Recovery of salt from

1 aqueous solution by eutectic

freeze crystallization
Mid Semester Review

Prepared by: Mr. Apurva D. Patel

M.E-Chemical(CAPD) Sem: IV
L.D College of Engineering
Ahmedabad-380015
Enrollment number: 160280716010
Name of Guide: Prof. C.G. Bhagchandani Prof. S.B. Thakore
Associate professor Associate professor
Chem. Eng. Dept. Chem. Eng. Dept.
L.D.C.E-Ahmedabad GEC-Valsad
Freeze Crystallizaer 5/9/20
2 Content
 Introduction
 objective
 Eutectic Freeze Crystallization process
 Brief Literature review
 Research gap
 Experimentation & Results
 Future work
 Project scheduling

Freeze Crystallizaer 5/9/20

3
Introduction:
What is freeze crystallization?

Freeze crystallization is the operation in which freezing as well as crystallization

occurs simultaneously.

Crystallization operation can be divided in two types.

(1) Solution crystallization in which diluent solvent is added.

(2) freeze crystallization in which crystals of solids are separated from its melt.

Freeze crystallization is a high energy efficient separation process that can be applied
to a wide variety of industrial requirements.
Freeze Crystallizaer 5/9/20
4 Applications of Freeze Crystallization
(Identified by Heist)
Application Conventional Freeze Crystallization
Evaporation (BTU/hr) (BTU/hr)

Fruit Juice concentration 365 85

Sea water Desalting 100 60

Acetic acid refining 8800 500

Acrylic acid refining 1600 190

Brine Concentration 120 80

Sugar production 3850 550

Freeze Crystallizaer 5/9/20

 Objective
5

 My main objective is to recovery of salt from aqueous solution by efficient,

cost-effective and sustainable management options for aqueous waste
streams.
 EFC is a promising low temperature desalination technique that can
retrieve salt and water from the aqueous waste streams, at relatively low
energy demand compared to conventional evaporation based separation
processes.
 Based on experimental result, Energy consumption by freeze crystallization
for the same separation at commercial scale will be calculated and the
same will be compared with energy consumption by multieffect evaporator

Freeze Crystallizaer 5/9/20

6 Eutectic point of salt and water

Freeze Crystallizaer 5/9/20

7 Schematic block scheme of the EFC process. A bleed stream is not
necessarily required but can be added for process optimization

Freeze Crystallizaer 5/9/20

8 Brief Literature Review
Year Journal Name Author Title of paper
2010 Chemical J. Van Spronsen, Recovery of sodium Carbonate and ice
Engineering M. Rodriguez from an industrial aq. Solution by EFC
Research and Design
2010 Chemical S.T. Reddy, Recovery of sodium sulphate from a
Engineering Reseach A.E. Lewis reverse osmosis retentate by EFC
and Design Technology
2005 Journal of crystal F.E. Genceli, EFC in a 2nd generation cooled disk
growth G.J. Witkamp column crystallizer for MgSO4.H2O
system
2009 Proceedings of J. Nathoo, Freezing your Brines off: EFC for brine
International Mine R. Jivanji treatment
water Conference

Freeze Crystallizaer 5/9/20

 Continue…
9
Year Journal Author Title of paper
name
2011 Desalination D.G. Randall A case study for treating a RO brine using
A.E. Lewis EFC-Approaching a zero waste process
1999 Journal of F. Van der EFC simultaneous formation and separation
crystal growth Ham, of two solid phases
G.J. Witkamp
2012 Master thesis Willem van Eutectic Freeze Crystallization: Separation of
of university der Tempel salt and ice
of Delft,
Netherland
2013 Water Science D.G.Randall, Improved CaSO4 recovery from a RO
and J. Nathoo retentate using EFC
technology

Freeze Crystallizaer 5/9/20

 10 Research Gap:

 From the literature review, I found most of the papers on salt separation
from sea-water and waste water stream, aqueous solutions by conventional
evaporation system. But, this technique required higher amount of energy
so to overcome this problem we uses a EFC technology for recovery of salt
and water as ice form. So focus of this dissertation is to recovery of salt
from it’s aqueous solution by eutectic freeze crystallization. Based on
experiment result, energy consumption by freeze crystallization for the
same separation at commercial scale will be calculated and the same will
be compared with energy consumption by evaporation.

Freeze Crystallizaer 5/9/20

11 Experimental Setup

Cascaded Refrigeration Apparatus

Cascaded refrigeration apparatus is suitable for operating
temperature up to -60 °C. The instrument is provided with
temperature control and all refrigeration system.

Freeze Crystallizaer 5/9/20

12
Experimental Procedure
 Liquid feed solution is prepared in beaker, weighted and
frozen in freezer of cascaded refrigeration unit.
 Frozen mass is taken out. Solid or ice is crushed into fine
solid particles or crystals. On crushing more amounts of
melt forms.
 Solid crystals are separated by filter from melt. Both
phases collected separately and then weighted and
analysed.

Freeze Crystallizaer 5/9/20

13
Experiment 01:Na2CO3-Water System
Process Flow Diagram

Freeze Crystallizaer 5/9/20

 14 Phase Diagram Of Binary system
%Concentration VS tEMPERATURE
Stages(Te Concentra
mperatur tion of 5.00%
4.48% 4.43%
e) salt 4.50%

I (-1º C) 2.4% 4.00%

3.50%

% cONCENTRATION
II(-2º C) 4.43% 3.00%
2.40%
2.50%
III(-3.3º C) 4.48%
2.00%

1.50%

1.00%

0.50%

0.00%
- 3.5 -3 - 2.5 -2 - 1.5 -1 - 0.5

Stage WISE TEMPERATURE (°C)

Freeze Crystallizar 5/9/20

15 Analysis:
 Titration:

 Prepare 0.5 N HCL solution in laboratory and fill the burrate with HCL solution. Now
take approximate 10 ml melt solution from above experiment in 250 ml flask and add
2-4 drop of Phenolphthalein and mix. Titrate the flask solution with HCL solution from
pink color to colorless.

 Observation:
 N1= Concentration of sodium carbonate in melt
 V1= Volume of sodium carbonate in melt
 N2= 0.5 N HCL solution
 V2= Volume of HCL solution

Freeze Crystallizer 5/9/20

16 Material Balance

 F = 250gm
overall material balance:
F = Effluent + Water + Na2CO3 crystals
250 = E + W + S…………………..(1)
Material Balance for Na2CO3;
F x 0.05 = E x 0.0079 + Na2CO3……………..(2)
Material Balance for Water;
F x (1-0.05) = E x (1-0.0079) + Water…………….(3)

Freeze Crystallizaer 5/9/20

17 Continued..
 Effluent = 95.3gm
we get,
Water = 143.25gm in ice form
and
Sodium carbonate in crystal form = 11.74gm
% Recovery = (11.74gm/12.5gm)x 100 = 93.92%

Freeze Crystallizaer 5/9/20

18 Experiment 2: Na2SO4-water system
Stage wise % % concentration Vs Temperature
temperature concentr 4.50%
3.99%
ation 4.00%
3.40%
Stage I(-1º C) 2.60% 3.50%

% concentration
3.00%
2.60%
Stage II(-1.5º C) 3.40% 2.50%

2.00%
Stage III(-1.8ºC) 3.99%
1.50%

1.00%

0.50%

0.00%
-1.9 -1.8 -1.7 -1.6 -1.5 -1.4 -1.3 -1.2 -1.1 -1 -0.9
Stage wise temperature

Freeze Crystallizaer 5/9/20

19 Experiment 3: MgSO4-water system
Stage wise % concentration
temperature
Temperature Vs % concentration
20.00% Stage I(-1º C) 7.6%
18.00% 17.19%
16.00% 14.75% Stage II(-2º C) 14.75%
% concentration

14.00%
12.00% Stage III(-3.9º C) 17.19%
10.00%
7.60%
8.00%
6.00%
4.00%
2.00%
0.00%
0.5 1 1.5 2 2.5 3 3.5 4 4.5

Temperature

Freeze Crystallizaer 5/9/20

20 Experiment 4: NaNO2-water system
Temperature Vs Concentration
4.00%
Stage wise % 3.70% 3.60%
Temperatur concentratio 3.50%
e n 3.00%

% concentration
Stage I(-1º C) 2.06% 2.50%
2.06%
2.00%
Stage II(-2º 3.6% 1.50%
C)
1.00%
Stage III(-3º 3.71% 0.50%
C)
0.00%
-3.5 -3 -2.5 -2 -1.5 -1 -0.5

Stage wise temperature

Freeze Crystallizaer 5/9/20

21 Experiment 5: CaSO4 Water System
% concentration Vs Temperature
7.00%
Stage wise %
5.73% 5.70% 6.00%
temperature concentratio
n 5.00%

% Concentration
Stage 1(-1ºC) 3.6% 3.60%
4.00%

3.00%
Stage 2(-2ºC) 5.7%
2.00%

Stage 3(-3.5ºC) 5.73% 1.00%

0.00%
-4 -3.5 -3 -2.5 -2 -1.5 -1 -0.5

Stage wise temperature(°C)

Freeze Crystallizaer 5/9/20

22

System name % Recovery of salt

Na2CO3-water 93.92%

Na2SO4-water 94.4%

MgSO4-water 98.33%

NaNO2-water 94.6%

CaSO4-water 95.33%

Freeze Crystallizaer 5/9/20

23 Energy Balance
 For Freeze crystallization
1. Heat duty required for freezing to 100 kg of dilute Aq. Solution of
CaSO4 = Latent heat of fusion of water(kJ/kg) x 100 kg
= 333.55 kJ/kg x 100 kg = 33355 kJ
2. Heat duty required for freezing to 83.1 kg of dilute Aq. Solution
of CaSO4 = Latent heat of fusion of water (kJ/kg) x 83.1 kg
= 333.55 kJ/kg x 83.1 kg = 27718 kJ
3. Heat duty required for freezing to 69.3 kg of dilute Aq. Solution
of
CaSO4 = 333.55 kJ/kg x 69.3 kg = 23115.01 kJ
Freeze Crystallizaer 5/9/20
24 Continue….
4. Total heat duty required for freezing = 84188.01 kJ
5. Total heat duty required for refrigeration plant
= 84188.01 kJ x 1.25 = 105235.01 kJ
6. Electrical energy required to dry the compression of vapour
compressing required cycle
= Total heat duty required for freezing/COP
= 105235.01/4 = 26308.75 KJ
= 7.3 KWh = 7.3 UNIT

Freeze Crystallizaer 5/9/20

25 Continue…..

 Rate of 1 unit is 7.75 ₹

So for 7.3 unit is 56.5 ₹
Also we got 5.72 kg of CaSO4 = 5.72 kg x 150 ₹/kg = 843 ₹

 For Evaporation
Latent heat of evaporation of water is 2257 kJ/kg
1. Heat duty require for evaporation = Latent heat of evaporation(kJ/kg) x 48.3 kg
= 2257 kJ/kg x 48.3 kg
= 109013.1 kJ

Freeze Crystallizaer 5/9/20

26 Continue….
 For evaporation of 1 kg of water, we require 1.13 kg of saturated steam in
evaporation system
so, for evaporation of 48.3 kg water, we require 54.58 kg Sat. steam

But the cost of saturated steam per kg is 1.8 ₹

So, Cost of evaporation is 87 ₹.

Freeze Crystallizaer 5/9/20

27 Results & Major outcomes

System name Evaporation(KW) In EFC(KW)

Na2CO3-water 89.3 17.3

Na2SO4-water 93.5 16.5

MgSO4-water 25.1 6.93

NaNO2-water 94.9 15.5

CaSO4-water 30.3 7.3

Freeze Crystallizaer 5/9/20

28

 From the above experiments study we can see that energy consumption
by this operation is relatively low compare to conventional operations.
 Hence, freeze crystallization can be considered for the recovery of salts
from its dilute aqueous solutions, particularly if it is eutectic system.

Freeze Crystallizaer 5/9/20

29 Energy consumption

Comparison of Energy requirement in Evaporation and EFC

100 93.54 94
89
90
80
70
Energy (KWh)

60
50
40
30
30 25.02
20 16.6 16 15.5
10 6.9 7.3

0
Na2CO3-water Na2SO4-water MgSO4-water NaNO2-water CaSO4-Water

Evaporation EFC

Freeze Crystallizaer 5/9/20

30 Cost comparison
Cost comparison in Evaporation and EFC
300
269 273
258
250

200
Cost (Rs.)

150
128 124 120

100 81 87

53 56
50

0
Na2CO3-water Na2SO4-water MgSO4-water NaNO2-water CaSO4-water

Evaporation EFC

Freeze Crystallizaer 5/9/20

31 Future work

 Based on experimental result, Energy consumption by freeze

crystallization for the same separation at commercial scale will be
calculated and same will be compared with energy consumption by
multi effect evaporator.
 Recovery of salt from reverse osmosis rejection stream

Freeze Crystallizaer 5/9/20

 Work Plan
32
2017 2018
July August September October November December January February March April

A A A A A A A A A A
B B
C C C C C C
D D
E

A LITERATURE REVIEW

B PROJECT GOAL

C EXPERIMENTAL WORK
D FINAL REPORT
E SUBMISSION
Freeze Crystallizaer 5/9/20
 References:
33

 F. van der Ham, G.J. Witkamp, J. de Graauw, and G.M. van Rosmalen,“Eutectic freeze crystallization: Application to process streams and waste

water purification”, Chemical Engineering and Processing 37 (1998) 207–213

 Yoshihito Shirai, Minato Wakisakay, OsatoMiyawak and Shigeru Sakashita, “Conditions of Producing an Ice Layer with High Purity for Freeze

Wastewater treatment”, Journal of Food Engineering 38 (1998) 297-308

 F. van der Ham, G.J. Witkamp, J. de Graauw, and G.M. van Rosmalen, “Eutectic freeze crystallization simultaneous formationand separation of

two solid phases”, Journal of Crystal Growth 198/199 (1999) 744—748

 Marino Rodriguez, Susana Luque, Jose R. Alvarez and Jose Coca, “A comparative study of reverse osmosis and freeze concentration for the

removal of valeric acid from wastewater”, Desalination 127 (2000) 1-11

 Olivier Lorain, Pascal Thiebaud, Eugenie BadorcAnd Yves Aurelle, “Potential Of Freezing In Wastewater Treatment: Soluble Pollutant

Applications”, Wat. Res. Vol. 35, No. 2, pp. 541–547, 2001

 C. Himawan*, R.J.C. Vaessen, H.J.M. Kramer, M.M. Seckler and G.J. Witkamp, “Dynamic modeling and simulation of eutectic freeze

crystallization”, Journal of Crystal Growth 237–239 (2002) 2257–2263

 R. J. C. Vaessen, B. J. H. Janse, M. M. Seckler and G. J. Witkamp, “Evaluation Of The Performance of a Newly Developed Eutectic Freeze

Crystallizer Scraped Cooled Wall Crystallizer”, Trans IChemE, Vol 81, Part A, November 2003

Freeze Crystallizaer 5/9/20

 References:
34
 Raymond Vaessen, Marcelo Seckler, and Geert Jan Witkamp, “Eutectic Freeze Crystallization with an Aqueous
KNO3-HNO3 Solution in a 100-L Cooled-Disk Column Crystallizer”, Ind. Eng. Chem. Res. 2003, 42, 4874-4880

 Frank van der Ham, Marcelo Martins Seckler and Geert Jan Witkamp, “Eutectic freeze crystallization in a new
apparatus: the cooled disk column crystallizer”, Chemical Engineering and Processing 43 (2004) 161–167

 F. E. Genceli, R. Gartner and G. J. Witkamp, “Eutectic freeze crystallization in a 2 nd generation cooled disk
column crystallizer for MgSO4 H2O system”, Journal of Crystal Growth 275 (2005) e1369 - e1372

 P. Pronk, C. A. Infante Ferreira and G. J. Witkamp“Prevention of crystallization fouling during eutectic freeze
crystallization in fluidized bed heat exchangers”, Chemical Engineering and Processesing 47 (2008) 2140-2149

 E. Hernandez, M. Raventos, J. M. Auleda and A. Ibarz, “Concentration of apple and pear juices in a multi-plate
freeze concentrator”, Innovative Food Science and Emerging Technologies 10 (2009) 348–355

 Cong ShuangLuo, Wen-wu Chen and Wen-fengHan,“Experimental study on factors affecting the quality of ice
crystal during the freezing concentration for the brackish water”, Desalination 260 (2010) 231–238

Freeze Crystallizaer 5/9/20

 35
References:
 J. Sánchez, Y. Ruiz, M. Raventós, J.M. Auleda, and E. Hernández, “Progressive freeze concentration of orange juice in a pilot plant falling film”,

Innovative Food Science and Emerging Technologies 11 (2010) 644–651

 J. Van Spronsen, M. Rodriguez Pascual, F. E. Genceli, D. O. Trambitas, H. Evers and G. J. Witkamp, “Eutectic freeze crystallization from the ternary

Na2CO3–NaHCO3–H2O system A novel scraped wall crystallizer for the recovery of soda from an industrial aqueous stream”, Chemical Engineering

Research and Design 88 (2010)1259–1263

 J. Van Spronsen, M. Rodriguez Pascual, F. E. Genceli, D. O. Trambitas, H. Evers and G. J. Witkamp, “A novel scraped cooled wall crystallizer

Recovery of sodium carbonate and ice from an industrial aqueous solution by eutectic freeze crystallization”, Chemical Engineering Research and

Design 88 (2010)1252–1258

 S. T. Reddy, A.E. Lewis, G. J. Witkamp, H.J.M. Kramer and J. Van Spronsen, “Recovery of Na2SO4·10H2O from a reverse osmosis retentate by

eutectic freeze crystallisation technology”, Chemical Engineering Research and Design 88 (2010)1153–1157

 D.G. Randall, A.E. Lewis and J. Nathoo“A case study for treating a reverse osmosis brine using Eutectic Freeze Crystallization—Approaching a zero

waste process”, Desalination 266 (2011) 256–262

 J. M. Auleda, M. Raventós and E. Hernández, “Calculation method for designing a multi-plate freeze-concentrator for concentration of fruit juices”,

Journal of Food Engineering 107 (2011) 27–35

Freeze Crystallizaer 5/9/20

 References:
36

 L. Otero, P. Sanz, B. Guignon, and P. D. Sanz, “Pressure-shift nucleation: A potential tool for freeze concentration of fluid foods”,
Innovative Food Science and Emerging Technologies 13 (2012) 86 –99

 M.J. Fernández-Torres, D. G. Randall, R. Melamu and H. von Blottnitz, “A comparative life cycle assessment of eutectic freeze
crystallisation and evaporative crystallisation for the treatment of saline wastewater”, Desalination 306 (2012) 17 –23

 M.J. Fernández-Torres, F. Ruiz – Bevia, M. Rodriguez Pascual and H. von Blottnitz, “Teaching a new technology, eutectic freeze
crystallization, by means of a solved problem”, Education for Chemical Engineers 7 (2012) e163–e168

 G. Petzold, K. Niranjan and J. M. Agulera, “Vacuum-assisted freeze concentration of sucrose solutions”, Journal of Food Engineering 115
(2013) 357–361

 Tarak C. Padhiyar“Removal of Organic Acids from Effluent via Freeze Crystallization”,International Journal Of Engineering Sciences &
Research Technology, 2 (5), May 2013

 F.L. Moreno, M. Raventós, E. Hernández and Y. Ruiz,“Behaviour of falling-film freeze concentration of coffee extract”, Journal of Food
Engineering 141 (2014) 20–26

 Khushboo C. Shah “Removal of Organicsfrom Effluent via Freeze Crystallization”, International Journal of Futuristic Trends in
Engineering and Technology, Vol. 1 (02), 2014

Freeze Crystallizaer 5/9/20

 References:
37
 Guillermo Petzold, Jorge Moreno, Paz Lastra, Katerin Rojas and Patricio Orellana“Block freeze concentration assisted by centrifugation
applied to blueberry and pineapple juices”, Innovative Food Science and Emerging Technologies xxx (2015) xxx –xxx (Article in press)

 Paul M. Williams, Mansour Ahmed, Benjamin S. Connolly, Darren L. and Oatley Radcliffe, “Technology for freeze concentration in the
desalination industry”, Desalination 356 (2015) 314 –327

 Buhle S. Manana ,P. Nembudani,Marcos Rodriguez-Pascual,” Eutectic Freeze Crystallization process for the treatment of ternary textile
wastewater concentrates”.

 W. Gao, Y. Shao,”Freeze concentration for removal of pharmaceutically active compounds in water”, Desalination 249 (2009) 398–402.

 James A. Heist, “Freeze Crystallization: Improving The Energy Efficiency Of a Low-Energy Separation Process”, Proceedings from the
Third Industrial Energy Technology Conference Houston, TX, April 26-29, 1981

 James A. Heist and Thomas S. Barron, “Freeze Crystallization Processes: Efficiency by Flexibility”, Proceedings from the Fifth
Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983

 Ray Ruemekorf, “Freeze Concentration Applied to Hazardous Waste Management”,Proceedings from the Twenty-second National
Industrial Energy Technology Conference, Houston, TX, April 5-6, 2000

Freeze Crystallizaer 5/9/20

 References:
38
 J. Nathoo, R. Jivanjiand A.E. Lewis, “Freezing Your Brines Off: Eutectic Freeze Crystallization for Brine Treatment”, Proceedings of

International Mine Water Conference, Pretoria, South Africa, 19 th – 23rd Oct 2009.

 W. Gao ⁎, Y. Shao, “Freeze concentration for removal of pharmaceutically active compounds in water”, Desalination 249 (2009) 398–402.

 Dr. William M. Conlon, “Recent Improvements to the Freeze Crystallization Method of Water Purification”, 1992.

 P.Pronk, C.A. InfanteFerreira, M. Rodriguez Pascual and G.J. Witkamp, “Maximum Temperature Difference Without Ice-Scaling in Scraped

Surface Crystallizers During Eutectic Freeze Crystallization”,2003

 AkzoNobel “Freeze crystallization saves 30 percent energy”, Industrial Chemicals, October 2014

 Rineshkumar Bharat Jivanji, “Industrial Application of Eutectic Freeze Crystallization”, Department of Chemical Engineering, University of

Cape Town, Feb 2011

 Willem van der Tempel, “Eutectic Freeze Crystallization: Separation of Salt and Ice”, Delft University of Tech., Netherlands, June 2012

 TarakPadhiyar, “Removal of Organic Acids from Effluent via Freeze Crystallization”, Gujarat Technological University, Ahmedabad, 2014

 JigarMalaviya, “Separation of Azeotropic and Heat Sensitive Material using Freeze Crystallization”, Gujarat Technological University,

Ahmedabad, 2015
Freeze Crystallizaer 5/9/20
39

THANK YOU

Freeze Crystallizaer 5/9/20