the
magnesium is washed from the crystals and by continuing washing all the magnesium is eliminated.
Some small amounts of potassium and bromine are present in the ice. These elements were also
present in the feed, but they are all washed from the crystals very well.
54
55
5.7.Energy balance
In this paragraph the energy flows will be evaluated during constant operation. In Figure 5-14 the energy
balance from the crystallizer is shown. The heat extracted from the heat exchangers is found back in the
enthalpy change of the flow. In this overview the leaving flows of the slurries are summed as one flow,
and the crystallizer and the settler are displayed as one system.
The enthalpy change of the solution going in and the slurries going out of the system is shown in Table
5-1. The enthalpy change consists of the heat of crystallization of the ice and the salt and a temperature
difference of the flows entering and leaving the system. The accompanying powers are calculated with
the mass flows, the heat of crystallization and the specific heat of the flows.
Table 5-2 summarizes the cold losses in the settler and crystallizer. The total losses are calculated by the
formula of Figure 5-14. The scraper is producing heat added to the solution in the crystallizer. This heat
is defined as the product of the torque and the rotational velocity of the scraper motor. The cold losses
from the crystallizer are evaluated with the experiment described in Paragraph 5.4 and calculated in Eq.
5-5. The final term consists of the remaining losses, which are the losses heat losses in the settler, tubes,
pumps etcetera.
56
Eq. 5-5
m hin
m hout
Pextracted HEX
Plosses
It must be noted that the energy balance here is only for the crystallizer and settler. Part of the
produced ice is melted on the ice belt filter and also on the salt belt filter additional losses occur.
For the system consisting of the crystallizer and settler the efficiency is calculated by Eq. 5-6. It is
concluded that 59% of the heat extracted from the solution is found back in the enthalpy change of the
flows.
crystallizer settler
h flows
Pextracted
2.96
0.59
5.02
Eq. 5-6
57
An overview of the total heat losses (including the belt filters) in the skid during continuous operation is
shown in Figure 5-16. For simplicity reasons and better understanding the settler is included in the
crystallizer in this overview. The arrows moving out of the system indicate the heat that is removed from
the solution. This is done by a pre cooler in the storage tank upstream of the crystallizer and by the two
outer heat exchangers in the crystallizer.
From Figure 5-16 if follows that for a mass production of 3.2 gr/s filtrated ice 5.02 kW is extracted by the
crystallizer. Converting to different units, it can be concluded that for the production of 1 m3 ice 436
kWh has been used or expressed as m3 of feed solution 395 kWh.
58
15E 5
436 3
3
Vwater. prod m prod . water
3.2 E
kg prod . water
m prod . water
Pextracted Pextracted . 5.02 1170
kWh
kWh
14 E 5
395 3
3
V feed
m feed
4.13E
kg. feed
m . feed
Eq. 5-7
This is based on the energy extracted by the heat exchangers. The cooling machine has a coefficient of
performance (COP), which yields that for a positive COP less energy is required to drive the compressor
in a refrigeration cycle than the energy that is extracted from the solution. In Paragraph 6.1 a
refrigeration cycle for EFC is shown with a COP of 3.0. Based on this COP the energy requirement is
calculated by Eq. 5-8.
Pextracted
436
kWh
145 3
Vwater. prod COP 3.0
m water. prod
Pextracted
395
kWh
132 3
V feed COP 3.0
m feed
Eq. 5-8
59
5.8.Conclusion
Continuous operation in the skid has been performed for five hours using the outer heat exchangers of
the SCWC only. During this experiment a total of 70 kg of filtrated ice and 18 kg of the anhydrate of
sodium chloride have been produced. The capacity of the cooling machine was the limiting factor in this
experiment.
The ice and salt have been washed on experimental scale and all contaminations are washed from the
crystals, for that reason it can be concluded that no contaminants are encapsulated in the crystals.
The mass- and energy balance for the total system have been analyzed. Heat losses for all components
in the skid during continuous operation are summed and schematically represented. The efficiency of
the crystallizer and settler together has been evaluated and is given in Eq. 5-9. Furthermore the energy
losses on the belt filter during the filtration process are analyzed. It is estimated that 42% of the ice
produced in the crystallizer, melts on the belt filter. In Chapter 6 improvements are suggested for the
energy losses.
crystallizer settler
h flows
Pextracted
2.96
0.59
5.02
Eq. 5-9
For continuous production of ice and salt without the washing steps the heat extracted in the
experiments was 395 kWh per m3 feed. Based on a theoretical COP for a refrigeration cycle of 3.0 the
energy use may potentially be reduced to 132 kWh per m3 feed (Eq. 5-10).
Pextracted
395
kWh
132 3
V feed COP 3.0
m feed
Eq. 5-10
60
6.1.Refrigeration cycle
The energy consumption of a process is highly dependent on the plant in which it operates. Waste heat
and or cold might be available which positively influences the energy consumption. Besides, there is cold
available in the products of the process which might be valuable to recover and recycle in the EFC
process or to re-use for other processes in the plant. For the worst case scenario, in which the process
runs as a stand-alone, an energy calculation is made.
The coefficient of performance of a refrigeration cycle is defined by Eq. 6-1:
COP
QCOOLING
PELECTRIC
Eq. 6-1
M
WATER
ICE
Q cooling
FEED
Evaporator
Teut =- 22C
Condenser
SALT
61
Condenser 2
Figure 6-2; COP for 2-step refrigeration cooling according to van Ham [VI]
COP vs the ratio of the condensor duty (condenser 1 in Figure 6-1) available at 278 K to the vaporizer duty
required. The lines correspond to different vaporizer temperatures.
For a temperature in the evaporator of 245 kelvin and a condenser duty of 0.5 a COP of 3.0 is
achievable.
Gunger and Winterton [XIII] developed a correlation for forced convection boiling in tubes. Based on
these correlations the two phase heat transfer of the CO2 is calculated.
The Total heat transfer equation (Eq. 6-2) consists of a pure liquid convective heat transfer term, based
on Dittus-Boelter equation [XIV] and a micro convective (nucleate boiling) contribution based on Foster
and Zubers pool boiling equation [XVI].
Eq. 6-2
l
D
Eq. 6-3
The enhancement factor (E) of Eq. 6-2 is a function of the boiling number (Bo) and the Martinelli
parameter (Xtt).
1 0.86
)
X tt
Eq. 6-4
The boiling number (Eq. 6-5) is a dimensionless measure for the amount of vapor being generated and is
a function of the heat transfer coefficient (U), making the calculation process iterative.
Bo
U
(hv hl ) G
Eq. 6-5
The other variable for determination of the enhancement factor is the Martinelli parameter. Besides the
effect of the evaporation, which is in the boiling number, the presence of the vapor itself influences heat
transfer. High axial velocities in the tubes disturb the boundary layer next to the surface. The effect is
measured by the Martinelli parameter, which correlates the void fraction and heat transfer coefficient in
two phase flow.
Eq. 6-6
P 0.67
)
AHEX
Eq. 6-7
1
6
1 1,15 10 E 2 Rel1.17
Eq. 6-8
Rev
Prl
G (1 x ) DHYD
Eq. 6-9
GxDHYD
Eq. 6-10
l Cpl
l
Eq. 6-11
Result
With the above mentioned formulae the heat transfer can be calculated. The spreadsheet calculates for
small steps in quality change the required length in an iterative manner. For each of these step changes
in quality the required length is calculated by Eq. 6-12.
Lrequired
qhlatent mCO2
U (TEUT TCO2 ) Dhyd
Eq. 6-12
The required length does not incorporate the pressure drop. Which is calculated based on LockhartMartinelli correlations.
64
Based on these calculation the heat transfer coefficient as a function of the vapor fraction is shown in
Figure 6-3. It must be noted that this is the heat transfer coefficient in the CO2 only. The overall heat
transfer coefficient also takes the heat transfer in the metal wall and the heat transfer in the solution
into account. These depend on crystallizer design, which is undetermined in this phase.
Figure 6-3; Heat transfer coefficient vs vapor fraction for evaporative CO2 refrigeration
65
66
NaCl.2 H 2O
NaCl 2 H 2O
2 M H 2O
grH 2O
mwater
2 18
0.9
mNaCl M Na M Cl 23 17
grNaCl
Eq. 6-13
mNaCl .lost
m
Csaturation water 0.24 0.9 21.6%
mNaCl
mNaCl
Depending on the contaminations in the system and the required product quality the dry salt has to be
washed. The filtrate from the recrystallization process is a good washing liquid so it can have a purpose
here. After washing the saturated solution is redirected to the crystallizer. Wahing and filtration with
such a scheme might involve large improvements on product quality and efficiency of the system.
67
68
Figure 6-5 shows a 2-step washing scheme with different washing solutions. The settler between the
crystallizer and the belt filter has been omitted in this schematic representation. Ice slurry enters the
belt filter from the left and after filtration and two washing steps ice with a high purity is produced.
The ice slurry entering from the left of the belt filter is first filtrated. Ineffectiveness of this process
results in mother liquor remaining with the ice on the belt filter. The mother liquor is a saturated
solution which is in equilibrium with the ice crystals. The melting temperature at this stage is still around
the eutectic temperature. For this reason lots of ice melts when washing with 0C water as occurred in
the experiments.
An initial washing procedure with a NaCl solution at its freezing temperature is expected to be more
effective. The concentration can be somewhere between zero and the eutectic concentration. In this
example a 14% NaCl solution at -10.5C is used for the first washing step. Based on the phase diagram of
Figure 1-2 this is the freezing point of the solution. With this method most salt will be washed off at a
low temperature, resulting in a decreasing amount of ice melting.
In the second washing step clean water at 0C is used to dissolve the contaminants still present in the
ice. Low salt concentration in the ice during the latest washing step involves a higher melting
temperature, so small amounts of ice melt and a product with high purity is obtained. The 14% NaCl
solution of the first washing step can be obtained by mixing the filtrate of the ice before washing with
the filtrate of the second washing step as indicated by the light blue lines of Figure 6-5. This washing
method is a conceptual idea, which has to be verified with experiments and optimized for a process
stream. Also the effectiveness is highly depending on process conditions, like contents of the mother
liquor and required purity of the ice product.
Water 14% NaCl
-10.5C
Clean
water (0C)
Ice
slurry
Ice product
Washing
filtrate 1
Filtrate
Washing
filtrate 2
69
Washed ice
Ice slurry
Unwashed
ice
T=-20C
Mother liquor
70
filter
For this perfectly insulated system the energy requirements are summed in Table 6-1. These values were
calculated by the heat of crystallization and the specific heat of the solutions.
71
This energy requirement per m3 of feed water is the energy that is extracted from the solution. A 2-step
refrigeration cycle as described in Paragraph 6.1 uses the cold of the produced ice that is available to
obtain a COP value of 3.0. This results in a total energy use per m3 of feed water of Eq. 6-14.
P
m
3
feed
Qrejected
COP
154
kWh
51 3
3.0
m feed
Eq. 6-14
It must be noted that this is a theoretical value based on perfect insulation and no energy loss. Energy
requirements for pumps, the salt belt filter and scraper motor have been ignored. For the washing steps
estimated numbers for flows have been used. In practice these numbers highly depend on product and
feed quality.
6.7.Conclusion
This Chapter proposed a number of possible improvements for continuous operation of the skid.
Washing and filtration methods have been proposed to increase efficiency. Furthermore it is expected
that scaling on the heat exchanger surface can be reduced by using different (non-adhesive) materials.
Furthermore a theoretical flow scheme for an ideal case of continous EFC operation has been described.
It assumes perfect insulation, no heat loss and the energy requirements for pumps, the salt belt filter
and scraper motor have been ignored. A 2-step refrigeration unit is used for this process. Based on this
evaluation 51 kWh per m3 feed solution is required.
72
73
Water
extraction &
distribution
Energy consumption
Use of chemicals
Cleaning
process
Water supply
Water use by
consumer
Energy consumption
The energy consumption for the most common treatment methods has been presented. LCA studies
have widespread conclusions, so maximum and minimum values are shown for each process. The
desalination processes by membrane (UF/MF/RO) or by thermal distillation require the most energy, but
as mentioned before, depending on the water quality of the resource (brackish water or seawater)
available.
Use of chemicals
Chemicals can have a major influence on the total environmental impact of a cleaning process. Of course
this is depending on the technique that is being used. Beavis et al. [XXIV] compared different
74
disinfection techniques and concluded that UV radiation had the worst impact based on energy
consumption. Other studied impacts are chlorine and hypochlorite injection, which are of less impact to
the environment. The reason for the high impact of UV radiation is the high energy consumption. It must
be said that not all sources can be treated only by chemicals. For example for desalination a more
energy demanding process is required.
Concentrate disposal
All techniques differ to a large extent in the disposal of concentrated waste streams. For example in
reverse osmosis and other desalination methods, a large concentrated stream is disposed into the sea or
ground water. It is remarkable that this not considered in almost all LCA analysis.
Vince [XXIII] argues that liquid discharges are neglected due to the lack of reliable data. If these impacts
are significant however, the total performed LCA would be meaningless. Peters and Rouse [XXVII] aimed
at assessing the impact of the brine discharges, but unfortunately only the construction impact of the
piping to the sea is taken into account. The writers argued that the brine disposal can be neglected,
because it is disposed were the source stream is obtained from. This is a false argument, because the
brine has much higher concentration than the source stream. These high concentrations in a large
amount influence local ecosystems.
Most of the time the ecosystem is not entirely known and if it is, it is hard to identify the impact of brine
disposal. However, that should not be a reason to discount the effect in, as the impact might be large.
What actually happens when a higher concentration of salt solution is disposed to the source of low
concentration has a higher impact than normally would be expected. Because of the high concentration
of salt the density of the solution is larger than the density of the sea water. The disposal immediately
descends to the bottom of the sea, where it agglomerates in deep ocean channels. Due to large amount
of salt dissolved the amount of oxygen in the solution decreases. Large, mobile species, such as fish are
able to get away from these high salinity waters, but other fish, fan corals, sponges, stalked and sessile
ascidians, anemones and attached algae might suffer from these conditions. Little information is
available on the actual impact that is created, so further research is required to perform a factual impact
analysis. It is a fact that the impact is there, so it should at least be mentioned in LCA.
75
It is concluded that brine disposal is poorly treated in Life Cycle Analysis in literature of clean water
production methods. For that reason no conclusion can be made whether to treat or to dispose brines.
However it is known that disposing might have large environmental impact to local eco-systems,
depending on each given situation.
7.2.Evaporative crystallization
Eutectic Freeze Crystallization for sodium chloride solution is technically achievable as demonstrated in
this report. An alternative method to separate the salt from the water is by evaporative crystallization.
This paragraph describes the technique and investigates the energy requirements. Investment costs will
not be considered, as these are unknown for large scale industrial EFC. Also in other studies, of for
example water production methods, the investment costs are relatively small compared to energy costs.
Furthermore there is no reason to assume EFC has higher investment costs than competitive methods,
once EFC is applied at large scale by industry.
Evaporative crystallization is schematically shown by Figure 7-3. The solution is fed in the crystallizer (1)
and heated such that the liquid starts to evaporate. The solids remain in the liquid solution, of which the
concentration increases to super saturation. The solid particles crystallize and a slurry is generated,
which leaves the system (5). Just like in EFC the slurry is filtrated and possibly washed and a dry and
clean salt is obtained. The evaporated water is the other clean product which leaves the system as
condensate (8). Just like in EFC the contaminants remain in the mother liquor. The amount of TDS (total
dissolved solids) in the mother liquor increases and can at some point be tapped and further treated
with other separation methods. The compressor (7) increases the pressure of the water vapor, which
results in a high temperature of the condensation process. Thus the condensation of the water occurs at
a high pressure. The heat is delivered to the lower temperature solution which starts to evaporate at the
low pressure. This method of working at different pressures results in high energy efficiency of the
system.
76
Evaporation of water (610 kWh/m3) requires 6 times more energy than the energy extracted during
crystallization of water (93 kWh/m3). For that reason it is expected that EFC is potentially a much more
energy efficient method than evaporative techniques. Multi stage evaporative techniques are highly
optimized however. Working at different pressures, optimization of the heat exchange network and
reuse of heat for other processes in a plant results in large efficiency improvements.
The Kuwait institute for scientific research realizes the complexity of environmental solutions for brine
treatment. They started research to investigate the ZLD solutions as presented in a symposium [XVIII].
Mechanical Vapor Compression (MVC) for a pure sodium chloride concentration is presented with a zero
liquid discharge solution and an energy use of 47.8 kWh per m3 of feed solution.
General Electric (GE) claims that for evaporative crystallization systems of salt solutions, such as shown
in Figure 7-3, a required energy consumption is absorbed of 40-45 kWh/m3 feed stream. This holds for a
feed stream of 10% TDS, which is separated into pure solids, pure water and a 5% purge, as
schematically represented by Figure 7-4.
77
90kg
Dry solids
1000kg
10wt% TDS
Evaporative crystallization
860kg
Pure water
50kg
Purge
P=40-45kWh
7.3.Conclusion
Wide spreading methods to produce clean water are applied nowadays. Depending on a local given
situation a comparison can be made for an environmental best solution, based on the Life Cycle Analysis
method. Unfortunately most life cycle analyses do not consider brine disposal, while this can have large
effect on local ecosystems.
Evaporative crystallization is, together with EFC, an alternative for disposing the brine to the
environment. Despite the large heat of evaporation of water, highly optimized plants are very energy
efficient by reusing the heat of evaporation. Highly optimized commercial evaporative crystallizers
typically operate with an energy consumption of 40-50 kWh per m3 of feed solution.
78
8. Conclusion
The aim of the research was to investigate the potential of EFC for sodium chloride and to develop an
EFC process from lab scale to industrial scale. In both the cooled disk column crystallizer and the scraped
cooled wall crystallizer experiments were performed.
The following conclusions were drawn on the heat transfer on the scraped wall of the CDCC for a pure
solution and for a solution containing 1 wt% magnesium:
The eutectic temperature for a pure NaCl solution in the experiments is found to be -21.1 C
which is corresponding to the theoretical value.
High temperature difference between coolant and solution (TLM) resulted in scaling on the heat
exchanger wall, which took place in a larger extent for a pure solution. This was confirmed by
increasing scraper noise, increasing scraper torque and a decreasing heat transfer coefficient at
increasing TLM.
The presence of magnesium resulted in up to 24% higher heat transfer at a TLM of 7C, which is
found to be 5.5 kW/m2. The same heat transfer was achieved for the pure NaCl solution at a
much higher TLM of 10C.
The same experiments were also performed with the CDCC for a pure solution and for a solution
containing 0.5 wt% magnesium.
The heat transfer coefficient in the absence of scaling is approximately 0.8 for the lower heat
exchanger and 0.6 kW/m2/K for the upper heat exchanger. The difference is caused by the flow
regime in the crystallizer.
The theoretical heat transfer coefficient calculated in Chapter 2 is 0.71 kW/m2/K. So the
average heat transfer measured in the upper and lower heat exchanger is corresponding well
with the theoretical value.
A maximum heat transfer of 8 kW/m2 has been attained at a temperature difference of 12C for
a solution containing magnesium.
At a TLM of 8C the heat transfer in the presence of magnesium is 30% higher than for the pure
solution.
79
During five hours of continuous operation of the skid 70 kg of filtrated ice and 18 kg of the anhydrate of
sodium chloride have been produced. These products have been washed on experimental scale and all
contaminants are perfectly washed from the crystals, so no contaminants are encapsulated in the
crystals. Mass- and energy balances resulted in the following conclusions:
The efficiency of the crystallizer and settler together is 59%, the remaining is heat loss.
42% of the ice produced was melted on the belt filter.
For continuous operation without washing 395 kWh per m3 feed was extracted in the
crystallizer. Using a 2-step refrigeration cycle to extract this heat only 132 kWh/m3 feed would
be required.
A number of possible improvements for the continuous operation of the skid have been proposed.
Based on an optimized process without heat losses and ignoring energy requirements for pumps, the
salt belt filter and scraper motor 51 kWh per m3 of feed solution would be required. Highly optimized
multi stage evaporative crystallizers typically operate with an energy consumption of 40-50 kWh per m3
of feed solution. Optimization of the EFC process might result in a similar or even lower energy
requirement than evaporative techniques require, depending on process specifications.
80
9. Recommendations
The aim of this research was to provide answers on a number of questions regarding EFC for sodium
chloride. Some interesting conclusions have been drawn, but also a number of questions have been
raised that I would recommend for further research:
Regarding the heat transfer in the crystallizer:
Look under different scraping rates and under different contaminant concentrations to the heat
transfer performance.
Look into the flow regime in the SCWC. The flow regime to a large extent influences scaling and
heat transfer, which is shown in the difference between performance of the upper and lower
heat exchanger.
Investigate the use of non-adhesive materials to cover the heat exchanger in the crystallizer.
This might significantly reduce scaling effects.
Investigate washing of the products for continuous operation. Find the most efficient way to
wash both ice and salt.
Combine the heat flows in a heat exchanger network to reduce energy consumption.
Success for EFC on sodium chloride solutions depends on the optimization of the process. The energy
uses for evaporative crystallization are to the result of decades of optimization.
81
Appendices
A. Vapor pressure vs temperature of CO2
82
83
84
step
quality
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.1
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.2
0.21
0.22
0.23
0.24
0.25
0.26
0.27
0.28
0.29
0.3
0.31
0.32
0.33
0.34
0.35
0.36
0.37
0.38
0.39
0.4
0.41
0.42
0.43
0.44
0.45
0.46
0.47
0.48
0.49
0.5
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
0.05
0.055
0.06
0.065
0.07
0.075
0.08
0.085
0.09
0.095
0.1
0.105
0.11
0.115
0.12
0.125
0.13
0.135
0.14
0.145
0.15
0.155
0.16
0.165
0.17
0.175
0.18
0.185
0.19
0.195
0.2
0.205
0.21
0.215
0.22
0.225
0.23
0.235
0.24
0.245
0.25
ReL
ReG
5047
5022
4996
4971
4946
4921
4895
4870
4845
4820
4794
4769
4744
4719
4694
4668
4643
4618
4593
4567
4542
4517
4492
4466
4441
4416
4391
4366
4340
4315
4290
4265
4239
4214
4189
4164
4138
4113
4088
4063
4037
4012
3987
3962
3937
3911
3886
3861
3836
3810
3785
0
370
740
1110
1480
1850
2220
2590
2961
3331
3701
4071
4441
4811
5181
5551
5921
6291
6661
7031
7401
7771
8141
8512
8882
9252
9622
9992
10362
10732
11102
11472
11842
12212
12582
12952
13322
13692
14063
14433
14803
15173
15543
15913
16283
16653
17023
17393
17763
18133
18503
Laminar=0
Turbulent=1
State L
State V
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
C
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Xtt
10
10
10
10
10
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
E
25.870
13.801
9.538
7.328
5.967
5.041
4.368
3.855
3.451
3.124
2.854
2.626
2.432
2.264
2.117
1.988
1.873
1.771
1.678
1.595
1.518
1.449
1.385
1.326
1.272
1.221
1.174
1.131
1.090
1.052
1.016
0.982
0.950
0.920
0.891
0.864
0.838
0.814
0.791
0.769
0.747
0.727
0.708
0.690
0.672
0.655
0.639
0.623
0.608
0.593
6.676989
6.736836
6.790454
6.84055
6.888293
6.934328
6.979059
7.022764
7.065643
7.107846
7.149492
7.190674
7.23147
7.271944
7.312152
7.352139
7.391947
7.431611
7.471164
7.510634
7.550047
7.589427
7.628794
7.668168
7.707569
7.747013
7.786516
7.826093
7.86576
7.905529
7.945413
7.985425
8.025578
8.065882
8.106349
8.146991
8.187817
8.228839
8.270067
8.31151
8.353179
8.395085
8.437236
8.479642
8.522314
8.56526
8.608492
8.652017
8.695847
8.739991
hl
0.47708
0.474099
0.471624
0.469445
0.467472
0.465653
0.463958
0.462365
0.460858
0.459425
0.458057
0.456746
0.455487
0.454275
0.453105
0.451974
0.450878
0.449816
0.448784
0.447781
0.446804
0.445853
0.444925
0.44402
0.443135
0.442271
0.441425
0.440598
0.439787
0.438993
0.438214
0.43745
0.436701
0.435965
0.435242
0.434532
0.433834
0.433148
0.432473
0.431808
0.431154
0.43051
0.429876
0.42925
0.428634
0.428027
0.427428
0.426837
0.426254
0.425679
227.2668
226.3527
225.4377
224.5217
223.6048
222.687
221.7682
220.8485
219.9278
219.0062
218.0836
217.16
216.2354
215.3098
214.3833
213.4557
212.5271
211.5975
210.6669
209.7353
208.8026
207.8689
206.9341
205.9983
205.0614
204.1235
203.1844
202.2443
201.3031
200.3607
199.4173
198.4728
197.5271
196.5803
195.6323
194.6833
193.733
192.7816
191.829
190.8752
189.9202
188.964
188.0067
187.0481
186.0882
185.1271
184.1648
183.2012
182.2364
181.2702
85
8337
4.228
htp(W/m2K)
U(W/m2K) UdT(W/m2) Lreq(m)
8520
3485
1704
8519
0.041
3480
1703
8513
0.041
3476
1702
8508
0.041
3472
1701
8503
0.041
3468
1700
8498
0.041
3465
1699
8494
0.041
3461
1698
8490
0.041
3458
1697
8486
0.042
3454
1696
8482
0.042
3451
1696
8478
0.042
3448
1695
8474
0.042
3445
1694
8471
0.042
3442
1693
8467
0.042
3439
1693
8464
0.042
3436
1692
8460
0.042
3433
1691
8456
0.042
3430
1691
8453
0.042
3428
1690
8449
0.042
3425
1689
8446
0.042
3422
1689
8443
0.042
3419
1688
8439
0.042
3416
1687
8436
0.042
3414
1686
8432
0.042
3411
1686
8429
0.042
3408
1685
8426
0.042
3405
1684
8422
0.042
3403
1684
8419
0.042
3400
1683
8416
0.042
3397
1682
8412
0.042
3394
1682
8409
0.042
3392
1681
8406
0.042
3389
1680
8402
0.042
3386
1680
8399
0.042
3383
1679
8396
0.042
3381
1678
8392
0.042
3378
1678
8389
0.042
3375
1677
8386
0.042
3373
1676
8382
0.042
3370
1676
8379
0.042
3367
1675
8375
0.042
3365
1674
8372
0.042
3362
1674
8369
0.042
3359
1673
8365
0.042
3356
1672
8362
0.042
3354
1672
8359
0.042
3351
1671
8355
0.042
3348
1670
8352
0.042
3345
1670
8348
0.042
3343
1669
8345
0.042
3340
1668
8341
0.042
step
0.51
0.52
0.53
0.54
0.55
0.56
0.57
0.58
0.59
0.6
0.61
0.62
0.63
0.64
0.65
0.66
0.67
0.68
0.69
0.7
0.71
0.72
0.73
0.74
0.75
0.76
0.77
0.78
0.79
0.8
0.81
0.82
0.83
0.84
0.85
0.86
0.87
0.88
0.89
0.9
0.91
0.92
0.93
0.94
0.95
0.96
0.97
0.98
0.99
1
quality
ReL
ReG
0.255
3760
18873
0.26
3735
19243
0.265
3709
19613
0.27
3684
19984
0.275
3659
20354
0.28
3634
20724
0.285
3608
21094
0.29
3583
21464
0.295
3558
21834
0.3
3533
22204
0.305
3508
22574
0.31
3482
22944
0.315
3457
23314
0.32
3432
23684
0.325
3407
24054
0.33
3381
24424
0.335
3356
24794
0.34
3331
25164
0.345
3306
25535
0.35
3280
25905
0.355
3255
26275
0.36
3230
26645
0.365
3205
27015
0.37
3179
27385
0.375
3154
27755
0.38
3129
28125
0.385
3104
28495
0.39
3079
28865
0.395
3053
29235
0.4
3028
29605
0.405
3003
29975
0.41
2978
30345
0.415
2952
30715
0.42
2927
31086
0.425
2902
31456
0.43
2877
31826
0.435
2851
32196
0.44
2826
32566
0.445
2801
32936
0.45
2776
33306
0.455
2751
33676
0.46
2725
34046
0.465
2700
34416
0.47
2675
34786
0.475
2650
35156
0.48
2624
35526
0.485
2599
35896
0.49
2574
36266
0.495
2549
36637
0.5
2523
37007
Laminar=0
Turbulent=1
State L
State V
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
C
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Xtt
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
0.579
0.566
0.553
0.540
0.528
0.516
0.505
0.494
0.483
0.473
0.463
0.453
0.444
0.435
0.426
0.417
0.409
0.401
0.393
0.385
0.378
0.370
0.363
0.356
0.350
0.343
0.336
0.330
0.324
0.318
0.312
0.306
0.301
0.295
0.290
0.284
0.279
0.274
0.269
0.264
0.260
0.255
0.250
0.246
0.242
0.237
0.233
0.229
0.225
0.221
E
8.784458
8.829259
8.874404
8.919902
8.965764
9.012001
9.058622
9.105638
9.15306
9.200898
9.249165
9.297871
9.347028
9.396647
9.44674
9.497319
9.548398
9.599988
9.652102
9.704755
9.757959
9.811728
9.866076
9.921019
9.976571
10.03275
10.08956
10.14704
10.20518
10.26402
10.32356
10.38383
10.44485
10.50663
10.56919
10.63256
10.69675
10.76178
10.82769
10.89449
10.9622
11.03086
11.10048
11.17109
11.24272
11.3154
11.38915
11.46402
11.54002
11.61719
S
0.425111
0.42455
0.423996
0.423449
0.422908
0.422373
0.421845
0.421322
0.420806
0.420294
0.419788
0.419287
0.418792
0.418301
0.417814
0.417332
0.416855
0.416382
0.415913
0.415448
0.414987
0.414529
0.414075
0.413624
0.413177
0.412733
0.412291
0.411853
0.411418
0.410985
0.410554
0.410126
0.409701
0.409277
0.408856
0.408436
0.408018
0.407602
0.407187
0.406774
0.406362
0.405951
0.405542
0.405133
0.404725
0.404317
0.40391
0.403504
0.403098
0.402692
86
8245
2.137
hl
htp(W/m2K)
U(W/m2K) UdT(W/m2) Lreq(m)
180.3028
3337
1668
8338
0.042
179.3341
3334
1667
8334
0.042
178.3641
3331
1666
8331
0.042
177.3927
3329
1665
8327
0.042
176.42
3326
1665
8324
0.042
175.446
3323
1664
8320
0.042
174.4706
3320
1663
8317
0.042
173.4939
3317
1663
8313
0.042
172.5158
3314
1662
8310
0.042
171.5363
3312
1661
8306
0.042
170.5554
3309
1660
8302
0.042
169.573
3306
1660
8299
0.042
168.5893
3303
1659
8295
0.042
167.6041
3300
1658
8291
0.042
166.6175
3297
1658
8288
0.043
165.6294
3294
1657
8284
0.043
164.6398
3291
1656
8280
0.043
163.6487
3288
1655
8276
0.043
162.6562
3285
1655
8273
0.043
161.6621
3282
1654
8269
0.043
160.6665
3279
1653
8265
0.043
159.6693
3276
1652
8261
0.043
158.6706
3273
1651
8257
0.043
157.6703
3270
1651
8253
0.043
156.6684
3267
1650
8250
0.043
155.665
3264
1649
8246
0.043
154.6599
3261
1648
8242
0.043
153.6531
3258
1648
8238
0.043
152.6447
3254
1647
8234
0.043
151.6347
3251
1646
8229
0.043
150.6229
3248
1645
8225
0.043
149.6095
3245
1644
8221
0.043
148.5943
3242
1643
8217
0.043
147.5774
3238
1643
8213
0.043
146.5588
3235
1642
8209
0.043
145.5383
3232
1641
8204
0.043
144.5161
3229
1640
8200
0.043
143.4921
3225
1639
8196
0.043
142.4662
3222
1638
8192
0.043
141.4385
3218
1637
8187
0.043
140.4089
3215
1637
8183
0.043
139.3774
3212
1636
8178
0.043
138.3441
3208
1635
8174
0.043
137.3087
3205
1634
8169
0.043
136.2715
3201
1633
8165
0.043
135.2322
3198
1632
8160
0.043
134.191
3194
1631
8155
0.043
133.1477
3190
1630
8151
0.043
132.1024
3187
1629
8146
0.043
131.055
3183
1628
8141
0.043
Bibliography
I.
II.
III.
IV.
V.
VI.
VII.
VIII.
IX.
X.
XI.
XII.
XIII.
XIV.
XV.
XVI.
XVII.
XVIII.
XIX.
XX.
XXI.
XXII.
XXIII.
XXIV.
XXV.
XXVI.
87
XXVII.
G. Peters and K. Rouse, Environmental sustainability in water supply planning; an LCA approach
for the Eyre Peninsula, South Australia, Melbourne, 2005
88