You are on page 1of 88

Eutectic Freeze Crystallization on

Sodium Chloride
Analysis of a full experimental cycle

Master of Science Thesis

Document number: 2461

Bruno (J.J.) Verbeek

Wb1179829

29-07-2011
Eutectic Freeze Crystallization on Sodium Chloride

2
Eutectic Freeze Crystallization on Sodium Chloride

Faculty: Process Equipment

For obtaining the degree of Master of Science in


Sustainable Process- & Energy Technology

Exam committee: Prof. dr. G.J. Witkamp

Dr. L Hartmann

K. Yasadi

Copyright © BJJ Verbeek

All rights reserved

3
Eutectic Freeze Crystallization on Sodium Chloride

Contents

Acknowledgement ........................................................................................................................................ 6
Abstract ......................................................................................................................................................... 7
Table of figures ............................................................................................................................................. 9
Nomenclature ............................................................................................................................................. 11
1. Introduction ........................................................................................................................................ 13
1.1. Eutectic freeze crystallization ..................................................................................................... 14
1.2. Sodium chloride solutions........................................................................................................... 16
1.3. Cooled Disk Column Crystallizer (CDCC) ..................................................................................... 18
1.4. Scraped Cooled Wall Crystallizer (SCWC) in skid ........................................................................ 20
1.5. EFRO project ............................................................................................................................... 23
1.6. Scope of the research ................................................................................................................. 24
2. Theoretical heat transfer on scraped wall .......................................................................................... 25
2.1. Overall heat transfer ................................................................................................................... 25
2.2. Heat transfer coefficient metal wall ........................................................................................... 26
2.3. Heat transfer coefficient coolant ................................................................................................ 26
2.4. Heat transfer in solution ............................................................................................................. 28
2.5. Overall heat transfer coëfficiënt ................................................................................................. 31
3. Heat transfer experiments 10L CDCC.................................................................................................. 32
3.1. Experimental procedure ............................................................................................................. 32
3.2. Results & discussion .................................................................................................................... 33
3.3. Conclusion ................................................................................................................................... 37
4. Heat transfer experiments 200L SCWC ............................................................................................... 38
4.1. Experimental procedure ............................................................................................................. 38
4.2. Results & discussion .................................................................................................................... 38
4.3. Corrosion in the 200L crystallizer................................................................................................ 44
4.4. Conclusion ................................................................................................................................... 45
5. Continuous operation of the skid and washing of the products ........................................................ 46
5.1. Experimental procedure ............................................................................................................. 46
5.2. General results ............................................................................................................................ 48
5.3. Mass balance............................................................................................................................... 49

4
Eutectic Freeze Crystallization on Sodium Chloride

5.4. Determination of heat losses in the crystallizer ......................................................................... 52


5.5. Ice filtration & washing ............................................................................................................... 53
5.6. Salt filtration & washing.............................................................................................................. 55
5.7. Energy balance ............................................................................................................................ 56
5.8. Conclusion ................................................................................................................................... 60
6. Optimization and up scaling................................................................................................................ 61
6.1. Refrigeration cycle ...................................................................................................................... 61
6.2. Evaporative CO2 cooling .............................................................................................................. 62
6.3. Teflon encapsulated heat exchanger .......................................................................................... 66
6.4. Filtration & washing of salt ......................................................................................................... 67
6.5. Washing & filtration of ice .......................................................................................................... 68
6.6. Energy consumption in an ideal case.......................................................................................... 71
6.7. Conclusion ................................................................................................................................... 72
7. Environmental analyses of fresh water producing methods .............................................................. 73
7.1. LCA on potable water production ............................................................................................... 73
7.2. Evaporative crystallization .......................................................................................................... 76
7.3. Conclusion ................................................................................................................................... 78
8. Conclusion ........................................................................................................................................... 79
9. Recommendations .............................................................................................................................. 81
Appendices.................................................................................................................................................. 82
A. Vapor pressure vs temperature of CO2 ........................................................................................... 82
B. ICP results of samples ..................................................................................................................... 83
C. Spreadsheet for evaporative CO2 cooling calculations ................................................................... 85
Bibliography ................................................................................................................................................ 87

5
Eutectic Freeze Crystallization on Sodium Chloride

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
couldn’t 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.

6
Eutectic Freeze Crystallization on Sodium Chloride

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 7°C, 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 10°C.

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 12°C for
a solution containing magnesium.
 At a TLM of 8°C the heat transfer in the presence of Magnesium is 30% higher than for the pure
solution.

7
Eutectic Freeze Crystallization on Sodium Chloride

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.

8
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

Nomenclature

List of symbols

11
Eutectic Freeze Crystallization on Sodium Chloride

List of subscripts

List of abbreviations

12
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

1.1.Eutectic freeze crystallization

Eutectic Freeze Crystallization (EFC) is an innovative separation technique, mainly applicable for salt
solutions in water. The technique operates best for solutions with a salt concentration near the eutectic
point. The main advantage is that a theoretical zero liquid discharge (ZLD) can be obtained and that very
clean water and sodium chloride are being produced.

Crystallization is a well known separation method in industry. It refers to the formation of a dispersed
solid phase from a solution or a melt. This is attained by pushing the liquid to a supersaturated phase by
cooling-, evaporating of the solution or another method. EFC is a crystallization form in which not one
component of the solution is crystallized, but two compounds crystallize at the same time. In this
research those components are water and sodium chloride. The process is described by the phase
diagram of Figure 1-1. Starting with a solution in a certain concentration (A) the mixture is cooled to the
point where ice is formed (B). Continuous ice being produced involves an increase in salt concentration
in the liquid. Finally the solution becomes supersaturated with salt upon cooling and the eutectic point
is reached in the phase diagram (C). At this temperature the largest amount of salt possible is dissolved
in the solution. When the cooling is continued ice and salt crystals are formed at the same time. By
making use of the gravity, both compounds are separated and filtrated to obtain the products.

Figure 1-1; Eutectic phase diagram of salt in water

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 1990’s 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
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

1.2.Sodium chloride solutions

Food grade salt accounts for only a small part of salt production in industrialized countries (3% in
Europe), but the majority is sold for industrial use. Salt has great commercial value because it is a
necessary ingredient in many manufacturing processes. A few common examples include: the
production of pulp and paper, setting dyes in textiles and fabrics, and the making of soaps and
detergents.

Salt is being produced by:

 Evaporation of seawater by the sun


 Brines (from rocks f.e.) are being treated by (multiple stages of evaporation). Chemicals are
required in the recrystallization process to eliminate impurities from the brine.

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 0.1°C. 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.

Figure 1-2; Phase diagram NaCl solution

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
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

1.3.Cooled Disk Column Crystallizer (CDCC)

The cooled disk column crystallizer is an experimental unit for small scale experiments, which has been
used for heat transfer experiments. The crystallizer with a volume of 10 liter is equipped with a stainless
steel heat exchanger in the bottom, which has a cooling area of 0.031 m2. Four rotating Teflon scrapers
prevent scaling and improve heat transfer in the set-up.

The heat exchanger is cooled with a freezium solution. Freezium is a cooling


liquid based on potassium formate to obtain a freezing temperature of -
60°C. The temperature of the freezium is accurately measured and
controlled within 0.1 °C by a cooling machine. The properties of the
freezium are shown in Table 1-1

Table 1-1; Properties of freezium

Cp  2.55kJ / (kg.K ) specific heat


v  11mm 2 / s kinematic viscosity
  1.36kg / dm3 density
  0.45W / (m.K ) thermal conductivity
Figure 1-4; Photo of the
CDCC

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
Eutectic Freeze Crystallization on Sodium Chloride

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 +/- .01°C. The flow rate of the coolant is measured with a Rosemount E-
series magnetic flow meter with an accuracy of +/- 1 liters/hour.

M
M
Pi-001

Pt-001

Tqt001 Tqi001 Ft-002

Fi-002

Ti-010 Tt-010

Ti-001 Tt-001

Coolant cycle Tt-009

Ft-003
Ti-009
Ti-002 Tt-002
Fi-003
Pi-003
Ti-005

Pt-003
Tt-005

Ti-003 Tt-003
Pt-002
Tt-004

Fi-001
Ft-001
Ti-004

Pi-002

Figure 1-5; P&I diagram CDCC

At the bottom of the crystallizer the scrapers rotate over the HEX surface

19
Eutectic Freeze Crystallization on Sodium Chloride

1.4.Scraped Cooled Wall Crystallizer (SCWC) in skid

Most experiments of this thesis are performed with the skid mounted unit. As shown in Figure 1-6 the
whole set-up has been mounted on a construction to make the unit portable. The unit consists of all
required equipment to separate a saline water solution into its pure components.

Figure 1-6; Photo of the skid mounted unit

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 pre-
cooler, 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
Eutectic Freeze Crystallization on Sodium Chloride

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

Figure 1-7; Process flow diagram skid mounted unit

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
Eutectic Freeze Crystallization on Sodium Chloride

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 Eq. 1-1

Figure 1-8; 200L crystallizer in skid

Figure 1-9; Heat exchangers in the 200 liter crystallizer in 3d view and top view

22
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

1.6.Scope of the research

Highly concentrated sodium chloride solutions are a large by-product in industry. These product streams
are often disposed in the environment, with possible environmental pollution. Zero liquid discharge
methods (ZLD) are able to separate the waste into the pure and valuable components. The most
commonly used ZLD method is evaporative crystallization, which is a high energy consuming process.

Eutectic Freeze Crystallization is a newly developed ZLD method, with potential benefits for sodium
chloride solutions. The aim of the research is to investigate this potential and to develop an EFC process
from lab scale to industrial scale. The following aspects are addressed in this report:

 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
Eutectic Freeze Crystallization on Sodium Chloride

2. Theoretical heat transfer on scraped wall

The performance of the heat transfer is of great importance for the crystallizer, because it directly
influences the capacity. In this chapter the heat transfer for the SCWC in the 200L set up will be
theoretically determined. In Chapter 4 the theoretical heat transfer will be compared with the
experimental performance under different operating conditions. In Paragraph 6.2 calculations are
presented for indirect evaporative CO2 cooling.

2.1.Overall heat transfer

The heat transfer between the coolant and the solution is defined by TCOOL OUT
the heat transfer coefficient U in the heat transfer equation (Eq. 2-1).
kstainless steel twall
Q
 UOVERALL * TLM
A Eq. 2-1

UCOOL
The temperature difference between the coolant and the solution
(TLM) is the driving force behind the heat transfer. The temperature in
the solution is constant and the temperature of the coolant differs

coolant
from in and outlet. The temperature difference between two fluids in a solution
heat exchanger is best represented by the logarithmic mean
temperature difference (Eq. 2-2). T(°C)
TEUT

(TSOL  TCOOL. IN )  (TSOL  TCOOL.OUT )


TLM 
T T
ln( SOL COOL. IN )
TSOL  TCOOL.OUT
TCOOL
T  TCOOL. IN Eq. 2-2
TLM  COOL.OUT
T T
ln( SOL COOL. IN )
TSOL  TCOOL.OUT
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 1 t WALL 1
 ( )
U OVERALL U SOL kSTAINLESS STEEL U COOL Eq. 2-3

25
Eutectic Freeze Crystallization on Sodium Chloride

2.2.Heat transfer coefficient metal wall

The thermal conductivity of stainless steel is dependent on temperature and is calculated for an average
temperature of -25°C. The empirical relation (Eq. 2-4) to describe this dependency is described by Man
[X] and is used to determine the heat transfer coefficient of the wall in Eq. 2-5. Furthermore the wall
thickness of 4 mm is used to calculate the heat transfer coefficient in the metal wall, which is part of the
overall heat transfer equation (Eq. 2-5).

W
kSS 316  0.0265T  14.593  13.9
mK Eq. 2-4

1 1 4E -3 1
 ( )
U OVERALL U SOL 0.0139kW / (m * K ) U COOLANT
1 1 1
   0.288
U OVERALL U SOL U COOLANT Eq. 2-5

1 kW
UWALL   3.5 2
0.288 m K

2.3.Heat transfer coefficient coolant

In the freezium flow convective heat transfer occurs. In this paragraph the heat transfer in the freezium
flow through the outer heat exchangers of the 200 liter crystallizer will be calculated.

The flow regime influences the convective heat transfer to a large extent. To determine the flow regime
the hydraulic diameter for the channels has to be determined.

As shown in Figure 2-2 the fluid flows from top to bottom and vice versa through the channels in the
heat exchanger. The channel is approached as a square of 20*20 mm. The hydraulic diameter (Eq. 2-6) is
a function of the cross sectional area and the wetted perimeter. The Reynolds number is calculated for
the freezium flow through the tubes by Eq. 2-8.

4 A 4  (20  20) 3
DHYD   E  0.02m
WP 4  20 Eq. 2-6

V 12
u   0.5m / s
A 1000  60  0.022 Eq. 2-7

u  DHYD 0.5  0.02


Re    909
 11E  6 Eq. 2-8

26
Eutectic Freeze Crystallization on Sodium Chloride

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 100–1000 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).

  0.0668  Re Pr DH / Lltube kW


UCOOL  Nu  [3.65  ]  1.05 2
DHYD DHYD 1  0.04(Re Pr DH / Ltube ) 2/3
m K Eq. 2-9

v    cp
Pr 
 Eq. 2-10

27
Eutectic Freeze Crystallization on Sodium Chloride

2.4.Heat transfer in solution

Heat transfer in the solution in the crystallizer is quite complex. The scraper passages involve good
mixing and a turbulent flow regime next to the wall. The presence of solid crystals of both ice and salt
influences the flow regime, heat conductivity and the effective viscosity of the mixture.

Accurate data on the Reynolds and Nusselt numbers inside the crystallizer are unknown. Experiments in
Chapter 4 show that the heat transfer differs as a function of the location in the crystallizer. With the
penetration theory an estimate of the heat transfer is made for a particular situation, which should
approach the experimental situation.

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.

  U turbulent 2
N min 
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.

T   2T
 
t   Cp y 2
Eq. 2-12
y  0, T  Twall ; y  ; T  Tbulk
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
Eutectic Freeze Crystallization on Sodium Chloride

T     Cp
Q(t )    (Tbulk  Twall ) 
y t Eq. 2-13

    Cp
U SOL (t )  2
t Eq. 2-14

    Cp     Cp  n  N
t t
1 s s

U SOL. AVERAGE    U (t )  dt  n  N    dt  2
ts 0 0
t  Eq. 2-15

Thermal conductivity in the solution of mother liquor and crystals


The solution in the crystallizer consists of a saturated sodium chloride solution containing both ice and
salt crystals. The conductivity for liquids containing solid particles is well described by Tareef (1940). In
Eq. 2-16 the relation for the conductivity of the mixture as a function of the solid concentration (ws),
liquid- and solid conductivity is described, which is valid for solid concentrations up to 0.4.

2l  s  2 ws  (l  s )
SOL  l  [ ]
2l  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 -21.1°C the thermal conductivity in
the liquid solution is 0.49 W/(m*K) according to Eq. 2-17.

29
Eutectic Freeze Crystallization on Sodium Chloride

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.

Specific heat ice slurry


The heat capacity at the eutectic temperature is an apparent heat capacity. Besides the sensible heat
effects, the heat effects of the phase change are incorporated. The specific heat of the slurry is
described by Meeuwisse and Infante Ferreira [XII]. For a NaCl concentration of 22 wt% and 10 wt% ice at
a temperature of -24°C a specific heat of 10 kJ/(kg.°K) is determined. The concentration in the
experiments is higher and there is a little deviation in concentration and temperature. Unfortunately
more accurate data is unavailable in literature, so this approximation has been used. It was tested that a
10% change in specific heat results in a difference of approximately 1% of the total heat transfer
coefficient of the process.

The penetration theory can now be used to calculate the average heat transfer coefficient with Eq. 2-15,
which gives a result of 5.9 kW/(m2.°K).

    Cp  n  N kW
U SOL  2  5.9 2
 m K Eq. 2-18

Determination of the Reynolds number


To get more understanding of the flow in the crystallizer the Reynolds number is calculated. In a stirred
rotational vessel, the Reynolds number is generally described by Eq. 2-19, where D is the diameter of
the stirrer, assumed equivalent to the scraper in the crystallizer. This formula assumes however that
there is no slip between the stirrer and the fluid. For Reynolds numbers above 10.000 the system is fully
turbulent.

 ND 2
Re STIRRED.VESSEL 
 Eq. 2-19

Thomas equations [XVII] describes the viscosity of the slurry as a function of the solid content.

ICE.SLURRY  LIQUID (1  2.5ws  10.05ws 2  0.0027e16.6 w )


s

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
Eutectic Freeze Crystallization on Sodium Chloride

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.

2.5.Overall heat transfer coëfficiënt

With the three components of the heat transfer resistance calculated above, the overall heat transfer
coefficient in the outer heat exchangers of the SCWC is determined with Eq. 2-21.

1 t WALL 1 1
( ) 
U OVERALL kSTAINLESS STEEL U COOL U SOL
1
 0.288  0.950  0.17
U OVERALL Eq. 2-21

kW
U OVERALL  0.71
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
Eutectic Freeze Crystallization on Sodium Chloride

3. Heat transfer experiments 10L CDCC

This chapter describes experiments on the heat transfer in the 10 liter CDCC. The effect of scaling on the
wall will be investigated under different conditions. The experimental set-up of the 10liter CDCC is
described in paragraph 1.3 on page 18.

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.

P  freezium  m  cp freezium  (T freezium.out  T freezium.in )


UOVERALL  
A  TLOG. MEAN 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
Eutectic Freeze Crystallization on Sodium Chloride

3.2.Results & discussion

Figure 3-2 shows the results of the experiments for the


pure NaCl solution. In the upper graph the temperatures
of the coolant and the solution are shown as a function of
time. After 5200 seconds the eutectic point has been
reached as shown by the temperature jump in the blue
line. Just before the jump the liquid is in the super cooled
state. Once the first nucleus appears, the crystallization
process starts and the eutectic temperature is reached
rapidly. The measured temperature is very well
corresponding with literature at -21.1°C.

The red line in Figure 3-2 is the entering freezium


Figure 3-1; Scaling in CDCC by Rodriguez
temperature. For five different temperatures of the
freezium the behavior has been investigated. In between those temperatures the freezium flow has
been closed so the coolant heats up, which results in the peaks. Closing the freezium flow makes it
possible to set the temperature to the required value more accurately.

The lower graph of Figure 3-2 has the same time scale as the upper graph. The green line is half of the
heat transfer per square meter of heat exchanger surface (P). This is half the value to better fit in the
graph scale. Dividing the power per square meter by the temperature difference (TLM) between
solution and coolant results in the heat transfer coefficient (U) as indicated by the red line.

33
Eutectic Freeze Crystallization on Sodium Chloride

Figure 3-2; Results CDCC pure NaCl experiment

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
Eutectic Freeze Crystallization on Sodium Chloride

Figure 3-3; Torque vs heat transfer coefficient at constant TLM

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 10°C between coolant and solution the maximum power of

35
Eutectic Freeze Crystallization on Sodium Chloride

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 (-23°C), 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.

Figure 3-5; Power vs TLM for two different solutions

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
Eutectic Freeze Crystallization on Sodium Chloride

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 7°C, 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 10°C.

37
Eutectic Freeze Crystallization on Sodium Chloride

4. Heat transfer experiments 200L SCWC

In the skid (set-up described in paragraph 1.4) a full experimental cycle of crystallization process at a
large scale can be analyzed. The skid is connected to belt filters to filtrate and wash the products for
continuous operation and production of clean salt and water. This chapter describes the heat transfer in
the Scraped Cooled Wall Crystallizer (part of the skid), which will be compared with the heat transfer in
the CDCC. This will be done for the pure NaCl solution and with magnesium added to the solution.

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.

4.2.Results & discussion

Initially all four heat exchangers were operational at the same time. A lot of torque was generated by
the scraper motor and a lot of noise indicated the presence of scaling. When the inner heat exchangers
were turned off, more than 4 times less torque was measured. Unfortunately, more accurate numbers
cannot be given, because the flows are unknown in the inner heat exchangers due to malfunctioning of
the flow meters.

The rotational velocity in the crystallizer results in centripetal forces. Due to density differences, ice
moves to the center and salt to the outer parts of the crystallizer. Ice might build up in the inner ring and
can hardly escape due to construction of the scrapers on top of the heat exchangers. An explanation of
the higher torque in the inner heat exchanger could be that the ice accumulation resulted in increasing
scaling effects.

Another explanation comes from the rotational Reynolds number of the solution around the inner plate.
Here laminar flow might stimulate scale deposition. As shown by Eq. 4-1 the Reynolds number is a
function of the squared diameter, which results in an almost 6 times smaller Reynolds number on the
inner plates compared to the outer plates.

 ND 2
Re STIRRED.VESSEL 
 Eq. 4-1

38
Eutectic Freeze Crystallization on Sodium Chloride

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.

Figure 4-1; Heat transfer pure NaCl in SCWC

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 7°C 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 13°C, increasing the
temperature difference does not increase the power per square meter a lot anymore.

39
Eutectic Freeze Crystallization on Sodium Chloride

Figure 4-2; Heat transfer NaCl + Mg in SCWC

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 8°C 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
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

Difference in upper and lower heat exchanger


The heat transfer between upper and lower heat exchangers differs approximately 40%. A large
number, considering that the dimensions of the heat exchangers are the same. An explanation could be
that the presence of ice rising to the top of the crystallizer limits the local heat transfer. To investigate
this, the heat transfer at temperatures of the solution above the eutectic temperature has been studied.
At this temperature, heat transfer cannot suffer from solid particles. For both heat exchangers the heat
transfer is a little better in the absence of solid particles as shown in Figure 4-4. The differences are
small however and the difference in power for the upper and lower heat exchanger cannot be explained
by the difference in solid concentrations.

Figure 4-4; Effect of solid particles on the heat transfer

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
Eutectic Freeze Crystallization on Sodium Chloride

Figure 4-5; Heat transfer coefficient under static conditions

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).

U AVERAGE LOWER  U AVERAGE UPPER


deviation under no stirring 
U AVERAGE UPPER
0.218  0.214 Eq. 4-2
deviation under no stirring   1.9%
0.214

Figure 4-6; Heat transfer coefficient under stirring conditions

43
Eutectic Freeze Crystallization on Sodium Chloride

U AVERAGE LOWER  U AVERAGE UPPER


deviation under stirring 
U AVERAGE UPPER
0.82  0.57 Eq. 4-3
deviation under stirring   44%
0.57

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.

4.3.Corrosion in the 200L crystallizer

The experiments on the scraped wall heat transfer took a couple of days, while the solution was kept in
the crystallizer during the nights. Despite the use of stainless steel, the salty solution stimulates
corrosion of the equipment to a large extent. Figure 4-7 shows ICP results of some metal components of
the samples from the solution that was kept in the crystallizer for a day. These measures are interesting
to see the damage to the crystallizer due to corrosion. In three days approximately 5000 ppb is the total
of the increased concentration. On a 200 liter volume this corresponds to approximately 1 gram of
metal loss in three days.

Figure 4-7; Corrosion in 200L crystallizer

44
Eutectic Freeze Crystallization on Sodium Chloride

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 12°C for
a solution containing magnesium.

 At a TLM of 8°C 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
Eutectic Freeze Crystallization on Sodium Chloride

5. Continuous operation of the skid and washing of the products

The heat transfer has been theoretically and experimentally analyzed. In Chapter 3& 4 it has been
shown that crystallization for NaCl solution works and the heat transfer on the scraped surface can be
effective. What is unknown yet is how the system behaves under continuous operation in a full cycle
from feed to products, and what the qualitative and quantitative products are for the process.

In an experiment steady state operation was simulated. For a period of five hours the skid produced salt
and ice under constant production rates. The mass flows in the system were kept as constant as
possible. Mass- and energy balances are made and the heat losses are determined. The ice- and salt
slurries are filtrated on the belt filter. Washing to obtain higher purity of the products has not been done
on the belt filter, but small scale washing experiments are performed afterwards.

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

Brine storage Pre-Cooler

Cooling machine

NaCl
Salt slurry

Figure 5-1; Simplified flow diagram skid

46
Eutectic Freeze Crystallization on Sodium Chloride

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 MΩ-cm. The cold room was set at -7.5°C and the washing water cooled to 1°C. 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 -1.5°C. The
temperature of the cold room was -7°C and the slurry temperature was -19°C. 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 -15°C. After weighing the mixture is filtrated and the solid particles remain on the glass filter.

47
Eutectic Freeze Crystallization on Sodium Chloride

Dividing the mass of the dry solid by the mass of the initial solution, the solid fraction (m solids/msolution) is
determined.

Figure 5-2; Experimental filtration & washing set-up

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 μm for a residence time of 1.6 hour. The ice
crystals (right) are approximately three times smaller with an average size of 100 μm.

 SOLVCRYSTALLIZER 1200  0.180


tresidence.crystallizer    5800s  1.6hour
mFEED 0.037 Eq. 5-1

48
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

Figure 5-4; Production of filtrated ice and salt vs time

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.

Figure 5-5; Mass balance continuous operation

50
Eutectic Freeze Crystallization on Sodium Chloride

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.

(  crystal   solution )  g  Dcrystal


2

u particle 
18solution 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.

Figure 5-7; Flow scheme settler (ideal situation) Figure 5-6; Top view in the settler (non ideal situation)

51
Eutectic Freeze Crystallization on Sodium Chloride

5.4.Determination of heat losses in the crystallizer

The skid is well insulated to prevent heat loss. Unfortunately heat loss can not be prevented totally.
Temperature differences between crystallizer and surrounding are around 40°C, so the driving force
behind heat losses is large. To get an idea about the heat loss in the crystallizer an experiment was
executed. At an initial temperature in the crystallizer of -17.5°C the cooling machine was turned off.
Under continuously stirring by the scrapers the temperature increase was measured. The main
difference with constant operation is that no solid particles were present. It is assumed that the effect of
solids in this experiment is small, so a good impression about the heat losses is obtained. The
temperature in time in the crystallizer during this experiment is shown in Figure 5-8. The heat loss is
calculated in Eq. 5-3.

Figure 5-8; Heat losses from crystallizer to surroundings

dQ dT
Ploss   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  constant  (Tenvironment  Tcrystallizer )


Ploss 0.51 kW
constant    14.2 E 3 Eq. 5-4
Tenvironment  Tcrystallizer 20  16 C

52
Eutectic Freeze Crystallization on Sodium Chloride

5.5.Ice filtration & washing

From the crystallizer and settler system, two liquid solid


mixtures are being produced. From the top ice slurry is
produced and from the bottom salt slurry is extracted
from the system. The solid liquid mixture has to be
separated into a solid and a liquid. By filtration this can
easily be done. However, some mother liquor is bonded
to the solid crystals, causing contaminations in the
products. In this paragraph washing of the ice crystals and
the influence on the product purity is described. It might
also occur that contaminants from the feed stream
incorporate in the solid crystals and cannot be washed out. Experiments have investigated these
phenomena. In the next paragraph the filtration and washing of the salt has been described.

Ice slurry enters the belt filter at its eutectic temperature of -21°C. The belt filter is an open system,
which is in direct contact with the surrounding air at approximately 20°C. This high temperature air is
sucked through the ice layer by the vacuum pump causing lots of heat transfer. The ice mixed with the
salty solution is heated up and melts at a temperature between -21 and 0 °C, depending on the amount
of salt present. Due to the steepness of the solubility line in the phase diagram of Figure 1-2 (page 16),
the salt concentration in the mother liquor stays close to saturation at elevated temperatures, causing
lots of ice melting.

Figure 5-9; Mass balance ice filtration

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 -17°C 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
(28.2•0.194) 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
Eutectic Freeze Crystallization on Sodium Chloride

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.

Soidum chloride (wt%) Other contaminants (ppm)

Figure 5-10; Contaminant concentration in ice after washing

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
Eutectic Freeze Crystallization on Sodium Chloride

5.6. Salt filtration & washing

The salt is filtrated on a different belt filter than the ice, but the
principle is the same. By creating a vacuum under the belt, liquid is
separated from the solid crystals.

As indicated in the phase diagram of Figure 1-2 NaCl-2H20 is


formed at eutectic crystallization instead of pure NaCl crystals. At
0.1°C the recrystallization to the anhydrate takes places, which is
the desired product in the process. It is possible to let the
recrystallization take place in a separate vessel, which heats up the
salt slurry to above the recrystallization temperature. During the experiments the recrystallization took
place on the belt filter. Extra heat was supplied to the salt slurry by opening the doors of the belt filter
as shown in Figure 5-11.

As a result cold is lost to the environment and the filtrate leaves the system at 1.1°C. By heating of the
flow from the eutectic temperature to the filtrate temperature a total of 0.73kW of cold is lost to the
surrounding.

The salt from the belt filter is less contaminated than the ice. Only 13% of the initial magnesium content
is found back in the salt. Furthermore small amounts of potassium and bromine are present in the salt.
These elements were also found in the feed stream of the process. As shown in Figure 5-13 all the
contaminants are very well washed from the crystals, which means that no contamination is built inside
the crystals.

Figure 5-12; Mass balance salt filtration


Figure 5-11; Photo of the salt belt filter

55
Eutectic Freeze Crystallization on Sodium Chloride

Figure 5-13; Contaminant concentration in salt after washing

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.

Ploss.crystallizer  constant  T  14.2E 3  (20  21)  0.58kW


Eq. 5-5

56
Eutectic Freeze Crystallization on Sodium Chloride

m  hin m  hout

Pextracted HEX

m(hin  hout )  Pextracted . HEX  Plosses Plosses


Plosses  Pextracted . HEX  m(hin  hout )
m(hin  hout )  5.02  2.96  2.06kW

Figure 5-14; Energy balance crystallizer and settler: In formula and schematically

Table 5-1; Enthalpy change solution coming in and going out

Table 5-2; Energy losses in the crystallizer & settler (Plosses)

Figure 5-15; Pie of the energy


flows in the crystallizer and
settler

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.

h flows 2.96
crystallizer  settler    0.59
Pextracted 5.02 Eq. 5-6

57
Eutectic Freeze Crystallization on Sodium Chloride

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.

Figure 5-16; Overview mass- & energy flows continuous operation

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
Eutectic Freeze Crystallization on Sodium Chloride

Pextracted Pextracted . 5.02  1000 kWh kWh


  3
 15E 5  436 3
Vwater. prod m prod . water 3.2 E kg prod . water m prod . water
Pextracted Pextracted . 5.02  1170 kWh kWh Eq. 5-7
  3
 14 E 5  395 3
V feed m feed 4.13E kg. feed m . feed

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 Eq. 5-8
  132 3
V feed  COP 3.0 m feed

59
Eutectic Freeze Crystallization on Sodium Chloride

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.

h flows 2.96
crystallizer  settler    0.59
Pextracted 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
Eutectic Freeze Crystallization on Sodium Chloride

6. Optimization and up scaling

The skid with 200 liter SCWC is an experimental set-up. Many improvements and optimizations of the
process are possible to promote industrial application. Heat losses can be prevented and cold that is
produced can be reused on different manners. Possible improvements for filtration and washing of the
products are proposed and improving heat transfer on the scraped wall is discussed. Furthermore an
introduction is given on evaporative CO2 cooling and a 2-step refrigeration method.

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:

QCOOLING
COP 
PELECTRIC Eq. 6-1

WATER
ICE

FEED Q cooling
Evaporator Condenser Condenser 2
Teut =- 22C

SALT

Figure 6-1; Heat recovery in EFC by means of a 2-step refrigeration unit

61
Eutectic Freeze Crystallization on Sodium Chloride

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.

6.2.Evaporative CO2 cooling

In the CDCC and the SCWC crystallizers cooling is done with a 2-step refrigeration cycle. The refrigerant
is not directly fed in the heat exchanger of the crystallizer, but an additional coolant (freezium) is used
as transport agent. This chapter describes theoretical analysis of 1-step refrigeration with CO2 as
refrigerant, directly fed to the heat exchanger of the crystallizer. The refrigerant is extracting heat from
the solution in the crystallizer by indirect cooling with a scraped wall heat exchanger. Liquid CO2 enters
the heat exchangers, in which it is (partly) evaporated.

CO2 has specific benefits in use as a refrigerant. First of all it is limitless available in our atmosphere. It
has no ozone depletion potential and insignificant global warming potential (at least in the small
amounts used in the refrigerator). Furthermore it is a cheap, non poisonous and non flammable
refrigerant.

This paragraph describes the heat transfer for evaporative CO2 cooling. A spreadsheet program has been
developed to analyze the heat transfer. Parameters such as dimensions of the heat exchanger and flow
rate of the CO2 are inputs for the spreadsheet so these can be optimized for design purposes. This
paragraph will calculate the heat transfer for the same tube dimensions as in the 200L crystallizer. A
pure liquid is assumed to enter the heat exchanger and a multiphase flow with a vapor fraction of 50%
leaves the heat exchanger.

62
Eutectic Freeze Crystallization on Sodium Chloride

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 Zuber’s pool boiling equation [XVI].

UCO2total  [ EU ]liquid  [SU ] pool .boiling


Eq. 6-2

Liquid heat transfer


The first term consists of the heat transfer in case of pure liquid in the duct. This is a function of the
liquid Reynolds number and the Prandtl number as shown in the Dittus-Boelter equation of Eq. 6-3.

l
U liquid  0.023Rel 0.8 Prl 0.4
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
E  1  24000 Bo1.16  1.37( )
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.

U
Bo 
(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.

1  x 0.9 v 0.5 l 0.1


X tt  ( ) ( ) ( )
x l v Eq. 6-6

Boiling heat transfer


The second term in the total heat transfer equation (Eq. 6-2) is the pool boiling term which consists of
the suppression factor S and heat transfer coefficient for pool boiling U, which is a function of the heat
flux, so again the process is iterative. The heat transfer equation (Eq. 6-7) proposed by Cooper [XV] is
used. The suppression factor (Eq. 6-8) accounts for the lower heat transfer in the vapor phase of the two
phase flow, compared to the heat transfer in pure vapor state.

63
Eutectic Freeze Crystallization on Sodium Chloride

P 0.67
U pool  55Pred 0.12 (  log Pred ) 0.55 MW 0.5 ( )
AHEX Eq. 6-7

1
S 6
1  1,15  10  E 2  Rel1.17 Eq. 6-8

General equations used


G (1  x ) DHYD
Rel 
L Eq. 6-9

GxDHYD
Rev 
V Eq. 6-10

l Cpl
Prl 
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.

qhlatent mCO2
Lrequired 
U (TEUT  TCO2 ) Dhyd
Eq. 6-12

The required length does not incorporate the pressure drop. Which is calculated based on Lockhart-
Martinelli correlations.

64
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

6.3.Teflon encapsulated heat exchanger

As shown by the experiments scaling plays an important role in EFC for sodium chloride. It limits the
capacity in a large extend, which influences investment cost, size of equipment etcetera. Finding a way
to reduce scaling effects might have large effects on overall performance. Adding magnesium to a
solution already has benefits, but the scaling is still present in the system. Also some negative effects
come with the magnesium. A lower eutectic point is attained and magnesium is found back in the
product. It can be washed from the crystals, but the washing decreases energy efficiency of the process.

Teflon surfaces in heat exchangers have shown to reduce fouling from various fluids, for example in
seawater evaporation. A negative effect is its bad conductivity and erosion occurring if used in a very
thin layer. Novel methods are covering heat exchangers with extremely thin surface alloys. With
different producing techniques and depending on the crystals almost all fouling is eliminated for
convective heat transfer in certain situations according to Muller [XXII].

66
Eutectic Freeze Crystallization on Sodium Chloride

6.4.Filtration & washing of salt

From the experiments of paragraph 5.6 it is concluded that large amounts of energy is lost by heating up
the filtrate. The slurry is heated to above the recrystallization temperature (0.1°C) to obtain the
anhydrate.

By insulating of the belt filter the filtrate can theoretically be kept around the eutectic temperature. To
prevent heat losses, the slurry should be filtrated at the eutectic temperature into the di-hydrate and
the mother liquor. The dry di-hydrate is transported on the belt filter and has to be recrystallized to the
anhydrate. The issue of heating on the belt filter is that the water being produced by recrystallization is
directly dissolving the salt that is present. In the worst case a saturated NaCl solution is filtrated.

For 1 gram of filtrated NaCl coming out of the system, 0.9 gram of water is being produced during the
recrystallization process as calculated by Eq. 6-13. In the worst case the water leaves the system as a
saturated NaCl solution and 21.6% of the produced NaCl crystals is lost.

NaCl.2 H 2O NaCl  2 H 2O
mwater 2  M H 2O 2  18 grH 2O
   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.

Figure 6-4; Conceptual filtration, recrystallization & washing of the salt

67
Eutectic Freeze Crystallization on Sodium Chloride

6.5.Washing & filtration of ice

As described in paragraph 5.5 a lot of ice melts on the belt filter during filtration. This can be prevented
by insulation of the filtration process. The washing of the ice also involves difficulties, caused by the
steepness of the solubility line and the low eutectic temperature of a sodium chloride solution. The
steepness of the solubility line involves a small difference in saturation concentration in varying
temperature. This property results in large amounts of ice melting when heat is added during the
washing of the ice in the presence of salt.

As stated in paragraph 5.3 the settler is not working properly, because the slurry from the crystallizer
enters on top. By pumping the slurry in the middle of the settler, it is expected that the salt
concentration in the ice product before washing is decreased. Despite of the high salt concentration in
the ice it is demonstrated by the experiments that all contaminants can be washed from the product.

Countercurrent washing of ice with NaCl solution on belt filter


In the experiments the ice, which is at the eutectic temperature, is washed with very pure water at 0°C.
Due to the large temperature difference and the presence of salt, the ice melts fast as experimentally
determined in paragraph 5.5. Washing with a different solution at a lower temperature would prevent
this undesired effect. However, washing liquids other than water might contaminate the ice rather than
wash it. A salt solution for washing can be cooled towards the eutectic temperature depending on the
concentration. A high concentration influences the dissolving process of salt from the crystals in a
negative way.

68
Eutectic Freeze Crystallization on Sodium Chloride

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 0°C 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 -10.5°C 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 0°C 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


M -10.5°C
Clean
water (0°C)

Ice product
Ice
slurry Washing Washing
Filtrate
filtrate 1 filtrate 2

Figure 6-5; Scheme countercurrent washing of ice

69
Eutectic Freeze Crystallization on Sodium Chloride

Washing with a wash column


Wash columns are available on the market which might be more effective than washing on the belt
filter. Experimental research is required to investigate the applicability for ice as a product from EFC for
NaCl solutions. In this paragraph only an introduction to the technique is given.

The ice slurry enters the column in the bottom as shown in Figure 6-6. The mother liquor is filtrated and
redirected to the crystallizer. The pure ice crystals are transported to the top surrounded by some
residual mother liquor. The ice is leaving the column on the top and heat is added to melt the ice. Here a
heat exchanger could be used to pre cool the solution that enters the crystallizer for example. Part of
the produced pure water is redirected to the column and used as a washing liquid. The washing liquid is
in contact with the ice through the column and dissolves the contaminants. Finally the contaminated
washing liquid flows through the filter and is redirected to the crystallizer together with the mother
liquor.

This is the basic idea of the process. Scrapers and stirrers might be introduced to optimize the process.
Also compression of the slurry can be introduced to promote the solid liquid separation and the
filtration process. As indicated there exists a temperature gradient in the column. The slurry enters at its
eutectic temperature and the ice on top must be close to 0°C. In case this temperature would be too
low, the washing liquid would instantaneously freeze and no washing takes place. By controlling the
temperature and the mass flow of the washing liquid the temperature in the column can be influenced.

Due to the washing liquid the energy consumption of a process increases. Ice is being produced that is
molten again to be used as a washing liquid. In industrial application typical amounts of required
washing liquid is 20% of the total amount of ice that is being produced. This is a rough averaged
number, which is influenced by desired product quality and the contamination of the mother liquor.

Pure product

Melting heat
M
Washing liquid
T=0°C

Washed ice

Unwashed
ice
Ice slurry T=-20°C
filter

Mother liquor

Figure 6-6; Wash column to purify ice

70
Eutectic Freeze Crystallization on Sodium Chloride

6.6.Energy consumption in an ideal case

The paragraph describes a theoretical flow scheme for an ideal case of continous EFC operation. As a
reference 1 m3 brine (corresponding to 1036kg) is used as an entering feed solution. The salt
concentration is 5 wt% just as the concentrated brine of the EFRO solution described in Paragraph 1.5.

The flow scheme is represented by Figure 6-7 with a wash column to wash the ice and a belt filter to
filtrate, recrystallize and wash the salt as described previously in this Chapter. Assuming that the feed is
separated in pure water and pure NaCl the products streams are 984 kg and 52 kg respectively. The
Figure will be described starting from the product streams. 20% of the produced water is used as a
washing liquid (as described in Paragraph 6.5). Ice slurry with a 20% solid fraction is fed to the wash
column. The mother liquor is assumed to have no cold loss here and is transported back to the feed of
the crystallizer. For the salt filtration, the system of Paragraph 6.4 is used. On the second belt filter
recrystallization of the salt takes place at the recrystallization temperature of 0.1 °C, and a saturated
sodium chloride solution leaves the system, which is the water separated from the di-hydrate. The
mother liquor from the first belt filter is assumed to undergo no cold losses and is redirected to the
crystallizer at the eutectic temperature.

Figure 6-7; Flow scheme of a theoretical ideal operation

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
Eutectic Freeze Crystallization on Sodium Chloride

Table 6-1; Energy requirements for an ideal process

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 Qrejected 154 kWh Eq. 6-14


3
   51 3
m feed COP 3.0 m feed

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
Eutectic Freeze Crystallization on Sodium Chloride

7. Environmental analyses of fresh water producing methods

In the previous chapters a study has been made to EFC for sodium chloride solutions. This chapter will
look into environmental and economical aspects for the process and make a comparison to other water
purification techniques by means of a life cycle analysis (LCA). Brine disposal is a common practice in
today’s industry for the production of fresh/clean water for industrial or domestic uses. The alternative
evaporative crystallization and eutectic freeze crystallization methods have principally no brine disposal.

7.1.LCA on potable water production

Nowadays many different clean water production methods are being used. Depending on the local
availability of water resources a comparison can be made between different methods. When seawater is
available an undepletable resource can be used, but seawater desalination is an energy demanding
process. Most desalination processes used nowadays involve a high concentrated waste stream which is
to be disposed. In LCA studies the treatment of the disposal will be evaluated for different methods, for
instance to produce a cubic meter of potable water satisfying the requirements for human consumption
(as established by the 98/83/CEE European directive).

Also the availability of water resources is different in each case making a water production LCA complex.
Even when in two cases ground water is available the required quality of the product water highly
influences the environmental and economical impact of achieving it; the initial conditions are different
for each case and alternatives are hard to compare.

In Figure 7-1 the water supply system has been decomposed in three sub systems. The first one is the
extraction and distribution phase. All transport from cradle to grave of the water is incorporated here.
The second sub system handles the most important part of the supply system. This is the cleaning
process. Energy consumption, the use of chemicals, the construction of the plant and the concentrate
disposal are the most important impacts on the environment in this process. Finally there is the use of
the consumer as a sub-system. For example the process of a person heating up the water to take a
shower is considered in this sub-system. In this Paragraph the focus will be on the second sub-system
and some water production LCA’s will be compared.

73
Eutectic Freeze Crystallization on Sodium Chloride

Water
extraction &
distribution

Energy consumption

Use of chemicals
Cleaning
Water supply process
Construction of the plant

Concentrate disposal

Water use by
consumer

Figure 7-1; Visualization of the water supply system

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.

Figure 7-2; Electricity consumption different water treatment processes


According to F. Vince et al [XXIII]

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
Eutectic Freeze Crystallization on Sodium Chloride

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.

Construction of the plant


In most LCA studies the impact of the construction and decommissioning of the plant has been
neglected, arguing that the impact of the operational energy consumption is much higher. Friedrich
[XXV] is one of the few that evaluated these impacts for a conventional plant and an ultra filtration
membrane process. It is concluded that the decommissioning phase can be neglected (less than 1% of
total plant impacts), but that the construction phase contributes for up to 15% of total plant impact.
Raluy et al. [XXVI] presented the impact of the construction- and decommissioning phase for RO- and
different kinds of distillation plants, but concluded that the impact is negligible.

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
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

Figure 7-3; Schematic representation of evaporative crystallizer by GE

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
Eutectic Freeze Crystallization on Sodium Chloride

90kg
Dry solids
1000kg
10wt% TDS 860kg
Evaporative crystallization
Pure water

50kg
Purge

P=40-45kWh

Figure 7-4; Schematics of evaporative crystallization

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
Eutectic Freeze Crystallization on Sodium Chloride

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 7°C, 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 10°C.

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 12°C for
a solution containing magnesium.
 At a TLM of 8°C the heat transfer in the presence of magnesium is 30% higher than for the pure
solution.

79
Eutectic Freeze Crystallization on Sodium Chloride

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
Eutectic Freeze Crystallization on Sodium Chloride

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.

Some other recommendations for full scale operation:

 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
Eutectic Freeze Crystallization on Sodium Chloride

Appendices

A. Vapor pressure vs temperature of CO2

82
Eutectic Freeze Crystallization on Sodium Chloride

B. ICP results of samples

83
Eutectic Freeze Crystallization on Sodium Chloride

84
Eutectic Freeze Crystallization on Sodium Chloride

C. Spreadsheet for evaporative CO2 cooling calculations

Laminar=0
Turbulent=1 8337 4.228
step quality ReL ReG State L State V C Xtt E S hl htp(W/m2K)
U(W/m2K) UdT(W/m2) Lreq(m)
0 0 5047 0 1 0 10 8520
0.01 0.005 5022 370 1 0 10 25.870 6.676989 0.47708 227.2668 3485 1704 8519 0.041
0.02 0.01 4996 740 1 0 10 13.801 6.736836 0.474099 226.3527 3480 1703 8513 0.041
0.03 0.015 4971 1110 1 0 10 9.538 6.790454 0.471624 225.4377 3476 1702 8508 0.041
0.04 0.02 4946 1480 1 0 10 7.328 6.84055 0.469445 224.5217 3472 1701 8503 0.041
0.05 0.025 4921 1850 1 1 20 5.967 6.888293 0.467472 223.6048 3468 1700 8498 0.041
0.06 0.03 4895 2220 1 1 20 5.041 6.934328 0.465653 222.687 3465 1699 8494 0.041
0.07 0.035 4870 2590 1 1 20 4.368 6.979059 0.463958 221.7682 3461 1698 8490 0.041
0.08 0.04 4845 2961 1 1 20 3.855 7.022764 0.462365 220.8485 3458 1697 8486 0.042
0.09 0.045 4820 3331 1 1 20 3.451 7.065643 0.460858 219.9278 3454 1696 8482 0.042
0.1 0.05 4794 3701 1 1 20 3.124 7.107846 0.459425 219.0062 3451 1696 8478 0.042
0.11 0.055 4769 4071 1 1 20 2.854 7.149492 0.458057 218.0836 3448 1695 8474 0.042
0.12 0.06 4744 4441 1 1 20 2.626 7.190674 0.456746 217.16 3445 1694 8471 0.042
0.13 0.065 4719 4811 1 1 20 2.432 7.23147 0.455487 216.2354 3442 1693 8467 0.042
0.14 0.07 4694 5181 1 1 20 2.264 7.271944 0.454275 215.3098 3439 1693 8464 0.042
0.15 0.075 4668 5551 1 1 20 2.117 7.312152 0.453105 214.3833 3436 1692 8460 0.042
0.16 0.08 4643 5921 1 1 20 1.988 7.352139 0.451974 213.4557 3433 1691 8456 0.042
0.17 0.085 4618 6291 1 1 20 1.873 7.391947 0.450878 212.5271 3430 1691 8453 0.042
0.18 0.09 4593 6661 1 1 20 1.771 7.431611 0.449816 211.5975 3428 1690 8449 0.042
0.19 0.095 4567 7031 1 1 20 1.678 7.471164 0.448784 210.6669 3425 1689 8446 0.042
0.2 0.1 4542 7401 1 1 20 1.595 7.510634 0.447781 209.7353 3422 1689 8443 0.042
0.21 0.105 4517 7771 1 1 20 1.518 7.550047 0.446804 208.8026 3419 1688 8439 0.042
0.22 0.11 4492 8141 1 1 20 1.449 7.589427 0.445853 207.8689 3416 1687 8436 0.042
0.23 0.115 4466 8512 1 1 20 1.385 7.628794 0.444925 206.9341 3414 1686 8432 0.042
0.24 0.12 4441 8882 1 1 20 1.326 7.668168 0.44402 205.9983 3411 1686 8429 0.042
0.25 0.125 4416 9252 1 1 20 1.272 7.707569 0.443135 205.0614 3408 1685 8426 0.042
0.26 0.13 4391 9622 1 1 20 1.221 7.747013 0.442271 204.1235 3405 1684 8422 0.042
0.27 0.135 4366 9992 1 1 20 1.174 7.786516 0.441425 203.1844 3403 1684 8419 0.042
0.28 0.14 4340 10362 1 1 20 1.131 7.826093 0.440598 202.2443 3400 1683 8416 0.042
0.29 0.145 4315 10732 1 1 20 1.090 7.86576 0.439787 201.3031 3397 1682 8412 0.042
0.3 0.15 4290 11102 1 1 20 1.052 7.905529 0.438993 200.3607 3394 1682 8409 0.042
0.31 0.155 4265 11472 1 1 20 1.016 7.945413 0.438214 199.4173 3392 1681 8406 0.042
0.32 0.16 4239 11842 1 1 20 0.982 7.985425 0.43745 198.4728 3389 1680 8402 0.042
0.33 0.165 4214 12212 1 1 20 0.950 8.025578 0.436701 197.5271 3386 1680 8399 0.042
0.34 0.17 4189 12582 1 1 20 0.920 8.065882 0.435965 196.5803 3383 1679 8396 0.042
0.35 0.175 4164 12952 1 1 20 0.891 8.106349 0.435242 195.6323 3381 1678 8392 0.042
0.36 0.18 4138 13322 1 1 20 0.864 8.146991 0.434532 194.6833 3378 1678 8389 0.042
0.37 0.185 4113 13692 1 1 20 0.838 8.187817 0.433834 193.733 3375 1677 8386 0.042
0.38 0.19 4088 14063 1 1 20 0.814 8.228839 0.433148 192.7816 3373 1676 8382 0.042
0.39 0.195 4063 14433 1 1 20 0.791 8.270067 0.432473 191.829 3370 1676 8379 0.042
0.4 0.2 4037 14803 1 1 20 0.769 8.31151 0.431808 190.8752 3367 1675 8375 0.042
0.41 0.205 4012 15173 1 1 20 0.747 8.353179 0.431154 189.9202 3365 1674 8372 0.042
0.42 0.21 3987 15543 1 1 20 0.727 8.395085 0.43051 188.964 3362 1674 8369 0.042
0.43 0.215 3962 15913 1 1 20 0.708 8.437236 0.429876 188.0067 3359 1673 8365 0.042
0.44 0.22 3937 16283 1 1 20 0.690 8.479642 0.42925 187.0481 3356 1672 8362 0.042
0.45 0.225 3911 16653 1 1 20 0.672 8.522314 0.428634 186.0882 3354 1672 8359 0.042
0.46 0.23 3886 17023 1 1 20 0.655 8.56526 0.428027 185.1271 3351 1671 8355 0.042
0.47 0.235 3861 17393 1 1 20 0.639 8.608492 0.427428 184.1648 3348 1670 8352 0.042
0.48 0.24 3836 17763 1 1 20 0.623 8.652017 0.426837 183.2012 3345 1670 8348 0.042
0.49 0.245 3810 18133 1 1 20 0.608 8.695847 0.426254 182.2364 3343 1669 8345 0.042
0.5 0.25 3785 18503 1 1 20 0.593 8.739991 0.425679 181.2702 3340 1668 8341 0.042

85
Eutectic Freeze Crystallization on Sodium Chloride

Laminar=0
Turbulent=1 8245 2.137
step quality ReL ReG State L State V C Xtt E S hl htp(W/m2K)
U(W/m2K) UdT(W/m2) Lreq(m)
0.51 0.255 3760 18873 1 1 20 0.579 8.784458 0.425111 180.3028 3337 1668 8338 0.042
0.52 0.26 3735 19243 1 1 20 0.566 8.829259 0.42455 179.3341 3334 1667 8334 0.042
0.53 0.265 3709 19613 1 1 20 0.553 8.874404 0.423996 178.3641 3331 1666 8331 0.042
0.54 0.27 3684 19984 1 1 20 0.540 8.919902 0.423449 177.3927 3329 1665 8327 0.042
0.55 0.275 3659 20354 1 1 20 0.528 8.965764 0.422908 176.42 3326 1665 8324 0.042
0.56 0.28 3634 20724 1 1 20 0.516 9.012001 0.422373 175.446 3323 1664 8320 0.042
0.57 0.285 3608 21094 1 1 20 0.505 9.058622 0.421845 174.4706 3320 1663 8317 0.042
0.58 0.29 3583 21464 1 1 20 0.494 9.105638 0.421322 173.4939 3317 1663 8313 0.042
0.59 0.295 3558 21834 1 1 20 0.483 9.15306 0.420806 172.5158 3314 1662 8310 0.042
0.6 0.3 3533 22204 1 1 20 0.473 9.200898 0.420294 171.5363 3312 1661 8306 0.042
0.61 0.305 3508 22574 1 1 20 0.463 9.249165 0.419788 170.5554 3309 1660 8302 0.042
0.62 0.31 3482 22944 1 1 20 0.453 9.297871 0.419287 169.573 3306 1660 8299 0.042
0.63 0.315 3457 23314 1 1 20 0.444 9.347028 0.418792 168.5893 3303 1659 8295 0.042
0.64 0.32 3432 23684 1 1 20 0.435 9.396647 0.418301 167.6041 3300 1658 8291 0.042
0.65 0.325 3407 24054 1 1 20 0.426 9.44674 0.417814 166.6175 3297 1658 8288 0.043
0.66 0.33 3381 24424 1 1 20 0.417 9.497319 0.417332 165.6294 3294 1657 8284 0.043
0.67 0.335 3356 24794 1 1 20 0.409 9.548398 0.416855 164.6398 3291 1656 8280 0.043
0.68 0.34 3331 25164 1 1 20 0.401 9.599988 0.416382 163.6487 3288 1655 8276 0.043
0.69 0.345 3306 25535 1 1 20 0.393 9.652102 0.415913 162.6562 3285 1655 8273 0.043
0.7 0.35 3280 25905 1 1 20 0.385 9.704755 0.415448 161.6621 3282 1654 8269 0.043
0.71 0.355 3255 26275 1 1 20 0.378 9.757959 0.414987 160.6665 3279 1653 8265 0.043
0.72 0.36 3230 26645 1 1 20 0.370 9.811728 0.414529 159.6693 3276 1652 8261 0.043
0.73 0.365 3205 27015 1 1 20 0.363 9.866076 0.414075 158.6706 3273 1651 8257 0.043
0.74 0.37 3179 27385 1 1 20 0.356 9.921019 0.413624 157.6703 3270 1651 8253 0.043
0.75 0.375 3154 27755 1 1 20 0.350 9.976571 0.413177 156.6684 3267 1650 8250 0.043
0.76 0.38 3129 28125 1 1 20 0.343 10.03275 0.412733 155.665 3264 1649 8246 0.043
0.77 0.385 3104 28495 1 1 20 0.336 10.08956 0.412291 154.6599 3261 1648 8242 0.043
0.78 0.39 3079 28865 1 1 20 0.330 10.14704 0.411853 153.6531 3258 1648 8238 0.043
0.79 0.395 3053 29235 1 1 20 0.324 10.20518 0.411418 152.6447 3254 1647 8234 0.043
0.8 0.4 3028 29605 1 1 20 0.318 10.26402 0.410985 151.6347 3251 1646 8229 0.043
0.81 0.405 3003 29975 1 1 20 0.312 10.32356 0.410554 150.6229 3248 1645 8225 0.043
0.82 0.41 2978 30345 1 1 20 0.306 10.38383 0.410126 149.6095 3245 1644 8221 0.043
0.83 0.415 2952 30715 1 1 20 0.301 10.44485 0.409701 148.5943 3242 1643 8217 0.043
0.84 0.42 2927 31086 1 1 20 0.295 10.50663 0.409277 147.5774 3238 1643 8213 0.043
0.85 0.425 2902 31456 1 1 20 0.290 10.56919 0.408856 146.5588 3235 1642 8209 0.043
0.86 0.43 2877 31826 1 1 20 0.284 10.63256 0.408436 145.5383 3232 1641 8204 0.043
0.87 0.435 2851 32196 1 1 20 0.279 10.69675 0.408018 144.5161 3229 1640 8200 0.043
0.88 0.44 2826 32566 1 1 20 0.274 10.76178 0.407602 143.4921 3225 1639 8196 0.043
0.89 0.445 2801 32936 1 1 20 0.269 10.82769 0.407187 142.4662 3222 1638 8192 0.043
0.9 0.45 2776 33306 1 1 20 0.264 10.89449 0.406774 141.4385 3218 1637 8187 0.043
0.91 0.455 2751 33676 1 1 20 0.260 10.9622 0.406362 140.4089 3215 1637 8183 0.043
0.92 0.46 2725 34046 1 1 20 0.255 11.03086 0.405951 139.3774 3212 1636 8178 0.043
0.93 0.465 2700 34416 1 1 20 0.250 11.10048 0.405542 138.3441 3208 1635 8174 0.043
0.94 0.47 2675 34786 1 1 20 0.246 11.17109 0.405133 137.3087 3205 1634 8169 0.043
0.95 0.475 2650 35156 1 1 20 0.242 11.24272 0.404725 136.2715 3201 1633 8165 0.043
0.96 0.48 2624 35526 1 1 20 0.237 11.3154 0.404317 135.2322 3198 1632 8160 0.043
0.97 0.485 2599 35896 1 1 20 0.233 11.38915 0.40391 134.191 3194 1631 8155 0.043
0.98 0.49 2574 36266 1 1 20 0.229 11.46402 0.403504 133.1477 3190 1630 8151 0.043
0.99 0.495 2549 36637 1 1 20 0.225 11.54002 0.403098 132.1024 3187 1629 8146 0.043
1 0.5 2523 37007 1 1 20 0.221 11.61719 0.402692 131.055 3183 1628 8141 0.043

86
Eutectic Freeze Crystallization on Sodium Chloride

Bibliography
I. Textbook; Handbook of industrial crystallization; Second edition; Allan S Myerson; October
2001; Elsevier Science & technology books
II. Textbook; Chemical engineering design; Coulson & Richardson Vol.6
III. Textbook; Heat & Mass Transfer Vol.12; PW Dittus & LM Boelter Vol.12
IV. Textbook; A.F. Mills; Basic Heat & Mass Transfer; 2nd edition; Los Angeles
V. Dissertation; D.A. Swenne, The eutectic crystallization of NaCl.2H2O and ice, Eindhoven, 1983.
VI. Dissertation; Frank vd Ham; Eutectic Freeze Crystallization; 1999
VII. Dissertation; R de Goede; Crystallization of Paraxylene with scraped surface heat exchangers;
Delft; 1988
VIII. Dissertation; RJC Vaessen; Development of Scraped Eutectic Crystallizers; 2003
IX. Dissertation; Marcos Rodrigues Pascual; Physical Aspects of Scraped Heat Exchanger
Crystallizers; TU Delft 2009
X. D. Mann, LNG Materials and Fluids; National Bureau of Standards; 1977
XI. Paper; Ramires & Castro; Thermal Conductivity of Aqueous Sodium Chloride Solutions; 1994
XII. JW Meeuwisse and CA Infante Ferreira; Freezing point depression of various ice slurries; TU
Delft.
XIII. KE Gungor and RHS Winterton; A general correlation for flow boiling in tubes and annuli;
University of Birmingham; 1985.
XIV. FW Dittus & LMK Boelter; Heat transfer in automobile radiators of the tubular type; University
of California; 1930
XV. MG Cooper; Saturation nucleate pool boiling. A simple correlation; 1984
XVI. HK Foster and N Zuber; Dynamics of vapor bubbles and boiling heat transfer. 1995
XVII. D.G. Thomas , Transport characteristics of suspension. Journal of Colloid Science 20 (1965)
XVIII. Presentation: Zero liquid discharge desalination for treatment of saline water waste streams;
Essam E.F. El-Sayed; 2010; Kuwait
XIX. World Water Assessment Programme; The UN World water development report; “Water for
people, water for life” Unesco; 2003
XX. S Myerson; Handbook of industrial crystallization; Second edition; Elsevier; 2001
XXI. Selechi Tunk; Eutectic Freeze Crystallization; 2010
XXII. Muller-Steinhagen; The effect of surface properties on CaSO4 scale formation during convective
heat transfer and subcooled flow boiling; 1999
XXIII. Francois Vince et al.; LCA tool for the environmental evaluation of potable water production; 30
January 2007; Elsevier
XXIV. Beavis et al; Integrated environmental assessment of tertiary and residuals treatment LCA in the
wastewater industry; Water Sci. Technol 2003
XXV. E Friedrich; Environmental LCA of potable water production; South Africa 2001
XXVI. Raluy et al.; LCA of water production technologies; 2004

87
Eutectic Freeze Crystallization on Sodium Chloride

XXVII. G. Peters and K. Rouse, Environmental sustainability in water supply planning; an LCA approach
for the Eyre Peninsula, South Australia, Melbourne, 2005

88