Water Purification by Freezing and Gas Hydrate Processes, and removal of
dissolved minerals (Na + , K+ , Mg2 + , Ca2 + )

Maryam Karamoddin, Farshad Varaminian

PII: S0167-7322(15)31010-2
DOI: doi: 10.1016/j.molliq.2016.08.099
Reference: MOLLIQ 6260

To appear in: Journal of Molecular Liquids

Received date: 8 November 2015

Revised date: 23 July 2016
Accepted date: 26 August 2016

Please cite this article as: Maryam Karamoddin, Farshad Varaminian, Water Purification
by Freezing and Gas Hydrate Processes, and removal of dissolved minerals (Na+ , K+ ,
Mg2 + , Ca2 + ), Journal of Molecular Liquids (2016), doi: 10.1016/j.molliq.2016.08.099

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Water Purification by Freezing and Gas Hydrate Processes, and removal of

dissolved minerals (Na+, K+, Mg2+, Ca2+)

Maryam Karamoddin1, Farshad Varaminian2,*

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1, 2 - School of Chemical, Gas and Petroleum Engineering, Semnan University, Semnan, Iran

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*: Corresponding author: fvaraminian@semnan.ac.ir, Tel/fax: +98 23 33654280

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Abstract:
This research investigates the potential of crystallization technologies containing the freezing

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method and process of gas hydrate formation in water desalination processes. For this

purpose, component of tetrahydrofuran was used as a hydrate former with hydrate structure
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II. The initial brine solutions were supplied from salts of NaCl, KCl, CaCl2, MgCl2 and also

Caspian seawater. After formation of crystal (ice or hydrate) and separation of those from
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residual brine solution, the distilled water was produced by melting the crystals. The removal
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efficiency of salts is estimated in range of 40 to 80% for hydrate-based desalination and

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freezing processes. The results show that the removal efficiency is further at the lower
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driving force and lower concentrations of salt. Also the removal efficiency of salts depends

on the ionic size and the electrical charge. The removal of Na+ and K+ ions is better than that
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of Ca2+ and Mg2+ ions by the desalination based on crystallization methods. Moreover, the

water desalination process based on hydrate formation requires the lower cooling to provide

the requirement driving force beside the higher efficiency.

Keywords: Crystal Separation, Freezing, THF Hydrate, Water Purification.

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1. Introduction

The increased population and the industrial expansion have caused a shortage of potable

water in the world. Hence the significant attempts have been performed to develop the

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desalination methods [1-5] beside the traditional technologies for providing a water source

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from the brine water. One of the developing technologies investigated during recent years,

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includes the crystallization process such as freezing and gas hydrate methods for desalination.

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Clathrate hydrates are crystalline solid compounds, composed of hydrogen-bonded water

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molecules and some other gas (or liquid) species [6-7].

The advantages of freezing technique have been given as an alternative for the seawater
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desalination, the purification of mixtures [1,2,8,9], the waste water treatment, and the food

liquid concentration [1-3,10-12]. The concept of freezing desalination was initially presented
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in 1950, 1960 and 1970 years [13-15]. The solidification procedure has combination of heat
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and mass transfer, flow of liquids through solid, solid–liquid separation and crystallization

phenomena. Two kinds of processes are including the direct and indirect freezing [1]. Mandri
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et al. performed the seawater desalination process by indirect freezing in water–NaCl

solutions (35 g/kg of NaCl). They investigated the effective kinetic parameters such as initial
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concentration of ice, sweating temperature and sweating time by experimental design [1].

Rich et al. developed a dynamic layer crystallizer for freezing desalination of water with

samples of seawater from Nice, Rabat and Marseille and NaCl solutions. They reached to

salinities lower than 0.5 g/kg, satisfying the standards of drinking water. Overall, the results

generated by Rich et al. indicated the feasibility of the freezing and sweating steps with good

operating conditions to produce drinking water [2]. Williams et al. assessed an ice maker

machine for desalting brines by Freeze desalination; also they investigated different

parameters influencing the separation performance [3]. Ice freezing around a finned tube was

studied by Kayansayan and Acar [16].

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The hydration methods for desalination of seawater have been studied for the past 50 years

considering to the capability of gas hydrates to form a solid substance consisting of distilled

water and hydrate former [17-20]. Gas hydrate formation was proposed as a novel method to

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produce the potable water from seawater in 1940 and received the significant attention in the

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1960 and 1970. In United States, many companies used this method in pilot plant scale [19].

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In 2011, hydrate-based desalination was accomplished with novel apparatus design to extract

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dehydrated gas from a reactor containing hydrate slurries by Park et al. [4]. Moreover

different hydrate formers such as refrigerants have been suggested for further desalination

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research [4]. Karamoddin and Varaminian investigated the hydrate growth process of
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HCFC141b refrigerant in different brine solutions to desalinate the saline water [21]. Also

they designed a new apparatus of hydrate formation in high pressure for water desalination
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experiments [22].
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This paper is focused on the solidification step in a static layer crystallizer for salt removal

from brine solutions. The desalination experiments were performed with ice and hydrate
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layers produced from brine solutions in presence of NaCl, KCl, CaCl2 and MgCl2 salts with
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different concentrations, and also with samples of seawater from Caspian. Also in this paper,
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a kinetic model based on heat transfer was employed to predict the thickness of moving layer

by solving of Stefan-type equations based on an approximate method [23]. The effect of

parameters including the ionic size, electrical charge, operating conditions and crystallization

process was investigated on the crystal growth and efficiency of desalination process. The

results show the dependence of desalination efficiency on the ionic radius and electrical

charge of impurities, the initial concentration of solution and the operating temperature.

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2. Experimental Process

2.1. Materials

Salts of NaCl, KCl, CaCl2 and MgCl2, and also tetrahydrofuran (THF) were purchased from

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Merck Company. Also De-ionized water was used in all experiments. The purity of used

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materials was presented in Table (1).

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(Table 1)

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2.2. Apparatus

The experiments were performed in a setup consisting of a reactor capable of pressure about
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60 bar, a jacket for heat transfer, and data control and acquisition systems. The detail of used

apparatus is shown in Figure (1). A typical setup for static crystallization was made in this
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work subjected to one-dimensional freezing. This apparatus is consisting of a vertical

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stainless steel tube (1) with approximate height of 15 cm, which is as the nucleation site in

crystallization process. The surface of tube can be cooled about -30 ºC by chilling cycle via
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refrigerant R12 (2) and the temperature of surface (T0) is recorded by thermocouple (12).

This thermocouple is placed on the internal surface of cooled tube (with contacting of
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refrigerant R12) and in the middle of reactor (versus of view window (8)). Also, this tube is

plunged inside a jacketed stainless steel tank (5) filled with 2000 cm3 of solution (4). The

temperature of wall in the external surface (temperature T1) is justified by flowing of

ethylene glycol through an external circulating temperature bath in the jacket (5). The

temperatures of T1 and T0 are measured by PT100 thermometers of (11) and (12) calibrated

with accuracy ±0.1 ºC. The both of thermocouples (11) and (12) are fixed at the same height

in reactor. The processes of ice freezing and hydrate formation take place on the wall of

vertical tube (1) in the zone (3), and the residual solution (unfrozen phase) is vacated from

the drain valve (7). A digital microscope camera (DigiMicro) (9) with the high magnification

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ratio (200x) is utilized in front of the view window (8) to film the growing ice (or hydrate)

layer. The images of crystal layer growth registered every 30 second were analyzed to

measure the layer thickness and its growth kinetics. The temperature measurements and

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images records were acquired through a data acquisition system driven by a personal

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computer (10). Also a conductivity meter (Aqualytic/AL20Con) was used with accuracy of

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±0.1 μS/cm to measure the electrical conductivity of brine solution in initial state and after

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solidification process.

(Figure 1)

2.3. Experimental Procedure

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The crystallization methods of desalination process are based on a phase change of liquid to

solid. This phase change occurs via the temperature variation by a physical process to
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separate the purified solid from the remaining liquid phase [24]. In this work, the
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crystallization desalination was studied in two sections including ice freezing and gas hydrate

formation. The problems related of hydrate formation in desalination process are the
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separation of hydrate crystals from residual brine, because of hydrate phase is only stable in
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special temperature and pressure range, and it melts with change of conditions. In the present
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research, the hydrate-based desalination was performed with apparatus design to easily

extract dehydrated high-density gas hydrates from a reactor containing hydrate slurries that

may solve the separation difficulty between hydrate crystals and concentrated brine solutions.

The design of this set-up is based on the ice-making apparatus. The several brine solutions

were injected into the stainless steel tank. In experiments of THF hydrate formation, the

initial brine solution had been mixed with the hydrate former (THF) at the molar ratio of 17:1

and then was introduced in the tank. The freezing step led to the formation of an ice (or

hydrate) layer on the external surface of the heat transfer tube (tube 1). After solidification

and stabilization in the layer thickness, the drain valve was opened to evacuate the residual

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brine solution. Hence the crystals held on the surface of tube were separated from the

remaining solution. During the water solidification process, the water molecules participate in

the crystals as pure and therefore the unfrozen solution is including the more salts and

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impurities. A sudden heating step (defrost process) on the surface of tube led to the fraction,

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separation and evacuation of crystal layer. Then the solutions of purified water, produced by

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the exact melting of crystals, were analyzed by Conductivity-metric, Complex-metric

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Titration and Flame Emission Spectroscopy analysis to determine the concentrations of

remaining ions in water. In hydration process, THF hydrate former was completely separated

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from the purified water by heating of solution about to temperature of 60 ºC.
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2.4. Design of Experiments

The many ions of saline-waters and seawaters are including Na+, K+, Ca2+ and Mg2+. So in
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this study, the several salts of NaCl, KCl, CaCl2 and MgCl2 were applied to prepare the initial
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brine solutions with similar concentration of ions in seawater. The desalination experiments

were designed in two sections containing freezing and hydrate formation in different
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concentrations of salts, mixtures of salts and samples of seawater from Caspian. Generally,
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the design parameters of this paper are following: (1) the operating conditions of setup (initial
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temperature of solution, Ti, and temperatures of T0 and T1), (2) the salt concentration (initial

salinity), (3) the salt type (ionic radius and electrical charge), and (4) the desalination process

type (freezing and gas hydration).

The desalination experiments were given in Tables (2) and (3) for ice freezing and THF

hydrate formation respectively. The temperatures of Ti, T0 and T1 are the calibrated

temperatures. Also the weight percent of salts is presented as follows: the soluble salt mass

(g) / the solvent volume (L).

(Table 2)

(Table 3)

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3. Kinetic Theory

A lot of researchers have exhibited the several techniques to solve the solidification

problems [25-28]. The solidification phenomenon of ice and THF hydrate can be modeled

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around the cylindrical tube to predict the crystal layer thickness by solving the Stefan-type

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equations. In Stefan model, the layer formation is affected by the heat conduction between

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the solution and solid surface.

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The experimental setup was considered as a one-dimensional crystallization (r-direction) of

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crystal layer around a cylindrical tube. The temperature of surface of internal tube was

assumed equal to the temperature of working fluid (cooling unit by R12). Supposedly, the
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flow rate of cooling fluids is controllable so that the temperature does not change across the

length of tube (z-direction). Moreover, the tube height of reactor is small (about 15 cm) and
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the distribution of cooling fluid R12 and also the water-ethylene glycol solution in
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thermostatic bath is steady throughout tube from top to bottom, hence the temperatures can

be adjusted on the uniform temperature T0 (on the cooled surface) and temperature T1 (in the
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external surface) respectively. So the temperature gradient is only purposed in radial

direction. The separating surface between the phases of solid and residual solution (liquid) is
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r= ri(t). The moving interface, ri(t), is supposed nearly the equilibrium temperature of ice (or

hydrate) formation (Tf), and T0 < Tf . The uniform temperature of Ti is related to the initial

temperature of brine solution. In Stefan-type heat transfer equations, the dimensionless Stefan

number (St) is correlated with the driving force for crystal formation. The driving force of

process is further for higher Stefan number. The Stefan number is defined as following

equation:

CpS (T f  T0 )
St  (1)


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Where, CpS and  are the specific heat of solid (ice or hydrate) and the latent heat of solid

formation respectively.

4. Results and Discussion

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4.1. Kinetic Results

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Firstly, the number of experiments were performed in pure conditions (without salt) to study

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the crystal growth morphology of ice and THF hydrate on the cooled surface. These tests

containing the experiments of (1-9) for ice formation and the experiments of (39-47) for THF

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hydrate formation, were accomplished in different operating conditions (different Stefan

numbers) to investigate the effect of driving force on crystal growth. The thicknesses of
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crystal layer were experimentally measured by the digital microscope camera. For example,

the images of ice and hydrate crystal on the cooled surface were presented in Figure (2).
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Figures (3) and (4) show the trend of ice growth in pure water for experiments (1-2-3-5-6)
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and experiments (4-7-8-9) respectively. The lower temperatures of cooled surface (T0)
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increase the crystallization driving force (equation 1) and subsequently the growth rate of ice
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crystals. The freezing point of pure water (Tf) is purposed 0 ºC. Also, the curves of THF

hydrate growth in pure water were presented in Figures (5) and (6) for experiments (39-40-
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41-42) and experiments (39-44-46-47) respectively. The equilibrium temperature of THF

hydrate formation is 4.4 ºC. Figure (5) shows the effect of cooled surface temperature (T0) on

hydrate growth kinetic. Moreover, the effect of liquid temperature (Ti) on hydrate growth

process was investigated in Figure (6). The growth rate of THF hydrate crystals decreases by

receding of liquid temperature from 4.4 ºC. In all Figures of (3) to (6), the points are the

experimental data and the solid lines are the calculated results based on Stefan model in

moving boundary conditions. The detail of modeling and the purposed method was presented

by Karamoddin and Varaminian [23] to solve the Stefan problem.

(Figure 2)

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(Figure 3)

(Figure 4)

(Figure 5)

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(Figure 6)

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In the brine solutions, the freezing point of water and the equilibrium temperature of gas

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hydrate are reduced (Tf<0 ºC for water freezing process; Tf<4.4 ºC for THF hydration

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process). The depression of this temperature is variant considering to the kind of salt,

hence the Stefan number (and kinetic curve) differs for different saline solutions even for

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the similar conditions of operating temperatures and concentrations. The number of
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experiments was designed in similar molar-volume concentration of salt to study the salt

effect on ice kinetic growth and the comparison between inhibition potential of salts in ice
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formation process and THF hydrate formation. For this purpose, the experiments of 12, 19,
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20 and 24 were performed in molar-volume concentration 0.25 mol/L (mol of salt/volume

of solvent) of NaCl, KCl, MgCl2 and CaCl2 salts and in the operating conditions similar to
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experiment 2 (pure water). Table (4) presents the freezing point and Stefan number for
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above experiments. Also the experimental results of ice growth were plotted in Figure (7)
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for several salts. Moreover in the hydrate formation section, the experiments of 48, 58, 59

and 60 were performed in molar-volume concentration 0.17 mol/L of NaCl, KCl, MgCl2

and CaCl2 salts in operating conditions similar to experiment 39 (pure water). Figure (8)

presents the measured thicknesses of hydrate layer for above experiments. The equilibrium

temperature and Stefan number were given in Table (5) for several solutions in hydrate

formation conditions.

According to this Figures (7) and (8), the growth rate of crystal layer thickness reduces by

decreasing of Stefan number and subsequently the inhibition potential of salt increases. So

the inhibition potential of above salts in solidification process is as following order:

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Mg 2  Ca 2  Na 1  K 1 . The inhibition effect of salts strongly depends on the ionic size

and electrical charge. The salts with more electrical charge and smaller ionic size are the

stronger inhibitors in crystallization process.

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(Table 4)

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(Table 5)

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(Figure 7)

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(Figure 8)

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4.2. Results of Water Desalination

In this section, the effect of parameters including initial salinity, driving force, salt kind and
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solidification process type was studied on the desalination efficiency. The removal efficiency

of each salt was determined by measuring the initial and final concentrations of solution and
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applying the equation (2). The analysis of Complexometric Titration and Flame Emission
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was used to determine the concentrations of (Mg2+, Ca2+) and (Na+, K+) in the purified water

respectively.
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Initial Concentrat ion  Final Concentrat ion

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Re moval Efficiency (%)  100 (2)

Initial Concentrat ion
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4.2.1. Initial Concentration and Driving Force

The measured electrical conductivities and concentrations were reported in the Tables (6) and

(7) for salts of group I (NaCl, KCl) and group II (MgCl2, CaCl2) respectively. The given

results of these Tables show the effect of initial salinity of solution and driving force on

removal efficiency of freezing desalination. Also Table (8) presents the results of freezing

desalination for Caspian seawater in different temperatures of cooled surface (different Stefan

number). Based on the performed analysis, the Caspian seawater is containing Na+:750 ppm;

K+: 225 ppm; Mg2+: 626 ppm and Ca2+: 180 ppm.

(Table 6)

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(Table 7)

(Table 8)

The effect of driving force in freezing desalination was shown in Figures (9), (10) and

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(11) for sodium chloride, calcium chloride and Caspian seawater respectively. According

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to these Figures, the removal efficiency decreases by increasing the driving force (or St

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Number). The decreasing trend of removal efficiency at higher Stefan numbers is obvious

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for each ion of Na+, K+, Mg2+ and Ca2+ in Figure (11). The driving force represents the

difference of cooled surface temperature (T0) and equilibrium temperature of freezing or

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hydrate formation (Tf), which is known as subcooling temperature degrees. In higher
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subcooling temperature, the Stefan number increases and so the crystal growth rate is

further. In higher rates of crystallization, the presence probability of salts and impurities
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is rising in crystal lattice due to absence of adequate time. The results presented by
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Mandri et al. [1] in the freezing desalination process confirm the results given in this part.

They studied the morphology of two ice layers formed from the same solution with two
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different cooling rates; and found that the purity of ice produced with the lower growth
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rate is further [1].

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The Figure (12) shows the effect of initial salinity on the removal efficiency for different

salts. In all of brine solutions, the increasing of initial concentration causes the decreasing

of desalination efficiency. Hence the purity of produced crystals can be increased by

rising of desalination stages.

(Figure 9)

(Figure 10)

(Figure 11)

(Figure 12)

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Table (9) presents the water desalination results based on THF hydrate formation for different

concentrations of NaCl and KCl salts. The initial and final electrical conductivities were

reported in this Table before and after of hydrate formation process. Similarly to freezing

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desalination, the removal efficiency of salt in hydration process is further at lower initial

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concentrations. Figure (13) indicates this fact.

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(Table 9)

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(Figure 13)

4.2.2. Salt Type

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The used salts in desalination experiments differ from viewpoint of the cation radius and
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electrical charge. So the number of experiments was performed at same concentration

(mol/volume) of salts to investigate the influence of cation radius and electrical charge. The
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freezing desalination efficiency was reported in the Table (10) for four salts of KCl (type1),
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NaCl (type 2), CaCl2 (type 3) and MgCl2 (type 4) in concentrations of 0.01 and 0.25 mol/L.

Moreover, the desalination efficiency based on hydrate formation was presented in Table (11)
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by the hydrate formers of HCFC141b (CH3CCl2F) and THF for above salts. Figures (14) and
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(15) show the desalination results for these four salts in freezing and hydration process
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respectively. According to results, the removal efficiency depends on the ionic size and

number of electrical charge as the salts with higher ionic sizes and lower charge improve the

desalination efficiency. So the dissolved mineral components are removed in the following

1 1 2 2
order: K  Na  Ca  Mg . Also Figure (16) show the removal efficiency of each

cations versus the ion radius. The later results are confirmed with the results presented by

Park et al. which was based on water desalination by CO2 hydrate formation [4].

(Table 10)

(Table 11)

(Figure 14)

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)Figure 15)

(Figure 16)

The further investigations such as interaction of hydrate-ion and crystal growth morphology

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by X-ray diffraction and MRI photography are required to clarify the removal behavior of

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dissolved salts. However the following justifications can be used:

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1) According to section (4.1) and based on crystal growth curves, the inhibition strength of

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salts was given as order: Mg 2  Ca 2  Na 1  K 1 . So the inhibition strength has the

inverse relation with desalination efficiency in crystallization process. Whatever the

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inhibition potential of salt is lower; the crystals of ice or hydrate can be easily formed during
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the shorter induction time, hence the involving possibility of ions is decreased in the crystal

lattice.
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2) The inhibition effect of salts strongly depends on the ionic size. The presence probability
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of ions with higher radius in crystal lattice is less; the larger ions issues easily from the ice

or hydrate crystals (see Figure 16).

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3) The relation of removal efficiency and electrical charge can be explained by the

electrostatic interactions between hydrate bulk and positive ions. Most dissolved
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components in water have the negative electrical charge due to the aggregation of negative

groups of chloride (Cl-); hence the hydrate bulk (negatively charged) attracts stronger

positive ions from the solution [4]. The attraction potential of hydrate particles increases at

more numbers of electrical charges. Generally, the removal efficiency of alkali metals (Na+

and K+) is higher than that of alkaline earth metals (Mg2+ and Ca2+) by the freezing and the

hydrate-based desalination processes.

4.2.3. Type of Desalination Process

The type of solidification process, including ice freezing and hydrate formation, can impress

the removal efficiency of salts. To purpose the proper comparison between solidification

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processes, the design of operating conditions in this section (initial and boundary

temperatures) is as the two processes are performed in the similar driving force. The studied

experiments in this part and their results were presented in the Table (12). The experiments of

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(32, 34, 35, 38) and (61, 62, 63, 65) were performed by the freezing method in conditions of

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(Ti=10, T1=7, T0=-6) and THF hydrate formation in conditions of (Ti=6.6, T1=6.0, T0=0.1)

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respectively. By applying the above conditions, the driving force is obtained as the similar

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values; thus St=0.037. The removal efficiency of ions was compared by two methods in

Figures (17) to (20) for solution (1) to (4).

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The results show that the removal efficiency based on hydrate formation is higher than the
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removal efficiency in freezing method for all of the studied ions. Moreover, the temperature

of cooled surface is about 0.1 ºC in THF hydrate formation while this temperature is -6 ºC in
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freezing process. So the water desalination process based on hydrate formation requires the
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lower cooling energy to provide the requirement driving force beside the higher efficiency.

Hence, the hydrate formation method can be economically advantaged than freezing method
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to desalinate the brine water.

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(Table 12)
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(Figure 17)

(Figure 18)

(Figure 19)

(Figure 20)

5. Conclusion

This paper studied on the solidification step in a static layer crystallizer for salt removal from

brine solutions and Caspian seawater based on crystallization method. The made apparatus in

the present research solved the separation difficulty between hydrate crystals and

concentrated brine solutions. The different parameters influencing the desalination process

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containing ice freezing and THF hydrate formation were investigated by means of Titration

and Flame Emission Spectroscopy analyses on the purified water. According to the results,

the removal efficiency of salts depends on the ionic size and electrical charge. The removal of

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salts with higher size and lower electrical charge is further by the hydrate-based and freezing

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desalination. Moreover, the efficiency of desalination by hydrate formation is higher than

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freezing desalination in the similar driving force conditions.

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6. References

[1] Y. Mandri, A. Rich, D. Mangin, S. Abderafi, C. Bebon, N. Semlali, J.P. Klein,

Parametric study of the sweating step in the seawater desalination process by indirect

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freezing, Desalination, 269 (2011) 142–147.

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[2] A. Rich, Y. Mandri, D. Mangin, A. Rivoire, S. Abderafi, Sea water desalination by

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dynamic layer melt crystallization: Parametric study of the freezing and sweating steps,

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Journal of Crystal Growth, 342 (2012) 110-116.

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[3] P.M. Williams, M. Ahmad, B.S. Connolly, Freeze desalination: An assessment of an ice

maker machine for desalting brines, Desalination, 308 (2013) 219 – 224.
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[4] K.N. Park, S.Y. Hong, J.W. Lee, K.C. Kang, Y.C. Lee, M.G. Ha, J.D. Lee, A new

apparatus for seawater desalination by gas hydrate process and removal characteristics
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of dissolved minerals (Na+, Mg2+, Ca2+, K+, B3+), Desalination, 274 (2011) 91-96.
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[5] A.D. Khawaji, I.K. Kutubkhanah, J.M. Wie, Advances in seawater desalination

technologies, Desalination, 221 (2008) 47–69.

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[6] E.D. Sloan, C.A. Koh, Clathrate Hydrates of Natural Gases, Third Ed., CRC Press,

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[7] A.L. Ballard, E.D. Sloan, Hydrate Phase Diagrams for Methane+ Ethane+ Propane

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[9] L. Xie, J. Ma, F. Cheng, P. Li, J. Liu, W. Chen, S. Wang, Study on sea ice desalination

technology, Desalination, 245 (2009) 146–154.

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[10] R. Rodriguez, S. Luque, J.R. Alvarez, J. Coca, A comparative study of reverse osmosis

and freeze concentration for the removal of valeric acid from wastewaters, Desalination,

127 (2000) 1–11.

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[11] M. Wakisaka, Y. Shirai, S. Sakashita, Ice crystallization in a pilot-scale freeze

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wastewater treatment system, Chemical Engineering Process, 40 (3) (2001) 201–208.

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[12] O. Miyawaki, L. Liu, Y. Shirai, S. Sakashita, K. Kagitani, Tubular ice system for scale

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113.

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[13] H.M. Hendrickson, R.W. Moulton, Research and Development of Processes for
MA
Desalting Water by Freezing, R&D Report 10, Office of Saline Water, US Dept.,

(1956).
D

[14] G. Karnofsky, P.F. Steinhoff, Saline Water Conversion by Direct Freezing with Butane,
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R&D Report 40, Office of Saline Water, US Dept. (1960).

[15] H.F. Wiegandt, P. Harriott, J.P. Leinroth, Desalting of Seawater by Freezing, R&D
P

Report 376, Office of Saline Water, US Dept. (1968).

CE

[16] N. Kayansayan, M.A. Acar, Ice formation around a finned-tube heat exchanger for cold
AC

thermal energy storage, International Journal of Thermal Science, 45 (4) (2006) 405-

418.

[17] A.M. Aliev, R.Y. Yusifov, A.R. Kuliev and Y.G. Yusifov, Method of Gas Hydrate

Formation for Evaluation of Water Desalination, Russian Journal of Applied Chemistry, 81

(2008) 588-591.

[18] D. Corak, T. Barth, T. Skodvin, R. Larsen and T. Skjetne, Effect of subcooling and

amount of hydrate former on formation of cyclopentane hydrates in brine, Desalination,

278 (2011) 268-274.

[19] A. Parker, Potable Water from Sea Water, Nature, 149 (1942) 184-186.

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[20] Y.T. Ngan, P. Englezos, Concentration of Mechanical Pulp mill Effluents and NaCl

Solutions through Propane Hydrate Formation, Industrial Engineering Chemistry

Research, 35 (1996) 1894-1900.

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[21] M. Karamoddin, F. Varaminian, Water Desalination Using R141b Gas Hydrate

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Formation, Desalination and Water Treatment, (2013) 1–7.

R
[22] M. Karamoddin, F. Varaminian, Water Desalination by Gas Hydrate Formation Process

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via a New Apparatus, 2nd International Training Workshop, Conference and Exhibition

on Desalination, Iran, Tehran, (2014).

NU
[23] M. Karamoddin, F. Varaminian, The modeling of hydrate growth kinetics in
MA
Tetrahydrofuran–Water mixture based on subcooling driving force, Journal of

Industrial and Engineering Chemistry, 21 (2015) 749-753.

D

[24] J.E. Miller, Review of Water Resources and Desalination Technologies, Sandia National
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Laboratories, Materials Chemistry Department, (2003).

[25] M. Salcudean, Z. Abdullah, On the numerical modeling of heat transfer during

P

solidification processes, International Journal of Numerical Methods in Engineering, 25

CE

(2) (1988) 445-473.

AC

[26] H. Hu, S.A. Argyropoulos, Mathematical modeling of solidification and melting: a

review, Model. Simulation Materials Science Engineering, 4 (4) (1996) 371-396.

[27] A.A. Samarskii, P.N. Vabishchevich, O.P. Iliev, A.G. Churbanov, Numerical simulation

of convection-diffusion phase change problems-a review, International Journal of Heat

and Mass Transfer, 36 (17) (1993) 4095-4106.

[28] C. Tangthieng, Effect of tube diameter on the specific energy consumption of the ice

making process, Applied Thermal Engineering, 31 (2011) 701-707.

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[29] H. Haghighi, A. Chapoy, B. Tohidi, Freezing Point Depression of Electrolyte Solutions:

Experimental Measurements and Modeling Using the Cubic- Plus-Association Equation

of State, Industrial and Engineering Chemistry and Research, 47 (2008) 3983–3989.

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[30] Karamoddin, F. Varaminian, Performance of hydrate inhibitors in tetrahydrofuran

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hydrate formation by using measurement of electrical conductivity, Journal of Industrial

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and Engineering Chemistry, 20 (5) (2014) 3815-3820.

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Figures:

Figure 1: Schematic of experimental setup

Figure 2: images of ice and hydrate crystals; (a): ice crystal, (b) THF hydrate crystal

T
Figure 3: ice crystal growth in pure water freezing process, marks: experimental data; solid

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lines: calculated results

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Figure 4: ice crystal growth in pure water freezing process, marks: experimental data; solid

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lines: calculated results

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Figure 5: THF hydrate crystal growth in pure water, marks: experimental data; solid lines:

calculated results (the effect of T0 on hydrate growth kinetic)

MA
Figure 6: THF hydrate crystal growth in pure water, marks: experimental data; solid lines:

calculated results (the effect of Ti on hydrate growth kinetic)

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Figure 7: ice crystal growth in brine solutions for molar-volume concentration 0.25 mol/L,
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operating conditions: T0=-11.5, T1=6.5, Ti=10.0

Figure 8: THF hydrate growth in brine solutions for molar-volume concentration 0.17
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CE

mol/L, operating conditions: T0=0.1, T1=4.4, Ti=4.4

Figure 9: freezing desalination results for sodium chloride in different driving forces
AC

Figure 10: freezing desalination results for calcium chloride in different driving forces

Figure 11: freezing desalination results for Caspian seawater in different driving forces

Figure 12: freezing desalination results for several salts in different initial salinities

Figure 13: desalination results based on THF hydrate formation in different initial salinities

Figure 14: the effect of salt type on freezing desalination results in different concentrations

Figure 15: the effect of salt type on desalination results based on hydrate formation

Figure 16: removal efficiency of positive ions versus ion radius

Figure 17: the comparison of desalination processes via freezing and hydrate formation for

experiments of 34 and 61

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Figure 18: the comparison of desalination processes via freezing and hydrate formation for

experiments of 32 and 62

Figure 19: the comparison of desalination processes via freezing and hydrate formation for

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experiments of 35 and 63

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Figure 20: the comparison of desalination processes via freezing and hydrate formation for

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experiments of 38 and 65

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Figure 1: Schematic of experimental setup. (1): cylindrical tube (S.S), (2): chilling cycle by
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R12, (3): ice layer (hydrate layer), (4): brine solution (seawater), (5): jacketed tank (S.S),
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(6): thermostatic bath (water-ethylene glycol solution), (7): drain valve, (8): view window,
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(9): camera, (10): computer (data acquisition system), (11): thermocouple (T1), (12):
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thermocouple (T0), (13): pressure gage, (14): display system and data control, (15): input

valve, (16): brine solution

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a b

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Figure 2: images of ice and hydrate crystals; (a): ice crystal, (b) THF hydrate crystal
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Ex. 1
16
Ex. 2

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14
Ex. 3

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12 Ex. 5
Ice layer (mm)

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10 Ex. 6

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8

4
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2

0
0 1000 2000 3000 4000 5000 6000 7000 8000
Time (S)
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Figure 3: ice crystal growth in pure water freezing process, marks: experimental data; solid
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lines: calculated results

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Ex. 4
14

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Ex. 7

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12
Ex. 8

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Ice layer (mm)

10

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Ex. 9

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6

4
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2

0
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0 1000 2000 3000 4000 5000 6000 7000 8000

Time (S)
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Figure 4: ice crystal growth in pure water freezing process, marks: experimental data; solid
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lines: calculated results

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12

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10

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Hydrate layer (mm)

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6 Ex. 39

Ex. 40
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4
Ex. 41
2
Ex. 42
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0
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0 2000 4000 6000 8000 10000 12000 14000 16000 18000

Time (S)

Figure 5: THF hydrate crystal growth in pure water, marks: experimental data; solid lines:
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calculated results (the effect of T0 on hydrate growth kinetic)

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12

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10
Hydrate layer (mm)

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8

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Ex. 39
6
Ex. 44

4
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2 Ex. 47

0
0 2000 4000 6000 8000 10000 12000
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Time (S)
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Figure 6: THF hydrate crystal growth in pure water, marks: experimental data; solid lines:

calculated results (the effect of Ti on hydrate growth kinetic)

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10

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Ice layer (mm)

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5

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Pure
KCl 1.9%
NaCl 1.5%
CaCl2 2.8 %
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MgCl2 2.4%
0
0 500 1000 1500
Time (S)
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Figure 7: ice crystal growth in brine solutions for molar-volume concentration 0.25 mol/L,
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operating conditions: T0=-11.5, T1=6.5, Ti=10.0

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10

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Hydrate layer (mm)

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6

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Pure
KCl 1.2%
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NaCl 1.0%
2 CaCl2 1.8%
MgCl2 1.5%

0
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0 1000 2000 3000 4000 5000 6000 7000 8000

Time (S)
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Figure 8: THF hydrate growth in brine solutions for molar-volume concentration 0.17
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mol/L, operating conditions: T0=0.1, T1=4.4, Ti=4.4

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80

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70

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60

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Removal Efficiency %

50

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40

30
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NaCl 1.5% wt
20
NaCl 3.0% wt
10
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0
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0 0.01 0.02 0.03 0.04 0.05 0.06 0.07

St Number
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Figure 9: freezing desalination results for sodium chloride in different driving forces
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70

65

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60

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Removal Efficiency

55

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SC
50

45

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40
CaCl2 0.2% wt
35
MA
30
0 0.02 0.04 0.06 0.08 0.1
St Number
D
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Figure 10: freezing desalination results for calcium chloride in different driving forces
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80

70

T
60

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Removal Efficiency %

50

R
SC
40

30
K+

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20 Na+
Ca+2
10
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Mg+2
0
0 0.01 0.02 0.03 0.04
St Number
D
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Figure 11: freezing desalination results for Caspian seawater in different driving

forces
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80

70

T
60

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Removal Efficiency %

50

R
SC
40

30
NaCl

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20 KCl
CaCl2
10
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MgCl2

0
0 1 2 3 4 5
Concentration %wt
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Figure 12: freezing desalination results for several salts in different initial salinities
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80

75

T
70

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65
Removal Efficiency %

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60

SC
55

50

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45
NaCl
40
KCl
MA
35

30
0 1 2 3 4 5
Concentration %wt
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Figure 13: desalination results based on THF hydrate formation in different initial salinities
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80

70

T
IP
Removal Efficiency %

60

R
SC
50

40

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Solution 0.01 mol/L
Solution 0.25 mol/L
30
MA
20
0 1 2 3 4 5
Salt Type
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Figure 14: the effect of salt type on freezing desalination results in different concentrations
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80

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70

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Removal Efficiency %

60

R
SC
50

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40

Solution 0.03 mol/L, R141b Hydrate

30
MA
Solution 0.17 mol/L, THF Hydrate

20
0 1 2 3 4 5
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Salt Type
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Figure 15: the effect of salt type on desalination results based on hydrate formation
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75

K+

T
70

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Removal Efficiency %

Na+

R
65

SC
60
Ca2+
Freezing

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Mg2+
R141b
55
THF
MA
50
50 70 90 110 130 150
Ionic Radius (Pm)
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Figure 16: removal efficiency of positive ions versus ion radius

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80

70

T
IP
Removal Efficiency %

60

R
50

SC
40

30
NU
Desalination by Freezing Process
Desalination by THF Hydrate Formation
MA
20
0 1 2 3 4 5
Salt Type
Figure 17: the comparison of desalination processes via freezing and hydrate formation for
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experiments of 34 and 61
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80

70

T
IP
Removal Efficiency %

60

R
SC
50

40

30
NU
Desalination by Freezing Process
MA
Desalination by THF Hydrate Formation

20
0 1 2 3 4 5
Salt Type
D

Figure 18: the comparison of desalination processes via freezing and hydrate formation for
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experiments of 32 and 62
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80

70

T
IP
Removal Efficiency %

60

R
SC
50

40

30
NU
Desalination by Freezing Process
MA
Desalination by THF Hydrate Formation
20
0 1 2 3 4 5
Salt Type
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Figure 19: the comparison of desalination processes via freezing and hydrate formation for
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experiments of 35 and 63
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80

70

T
IP
Removal Efficiency %

60

R
SC
50

40

30
NU
Desalination by Freezing Process
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Desalination by THF Hydrate Formation
20
0 1 2 3 4 5
Salt Type
D

Figure 20: the comparison of desalination processes via freezing and hydrate formation for
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experiments of 38 and 65
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Tables:

Table 1: purities and suppliers of materials

Table 2: the experiments design of ice freezing

T
Table 3: the experiments design of THF hydrate formation

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Table 4: the freezing point of brine solutions in molar-volume concentration 0.25 mol/L

R
Table 5: the equilibrium temperature of THF hydrate formation in brine solutions for molar-

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volume concentration 0.17 mol/L

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Table 6: freezing desalination results for salts of group I (NaCl, KCl)

Table 7: freezing desalination results for salts of group II (MgCl2, CaCl2)

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Table 8: freezing desalination results for Caspian seawater

Table 9: desalination results based on THF hydrate formation

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Table 10: freezing desalination results for different salts

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Table 11: desalination results based on hydrate formation for different salts
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Table 12: desalination results by freezing and THF hydrate formation for different solutions
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Table 1: purities and suppliers of materials

Chemical Supplier Purity (%)

THF(C4H8O) Merck 99.5
NaCl Merck 99.5

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KCl Merck 99.5

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MgCl2 Merck 98.0
CaCl2 Merck 98.0

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H2O - Deionized

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Table 2: the experiments design of ice freezing

Exp. no. Salts (% wt) T0 (ºC) T1 (ºC) Ti (ºC)

T
1 0.00 -20.0 6.5 7

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2 0.00 -11.5 6.5 10
3 0.00 -5.2 6.5 10

R
4 0.00 -20.0 9.5 20

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5 0.00 -3.0 9.5 15
6 0.00 -1.4 9.5 15
7 0.00 -8.5 9.5 10

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8 0.00 -3.0 9.5 10
9 0.00 -1.5 9.5 10
MA
10 NaCl: 1.50 -2.5 6.5 10
11 NaCl: 1.50 -5.5 6.5 10
12 NaCl: 1.50 -11.5 6.5 10
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13 NaCl: 3.00 -3.5 6.5 10

14 NaCl: 3.00 -6.7 6.5 10
TE

15 NaCl: 3.00 -11.5 6.5 10

16 NaCl: 4.50 -11.5 6.5 10
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17 KCl: 0.50 -11.5 6.5 10

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18 KCl: 1.00 -11.5 6.5 10

19 KCl: 1.90 -11.5 6.5 10
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20 MgCl2: 2.40 -11.5 6.5 10

21 CaCl2: 0.20 -3.5 6.5 10
22 CaCl2: 0.20 -6.0 6.5 10
23 CaCl2: 0.20 -14.0 6.5 10
24 CaCl2: 2.80 -11.5 6.5 10
25 CaCl2: 0.70 -5.2 6.5 10
26 CaCl2: 1.50 -5.2 6.5 10
27 CaCl2: 2.00 -5.2 6.5 10
28 NaCl: 0.06 -11.5 6.5 10
29 KCl: 0.08 -11.5 6.5 10
30 MgCl2: 0.10 -11.5 6.5 10
31 CaCl2: 0.12 -11.5 6.5 10
NaCl: 1.50
32 KCl: 0.50 -6.0 6.5 10

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CaCl2: 0.10
MgCl2: 0.10

NaCl: 1.00
33 KCl: 0.25 -6.0 6.5 10
CaCl2: 0.25
NaCl: 1.00

T
IP
NaCl: 1.00
34 KCl: 0.25 -6.0 6.5 10
CaCl2: 0.10

R
MgCl2: 0.10

SC
NaCl: 2.50
35 KCl: 0.50 -6.0 6.5 10
CaCl2: 0.10

NU
MgCl2: 0.10

36 Caspian seawater -2.0 6.5 10

MA
37 Caspian seawater -4.0 6.5 10
38 Caspian seawater -6.0 6.5 10
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Table 3: the experiments design of THF hydrate formation

Exp. no. Salts (% wt) T0 (ºC) T1 (ºC) Ti (ºC)

T
39 0.00 0.1 4.4 4.4

IP
40 0.00 1.0 4.4 4.4
41 0.00 2.1 4.4 4.4

R
42 0.00 3.3 4.4 4.4

SC
43 0.00 0.1 4.7 4.7
44 0.00 0.1 5.7 5.7
45 0.00 0.1 6.5 6.5

NU
46 0.00 0.1 7.2 7.2
47 0.00 0.1 8.6 8.6
MA
48 NaCl: 1.00 0.1 4.4 4.4
49 NaCl: 1.50 0.1 4.4 4.4
50 NaCl: 3.00 0.1 4.4 4.4
D

51 NaCl: 4.50 0.1 4.4 4.4

52 KCl: 0.50 0.1 4.4 4.4
TE

53 KCl: 1.00 0.1 4.4 4.4

54 KCl: 1.50 0.1 4.4 4.4
P

55 KCl: 1.90 0.1 4.4 4.4

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56 CaCl2: 0.10 0.1 4.4 4.4

57 MgCl2: 0.20 0.1 4.4 4.4
AC

58 KCl: 1.24 0.1 4.4 4.4

59 MgCl2: 1.50 0.1 4.4 4.4
60 CaCl2: 1.80 0.1 4.4 4.4
61 NaCl: 1.00 0.1 6.0 6.6
KCl: 0.25
CaCl2: 0.10
MgCl2: 0.10

62 NaCl: 1.50 0.1 6.0 6.6

KCl: 0.50
CaCl2: 0.10
MgCl2: 0.10

63 NaCl: 2.50 0.1 6.0 6.6

KCl: 0.50
CaCl2: 0.10
MgCl2: 0.10

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64 NaCl: 2.50 0.1 6.0 6.6

KCl: 0.50
CaCl2: 0.20
MgCl2: 0.20

65 Caspian seawater 0.1 6.0 6.6

T
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Table 4: the freezing point of brine solutions in molar-volume concentration 0.25 mol/L

Exp. no. Solution Tf (ºC) [29] St

T
2 Pure 0.0 0.072

IP
19 KCl: 1.9 (%wt) -1.0 0.067
12 NaCl: 1.5 (%wt) -1.2 0.065

R
24 CaCl2: 2.8 (%wt) -2.4 0.057

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20 MgCl2: 2.4 (%wt) -3.3 0.051

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Table 5: the equilibrium temperature of THF hydrate formation in brine solutions for molar-
volume concentration 0.17 mol/L
Exp. no. Solution Tf (ºC) [30] St
39 THF+ pure water 4.4 0.035

T
58 THF+KCl 1.2 (%wt) 4.0 0.032

IP
48 THF+NaCl 1.0 (%wt) 3.9 0.030
60 THF+CaCl2 1.8 (%wt) 3.8 0.029

R
59 THF+MgCl2 1.5 (%wt) 3.7 0.027

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Table 6: freezing desalination results for salts of group I (NaCl, KCl)

Exp. no. Solution St Initial Final Initial Final Removal

(%wt) Concentration Concentration EC1 EC1 Efficiency

T
(ppm) (ppm) (mS/cm) (mS/cm) (%)
10 NaCl: 1.5 0.008 15000 5175 37.10 12.61 65.5

IP
11 NaCl: 1.5 0.027 15000 5970 37.10 14.40 60.2

R
12 NaCl: 1.5 0.065 15000 6570 37.10 15.50 56.2

SC
13 NaCl: 3.0 0.007 30000 14640 79.70 38.20 51.2
14 NaCl: 3.0 0.027 30000 16350 79.70 43.80 45.5
15 NaCl: 3.0 0.057 30000 17550 79.70 47.00 41.5

NU
16 NaCl: 4.5 0.051 45000 27900 100.00 60.00 38.00
17 KCl: 0.5 0.071 5000 1450 8.76 2.50 71.00
MA
18 KCl: 1.0 0.069 10000 3050 20.00 6.00 69.5
19 KCl: 1.9 0.067 19000 6118 43.60 13.90 67.8
D

1: Electrical Conductivity at 18 ºC
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Table 7: freezing desalination results for salts of group II (MgCl2, CaCl2)

Exp. no. Solution St Initial Final Initial Final Removal

(%wt) Concentration Concentration EC1 EC1 Efficiency
(ppm) (ppm) (mS/cm) (mS/cm) (%)
21 CaCl2: 0.2 0.021 2000 760 3.76 1.38 62.0

T
22 CaCl2: 0.2 0.036 2000 794 3.76 1.50 60.3

IP
23 CaCl2: 0.2 0.087 2000 1034 3.76 2.01 48.3
25 CaCl2: 0.7 0.029 7000 2590 14.25 5.25 63.0

R
26 CaCl2: 1.5 0.027 15000 6000 26.80 10.01 60.0

SC
27 CaCl2: 2.0 0.025 20000 8460 33.50 14.50 57.7
30 MgCl2: 0.1 0.070 1000 441 1.18 0.53 55.9

NU
20 MgCl2: 2.4 0.051 24000
MA 12552 19.80 10.49 47.7

1: Electrical Conductivity at 18 ºC
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Table 8: freezing desalination results for Caspian seawater

Exp. no. St Initial Final Removal

Concentration Concentration Efficiency (%)

T
(ppm) in Freezing Process
(ppm)

IP
36 0.012 K+: 225 K+: 78 K+: 65.3
Na+: 750 Na+: 310 Na+: 58.6

R
Ca2+: 180 Ca2+: 88 Ca2+: 51.1
Mg2+: 626 Mg2+: 350 Mg2+: 44.0

SC
37 0.025 K+: 225 K+: 90 K+: 60.0
Na+: 750 Na+: 345 Na+: 54.0

NU
Ca2+: 180 Ca2+: 100 Ca2+: 44.4
Mg2+: 626 Mg2+: 400 Mg2+: 36.1
MA
38 0.037 K+: 225 K+: 105 K+: 53.3
Na+: 750 Na+: 370 Na+: 50.6
Ca2+: 180 Ca2+: 108 Ca2+: 40.0
Mg2+: 626 Mg2+: 440 Mg2+: 30.0
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Table 9: desalination results based on THF hydrate formation

Exp. no. Solution Initial Final Initial Final Removal

(%wt) Concentration Concentration EC1 EC1 Efficiency
(ppm) (ppm) (mS/cm) (mS/cm) (%)
48 NaCl:1.0 10000 3380 28.00 9.50 66.2

T
49 NaCl: 1.5 15000 5730 37.10 14.40 61.8

IP
50 NaCl: 3.0 30000 12450 79.70 23.00 58.5
51 NaCl: 4.5 45000 21330 100.00 47.00 52.6

R
52 KCl: 0.5 5000 1235 8.76 2.10 75.3

SC
53 KCl: 1.0 10000 2680 20.00 5.40 73.2
54 KCl: 1.5 15000 4410 25.50 7.50 70.6

NU
55 KCl: 1.9 19000 MA 6422 43.60 14.70 66.2

1: Electrical Conductivity at 18 ºC
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Table 10: freezing desalination results for different salts

Removal Efficiency (%)

Concentration Type 1 Type 2 Type 3 Type 4
(mol/L) (KCl) (NaCl) (CaCl2) (MgCl2)
0.01 72.1 63.2 57.2 55.9

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0.25 67.8 56.2 50.1 47.7

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Table 11: desalination results based on hydrate formation for different salts

Removal Efficiency (%)

Hydrate Concentration Type 1 Type 2 Type 3 Type 4 Ref
Former (mol/L) (KCl) (NaCl) (CaCl2) (MgCl2)
THF 0.17 73.0 66.2 58.0 57.5 This work

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HCFC141b 0.03 70.7 67.0 61.0 59.0 [21]

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Table 12: desalination results by freezing and THF hydrate formation for different solutions

Solution no. Exp. no. Initial Final Final

Concentration Concentration in Concentration in
(ppm) Freezing Process Hydrate Process
(ppm) (ppm)

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1 (34-61) K+: 1308 K+: 550 (57.9 %) K+: 300 (77.0 %)
Na+: 3937 Na+: 2100 (46.6 %) Na+: 1000 (74.0 %)

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Ca2+: 360 Ca2+: 202 (43.9 %) Ca2+: 115 (68.0 %)
Mg2+: 252 Mg2+: 150 (40.4 %) Mg2+: 134 (47.0 %)

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EC: 31.40 EC: 18.00 (42.6 %) EC: 10.30 (67.1 %)

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2 (32-62) K+: 2600 K+: 937 (63.9 %) K+: 816 (68.6 %)
Na+: 5897 Na+: 2300 (66.1 %) Na+: 2000 (66.0 %)
Ca2+: 360 Ca2+: 215 (40.2 %) Ca2+: 194 (46.1 %)

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Mg2+: 252 Mg2+: 153 (39.2 %) Mg2+: 140 (44.4 %)
EC: 42.90 EC: 19.92 (49.5 %) EC: 18.00 (58.0 %)
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3 (35-63) K+: 2600 K+: 920 (64.6 %) K+: 750 (71.1 %)
Na+: 9842 Na+: 3600 (63.4 %) Na+: 0573 (61.8 %)
Ca2+: 360 Ca2+: 180 (50.0 %) Ca2+: 200 (44.4 %)
Mg2+: 252 Mg2+: 151 (40.0 %) Mg2+: 164 (35.0 %)
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EC: 68.10 EC: 27.93 (59.0 %) EC: 23.10 (66.0 %)

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4 (seawater) (38-65) K+: 225 K+: 105 (53.3 %) K+: 82 (63.5 %)

Na+: 750 Na+: 370 (50.6 %) Na+: 300 (60.0 %)
Ca2+: 180 Ca2+: 108 (40.0 %) Ca2+: 80 (55.5 %)
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Mg2+: 626 Mg2+: 440 (30.0 %) Mg2+: 400 (36.1 %)

CE

EC1: 14.9 EC: 9.50 (36.0 %) EC: 7.30 (51.0 %)

EC: Electrical Conductivity at 18 ºC (mS/cm)

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Graphical abstract
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Highlights:

 An apparatus was designed to solve the separation difficulty in hydrate crystals.

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 The techniques of freezing and hydrate formation were used to produce the purified water.

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The removal efficiency of salts is in range of 40-80% for desalination processes.

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