US 20090175781A1

( 12) Patent Application Publication ( 10) Pub. N o. : US 2009/0175781 A1

( 19) United States
Kumar et al. ( 4 3 ) Pub. D ate: J ul. 9, 2009
( 54 ) PROCESS FOR THE PREPARATION OF ( 22) Filed: Sep. 29, 2008
COMMON SALT OF HIGH PURITY FROM
BRIN ES IN SOLAR SALT PAN S ( 3 0) Foreig n Application Priority D ata
( 75) Inv entors : Arv ind Kumar Bhav nag ar ( IN ) ; J an. 7, 2008 ( IN ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57/D EL/2008
Indrajit Mukhopadhy ay , . . . .
Bhav nag ar ( IN ) ; Pus hPito Kumar Publication Clas s i? cation
Ghos h, Bhav nag ar ( IN ) ; Vadakke ( 51) Int. Cl.
Puthoor Mohandas , Bhav nag ar C01D 3 /06 ( 2006 . 01)
( IN ) ; J ig nes h J as v antrai Shukla, ( 52) us . Cl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 23 /4 995
Bhav nag ar ( IN ) ; Rahul J as v antrai
Sang hav i, Bhav nag ar ( IN ) ( 57) ABSTRACT
Corres pondence Addres s :
D LA PIPER LLP ( US)
4 3 6 5 EXECUTIVE D RIVE, SUITE 1100
SAN D IEGO, CA 92121- 213 3 ( US)
COUN CIL OF SCIEN TIFIC &
IN D USTRIAL RESEARCH, N eW
D elhi ( IN )
( 73 ) As s ig nee:
( 21) Appl. N o. : 12/24 0, 76 2
The proces s of the inv ention is an improv ement ov er the
ex is ting proces s of producing s alt of hig h purity from alum
treated brine dis clos ed recently in the prior art. More particu
larly , the inv ention recti? es the ratio of Ca2+ to Mg 2+ from a
v alue < 1 to a v alue in the rang e of 2- 3 des ired by chlor- alkali
and s oda as h indus tries . The improv ed proces s inv olv es the
adjus tment of pH of clari? ed brine With aqueous HCl s o as to
carry out s alt cry s talliz ation at a pH of 6 . 5 ins tead of at the
natural pH of 7. The pH adjus tment reduces the Mg 2+ impu
rity in s alt While s lig htly rais ing the Ca2+ impurity in the s alt
and thereby achiev ing the des ired ratio.
Patent Application Publication J ul. 9, 2009 US 2009/0175781 A1
AT
I I I
3 000 3 5: 3 0
I I I
ZUUU 25GB
1 ' I I I
SUD 1 BUD 1 SUD
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FIG. 1B
US 2009/0175781A1
PROCESS FOR THE PREPARATION OF
COMMON SALT OF HIGH PURITY FROM
BRIN ES IN SOLAR SALT PAN S
CROSS REFEREN CE TO RELATED
APPLICATION
[ 0001] This application is a utility application and claims
the bene? t under 3 5 USC 119( a) of India Application N o.
57/D EL/2008 ? led J an. 7, 2008. The dis clos ure of the prior
application is cons idered part of and is incorporated by ref
erence in the dis clos ure of this application.
BACKGROUN D OF THE IN VEN TION
[ 0002] 1. Field of the Inv ention
[ 0003 ] The pres ent inv ention relates to an improv ed pro
ces s for the preparation of s olar s alt from s ea and s ub- s oil
brines . More s peci? cally the inv ention relates to a cos t- effec
tiv e proces s for preparation of common s alt Wherein both the
abs olute purity of the s alt as Well as the ratio of Ca2+ to Mg 2+
are important, s uch as in chlor- alkali and s oda as h indus tries .
Still more s peci? cally , the proces s relates to preparation of
the abov e s olar s alt throug h an improv ed proces s Wherein
prior to charg ing of brine into cry s talliZers it is treated With
alum to y ield hig h purity s alt as reported in the prior art
folloWed by the inv entiv e s tep of controlled adjus tment of pH
to als o effect the des ired ratio of Ca2+ to Mg 2+ in the s alt.
[ 0004 ] 2. Backg round of the Inv ention
[ 0005] The World s alt production has cros s ed tWo hundred
million tons per annum. About 6 0% of the s alt produced is
us ed for indus trial applications , chior- alkali and s oda as h
indus tries being the major cons umers . Superior quality indus
trial g rade s alt With s peci? ed Ca2+ to Mg 2+ ratio is preferred
by thes e indus tries as the us e of s uch s alt reduces the brine
puri? cation cos t and ef? uent g eneration. 4 0% s alt g oes for
human cons umption Where the caking of s alt on s torag e pos es
g reat problems . This is attributed to the hy g ros copic nature of
the mag nes ium impurities pres ent in s alt. The loWer mag ne
s ium content can als o enhance the s tability of iodiZing ag ent
in iodiZed s alt.
[ 0006 ] Solar s alt is produced us ing s eaWater, s ub- s oil brine
and lake brine. All thes e brines cons titute a multi- component
s alt s y s tem With a number of ions in the dis s olv ed s tate and
recov ery of any of thes e s alts in its pure form directly from
thes e brines pos es a problem. Hence s alt produced from s uch
brines is inv ariably contaminated With impurities s uch as
Ca2+ , Mg 2+ , SO4 2 and heav y metals . All thes e impurities are
detrimental for indus tries Where s alt is us ed as a bas ic raW
material. On the other hand, s olar s alt production from natural
brines is mos t cos t- effectiv e. It is , therefore, important to
dev is e means of making s olar s alt With minimum impurities
While retaining the adv antag e of cos t- effectiv enes s .
[ 0007] Reference may be made to the paper entitled Pri
mary Brine Treatment Operations by D . Elliott pres ented at
the 1999 Eltech Chlorine/Chlorate Seminar on Technolog y
Bridg e to the N eW Millenium, Ohio, 13 Sep. 1999, Wherein
the critical importance of s alt purity and the deleterious
effects of v arious contaminants including heav y metals on
chlor- alkali manufacture are hig hlig hted.
[ 0008] The Webs ite WWWl . eere. energ y . g ov /indus try /
chemicals /pdfs /pro? le_ chap6 . pdf prov ides information on
the chlor- alkali indus try and als o s ome information on the
s oda as h indus try , Wherein brine caus tic s oda production
res ults in brine mud, one of the larg es t Was te s treams from the
J ul. 9, 2009
chlor- alkali indus try . About 3 0 kilog rams of brine mud are
g enerated for ev ery 1000 kilog rams of chlorine produced, but
this v aries With the purity of the s alt us ed to produce the brine.
The brine mud contains a v ariety of compounds , ty pically
mag nes ium hy drox ide and calcium carbonate, Which are pro
duced in the proces s of remov ing calcium and mag nes ium
impurities in the s alt throug h s oda/lime treatment. FolloWing
the treatment the Ca2+ and Mg 2+ impurities in the brine are
reduced to ppm lev els . The brine may then g o throug h further
puri? cation utiliZing ion s electiv e res ins .
[ 0009] Reference may once ag ain be made to the article on
Primary Brine Treatment Operations pres ented at the 1999
Eltech Chlorine/Chlorate Seminar on Technolog y Bridg e to
the N ew Millennium held at Clev eland, Ohio on Sep. 13 ,
1999, Where in the importance of maintaining Ca2+ to Mg 2+
ratio in s alt is clearly ex plained. The hig her mag nes ium con
tent in s alt pos es the problem of s ettling the ? occulent pre
cipitates during the primary treatment of brine before its
proces s ing for chlor- alkali manufacture. It has been ev i
denced that the hig her the mag nes ium content loWer is the
s ettling rates . Hence the chlor- alkali manufacturers ins is t on
Ca2+ to Mg 2+ ratio in rang e of 2- 4 . This abov e prior arts teach
us that the abs olute purity of s alt as als o the ratio of Ca2+ to
Mg 2+ are both important for a facile brine puri? cation proces s
With minimum Was te g eneration.
[ 0010] Reference may be made to a larg e number of articles
des cribing the manufacture of s oda as h from s alt by the
Solv ay proces s . Here ag ain, brine puri? cation throug h s oda/
lime treatment is of crucial importance.
[ 0011] Reference may be made to US. Pat. N o. 7, 03 7, 4 81,
dated May 2, 2006 , Wherein, Becenel, J r. reports the methods
and ins tallations for producing ultra pure s odium chloride s alt
cry s tals primarily for us e in s aturating depleted brine res ult
ing from the electroly tic decompos ition of s aturated brine in
chlor alkali membrane cells for the production of chlorine,
caus tic s oda and hy drog en. This inv ention particularly relates
to the production of ultra pure s odium chloride s alt cry s tals by
proces s ing primary treated brine by ? rs t acidify ing the pri
mary treated brine, then s tripping the carbonic acid produced
by acidi? cation as carbon diox ide, and then returning the
brine to a pH of about 6 or hig her Which is s uf? cient for
proces s ing it in ev aporation equipment Where the ultra pure
s alt cry s tals are produced.
[ 0012] In the article Was hing of Strip Mined Rock and
Solar Salt at Les lie Salt Corporation US ( Sy mpos ium on
Salt- I, Vol. 1, the N orthern Ohio Geolog ical s ociety Incorpo
ration, Clev eland ( 196 1) , p 4 4 9- 4 6 4 ) , A. Woodhill has
reported that Ca , Mg , and SO4 2- impurities in s olar s alt
can be reduced by mechanical Was hing . The main dis adv an
tag e of the method is that there is a 15- 20% los s of s alt and the
method requires hig h capital inv es tment. Moreov er, the max i
mum lev el of reduction of Ca2+ is 70% and embedded impu
rities are dif? cult to remov e.
[ 0013 ] In the patent application GB 200200283 51 and
20021205 dated 9 J un. 2004 entitled Ex tracting Sodium
Chloride From Sea Water Us ing N ano Filtration by Kenny
Conor et al. it is reported that s ea Water is pretreated to make
it s uitable for nano? ltration and the nano? ltered s ea Water is
s ent to a thermal des alination plant Which operates as a
s odium chloride concentrator and a dis tilled Water producer.
Sodium chloride is cry s talliZed from the concentrated s olu
tion and the proces s prov ides a hig h purity s odium chloride
s uitable for many indus tries . It is claimed that the s alt s o
produced eliminates many of the requirements of the primary
US 2009/0175781A1
and s econdary brine treatment for the chlor- alkali indus tries .
The nano? ltration proces s has a hig her rejection rate for
calcium, mag nes ium and s ulphate ions as compared to N a+ or
Cl- ions . The drawbacks of this proces s are that it Would entail
hig h capital inv es tment and additional unit operations Which
Would be uneconomical for s tandalone production of com
mon s alt in s olar s alt Works . Moreov er, it needs to be noted
that Whereas N aCl s olubility in Water is 3 5%, its s olubility in
brine is only 25% Which means that adv antag e can be taken of
the common ion effect to reduce N aCl s olubility in brine
Which adv antag e Would be los t if the div alent ions Were to be
completely remov ed by the proces s of nano? ltration and
more time Would be required for ev aporation.
[ 0014 ] Reference may s imilarly be made to Central Salt &
Marine Chemicals Res earch Ins titutes Biennial reports
2000- 2002 and 2002- 2004 appearing in the Ins titutes Web
s ite ( WWW. cs mcri. org ) Wherein the puri? cation of s aturated
brine throug h a nano? ltration proces s is reported.
[ 0015] In the patent application GB1954 003 3 194
1954 1 116 dated D ec. 19, 1956 entitled Improv ed Method of
Preparing Sodium Chloride Brines of Hig h Purity Albrig ht
and Wils on hav e claimed that s odium chloride brines loW in
calcium s ulphate content are prepared by dis s olv ing s olid
s odium chloride contaminated With calcium s ulphate in Water
in pres ence of a poly phos phate s oluble in brine in the con
centration rang e of 50- 100 ppm. It is claimed that the amount
of calcium s ulphate is further decreas ed by dis s olv ing s olid
s odium chloride in the pres ence of both the poly phos phate
and Water- s oluble alkaline earth metal compound s uch as
calcium chloride or acetate or barium chloride up to 1% lev el.
The draWbacks of this proces s are that it is les s appropriate for
s olar s alt production and more appropriate as a means of
pos t- treatment of brine obtained by dis s olv ing s alt.
[ 0016 ] Reference may be made to the European Patent N o:
EP 1, 54 5, 73 3 , B9 ( WO 2004 /01806 8) dated Apr. 21 1999 by
May er et al. Wherein an ev aporativ e s alt cry s talliZation pro
ces s that produces pure s alt is dis clos ed. The proces s utiliZes
s accharide or its deriv ativ e in an ev aporativ e proces s occur
ring at room temperature. The main dis adv antag e of the s aid
proces s is that the s accharide is us ed in about 5% ( W/v )
concentration Which Would increas e the v is cos ity of the brine
and s loW doWn ev aporation and als o add s ig ni? cantly to cos t.
[ 0017] In their patent application ( US. Pat. N o. 3 , 891, 297
dated J un. 24 , 1975) entitled Cry s talliz ation of s odium chlo
ride of reduced calcium s ulfate content in pres ence of about 5
to about 500 ppm by H. W. Fiedelman a proces s for the
preparation of the cubic cry s talline form of s odium chloride is
des cribed us ing either ( 1) a feed and bleed procedure com
pris ing admix ing an alkali metal phos phate With an aqueous
s olution of s alt to increas e the s uper s aturation of calcium
s ulphate there in and ev aporating the brine at an elev ated
temperature and reduced pres s ure to caus e cry s talliZation of
pure s alt and concomitantly bleeding brine from the chamber
to the feed brine s uch as to maintain the calcium s ulphate in
the dis s olv ed s tate and prev ent its precipitation With s alt or ( 2)
s ubjecting the brine to s olar ev aporation to concentrate the
s ame to the s alt point, i. e. , that point at Which the s alt Will
cry s talliZe from the brine, adding an alkali metal poly phos
phate to brine at this point to increas e the s uper s aturation of
calcium s ulphate there in and proces s ing the brine for s alt
production folloWing the conv entional method. The proces s
inv olv es addition of cos tly chemicals at a v ery hig h dos ag e
lev el. In the US. patent ( US. Pat. N o. 6 , 812, 011 dated 2 N ov .
2004 ) entitled An Improv ed Proces s for the Remov al of Ca
J ul. 9, 2009
ions from the Brine by Marine Cy anobacteria by S. Mis hra
et al. it has been claimed that common s alt With reduced Ca2+
impurity can be produced from s ea/ s ubs oil brine by mopping
up Ca2+ in the brine throug h certain ty pes of marine cy ano
bacteria. The draWback of this proces s is that althoug h the
proces s has been demons trated in s mall s olar pans , it is not
readily amenable to s cale up. More ov er the proces s des cribes
the method of reduction of Ca2+ impurities Whereas the pro
ces s does not des cribe the reduction of remaining impurities
s uch as mag nes ium and s ulphate.
[ 0018] In their paper entitled Improv ement in quality of
s altfrom in- landbrine ofKharag hoda area, India ( Res earch
and Indus try , Vol. 3 7, March 1992, pp 4 6 - 4 8) , A. U. Hami
dani and J . R. Sang hav i hav e ex plained a method of reducing
the Ca2+ content in s alt by es tablis hing a common ion effect
in the s aturated brine by increas ing the s ulphate content
throug h addition of either Mg SO4 or N a2SO4 . The draWbacks
of the method are that thoug h the Ca2+ content of s alt is
reduced, the Mg 2+ and SO4 2 content cannot be reduced.
Moreov er, it inv olv es compos itional chang es Which are
s ometimes dif? cult from a log is tics and cos t point of v ieW.
[ 0019] In the US. patent ( US. Pat. N o. 6 , 776 , 972 dated 17
Aug . 2004 ) entitled A Proces s for Recov ery of Common Salt
and Marine Chemicals from Brine in Integ rated Manner by
R. N . Vohra et al. it is claimed that common s alt and marine
chemicals of hig h purity can be recov ered in an integ rated
manner by forced des ulphatation of brine With inex pens iv e
s ources of CaCl2 s uch as dis tiller Was te of Solv ay Proces s
prior to cry s talliZation of s alt. The proces s Works Well for any
kind of brine and can als o be carried out at larg e s cale but the
main draWback is the lack of av ailability of s uch calcium
chloride s ource in the v icinity of mos t s alt Works . Another
draWback of the proces s is that care mus t be taken to ens ure
that fres h brine does not mix inadv ertently With des ulphated
brine in the cry s talliZer s ince the ex ces s calcium chloride can
form g y ps um in the cry s talliZer that Would deteriorate the
quality of s alt. Yet another draW back of the inv ention is that
thoug h the calcium impurities are reduced the mag nes ium
content is not affected g reatly by the dis tiller Was te treatment.
More ov er, a chang e in compos ition of brine is effected by the
addition of dis tiller Was te liquor.
[ 0020] H. M. Patel, in his res earch article that appeared in
the Proceeding s of 6 th International Sy mpos ium on Salt, Vol.
2 pp. 515- 53 3 , has dis clos ed that Ca2+ and SO4 2 impurities
in s alt can be reduced us ing the difference in dis s olution rate
of N aCl and CaSO4 . The main draWbacks of the proces s are
that it employ s unit operations like dis s olv er and chemical
proces s reactor. It als o requires addition of lime and s oda for
the remov al of Mg 2+ and Ca2+ and s ubs equent ? ltration of
brine.
[ 0021] Reference may be made to the res earch article:
Rain Was hing ofCommon Salt Heaps by M. P. Bhatt et al.
( Salt Res earch and Indus try 10 ( 2) , 1974 , p 13 ) Wherein it is
reported that s ea s alt, as produced in s olar pans contains
0. 16 - 0. 18% Ca2+ , 0. 3 - 0. 4 % Mg 2+ and 0. 70% SO4 2 , Whereas
after rain Was hing the s alt contains 0. 21% Ca2+ , 0. 06 % Mg 2+
and 0. 6 0% SO4 2 . Althoug h rain Was hing reduces Mg 2+ im
purities to s ome ex tent, the Ca2+ and SO4 2 impurities cannot
be reduced from the harv es ted s alt ev en by repeated Was h
ing s . On the contrary , it is obs erv ed that the concentration of
Ca2+ increas es after rain- Was hing . The effect of mag nes ium
impurities at reduced lev els of calcium to maintain the Ca2+ to
Mg 2+ ratio in s alt is not des cribed in the article.
US 2009/0175781A1
[ 0022] In the article Manufacture 0fS0lar Salt by Series
Feeding Sy s tem by R. B. Bhatt et al. ( Salt Res earch and
Indus try , 1 1, 1979, p 9) it has been reported that s olar s alt with
les s impurities of Ca2+ can be produced from s ea water by a
s eries feeding method wherein the s alt is harv es ted in two
s tag es i. e. between 25. 5- 27o Be' ( Sp. Gr. 1214 - 123 0) and
27- 290 Be' ( Sp. Gr. 123 0- 1250) . Salt harv es ted in the ? rs t
s tag e is of a s uperior quality . Althoug h this is a g ood proces s
the drawback is that calcium and s ulphate impurities cannot
be reduced bey ond a point ev en thoug h hig her lev els of reduc
tion are des irable. The article does not des cribe the proces s ing
of s ub- s oil brines which is de? cient in s ulphate content as
compared to s ea brine. More ov er the Mg 2+ content in the
s econd fraction collected between 27- 290 Be' ( Sp. Gr. 1 . 23 0
1250) is found to be hig her which can only be remov ed
throug h mechanical was hing inv olv ing los s es of s alt and
additional cos t.
[ 0023 ] In the Indian Patent N o. 191912 ( noti? ed in the
Indian Gaz ette) entitled Preparation of Sodium Chloride
Containing Low Ca Impurity from Sea Brine in Solar Salt
Works by J . R. Sang hav i et al. it is claimed that addition of a
poly s accharide additiv e namely s tarch in concentration of
50- 150 ppm into concentrated brine can reduce calcium
impurity in s alt to les s than 0. 05- 0. 1 percent as Ca2+ . The
drawbacks of the proces s are that it requires addition of hot
s olution of s tarch which is both cumbers ome and cos tly ,
addition has to be repeated s ev eral times and no mention is
made of the effect of the treatment on other impurities in s alt.
N o ex planation is als o prov ided for the orig in of the obs erv ed
effect. Moreov er the mag nes ium content of s alt cannot be
reduced by the cited proces s .
[ 0024 ] In their patent application ( WO 2004 06 93 71 dated
19 Aug . , 2004 ) , Kamis hima Hiros hi et al. hav e claimed that
s odium chloride cry s tals with reduced impurities can be pro
duced from aqueous s odium chloride s olutions by pas s ing the
s olution throug h a column packed with an ads orbent on to
which the impurity is s electiv ely ads orbed. The method als o
prov ides a s odium chloride compos ition for preparing arti?
cial s eawater for us e in alg ae cultiv ation, which is reduced in
Mg 2+ ion or Ca2+ ion concentration. The drawbacks of the
proces s are that it is not applicable to a multi- component
s y s tem like s ea/s ub- s oil brine. This proces s does not g iv e any
clue about the production of s uperior quality s alt directly
from s ea/s ub- s oil brine in a s olar s alt works .
[ 0025] In the patent ( US. Pat. N o. 4 , 072, 4 72 dated Feb. 7,
1978) on Hig h purity s alt from hig h s ulphate s alt depos its by
A. Lukes J erome it is reported that s ubterranean s alt depos it is
s olution mined, and the res ulting calcium- and s ulphate- con
taminated brine is treated with s oda as h to precipitate calcium
compounds . After s ettling the s lurry the clear brine is ev apo
rated in a s eries of s olar ponds to produce hig h- g rade s odium
chloride. This proces s is not economically feas ible for larg e
s olar s alt works where s alt is produced from s ea/s ub- s oil
brines . Moreov er, the proces s remov es only calcium content
from s alt and the mag nes ium and s ulphate impurities remain
unaffected.
[ 0026 ] In the US. Pat. N o. 3 , 6 4 7, 3 96 dated 7 Mar. 1972
entitled Production of Hig h Purity Salt , H. W. D ewittie et
al. hav e claimed to hav e dev eloped a proces s for the recry s
talliz ation of s odium chloride in the form of hig h purity cubic
cry s tals from a s odium chloride s ource containing calcium
s ulphate impurity by multi- effect ev aporation preceded by
treatment of the hot s odium chloride s aturated brine by ? oc
culants and s ettling , to caus e the undis s olv ed calcium s ul
J ul. 9, 2009
phate particles and other s us pended s olids to ag g lomerate and
s ettle out of the brine prior to recry s talliz ation of s odium
chloride eliminating the conv entional requirement for ? lter
ing the hot brine. The main drawbacks of the proces s are that
it inv olv es recry s talliz ation which is ex pens iv e, time cons um
ing and energ y intens iv e. There is no mention of the utility of
the method for production of pure s alt directly from s ea brine
or s ub- s oil brine in s olar s alt works .
[ 0027] A] K Env ironmental Specialties , Inc. , Marchant
Ville, N . J . , USA has als o come out with a commercial ? oc
culating ag ent by the name of Aquas orb which is a cros s
linked poly mer compris ing s olely of s odium poly acry lates . It
is claimed that the product works well for brine clari? cation
and remov al of Ca2+ and Mg . Qumi International, Inc. ,
Tex as , USA has als o claimed to hav e produced s uch poly
acry lamide- bas ed ? occulants and coag ulants for s imilar pur
pos es . Thes e ? occulating ag ents are us ed to reduce res idual
Ca2+ and Mg 2+ impurities in brine, s uch brine being thereafter
us ed directly in indus trial applications s uch as in chlor- alkali
and s oda as h indus tries . The reported proces s is s peci? c to the
treatment of brine prepared from the harv es ted s alt and may
not work directly with concentrated s ea brine or s ub- s oil brine
for the production of s olar s alt with hig hly reduced lev els of
calcium and mag nes ium impurities .
[ 0028] In patent N o. WO200703 6 94 9 dated: Apr. 5, 2007,
entitled a cos t- effectiv e proces s for the preparation of s olar
s alt hav ing hig h purity and whitenes s Mukhopadhy ay Indra
jit et al. hav e claimed to hav e dev eloped a cos t effectiv e
proces s for the production of hig h purity s olar s alt ( > 99. 5%
purity on dry bas is after heap was hing ) with improv ed white
nes s hav ing hig hly reduced lev els of calcium and s ulphate
impurities and als o of heav y metal ions . Althoug h the proces s
as dev eloped has many adv antag es in terms of eas e of opera
tion and eliminating the calcium and s ulphate impurities to
the minimum pos s ible lev els , mag nes ium impurities , unfor
tunately , are not reduced in the s ame proportion as a res ult of
which the Ca2+ to Mg 2+ ratio in the s alt is < 1 and, cons e
quently , fails to meet the preferred ratio of 2- 4 des ired for
s oda/lime treatment for brine puri? cation in chlor- alkali and
s oda as h indus tries as alluded to abov e.
[ 0029] It is ev ident from the prior art that there are draw
backs in all of the prior arts , es pecially as applicable to s olar
s alt production in the ? eld. There are many proces s es where
a s alt of hig h purity is obtained but the proces s es are either
cumbers ome or cos tly and not practical for implementation in
the ? eld. There are other proces s es where the des ired Ca2+ to
Mg 2+ ratio is obtained eas ily in the ? eld but the abs olute
purity of the s alt is poor. On the other hand, treatment of brine
with alum to produce hig h purity s alt as reported in the recent
prior art is an attractiv e proces s for production of s olar s alt in
the ? eld, with purity > 99. 5% on dry bas is . But, here ag ain, the
proces s s uffers from the important drawback of y ielding s alt
hav ing undes ired ratio of Ca2+ to Mg 2+ becaus e of which
chlor- alkali and s oda as h indus tries may be reluctant to us e
the product. It is therefore hig hly des irable to improv e the
alum treatment proces s to obtain s alt with des ired Ca2+ to
Mg 2+ ratio while retaining all of the obv ious adv antag es of the
proces s .
OBJ ECTS OF THE IN VEN TION
[ 003 0] The main object of the pres ent inv ention is to pro
v ide an Improv ed Proces s of Preparation of Common Salt of
Hig h Purity from Brines in Solar Salt Pans which obv iates the
drawbacks as detailed abov e.
US 2009/0175781A1
[ 003 1] Another obj ect of the pres ent inv ention is to produce
common s alt hav ing purity > 995% N aCl on dry Weig ht bas is
and ratio of Ca2+ to Mg 2+ in the rang e of 2: 1 to 3 : 1 after
Was hing of s alt heaps With Water.
[ 003 2] Still another object of the pres ent inv ention is to
prov ide an improv ed proces s of producing pure s alt us ing
clari? ed alum- treated brine s o as to not only achiev e hig h
purity of s alt as dis clos ed in the prior art but als o the des ired
Ca2+ to Mg 2+ ratio currently not achiev ed With this proces s .
[ 003 3 ] Yet another object of the pres ent inv ention is to s hoW
that hig her than des ired lev el of Mg 2+ in the s alt obtained
throug h alum treatment is due to pres ence of ins oluble mag
nes ium compounds Which cannot be eas ily remov ed throug h
Was hing of s alt heaps With dilute brine or Water.
[ 003 4 ] Yet another object of the pres ent inv ention is to s hoW
that formation of s uch ins oluble mag nes ium compounds is
minimiz ed by reducing the pH of the alum- treated s aturated
brine in the cry s talliZer.
[ 003 5] Yet another object of the pres ent inv ention is to s hoW
that reducing the pH leads to pronounced increas e in the lev el
of Ca2+ impurity es pecially for pH< 6 5.
[ 003 6 ] Yet another object of the pres ent inv ention is to
utiliZe the abov e obs erv ations to optimally reduce pH of the
brine to 6 510. 1 to realiZe max imum adv antag e both from the
v ieWpoint of proces s economics and als o from the v ieWpoint
of s alt quality for chlor- alkali and s oda as h indus tries .
[ 003 7] Yet another object of the pres ent inv ention is to s hoW
that s uch chang e of pH is carried out eas ily in the s alt pan.
[ 003 8] Yet another object of the pres ent inv ention is to s hoW
that the incremental cos t of pH adjus tment Works out to < 5
US. cents per ton of s alt.
BRIEF D ESCRIPTION OF THE D RAWIN GS
[ 003 9] In the draWing accompany ing the s peci? cation,
FIG. 1A is the FT- IR s pectrum of s alt produced from clari? ed
brine Without pH adjus tment, i. e. , at pH 6 . 95. The heaped s alt
Was Was hed With Water ( 200 liter of Water per one ton heap) .
Peak at 6 6 8 cm 1 is indicativ e of impurities of mag nes ium
ox y compounds .
[ 004 0] FIG. 1B is the FT IR s pectrum ofs alt produced from
clari? ed brine after pH adjus tment to pH 6 . 5. The heaped s alt
Was Was hed With Water ( 200 liter of Water per one ton heap) .
Peak at 6 6 8 cm' 1 indicativ e of impurities of mag nes ium ox y
compounds is much reduced in intens ity compared to FIG.
1A.
SUMMARY OF THE PRESEN T IN VEN TION
[ 004 1] The pres ent inv ention relates to a nov el, eas y - to
apply and cos t- effectiv e method of production of s uperior
quality common s alt With des ired Ca2+ to Mg 2+ ratio as
required by the chlor- alkali and s oda as h indus tries . The
proces s is bas ed on the clari? cation of brine With alumi
Which y ields s alt of v ery hig h purity as already reported in the
prior art of PCT patent application N o. WO200703 6 94 9i
folloWed by adjus tment of pH of the clari? ed brine to arres t
the formation of ins oluble mag nes ium ox y compounds in s alt,
s ince s uch compounds are dif? cult to dis lodg e from the s alt
ev en after Was hing . As a res ult s alt hav ing both hig h abs olute
purity and des ired Ca2+ to Mg 2+ ratio is produced.
STATEMEN T OF IN VEN TION
[ 004 2] According ly the pres ent inv ention prov ides a pro
ces s for preparing in the ? eld an improv ed quality indus trial
J ul. 9, 2009
g rade s olar s alt from brines , the s aid s alt hav ing > 99% abs o
lute purity and the des ired Ca2+ to Mg 2+ ratio in the rang e of
2: 1 to 3 : 1 after heap Was hing and the s aid proces s compris ing
the s teps of:
[ 004 3 ] ( a) s ubjecting the brine to s olar ev aporation to
cry s talliZe out carbonate, s alt and g y ps um to obtain con
centrated brine as reported in the prior art;
[ 004 4 ] ( b) feeding the brine of ( a) into pre- cry s talliZer
and dos ing alum into the brine as reported in the prior
art;
[ 004 5] ( c) s ettling of the s us pended particles under g rav
ity With concomitant clari? cation of brine as reported in
the prior art;
[ 004 6 ] ( d) feeding of the abov e s aid clari? ed brine into a
cry s talliZer by g radient ? oW throug h brine channels as
reported in the prior art;
[ 004 7] ( e) treating the brine in the cry s talliZer With acid
to loWer the pH in the rang e of 5. 5- 6 . 9.
[ 004 8] ( f) continuing s olar ev aporation to cry s talliZe out
s alt;
[ 004 9] ( g ) draining out the bittern from the cry s talliZer as
done routinely in the prior art;
[ 0050] ( h) harv es ting and heap Was hing and dry ing in the
open s un to obtain the des ired s alt.
[ 0051] Throug h out the s peci? cation, the dens ity of brine is
de? ned in terms of 0Be. 0Be is a conv enient and Widely us ed
s cale for meas uring dens ity of brines . It g iv es a direct meas ure
of the quantity of s alt dis s olv ed in 100 g of s olution. In
American s y s tems , deg ree baume is related to the s peci? c
g rav ity by the equation
Speci? c g rav ity : 14 /( 14 5 OBe) .
[ 0052] In an embodiment of the pres ent inv ention the brine
us ed is natural brine and more particularly s ea or s ubs oil
brine.
[ 0053 ] In an embodiment of the pres ent inv ention the con
centrated brine after the proces s of s tep ( a) has a dens ity in the
rang e of 23 . 5- 24 . 5 0Be' .
[ 0054 ] In an embodiment of the pres ent inv ention alum is
prepared as an 8- 1 2% ( W/v ) s olution in dilute brine and added
up to a concentration in the rang e of 25- 75 ppm and prefer
ably in the rang e of 3 0- 4 0 ppm.
[ 0055] In an embodiment of the pres ent inv ention the tur
bidity of the brine after alum treatment is reduced to 2. 0- 2. 5
N TU.
[ 0056 ] In an embodiment of the pres ent inv ention clari? ed
brine y ields s alt With > 99% abs olute purity according to the
prior art but With the drawback of hav ing Ca2+ to Mg 2+ ratio
< 1 detrimental for demanding indus trial applications .
[ 0057] In an embodiment of the pres ent inv ention the
reduction of the pH of the clari? ed brine reduces the forma
tion and co- precipitation of mag nes ium ox y chlorides and
mag nes ium ox y s ulphate With s alt as con? rmed throug h IR
s pectros copic analy s is .
[ 0058] In an embodiment of the pres ent inv ention the pro
g res s iv e reduction of pH beloW 6 . 8 increas es prog res s iv ely
the Ca2+ to Mg 2+ ratio.
[ 0059] In another embodiment of the pres ent inv ention the
pH of the clari? ed brine after acid treatment is preferably in
the rang e of 6 . 8- 6 . 0 and s till more preferably in the rang e of
6 5- 6 3 to achiev e the des ired ratio of Ca2+ to Mg 2+ in the
mos t cos t- effectiv e manner.
[ 006 0] In another embodiment of the pres ent inv ention the
acid treatment is g iv en to brine under ambient conditions .
US 2009/017578114 11
[ 006 1] Yet another embodiment of the pres ent inv ention the
acid us ed for altering pH of the clari? ed brine is a mineral acid
or an org anic acid.
[ 006 2] In an embodiment of the pres ent inv ention the acid
us ed for altering pH of the clari? ed brine is preferably con
centrated hy drochloric acid.
[ 006 3 ] In an embodiment of the pres ent inv ention the pro
ces s is cos t effectiv e and Wherein the requirement of hy dro
chloric acid us ed is only 1- 10 parts by v olume for 100, 000
parts by v olume of brine.
[ 006 4 ] In another embodiment of the pres ent inv ention the
concentrated hy drochloric acid is diluted to a concentration
rang e of 0. 01 N to 1. 0 N prior to charg ing into brine.
[ 006 5] Yet another embodiment of the pres ent inv ention the
heaped s alt is initially Was hed With brine or Water hav ing
acidic pH in the rang e of 5. 5- 6 . 9 to eliminate adhering impu
rities While ens uring minimum precipitation of mag nes ium
ox y chloride and further Was hed With untreated brine or Water.
[ 006 6 ] In an embodiment of the pres ent inv ention the abs o
lute purity of s alt is more particularly in the rang e of 99. 4 - 99.
8% ( WlW) on dry bas is and the impurity lev els of Ca+ 2 and
Mg + 2 in the s alt obtained are 0. 051001% ( W/W) and 0. 03 : 0.
01% ( W/W) , res pectiv ely .
D ESCRIPTION OF THE IN VEN TION
[ 006 7] Concentrated s ubs oil or s ea brine hav ing dens ity of
23 . 5- 24 . 5 Be' ( Sp. Gr. 1. 192- 1. 205) is clari? ed With alum
s olution at an optimiz ed concentration of 3 0- 4 0 ppm as
des cribed in the prior art ( Patent N o. WO200703 6 94 9 dated:
Apr. 5, 2007) . The clari? ed brine is further concentrated up to
25 Be' ( Sp. Gr. 1. 209) and then charg ed into s pecially
des ig ned s olar s alt pans . The pH of 25 Be' ( Sp. Gr. 1. 209)
brine is meas ured as 6 . 98- 7. 00. The clari? ed brine of 250 Be'
( Sp. Gr. 1. 209) is treated With a calculated quantity of hy dro
chloric acid s o as to achiev e a pH v alue of 6 - 6 . 5, more s pe
ci? cally 6 . 4 - 6 . 5 of the clari? ed brine. It is es timated that
0. 04 - 0. 05 ml of 0. 1 to 1 N hy drochloric acid is required for
reducing the pH v alue of 1 L of the clari? ed brine of 25 Be'
( Sp. Gr. 1. 209) from 6 . 95: 0. 10. Hy drochloric acid us ed is
only 100 to 1000 parts by v olume for 100, 000 parts by v olume
of brine. The total v olume of brine in the cry s talliz ing pans is
meas ured as per the knoWn procedure g enerally folloWed in a
s olar s alt Works . The requirement of acid for altering the pH
of clari? ed brine is calculated bas ed on the total v olume of
brine charg ed in the cry s talliz er for s alt cry s talliz ation. The
clari? ed brine of pH v alue 6 4 - 6 5 is further ev aporated in s alt
pans as per the normal methodolog y being practiced in s olar
s alt Works . The concentrated brine on attaining 28- 28. 5 Be'
( Sp. Gr. 1. 24 0- 1. 24 5) , termed as bittern, is dis charg ed and the
s alt cry s talliz ed betWeen 25 and 285 Be' ( Sp. Gr. 1. 209 and
1. 24 5) is harv es ted and made into heaps as per the normal
practice. The s alt is heap Was hed us ing s ea Water and the
requirement of Was h Water is calculated as z 20% of the total
Weig ht of s alt Which is s u? icient to g et rid off the adhering
s uper? cial impurities pres ent in the harv es ted s alt.
[ 006 8] The mechanis m of the reduction of mag nes ium
impurities is g iv en as folloWs : Mg 2+ ex is ts as a s imple
hy drated ion [ Mg ( nH2O) n2+ ] in acidic medium Whereas it
precipitates out as ins oluble Mg ( OH) 2 under alkaline condi
tions . In the intermediate pH rang e, e. g . , the pH prev ailing in
natural brines , Mg 2+ can ex is t in the form of trans ition s truc
tures of ox y compounds s uch as mag nes ium ox y s ulphate
[ Mg ( OH) 2] 3 . Mg SO4 . 8H2O or mag nes ium ox y chloride [ Mg
( OH) 2] 5 . Mg Cl2. 8H2O. Thes e ox y compounds are ex pected to
J ul. 9, 2009
be les s s oluble than the s imple hy drated [ Mg ( nH2 O) 2+ ] and
could therefore co- precipitate With s alt. Moreov er, the former
are believ ed to act as g ood binders ( Shand, MA. ( 2006 ) . The
Chemis try and Technolog y of Mag nes ia, Wiley Inters cience)
Which may caus e ag g lomeration of s alt cry s tals making the
s ubs equent puri? cation of s alt throug h Was hing more dif?
cult. Since mag nes ium ox y chlorides and mag nes ium ox y
s ulphates are les s s table at loWer pH ( equations 1- 2 beloW) , it
Was reas oned that a s mall reduction in the pH of the clari? ed
brine may reduce the formation of s uch compounds and their
co- precipitation With s alt. It Was further s hoWn that Mg impu
rity in s alt decreas es prog res s iv ely With reduction of pH and
the FT- IR s pectrum als o con? rmed the reduced pres ence of
mag nes ium ox y compounds in the s alt.
( aq) + 18H2O ( 2)
[ 006 9] It Was s ubs equently s hoWn that While reduction of
Mg impurity of s alt is indeed obs erv ed at loWerpH v alues , the
Ca2+ impurity , unfortunately , s hoWs a concomitant ris e due to
pH- dependent chang es in the s olubility of g y ps um. The ideal
balance Was achiev ed at pH of 6 . 5 leading to a near ideal ratio
of 2: 1 of Ca2+ : Mg 2+ , While als o ens uring that the abs olute
lev els of the impurities are loW.
[ 0070] Since the pH reduction required to control the lev el
of Mg 2+ is rather s mall, and further g iv en that pH is a neg ativ e
log arithmic s cale Which trans lates to s mall chang es in H3 O+
concentration ( from 10_ 7M to 3 . 2> < 10_ 7M) , the economics of
the proces s and its practical implementation become attrac
tiv e, and only 200- 3 00 mL of 0. 1 to 1 N HCl is required per ton
of s alt produced from the brine. The proces s could be dem
ons trated in the ? eld and the bene? t of the inv ention con
? rmed throug h analy s is of the s alt.
Inv entiv e Steps
[ 0071] The main inv entiv e s teps are:
[ 0072] ( i) Recog niz ing that While alum- clari? ed brine
y ields s alt With hig h abs olute purity , the ratio of Ca2+ to
Mg 2+ is < 1 Which is not fav ored in demanding indus trial
applications .
[ 0073 ] ( ii) Hy pothes is ing iand thereafter prov ing ithat
the relativ ely hig her lev el of mag nes ium impurity is on
account of mag nes ium ox y compounds Which can co
precipitate With s alt during cry s talliz ation due to loWer
s olubility and may als o act as binder.
[ 0074 ] ( iii) Recog niz ing that formation of mag nes ium
ox y compounds during s alt cry s talliz ation can be pre
v ented by loWering the pH of the clari? ed brine in the
cry s talliz ers .
[ 0075] ( iv ) Obs erv ing that reduction of pH can, on the
other hand, adv ers ely affect Ca2+ impurity lev el in the
s alt and thereafter identify ing pH 6 . 5 as mos t optimum
to achiev e the des ired Ca2+ to Mg 2+ ratio While s till
maintaining hig h abs olute lev els of purity .
[ 0076 ] ( v ) Recog nis ing that the inv ention can be applied
to different ty pes of brines .
[ 0077] The folloWing ex amples are g iv en by Way of illus
tration and therefore s hould not be cons trued to limit the
s cope of the pres ent inv ention.
EXAMPLE 1
[ 0078] Concentrated s ub s oil brine of dens ity 24 Be' ( Sp.
Gr. 1. 198) and hav ing the chemical compos ition: Ca2+ : 0. 90
US 2009/0175781A1
g /L, Mg 2+ : 13 . 5 g /L, SO4 2_ : 8 g /L, N a+ : 92. 4 g /L ( 23 5 g /L as
N aCl) Was taken in a 2 L capacity g las s beaker, the v olume of
brine in the beaker being 1 L. The brine Was treated With a
s olution of alum s o that the alum concentration in brine Was
4 0 ppm. The pos t- treated brine Was left undis turbed for 12- 16
hours for clari? cation. The brine Was further concentrated to
25 Be dens ity ( Sp. Gr. 1. 209) . The pH of the clari? ed brine
hav ing a turbidity of 2. 5 N TU Was meas ured as 7. 0. The
clari? ed brine Was ev aporated up to 28 Be ( Sp. Gr. 1. 24 0)
and the s alt fraction collected betWeen the dens ity rang e
25- 28 Be ( Sp. Gr. 1209- 124 0) was centrifug ed. The s alt
cry s talliz ed had the compos ition Ca2+ : 0. 05%, Mg 2+ : 0. 09%
and SO4 2_ : 0. 15% With 99. 6 % N aCl on dry bas is .
EXAMPLE 2
[ 0079] In this ex ample concentrated s ub s oil brine of den
s ity 24 0 Be' ( Sp. Gr. 1. 198) and hav ing the chemical compo
s ition: Ca2+ : 0. 90 g /L, Mg 2+ : 13 . 5 g /L, SO4 2_ : 8 g /L,
N a+ : 92. 4 g /L ( 23 5 g /L as N aCl) Was taken in a 2 L capacity
g las s beaker, the v olume of brine in the beaker being 1 L. The
brine Was clari? ed by treating With a s olution of alum and
further concentrated to 25 Be dens ity ( Sp. Gr. 1. 209) as
des cribed in Ex ample 1. The clari? ed brine of 25 Be hav ing
a pH v alue of 7. 0 Was then treated With 4 . 4 ml of 0. 1 N
hy drochloric acid and the pH of the brine Was loWered from
7. 0 to 6 . 5. The res ultant brine Was ev aporated up to 28 Be
( Sp. Gr. 1. 24 0) and the s alt fraction collected betWeen the
dens ity rang e 25- 28 Be ( Sp. Gr. 1209- 124 0) was centri
fug ed. The s alt cry s talliz ed had the compos ition Ca2+ : 0.
06 %, Mg 2+ : 0. 03 % and SO4 2_ : 0. 15% With > 99. 6 % N aCl on
dry bas is .
EXAMPLE 3
[ 0080] In this ex ample concentrated s ub s oil brine of den
s ity 24 Be' ( Sp. Gr. 1. 198) and hav ing the chemical compo
s ition: Ca2+ : 0. 90 g /L, Mg 2+ : 13 . 5 g /L, SO4 2_ : 8 g /L,
N a+ : 92. 4 g /L ( 23 5 g /L as N aCl) Was taken in a 2 L capacity
g las s beaker, the v olume of brine in the beaker being 1 L. The
brine Was clari? ed by treating With a s olution of alum and
further concentrated to 25 Be dens ity ( Sp. Gr. 1. 209) as
des cribed in Ex ample 1. The clari? ed brine of 25 Be hav ing
a pH v alue of 7. 0 Was treated With 8. 8 ml of 0. 1 N hy drochlo
ric acid and the pH of the brine Was loWered from 7. 0 to 6 . 0.
The res ultant brine Was ev aporated up to 28 Be ( Sp. Gr.
1. 24 0) and the s alt fraction collected betWeen the dens ity
rang e 25- 28 Be ( Sp. Gr. 1209- 124 0) was centrifug ed. The
s alt cry s talliz ed had the compos ition Ca2+ : 0. 08%, Mg 2+ : 0.
03 % and SO4 2_ : 0. 20% With > 99. 5% N aCl on bas is .
EXAMPLE 4
[ 0081] In this ex ample concentrated s ub s oil brine of den
s ity 24 Be' ( Sp. Gr. 1. 198) and hav ing the chemical compo
s ition: Ca2+ : 0. 90 g /L, Mg 2+ : 13 . 5 g /L, SO4 2_ : 8 g /L,
N a+ : 92. 4 g /L ( 23 5 g /L as N aCl) Was taken in a 2 L capacity
g las s beaker, the v olume of brine in the beaker being 1 L. The
brine Was clari? ed by treating With a s olution of alum and
further concentrated to 25 Be dens ity ( Sp. Gr. 1. 209) as
des cribed in Ex ample 1. The clari? ed brine of 25 Be hav ing
a pH v alue of 7. 0 Was then treated With 13 . 2 ml of 0. 1 N
hy drochloric acid and the pH of the brine Was loWered from
7. 0 to 5. 5. The res ultant brine Was ev aporated up to 28 Be
( Sp. Gr. 1. 24 0) and the s alt fraction collected betWeen the
dens ity rang e 25- 28 Be ( Sp. Gr. 1209- 124 0) was centri
J ul. 9, 2009
fug ed. The s alt cry s talliz ed had the compos ition Ca2+ : 0.
09%, Mg 2+ : 0. 02% and SO4 2_ : 0. 22% With > 99. 5% N aCl on
dry bas is .
[ 0082] Quality of the s alt obtained at v arious pH lev els is
s hoWn in Table 1.
TABLE 1
Ca2+ Mg 2+ and SOAZ impurity lev els in the s alts ofFx amnles 1- 4
Ex ample Ca2+ to Mg 2+
N o. pH of brine Ca2+ Mg 2+ ratio SO4 2
1 7 0. 05 0. 09 0. 6 : 1 0. 15
2 6 . 5 0. 06 0. 03 2. 0: 1 0. 15
3 6 . 0 0. 08 0. 03 2. 7: 1 0. 20
4 5. 5 0. 09 0. 02 4 . 5: 1 0. 22
EXAMPLE 5
[ 0083 ] In this ex ample s ub- s oil brine from Bhav nag ar ( Gu
jarat, India) Was concentrated to a dens ity of 24 Be' ( Sp. Gr.
1. 198) at Which point its chemical compos ition Was : Ca2+ : 0.
90 g /L, Mg 2+ : 13 . 5 g /L, SO4 2_ : 6 . 5 g /L, N a+ : 92. 4 g /L ( 23 5
g /L as N aCl) . The brine Was taken up to a depth of 13 inches
in a s olar pan of 4 00 ft> < 125 ft s iz e and dos ed With 4 0 ppm of
alum s olution as des cribed in the prior art. After 4 8 hours the
clari? ed brine of 25 Be' ( Sp. Gr. 1. 209) hav ing a turbidity of
2. 5 N TU Was charg ed in a s alt cry s talliz er of s iz e 27. 5 ft> < 13 . 5
ft lined With a black plas tic liner up to a depth of 12 inches and
the total v olume of clari? ed brine in the cry s talliz er Was
meas ured as 11 m3 . The brine in the cry s talliz ing pan Was
treated With a calculated quantity of 4 8 L 0. 1 N hy drochloric
acid s o as to reduce the pH v alue from 7. 0 to 6 . 5. The brine
Was s ubjected to s olar ev aporation in the open pan till a
dens ity of 28 Be' ( Sp. Gr. 1. 24 0) Was attained. The bittern of
28 Be' ( Sp. Gr. 1. 24 0) Was dis charg ed in another pan and the
v olume of bittern Was meas ured as 2 m3 . The s alt cry s talliz ed
betWeen 25 Be' ( Sp. Gr. 1. 209) and 28 Be' ( Sp. Gr. 1. 24 0)
Was harv es ted and heaped. The s alt heap Was Was hed With
20% ( W/v ) fres h Water to y ield about 2 Ton of heap Was hed
s alt hav ing the s peci? cation as Ca2+ : 0. 06 %, Mg 2+ : 0. 04 %,
SO4 2_ : 0. 15% With 99. 6 % N aCl on dry bas is . The mois ture
content of s alt Was meas ured as < 0. 2%.
EXAMPLE 6
[ 0084 ] In this ex ample the ex periment Was conducted in the
? eld us ing s ea brine from creeks in Bhav nag ar ( Gujarat,
India) reg ion fed by the Gulf of Cambay . Brine of dens ity 24
Be' ( Sp. Gr. 1. 198) hav ing the chemical compos ition as : Ca2+
: 0. 54 g /L, Mg 2+ : 12. 5 g /L, SO4 2_ : 17. 4 g /L and N a+ : 92. 4
g /L ( 23 5 g /L as N aCl) Was ? lled in an open pan of s iz e 100
ft> < 3 0 ft and Was g iv en alum treatment to the lev el of 4 0 ppm.
The alum treated brine Was left undis turbed in the pan for 24
hours enabling the ? ocs to s ettle completely under g rav ity as
reported in the prior art. The s upernatant brine of dens ity 25
Be' ( Sp. Gr. 1. 209) Was then fed to a cry s talliz er of s iz e 27. 5
ft> < 13 . 5 ft lined With a black plas tic liner up to a depth of 12
inches . The total feed brine v olume Was 11 m3 . The clari? ed
brine of 25 Be' ( Sp. Gr. 1. 209) Was treated With 4 8 L 0. 1 N
hy drochloric acid to chang e the pH of brine from 7. 0 to 6 . 5.
The brine Was s ubjected to s olar ev aporation and proceeded
US 2009/0175781A1
as des cribed in Ex ample 3 . The Was hed s alt ( 1 . 8 ton) analy z ed
Ca2+ : 0. 05%, Mg 2+ : 0. 03 , SO4 2_ : 0. 14 % and N aCl: 99. 6 %
on dry bas is .
EXAMPLE 7
[ 0085] In this ex ample clari? ed s ub- s oil brine of dens ity
250 Be' ( Sp. Gr. 1. 209) hav ing s imilar analy s is to that of
Ex ample 3 Was fed into the cry s talliz er ( 27. 5 ft> < 13 . 5 ft) up to
a depth of 12 inch Without any alteration of pH. Salt Was
cry s talliz ed from the brine under the s ame conditions as
des cribed in Ex ample 3 . The heap Was hed s alt analy z ed Ca2+
: 0. 05%, Mg 2+ : 0. 09% and SO4 2_ : 0. 15% With > 99. 6 % N aCl
on dry bas is . The mois ture content of s alt Was meas ured as
< 0. 5%.
EXAMPLE 8
[ 0086 ] In this ex ample untreated s ub- s oil brine of dens ity
250 Be' ( Sp. Gr. 1. 209) hav ing s imilar analy s is to that of
Ex ample 3 Was fed into the cry s talliz er ( 27. 5 ft> < 13 . 5 ft) up to
a depth of 12 inch Without chang ing the pH. Salt Was cry s tal
liz ed from the brine near neutral pH under the s ame condi
tions as des cribed in Ex ample 3 . The heap Was hed s alt ana
ly z ed Ca2+ : 0. 21%, Mg 2+ : 0. 12% and SO4 2_ : 0. 55% With
98% N aCl on dry bas is .
[ 0087] It can be s een from Ex amples 2, 5 and 6 that the
adjus tment of pH from 7. 0 to 6 . 5 of the clari? ed brine at 250
Be' ( Sp. Gr. 1. 209) facilitates the production of s olar s alt With
reduced lev els of Mg 2+ impurities and als o maintaining the
Ca2+ to Mg 2+ ratio in the rang e of 2: 1 to3 : 1 required for
chlor- alkali and s oda as h manufacture.
Adv antag es of the Inv ention
[ 0088] The main adv antag es of the pres ent inv ention are:
[ 0089] ( 1) Sea brine or s ub- s oil brine, as the cas e may be,
can be upg raded throug h the proces s of the inv ention to
y ield improv ed quality of s olar s alt With hig h abs olute
purity and als o With des ired Ca2+ to Mg 2+ ratio directly
in the ? eld.
[ 0090] ( 2) The proces s is cos t effectiv e as it inv olv es us e
of inex pens iv e alum at loW dos ag e lev el as already
reported in the prior art folloWed by minor adjus tment of
pH With s mall quantity of hy drochloric acid Which does
not add s ig ni? cantly to cos t.
[ 0091] ( 3 ) The proces s of the inv ention can be practiced
in any s olar s alt Works reg ardles s of its s iz e and location.
What is claimed is :
1. A proces s for preparing in the ? eld an improv ed quality
indus trial g rade s olar s alt from brines , the s aid s alt hav ing
> 99% abs olute purity and the des ired Ca2+ to Mg 2+ ratio in
the rang e of 2: 1 to 3 : 1 after heap Was hing and the s aid proces s
compris ing the s teps of:
( a) s ubjecting the brine to s olar ev aporation to cry s talliz e
out carbonate, s alt and g y ps um to obtain concentrated
brine;
( b) feeding the brine of ( a) into pre- cry s talliz er and dos ing
alum into the brine;
( c) s ettling of the s us pended particles under g rav ity With
concomitant clari? cation of brine;
( d) feeding of the abov e s aid clari? ed brine into a cry s tal
liz er by g radient ? oW throug h brine channels ;
J ul. 9, 2009
( e) treating the brine in the cry s talliz er With acid to loWer
the pH in the rang e of5. 5- 6 . 9.
( f) continuing s olar ev aporation to cry s talliz e out s alt;
( g ) draining out the bittem from the cry s talliz er as done
routinely in the prior art;
( h) harv es ting and heap Was hing and dry ing in the open s un
to obtain the des ired s alt.
2. A proces s according to claim 1 Wherein the brine us ed in
s tep ( a) is natural brine and more particularly s ea or s ubs oil
brine.
3 . A proces s according to claim 1 Wherein the concentrated
brine obtained after the proces s of s tep ( a) has a dens ity in the
rang e of 23 5- 24 50 Be' .
4 . A proces s according to s tep ( b) of claim 1 Wherein alum
is prepared as an 8- 12% ( W/v ) s olution in dilute brine and
added up to a concentration in the rang e of 25- 75 ppm and
preferably in the rang e of 3 0- 4 0 ppm.
5. A proces s according to s teps ( b) and ( c) of claim 1
Wherein the turbidity of the brine after alum treatment is
reduced to 2. 0- 2. 5 N TU.
6 . A proces s according to claims 1 and 5 Wherein clari? ed
brine y ields s alt With > 99% abs olute purity and not hav ing
Ca2+ to Mg 2+ ratio < 1 being detrimental for demanding
indus trial applications .
7. A proces s according to s tep ( e) of claim 1 Wherein
reduction of the pH of the clari? ed brine reduces the forma
tion and co- precipitation of mag nes ium ox y chloride With s alt
as con? rmed throug h IR s pectros copic analy s is .
8. A proces s according to claims 1 and 7 Wherein the
prog res s iv e reduction of pH beloW 6 . 8 increas es prog res
s iv ely the Ca2+ to Mg 2+ ratio.
9. A proces s according to claims 1 and 6 - 7 Wherein the pH
of the clari? ed brine after acid treatment is preferably in the
rang e of 6 . 8- 6 . 0 and s till more preferably in the rang e of
6 . 5- 6 . 3 to achiev e the des ired ratio of Ca2+ to Mg 2+ being
mos t cos t- effectiv e manner.
10. A proces s according to claims 1 and 7- 9 Wherein the
acid treatment is g iv en to brine under ambient conditions .
11. A proces s according to claims 1 and 7- 10 Wherein the
acid us ed for altering pH of the clari? ed brine is a mineral acid
or an org anic acid.
12. A proces s according to claims 1 and 7- 11 Wherein the
acid us ed for altering pH of the clari? ed brine is preferably
concentrated hy drochloric acid.
13 . A proces s according to claims 1 and 7- 12 Which is cos t
effectiv e and Wherein the requirement of 0. 1 N hy drochloric
acid us ed is only 100 to 1000 parts by v olume for 100, 000
parts by v olume of brine.
14 . A proces s according to claims 1 and 7- 13 Wherein the
concentrated hy drochloric acid is diluted to a concentration
of 0. 01 N to 1. 0 N prior to charg ing into brine.
15. A proces s according to s tep ( h) of claim 1 Wherein the
heaped s alt is initially Was hed With brine or Water hav ing
acidic pH in the rang e of 5. 5- 6 . 9 to eliminate adhering impu
rities While ens uring minimum precipitation of mag nes ium
ox y chloride and further Was hed With untreated brine or Water.
16 . A proces s according to claim 1 Wherein the abs olute
purity of s alt is more particularly in the rang e of 99. 4 - 99. 8%
( W/W) on dry bas is and the impurity lev els of Ca+ 2 and Mg + 2
in the s alt obtained are 0. 051001% ( W/W) and 0. 03 1001%
( W/W) , res pectiv ely .