21st Mid-year Meeting of the Indian Academy of Sciences

Faculty Hall, IISc Bangalore
CSMCRI
July 2, 2010

Case Studies of Recent Innovations in the

Area of Salt and Marine Chemicals
Pushpito K. Ghosh
 
Central Salt & Marine Chemicals Research Institute (CSMCRI),
G. B. Marg, Bhavnagar 364002, Gujarat

www.csmcri.org
CSMCRI

CSMCRI

Marine Biotechnology
& Ecology
Solar
Applications
The CSIR
Family
Corrosion Solar Salt & Marine
Salinity Sea
Evapo- Chemicals
Water ration

Wasteland Specialty Coordination

Catalysis Materials &
research Chemistry
Fertilizers

Desalination &
Membrane
Technology
 Source: Ullmann’s
Encyclopaedia
CSMCRI

Improvement in
industrial grade
salt quality has a
profound impact
downstream.
The recovery of common salt & marine chemicals from
seawater is based on fractional crystallization
Sea Brine
3-3.5o Be Conversion factor : Sp.gr. = 145/(145 – 0Be’)
Magnesium
Chloride
Recovery

Kainite Type
Mixed Salt
CaCO3 Gypsum Pre
Salt
Crystallization Crystallization Crystallizing Salt
area Storage
24-25o Be’ 35 - 37.5oBe’
6-10o Be’ 12-240Be’

Bromine
Recovery &
Separation of
Crude Salt
29 – 35 0 Be’

Bittern
Reservoir

Reservoir Condensers Crystallizer

25 - 29o Be’
CSMCRI
 Recognising that desulphatation of brine holds the key to pure salt and KCl
and using the effluent of soda ash industry to make this happen economically
Distiller Waste

Solar Evaporation Desulphated

Desulphated
Sea Brine Bittern
Brine

Evaporation
High Purity NaCl
Gypsum
Carnallite
Constituents Salt through Salt from KCl.MgCl2.3H2O
Traditional Desulphated Solvay Process
Process (%) Brine (%) CaCO3+ CaO+CO2
Ca 0.3 – 0.4 0.07 NaCl/ KCl
CaO+H2O  Ca(OH)2
(low sodium salt)
Mg 0.1 – 0.12 0.03 NH3+H2O  NH4OH

SO4 0.80 – 1.00 0.09 NaCl+NH4OH +CO2  NH4Cl+NaHCO3

Source: sub-soil brine 2NaHCO3  CO2+H2O+Na2CO3

Naturally formulated low sodium 2NH4Cl+Ca(OH)2  2NH3+2H2O+CaCl2

salt will reach people globally Immediate beneficiaries would be soda ash
through Unilever Food Products industries who are backward integrated to salt
production.

US patent Nos. 6,776,972 (2004);

6,890,509 (2005)
CSMCRI
Making solar salt quality less sensitive to brine composition
CSMCRI
28
28
26
26
24
24

22 22

20 20

%T

%T
18 18

16 16

14
14
12
12
10
10
8
500 1000 1500 2000 2500 3000 3500 500 1000 1500 2000 2500 3000 3500
-1 -1
cm cm

Solar salt of exceptional purity – never before

Peak at 668 cm-1 (FT-IR) indicative of
achieved in the field – was obtained through an
impurities of magnesium oxy compounds are
inexpensive process of brine clarification (for
much reduced through the invention.
nucleation control) and pH adjustment (to prevent
agglomeration as a result of magnesium oxychloride
formation).
Brine Constituents (%w/w)
  Ca2+ Mg2+ SO42- I- NaCl
(ppb)
Normal 0.16 0.27 0.60 >800 >98.5
Clarificati 0.07 0.04 0.18 <150 > 99.3
on & pH
control
Technology demonstration at 10,000 tons scale
EP1928569; US Pat appln No. 11/992533 dtd: 25/03/2008 for Grasim Ltd. in Navlakhi, Gujarat
US Pat appln No. 12/240762 dtd: 29/09/2008
 Near spherical (Rhombic Dodecahedron) Common Salt : The idea was
to enhance free flow property (CSMCRI-HUL collaboration)

CSMCRI

THE 6th ANNUAL YEAR IN IDEAS; Salt

That Doesn't Stick
By CLIVE THOMPSON
Published: December 10, 2006

Key Inventions
• Suitable for production in solar pans
• Recycling of glycine (habit modifier) US Patent No: 7,220,435 dated 22 May 2007
without affecting salt morphology
Cryst. Growth & Des., 2006, 6, 1591-1594
 We have now made round salt without any chemical
additives.
a b c
Indian Patent Application
0060/Del/2008;
PCT/IN08/00568

“We wish to thank you for

your ability to provide us 500 µm 600 µm 500 µm
with exactly what we had
been searching for and d e f
expecting to find.” 

Allergan Medical, USA

800 µm 1000 µm 1200 µm

Cubic and Spherical salt from different brines

a
Cryst. Growth & Design (submitted)

The flowability of round salt is superior

to that of the commercially available
branded salt P1010103 salt flow.mpg
CSMCRI
500 µm 300 m
 The Invention of Vegetable Salt
CSMCRI

US Patents 6,929,809 and 7,208,189

CSMCRI has successfully developed a
process of densification of the natural habitat
(left inset) of Salicornia brachiata and over Key Inspiration: To make cultivation
100 hectare of such densification has been of Salicornia on saline wastelands
undertaken since 2005. Growing popularity of more viable by utilising the waste
vegetable salt could spur large scale demand biomass after removal of seeds.
for Salicornia.
 “Green Bromine”: A New Concept in Eco-
friendly Bromination
Bromination with "Green Bromine"
Eco-friendly
Versatile CSMCRI
Atom Efficient
Cost-effective Green
Bromine
4NaBr + 2NaBrO3 + 6NaCl
Salt bittern
pH 2-3 Cl2
NaOH + Cl2
5:1 Br/BrO3 (BR-A) (addition)

2:1 Br/BrO3 (BR-S) (substitution)

6RH Aq. NaCl
+ 5NaBr +NaBrO3
6H 1:8 Br/BrO3 (BR-O) (oxidation)
(Bromine precursor)

6RBr H+
Debrominated Br2
bittern (Transient
formation) 3 Br2
Aq. NaOH Liquid Collaborations with Professor B.
Bromine C. Ranu and Dr. D. Basavaiah
are gratefully acknowledged.

US Patent No: 6,740,253 dated 25 May 2004.

Green Chem. 2006, 8, 916-922 ; Green Chem. 2008, 10, 232-237 ; J. Org. Chem. 2009, 74, 7947-7950;
Ind. Eng. Chem. Res. 2010, 49, 1236–1241
 Atom efficient syntheses of useful organic
compounds with green bromine
CSMCRI
Isolated Halogen atom Isolated Halogen atom
Substrate Product Substrate Product ef ficiency
yield ef f iciency yield

Br Br Br
OH
92 92 OH 99 99
HO OH HO OH NC
NC Br
Br Br
O O
Br
N H N Br 81 81 NH2 NH2 91 91
O O Br Br
Br
O2N O2N 95 89
OH
Br
89 89
74 78
Br
O
COOH COOH Br CH2OH Br 85 NA
OH OH 75 90

Br

NHCOCH3 NHCOCH3
86 86
F Br F

Green bromine-related technologies have been licensed

to two companies. A number of process patents have
been granted.
PROJECT PROGRESS

Archean’s potash project gets

CSMCRI
first-stage
environment nod
The Ministry of Environment and Forest has specified terms of
reference for environment impact assessment (EIA) for Archean
Chemical Industries P. Ltd’s (ACIPL’s) potassium sulphate
fertiliser plant to be located in Kachchh region of Gujarat. The
project envisages manufacture of 100,000 tonnes per annum
(tpa) of sulphate of potash, 12,500-tpa of liquid bromine, 2,500-
tpa of green bromine,...... .
Chemical Weekly June 22, 2010

“The project concept of CSMCRI remains unchanged.

We are investing based on the conditions in the
market, project execution plan and a phased
program.”
C. G. Sethuram, Archean (March 25, 2010)
 SOP (K2SO4) offers an advantage over MOP (KCl) currently
used by farmers with special focus on the following:
CSMCRI
• Chloride sensitive crops
• Dryland agriculture
• Sulphur responsive crops
• Drip irrigation
• Areas deficient in K & S

Product strategy was also

guided by the compositional
advantage of sea bittern in so
far as SOP production is
concerned.
 Making SOP Production Viable through Co-production of MgO
KAINITE TYPE
US Patent 7,041,268 (2006) Ind. Eng. Chem. Res. 2006, 45, 1551-1556
MIXED SALT
KCl.MgSO4.3H2O
WATER KCl SOLUTION

SCHOENITE
DECOMPOSER CF REACTOR CF
SOP

SCHOENITE
CSMCRI END LIQUOR
SOP END - LIQUOR

CaO

CaCl2 Crude MOP

REACTOR Filtration Salt Pan Salt Pan Refining

Mg(OH)2 CaSO4

Key Innovations: NaCl

MgO
• Lime and bittern are the only raw material inputs CSMCRI
• All operations under ambient conditions
• Avoids froth floatation
• Generates required KCl for SOP as part of the process
 Ultrapure MgO
suitable for LD
converter for primary
steel making and Mg
production

RUL > 1680oC

“The undersigned and Dr. Haldar had developed the magnesite refractory from
your magnesia. The refractory properties along with the photographs of the
samples after the test is given in the attached file. The 99% MgO grade gave
excellent results. “11 May 2010
(Dr. Arup Ghosh, Scientist F, Refractories Division
Central Glass and Ceramic Research Institute)

“We have analysed the MgO sample (99% pure sample was sent) of CSMCRI and
found it suitable for Mg production.”
Swatantra Prakash, Sct G and Head Metal Extraction and Forming Division, National
Metallurgical Laboratory, Jamshedpur
Potash can be recovered through selective extraction from bittern instead
of through fractional crystallization. This would help conserve land
requirement.

H
NO 2 O2N
N

O 2N NO 2
NO2 O2N
Dipicrylamine (DPA)
Ca(OH)2 CaSO4

-
DPA Ca 2 +(DPA ) 2
+ (sol.)
CaSO4
Bittern
K Cl + +
( Na +, K , Mg 2 ,
2-
Ion chromatogram of sea bittern
Ca 2+, SO4 )
(top) and the precipitate separated
+
K -free bittern
from bittern with DPA- .
HCl -
K + (DPA )
+ PCT/IN2005/000441
CaSO4
CSMCRI (ppt.) Eur. J. Inorg. Chem. 2005, 2198-2205
 Macro- and micronutrients in Kappaphycus sap
g/L mg/L
Protein 0.85 Phosphorous 29.6
Fat 0.024 Iron 85.8
Carbohydrate 18.00 Manganese 2.2
Sodium 0.18 Nickel 3.5
Potassium 3.58 Copper 0.78
Magnesium 1.17 Zinc 4.74
Calcium 0.33 Iodine 1.60

Data courtesy: National Institute of Nutrition,

Hyderabad,
US Patent No. 6,893,479; EP 1534757  (to CSIR)
J. Agric. Food Chem. 2010, 58, 4594–4601
17

CSMCRI

Kappaphycus alvarezii cultivation may offer a

potential opportunity to recover potash by biological
means besides the direct use of the sap as a potent
foliar spray and biomass as source of energy.
Conclusions
CSMCRI
The presentation attempted to illustrate case studies
of inventions in the seemingly mature areas of salt &
marine chemicals.
These inventions originated from genuine needs,
street smart thinking, systems integration and
application of basic chemistry.
Acknowledgement
• All those who have contributed to the work
• Funding agencies
• Collaborators and licensees
• CSIR

Thank you