STUDY ON THE SYNTHESIS OF SODIUM CHT.ORIDE (NaCl) PYRAMID CRYSTAL BY THERMAL CRYSTALLIZATION OF BRINE

A thesis submitted in fulfillment of the degre€ of Doctor of PhilosophY in chcmistry.

By

Farhan Ullab Khan

M.Sc. M. Phil

At

Department olChemistry

University ofKarachi

2013 Dedicated to my parents ,teachers, wife, children and friends Acknowledements

I wish to expr€ss my sincere gratitude to Professor Dr' Ma.jid Mumilz' Depaiment of Chemislry for his continuous guidanc€, valuable advices and encoumsement form the beginninS.ill lhe finalization ofthe thesis'

I am thdkful to forn€r chairman Professor Dr. Fahim Uddin dd Professor

Dr.Nizami ihe D.esent Chairman , Depanment of Chemistry for iheir suppod and required facilities in th€ depanmenl for lhe laboratory work oflhe research project. My thanks are also due Mr. Yousuf Incarge Central Labomtory Lnher'ity of KaEhi for erlending laborarory facilir) for rhe rcsearch work

Thanks are also due to Prof€ssor Dr. Iqbal Chudhary' Dir€clory HEI for their valuable guidaic€ and encoumgemenl l am also thanktul |o my young colleasue Dr.Tehs€en Ahmed who helped me and suiden me for submittinS the research articles- My Sp€cial thanks are also due l,{r. Morton Satin. vice

President of Science and Res€arch al lhe Salt Institute for their guidance Mrs

Manina for providing res€arch aiicles from the satne inshtute'

This acknowLedgment cannot be completed without the name of Dr'Azhar Siddique and tvft. Shamim Rauf for their suppoll at every stage

I am much gmteful ro my mother who continuously praved fbr my success' my wife and my little children who encourage m€ ad released me froft all domestic r€sponsibilities and family affairs for mv devotion towards mv

research work ed it completion . cor{TE rs

Section Contenb Page N Acknowledgment --- Contents t-xv Absvact 1 Introduction 1to3 1.1 Fleur De Sel ( Flower of Salt) 3to9 1.2 Work Plan 9 tol r S€a Salt 10 1.3.1 ChgEae4C!!! qElEt q!4lemistry of sea brine 11to 1 1.4 Lake Salt Rock Salt M I4echanically Process Salt !1!o 1 Description of Process 1.7 waste brine oeneGted by salt Refineries 1.8 AR arade Sodium Chloride with different additrves 17 1.9 Kubota and Mullin model for crystal growth in the presence of impurity. l7-18 1.9.1 In this Thesis 18-19 r.9.2 Previous Work 19to4 Pilot plant study to utilize waste brine generated by salt 2 industries 4l 2.1 Introducton to environmental impact of salt 42to4 2.2 Salt Refining Process 46 l4aterial and Nlethods 46 coI{TEitts

Section Contents Page n Collection of Samples 46 Preheatment of Brine 47 2.3,3 Removal of Magneslum 47to4 2.4 Crystallization method 48to4 Results and Discussion 50to5 2-6 X-Ray powd€r Dift.adion (XRD). 54 2.7 Conclusion 3 Laboratory s(!le study for the control crystallizauon of sodium chloride pyramid crystals (fleur de s€l), 56 9repared bv solar salt 3,1 Introduction

Experimental 3.2.r Iteparation of Brin€ 5 3.3 Crystallization Me$od 58 3.4 Scanning Elechon microscopy 58 3,5 Result and Discussion 60 to 7 Conclusion n Study and obEervation with sea Salt brine for 1OO hours oc. 7 Temperature range between 55 to 65 3.8 Individual Pqrameter of brine n 3.8.1 Calcium in brine 3.8.2 llaqnesium in brine 74to7 cot{TEt{rs

Section Contents Page N 3.8.3 Potasslum in brine 3.8.4 Sulphate in brine 76 3.8.5 Bromine in brine Sodium Chlorld€ in brine 3,9 Four Hourly Observations 78 3.9.1 At 4 hours 78 3.9.2 At 8 hours 78 3.9.3 At 12 hours 79 3.9.4 At 16 houc 80 3,9.5 Between 19 to 32 hours 80toB 3.9.6 At 36 hours 81 3.9.7 At 40 hours 81 3.9.8 At 44 hours 81to8 3.9.9 At 48 hours ; 3.9.10 At 52 hours 82 3.9.11 At 56 hours ; Between 60 to 64 hours 82 to 8 At 68 hours ; cor{TE1{TS

Section Contents Page Nc 3,9.14 At 72 hourc 84 3.9.15 At 76 hours 84 At 80 hours 8+85 3.9.17 Between 84 b 96 hours 3.9,18 Al 100 hours 85 4 Study and obsewatotwiur Late Saft brtne at pn 6- Z temperature ralEe between 55 to 65 oC 86

4.1 Brine Prepardtion 86 4.2 crystallizauon 86 to 92 4.3 Twelve hourly observation for crvstallize salt 92 4.3.1 Ob6ervaUon 1A 92 4.3.2 Obs€rvation 18 lr-1 4.3.3 Observaton 2A 93 4.3.4 Observation 28 93 to 94 4.3.5 Ob6ervaUoh 3A 94 Observation 38 94 4.3.7 Observation 44 94 4,3.8 Observation 48 ObseMdtion 5A ,5 CONTENIS

Section Contents Page N 4.3.10 Ob6ervation 58 96 4.3.11 Observation 64 96 4.3.12 Observation 68 96 5 Study On The Synhesis Of Sodium Chloride (NaCl) Pyramid Crystal By Thermal Crystallization Of Rock Salt 97 Brlne 5.1 Crystallization 98

Results and Discussion 98 to 10 5.3 Conclusion 106 Ko|e or ov€€nt and tnvaEnt ions on the pyramictat c.ystal Fo nation of sodlum chtodde 107

lnuoouction 107-10t grysta iztton wl$ 0.01 gm of FeCl3.6HrO and 1369 sodium chloride/4oom1 water 108 6.2.1 Experimental section 108 Resuft and Discussion 119-110 LrysutEatlon with 0.02 g of FeCh.6HO and 136q godium chloride/4o0m1 water 111 Expenmemat s€cton 111 Resu[ and Discussion !!L_!?: 6.4 crystallization with 0.05 9 of Fect3.6Hro t;dl56q godium chlolide/4o0m1 water 113 6.4,r Expeflm€hti|t section l 113 5.4.2 ffi 113to 115 cot{TE rs

Section Contents Page Nc 6.4.3 Experimenbl section 116 6.4,4 Result and oiscussion 116-118 6.4.5 Conclusion 118 Influence of calcium on the crystal morphotogy of 118 6.5 sodium chlorlde for qrystallization of pyramidal crystals 6.5.1 Experimental s€ction 118-119 Result and Discussion 119-121 Conclusion 121 6.6 A mixture of cakium ,iron and sodium chloride t2l Experimental section t2t Sesult and Discussion lrr-nt IIBAy Powder diff raction 6.6.4 Conclusion 12s Influence of calcium on the crystal morphology of sodium chloride for crystallization of pyramidal crystals 126

Erperimental section 126 6.7.2 Result and Discussion l16--Ds 6.7.3 Conclusiol r29 6.8 A mixrure ofmagnesium ,iron and sod iun ih toriE 129 6.8.r Experin€ntal section 129 5.8.2 Result and Dlscussion 6,8.3 1414 Conclusion 132 COIITEIITS

Section Contents Page N( 6.9 A mixbjre of cakium, magnesium ,iron and sodium chloride t32 6.9.1 Experimental section 132-133 6.9.2 Result and Discussion 6.9.3 X-ray mwder oiffilq on (XRD). r:arrz 6.9.4 @nclusion 138 6.10 A mixture of badum ,iron and sodium chloride 139 6.10.1 Experim€ntal section 139 6.10.2 Result and Disaussion 1!9:!4c X-ray powder diffractjon(XRD) 140 6.10.4 Conclusion t41 6.11 A mixture of potassium ,iron-nd sodium chioiide 141 6.11.1 Experimentalsection t41-142 6.11.2 Result and Dlscussion 142-145 6.11.3 X-Ray Powder difrradion fff,qe 6.11,4 Conclusion 146 7 General conclusion for be formation of pyramidal crvsctls 147 7,1 eoncluslon 147-1s0 7.2 Suggestions rsors: 8 References

Selectlon of samplinq materi4l and site 165-1-7. A brief introductbn of brine purifkation 179-186 Table Raw material analysis 185-203 Appendix 2 B Table Brine and cn/slallized pyramids analysis 20+209 Appendlx 2C !!!t of publicauon LIST OF FIGURES

Hon Con!ents Page N( I Fig 001: A view of S|e Pyramjds of Egypt 1

1.1 Fig 002: A vlew of Crystalllzed Pylamldal crystals I pakstan 1.2 Fig 003: GIS Data for Satt Prcducers and Processors in 7 Fg ofir A liew of Sea Salt Cry$lttizatton ponds 1 1

1.3.1 Frg 005: A vlew of Satt Lake 14 1.4 Fig 006:

ng OOZ: CS DaU Or Salt Produce6 and Processors in pakistan 2.4 Fig 008:r EsD€cially D€slgned :actreteO Cmtatttzer for rynrnfd Crystals 49

2.4 Fig 009:: Well Shaped Pramtdat Crystats foflnaton by Waste Brine s0

2.t4 Fig 010: Iregular crystalfomaUon resutt high magn€sllm

2.4 Fig 011r Well shaped Pyrdmdat Crystats n 2.4 Fiqurc 012r SEM vtelv ofi\/i-dm6at crvsats ot NaCt Fig pyomiiiiifriii 013: Xao Pattern of cr.ysra lzed t 3.4 Fig 014: Needte tike crystat wittr pynmtdat crrstats 3.4 ffi ; 3.4 Flg stabe of crystalhzation a 3.4 Fq 017 : Crust brmarion at high temperaure regid;boG-6t g 3.4 Fig 018: Well-fonned singte crystat noaiiirg on thE-Gace * LIST OF FIGURES

s€cuon contents Page No 3.4 Fig 019: Few laB€ sized pyramldal crystals. 3.4 Fig 2o:Pmduction rate d diffcrcnt Gmp€nlur€ 58 3.4 Fie 2l :Scan electron microscopic view of pyramidal crystal of salt 69 3.4 Fig 22rsupporting block at the comer of pylamtdat crystit that 59 plays vltal rcle in construction of this moryholoqy 3.4 FE 23: A clos€ vlew of wa[ consBucuon pyramidat of c.ystal 70 3.4 Fr924r EOS result for naturat pyramidat crysbts 70 3.4

Fjg25: EDS re$lt lor py.nmidal cfystats prepared by sotar satt 7l

3.8.1 Fg 0251 100 hou6 obs€rvatic,n tor catctr:rn Wd tn Urine qrr

3.8.2 Frg 027i 100 houE obG€ruation for magnesium tevet qst- ln brine ,: 3.8.3 rig 0zer roo hours otservation fotpoGEi!fr]&ain bitne g^ 75 3,84 Fig 0291 100 hours obseruatjon for sutphate tevet intne g/L 76

3.85 Fig 0301 100 houls obseruatton for bromtne tevet in brjne oom 77 3.8.6 Fig 031: 100 hours obset\ration for sodtum tev€t in brine o/L 77 3.9.2 Fig 032i Aviewto morphotogy m of salt 79 3.9.8 Fig 033: Another vtew m* morphotogy of of satt 81 3.9.13 Fiq 034: Pvramldat satt crl,stats yew cL 3.9.14 Fig 035: Slngle crystat measurement pvramiOat tor satt 86 4.2 F,q 036r t2 hourty obs€rGaoi foiGiaiL;l;let r-;b ne q/L |.ISI OF FIGURES

Se.tion contents Page NO 4.2 Flg 037: 12 houdy obs€ auon for magneium tevet in bnne 9/L 88 4.2 Flg 0381 12 houdy ob6eruaton for po6-ium level in brtne r g/L 89 4.2 Fg 039: 12 hourt obc€rvation for sr phate tevet tn brine grr 90 4.2 Fig 0401 12 holdy obs?wauon foiaEumlevei|n'in€;fl 91 4.2 Flg 041:12 hourly obse ation for NaCt le!€t In brine mq/L (x2r 4.3.3 Flg l'4x morphotogy cryst! zaton view fyom take satt bnne 93

4.3.3 Fig 043: IBegular moryhology frcm lake satt brine 96

5.2 frg U44t Inittat crystaltization observauon at 5E C 99 Flg 045r Formaton of pylamidat crysbts at SfC 99

5.2 Frg rrz16: wel shaped pyramidal cr]€tats formauon 640c 100

5.2 rg uclt uDservadon oflointed py.amldal crystats of roc,( satt 101 Hg u4ar A crose vtew of Jotnt€d pyramtdat d\,stats of ro(k satt at 70t r02

5.2 n9 u{ei uo6eMalon of stolv cjysblEation at temperature 48oc r03

n9 u)ur Me|,(p pramidat crystats at htgher temp€ratue abo/e 800c 103

5.2 Frg u5t: tterge pyramidal crystals at higher temperddre aDove 80"c 104

5.2 r-rg u5z r Gust tormation at the temperaturc go.c above 105 LIST OF FIGURES

Sectlon contents Flg 53: shows c'lstalltzation of hopper cube and pylamtdal

ng54: A dear view of recbngutar pyramidat cn alab and setd€d nopper cub€ Into the bottom Flgssr Crust fomation at temperature ao"C

6.3.2 Flg 56 and 57r Mix morphotogy rew -quare@mrOat anC rectangular pyramidal crystals F1958: F€lv setted crystaton tne mEm otirysWtzei

ngsg: *rows a oose viiw or uleseEGl6idtuiiiiipvra Ear

Eg 0o: necrarputar ana sqr:arelEiiEii@G

nset: crystaltzed square ana6illiiilEijiiii@G

Flg6Z: longttr.rdtnat pynmtdd @i agei: recOngutar pyramiOat crystal Fig 5a: NaCl crpiltaries crysr.ltirA in rh"tnsenc€ ofGn impurity pH 3.66 FIs 65r EDAX ofpyranidat crysrats sr,o"nli-EM. rrc qrysbls are sodiurn chloride Fig 066 |.IST OF FIGURES

Sectlon Contents Page No

119

Fig 58 119

Flg 70 rt9 Fig 7l 119

n9 72, lnltral formaUon of pyrdmldal crystals r2z

flrgz3: A ctce vien ot pyamldal crystals 123 a8"c 6.6.2 rrgTa R4ulaicty$E bnnaton at low temp€tat'ire at r23 ng zs pyrarniOar cry*:r gffi of sod,tin chlo de at 56qc 124 Fit6 : Crystalllzatlon aRer bine feedlng t24 pvnmldal ctvslals futj. Emrauon-iGiEpe brge t24

ze: xeo pattem ot oaum ctrlodde crvstals obtained bv Fi-g 125 calclum and lmn impulfies added brine

t27 Fig 79r The cmtalllzer vlew of hopper cubes

Fg 80: shows a clos€ view of fopper cub€s with magn€sium r28 lmpurity bv the FigSli (P. Fonbna)tgl Hoppe'r cube grcwn on eafi 128

130 Flg 82: Formalon of hopp€r cube crYstals

dC Flg 83: formatlon of well shaped pyramldal crystak at 60 LIST OF FIGURES

Section contents Page No 6.8.2 Fi9 84: R€gular fonnaton of pyramldal crystals 131

6.8.2 Eg 85: Regular fomauon of pyramldal q/stals 132

Fig 86: JolnH pylamidalcrysbb d 78C 134

6.9.2 Fiq 87r growing €rystals observation 135 6.9,2 Flg 88 another view of crysiallizadon at 769C r35

6.9,2 Fig 89r lointed pylamldal crysbl fomation 136 6.9.2 ng 90 : A vlew of la€e and well shaped geonrtsy pyramidal t37

6.9,3 Figgl: shows dle XRD pattern of crystallized pyramidal salt 138 6.10.2 F9 92 : Crysbllhed pyami(|al cmlaB nom barium ,lron and 140 sodlum chlorlde bine 6.10.2 Fig 93: )(RD pattern fo. tf€ mo(ulrc of badum, lron and sodium t41 chloride

611.2 Fig 94: Fomadon of squa.e and reatangular pyramidal crystals with Solution*l 143

611.2 Fi995r formatlon of large number of nuclei at tempehturc 78'C 143 6.11.2 Fig 96r shows fornation of square pyramidal crystals at the t44 tenpeGture range of 50 to 5fC and pH 2.52

6.11.2 ng 97r 109 /L KO efftd on crystalllzrtlon of NaCl wi$ow iron(IIr) r44

611,2 Fig 98r lDmaton of oust on U|e sirface of thls bdne solution t45 6.11.2 Fig 99i XRD patbern for poiassium, Iron and sodlum chlodde lz|5 UST O' TAALES

contents Page No Table l: Average compoEitjon of Upgraded in salt Patlstan 45

Table 2r Averdge composttton of Waste Bnne 46

Table 3: Colnposidon of waste &ine before cmialtizauon 48

Table 4: Suface Are. (Specificnuon) of Crystalizer 49

Table 5: Chemlcal Compo6ition of pylamtdat Crystats

Table 6 Analysis of satt sotution prepareOlfEa lUrine; satt 59 Table 7: Analysts of pyEmtdal crystals of saf 59 Table 8: Analysis of prepar€d satt sotution Orine) by rocf ,att r05 Table 9i Amlysls of pyEmjdat crvstats of salt r06

Table 10r Obs€ryations for Ctremtcat anaGts of bttern from sa plont crystallize W dtrect heatino 188 taute rr: obsenauons roi crremtdGEiFiiiEiEE6EfiGii plant crystllllze by dl.ect heaung 189

Table 12: Obseruatlons for Chemical anatysis ot crysta ized satt @m bittem of salt Dlart, c Ilized bv direct heatin r90 Table 13: Observattons ror ctremicar-naiysiiSiiffi iiiEEit llized by direct heaUn l9r Table tr: ouservarons for clemioGiifrEGamem bri-ne rrom satt olant , c.ystalized by Indkect heaflno t92 lalte rs: Oteervauons tor crremicariEifriiiG-iEm onn- rrom sNirt Dbnt, crysta zed bv lndlrect heatnd r93 ram r0: ooservatrons rorcremicaiiiifGi-fiGiiii-Eii] qystalllzed bV Indirect h€atim r94 talte t z: ouservatiom roicnemrcatf, iiGE?iGliEiiEli lrystalrzed by hdt€ct heatno 195 IIST OF TABLES

S€cuon contents Page No Table 18: 100 hours obs€rvations for S|e Sea Salt brine 196 2A Table 19r 100 hours obseruation ior the Sea Salt brine t97 Table 20r 100 houls s€a salt obseruattons Pyramldal satt crystals 198

raOe Zr: IOO trours seaEf obsewabonflEmEiiEtt crysrai- 199

Table 22r Chemical Analysis ot Khipro LakeSaft Bnne 200

Table 23: Chemlcal Analysis of pyramldal crystals crystalize by lake salt 20r Iable 24j Analysls of pyramjdat ffiI crystats of satt 202 203

20.1 I cD'r zo r n.m'cd puherE o, s satr atonS wiLh pDfitqpsHj 28 205 ( I aor . , Emrcll paEndd ofe *tr alon8 wid pmfit. (psrX J. 206 r abrc zEciemical perarnelers of lake satt rlong with profila (PI-K) 207 orrock "n.^,",1 n"*^",.rs sat! aions with profiG ,,fffir/ 208

:o ct'"'t.rt n","tet"" of ro

In this study, accelented methods to crystallize welLfoftied pyrainidal cryslals of salt are achiev€d. Tlte square pymmidll crystals of salt, Fleur de Sel sah arc known for their unique crystal structure and us€d in specialty gourmet foods. The natual crystallization conditions include hot surnme. days on the surfa@ of ponds co aining concentnted s€a water. The cuFent study has established a conrol production ofpyramidal cryskls as an alremab to nalural crystallizadon whicb is only possible in summ€r w€athers.

For the study of vell shap€d and contol pyramidal crystals formation ,natulally crystallized p),ramidal crystals, rock salt , sea sah, Lake salt ,waste generated ftom salt processing plants were collected and investigated chemically for major impuities of salt. These major impuitics iNestigated *ere calcium, masnesiun. potassium , sulphate, broinine . Puriry of salt as sodiun chloride was also

Satunted solutions of salts (brine) arc prepden by dissolving above mentioned sall in waler. Anificial brine h prepared with the help of anary'tical regent grade of chemicah. Ihis brine is evaporated in an open cryslallizer by gentle evaporation with heatiog tom bosom of the crystallizer. Tempemtur€ plays an imponant role in formatior of plaamidal crystals. Observations were talcn al different tenperatures. h was noted that neia+lable condition in brine for rhe nuclslion and crysral gro*,th is achi€ved b€treen 50 to 65'C temperatur€ mnge.

Brine purification was also applied for rcmoval of calcium, magnesium ,sulphate and subsequen! crystallization of unintenupted pyramidal shaped crystals. The study, wh€n applied. nor only yi€lds rhe well defined shap€ of pyramidal crystals but also produces high pudty fonn of salt crystals in comparison with nsturally

crlsrsllE€d fleur de Sel.

Th€ main purpos€ of rhis work was ro achieve synrhesis of pyrdmidat crystals of sodium chloride. Considering salr industries and environmental hsu€, the waste brin€ generated by sait indultry was successfully converted inio laluable p)ramidal crystrls. Brine pudfication wa! also apptied to achieve this targer. Environmental nnpacts of sah indusrries were aiso discussed in lhis regard_ An indh€ct h€a1 crysrallizer was suc.essfully uled and plaamidal crysrals werc made

Brine pfepared by sea salt, lake salt and rock satt was .lso used to crystallize plrrmidal crystals of sodium chtoride ond rhe observarion was raken at differen tempemtures. Ir was nored that with the chemical composition, pH ,nd lemp€ratur€ play vital role and with the chang€ i, lempemture and pH differenr morphologies ofsalt forned in$ead of plmn dal crysIals.

As we know rhat litrle arnounr of irnpuriti€s some rime play a sigificflt role in crystallization and by suppressing crysral growlh sometimes conplet€ change in crystal morpholo$/ obs€rved. is Anificial crylralli4tion of p),ramidal crysrals was also attemped by adding differcnr impuriries tike, calciurD, magnesium and iron, separately and as a mixture ioo. For thc success of work addirion and subtraction of differenl chemicst impudties werc applied with th€ helD of some saturation tectmiques. very A successtul atlelnpt was observei wirh rhe Fe( r) rmpurities thar compleiely convert rhc crystajs moryhoto$/ inio the pyramidai q'/,9 ta4

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Pyrmid. wher we intera th;s word, abruprly our nind movcs toward Egypr rnd the ihinS which appcan,n our inaSnrarion is ln.wi as Pyranids of F.glpt

These pyramids de fmous due to their unique pyramidal sttucturc. size and Dvsle.ious stones aboul lhen conslrrction in mcicDr timcs. The consrrucrions ofthese wondcB de stilla rnyslery with many theo.ies about thcn lhc onl)' reaion to slan this iutroduction Fi$ I-le}?l: py.amid was snnilarity" ol' slmtlesircd crystal stnclu.e of sodrum chloridc by lhenul cryslallizalion Sodium chloridc is d ioDic compound aod pue sodn'm chloridc crysral is reognted as cubical shcrure in nanrc

F,glrlrl A Uctr orih hnm'Jsul [s\nt

F'g 0o? A c\ of C[$!lh/cd hftn'dd c^ {rh Softetime impurities play an impodad rol€ to deternine lhe cryslal sructure of many compound! even in tbe pres€nce of a little amount of foreign subsbnce, crystal habiis ar€ complelely changed.l] Th€ suppression of crystsl

sroMh was also observ€d in tlle presenc€ of impudties in aqueous sotution.t2l 'fte temperatur€ of cry$rllization is tlle key factor specialty for th€ formadon

of pyramidal crystal of sodium chtodde and change in crystat habit were also observed wiih pH vadatioN. I3l In the crystrlizalion ofsmmonium suhhate, the reduclion ofsoluble iron io below 50 ppm of fenic ion is sufficient to caus€

a sigoificant change in rhe habil of crystal form a long narrow form ro relatively chunky ard compact fom. [4] The existence of cosotvents for inst$ce urea and formarnide can modit the morpholory of sodiun chloride crystals groM fton solution.lsl The presence of soluble anions and caiioN otun has similar influence. fte pr€senc€ of pb, It& Bi, Sn, Ti, Fe and Hs were r€ported ro help in go$rh of Nact.l 6l In known history just a few hundred years ago, crysbB wer€ consid€red 6 magical cr€ations. Even in today's nodern ages, anything no! undeNtood by logic is ascrib€d !o being magicat. The appcarance on ftmemr crysrals that have shiny, eansparent, perfect hcets and shaQ come$ su€iy heiped lhe genenl belief as cryltals being r€lated to ma8ic. Throughour the c€duri€s, s€veral ressrch€rs booked historical brcakhmwhs and as €a_rly as 16ll, Kepler proposed rhat cryslats mighr cotrsist of regutarty sracked buitdins blocb. l,ater in 1669, Sreno discovere! thar all quanz cryslals tilm srouod the world have idenrical angl€s berw€en tleir facers. nis mncepi was formally acccpted by Hauy in 1784 rhrough rfie Law of Rarional lndices. Bnvais report€d an enpirical rule in 1866 ihat rhe size ofcrysiat fac€ts is proponional to the distances berw€en the arons perpendicular to its orietrtation. This rute is cblpla#l

still used in mod€m times to pr€dicl the shape of crystals. Since optical micros€opy doe, nol hav€ sufiicient resolution to observe building blocks dir€.dy, on€ had to reson to the shape of crysials. In 1907, Friedel could deduc€ cell dimensions of certain building block solely fron lhe shap€s of crystals and rhe density ofnaterials.

Genenlly we are all hmiliar witl crystds and use tlem in our daily routine lif€ in form of salt and sugar crysLls that we conJume as food or ahe natuml crystals we know as min€rals. Howcver, many people do not r€aliz€ rhat pmcticaly ev€ry chenical compound t€nd! to crystaliz€ when th€ tlmp€Bture is brought bclow its nelting point. nl€ proc€ss ofcrystauizltion involves the g€n€.ation of order. f/]

't,'l Fleur Do Sel { Flower of Saltl

Fleur de S€l (Flow€r of Salt) is ih€ most common name of naturally crystalliud sea sal! The pyamidal shap€ of Fleu de Sel is different and unique in its structue ftorn olher s€a salrs. The natural crystriliation ofFleur de S€t is reponed at coast ofBrittany (France) and Algarv€ region of Portugal [8] where it is crystallized in pon& conraining concentrared sea-water. Furthernore,lhe hollow pyami& sclf-cre3te, floar and grow on the surface of pond in only hot werthers. A clmpadsor of plmrnidal salts crystallized in Earth's natural atrnosphere and NaCl crysbls gown by th€ evaporation ofan aqueous salt solution in microgavity, has also been reported [9]. lleur de S€l ha! a uniqu€ morpholos/, lower bulk density, larye sudac€ arca, inproved tsst€ and npid dissolution as compared !o the common cubic salt.

Oth€r tt?es of sahs wilh low bulk densi9 c{n b€ found in J.p6n and ar€ commonly known 6 flaky salr [ 0]. chaprs #l

Th€ nicro h€ter size pyramid's gropth has been obsewed by many $ienri$s in their differenl oq'erim€nts I , l2].

The beautitul pyramidal crystal of salt (Fleur De Sel) flow€r of salt now days has bcen reclgnized a! the world's most €xp€nsive ssh, b€caus€ ofits.ast€, beautitul structure but reality is little bit r|ore, lhese plramid crysrals have

mor€ suface are in compa.rison wilh normal cubic salt, rapidly solubl€ and thh is not only sodium chloride but also rich with others solubl€ minemls. 'nr€ crystallized pranids dmugh this work are w€ll shap€d as mmparE ro

naturally crystallizd Fluer de Sel. It will not b€ jusrified to recognize this wolk as the crystallization of Fluer de S€l only or an alt€mate of nature crystallization. The study €nsures fte control production of well shaped and

well geometrical crystals. Which do€s not specificdly crysra iz€ with the coru€nFated sq warer but wilh frke salt, Rock satr, binern of salt industry and a control dystallization with difierent m€tal and cltions.

The utilizatioo of waste brine and its conveNion into a valuabl€ produci is the key succqs ofthis work. 'nle impact of high saliniry on environmedt especialty on living being and metal is w€ll knorm and nany papers have be€n published on rhe same I 13- 161. It is irnponan| to make the salt industsy friendty to the environmenl, if rhe

w4te brine ofsalt indusrry is not utilized properly, it coutd have a very adverse effect on the environmenr. The high d€nsiry wasre of satt indusrry should nol coire in the conla€r of extemal boundrry ofsalt industry to minimize its efiecl on n€ighboring lsnd, on the sea side nanerove plants. The un.terground s$€€r water stream flow should also b€ tlken into consideralion olheois€ satt indusuf operation could aff€cl adv€rsely on sunounding swe€t water. Ih€ discharye bitt€rns will aff€ct th€ nsrinc life dso. Marire mviro,m€nts are atso Ct pldrl very diverse. The organisms that choos€ a panicular home in lhe orean are adapt€d to survival ther€. Changes in lhe natual factors, no matter how minor, can have an enornous effect. Factors such as sunlight, pH balance and salinity challenge lhe survival ofmadne lift on s daily basis I l7].

To upgldc salt quality. mechanical sak washing is used in many countri€s. The counter cunent *ashing 6. diff.rcnt st g€s and dewal€rin8 by c€ ritug€ upgrades salt quality from 94 - 99.4 %. The najor impurities of salt like calcium, magn€siun, poiassium and sulphate are separated ftom salt in upgradation proc€ss. During this up $adation process l0 - 15% of salt is convert€d inio satumted solution by dbsolving in wster and known as "waste brin€". All the €xc€ss brine dmiru into sewerage by almost all of salt proc€ssors and may caus€ harmful envirorunedal €fect on the living organism and s€3 life fl7l.

The current study cov€rs the utilizstion of same was& brine by convening it into environm€ntal lriendly solution snd msking it a value added produci for utilizarion in food and industdal purposes 0l. Many applications to utilized waste brine have been reported by diff€rent scientists [8-21]. Preparation of some value added products like, KCi with double effect vacuum ev.pomtion, bromin€ extraction by distillation and production of MgClr.6HrO and MgSOa by mono efect evaporaror [21]. In the current study we converted this wasle bdne into world famous salt *nown as Flucr dE Sel, which is famous for its iaste and lmique crystal struclue.

Mechrnicsl refining ofsalt for the uFsradation was intoduced in Pakist n

in early 80s, wherc consumer mffket srrft€d 0o enjoy 'snow like instead Chapter #l

of"dirq erind€d" sdt. 'mis up-gradarion provides inproved quality ofsalt

but the waste Senerat€d caus€ environne al pollution. The quality d€maDd

of industries has atuacted th€ salt processers to ifiroduce the same typ€ of

salt for difierent induslries such as texrilq soap, warer softening, chloro

slkali and hundr€d of many other applications. Th€ washing process not only improv€s the vhiraless of sat but also r€ducas the major and minor impurity of salt, like calcium, magnesium, potlssium, sulphate and bronide [22]. Unfonu]ately instead of nodem techniqu€ lik€ recry$allization for naking the superior qualiiy of salt like pure Vacuum

Dried, dle mechanical wsrer washing for upgmding the satt is very common in Pakistan especialy in Sindh and Balochisran regions due lo its

Iow procesing cost. The pr€sence of impudries in satt llas s€rious economic and envimnmentat consequmc$ [23]. Tw€nty thrce satt pro.essors arc using mechanical r€fining process and Foducing approxinately 28m0 ton / mondl finished producl (Fig. l) 1241. tt 03: GIS De for S.n Prodss dd Prw.s in Prlifu t24l

Tt€ r8t conc.nt-d.d b(inc solurion €n b. Ds.d ls a sourc€ of runy usctul products whrch cln also b. urilzd aftcr renovin8 ruJor inpurincs bd mfonunalely it is d.posit d br.k irio thc s€a wirhout utiliz.riotr It9- 251. Thb rrocess causcs sn osnrotic shock of lhe tivirg dsanisns (.cosy$€tus) h thc sea Tr'c cmuc|lt b |nc w'st! is ! hcwily [email protected] brine solution. This dichlrged efiluenr has rhe por€ntial ro kill o.ganicms. Althowh tl€ brin striotr conbins nr$r.l ing.didts ofthc aa er&r lnry causes dnnag€ by unnatual concaF.tior to marine populatior rcar ourl€t 9-251. Ir is iDponanr ro mkc th. sair induslry friodly to cnvircnmenl, b€caB. ir could havc v€ry advdse effcct on lhe cDviromcnt. Thc pr.s.rt srt dy is ba!.d on thc uriliz{iofl of *stc b;i. ro prorcct €nvironm€nt. The main idea is to utilized natu_al r€sourc€s to ke€p thc

Only money and dte pdces cannot attract a irue research€r to *ork on a topic but sone hidden facts, to know some phenomens, to establish som€ laws, to understand mble lhat w!! the resson lo work on lhis topic. Fleu De Sel i[spiEs s to work on its myth that it can be crystdlize in a v€ry f€w pan of the wod4 in a very spe.i6l stasoq atr entirely diff€r€nt crystd structure iorn small cubic crystst to hollow p)T arnid shape up to 2 cm floating on the surfa.e of brine, having four times geater surface ar€a tnd many times lesser bulk d€nsity rs compared to common salr' Th€ natural crystallization of Fleur D€ Sel Pyramidal crystals at a particuhr place in a p.niculsr weather generates . gcnersl view and hlpothesis that the "Fleur D€ Sel or pyramidal crystals of salt ody formed naturally and camot b€ synthesizld". ln ihis work w. did not only crystaliz€ lh€se p)Ta$idal crystals but also did the contsol production of Fleur Del Sel which doesn\

only mak€ it affoidable for c.mmon peoPle but may also caus€ to ftnspon

some beneficial minemls to th€ hurnan body.

The utilizltion of wasl,e gen€ral€ ftom lhe salt proc€ssing industries is thc

key word to higblight lh€ inportence ofthis work

Fornrnat€ly Pakistan msy b€ one oflh€ very f€w muntsies which has all

lhiee typ€s ofsalts ( Rock Salt , S.i Salt, Lrke Salt) in ihe world[55]

Salt availabl€ in Pfistan is assumd to be b€st in quditv b€caus€ oflhe low standard of codex that recommends only 9?% of purity of sodium

chloride [26] . fte Pakislan standard of food gmde sah and others induslrial gades of salr sp€cifications also acc€pt 98% ofsaft as a food gnde ofsalt [24 . Salt is a pad ofour lif€ like wat€r, ev€n our foods are incomplete without it and the Fleur de Sel with no doubt the king of salt. As the application of salr has been increased more lhan 14000 and with ev€ry day new applicarions are gen€rat€d, Fleur De Sel with i$ Sreat prop€nies, Surface ar€a, Light weight, exc€lleDt bsre, quick solubili9 rEachd with ninelals will find many othe6 application to sivcs Fl€ur De S€l its rcd status. l.2Work Plan:

In sea water seven caiions and anions arc most abundant include. the cations.

Na', Mgl', Caz* and K' and rhe anions Cl' ,SO{! , and HCOr. When s€a water is concenFaled by evapomtion, thes€ ions should combine to fonn a s€ries of minerds.[28]. For th€ crysullizstion of Pymmid crystal of salt fte above mention€d cations End anions were und€r study. "The mrin obi€ct oI thtu work wss to crystrllize pynmidel crystlls ofslll rrth.r thm mtunl crystrlliz.tior to ensrrc th€ quclig !trd lhe quartity witb control in every s.8sotr".

The naturally crystallized pyrmid crystals of salt first analyzed for investigating there chemical composition then the crystallizllion of pyranid crys.als of sodium chloride was attmpied wirh the help of brine preparEd by different origins of salt with different chemical compositions. For the success of *ork addilion and subtraction of diflcrEnt chemical impudties was applied with de help ofsome saturaiion technique [29] and brine purification was also applied for the rcmo\al and balancing rhe Dajor anion like SO"'od catioro ca" and Mglt22,3ol . chaprd #l

Each and every sel€ct€d source of salt ond their brine before , during and after crystallization were modtorEd for tlle sodium chloride and its major inpurities

lik€,calcim, magnesium,porlssiun and sulphate[31,]2,331. According to lhe back ground infornation of Fleur d€ Sel (plrarnid crystal of

sodiurn chlorid€).tl 522llhe cryst l arc grl'Tl at the brine surfac€ so brine were evaponted in a pan typ€ evaprator clnsisting a stainle.ss sleel r€t ngular tray heving a size of 12 + I 8 inches by dircct h€atins ftom the botom or indir€.t heat by th€ help of water bslh for constant and uniform temp€ranje. Th€ tempe€ture was monito.ed regularly as one of the main factor. The size and shap€ of the crfsiallization prn had b€en changing with $e Fogress ofwork. As p€I proposed plan the wo* was clnid out with below listcd salt and brine. Waste brine generated by Salt R€fineries.

Raw Sea Salt ( Solat Salt)

Raw Lake Salt

Ro€k SalL

AR Srade ofNacl( Anificial crrslali"ltion)

All th€ experimentsl obseraations are discussed in the experimentai and obseryation s€stion here we think thst a little explanation is requir€d to undersland the chemisFy of above mentioned salt.

1,3 Ses Salt To undeNt nding rhe chernisq of sea water is very import nt for our invesdgatior The oc€lns, containing between 2.7 and 3.5 percedt by weighl of sea salt, are an inexhaustible sourc€. Pfistan is fortunrt€ to have van r€sources of S€a Salt on the coasLl area.

l0 F'g 004: A vic* of Sq Salt CryshuiTaud pu& I.J.I-CHARI]CTIRSITC OF SEA SALT AND CHEMISTRY OT Sf,A aRIND:_ Sea salt is produced by natual evaporation ofsqwaler or brine in large. liked eanlen ponds Solar mdiarion and wind acrion con@ rare rhe seawate. narml brin6 unlil sodium chlonde crysrallizcs. Solu salt producrion rcquires a ldge area of llat. low cost land. Clinal;c condi,ons must ensure high claporarion rates and low ra'nfall A d€op-water sitc tor bulk loading ofocean-go'ns vessel

desirablc for hish yolume shippins for expon. Alihoud rosr solar sah 's production facililies Be seawater a f@dslock, naiual bnne ntrd solulion- mired brine arc ale used Solar ponds are constructed io rakc advantagc of natural Sround conrous 10 aid in brinc molcmcnt. At somc point in most pond systems! pu'npog must elevare soawater or brjre

The concennation ofdissolved solid in seawater although ve;able by location and depdr. alerages 3.5 Ft% (3.6'Be) and 77% oflhe to1al dissolled solids. ie,2? w(o/o of $awarer is $diun chloride Seawal€r must be reduced in volume by ahoul 90% befor€ sodiu'n chloridc b.gins ro cryslalliz ar Chlpter #l pr€cipitation o&urs b€tw€€n 25.9 *1 % NaCl (25.4ts€). The Erost favonble sodium chlonde precipitation c4urs hwcen 26" Be and 29 or 30 " Be. Above 30" B€, high lev€ls ol magnesiun reduce the evaporation rat€ to unacceptable levels. At 29 " B€ 72 % of the NaCl hss precipitat€d; at 30 Be 79 % has precipitated. The high pmduct renoval or is discharg€d. Newly conent"dted brine b added and lhe crystallization process continues. A solar s3lt works producing 400.000 t/yr ofsodiun chloride may hav€ an ar€a of400 ha or more, dep€nding on climatic condi.ions. A proper brine f€€d control system during saturation and crystallization rerults in salt of Purity > 99.70lo NaCl on a dry

Typically, seawater enten the solar pond system and moves successively from on€ pond to the next. OpeBtors control the quantity of flow with m€chanical gates to maintain rargel brine densities and pond l€vels, Irorr Calcium, and

Magnesium csbondes crysrrlliz€ when rhe concentralion of brine is 3.5- I30 Be. About 85% of lhc calcium sulfate cryslalliz€s a! gtpsum and lheir anhyddte at brine conc€nintiom ftom 13- 25.4ts€. Solar slar production is a fon of the fmctional crysrallizarion. Brine reaching the cryst4llizers contahs in solution calcium sulfate, magnesiun sulfate, maSnesiun chloride, and srnall amount ofpotassium chloride, pl|ls minuscule amou ofother elements. The saturat€d brine at a speoific gavity of 25.4" Beo is feed onto level, rectargular crystallizing ponds to mainlain a brinc depth of30 cm or less. As evaporalion proceeds, sodium chloride Fcipirates and forms a s.lt layer vhich is l0- 25 cm thick. In many solar salt facilities, fte first crop olsalt deposited remains on the crystallizer bonons s3 salt floors to prevent conlamination from soil and to incretse tlt€ strength of the cryslrlli?rr bottoms to suppon brlvesting €quipm€nt. When the brine r€aches 25-30" be, the bittem is discharged. Most

t2 Chnple! *l

oflhe magnesiuE sulfale and magnesium a pota.$sirjm chloride rcmain in the biltem.

The salt crop is haflesicd using !6lt hafl€ste.s, elevating s.rapers, or iarge and

load€B. The harvest€d sslt is loaded into rruckr and hansport€d to a wash planr.

The salt is washed wi.h clean, nearly slturated bride ro remove parriculare mauer and to replace magnesiurn-Laden bdne clinging to the salt crystals.

Uncontaminaled brine is made and rccycled in a s€tding l'ond by adding seawarer to dissolve fin€ salt collected by the wash brine. Brine mad€ by dissolving lhe fin€ salt is ftee of magnesium rld sulfate inpuiti€s. Werk bdne or seawster is sonetimes us€d as a linal stsh. How€v€r, production loss€s by dissolution are significant. Aner washing, the salt is sr,ockpiled and allowed to drain. Limit€d minfall is r€lid on to improve salt quoliry by rinsing action. Solar salt typically dmins naturally to a noisturc level ofabout 3.5%.

!.11U[EjAU L.k€ Sal. is one kind ofsolar sall, which arc situared dep irlside th€ deserrj. The underground brine channel of ancient tiin€s, caus€s rhe crysrallization of Salt. Tlle int€r€ning phenomena obs€rved is recrystdlizdion after hdestina lhe salt. On lhe hdestin8 dle undergound brin€ fills rhe place of hary€sled salt and recrystallization proces, stan and within the few monrhs d€p€nding on climate condition th€ same arca is ready for fiesh harvesting. Th€ cheDisr-y of Leke salt some time obs€rv€d litrle different fiom sea salt b€.ause lhere is no series of crystallization involve in lake salt crystallizstion and rhe whol€ brine is conc€ntrared at the sarne place md no sysr€m ofremoval ofbittem obs€rved.

ll Ft 005. A v.* of S.h L.t!

t,5 noct San

P*iltan hrs onc of ltc b4csr d.po3iB of .ocl ssl ;r dE wo.ld .ftcac d.posits of.lcl slt s. in h|njrb. rn N.W.F.P roct !.lt qurri.s ,rc tMbd Jatt4 Bahdur Khel dd K.rrt in lhe Koh.t dilt ic. 'ntc quality of Roct rdr as mr cry{rtr i! cllc.rncd cs bc folmd h.fc of '3 fou ditrcr€ typ6 iiclurthg drt rld *irh sotid crystrt ed dE othcr two avrilable are soft lulip md soft c.ysrrllinc luDp. Th. soi crysrdtino lurnp is so lofr lhrt it o.n bc lEy erlily bmkd dom ro tiny cryit b by otrc's ovn t€rd!. Th. iDprritica lcvel ofdiv.l.ot i'|s obe.nEd coqrr.ircIy low fiom s.!,nd bkc salt, sulph e coDLnr ofsom€ Rock Srlt obs.rvcd vcrvhich. Fia(n6: Atidoftu t S.I 1.6 Mccbrk lD Pl! .rr s.ft-

Mahy diff€rent additiv€s wer€ oh€ervcd in necha"icsly proclss tu Srade salt available in m.*€f sDecially added t!€ flowin8 agcnt ,nd aiti citirg agents! pr€sence creat€ some pIobl€Ill, which nuk€s solution of bdn€ turbid For this wor* $lt rv's collecled non differcnt nechadoal salt prc€$ing units *llting in Paki$ar Iniiialv sah was snab'z.d to find out its impuriti€s lcvel by lJlet ondy'icsl m.lhod and ih€n ,stirated 3oluion of salt nas plEpn€d to us for crysulli"nion Erpos€.

1.6.1 Dcrcriptiotr of Procas3:-

I('w salt is tr {ortad by lruck fotm the h!rycatiog a,a n€ next $ag€ is washing the sslt in t coni@l tank by odlnr€r flow efr.ct ofl}e srhml€d brine haviry a dality of23'Be thc ovcrflow ofthis tank is puged oubid€ The salt afrer having b€en washe4 is pr.mpcd a! a sluny io tl€ hydm cvolon$ and $en to dcwat€rhg conv€yo$ lir'hich !t€ follor,€d bv hvdm mills to mlk€ the salt

l5 ready for th€ second wa3hing s.age which is sinilar ro the ftst one, but with different washing brine which is nore cl€an. Th€ last stage is the fmal dewatcdng by worm scmll g?e centrifuge to have a moistlre contenr of4.0 /o by weight max.[24] Some of Focissors ftIther use Roiary Dry€r for fifiher drying th€ produci up to 0.005% moisture,

1.7 W.!ac brine gener.ted by Srlt Refimd.&

The mechanical wa&r wNhing for upgrading lhe salt is very common in kkistan. This proc€ss for upgradinS of sslt geneEtes 10-15 % of waste salt in form of concentratad brine solution. This brine solution has norc inpurities becruse lhe process is design for upgrading salt and its nmove otler impudties of salt during th€ process and also concentat€d by th€ sodium chloride it selft22l. Unfortunately this high concenlat€d bdne that can be used as a sourccs of many usetul product and also can b€ utilized by renoving major impuriti€s ,this brinc is deposit bsck into rhe sea. This process csuscs an osmoti€ shock ofth€ living organisms (ecosystems) in the sea [7] the efituent h the wast€ is a h€avily concotrated brine solution. This discharged emuent has thc potential to kill organisms .Afthougb the brine solution containing natual ingr€dient of the s€a watier it may cauie &mege by il unnatural concentation to marin€ population near outleL

It is ifiDortant to m.ke lhe salt indusEy fii€ndly to environmert, b€cluse it could have v€ry adverse effect on the environm€nt.

l6 ch.pr€! #t

l.E AR grade Sodium Chloride wiah differert rdditive. As we observed and discussed in th€ n€xt chapt€r rhat crystallizaaion of pyramidal crystal is not only finction of pllre NaCl but presence of orher

impurities take part and act th€ir role. For the purpos€ a mixtur€ wirh sarurated

brine wa! prepared by adding calcium chloride, nagnesium chloride, sodium

sulphat€ and poiassium chlorid€, For th€ said purpose 6tl rhe chenicals were selected ana$ical grade ed rhe conposition of brine prepared exactly matched wilh by gexin8 the rEsult of natural brine. A serious of experiment was perform€d by addition of one and more above listed chemical to ch€ck their b€havior and role in crysrallizarion of plramidal crysiats.

1.9 Kubot! aDd Mullin nodd for crystrl growth in rh€ pr€serce of inpurity.

Kubota snd Mullin proposd a kineric model , accoding ro rieir proposed

mod€l , rhe step velocity ifreduced by rdsorytion ofan impudty sp€cies at the step lines of tle crystal surface. The step velo€iry is given a linear tunction of the equilibriun covemge, e €q, ofth€ activ€ sit$ ar u/ 1)o =l-a 0 eq, (o 0 eqsl)...... E4 (|)

Where o and o" arc the step velocities in the presence of impurity &d in the pure system, rcsp€ctiv€ly and d is the inpuriq €ff€ctiveness ofan impurity at given growth a condition (sup€rasturarion end temp€mtue).Eq.( I ) is valid only when a0 €q<1. For a0 eq>1, rhe liep velocity is always zero. If $e sicp; h€i8ht and st€p density ar€ unchanged on inrroduction of an inpuriry, the face gol*th rate is proportional to the step velociry. Th€ step velo€iri€s in Eq.(l) mn be r€placed wilh Ihe fac€ srowth mre as G/C,= l-a0 eq, (a 0 eq

Wh€r€ G and C" arc th. fac€ growdl tstes in impure and purc solutions rspectively.

Thc impuriry €ff€ctived.ss faclor, o, csn bc rcLted !o supeEaturalion, O can be related !o sup€Faturation,E, and tempcraturc, T [77], by aasuming thc Cabr€n and Vermilye! pifffng mech6nisn [78] ro atply: a =laikTEL, (o<< 1)...... Fq (3)

Wh€r€ I is the dge-tle €ner$| ofrhc slep, a is the s I slhc gswth unir size or are3 pcr gowor unit appsdng on the cryst l sufac€ and k lhe Bolrznkfln conshnt. The ofi€r paramcter,L, is thc dist6nct bctwr.n dle ncighboring active sitls locst€d on lhc st€p lincs, which is the nost inportant qulntig in tbe model. I! is d€crmined by mutusl incraction ( ch€micd or physic,l) berween funpuity sp€cias ,nd crystalizing Aecies em€rging on thc dysral surfacc.

116,77'1,

1,9.1 Itr ahis Th€is.

In rhis thesis w€ speciauy focu€d on thc crysrallization of pyrunidal cryslsls of salt sodiun chloride .Attention b mlinly focus€d on tll€ norpholog/ rnd rnacro siz. formation of pyruidrl crysd of sodium chloridc . Crysbllization of pylllnidal crystals of sodiu& chloride is an exaq,le of low t€mp6atu! surface cryslallization 6om solution. For this purpo€€ sodiurh chloride pyramidal cryslals u/ere Srown tom thc brine solution contrining difi€rent impudtics ar difierent t npcrrturc and pH. For rhe sme purpo,s€ anificial brines werc dso prepalld n|d effect of difrcrlnt impuritics were dso monitored for rh€ cryslsuizrtion of plmmidrl crysirls of sodium chloride.

Thes€ pylrnidal cryst l were amlyz.d by wct and insEumenial methods rnd X-ray diftaction , S.an Elcction Micro6copy and EDS( Encr5/ disp€Five X-

IE Chlpter #1

my analysis) lechniqu€ was also applied to ger ih€ infornstion of eleh€ntal composition of crystallizeipyramidal crystalsof sodium chloride.

In lhe five cryslalizrrion chapters w€ att€inptd to crysrrllize plrmidal

crystah . Chapter t/o conaibut€s in green chemistry by utilizing walte brine

g€ne.al€d by salr industries. In lhe rhid chapter laboratory scal€ sbdy for the

control cryst lliz:fion of sodium chlorid€ pyramid crystals (fleul de set), p.epaEd by solar salt, which is rh€ €xanple of mpid crysraltizarion of pyraridal crystds and crystal groerh which was previously possible in many days[8,91, and 100 hou$ study md observation was slso performed in this

Study and obs€rvarion wirh Lake Sah brine at PH 6- 7 rempeErurc mnge oC between 55 to 65 war perfom in chapter four and similar work in acidic medium with rock salt l'?s perfonn in chapter five. In chapter six artificia y prepeed brine wilh iron , cdcim , magnesium ,ba.riutrr and potarsium impurities is discussed for the crysralliation ofpyramidal crysEts.

1.92 Previous work

Yamsmoto , Tskemcro. Rik.tglku Kerkyuso Lho (1935) The dev€loDm€nt of star-like crystals of NaCl and KCI in pr€sence ofBi ed of MlCt in rhe pr€senc€ of Ti, ZO, Cd, Pb, Fe'3, Crund other ions was studied microscopically. Small cub€s are formed which becom€ pyramidal, snd rhe bas€ of the pyramid then extends diagonally .o give stlr-like crysrais. Ih€ structure oflhe crystal planes is disculsed.

t9 Jose Maria Rofols et al(1970) her work was based on the personal experience

and also of th€ projecr of norms of Europ€an commitlee for srudy of salt, such study has be€n divided in four subiects:

Chloride: the m€rcurinetic merhod is recommended fo. its derennination , which proc€dur€ is explain in detril.

Macro impurities: in ir explained the sysrem of determinarion of moistue,

isoluble matler in waier calcium and magesium , sutphales and also rhe ev€nhai one ofpot ssiun and bromides , exptaining in deiail in one side lhe

technique ofth€ conpl€xometric dererminarion of calcium and magnesium and on the other side the volunerric one ofpot ssium wirh STFB.

Micro impurilies: commenting thei determination snd giving spe{ial reference to the analysis ofcopper wirh A?DC by atornic absorption spectrophotonery.

Additiv€s: also commenting the der€rnination of iodide ,fluorid€ and fene.yanides sp€.ially .Alt the procedues of the d€te.mination arc not includ€d by rnuch literature is ciied wirh includes th€ most imponad ftemes conceming this que$ion.

B$inski/{nlonii Cz.rwiaskirerorprrrgtrd comiczy (1950) discussed on the assumption that the suface of a crystal has practically rhe same crystd suucture as the inside ofthe crysrrl and that molecules., on crysralliarion r€nd to go to the place of minimun eners/ scales. the repulsive fon€s at various places in rhe crysrd and concludes that in a crystal ofth€ NaCl g?e o, y lhe (100) surfsces aft stable, that the surfaces (l l0) and (l I l) are (in vacuuin) onty

20 Chapler *l

imaginable as a great no. of cube surfac€s which aI€ gouped in dome or

p,"amid formations, that two{unensional crystsl. Kemels arE formed on the cube surface on gosth, arld that th€ ions or molecules crystallize out most €asily on a cube com€r, lhen on an edgc, and nost difiicutdy on the niddle of a surfac€ solution takes place in the reverse order.

GJrs.ggio rnd G.A.Mrctelsor 0960 modified ,nd improved rhe accurale derect ad determine lev€l of cdcium snd rdsgnesium b€tween 2 and 40 ppm

in salt. Aaled on 250 dererninations rhe skndard d€viation is +/- I DDm

The modification in procedure invotves adding a sma amount of calcium ro hydrGrylamine hydrochloride solution and equilenr amounr of EDTA to rhe buff€r. T is lhus possible to d€te.t as lidle a3 10 microgran ofcalcium in the titadon at PH 12.5, Without this modificarion it woutd nor b€ posribt€ ro detect l€ss thEn 120 nicrogran of cslcium at pH 12.5 with th€ calcium indicalor used and magn$iun would be overestimated by up to 76 microsams.

Magnesium was der€rmined on a numbcr of satr samples both by rhis improved EDTA method srd by the colorimetic clayon-yelow method. Exc€lt€nl agr€ement \r"s found b€rwe€n th€ rwo anaMical methods

K.miyoshl, Krnichii Yrmaklni, Tsuromu (1960) The gro\rrh of NaCl whisken grown by the cetlophane method w6s sntdi€d. N€€dle, plat€te! snd pyrarnid-type crystals w€re grown on the crllophane surfaces. The crystal grew entirely at the base. Tip gro\'rh or lareral thickening did not occur. The whisker exhibit€d large ptastic deformstion (O 140 = 5G.90%) beforE iacturE occun€d. The crit. strain (Ilastic elongation al fracture) increased with qoss-s€ctional d€cr€€sing are€, but it decre$€d rapidly to zero when the crose 2l Chap!.r rtl

sectional arca d€creas€d less than I 0 10-3 sq. mm. The rensile strcngrh

incr€ased significantly with decrease in cmss-sectional arca b€low I O l0-3 sq. mtrt. Plastic defornation producrd slip lines otr the cryslal surface which wer€ s€en by the optical nicroscope rnd €lecron microscope. The slip ulually occun€d on a single set of(l l0) slip plsne sysrems in relativ€ly large rcgions

ofthe whisker. In some cases, th€ transverse (908) slip planes w€re waw, and

branching was observed. In olhcr cas$, they were sraight ahd pan el. The 45tr slip lines could nor b€ s€€n by th€ €l€rtton microscopc. Cross stps wer€ mr€ly obsereed. Etch-pit obs€rvations revealed thar the whilker contained many dislocations. The results ar€ interpreted.

Richrrd R , Mltchell(I97o) Investigaled to eer hiSh€r rsw brine purity from rock salt, brine prepared ftorn rock salt is known to conrain as impurities calcrurn ,magnesium and sulfare ions, before it is suitabl€ for us€ in chtor_slkali ce , bdne rhust be pudffd by chenicat pr€cipitation , s€Oling and filr.ation. The cost of tle3ting cheinicals and , ro a certain exlent , the size of trcating equipmmt depends on the raw brin€ purity, i.€, for brines containine larg€r amoun ofdissolved impuiri€s, flore trerting chemicd ar€ required , more floc must be t ken form !h€ scttling tanks, and morE etuained solid must b€ removed by the filrcls. If the purig of r6w brine could be subsrantialy improved, equipnenr and chemical u€aring cosls could be reduc€d €oNiderably, or possibly, the need for brine treatmenr coutd be €liminated allogether, purpos€ It wrs of this work to determine lhe pot€ntial optimum Ew brine purities which cln be achi€ved und€r vdious op€rating conditions and wifi

22 ChapL. *l rock salt from various sources. ffiere$ inhibito$ such as the polyphosphates have be€n us€ to improve bdne purity, these will not be covered hcrc. Also, the work will not cover th€ nany types of dissolving equipment which ar€ availabl€.

A key to higher raw bdn€ purity lies in dle fa€l lha! the sodium chloride fi"ction ol rock salt dissolves many tines fsster rhan the non- salt impurities. An aqu€ous solv€nt in contact with rock salt will become saturated with sodium chloride in a mater of minules, wher€as hours are r€quircd to reach satuation levels of irnpurities.

Willion H. Lyrch (190) Studied tncc mineral in salt by alomic absorption spectrophotom€ter. A trsce mineral salt is a mixture of salt and Aace minerals in a ration ofaboul9:2 sslt, in addirion to iis nutdtional value, is used as a canier for trace minelals.

Prior to use of atomic sbsorption as a anal,,tical mesns, quality control of th€ fmished lrac€ mine.al salt prcduct was mainly dep€ndent on inventory control, convention6l anabtical mesns for nany trac€ min€rab are so cumbersone and lengthy thar the analyses werei " aft€r- lhe-fact," and only hirtorical vslue.

Alomic absorprion sp€ctroscopy is rhe study of absorption ofradiant enetEi by atoms. An analltical process it includ€s the cowersation of coftbined €lement to atoms and the absorption of radiant eners/ by thos€ atoms. The najor application of atomic absorption sp€ctoscopy is the detection of trace metal consdnrents. Advantag€s of his means sre: high s€nsitivity, relaliv€ly fiee of int€rference, sd rapid and minimal smount of pre- teatment. A trace nineml

23 Cha'tf #l salt is a lEce minenl actually mixed with salt is such a matrner as to ideslly produce a non-segregating, het€rog€neous nix of salt and a trace miner.l essential to animal nutrition. Salt, in sddition to its nutritional value, is a calrier for tr".€ mineral. The author conclud€d lhen work wifi saving of man hou6, €qual and b€tler precision wirh clmpare !o others melhod, gre€r€r rcproducibility ofrcsub saving of chenicrls.

Rog.r c }lorris C.M. SrDirhey (r94) discussed the analysis of a wid€ assortrnent of mat€rials for traces and larger amount of a great many melalB now routinely accomplished by the atomic absorption sFctrophotomerric (AAS) t€clnique. Tl s paper desuibes lhe AAS determination ofsix nineral nuidents in agricultual salt producr. It dis.ussed the s€l€ction of sanpl€ sizes lor poducts containing cnlcium , cobah, copper, imn, mangeese, and zinc, usually in lhe tange of o.0to/(Co) t 2.0/o (Cs); lhe prepamrion of s3mpl6 for analysis by AAS; and the concent_alion of s€mpl€ solutions mosl convenient for analysis .I. oudines the choice of irubllment operaring condirions and panmeters and coDsider some of the ncans for overooming interfer€nc€s. Thc suftor explained th€ dilution facror for differ€nt trac€ nelal to minimize rhe enor and inlerfer€nc€

Atrthory Serutton (1979) studi€d th€ evaporative of sodium chloride fiom puriffed ammonia-Soda brinc using a laboratory codinuous mixed suspension mix€d product renoval qyslallizer (CMSMPR) wifi a crysral production ftre I kg/ hr. The crystallizar design incrQoratd a pneunatic pmduct removsl syslem which allow€d the crystal reeidence time, magna conc€ntrarion and production de io be varied ind€pendently. Chapter tl

When producing cubic habit crysrals , gowih rate wer€ fourd io be independent of crystal siz€ for crystal larger rhen 75 Fm, rhat is Mc @be' law was ob€yed . This law wEs obey€d .The law was not ob€yed when rhe product

contained a larg€ proportion ofparry spherical or spherical crysists. Th€ crystal glwth and nucleation Btes obs€rved at consrant maSma concentration, over a range of residenc€ tin€s and sriner speeds fit a power o=K lawnodelofrhetypeB rMdNz inwhichKavariedwith stinerd€sign. This paper d€scribes the d€sign of a laboratory evaporative crystsllizer which clos€ly appmxima@s ro the ideal CMSMP& and sorne of|he resulrr obtain€d with it.

Thc d€sign of the crystalliz€r us€d for rhe work was of6 slir€d vessel with a drafi tub€. The inside diam€ter was 20 cm and ovemlt height was 76 cm with a liquor volurn€ of 10.5 line$.

For all experimental work reporred herc, purified ammonia- soda brin€ used, similar to th€ suppli€d lo rhe production plants; the crystaliz€r opemled in tempemrure range lt'9 ro 5"C.

At lh€ end of €ach €xperimentd run, two $mpl€ of approxinately 60 g €ach,

ofthe salt being produc€d werc taken hstfan hour apan. From these rhe csjrier brin€ was r€moved and they were wrshcd first wilh a erhanol- water mixnre lo remove residual brine and then with acelorc. Finally the sarnples w€re dried under an infra- r€d lanps and sieves anat)ris werc carri€d out wirh st€ndad Bri sh Sieves using pascatt hctio,hakinS machine. M.A.Perirelli (1979) sMied to deoermine th€ €fiecrs of some narine pollut nts on lh€ solar salt produc€d for nutdrional use. Th€ conclusion is rhar inorganic cont minants behav€ in two difTerent ways, if th€y crystalliz€ before or toSether with satt and ifthey crystallize after. The study was perfonned firsr on samples coming from the ponds in order to veri& the b€lBvior ofnatual

25 Chapret #l

cont{ninants, Adequate anal}ticd i€chnique were use. In particular, trac€

metals w€re detemin€d dir€ctly in 6e brine al|d in rhe sat solurion without any

pr€ concentration by a flam€l€ss aromic absor?rion method. Moreover, in order to invesligate the behavior of the same contrminsnls under heaw pollution

conditions, natural crystdliation conditio$ werc r€pmduced in a laboralory a magnifi€d adificial pollution was simutated for borh rhe rypes ofconraoinating

agents, il was verificd tha! under such mndition, salr ofdifierEnt purity level is

obLined sccording !o rhe type ofpolluring agent. Ways to obtain satt suirable for nutritional use, €vcn form poltuted brines, w€re re$ed. H€ conclud€d that solar salt is used for nutdtional purposes , a sea water brine polluted pb by l€ad might resul. in a maximum content in the salt of I ppm, a figure which coutd be lowered by dtucsrding the tusr fraction of crysrallized In salt lhe case ofzinc pollution, the only limirirE facror appejrs to b€ the poor solubility of such compounds as carbonates and hydroxid€; howcver. fifther sludi€s will be cffried out on this subj€ct, in the cas€ ot a s€awaler brinc polluted by boron, salt nay e r€crystallized, lowering the boron anounr occlud€d with th€ moth€r tiquor in the crystals, or it may b€ enough io *ash rhe harvest€d salt on lhe siockpiles.

The conclusion of this study is th6t inorganic con&minanrs ditrqenrly innuence the solar satr purity tevel according to the s€quence of the crystallization time!. At pr€sent sea pollution is not aa all a souc€ of concem !o the produclion of food gnde solar salr , since lhe conred ofrhe coniaminants are very low ad in any case for from reaching drngerous levels to human health.

Gcrrrd cubert rnd Michcl Vi.rd (1980) Pcrforned thernal crysrallizarion of untr€a&d brine_ Th€ raw mat€rial avrilable for production was geneGly a

26 Chrtt . #l

mw b e obtahd by dissolving halit€ nom injecred warer or film non_ controll€d underground warer. Th€ raw bdne, saturated wilh sodium chloride , also contains impuities such as Na, ,Ca, Mg, SOa, the hypothetical groups of which can bq CaSO., MgSOa, Na,SOa, CaCl,, MgCl!. Aulhor explain€d thar lEw brine is gcnrally satu{ed wirh calcium sutphale and he{ting ofsulphare on io lh€ hearing surfsc€ and depending on tempemrure and conc€ntrarion factors to a panial hydmlysis ofthe Mg ion which can cause accident5 because of corosion. The funher disclss€d rhe six treatmentr addilion of sdium h€xameraphosphsre as sequ€sr,adon agmt ro avoids crystaijialion of alkatin€ edh salts aDd exptained tha! the quantity ofsodium hexam€taphosphate r€quired is eight times lhe quantity of calcium sulphate existing in brine. An .ddition to soturion water injected into the sulfirous, deposit ofalkalin€ cabonate and alkaline phosphar€, sotuble in wat€r. Dissolving ofhatile ,,vacainated,, wilh *arer by nejns ofalk tine phosphare. Additional to the dissolution warer ofsnall quantiry ot an aikaline carbona@ or alkalin€ phosphare or addition to dissolve wat€r of an alkalh€ carbonate or alkaline phosphate or addition to dissotve warer fan alkaline phosphsre and of a hesry me!61 ion , in paricular aluminum. Us€ ofwat€r having a mininun pH 7 snd contlining sodium ca6onst€ and ri basic sodium phosphate. Addition !o the brirc of an alkatin€ phosphale treated with sL-rch and r€circulation ofmorher brin€. Additior to raw brine, upstream tom lhe evapotatols ofa smal quantiry of sodiun hexa nel, phospharqs-Io0) ppm , solubitfy ofcrtciun lhis doubled. Thus avoid! scajing by limiting the concentration facaor to 2 and temp€ratues oC. ro 100 Ilis alows pur€ a salt ro beproduced;50 ro 60% of6e feed brine are tlEn bld . The brine thus bled is rEticutat€d to tne head ofrh€ ptant into rhe cvaponiors openting ar a hiSher &nperatur€ , with Sermination. These 27 process€s only give brine having a calciun sulpbare conrent lower than sahlrstion. They involve a few problens. Therc is high regent consumprion of poly phosphate and sodium ca$onale.

Hrnhrd M.Pe.et (1983) conducred a study ro determine factor for optimum brm€ Featment process design. In his paper he discussed the brioe rearnmr of chlorine/ causric soda which is genera y comisrs of redu€iion of calciurn, magnesium sulpha@ and orhe$ heavy met6ls impurities fiom brine. Aulhor ftrthcr explained $ar lhe.e are s€veral sigfficant f.cro$ invotve in bdne lr€-aftent d€sign and tfie failue to consider these factor during design can result in high cnpilal cost, chemical Ee3rlnent cosls, rnaint€.nanc€ cosr! and will somelimes resulr poor in brine quatity. Th€ procrss design discusled is for brine laturarion, soda ash and caultic reaction sysaems, sludge senling, brin€d filtarion and lime re{unenL The factor !o be consider in brine saturalor design are salt charging tat€, undissolved solid removal, wq carryover, rhe Dobntial for ma$esium spiking and salr caking . Five major factors involved in reactor d€sign a.e reremon trme, brin€ rempemture, degree of agitation , €xce$ reactanr and supenatumting of pr€crpitat€s. Sludge settter design is b6sed upon rhe quality ofprccipiraies and thcir scttling rare. Tenp.ratre invqsion and slugghg of flow should b€ avoided. Improvement in sdtling €tes can b€ obtained by using coagulanls. The facrors io coDsid€r in filter d€sign should Fovided for senler upsels and overloading of rbe fiher A te$ proc€due is discussed. The retative opeEting cost due to body feed. prc-coating versus incr€ssed setder capiial cosls ro improve settli.g should be evaluated.

28 Chapt ( #l

Sulphate in the recirculalion brine system is controlled by lime, calcium chloride, badum chloride or barium carbonate, pmper dosaS€ and sizing of €quipment is nec€ssary to avoid s.aling ofline and piping. Lin€ is also used to 6ise lhe crlciurn - 0o magnesium mtio ro impmve setUing of the nagnesiunr hydroxide precipitate. The optimm catcium /magnesiun mtion is discussed.

In their saturator sodium chloride rapidly dissolve with in t0 min, impurities such as calchlrll sulphate aake a long.r time ro dissolve. These differEntial solubility rates are important in ddigdihg tl,e saturator.

Rob€rt J, Hit€ (r98) discussed the sutfate problcm m maflne evapontes. One ofth€ puzzling chaftderistics ofmarine evaporite d€posias is sulfare d€ficiency €xclulive ofcalciun sutfate. Sutfate is the lhird nost abundant ion in sea war€r, yet lces thrn 40 p€rcmt is lEtnoved by SFsur anhydrite pecipiration. Therefore, marine evapomtes should normally contain an abundance of other

H€ conclude thAl bact€rial rcduciion of sulfar€ in nodem €vaporite envimnments is a w€lt-tnown ploc€ss and it,s exrs@ncc n lhe ,ncient mvronm€nt is not dcnied. How€ver, because of questionable adequacies of reductrcn and ntes supply of organic marier, it is u ikely ihat its proc€ss €fectiv€ly depleted evaporite brines in the sulfare inn. If bacterial reduction of sulfat€ was quanti&livety an imporrant proc€ss ir should have leli b€lind ce.tain hin€ralogical g€o or chemicat evidence, rhis evidmce haj not been observed in narine evaporite d?osirs. The compo€ition fluid of inclulions, associated connste brine , and the minemlo$/ of many marine evaporite d€posirs suggest rhar brines fork which

29 Cb.ptct #l

these deposits form€d were €nriched in the calciun ion , Such brines tt€come depleted in the sulfate ion due to rhe srong re6clion.

caz* + so.} +2H,o------caso. . 2t{o.

Studies of geochemical and inineralogical r€larionships in the evapomres of Middle P€nnsylvanian a8e in the paradox Basin suppon this mechanism of

sulfate depletion and suggest thar dolomitiarion is rhe principal cause of th€ Ca 'z* enrichrnent. ftis t}?e of brin€ modification mrher than bacrerial reducnon of sulfate Inay b€ largely responsible for the d€ficiency of magnesium sulfat€ ninemls in marine evaporties.

Horak., Mrsahiro; Miyrra, Trke3hii Trki, Ssdoo'{ lgSO obs€rved the process of variation of 8roi1h pan€ms on the prbn (m) faces of synth€tic quartz cryslals fiom striations !o plTanid.shrp€d overyro*th was studied by changing th€ conc€niration. of rhe NaOH and NarCO3 solutions. In a NaCl soltltion or in pure HrO. When rhe conceft"a.ions ofthe added atkali sotutions

vr€r€ exheftely low, the stiations werc obraind on th€ face. Th€s€ striations

were oflhe sane Ep€, which can be s€€n on crystats gorn in a NsCl solution. pBC or rn pur€ HrO- Th€ anisotropy due !o rhe vecto$ affects rhe growtt of srriations and causes frster gro"lh in tlle tuol dir€.tion in compdison wirh the [001] dir€ction.

Joachih Ulrich et rt (t93) sMi€d rh€ growrh behavior of sodium chtoride crystals by usinS addirives ,nd wirhout additive !o undersrand the grc*th behavior add gro$,th kinetics. tn their work they used ditrerent iypes of labomtory equipment and inJtuence of lcad chloride , magnesium chloride and potassium f€nocynide *as noted. It was obsewed thar nagn€sium chloride in t0 Cbrpte.tl concenuation of range ( 40 to 500 ppm) cauet lhe sifring of sup€rsaturalion of

S,-B zhrry et rl( 1996) They discussed the effect of imPurities on the NaCl gowth . They concluded their work by dividing inpurities etrecl on the SroMh mte of NaCl in tk€€ difierent ellecls. ThermodvnaDic effect, Kinetic eff€ct and Insen impurities effect. nl€y atso conclud€d that in the pr€s€rce of impudries of all different q?€s in se3 waier the grorth mte of NaCl is

Noriaki Kubotr et rl.(1999) Measure the gow1h rate ofth€ {l I 0} fac€s of (Ut) KrSOa. A flow cell \{as used id the pres.nce oftraces oflrnpurities Fe and thc pH lange was naintained 2.5-60. In their wo* thev dis'ussed their propos€d kin€tic nodel thst state, the sleP velociiy is reduced by adsorption of an impudty sp€cis at th€ slep line ofthe cry$al su'face'

Chr. B.hrow,D.Rrbadiev, cDd S.Tcplvitchlrow (2000) worked for a rerhnology pennitdnS practicatly conpl€te urjliztion of fte main -'?) obtaining compon€nts( Na', Mgl+, Kt, CL ana sO, in tne *aste brin€ alier of sulphate alt from sea waler .This method comPrises 4 st ges(l) elimination (3) prepamlion of ions; (2) precipitation of Mg(OH! and fomation of WO; KCl, NaCl and CaCl, .aq: (4) convenion of s/Fum into cacor' from Sea' The t€chnology developed for improved trertnent of waste brines 2 aspects: a Salt plant "Tcheronmorski solnitzi", Bwgas, Bulgaria, has ') 3t Cbipld tl

n€lhod allowing practicrlly cornplet utilizalion of tll€ major components ( Na', Mg'., K', cf and soa '2) pre€nt in rhe waste brin€ afier sea - salt production and isolation ofsome inorganic salts; and ii) a way ofprotecting the

living oryadsms forn the hnmtul efrect ofihe deposited wast€ brines.

Hir$hi Trkiyena sDd M$rkuDi M.stsuokr,(2000).Used the addition of and solvert addition t€rhnolog/ to precipitated thc sodium chlodde crystals by producing supersatuation. They discuss€d th€ drowning --out precipitation

advonrage! and disadvantages aDd chsnge in crystd norpholo$/. On addition

ofethanol some cubic , platc and rod like qyst ls shapes arc obaew€d which were agglonerated with eighr constituent hollow cubic- like crystals. Th€y concluded that the crystal moryholory €haryed when ihe degree of inirial

supersahuation D€lta Cd was differEnt even as th€ same initial supersaturation

J"{.M.Meirer ' lort KJ,l,..u*D (2000) otilzed srand alone, ener&/ efiicimt and small vapor compr€ssion unit as produced by Gend firm w.s converted from and evaporator to and €vaporator/crysralliz€r. Also ihe basic unit was €xlended wilh a vibntinS sieve and a desnter centrifirgc. In this way an idlallation was created which produced only distilled water and a solid product consisting ofsalt plus th€ orh€r compon€nts pr€sent in rhe wast€ brine,

Using original wane brine fom a chc€se plan this installation was severcly tested whereby major lechnical problems had to be solved. Th€y also worked to trFlt the solid s"sle salt and thc wrsie brine fron a hid srlriDg plan a wasvclarific.lion toapor comprEssion installation was eoeineer€d. Hereby the wasb,/clarification part had to op€ra1e for about 8 hous per day where3s the vapor compr€ssion pan had to op€tat mntinuously dwing the we€k. Ih€y

32 chrprr #l

obs€Ned th€ l/3 salt wrste ftom cheese plant , 40% wasrei by hid6 and fie salting fish sonetine 85 to 90% solid waste salt is produced.

S.kowrkid Ostubo, aDd Y, Kikucb(2m0) the superior Characterisrics of Flake Salt from a multi plate crysrdlizer were studi€d in this work. In

consid€ration ofmpidly deyelop xdarket of flake salt in Japan due !o it5 unique

properties of beu€r loft, dissolution and water re.ention propeni€s the above

staied work cffded out. Flake salt is crysralliz€d in shap€ of tremie crystal

genemlly, in ca* where the crystal nucleus is gev€nred ftorn sinkine by the surface tension and crystal groMh proceeds only at the brine surfac€, r€sulting

m a crystd having a hollow inven€d pyrarnid conliguation, wirh th€ qua&ilareral base at eh brine su.face and the ap€x gmdually subn€rging fadher int the bnne under lh€ weight of the growing crysral. The tcrm " tremie" or alternatively ' Hopp€/ rcfcr to inven€d- pymmid configumtion of the crystal. The chancterislics ofrhe flake satr wer€ also discussed as its faster dissolrtion time ,grF!r!r mixing and s€pafation r€sisrance, r€adier adhesion.

S.lmueJ{. Suginoto rrd M.yoshida (2000) investigated flaky salr equipment used for manufacturing in an effort to improve the manufacturing effci€ncy and th€ ch.ract€risrics of ttle flaky sah Tlle study wa! conc€med l)the improv€inent in the p€rfornance of the crystalizing part of the evapomtor and 2) the manufactudng ofsalr flakes oflarger Fnicl€ size. A pan type evaporator has been developed which conpris€d both th€ heating part and lhe crystalization pan.Thes€ two p6rrs arc s€Frated by s sluice. The sluic€ is open at both the upp€r tuxl lower €nds and incorpomtes heating pipes, Under the sluice, santmt€d brine crn nove folm th€ crysializing part due to and air- ll Cbpi€.#l

lift effect, whereby evaporation and natural coolios from the surface ol the brine induce the formation of naked (remine) crystals. The brine is then tra$ferred und€r the sluic€ forn the crysrallizing part to lhe heating pan. This

structure enables w to separale boiling-induced disrurbance form rhe

cryslallizing pan, and as a icsllr the iemper.ture of brine in rhe pan could be rarsed nearly to the boiling point. ft€ operarionai perfornance of this equipment was abour 8-10 lq/mz,4r for fleky satt production st a brine

temperature of 103-l05oc in the cryst llizarion part. The production mte was increas€d to abouftwice forjacket earing t"€ and other typ6 ofequipment.

In flaky sdt cryslallization equiptrent, brinc \,?s first hear€d in a pan (size 200 cll'1) and th€n evapont€d !o poduce flaky salt. The coll€ctei flaky salt crystals were then washed using €thsnol satuated with sodium chtorid€. After drying at for 60t 30 minutes, a sieved anatystu was perforined in order !o derermine rhe paffcle size distriburion using thc JIS srandard sieves.

O. Sabrtin (2000) studied the salt exracted from Dead Sea by solar €vapomtion plocess. pot For lhe producing sh (KCl) the d€ad sea waler is dmwn to fte salt pond the slrface atEa of whi€h is abour seventy square klom€ters. Due to the subEtantiat Ngh remp€ratue padicul&ly in surnmer season in that area locared in rhe southem pan ofDead S€a, which is the lowesr point all over the world, i.e is (400) melers b€tow the s€a tevel so the most part ofthe sodiun sulphare which forms about 75% by weight ofDead Sea water pr€cipitatEs on the bottom of &e salt ponds. For the prodoction of potalh is conc€med ihe brine, after having been crnc€nrrated due to th€ salt precipitation, is drown by gavity to lhe nexr s€ri$ of whar is calt€d camaltiie ponds in which the camallit€ is precipitaled .CsmaIi& ( KCI-MgClr.t2 H:O) is rhe hafl€sled and punp€d in the folm ofslury to the refin€ry to extra.t KCl

34 Chalt r #l

Sodium salt has been precipitaring in the salt pond ro form what is called Mushrcoms as they take th€ shape of th€ mushrooms of about two met€ls

height spreading in the whol€ surface arca ofthe salt Dond( abour 50lo ofthe

These musluooms cause problem by dccrcasing rhe surface area ofei?pomliotr

and cre.tes some scagnrnt area rhal r€stricts brine fow in the pond and camallite s(art crystdlization in salr pond instejd ofcjmallite ponds.

To r€solve pmbleE rhey instaled a planr !o produce sodium chloride and raw salt is rransponed by trucks tom thc satl dift€s a. the salr pond through a distance ofaboul 5 km ao the washing plant. The next srage is ir€shinC the salt m a conicrl t nk by counter ftow effecr oflhe saturatad bdne having a d€nsity of 23' B€. The salr, after taving b€en *ashed, is pump€d as a sturry to rhe hydro cyclones ard then to dewat€ring conveyors which s,e followed by hydro mills to nake the salt ready or s€cord washing stage which is sinilar to rhe first one, bui with different wrshing brine which is oore clean. Ttle last siage is the fnal dewatering by worm scroll rype crntrifuee ro have a moisture conient of4.0 % by w€ighr max. The recovery ofrhis Foc€ss h 85 to 90%.

Shimrd!,Osanu (20Or) Oc€an water is flown inro ponds at tuI tide, narurally evapd., filter€d wirh seawe€ds, evapd. under srining by sun light and wind for crystr, and th€ salt is piled up as a p',rmi4 and sun_dried for l0 rno. The sun-dried salt is mixed with foo& conrg. enzym€s(e.g., anylas€, lipas€) to give enzyme-contg. sun-dried salt.

Nedr Ridenvic ci (2002) .l investigated (l 0 0) NaCt €tched in fornanide as a model system ro improve iheir undn$.nding of rhis phenonenon. They l5 Ch.Pter *l

observed that p''.amidal hillock are often formed during w€t chemical etching of the silicon for micmmechanics applications. nley observed wh€n they

submerg€d NaCl crystds into a b€aker witl formarnide without stining , pyramids are formed in very small numbers and only near edg€s of the crystal

and near various scmtohes.

Mumtrz.A.Qutob ( 2005) studied large-scale dcsalination planrs consruct€d in the coastal region of tle M€dit€ranean Sea of Israel and the Palestinian

Authoriq have stong impacts on lhe environmenL tn the south€m zone the coastal region is wide. This zone is an overpopulated r€gion with extremely high population growth rates. The impact ofthe noise and land use will be high.

The sourhern coasral pert also has a wide continenral sh€lf, giving high impacts lo the Marine llabitats. On the orher hond th€ nonhern pad of d|e coasiat zone is a nanow region with a narow clnlinenral shelt On rhe northem parr there is a strong impact on th€ uiilization of rhe nanow coastal land by destination the for using it for recreation and tourism. In addition to the impact desalinarion acdviti€s instead ofthe narine life and mainjy rhe seaweeds.

ZHOU Xuyur CHEN xie (2009) studi€d on th€ salb crystallization bchavion during bitt€m boiling evaporation at 70"C. Normally the production pro.ess to deal with the bittem includes tbee sreps: KCI production with 2- eflect vacuum evapomtion of th€ mixrure of bittem and mothe. liquor aner KCI production ; Br2 €xhaction through disrilation process, and MgCl?.6HrO productior by mono4ffect evaporation For tlle production in dre first evapo|alof, and separ.te th€ Nacl and bittern snd morher liquor aner. its prodoclion in lhe s€cond €vaporator. In th€ s€cond evapontor, th€ MgSOa solids forn the rnorher liquor in the second evapomtot lhe operation tempemturc is 65 to 70"C, but th€ mncentration is €ontroll€d by operation experi€nc€ only, lhat ftay lead to NaCl and MgSOr solids cabnot be sepalat€d fiom the liquor crmpletely, lhen the output is low, meanwhile big qusntity of nother liquor is mixed in th€ solid, so the rhroughput of KCI product will b€ low aho, and the fiuther separation of lhe NaCl and MgSO4 solids will be not 2, €asy. Based on tle analys;s ofNa', K', Mgz'//so. Cl -H,O phae diagmm and the experinedation of the bittem €vapontion in the laboralory, $is pap€r shrdi€d the salt crystallizrtion behaviors of bitt€m evaporation under 70"C, which will supply reliable dala for opentiod ofthe second evapor.lor in the production of KCI poduct. They stlred that the chemical composition of biitem is compl€x and lhere are many factory such as leftperature, evaporation rate and agrtation rate that will aff€ct th€ crystallization b€havior ofsalt . wei Wrry, Broji.g CHEN(20{D) Analyz€n fte differen! paramel€rs and studied lhe factoF lhat are influence the quality of crud€ sab th€y worked 1o check lhe formation of impurities dudng crysrallization of crude salt and also analyzed lhe method which decrsse th€ impuritie.s. The author also discussed the effect of the qualiry of salt in the ohloro Alkli industries as lhe chloro Aldi is one of the gowing industry of China. the impuities present in salt or in form of mother liquor rapp€d in lhe crystal incre$€ the pre treatnent cost of brine. The paper stnt€d that sude salt pmduction is crni€d out in comPlex solution brin€, which contains a variety of ions, including sodium ion, chlorine ion, cslcium ion, nagnesium ion, suhh6te ion €tc. When Nacl is cryslallized and s€parated fom $e brine , some brine will remain on the surface ot ihe cEnnies of NaCl cry$ll par.icles .At the €ryslallizltion process , if lhe Cbipter *l

cryslallization speed is too fasl, pan of brine will sealed in lh€ NaCl cryslals , r€sulting in wat€r - soluble impurities .m€ paper explained thar by stricdy coDtrol the coefficient of Na'/Mg-, and implement rhe t€.hnolo$/ of crystalization " Prcvent use brinc" iom being added into new brine beciuse this action incrises dl€ inpuritics level such as Mg and Sulphat€ in brine. This paper emphasiz€d that to gel the good quality salt and tansparent crystals it is recomm€nded ro not use low depth ofbrin€ and log -{erm dystallization the r€asoning behind this phenomena wss explained as if the depth is small dte brine's temp€mtue varies significantly during one day, so do the €vapom.ion sp€ed and sup€rsstumiing degree, leadinS to frn€ salt , flake salt and more nolher liquor remaining on or in the $lt , and turther cause bad crude salt quality inst€ad of brine high brine level. lt was also observ€d during study when the Rrrio of Na+/Mg++ ntio goes lower due to uystalliz.tion of

NaCl ,its indicates lhat the impurities concdeadon in brine end brin€ vismsit set hishq and higher , r€sulting in spont$eous nucleation on lhe brine surface, , forning fine salt or flake srlt., l€ading t poo. crude salt quality. The paper also discussed the t€mpemture effect on the pr€cipiiation of sodium and

Calciun Sulphare. Done Weiyi (2fiD) In this paper suthor dis€ussed the d€velopment trend and cunent situation of wash salt producing in china by grinding and washing of $lt. Two t}?es of edibl€ refined salt production Vacuum evaporation in which raw salt may dir€.lIy enter the evapomtor to start evaporation and crysialization duough pro.essed brine and anoiher mefiod is ginding the raw salt by aprropdale method, dl€n washing m€thod are discussed.

Ahrron Oren (2flD) In ihis study the qudity ofsalt crystals were discusse4 It was explained that in lhe solar salt€m crysialliz€r ponds the size dd quatity of

3E Ch.pter I I

the s.it crystals form€d is highly vadable worldwide. It was obs€rved during

snrdy that in some places larS€ solid halit€ crystals precipitate that are easy to p.ocess and yield a high quality product while elsewhere crysrli are soft , have high content of €ntrapped mo6er tiquor, and are difiicult to harvest and to

puriry. The pres€nce ofa community of red halophilic Archaea and the atga

Dumliella salina in the crystauizeN is gen€rauy consider€d beneficiat ro lh€ s3lt production, It is often assumed thar biological processes in the evapomtion

and /or cryslrlliz€r ponds ma be respotrsible for lhe ditrerences in th€ s6tt qualiry as rh€ lEw mat€rial in alt cases is seawater of n€arty identical

Yu.r JritrjuD .d SI|A Zotirrg (2009) Exptain€d Ue complexity oflhe srlr cryslallization proces!, Indultriat crysrallization process is a process which crystal gmwlh and nucleation occu in suspension .Ler€fore th€ fluid dynamics which provides dl€ exremal €nviro nent of crysrd nuclearion and growth in crystdlizer has an impo&nt ml€ on crystdlization proc€ss, On the other hand , crystallizrtion kinerics are the intcrior facloF lhat d€termine rhe crystal shape ald size and has a relationship wirh crystal nar,erial and crystalizetion ddving force,' super sarumrion" Pictro Fotrt m, Jurg Scchefcr, a[(l Dotrsld pettit( 20rr) The Internarional Sp6c€ Siation (tSS) w€re chancrerized and compar€d to salr crystal grown on effth with NaCl cry$sts 8ro*n by the evapontion of en aqueous salt solurion in micrograviry. In this work th€y comp!.red Fl€ur de Sel cryslal wi$ th€ crystals which were grown in lhe spacc. Illey inveniSaled dlat th€ir crystallizaiion process allow eith€r two or thr€e dimensional crystal 8rcwlh ftom aqueous solution .They also obseryed lhat $€re is no change in crystalline stuotru€ berwe€n €adh grown crystal and crlsra.l groslr in

39 chaFd {l

micmgravity. In this work th€y inv€ ed a new process of crystalliation by which, we can crysiallt! two or tbr€e diDensional crysials. They also studied the chanse in the crystallin€ strucbre by n€urron single crysial diftaction

ClaI! Don.dio €t cl (2011). Studied th€ coll€ction brine and sea salr (fl€ur de sel) and appli€d the gas chromatography mass specrom€try ( HS_SPME-6C_

MS) analysis in ord€r to find etem€nrs to link the salt production and ils ar€a

of production. During then work lh€y id€nritied 58 volatile cornpounds. Concentrdted sea warer and floadng crysr€ts of fleur de Sel wcr€ colected to b€ analyzed.

De Medeims Rocha €t ot.(2012) work€d at coastal solar salt works to urilize their corc€ntrated bittem. In BEzil they obs€ryed rhe natural crystallization of Fleur de Sel with th€ brine thar was rich with otheF salrr. nl€y frfiher added that flower of salf is a thin layer that forms on the suface of the salt tide, during the continuous evaporation. Thc salt does not suffer any tllnsformarion, besides dle mtural drying in lhe sur\ which eliminar€s lhe ros€ tone.

40 Chapte r #2

Pibt Plam Study to lrd{ze Waite Brlne

Gen*eted By Seh Industrics Pilot Plant Study to Utiliz€ Waste Brine

Generatod By Salt Indust es

Sinc€ €arly 80s, p€ople ofPakistan have been enjoying good quriig of salt knoMr as refined salt. Mechanical salt washing is used in many countries to upgrade 'ttte salt qualiry. counter cun€nl washing at mulriple stages and dewa@ring by centrituge is iinprovd salt quality. During lhe process almost l0 to 15% of salt is conv€rted into satulted brine sotution containing hieh anount of sodium chloride, cacrum, magnesrum, potassium and sulphate. In rhe cunenr pmctice of most of the salt p.ocesse6, this wasre soturion h drained into fte draiMge systen. In rhis study, a method to urilize rhis wasle b{ine is develop€d. Brine wa3 treated with calcnm oxide ed ircn chloride ro rcmove som€ soluble snd insorubte impuities. The prepared brine is €vaporated in a sp€cially coisruct€d crystallizer JackeGd connecred wirh a hor water geys€r. Heaa is transferred brcugh botrom by counrer cunenr flow. The temperature $ nainrained b€tw€en 55 io 65 "C at pH 3-4. The apptied srudy yield tlle well shaped pymmidal cryshl of satt known as Flu€r de s€l (flower of s:lt). rhat ar€ world famous to used gourmer in foods and have a Srowrng markeL chrFe# 2

2.1 Introductior to eovirorm.[trt imDlct oflrtt

The inpact of high salinity on environmenr cspeciatty on living being and

m€tal is well known and many pap€rs have b€en publishcd on the sane

[34-36]. It is inporrsnt to make the ssh industry friendly ro th€ environm€nt, if the waste brine of salr industry b not utilized pfop€rly, it could have a very adverse effect on th€ environmenr. The high deffity wasl€ of salt industry should not come in rh€ conlact of exlemal boundary of salt indusrry to mininiz€ it efiect on neighboring land, on th€ sea side mangrove plants. The undergound swe€t water stream flow should also b€ laken into considemtion otherwis€ satt indus.r.y opcmtion could affect adversely on surrounding sw€er watq. Th€ discharge biltems will affect the marine life also. Msrine environrnents are atso very diverse. The o.ganisms rhat choose a palticutar home in rhe ocern ar€ adapt€d to suvival ther€. Changes in rhe narural factors, no natt€r how minor, can nave an €nonnous effect. Faclors such as sunlight, pH balance and srlinity challenge the suvival ofmarine life on a daily basis [37j.

To upgrade quality, salt mechanical salt washing is used in many countri€s. The coum€r cunent washing at differ€nt srages and dewarering by c€ntritug€ upgrades satr quatity fton94 - gg.4 o/o. ftE major inpudries of salt like calcium, magnesiun, potassium and sutphate arE sepqmted Gom sall in upgradation process. During this up gradation proc€3s t0 - l5yo of salt is converted into saturated solution by dissolvng rn warer and known ar "walte brine". AII the €x@ss brine dmins into sel'€|6ge by atmost r of salt processors and may cau.a harmful environDenbl effect on the livinc organisn and s€a life [17]. Chspted 2

The current siudy coveF rhe utilizarion of s6me waste bdne by c.nvening il into environmental friendly solution and make value added plduct for ulilization in food and indusrrial purpos€s [38]. Many applications ro utilizcd waste brine have been reponed by ditrerenr scientists [18-20].

P.epamtion of some value added producls like, KCI with doubl€ efiecr vacuum evaporation, bromin€ exrraction by disriltation and production of MgClr.6HzO and MSSOa by mono €ffecr evapoEtor [20]. In rhe current

study we oonv€rted thb wasl€ brine into world fainous salt known as Fluer d€ Sel, which is famous for its laste and uniqu€ crystal $ructue [39].

Mechanical refining of sah for the upgradation wa! introduced in pakistln in (snow eirly 80s, whe.e consumer market starts to enjoy like,, inst€ad of gind€d" "dirty salt. Itis upgmdadon provides improved quali, of salt but the w'sle g€nerated csuse envircnmental pollution. Th€ qualily demand of industries ha! rtlracted rhe s.tt proc€ssers io inroduce the same type ofsalt for differcnt industries such as rextile, soap, *aler sofiening, chto.o atkali and hundreds of many olher applications. The walhing proc€ss not only improves the whiteness of salt but atso reduces the major and minor arnpuriry of salt, like calcium, magnesium, polassium, sulphat€ and bromide [22]. Unforrunarely inst€ad of modem t€chnique tike recrystallization for ftaking rhe sup€rjor quatity of salt tike pure Vacuum Dried, ih€ mechanical *ater washing for upgnding rhe satt is very common in Pakisran €specia y in Sindh and Balochistan regions due lo irs low processing cost. The prcs€nce of impuriries in sall haj s€rious economic and enviroftnenrai consequences 1231. Twenty rhr€e sak 4l proc€slors ar€ using nechanical refning prcc€ss and producing approximately 28000 lon / month tinished produor (Fie.007) [24].

Fis 007: GIS D.la fo. SlL Prodm ed Pl1'!$6 in Palisrs t24t

'fte \rrsie concentraa.d briDe sohnion can be used s a source of many us€tuI producls which can also b€ affer r€moving najor iinpuriri€s 'ililized but mfonsaldy it is dcposited back in o dr€ ,r! witllod utiliz4ioo I4G all. Thh pro.ess cau!€s ar osrnolic shock of the living organisms (ec$Fr.ms) in the s€r. The efftu€nr in the waslc is r he{vily concentrated brine solution. This dirchfged emucrlt hA! tlle potentiat io kilt organilms. Althoud lhe brine solution containhg ralural ingr€dieri of rh€ ,ea water which inay causes damag€ by unn.tur|l concentration to marine popularion n.lr oullel [7,37]. lt is inl|ort nr lo make thc aalt induslry fiieidy io environm.nt, b€caulc it muld havc very advers€ €tret or lh€ €nyimment. chalter# 2

The present snrdy is based on Ihe utilizstion of waste brine !o prol€ct main idea is to utilized nabml r€sourc* to ke€o the

t: Sslt Refioiry Procas

Raw salt is n-dnspon€d by Euck from the haflesting ar€a. The next stage is washing of salt wilh water in a conical lrnk by counter flow effect. Satural€d brine having a densily of23" B€ (Boum6), the overnow ofthis tank is puged ouiside. The salt after washed is pumped as a slurry to $e hydro-cyclones and then to dewstering conv€yoN which are follow€d by hydrc mills to nak€ the salt r€ady for the s€cond washing stage. The second stage is silnild to the first one wilh difler€nt washing brine which is cleiner than the previous brine. The last stage is the final dewat€ring by worm scroll 9?e centdtuge to hav€ a moisue contmt of mdimm 4.0% by weight [42,44]. Some processors furlher use Rolary Dryer for &ying tr€ pmdud up 0o 0.005% moistur€.

NaCl 98.99.4

Ca 0.07.0.2

Mg 0.01-0.05 so"' 0.2,4-0.7 Bi 0.0078-0.0095 K 0.0016-0.0010

T.bh l: Aveng. @nposition of Up!r!.Ld ir ett Pslislan

45 Chapteri 2

(9L') Nlcl 250.290

Ca 1.1,2.1 Mg 6l l.l soi' 4.]-t0.7 Bi 0.0.t{.t 0.t2{_%

T.bl. 2: Avdgc composirjon ol wast Bdn

2.3 Mrterill 8nd Methods

23.1 Collcctionof Senplc:

wast€ bdnc samples were collect€d ftom differ€nt salt processing units situated in Sindh and Balochis!0n provinces of Pakistan. The ws3te brine sa.rnples w€re collect€d from different salt Focessors and previously cl.rned snd dri€i plastic caxs were use to collected. Tlle collect€d bdne was imncdiately tusponed to lhe labontory for turther chenical analysis and brin€ treatnent The samples t{€r€ analyzed for lheir chenicrl

composition ofmajor sala impurities such a! calcium, magn€sium, sulphate

potassium and bromide 2.1,2 Pretreatnetrtof Brin€

Duing many pr€vious experim€nb, influence of dl€ concentration of

magnesium ions on the crystal shape was observed. It was noted $ar high

concentration may cause the formation of irr€gular pyramidal crystals and

sometimes only crusl formation is observed. Th€ some phenomenon was

obsered by S.Inoue ?r ai [38].

Finally for dle pr€treahenr of brin€, precipiration of megnsium as

rnagnesium hydroxide was perforned to eliminat€ or decrease the concentration ofmagnesium ion fiom wasle brine.

2J3. Rcnovd of Magtresiun The wast€ brin€ was laken in a 150 L cylindricat tank. The mounr of magnesium was calculated by analynng the brine votumetricdty. Calcium hydrcxid€ was added to wasre brine sroichiometricalty, unril ihe compt€te precipitrtion of magneium aj maSnesium hydroxide. It *as observ€d lhat some nount of cdcium sulphat€ also precipitate due to common ion eff€ct and limited solubility ofcalciun sulphate in brine t451. Reaction was perform€d with g€ntle stining, as vigorous stining may increase the s€tdin8 tim€ of magnesiun hydroxid€ [46j. Fenic chloride was utitiz€d as coagulanl to precipitate all insoluble impurities. Aft€r a'alyzing and io ensure complele removal of magn€sium from wasle brin€, six hours rilne was giv€n to solurion lo be s€ttled. All the impurities wer€ settled down into dle bofom and rhe clein and cl€ar bdne was transfened into arother clean tank. Th€ brine was analyzed for its chemical composit'on Clabte 3). It was observed ihat in rh€ absnca of magn€siu. The mncertration of chapre# 2

calcium is noticeably 106 L ofbrine was tiansfer for fudher crystaUization.

G.LT) N.cl 241 C. LJ5 M8 0.02 soi' 4.69 Bi 0.01-0.t 0.12.0.96

Trble 3r Conpqirion ofvdi. Bri& b.fore crysialtiztion

2.4 Crlrtallizrtion nerhod

During over prcviou! worlq we oherved rempemturc impact on ihe wetl

shap€ pyrtunidal crystals. The Meta stable zone for the nucleation and crystal gro\r'th was obs€rved b€rween 5H5 'C. It was not€d thar diEcr h€ating ftom bottom may cause the irregular crystal grorth, a! a result of unev€i ternpemnrr€ in th€ sane crystallizer d@ io rhe fo.nation of differ€nt crystallizaiion zones. A small scale pilot proj€ct is designed for the utilization ofwast€ brine.

For ihe crlstallizrtion of sodiurn chloride, 5x6 f€€t staii ess sleel (316L) jackeied crystallizer was designd which was attached with Seyser thowh pip€s and hot water were circulating for constanr heat transfer (Fig. 008). Was0e brine was filled in the open qT€ crysrali"lr and tempersture was maintained by circulating hor waler inside rh€ jacketed crystauizlr.

4E Tcmpentur€ aas rdjusLd by l[c sp)€cr flamc or codrolld flow of cir.ulding hoa w&r. Ilc obd€rvrtions lNt.c tat€o for th€ crtstalizdm of squar€ p}rmid.l crystals. Crptalliz€d plmnidd c1y*als \r€r€ coll€ct€d and aoab"rd for th.ir clcoical conpollition! Glbb a). Thc b.ine solu.ion l*t,3 also analyz€d dtmughotr rhe oe€rimcnr Fr€sh brine was f€d fron rh€ bottomcar|. ofcryltlliz.r ro mairrrin brin€ lev.l in cryg.llizer.

Totd ede. Aa ofqy$allialio *.lion 2,141^'

T.U. a: SufE AE (SFcificdir) ofct*JE

Fis ot:r E?.ci.lty D6ig".d ,..t ..d Cyr.ltid ffi frmi

49 2.sR.rult!.nd Db.o$lor

At tl|c $&ting poini, ihc level of ttiE ers 25 nm b tbc erysrliz€r ad tenFranlrE e"3 mtintlircd 4 58 "C. No .rysttb *@ obd.rv€d- Ae thc initisl suFr-etaur.lion wr"e obariD!4 fsw ttbdl nrlei w'ft oh€rv€d As a r$ult of gentle cv4onuion of {,.!cr and subs€qucd rcduoiioa of volumg morc nucl€i $att€d to gpn€raae abd demonltrtlcd 3 nm width of dl€ bds€ while ftw crystsls sant to thc botton of the systaliz€r' DurinS the crys.lizrtion prc.$, rh€ tcvel ofbri& h the cr]$6llia w!! m'inrrin'd b.tw€cn 23-25 mn CrS 009). Sampl€s of briDc tctc collcot€d dd btooidc' ntlph'& and an b,zed for crlciuq lDagHitit! pot lsiun' sodrum chloride conicnts.

!v wts' BdF Fis ooc: Wen she€d rymi.bl cryctlt f@rim

oC tim€ to coll€ot orysbls The iemp€ran[e wss mlintained d 60 bllt !t the drpl€t€d sliShtly but ,!d os r &!ult of fresb briD. additioo t mFatu€ mrye of 5t6O "C' during thc o$..in€nt it wte rnairitin€d in th€ 'holc

50 T€mp€mture was controll€d by maiftain lhc flow of circulation wat€r in jacketed wall ofcrystallizer or by adjusting the flane ofgeys.r. Formation of large numbeN oftiny nuclei was obs€rved as a result ofagitation during collection of crynals. Once the unstable crysralization zone wss crt]|req fie sysrem lost irs mela-sLable region. Agitation in any reason was oh,served as lhe formation of inegular morpholog/ of crystals. Crystals grow on the surface as invert square pyranidal shape. Brine cornposilion, ptl terdp€raturc and stalic environment were noted ds lhe key facro$ to co rolled crystallization. In general the pyranidal dystals can be crystallized by the bittem of salt indust e! but du€ to high level of irnpurities like nagrrsiun and sulphak which decreases the solubility of

€alcium in brine is the msin reason to formation of irregular norphology. The solubility ofcalciwn sulphat€ in brine incrEas€d with dle incr€ase of the sodium chloride concentration [8]. A few exp€rimenh werc also pcrformed to study th€ crystallzalion because due to high level of sulphat€ snd magn€sium nela-stable zone of cryst llization dislubs and as an imprcr crystallization of pyramid w€re discontinued or irrcgular inorphologics were obslrv€d in Figure 010. Some well shaped pyianidal crystals can be seen in Figure 0l I and Tabl€ 5 shows chemical analysis of pymmidal crystals. Figure 012 shows the scan electron microscop€ (SEM) vi€w ofa single plradidal crystal.

5l Fis 0l0: lnEguL'l qydal foEllliod @lr high @g6i@ @nr.d hir

Fig 0 | l: W.ll sh.Fd PlMidd C4Ards Cbrtt r* 2

rigu.012: sEM vis oflFdidd crystlk ofNlcl

TtU. 5. C!.hicrl composilio! ofPy@idal OFllls RBull R€!!lt R.ruli l%l sl s2 s3 98_l 97.6 97.t5

0.74 0,E5 0.915 0.24 0216 o2g N.D N.D N.D

0_053 0.048 0.0104

0.00E0 0.003E 0.0061

' N.D rot d.recr.d by rclmcEic mctbod of c@plq Dctic titdion Chlrttr* 2

2.6 X-R.y powtLr Dtft..dor (XRDI

C.yst llized pyr.midd crrrak w urvr.d or )(lD powd.r dimlc$ob. Th€ x-ray diftetiod Q(RD) pd.rn of pylnidd c.ylirts s.nple $Es obtaincd usin8 X-my ditr&torneta 6t 40 kV, 40 nlA !d sc5Ilniry ntc of t/ nin over . lEngc of 5 -?0 20. XRD pd€'tr coofuru th.t crrrrlize,l pyamids a.! sodi n c.hlodd€. Figur€ 013 rprffits )nD paaltl for sodiun c oridc

I

Fig Ol r: )(RD I&d of Qys.tti4d ptmih of NlCl

54 Chapter# 2

2.7 Corclu3ioD Tltis study develop€d a new mcthodolog/ to utilized selt industiat wa$e brine. This ensues st bl€ cryst llization of regul€r plramidat cryst ls of NaCl ftom walte brinc. ftemoval of magnesiun as nagnesium hydroxide was noid as a key fa.tor to avoid the hindrance of msgnesiun during oC crystallization process. The rcmpcrat[e mnges b€tw€en 55{0 and pH b€tween 3-4 is found to be lhe most suiiable for crystallization of rcgular pyramidal crystals fi-om wasre brine.

The crysiallizd py"nidal crysrals gave a new id€a !o conven wortl €ss and waste brine into a valu€ add€d product. Pyramidal crystals formed, has different propenies from lbos€ of cubic salt. Crowing intemarional market for pyramid salt, hav€ led to the manufactur€ ,ltd comm€rcial availabiliw ofdis salt in Pakisian.

55 Chapter #3

Laboratory scale study for the control crystallization of sodlum chlorlde pyramid crystals (Fleur de sel), prepared bysolar salt Lsborstory scale study for the cotrtrol crystlllizrtiotr of sodium chloride pyramid crystals (tr'leur de Sel). prepNred by solar salt

In lhis study, an acc€lerated method io crystallize well-formed pyramidal crystals of $h is achieved. Th€ square pyrarnidal crysbls of salt, Fleur d€ S.l salt arc known for their unique crystal structure and us€d in specialty gourmet

foods. The natursl crystallizltion conditioN include hot summet days on the

surface of ponds @ntaininS conc€ntraled s€a wat€r. The cunent study hss establish€d a control producdon ofpyramidal crysrals as an altemale to natuml crystallization which is only possible rn summei weathers.

Sdumted solutioD of salt Orine) is prcpared by dissolving sea salr in water. This brine is evaporared in an open crystallizer by gend€ evaporation wilh heating ftom bottom of the crystallizer. Temperature plays an impons role in formation ofpyarnidal crystals. lt wss nor€d thar meta-srable condition in brin€ for the nucleltion and ciysral growth is achieved betw€€n 55 lo 65oC lemp€mtire mnge. Brin€ purificarion was also applied for removal of sulphd€ and subs€quent crysrallization of udnlenupled pyramidal shaped crysrats. The study, when applied, nol only yield! the well defined shape of pymrnidal crystals but also produces high purity form of salt crystals in compeison wilh natu ally crystallized Fleur de S€1.

56 3.1 Introdoctior

Fleur de Sel (Flowe. of Salr) is th€ most common name of natura y cryslallized sea salt. The pyramidal shape of Fleur de Sel is differenr and unique in its strucbre lion orher sea salts. The narural cryst{llization of Fleur de Sel is repor&d at coast of Brittany (France) and Algarve region of ponueal

[8] wher€ it is cryslallized in ponds coniaining concentrar€d sea-warer.

Funhermore, the hollow pyramids self-cre6re, float md grow on rhe surface of pond in only hot weathers. A comparison of pyramidal salts crystaliz€d in

Eanh's natural atmospher€ and NaCl crysials grown by rh€ evapomtion of an aqueous sall solurion in micrcg.avity, has atso be€n repoftd [9]. Fleu de Sel has a unique morphoto$/, lower bulk densiry, targe surface alea,

hproved taste ard rapid dissolutior as compared to th€ colnmon cubic salt.

Other types of salts with low bulk densiry can be found in Japan and are conmonly known as flaky salt [10]. The micro m€ter size pyrsmid's gro\r1h has been observed by nany scientist! in their ditrerent exp€riments Il I, t2].

3,2 Experimental 3.2.1 Prepsratiotr of brine

Selected sea sah which was high in cslcium and low in magnesium content was rak€n !o prepare the brirle solution. lt was obsefl€d thal lhe high corcentration of magnesiun shitu thc $tuntion point of sodium cnoride in brine [47]. The brine was pr€parcd in a smslt tank at room temp€ntue and four hours contact rirhe was given wirh vieorous stining to increase catcium chlDrr f 3

sulphate conccnFarion. Aluminum sulphate was us€d as co€gulant rgent (pH 3.6) and all th€ insoluble inpuriti€s wlre precipirated i. ihe rcn two hours. The brine treatnent wa! perforned to elininal€ sulphate as b€riwn $dphate

[45].Qualitative tests were performed to check the pres.nc€ of bsriun and sulphate ion! in th€ brine solution [a8l. Seded bine lolution *ts furher fiLered through vacuum filtration with 20 Im paper to ehsure lhe removal of

susp€nded solid. The resulrs ofth€ brine anslysis ar€ Siven in Table 6, Bl.

3.3 Cryslllli4lion Mcthod

For the crysrrllization ofsodium chloride, a I0 x t0 inch stainlcss sleel (316L) open squar€ crystallizer was heated fion the bottom on s hol plate. Five lileB ofprepar€d bride wcre allow€d to evapomt€ at ditrcrcnt t€mperatur€s from 50 lo 90oC without stining. Th€ observarions were uken for the clystaltization of squ8re pyramidrl crysrals. Crysrajtiz€d plmmidil cryst ls were c! ectd twic€ and analyz€d for th€ir chemicd crmpositions. The bdn€ solution was also analyz€d at tlle time ofit! supeFsaifation and at the end ofthe experinent. 3.4 Scmdng Electmr micrGropy.

Electron nicrograph of crystal was obtained using a scaming elecrion micro scope (JSM-7800F Thermal Field Enission Scanning Eleceon Microscope) operaling at lokv. The pramidal crysral *?s mounred on a metal stub with doublc sided adhesive tape and coatd under vacuun with gold in an argon atrnosphere prior to observation.

5E Table 6 Analysis of rah solution (brin€) prcpar€d by s€a s5lt.

Chenical R€sult Result Result El€menrs Bl 92 83 (mdLnpm)

Sodium 305000 315000 30700{) chloride Sulph.t ' .ND .ND *ND Calciun 1t95 2054 3632 !,la€ne3ium 447 546 684 zx 478 592 Bromid€ 68 62

T.ble 7 Analysis ofpyramidal cryst ls of3alt Ch.micrl Itesult R€sul! Icsult Elem€ni! sl s2 sl (%)

Sodium 99.07 99.1 96.95 Chloride Sulphate' +ND +ND 0.975 Calcium 0.105 0.144 0.264 Magncsiun 0.032 0.052 0.156 Potr$ium 0.0158 0.0094 0.0104 Bromide 0.0080 0.0038 0.0064 .Not deEcted in 200 ppm qualitative t€st

59 35 Relult! aod Dnculsion

At the sl&ting poid, the volume of brin€ was 5L in dle crystallizer end temp€r.tue was mainiain€d ar 64'C. No crystals were observed initially for three hous and as thc initial super-satumtion was oblain€d, few small nucl€i were observ€d. As a result ofthe g€nle evaporation ofwater and subsequent rcduction ofvolume, nore nuclei startrd to genera!€ and demonstaten 3 mn width of the base while few crystals srnk to th€ botlom of the cryst llizer. During the 4 hours ofthe crystallizarion process, th€ volume ofthe crystsllizer was reduc€d to 0.61L. A ssmpl€ of 9mL was colleoled and analyz€d for calciun, masnesium, polassium, bromide, sulphale and sodiu chloride cont€nt. Th€ results obrained ar€ present€d in Table 7, 82.

During the regular pyrsmid crystallizrtion, volume of brine was reduced up to

4.38L. Initially, a few needles like crystals were also oberved wilh the small neur de Sel crystals (Fis 014).

At th€ volume level of4.26l, t€mperau€ was depleted slighdy but still it was mainbin€d at 600C. ViSorous stirrinS of the brine r€sulted in the noating crysrals being setded do*n. The saln€ crystals were then collected for analysis. The r€sults of the collected pyramidal cryslats are presenkd in Table 2, Sl.

Formstion of large number of tiny nuclei was obseraed as a rcsult of agitrtion. Orce ihe utstable crystalli"rrion zone q,as cr€ate4 th€ system losa ia neta- stlble region (Fis 0l 5).

60 Clt4i.r d 3

FE 014: N.€dle lik€ crr|id with lynEidrl cry$b.

rt 0l5: SDdl truchi ftrmdid bcforc ltrriDg 6. crur.

6l Ch4.ti 3

As the meta-stable region slrrts to re-€stablish the tiny nuclei, a large nunb€rs of thes€ nuclei were obs€rved to sink down and less€r numb€6 of nuclei app€arcd to stay on the surface and grow At rhe volume of4.l3l atrd over the penod of 20 minu&s, approxinately 80% of lhe nuclei had senled ar the bottom and well-formed pyramidal crys&ls commenced to gen€rste. The results ofthe pyrainidal crysrals are presented in Table 7 6 result SL

The newly appeared nuclei continued to forin inro perfect squarc baled

p)T anidal cryshls. The majority ofcrysial forinations had beler siz€d up to I0

Inn of on€ lide width ofirs base. A conparatively b€tter mera-stable zone was

obs€Ned with temperatures mainrained at 60oC. In such temp€ratures, crysuls

grew in la€e sizes and lesser numb€r of nuclei was forned. A very stabte

crystal formation and size Sain wer€ observed for rhe next 3 hours, the (Fig 016) shows the crtstallizrtion ofpymrnid crystals al 60oC on the surface ofthe bdne solution. It was obsrved that $e cotlected pyrarnidal crystats w€r€ very fiagite

Once ir was establish€d that rhe fonnarion ofcrystats was effecrive ar 600C, the t€mperature was then lowered to ch€ck irs effecls on the fomation ofcrystah. All lhe crysiallized and settl€d salt was extmcied ftom th€ bottom while the temp€Iairr€ was gradually lowercd and fmally mainrained ar 50oC. The agitalion dudng the extraciion of sah disnr$ed the netr-stsbl€ condition again and as a result, large nunbers ofnuclei gen€rated ard app€ared in form! of clusten. lt was again noted lhar in casc ofturbulence in the brine system, mer2- slability was lost. At 50"C, comparsrively slow crystallizerion was

62 CbaPler * 3

Before increasing the t€mpemtur€ up to 70oC for further sludy' the cryssllization was again monitored at 60oC and nonnal formalion ofptdmidal crystals were observ€d and hereby re-confirmed. Before the crystalliution at ?00C, all the crystalliz€d pvamidal crystals produc€d at 60"C temperature were collected. The volume of brine in the crystalli.zer was noted as 2.9L and ih€ temperature was accel€ra1ed and nainEined at 70"C. However, lhe brhe took 20 minules to reach the tenperatur€ of 70'C. Initially, a small sized nucleation was se€n to s€ttle doln and as well as merge togelher. A few uns€ttled plrsmidal crysials shn€d lo grow in size on the surfac€. Th€ width ofth€ p)'ranid's base measur€d up to 4mn, however, the nunber of tiny plmlnidal cryslals wilh I to 2mm wide

bases were compadively more in number.

DurinS a firther exp€rimentation with the tempemture, the brine was acc€leEted dd moniiored at 80t. The crysi.als merged logether and

individual pyramidal formalion was rarcly obseNed (Fie 017). As soon as the tempemture of the brine wss increas€d tuiher to reach 90'C, inegular p)ramidal crystals that merged with €ach other and formed a crust rapidly sank into the botlom of the crystallizer. A rapid formation of the small nuclei was oherved which merged togerher witlin minures ar this tempemtur€ rog€ther with a few crystals formations of pyramidal crystals which also merged wirh each other to form a crust.

6.1 ch$(' | 3

fE 0f6: Itetr.lt ble natc ofcryltrllizrtioo.

Ft Ol7 : Crud fomji@ d hiel alopcrdu! rEgi@ $ov. S0T-

64 and the obsewation of crystal The sam€ brine was allowed to cool off of 65 to 55"c Generally' formation was taken again between the Fmperatur€s crystals was observed at the formation of the stabl€ ud accelerated Plmrnidal agitarion The results of the lhe tenperature regioDs of 55 to 65"C without given Table 6' B3 and the resuli! of brine at the end ofthe exp€riinent arc in Table 7' 52 With the sulphare- the harvesred pyramidal salr are pres€nled in nakes hopper cube and comained brine. other llpe' of morphologv like pvramidal crystals The calcium deform€d crysBls also crvstallized with the the caus€s for improper pvrdnid sulphale precipitalion was nored as one of brine it ensures the crysBlli,ation When we crlsBlliz€ sah with sulphare-fi€e sah' natural complianc€ of salt with codex staodard of food srade Pvramidal meets lhis criteria [26] The crystals (Fleur de Sel) howev€r' occasionallv it BJ The concentration of resulls ofthe narural pvramidal are git€n in Table-? mav vatv but calcium rich brine ditrerent parameters in brine for crvs!'tlization solubilitv of calcium was preferred for an improved crystslli?adon The the sodium chloride sulphate in brine increased witb th€ increa* of brine caused the formation of concentration t4gl The presence of sulphate in to be ideal fo' w€ll- calcium sulphate to ris€ A range pH 3 lo 4 was noted FigolS shows formed and geometrical shaped pvramidal crystals fotmation ofthe brine' the well-forn€d single crystal floating on the surfd

0l9 shows a few large The pyramidal crysrals growing in different sizes, Fig ofcry$al's base' sized pylamidal crystals wilh up to 24mm width

65 Ft 018: W€ll-fod.d liDglc.rysial fodiDg d thc al!fte ofhriDc.

f: af9: Fcw lat8. ri,od pFmidrl .rylrrls

6 The t€mp€ratue of brine ai 50oC d€monstrated slow goirth of pyanidal crystals. For the b€st crysiallization results, temp€raore of brine should be maintained between 55 to 65"C. At high tenp€rature regions abov€ 70 to 90'c, the formation of large numb€rs of nucl€i rumed into crust. It was also noted that ai high tenperature regions snd due to boiling efTecl, f4t changes in th€ concentmtion of dilTerent layers of brine lost ils m€ta-stable condition which was ne€ded for py.srnidal crystallization. A producrion rate was cslculated at differ€nt &nperature range Fig 20 shows the mte of production p€r square meter per hour. Production rate were noted at 50, 55 snd 6M and lhe increasing rate of production of well- shap€ pymmidrl crystal wilhin the range of oeta $able mne also gives ihe €vidence of temp€mtue efrect not oDly crystal shap€ but crystal groMh loo. Fi8 2l shows scanning €lecton scanninS electron micrograph of crystallized pymmidal crysial fiom brine solution. It is clear fiom the fisurE that crystl is pyrunidal in sltape. Fig 22 shows a close view of pymidal norphology where we observed blocks at every comer of square pyrarnidal crystal that suppon this crystal to grow in form of inven plmnid on lhe sudace of brine solution , Fi8 23 shows the close view of th€ side wall ofthis pyrmid.l cryslrl.

Fig 24 shows natural Fleur de Se I al Acquisition Paraneter ,Instrum€nt : 6380(LA),Acc. Voltage : 20.0 kv,Prob€ Curent: 1.00000 nA,PHA node : T3.Real Time : 35.26 sec Live Time | 30.00 sec ,Dead Time

14 %,Counting Rater 2874 cps,Energy Range | 0 - 20 kev. Fic 25 show Acquisition Ptrmeier ,lNtrument | 6380(LA) Acc. Volias€ | 20.0 kv.Pobe cure : 1.00000 nA,PHA Dode : Tl,Rcal Time :4302 ec.Liv€ Tim€ :

3o.oo sec,Dead Tim. : 32 o/o,couning Rat r 7434 cps,En tgy R@ge : 0 ' 20 kev

67 6da ..''

vro

Produdion|3^qh h

Fig2or l)roduction rate aI diffcrcnl lcmpcralDre orsalt Fis 2l: S@ .tcclron mi6o$oPic view of pv@idd crFd

I,lenl pynnid'l crts tlrt Pl'y' vit'l rcle ln Supporliog block d lbe coE.r of 'l

69 @ncn rid ol|lh Eorphoh6'.

nr : Zi A cb.. vLi dr.l ..rrrrdir d pynii.bt cry.r

6,*rn6

lm t00 46

rtz: f,DS rtiult for mtur.l Wr|mldrl .ryit* m Fig25: Em r..uX for pyr.midrl cryi.L prcp|rcd by rot'r.rtt

3.5 Corclullor

nte m€thod ddelop.d throueh this study €n$lrts acc€lenr.d ,rd srabte cryrrilli';on ofr€gular p)mbid.l cry$sls ofsalt *ith prop€r conrrol.

The lemp€r.tu€ mnges between 55 ro 65"C and pH of 3 to 4 is found b b€ most suibble fo. crystrllizdion of.!gDl8 pymmidal cry$ats. Elimin tion of sulphate ions tom brin d€clss€s th€ cryirrlli-.rior of diflercnt tyF's sslt ad their moQholos/ e.g. flak€s, hopper-cub€s ard other in€gulr crysr.ts. The nedlod dso inprcves the purity of sodium chtorid€ plnnid.t cryst ls in c,onpliaff€ wilh codex standld offood grsde s.lr

1l Chapt.I # 3

3.7 Study rnd observation with Sea Salt brine for 100 hours Temperature range between 55 to 65.C. To achi€ve the target and undedanding the phenomena of pyranid dystallization dificrent expedment lwe been monitored, observed snd performed. To establish a continuous p|ocess of crystallization an e4,eriment for t00 hours wa3 perforned. A 30 licr of brine wa! prepared for rhe same purpos€ and analyzed for the major ions calcium , magnesrum, potassium, sutphale ,bromine and NaCl €onrent. After each four hous stunple ',Jas tak€n iom the crysblti"jrion pan qnd analyzld for the all above parameler mentioned. fie crysra ization behavior wes also monitored to undersrard $€ cryst llization behavior and factor for plranidal crystals fonnarion. h was nor poslibt€ ro precisely coll€ct the salt ftom the same r€gior by whom brine sampie was taken so small crystallizer was considered as a syslem and the small size of crystallization pan were used to ninimize this error. The frEsh brine has b€en adding jusr aier colt€crion of crystaltiz€d salt from brine ro mainiain fie crystallizer level up 10 25 nm. The c.ysralliz€d satt which was lhe ftixture ofpyr&ridat cryslal and others morpholo$/ ofsalt werc also examined and invesrigaled to find tle relstionship betw€en nother liquor and crystallized salt_ tn most cases th€ process of crystallizarion was slow, and the fmal mother liquor was in contact with ! sufficienrly large crysial suface, as the evapomtion was involved, the solvent .emoval was taken into account in examination of the crvstalized

72 When w€ k€€p brine for crysbllialion brine start to obtain its super san'|lation on herring initially, due to gende h€aring it lsk6 few minl'€s or s€veral hou$ dep€nding on the size of vess€l to be utilized. The oc temr'€mture was maintlined b€twe€n 55 lo 65 and a meta stable mndition &ring this €xp€rin€nt wa! observed at 60"C . During expedment the t€mpen urc werc kept above 60oC but due !o addition ofbrin€ temperatue some tim€ went down up to 550C.

3.t Itrdividrrl Psr.meter ofbriDer

3.8.1 Crlciun h brioef

If we discuss individual parameter of brine b€fore comparing the crystaliz€d product with its norher brine composition so we obEerv€d tbat calcium level initially increas€d ti[ aO hours and went down dujng no( 20 hours and lh€ diff€renc€ in concenhtion of cilcium cont€nt in brine was observed wid| the difference of0.27 g/1. The maximrm lcvel was noted as 2.2044 g/L and the lowesl was observed as l-17 glL. The concedFation of calciun ;n brine was based on many faclors as the increase of temp€ratur€ the solubility of calcium decr€as€ and its precipitate after forming calcium sulpharel2s] .

73 cbp|!.{ 3

Brine Glclum g/

2 s I I i - _ _r c.bd/t

020 10 6a ttih ls 1. Fig 026: r00 !orr, .L.w.llou ftr cddrD Lvd lr brh. r& 3.u ltftgldlotr ir hrhf' Thc prcs€m. of othd inpudtics like e.go€siun rad potas8fua ebo inpsa m lh. cooc€trrtio ofcslciun ad .B a radt , soldility rLoliD obdcrv€d Th. .ffect of NsCl loncdnt ati@ iE brlrc oo tl| calciulr $|hbc c@dio i! also llFctrd.t 6tl SrhcM|3|s||nts/l 13

t- tos

OI

Ftcft-r. n|l. a-trnnE r.dd r.v.t h hi..n

71 Chapter # 3

Magnesium has tendency to keep retain in brine and it is vafy with the

tenFranlre [58] fte naxirnum level of nagnesiun hrs b€€n obGerv€d

dudng thc expqimenr wa! l.5ll g&, however the asc€nding and dB.ending behavior of magn€sium wer. slso obserycd and v.riarion in bsgn€siu,rn corc€ntatior were noted &om 0.729 g/L to l.6l I gil. nc initial level ofmagnesium was noted as 0.92 gI and it wa, obscrved that it's varyiry dudng crystallizarion.

3.83 Poa.rsiun h briD.!

Brine Potassium ppm

i rooo E i 3ooo I 2ooo

rt 028: 100 lou obr.draio. for pohlriun la.l h bnla r& fuomdous behavior ofpota*iwn w,3 ob6e{ved in brine, incrssing decre$ing and somc rime con$rnt level was nored during crystallizarion. ctqt a #,

3.&4 $lpbt h bri!.F

Brhe Srlphete &/l

Es l!

Drdog eb ogai*ot tt! c@cduuio of etbh& x,q! nocd bf,wst 4.77 L to 6-7t gn- F,/ ft. iritial hvel of ,&tre ia f€.d bdB v/.3 4.88 g/l so crqy additia fu n Lalp hi!. lo fidt.tr cry.&llizdo !o k€ap thr paoce6 codh&tr3 wa, @ oftta ca|rlc ftr arcanditrg a[d d.sc€odiog bdrvior of rulpbdE howve. .rh@ of DlgGiuo Sulphll€ in biin fuiog cryrtaliiutioq w.s ,!o{t€. r€solr ftr tbs! Ct{FE# 3

3.8'5 EroDtrc i. brh.!-

8dn€ pt||l r Brqnha

:30 t."

!50

It@B lr l.|'.;l..rd.a n b.a-|.tdh.rh. no Ov.r6I Lvel-oJ bn@iD. wr! ob..rv!d bctuD.o 80 to I20 ptr'lr In brine dlliDg qyltsliz.dm Fiod-

3.a.6sdL. Cl|ori&L brl|.F

Brhe ed dt

020la603o16DO rb.h ts n!03r; roori''|t|;n .rydo tui.ai ba b a;sL-

n chaptd # 3

Sodium chloride in brine was atso obsewcd in a particutff range and lhe solubility of sodiun cl orid€ was fluctuatinS wirh the tevet of others par&n€ter in brine. Highesl levet of conrena in brin€ wss not€d a! 324 {L.

3.9 Four Hoort Obs.rvadoolr

3.9.1. At 4 ioursr Brine bok few hours ro obtain supersatumtion and p.ocess of crysra ization was $arted and rhe tempemrre of brine was marntahed al 64'C. Initia y very snall size cry$8rs up to lnm were obscrvcd and fte incr€asing lrend for the tevel ofimpurities like c.tcium, rnagnesium, sulphate ,nd potassiurn were obs€rved. The bromine and sodiun chloride content of brine we.c not€d slighlty tow as compare to initial brine fed. T},e l€vel of catcirrr 0.22%, magnejum 0.09.2, snlphate 0.77o/o, poralsium 327 ppm and NaCl conrent was noted as 97.4% io the crysialtized produ4. 3.9.2. At 8 ho'rrsr The graduai improvemenr in account ofcrysrals size was ooserved and growinS crystals sized w€re nored up Lo 3 lnm in the side length ofits base, however a mix size among crysBrs werc observed. At this momenq ahe laken sample of brine showed decressing rrend of caicium, magnesium and suphate. The one of the rcason of rhis decrcasing rr€nd inay addirion of Fesh brine to make up th€ volume of crystallizition pan. The calcium and magnesrum m crystallized pyamidal crystals wer€ compararivety hidt , 0.6250/0 and O.1tq/6 respectively and A€ d€cre€sing rend fo. $tphate and NaCl content was obs€rve.[Table 20]. A stighrly ircrease in lhe amount ofporassium and bromine crystaltized in salr were also noted es few ppm.

J8 oftheir square bas€. The rEnge of calciun in brine was b€rween 1,6 s/L l,o 1.75 g/L, magnesiuin 0.85 g/L ro 0.91 gil, sutphat€, 4.88 g/L to 5.55e/I-, porassiurn in rhe decr€asing rend up to 200 ppm was not€d. The level of bromine in brine wrs nored with rhe ditrerenc€ of8 ppm and Sodium chlorid€ cot]Ltenr 292 gL to 329 g/L werc noted. Th€ impurities level in salt were noted as catcium 0.2 to 0.25%, magnesium 0.03 to 0.08%, sulphate 0.78 ro 0.92%, porassium 254 ro 327 ppm and bromineobserved 66.7 ppm ro 83.9 ppn . Beautitul square pylanid was crystallizing during 19 to 32 hour and meta stabl€ zone was establish€d, l€ss€r number ofnuclei wer€ forming and growing .

3.9.6. At 36 houn: The obsenud rrcnd of rhe size decrease wilh lhe chang€ of magnesium concentradon in brine al ihis stage solubility of calcium was observed in decreasing nanner and the sutphate in increasing mann€r Some snal size crystats of pymmidai shap€ strned to crystallize wirh rhe lege pyramidal crystals. Decreasing r€nd for

magn€siuln and bromine were observed.tTable 201

3.9.7. At 40 hours: Dmstic change in magnesium content m brine was obsered as ir decrcases from 1.47gl ro 0.S6gn, sutphare conlent was noted as very $able and calcium has rcached its sotubiliry up to 2.2 gr_. At this stage crysbllizarion of sorne lolid eatc of irregular shape NaCl crysials were formed with larger size pyramidal crystab.

3.9.8. At 44 hours: Decreajng catcium level and increasing magnesium and sulphate werc nored increasing trend h poiassium and bromine conc€ntranon wer€ also obs€Ned. NaCl conlenl in brine was2g6 elL ^ 80 3.9.10. At 52 HouB: The impact of high volum€ of fiesh brine wss not€d and resulted as discontinuation of normal in€gular salt, only pymmidal crysLls had bccn seen on th€ surface of brine duc io sudden temp€ralrrc differ€nce which was the consequenc€ of fr€sh addition,

lesser nuclei app€ared on the surface and grew .The tempenture has oC been decrease to 50 at this stage only smal pyramidal crysrals were

observed having bas€ size on th€ir length b€tween 2 to 4 nm. Constant

level of magnesiuin in brine obsened and decreasing lev€t of sulphar€ and calciurtr w€re not€d and significsnt chang€d row?rd low€r conc€niration was rnonitored for pohssium lhat was t0j4 ppn . A coinparatively low smoutu of calcium ,magnesium and sutphare were obs€rv€d during rhe analysh of pyramid crystals. It is nored that snall pyranids observed l€ss c]rntent ofimpuriries duing the exp€rifienr.

3,9.11. At 56 hou.s: A tiltle impfovement in size in r€rm ofparricle size distdbution was roted and rctalively targer bas€ crystats inore crysblized during 56 hours. A collsranr b€havior of magn€sirun was observed and level incrcasing trend for sutphate, potassiun and bromine and decre$ing l€vel of calciun in brine were nored. A lesser tevet, just 0.096% of calcium was noted. Sutphate l€vel of smalt crystals was also noted lesser in compadson with targer cry$51s.[Table 2 I ]

3.9.12. B€tweer 60 ro 64 tours: decreusing A panem for $tphat€ , magnesium and specially catcium was nored and significanr chang€ in potassiun level was noted which was at increasing side .The pora$ium cort€nt jumped froln 1236 ppm lo 2980 ppm durina 56 ro 64 hours in

E2 chlper# 3

at lhe same time few big crystals having base size up to 6 tnm also ob€en€d. Fable 2ll

3.9,17. Betweer 84 to 96 hours: During this period control production of moderde size pysmidal crystals ob€€rved and dle cryshllzarion syslem was h m€ta siablc zone snd a lirle voiation in bdft D6rsmet€rs ob€rved. lTabl€ 2l]

3.9.18. At l0O houn: At t00 hours we disconrinued heating system and only allow€d the crystals to grew, which were floating on thc surfrce of brine. W. gave then rim€ for lcw hous and they wer€ continualy and slowly gowing on the suface of bnne. Som€ big crysral up to 12 rnm *e5 also collectld at thb stage.

85 Chapte r #4

Study and obs€Jvatlon wlth Lake Salt brine At pH G 7

Temperaturc Jange betw€€n 55 to 65 'C, Study atrd observatiotr with Lake Salt brine at pH 6- ?

temperature range between 55 to 65 "C.

4.1Bdne Preparntion:-

Brine was prcpared in small tank and four houN coniact time was give with vigorous slining at room lemperaturc. Salt was collecred Fom the Iake direcrly and was anallzed for their chemical composition IAnx 2l . lnsoluble impuriries were s€[led down with rhe help of alum sulphar€ lhat was used as coaSulant ageni The brine was allowed to setle for the next few hous and crysral cleff solution w's transfen€d into another tank for storage. Brine was analyzed for the major ioff calcium , magnesium, porassium, sutphate ,bromine and sodiun chloride content[47.]31. Aner every twelve hours crystalljzation , a sample was taken from the crysl,lizer and anallzed for rh€ alt above mendoned

4.2, Crystclliz.tiotr The crystallizarion behavior was also monitored io understand the faciors involve in formation ofpyEmidat crysals. tt was not possible ,o precisely collecl the salt from rhe same region by whom brine sampl€ was taken pan so was consider as a sysrem and the smalt size of sta'nless steel crystallizer were used ro mininize ihis enor. Ihe fresh brin€ had be€n fe€ding !o maintained rh€ crysratlize volume and the crystallized salt has b€en co ected b anatyzed rheir chemicat compos,tion. Th€ lev€t of brine wa mainlained up 10 2j mm rhroughout

86 the experiment. The crys.alliz€d salt which was a mixture of pyrainidal crystals and ofters typ€s of morphologies of sal! were also examined and investigate to find the relation between moiher liquor and crystallized $h. In most cases the prccess of crysrallization was slow. and the fnal mother liquor was in contacl wirh a sufiiciemly larg€ cryslals surfAce, 3s evapomtion was involved, the solvent removal was laken into account for examination ofthe crystallized product.

Brine was allowed to crystallize and observarion was hken for the cryslallizadon of pyrami&l cryshls of sodium chloride. At rhe sbrting point no crystallization obseNed as with the ihcrease of temperature super saturaion poitu is shift€d due to presence of impurities l I 8l_ As a result of few hou6 gentle evapoBtion and subsequent reduclion of volume, a few neculi starled to genemre on rhe surface ofbrine. at this moment the lemperature as maintained at 55'C innialy[s0j.

BrineCalcium g/L

Fi8 036r 12 hou y ob$n.don lor ..hiun tevet iI bri.e g/L

87 Cha?m # 4

The corc€ntration of calcium was observ€d in increasing rend thh may be due to reduction of volume for g€uing superstation poinr ofthe brine. Inilial

concentration ofcalcium in bnne wa! t.3777 g/L and m i,crcasing rend up to

1.7034 s/L was nored. Calcium chlo de has tend€ncy to rcrain in brine bul rhe calcium sulpha.e solubility is conpararively low in waler as well as jn brine[5t]. As the calcium sulphate conc€ntrarion in brine is rhe fMction of temperaure [45] eithe. this variation in the concenhtion ofcatcium contenl in

bnne may due to lemperalure effect or precipiralion of calcium sulphate.

Anothe. major .e"son is fresh addirion of bnne which has €ffecr on rhe concentmrion of brine. The maximum level was nored as L70 8r_ and lhe lowest was observed as 1.077 e/L. The concentrarion ofcalcium in brin€ is based on many factors as incrcase lhe of temperaturc rh€ solubiliry of calcium decrease and ils precipitate by forming calciun sulphate. The presence of others impuritjes like magnesrum polassium and also impacr on the concentmtion of calciun and resulFd as solubility decrease. The effect ofNacl concenlrarion in tbe brine on the calcium sulphate concenr?tion h atso report€dlstj.

Brine Magnesium g/L

2A 23 3A rS 4a (87: Fig 12 hurly ob.n io. for rlgr6ioE ld.t in b,ir. g/L

88 Magnesiun has tendency ro ke€p rclain in brine and its vary with th€ temp€rature [5]1. The naximum concentradon level of magnesium hs

been obsened durinS fie experimeni noted as 5.624 g/L, however the

as.ending and desc€ndin8 behavior of nagnesium was aho observed

and rhe level ofmagnesium nored from 3.13g/L 10 5.624 g/L . Tbe initial level of magnesium was no!€d as 3.l3 g/L and ir was obs€rved rhar it was varying during crystallialion. Duing rhis particular exp€riment the

maSnesium conte of brine was nored as very high as cohpare lo s€a salt and a very high varislion of soluble €ontent of magnesium was

Brine Potassium ppm

rig038l 12 hourly obsen.tion rorpolr.riun tevet ib britu ng/L

Tle initial level of porassiun in lhe brine was v€ry high, which was

noted as 4l l7 ppm , m upward rained and rhen downward tlained was monitored .For rhe forth obseBarion a gEdual increase was noted rhen a decline train€d was obsened. The lowest concentmtion was noted 6 3529 ppm, howeverrhe highesr one was 54 t5 ppm.

89 Anomalous behavior ofpotassium was observed in the brine, increasing decr€a$ng and some time consrant levet was nor€d during crysrali4rion.

Poiassium also crysbllize with rhe sall bu! in rhe larer srages mean with

the bittem it crysrallized and somedme form beds in satt lakest54l.

Brine Sulphate g/[

l^ 1s ,A )s 3A FiC 039: 12 houdy;bsrltton for eutpnat€ levet In brin. g/L

The initial lev€l ofsulphare in feed brine for crysralizjrion was 4.g8 s,{_ so every addition ro make up brine for furthe. crysta izarion for conlrnuous crysrallization process was the cause of a$ending and descending b€havior of sutphate, however retenrion of magnesium sulphale in brine durinS crysrallization was no&d another faci,or. The concentration of sulphaie was obs€rved belween S.0 I et L to 1 .t3 gtL. Th€ decrease trcnd may due to precipitstion of catcium sulphare anij Increas'ng u€ad due ro r€tentjon of sodiun and nagnesim sutphale in lhe bnne in$ead ofcrysrallizarion with satr. Brlne Bromine ppm

r^ u 2A rB :r,{ 3a a3 9a sa 6,1 6a 'ra rig |M)r 12 tody ob.d.dd lor qld.D hv.t i! b.h. ldr.

Ovemll level of bromine was obccrv€d betwen 34 ro 103 ppm in rhe brine dudng cryslallizrrioo proc€ss. Iniriatly an incrcasing rEnd wrs noted that had convert d ro in sudd€o decrqs€, it was observed tha! during the crystalliz.tion thc brorninc did noi r€tain in rhe brine and

Brine NaClg/L

lA lt 2a 2s 3A 38 aA a3 5A t3 6^ 63 rk 0a | : 12 hourly ob..ddor (or N.Ct ld.l h brh. ss/L

9l Sodiuin chloride in brine was also observed in a particular range and the solubility of sodiuftr chloride was fluctuating \,,/ith the level of oders

pardmet€r in brine. Hish€sl level of content in the bdne was noted as 310 gr-. It was observed that the concentration of sodium chloride

increase with incr€as of calcium contenl in brine solulionl47] as initial

calciuin lev€l inc6e th€ sodium chloride act in th€ saine way.

4.3.Twelve hourly obsenrtion for crystrlliz€ srlt

4,3.l.Ohervrtiotr lA: Due to gentle evaporation of rhe brine supersaturation was ob.ain€d in a ftw houi. Idtially very small size

plmmidal cryslals up to lmm were observ€d and lh€ incfeasing rrend for

th€ level of impurities like c6lciun, magn€sium, sulphate and potassium

were no&dlTable 231 .The bronine and sodium chloride content of brine werc noted sli8hdy low as compare ro initial brine fed. The analysis results of crystalliz€d small pymmidal crysr.als shows calcium 0. I 92%,

magnesium 0.048%, sulphate 0.61%, potassium 433 ppn and NaCt conlent noled as 96.3%.

4.3:.Ob!€rvr.ioD lB: Few sftsll in siz€ and lesser numb€r of the plramidal cryslals were obs€rved and cubical sah conraining few potassium 400 ppm and NaCl contenl not€d as 97.76%. A comparadvety high content of magnesium and sulphare were observed hopper cube were observed in the lareer numb€r.lTable 23]

The aalysis r€suhs ofcryslallized small pynmidal crjstats and hopper cub€ sall arc mentioned as calcim 0.248%, nagnesium 0.t?%, sulphale 0.70%, and n could be one of ihe reasons for improper, iFeeular and other types ofmorpholo$/ like hopp€r cubes as presence of

I nrgnesiun in brine has iendency ro crystallized hopp€r cubc norphology ofsalt[9].

Flg 042: Mn norp[otog, cry]t lizorio. vid tdh trke.rtr brin. 433-Oba.rv.tior 2,|: Co €coed sample was high in poralsium , magnesium and sulpate and gndual increase ofthis impurities resulted thc crysiallization ofinegular morpholo$'. Calcium @ncenFaron wa! u optimrun and a decr€as€ trained for magn.sium and sulphate in the brine was obsened which shows Ihat cat Ihis slagc crystallizarion of nagnesium sulphate cause hindmnce during crysralliarion. The crysklliz€d salt wss very hydroscopic in nature. A decreasing trend of bromine contein was observ€dlTable 231.

4.3.4.Observation 2Br R€sult obtained fiom the analysis of salt in which most of crystals w€re consist on $nall size and pytalnidal shap€, however f€w larger crystals up to 6 lllln in ihe leogth oftheir square base were also observcd. A comparatively less amount of iftDurities tl?! notedlTable 231. The anatysis rcsutts ofcrystaltized smalt pyramidat sstr

93 are noted as calcium 0.136%, nagnesium 0.116%, sutphate 0.458%, potassium 385 ppm and NaCl conlent noted as 9?.3t%. Decreasing

concenMtion of calcium and increasing amount of magnesium and

sulphat€ a.e obs€ned in brinelTable 221.

.l,3.5.Observation 3A: Very good siz€ and well shaped pyramjdal

cryslals w€re crystalliz€d up ro t0 mm. The range ofcalciun;n brine was between 1.6 dL ro 1.75 gn-, magnesium 0.85 dL to O.gt gL, sulphare, 4.88 g/L to 5.559/L, poarssium in th€ decr€asinA tend up to 200 ppm was noted.

43.6.Observatio'r 38: : Pyramidal crysrats were observ€d witt other tlpes of irregular and hopper cube morphotogy. Increasing levet of calcium in brine and decreasing concentralion of magnesium and sulphate wd obs€ded[Table 22]. A significant drcreas€ of magnesium

in the b.ine fron s.2jtgtL ro 4.225 g/l ce be observed. The

nagnesium conteni in the colected salr was obs€ned as 0.t93% and

calarum content was noled as 0. t44%.

43.7. Obsenstion 4A: Wirh lhe decreasing t€vet of magnesium

conlent in the sal! b€ner g€ometrical shaped ofpymmidal crystats were

observed bul other lypes ofmoQhology also noted. The decreasing levei

of calcium in brine and rhe increasing l€vet of mag.esium and sutphate were obsesed. The catcium conrent of brine was at fte minimum levet during entire experiment. A slight increase ofcalcium in salt is also noled lTable 2]1. 4.3.8. Observation 48: A different observatio. was noted in brine wherc calciun magnesiun , sulphate and broinide were noted in d€crea;ng trend simultaneously and resuh€d as mre plramidat crysrals

formalion ,most of $k was consisied on irregutar morphology. A drastic

chang€ ofcalcium and sulphac cont€nr in salr obseryed that may du€ to precipiation of calcium sulphaielTable 2Zl.

4.3.9.Obsenation 5A: A v€ry signiticanr decrease ofmagnesjum ad sulphate content were noted at this srage , maSnesium decreases form

5.244 elL ro 3 .724 gn- and sutphate is decr€as€d from 6.99 gtL to 5.g gtr. High conrent ofmagnesium sas obsened and nored as J.8420.

4.3.10.Obse dation 58: The effecr of decreasing concenrmtion of calcium and increasing concenration of magnesium in ahe brine and ;n lhe salt were nored .As incrcasinS contert of @lcium and dereasins conient of magnesium and sulphate corlenr. A mix mortholo&v obsered and pyramidal crystak were observed in variabt€ sizes up ro 2

4J.ll.Obseratior 64: An increasing trend of calcium and nagnesium and decreasing lrend of sutphate was obs€rved in brine. Small size of p'ftmi&t cryslals was observed.

95 43.12.Obc.rv.aiotr 6B! : An inplve size of cryri.ls w€rc notld havirg calciurn 0.237%, m.gn6ium 0.09170, sulphat€ 0.583%, poa.ssfum 76 ppor rnd NaCl coDt |or nobd .s 98.2%.

rir 043: lrrlt|tbr lorytoto5/ toc hk {tr b.i!e

96 Chapter #5

Study On fte S$rthedr Of Sodlun Clhlodd! { sd} Ptramld Cryltal 8y lhlrn.l Cryst.llhdlon Ot Rock S.lt Edne Crvstals b] Srudv otr th€ Synth€stu of Sodium Chloride lNrCl) Pyramidrl ' thermtl CrFtalliztrion of Rock SrltBrine

as miner€l Rock $h occur) on the eanh in form ofdry deposir' h is also lnowr halite. The bedded deposits ar€ true sedimentary rocks form€d from evaporation of large in land sea in the Cambrian and pre-Camb anperiods[55]' deposited in Rock sall is very important source of sall and there are appreciable

Pakistan as well as other pans of$e world. Brine prepared ftom rock sah is known to conlain as impurides calcium' io magnesium and sulfate ions[56]The chunk of rock salt were dissolve ro prepare brine solution and comPaBtivelv more dissolving lime sas Siven no doubr make brine soluiion as o$ers sah The qualily of rock salt ;n Palishn sak was folnd above best in lhe world t 551. Ite puritv of b€$ qualilv of rock 9.5% dld the levels of impurities are obcerved also very low The main r€3son mosl of lor longer dissolving iime lo g€t lh€ d€sire impurilid level in brine a5

the rock salt ha5 contained l€ss amount of impurities sp€cially magesiun' in As di$ussed above In comparison of sea and lak€ salt, rcck salt found magnesium irnpurities a Pakistan contain less amount of calcium and 'howevef few tlTr€s of rock salt were observed with very high level of sulphale impurities in differ€nt combination wifi calcium and sodium[5s] Seleded Rock salt qhich sas contained lesser anount of calcium md magnesium impurities .As it was observ€d that the hid conc€ntation of magnesium shifts prepared ln th€ saturation point of sodium chloride in brine [47] The bnne was wilh a srull tank at rcom lenperature and four hours conud rime was eiven viaorous sriring to increase calcium sulphate concentrstion lron chloride was used as coagulant aged (pH 3 6) and all the insoluble imPurides were

91 Chntter,5

treauned was precipitated in the next two hours. ln the rock salt cas€ no brin€ brine soluton performed to elirninate sulpha& as badum sulphate [45l Settled paper to ensue the was fufther fill€r€d tfuough vacuum filuation with 20 pm gnalvsis given in Table removal ofsuspended solid Th€ results ofthe brin€ ar€

8, Bl. 5.r Cryst'llization petd was used as For the crystallization an eight inches diamerer circular dish brine crystailizer heared from bonom through hot plal'e A 400mL ofprepar€d wilhout was allowed to €vaoomte al differ€nl temperatures ftom 50 to 90'C stirrins. The obs€rvations w€re taken for lhe crystalliation of squaE pyr3midal crysirls. Crystallized pvramidal crvstals were collect€d lwice and

analyz€d for their chemical compositions. The brine solution wa! also analvzed

ai the time of its super-salrllation and at the end of the experimenr'

5: Results .rd Dis.ussion

At th€ starrinS poid, the volune of brine was 400mL in the crystallizer and at temperatur€ was given through hol plat€. Th€ first observation was uk€n 56t. No cr,/stals wer€ observed initially for half an how and as the initial super-saoration was obtsined, few $nall nucl€i were obs€rv€d The first

observation was taken ar 56"C. (Fig 044).

98 Ft aa+ ldti.l cryfliraio oh.svrio d 569C

A! . rllult of thc SGdh cv4ordio of flLt &d $b6.qu.dl tldudin of rci6€, no€ r|rcLi ddlcd lo Sddc d .lffiacd 05 nE siddt T.opcd0nc ws alldtd to iEt rc d Dod ob..fivttio wt! mt d !t 583C

(Fig 045) srd a cl€ar lize g.ln rr!! mtcd.

It 0.16c FqDdid ofltnmidll Crydals .r 58lC

99 ch.!a..{ 5

A fe{ cryst8ls werc also obr.&€d ivftich joint€d with c} oth€r at lhe sane tine (Fig OAO. A f.w crysob grcw |4|o 6nm side witrh d l$b t oFrdll! of the b.rc d tb. t oFrdlrc of 5fC udile d ttc tis. of oising &nFrrtut an obg.rvltion wa! tst€n d 64'C $,tl.f! cnyltilr bving I nm sidc {,idlh obssved in lrrgc ounter-

Fl0a6: W.0 d+.d Fyonidd 6ynd! tuiuli[ 6at

It ers ob6.rv€d ltd c.rs.ls grow in h4!] riz. t c6!rd t At 6. 'r|Fdurc. sane temp€ralun nany of tiny lyranidal crrEtab wer€ oh.rved thltt npi{ y lunk douD ido lh. boriom of crtlt liz... Ttc dctr ob..reati@ st ?dC shows $!r d tli! oeaperdurc regc, I disord.n rrls Dot d id th! indivfttud growdr ofpyr"nidsl crftrls rod ney ofpynmi&l ory{.h $,!te obacrvcd to joid w h en o(b.r (Fis (X7& (X8).

t(I) qysds ofrock salt Fig 04?: OtEervation ofjointed Pvraoidd

t0l of rock salt at 70"C Fig 048: A close vi.w ofjointed pyranidd ciysiab

at 48"C To slow Tempersu€ wss slightly dcPl€led but still it wss maidahed r€sult of slow crysialization down rhc tcmPcratrrE, efrects w€re dpP'€rd as t (Fi8 049)' arf the slow rate ofsvsttllizslioh was obs€rv€d

102 Ci|Fd# 5

Fig 049: Oh.dv.ttd of rlo,N drtrllirrhd r EDFr|e 4SC

Dudog a tu6.r oqcdMlitim l,i& lh. t mp.'dn!, tu tiiD. ac.€le.aled rd nodtond d 80'C. Ttc crysld! n€rged togeth.r individrd D,y.rDidd forndioa w!3 rarcly ob!{|fv€d. (Fig 050,051).

Fis 050: Mag. ptirrnid.l crldlt! d tigLr tdPa!!rc .boe 8dc

103 higher remperaturc above 80oc Fig 05 I I M€rge plmmidal cryst'ls at

was increased further to reach 90'C' As soon as the temp€mture of the brine with each orher were observed lhat in€gular pyramidal crysrals that merged mP'd rhe bonom ofihe crvstallizer' A formed a cru$ rapidlv sank down ifto within obs€rved which merged together formation ofthe small nuclei wer€ also formations of a few p)ramidal minutes at tlus l€mperature togeiher with $ith each oLher' Within nexl l0 minLnes crysEls thal formed crusl by merged (Fig 052) has shi{ied in rhe form ofcrust all rtre formation ofpvmmidal cryslals

l04 90"C Fig 052 | Cru51 formalion at the t€mpemtur€ abov€ ofsalrsolution bv sea Table 8Analy.is Orine)prcpared 'sal' Chemical Result Result R€sult Elements Bl B2 83 (mgl=ppm)

Sodium 280000 317000 I17000 Chloride

Sulphate 1800 2800 4520 Calcium 420 520 850

Magnesium 160 280 500 245 947 1350

Bromide 92 68 62

105 TrbL 9 Analysis ofpyramidrl cryslrl3 ofsdt

Ch€mical Result Rcsult Result El€ments Sl 52 53 ('t) Sodium 280000 3I?000 317000 Chloridc sulphat ' 1800 2800 4520 Calcium 420 520 850 Magnesium 160 2aO 500 Polassium 245 947 1350 Bromidc

53 Corclursiotr:- for crystallialion of It is conclueded that rock salt was found suitable prEpared brine soluiion pyramidal crystals altl|ough a longer tifie is requir€d to in geometry The of ro.l salt. Formed pyr.mdal crysLls are well shap€d temPalatue of pyrmiadal cryaslrl form in acidic m€diurn and suilable crfstallziation is observed between 50 to 65"C'

r06 Chapter #6

CrYstal Role6 Of Div.lent Ar|d Trlvabnt lonr On Th. Pytamldd Fomatlon Of Sodlum (| oddt Role! ofDivllent And Trivolent lo[s on The Pvrsmidrl Cryshls Formrtior of Sodium Cbloride

Abstrrctl The innuence ofFe*r individuallv and wilh divalem calions such as ca", Mg-': , Ba" and monovalent K' is to studv as an example of impurities on lhe crystallization of sodium €hloride that has abilitv to change morphologv of NaCl crys.als and formation of pymmidal cryslals of sodiuft chloride Diflerent amounts of iron .s FeCl3.6H?O werc usen and a metastable zone for the crystallization of pyranidal crystals grc*1h for NaCl was crealed The crystal morphology wa control with the help of temp€rature and pH and a smooth and metaslable zone is noted.

6.1 lntroductiod: The nucleation, growth and moryhology of crystals can be significandv altercd

by the presence of low concentrations of inpuriiies These impurities may be leaction by-products or impurities present in the reactants or tbey may be

additives puQosely add€d 10 alter the cryslalliarion process [7]l Additiv€s can reduce crystal gowrh rale and alter morPhologv bv binding to

cryslal faces and int€rfering wilh propagation steps [74].

Thenml crystallization ftom solution is s very old leclmiqu€, sc;entists have been using same ftom rhe incent time, So far many papen has b€en published on the pyramidal crystals and observation wer€ raken for sodium chloride pyramid crystal formation[2] and some small size p]mmidal crystals are also observed durins etchins process ( formaldiyede)l3] A method is als

l0? cha$e. f 6 eslablished to crystallize plmmidal crystals with some olher morpholos/ ;n microgra\rily conditiont9l In our work we are irvestigating possible inpact ofdivalent and trivale ions

on the formalion of well shaped pyramidal crystals of sodium chloride. The rnethod of crystlllization is adopted ftom our previous work on acc€leEted c.ystallizfion of plmmid crystals. magnesium , calcium and barim chloride

were chosen divalem ions and lhe fenic chloride hexahydrale was urilized as

th€ source of trivalent ions. In rnay pr€vious work important role of ferdc lll

was discussed as an imponart and most €ffective catalyst for eslerfication of lons chain acid cstalyst t75l- In lhe crystalliztion of poussium strlphate crystals feniclll ions presenc€ as impuriry discirssed and the growlh rate of polasiun sulphate was monilored , it was noted that presence of Fe III suppress th€ growth rate ed even large amount ofFe (III) in the solLrtion may

sLop rhe srowrh ofpoblsium sulphate cr)$alsl76l. Joachim UHch et .al studied lhe Fe'3 additive eff€ct on the crystallization of

ammonium su,phate. The noted lhat meta stable zon€ widh has increased up to 4.5 time by 100 ppm of impurity, proved thal Fe'3 has very effective growth

and dissolution rate suppressor [4].

6-2 Crystrllizrtior with 0.02 gn of Feclr.6flro trd 136g sodium chloride/400mL w!ter 6.2.r Eryerinental Section 0.01 sn of FeCli,6H,O were dissolve in a 400 nrl of dislilled water ,further 116 g ofNacl was dissolved in this solution to make il salurated with sodium chlonde. Solution was slined vigorously to dissolv€ all reagents.

108 CbrpLr f 6

6.22 Re!||lt rnd Dircu$ior

An Eight inch€s in dianet r clruhr fllr body glsss crtsrallizer dish was h€aled fio$ botton tbrowh bot pla&. For clyslalization of thb solurion prcp€rd brift were alowEd to lvaponr! x ditr€rlot iedpcr6trE tom 50 to 8dC withort stiniD& The i6itirl tmp€r.turE was mainraided !t 7dC and oh€rvation wb! noled. Bdn€ was hcatld at 8dC for a few ninutls and tlEn thc aolution was allowed to cnol up !o 50oC. The obs€rvations wc|r taken for fte prcs.nc€ of squ6€ pyramidal salt crystals. Cr/stallized p'runidal and hopp€r cube6 crystals w€re coll€ct€d. Collected pynnidr.l atrd hoppd cub. cryst8ls w.rc colrcained on ddc& *dls !trd due to the h€{ty weidt the sunk down into boltom aDd dlc glowth ol lrrgc cryBuls wer€ nor ob6crvc4

rL$:rtM.rtrr.nn dorof t.ppr.rb.Ddlynuidrl.ry.,.h

109 FiC54: A .la. vid of ktroguh. pynntdd cry.lrb &d Betit.d hoppcr .tbs iDro rhe

fig55: Crut foir.rion.r tenoemtu.e Eo.C

ll0 Fig58: Few setd€d crystil on thc botiom ofcrysiallizer.

Fig59: shows a clos€ view ofthcs. s.filed longitudinal pFanidal crystels

|l2 Cbpld * 6

6.3 Cry$allizetiotr with 0,02 gn of FeCl3.6HrO .Id 1369 sodiun chlorideJ4oodl w.tcr 63.1 Erperimeot l S..tior TIle next €'eeriment wEs perfom by .ddition 0.02 go of FcCl3.6ItzO wen dissolvc in a 400 mL ofdistilled w6t!r,tunhcr 136 g ofNacl wss dissolved in this solution to make it saturat€d with sodium chloride.

63J Re3olt .nd Dilcoslior Figu€s 56 and 57 show crystallizd salt on the sulfrcc ofbrine and a cl€ar view ofmix moryhdogr cm be s.€n, solnc squar€ pramidal snd r€ctangular p)ramidsl crysuls togclher with crust were obs€rved at the tdnp.ratue mnge betwe€n 55 to 65"C . Fig shows a close view of formed cryslrls.

fig t6 a.d 57: Mix mfltolos' f.w squ4 p'Iuidd and Errtrgtie prmidd cryialj

It was interestingly observed that few qystals gow in longitudinal squarc pFadidal cryst.l fomed, neans thc aquarc base width ofthose pyfamids were comparativ.ly le$€r lhan square pynmidal crystal formed wilh othcr brine

lll Clupr.rt 6

Fig58: Fow s€ttled crystel on the bot0om ofcryslallizer.

rigsgr shows a close view offiesc aenl€d longitudinal plmnidrl cryslals

l12 6.4r 0,05 gn FeClr.6H:O rnd ll6C sodiun chloride/400mL wrter

6.4.1 Erperimentrl Section

Solulion r 0.05 g of FeClr.6HO and I 36 g of NaCl w€re d;ssolven in 400 mL of distilled and deioniz€d water. pH of solution was noled a 2.64. chemicals were obtained Aom Merck KgaA, extra pure AR grade.

Solution# 2 0.05 g of FeClr.6HrO and t36 S ofNacl were dissolved in 400 ml ofdistilled and deioniz€d water. pH of solution wa! no.ed as 3.66. All the chemicals were obtained fiom Merck KgaA, extra pule AR grade.

Both Solutions were stined vigorously lo dissolve alt reagenrs. Eight inches in diameter circular Flal body glass crystaltiz€r dishes w€re heared from bottom tlrcugh hot plaie for crystlllization of thes€ sotutions; preparcd brines were allowed to evaporate at different t€mp€rature liom 50 to ?0"C without sriring. The obseryations were taken for the presence of square pyramjdal cryslals of sodium chloride. Crysrlllized plmmidal crysrlts were colt€cr€d.

6.4: Result r.d Discu$ion

SolutioD #l: Solution one pH 2_64 was allowed to crysta ize at different temperature from 50 1o 70oC and obs€rvation for pynmidal crystals formation noted. Crysrallized pyramids bases werc square in shape bu! lhe crysuls grow in lhe longitudinal dir€crion and the height of crystals as compamtivety long and base was small. Sizes of squarc bases were measure I lo 4 mm_ A few rectangular shape pyramidal crystals were also obsened. Fig 60 shows lhese rectangular pyrahidal crysrals. Collected lonS udinal rectangutar and square lll cn Fat 6 basc DytlDidrl crysirb crn b€.rl s.cr in Fig 6l too. Fig 62 and 63 3lrow dlc dilr nsion ofcrystrlliz.d It tegule pyr&rid.

fis 60: R.(rdSuLr !n 3q'm lrmidd qrr.l3

Fir6l : qr$llird tq@ td E r'rguL. pyMi&l 6rt 13

|l4 Fig62: Lngitl|ditr l pytuid.l cryn l

Fig6l: Etdgule ptmtu l 6rerl

5 6.43 f,rperinentrl

Solutior #2 Solution Two having pH 3.66 was allowed to crystallized at differdt tenperature fiom 50 to ?0"C and observation for plmidal cryslals fomation were noted.

6.4.4 Result and dbcussioDl

Solution two at pH 3.66 was allow€d to crysiallize at different temperature from 50 to 70"C and obsewation for plramidal crystals formation noted. V€ry small base pyramidal crystals wer€ observed form 0.5 ro 2 mm and a many crystals were ob$rved capillary morphology insread of plmmidal crystal and l€ngth oflhe* capillary d€pend upon the size ofvess€l for cryslallization. A few reclangular shap€ pyranidsl cryst ls wer€ also obs€rved EDS anlaysis wa! perfom vith following acquisition pa$merer,Inslrment : 6380(LA),Acc.

Vollag€ | 20.0 kvProbe Cur€nt 1.00000 nA,PHA mode : T3,Real Time : 49.78 s€clive Tine : 10.00 sec,Dead Time : 39 %,Counting Rale: 8914 cps,Ene.gy Range : 0 - 20 k€V. Fig 65 shows obtain€d EDS chan.

ll6 Fig 64:NaCl capillaries crystalliz€d in lhc prcsence oflmn iftpuriry pH 3 66

ll? Fig 65: EDAX of pyEnidal crFtals shown h SEM. nle cryskls ar€

6.{5 Corclurior rl is mrcluded tha! iron 0ll) has imp.r! for dte formation of pyrrDidal crystal

ofsodium chlorid€. The iempedur€ mnge b€t$€en 50 to 65uC and pH below 3 was noted a! b€st for the forDation of reciangular lnd squ{€ b!& pyamidnl crystak *nicn arc compamtively long in heisht as comparE to pymidsl crysi.ls crtsrallizld by mnnal brine of salt. At ib€ pH bctw€€n 3 to 4 holtow sah capilaries werc dso form€d. It is also concluded thar €v€n v€ry small amount of imn 0lI) 5 mg/L help for th€ formation of pramidsl ctrstals. The ob$in€d EDS daL shows only psts for sodiu ad chloridc.

6.5 l uenc. of crlclun or th. cryrtd norlhok'S/ of .odlun chbddc for cry.l|llizrtior of pyr.midd cryrbb. 6.5.1 f,tp.riD.trt|l !.ctioD

ltE Chapter r 6

2.5 g ofcaclr.2Hro and 136 g ofNacl w€r€ dissolved in 400 ml of distilled water. Ll ml (0.4N) was added to maidain the pH 5.20. All lhe chemicals werc obtained fton Merck KgaA,€xta Pure AR grade. Solution was stined vigorously to dissolve all reagents. A eight inches in diarneter circular Flat body glass crystallizlr dish was healed from botlom through hot plale for crysrallization of this solurioD, pr€pared brine was allow€d 1o evaporate al difrermt tempemture from 501o 80'C without stining. The observatioB were taken for th€ presence of square pyramidal salt Crv$allized pvramids were

6.5.2 Re! lt tnd Di!.usrio!. 400 mL of prcpared solution was filled in the crystalliz€r and the obs€rvation wa! &Ien. Like other experimenlal condiiion aPproach thal were used io noi incrcase temperature gradually any formation of pyrunidal crysral could Another been s€en and €xPerimenl wd rcp€ated mev rime lo confirm Lhat approach by mai aining initial tempemture high md then cool down the Inilially solution was applied. The temp€rature was maintained at 70"C jointed pymnidal crystals were appeared but with tlt€ passage of time thev was with each other dd formcd crust ( Fig 66) The temPerature of soludon for fte next increce upto 10 "C al the rate of loc/min and ma;ntained at 80t joinEd few mnutes. As a result of this incr€ased in tempemtur€, a crust of plmmidal cryslals formed and sink in !o the bottom ( Fig 67) Sone p)Tamidal and few crystals crysrals formation w€r€ also obs€rved on th€ surface of curst lhe botom'(Fig w€re floating on the surface of brine as crust seflled down into of 68). Some well formed p)ramidal crystah can be s€en in the botto$ crystal crysbllizer,( Fi8 69) and (Fig ?0) show rh€ view of a well defined shape of pyiamid. During th€ experiment few regular Dtamidal crystals were l19 observed and the maximum size of the sidc length of square base ls 5 mm.

However some irreguls.r pymmidal crystals were also observ€d which grow up to l0 mm. Fig 7l show few regular p,'ramidal cryslal crystrllized during

120 6,5.3 Conclusionr It is concluded thar at CaCl, as inpurity has little to suppress crystal glow but the regular formation of pyramidal crystals specially perlect squar€ plmnidal cryslals is not the fiDclion of calcium separately

AlthouSh the pres€nc€ offew pramidal crystals Sive evidence lhat pr€sence of calcium play a role in the formation of sodium chloride pymmidal cryslals at low€r pH, as purc sodim chloride irself do€sn't show tendency to form this morphology.

6.6A m ixlu re of calciun ,iror and sodiun chloride

6.6.1 Expernn.ntal Section 2.5 g ofCaCl?.zH,O and t40I ofNaCl w€re dissolved h 400 mL ofdistilled water. 0.049 of Feclr. 6 H, O vias add€d and pH is noted as 2.59. All tlte chemicals were obtained trom M€rck KgrA,extra pure AR grade. Solution weas stined vigorously to dissolve all r€agents. A €ight inches diameter circular ilat body glass crystallizer dish was heated fton bottom ihrough hol plsle for crystallization of this solution Pr€pared brin€ w€re allowed to

evapomte al differe &mperature from 50 to 80'C vithout stining. Th€ inilial remp€Erure w5s maintaind ar 70dc snd obseration wd noted. Afi€r the end

of crysrallization ihe Ploducad solid pyramidal crystals were characterized usins XRD.

6.6.2 Resuh strd Discussion.

l2t 400 nL of pr€paftd solution wss fillcd in rhe crFlallizs and the obs€rvation was tak n, The tenp€rature wa, naintained at 48'C. Nucleation has stded without dclsy due to the saturaied solution( Fig 72).

Fi8 72. Iritia.l iorntation ofpFamidal crystals

Smatl pyrimidal crystab obca1/cd inilially that were Srowing uPlo 3 nm of the side length of square b6{Fig 73 shows a clorc few of well shap€ pyraraidal crystals and Fig 74 shows regular cryst61s formation al low

122 73: A clo!. view of

Fig?4: ReguLr crtdak forndim d low t€up€ratur at 4yC

The trdpctrtj|! ws! l$r.d ot| up ro j6oc ed 6e gDUiig c.ystd! f'henoh€n' $rerE oblcwed Sonc briDc w!3 a.td ido th€ bdom geotly io incr!€lc iL lcvcl ofbiim wirbou dislurbio8 Oc crysralizatiotr, Fig 75 and ?6 $ow tlc ciystlb growm .f.r iE €!!.d volunc of thc briF sottxim- Wcl !hAG4 shiry ory{als cor bG rc€a iD dr. F,g 77.

t23 tbt! drdt rrrad a''rt alh *rb.5rac tl ta : c.r-trt- ri. tft 'i-

Fis u: s+c-t * ., l-T!g.f ""t-l F-;@;- rDe cryrtai! were ide ified as sodium chjo.ide by X_raypow&r diffuctid Snnll pcak! ofhydm udndire, which oont incd cdciuD an t lron confrm rhc plts€ncc ofelciurr aDd iroo in Eothcr brinc mlt cryrlliz.d pyrdmidal ciys.b Fi8 7E lhows XRD !d!rD oflodiun cfloii& cry*rk otarincd by c.lciun 3d iroo iDpurities dd.d bri[! 6.5.3 X-Rry Psd.r dfhr.dor, thc cwity of ihc metal smple bolder ofx_rry diflncloneld wr! fiIed with o|G groud povd.r srnplc &d ttlc lmoott wi[h spoob, X-Fdy .liftldion p.rlar of sodiun cllorit lyreidd cryd.ts w!rc otrsined usitrg X-rry lu CMdd { 6

diftltom€ter (Bruk€r axs, D8, Advancc) at 40 kV, 30mA ad a s.arire nr€

of 2"/Dir over . llDgc of 5- 70 2e .adiatio ofwavel€ngtb | .5446 A-

fig ?8: XRD pddn ofsodim .,htdidc c.yrrls ott incd by oldm 4d ircn idqniB

65.4 Cotrlulabnr It is conclded d|.t abovc conimlioh of conpou.d is the exc€llent conbinaitor to forncd *tI sbape pynnidrl crystats. Thc wctl shaped p)nrnidal crysbt formation intialy srsft€d at 48oC. I|e meel st bte zon€ of crysrallizatior of anificial brinc was os.rved very $imitar to mtural brine p.rfomed lhrt in ou prEviou! wo.*. It is concluded thal ch€incal composrim of b.ine ptay viral rolc in fornstion of th€!€ pyrDidd crysrat d th. p€nic.ul,r .C. t€rnp{fatun |!Dge bdwe€n 48 io 65 Afthoqh ar dr o6er tndnpatltur€ py.rDid.l cryslats form bur for thc coflrol ed rccular

t25 was obsen'ed very crvslallizalion the above m€ntioned t€mpanturc region

cbloride for 6.t IntlueDc€ of calcium on the crvstrl morpbolog/ of sodium crFtrlizrtion of pyrsmidal cryst{ls

6,7,1Elperimental Section of distilled 2.5 g of Mgclz 6H?O and 116 g ofNacl were dissolved in 400 ml wat€r. 1.1 ml (0.4N) was added to mainiain the pH 529 All the chemicals rras were obtained from Mer.k r.gaA,exia Pure AR grade Solution snrrcd vigorously to dissolve aU r€agents. An eight inches in diamelef circular Flat body glass crystalliz€r dish was hert€d ftotrt botton ttm'rgh hot plate for crystallialion of rhis solution, prepar€d brine was allowed to evapomte at different temoemture ftom 50 to 80"C without stining The obseNanons wer€

raken for th€ pr€sence ofsquare p)ramidal salt

6.?.2 R€sult and Dbcussior:.

Observation of this soluiion was taken at different temperature and solulion was alloved to crystallize. Il wss noted ftat presence ofMgcl, alone doesn t

impact to change crystal morpholo$/ to plmmidal shap€ and no observation of pyramidal crystal not€d. Forned crysbls w€re hopPer cube as oth€r scientist

also noted same obs€rvation in th€ir exp€riments [9] Raup el.al [?l] described hopper cubes. which werc produced on eanh bv th€ salting-out prccess b)

mixinc a satumted N6Cl solution with s satumted magnesium chloride (Mgclr)

126 solution. Solution of NaCl and MgCl2 was stino4 dl€ descnM hoPPer cubes wer€ formed after a shod incubation period under high supersa$ration lnstcad ofa few lalge crystals numerous small crystsls with an edg€ length ofo 2 mm w€re formed. The saxne obs€rvation of lh€se smdl hopp€r cuhs w€r€ taken during our expedmer too. Wc crystalliz€d tbis solution wiliotn stininS ,nd il is th€ only difrennce bd\ €€n thes€ two oQeriments but obc€rvation Lkcn w€ru saltre, the formation of smrll hoppcr cub€ crystds. Thes€ hoPpcr cubc crystsls du€ io lheir heary ma$ s€ttlcd down into the bottom rapidly and i! has mention€d in ow previous chaptors lhat fonnation of well shaped pyranidal crystals are only possible by surhre crystzllizstion without agitrtion. Fig 79 shows th€ crystalliz€r view and Fig 80 shows a close view of hopper cube formcd by this brine soluion. Fig 8l,hoppcr cubes grown on €arth by the salting-out process l9l

Fig 79: Tbe crFtrlliz.r vie'rv of hopp€r cubes

t27 ct prr*6

Fig E0 showr a clo|e vl.n, oI hopper cubcs with magdelirn inPurity

Fig8l : (P. Fonam)fg] Hoprcr cub. soM or d6 by t]G sdrils{u! p!l!s

l2a Chapt€r # 6

6.?3 CoNlusion: It is concluded on the base ofabove experiment that anificiat crystalliza tion of sodium chloride pyramidal crystals canno. be

achieve by only addinS MgCl! 6 HlO inlo brine or sodium chloride elution.

however rhe pres€nce of hopper cubes wer€ observed-

6.8 A miiure of msgr€sium ,irotr .rd sodiuD chloridc

6.S.lExperimentrl SectioD

2.5 g of MgCl?.6 H1Of0.05 gFeCl3.6HrO and 136 g ofNaClwere dissolved in

400 mL of distilled water. AII th€ chemicds werc ohained Fom Merck KgaA, exlra pure AR grade. Solution was stirred vigorously to dissolve all reagents. An eight inches in dianet€r circular Flat body glass crystallizer dish was heated ftom bottom trough hot plate for crysr.llizlaion of this solution, preparcd brine was allowed to evapomte at different temp€mture fiom 50 to 80t withour slining. The observalions were taken for the presence ofsquarc pyranidal salt. After the €nd of crysbllizalion the produced solid pynmidal crystals were chancterized using xRD.

6,E 2 Result r[d DiscuslioD Differ€nt obs€rvadons wer€ taken at differ€nt t€mperature. Initially tenpemture was sel ar 50oc till rhe nuclearion observed and then these small nuclei were allowed to grow. Initially appeared nucl€i werc hopper cube in

naturc Fig 82 shows the formation of rhese hopp€r cube crystals. Th€se hopper

cubes has b€en growing for few mioules and th€n settled down into the botbm

due to their weighr.

129 Chapter * 6

rE &: Fotutio! ot bopp.r cub..ry!t b

Temp€rature ofbrine was increased @ l"C/min for next l0 minutes and adjusted at 60'C . Crystrls wer€ allowed to grow &t this temperatue 6nd alier sesling of initially crystallized pyanid.l crystals. The newly appesred nuclei has stadcd !o gow in square pyramidd shape and obervation was taken dn can be se€n in the Fig 83, ihat shows the fonnation of well shaped pyramidal

130 oC Fig 33t formadon ofwell shar€d pyranidal crystals at 60

A stabi€ crystalliation of p,,r.midal cry$als was obsera€d dudng rhe experim€nt wirh in the temp€mture range of 55 to 65oC. Fomation of thes€ p)nmidal crystals can be observcd in the Fig 84 and 85.

Fis 84: Regulu fomadon of pytuidt cr,Bt l.

lll Fi8 65: Regular fomalion ofpr1midal;FE

6.8.3Cotrclusion: It is conclud€d by above expefiment rhar an eff€ctive cryslallization of pyramidal cryskls of sodium chloride is possible with the mixrure of magnesium, iron and sodium chtoride , however the presenc€ of magnesium ha! tendency ro rurn crystals morpholos/ itlto hopper cube hslead of plranidal crystals. The pH of solution was nored acidic tha. was 2.59 and ternpemture ranSe was jS nor€d as to 65 'C for w€ll shaped pyramidat crystals formation.

6.9A mirture ofcstciuln, n.gn€sium,iron sDd sodium chtoride

6.9.lErpcrtmertrt S€ctior

CaCl,2H,O 1.4 grn MgCb , 6HzO 2.g E, FeCb 6HtO 0.04 e and 136 s of NaCI were dissolved in 400 nL of distiled water and pH is noled as 2.59. Alt the chemicals were obrained from Merck KgaA,exrra pure A-tt gEde. Solulion ll2 was stin€d vigorously to dissolve all rcrgents. A eiSht inches dianeter circu)ar flar body glass cry$allizer dish was healed tom bottom through hot plale for crystallization of this solution Prepared brine wer€ allowed to evaporale al different remperature fiom 50 to 80"C wirhout stiring The initial tenperature was naintained at 70"C and observation was noten After the end of crystallization th€ produc€d solid pFamidal crysEls w€re chamcrcrized using )RD.

As crystallizer a flat body glas5 crystatlizer dish having 8 inch diaitet€r was

heated ftom bonom ftrowh hoi plate for rhat purpose and 400mL ofpreparcd brin€ wa, allowed lo evaPoral€ at difTerent lemp€ratures fiom 50 to 80"C wilhout stining. The obs€rvations were laken for the crysiallization of squde

pyramidal salt.

6.9.2 Result and DhcNsion. 400 mL of prepared solution was filled in the crystallizer and the observation was taken. The tempemtur€ wa! maintain€d at 78oC initially. Afte. getting supersaturattion smatl nucl€i wer€ stffted to form .Initiallv plramidal cryslats

were app€ared ad golrth was se€n bul with the passage oftimc some ofth€m

sr.rr€d ro jointed wirh each other and formed orusr.( Fig 86)

lll Fig 86: ioitrted pyrrmidrl crlEtrb tt ?8"C

The temp€ratue of solution was tumed down and hot plate was adjusted at low h€ating rcgion . crowth in size of syst6ls was obcerved as we can se€ in

Fig (87) wher€ pyrsnids are forming after tumed do*r| th€ Gmp€mture and adjust lhe hear transfer ar low rste.

t34 cl"pte.l6

Fi8 87: erowing crystals observation

Fig 88 : Anolhcr view of crysrallizarion sr ?6"C

lJ5 Fig E9r joint d pynold.l cry.tll forEtrion

At this saag€ the temperature was found at 760C. Fig 88 shows anolher view of crystalliztion. It was noted thar individual cryskls has started to joint wirh each other at ihis remperatue regiod as observed in Fig 89. Some brin€ was sdded carefully added inio the botlom of crystallizer to decrease the temperature as well as increasing the lcvel ofbrine in crystallizer. As a resuh temp€mture was do*n at 68oC and many floating pyrarfdal crlNsrals werc obs€ned that were growing up !o a imEove size l0 mrn in $Eir side length of the square b6se. Fig 90 shows a view of well shaped g€omerry pyramidal crystals that was glwing on ttle surfa.€ ofbdne.

r36 Fig 90 : A view of lrrge and well shlped geomctry pyrrmidal crystals

6.93 X-Rry pox/d.r Difi.rction (XRD).

CrysLllized pyramidal cry$als wer€ analyzrd on XR-D powdcr diffiacrion. The x-ray difhaction (XRD) paxem of pyramidal crystals sample was obtained using X-'ay difiacton€t€r at 40 kV, 40 inA $ld s.ainina |are of 2"/ min over a range of 5 -70 2e. XRD patlem confirms that €rystalljzed plmnids are sodiurn chloride. Figlre 9l repr€sents )(RD pattem for sodium chloride 6nd the presence of calcium and magnesium also confirm the brine composition utiliz€d for crysrallizarion. fiS9l: shows rhe )(R.D p.arcrn ofcrysralized pylamidd salt 69.4 Colclurior- It is .orclud€d ll.t the brin€ co aini,g c€lciurr magnesiurn and sodiun chloride,wbich ar€ few major oomponenr ofn tud salt too we.e obsrved suitable for the crysrali"jtion ofp)rEmidal crFtds al m€ lemp€mrure mnge betw€cn 50r io fO"C in a.idic rncdilun. The pH of particuLr exp€riinmr was nolcd as 2.59 bur on lhc basis ofdifrer€nt suc.essftl and unsuccecrtul exp€iincnt with ditr€r€nr composition rhe nng€ of pH i! defined a! 2.5 to 4. Ir r/!3 atso nored th4.tla€Dcc ofsulphrle ion is favombl€ fo. wlu slup€d plTartdrt c.ysiats fomation

|]8 6.10 A mirlure ofbrrium ,imn .nd lodiom chloridc

6.l0.rf,,rperimeDt l S.ctior

2.5 s of BaCl,.2 H2Gr0.05 g F€CL.6HrO and 140 e of NaCl were d;ssolved in 400 mL of distill€d water. All the ch€micals were obtained fiom Merck KgaA,extra pure AR gride. Soludon was stin€d vigorously ro dissolve all r€ageds. Ahhough bariurn and specislly bsrium chloride d€hydrate is lhe compound which is included in the list of hazardous chemical [72] and p)rarnidal cryslal crysdlized carmor u* as food gad€ $lr or any medicinal or edible puposes.

6.10.2 Resrlt and Discossion

Fornadon of square pyranidal crystah was observed in the rempemture l?ng€

50 to 65oC and pH 2.76. Cryslallized pranidal crysials height nored form 2 to t0 mrn, however base of th€se squar€ plmmidal crystal were noled I to 5 mm which is basic.lly depend upon lhe .im€ of crystallization for a panicular

crystal and if supersaturation is maintain€d ar a low level, nucieus fonration is nol encouraged but the available nuclei will continue ro 8mw and large cryshls will result. lfsupeBatumtion h hiSh,lher€ may be tunher nuctearion and so rhe growth ofexisting crysrals will not b€ so great. Fi8 92 shows the crys.allized pyrainids from this brine.

l]9 Flg 92 : Cr$tlli&d pynbidrl .ry!t L frc! b.rtrn ,tN! ..d rodiuo .hbnd. hrin. 6.103 X-Rry powd€r Diffr.ction (XRD).

Crystallized pyramidal crystals were analyzed on XRD powder diffraction. The

x-ray diflraction OG.D) pattem of pyranidal crystals sample was obrajned using X-Ey diffi?ctomcter ar 40 kV, 40 mA and scaming rate of 2ol nin ovtr a rErge of 5 -70 20. )

140 I

qlr Fig xRD Fn n aorrr. Dit.|E of b.rnn, tM.iir sdl.r.tbra. 5.1O{corcL!b} is It c4ncluded on thc basis of abovc exp€riment tbar bariurh srppor! in the fornution of pyrDidal crystats brine hsving iron and sodiutr chtoride. .Ite ba!€ size inprov€ne wrj notd fu rhc p.€€enc€ of bariusr impudty at a.id pH ald tcmFratuE rlDge b.iwe.n 50 ro 6yC.

6.11 A nitrult ofpourltum,imr .Id rodtrn chtorirt

5.rllErFrin nr.t S..rior Solutio.#l 2.5 g of KCI and 136 I of NaCt wer€ disrolyed in 400 nr of distilcd and d€ionised *"ter. 0.059 ofFdlr. 6 H,O was added d pH is noted as 2.52. Soloilod2

t4l Chapler t 6 a g of KCI aid 136 g of NaCl wer€ dissolv€d in 400 mL of dislilled and deionised wal€r. 0 05g ofFeclr' 6 HrO was added and pH is noted as 2 52 Solulion #3 of disdlled and 5 8 of KCI and 136 g of NaCl were dissolved in 400 mL

All the chemicals were obtained from Merck KgaA,extra pure AR grade' Solutions were stirred vigomusly to dissolve all reagenb Eight inches diameter circular tlal body glass cryslalliur dish w€re heated fiom botiom tttrough hot plate for crystallizarion of these solution, prepared brine were allowed lo evaporate at different tempemlure liom 50 to 80'C wiihout stinin8 6.1l.2Resolt rnd Di!.ussiotr Solution having 2.5 g of KCI lr€s obs€Ned initially and it is noted that bodr recbngular ad square pl.ramidal crystals ar€ forming at the lemp€raturc range 50 to 65"C Fig 94 . Temperature was increis€d up to 78'c and it was noled lhat al this temperaturc larye nurnber of nelie formed and st3rt 1o grow. Which don'l allow crystals to grow large fig 95. In the solution having 4 g ofKcl, most of crystalliz€d pyramids w€re square bas€.Fig 96 shows formation of square pyranidal crysisls at lhe lemperature range of50 to 65"C and pH 2.52. It was observed that l€ss than 10 g/L ofKcl do€sn't have any impact on the crystal formation. Another solution# 3 prepar€d by 5 g/400ml KCI and 1369/400mL NaCl pH 5.20 was crysirllized al htween the temperatufe mnge 50lo 65"C .Fig 97 shows that there is no fonnation of pFamidal crystals with

KCI solution was observ€d. This solution was acidiry with dilute HCI and pH was mainlained at pH at 3.0 and observation wer€ taken. It was noled thar a layer of crust was formed on the surface of brine and no evidences of pyramidal cryslals formation w€re obs€rved. Fig 98 shows the formation of crust on lhe surface of this brin€ solulion.

142 Clapter d 6

F ig 04: Fomaton of squ4 and i.cMguld plramidal cryslals wth solutionr I

Fig95: fodrtion of l.A. udb.r ol nucLl .l tenpedhe t8'C

t43 Fig 96r shows fornation ofsquarc p''ranidal crystals at th€ temperanre rang€ of50 to 55"C and pH 2.52.

Flg 9?: lot /L KCl llh..lo! ol N.Cl i.on(IlD .rfl o! ctrrt 'idout

t44 I_t tt: lo.D1ior olcmrt or 6. rrf..r ot Ob b}'no lo|ofior

5.rB X-Rry pord.rDk .d.. (XRt I Cq/$rUiDd e,tmidd ('y*rb w|t o.lyz.d o r{RD powd6,lifr-ti@. fb x{ay dift!.rid OAD) pd.rtr of lyrmid.t cryd.ts 3rDph wt3 ot ri!€d uling X{ry difrldond.r a a0 w, aO mA |[,1 ,@iA rde of ,f / mio ov., a tuac of 5 -70 20. )(RD pat!.m omfros thrt crylt liz.it ,ynnidsl ..ygals al! sodiuD chlmide FigrE 9 r€!rc!€ob )(RD p.reil for sodiu chlorid! od thc pr€sence of pot rsiun abo cotrirtDs thc brinc comllodfioo utiliz.d for crlstaltiz.tion-

t,l5 -.- - *i l--:i- -*---i - --'Y.:. -- I - ::-- i:: jj - .:r-.. :.i, :: :::..- ::--5--:i,=-._-::

Ft 9:- tRD Ft .i lor Fo.i.r, tm rd nli. .$ort t

6.rlJ Crrc|||.lor It is conclud€d rl|t h th€ lolutioD clnrain iffr and lodium cl orid! thc pr€scnce of potassilm chtoride mo.! thrn l0 g/L has implct io ol,mSc rccrangul& crystals into squlr! b€s€ pyrmidsl orystals ar the lcmp€nrurc nnge b€twen 50 to 659C in scidic n.diun. No cvid€nce w.s ob3.ivcd the KCI in idividual capacity h.ls t€trdacy to chroge NaCI norphotog, in to plruni.ld lbapa

t46 Chapte r #7

GeneralConclusion and Suggestion 7-General cotrclusion for the formatiotr of pyramidal crystals atrd sugge$tiotr

7.1 Cooclusion salt' o$€r The nain objecl ofthis work was to crvstallize pvmmidal crystals of with control in lhan natural crystlllizaiion to ensure the qualily and the quandry take every season. The understanding ofthe factoN which have influence and pan in thL panicular morpholog of sod;um chloride and crystal shape and help to grow crystals in the well shap€d' regular narner and slz€' As per proposed plan study of the pvranidal crystals of sodium chloride crystallization wer€ canied out with below lisred sax md brine rciineries' Raw sea salt, saw lake salt, rock salt, wast€ brine generat€d bv sah

and by adding difTerent imputities to the sodium chloride solution' wfth help I! is concluded that pyramidal crystals of salt ce be crv$allized fie of all above mentioned brine for keeping sone kev faclors in the mind al the time ofcrystallization. It is also concluded th3l impurities naturally preseni 'n $e salt or brine in the salt or add€d bv extedlal r*ource have sigificant ;mpac! on the crystal grorth 4d morphology. The pr€sence ofthese impurities is supprssed the rat€ of crystallizarion th suppon cDs[al to grc$ in $e

desirable and favorsble direction that is pvramidal or telragonal pFamid shape' ft is also included that presence of small amounl of Iron can conven the morpholog/ of slt and allo* lhe atom to arrege in th€ well shape pvramidal form. The presence of these impuritics can rcduce crystal grorth rate and alter morphology by binding to crystal faces. The others impurities lhat is calcium ' role to magnesium , sulphate. Porassium have also plaled an imponanr

t41 Cha er# 7

presence of high amo'int determine rhe pyranidal cryslal morphologv as in the of well shaped of magnesium and sulphate impwities nav inpede fofmalion has pFamidal cry$als Calcium its€lf plav end vital role and individoallv crystal capacity to modiry crystal moQhologv that is proven bv artificial as added formation (not in very regular manner) by using cal€iun chlorid€ impurity. h is also conclud€d rhat rcSether with calcium ' sulphate cleates calc'um hindrance !o get desire pranidal morpholo$/ bv pre€ipitsting as and even sulphate- As calcium sulphate solubiliiy h the tunction oftemperatur€ above 100 calcium sulphate has observed practicallv at hiSher t€mperature "C ' insolubl€ in wat€r as well as brine solution of sodium chloride Other direct considered impurilies for the proposed work like poussiurn and bromine to significant impact could not be observed during rhis srudy and il is suggested crysral more practical work in this regards. Some observations for tansparent was noted in the presence of high concentmtion of potassium lt is concluded

thal presence ofmagnesium in brine may alt€r crystal in to hopper cube shape' ll is concluded that v€ry low conc€nt"don (5 mgA ofbrin€) ofiron(lll) has significant impact to fo.m pyrarnidal shape crysials of sodium chloride The crystallized pyrami&l cryslals with added impuntv of iron(III) were longirudinal pyranidal shape ln the pres€nces of iron(lu) in brine salt hollow

salt capillaries wer€ also form. It is also concluded ihat with the mixture of iron, calcium , iron magn€sium ,iron potassium and iron barium well shap€ pv'amidal crvsal of sodium chloride can be crysLllized Th€se added impuriries increases lhe density ofbrine solurion that allow the crystals to grow on the surface ofbrine for a longer period consequ€ntly w€ll shape wide square base pvramidal

l4E Chaptei I 7

Therefore it is concluded that the nucleation, grcw1h and moryhology of

crystals can be significatly alt€r€d by the pr€sence of above medioned added

impurities.

The pH eff€ct cd b€ concluded 6 lhal lhe lower pH scal€ that is acidic side is more favorable for the crystallizadon of pyramidal crystal although formation was observed at neutral pH ioo. The higher scale of pH that is basic side is inteF.pt to forn well shaped pyranidal crystals.his mav be because the maJor impurities of salt that are calcium and magnesium are found favorable condition al this pH to be precipitated as their carbonates and hvdroxides Il is also concluded that temperalure plays signilicanr role ro determine lhe crystal moQhology and as w€ll as to accelemte lhe cry$allization proc€ss wilh

control and well shape morphology. It is also concluded ihar plmmidal crystals can be crystallized from roon temp€mture to 90"C but for regular fornation and conirol producdon of well slBped pyramidal cryslals temperature mnge uC b€F{€en 50 to 65 w6 noted. At lhis temp€rature mnge a rnetastable zone

crcates fof the proper pymmidal shape crystals The nonitored production rate

at difiercnl temp€mtwe from at 50, 55 and 60' shows that produclion rate of pyramidal crystzls is directly proponional with temPeraturc in lhis Panicular tempeEturc .ange. some time a little variation was observ€d due !o the method of crystallization and size of lhe cryslallizer in which crystallizalion

wss occurrcd. The large number of nuclei can be conuol by fie decreasing the remperature for a l;ttle tim€, once a meia slable condition is develop€d lhe crystal grow for long tine and gel tle good size up to a i.ch or more The level of brine in pan is also help to crystal to grow large. The solubility and

meta srable zone in crystallization ofFleur De S€l or pyramidal crystals were

assessed as a tuncrion of temperatur€ in range of 50oC to 65'C, as tempemture

t49 Cha$er i 7

of square pFamid crystal rises the some small flex are s|aned 1o fo'm instead ofFleur de Sel successtullv applied Ii is also conclud€d by lhis work, bnne purification can be and anton for il|€ removal of divalent cations thal are calcium and magnesium like sulphare. The elimination or reduction of thes€ impurities heLp to form well shaped pymnidal crystals The gre€n chemistry was one of the key objective of this work and not only utilizadon of thousands of rons g€nerated waste brine bv salt and othe' is industries but conversion ofthe wa51e brine into value added producl, which know sah hisiory' Nol soing lo be world fanous and most delicious salt ever only in Pakistai other pan of the worl4 mechanical salt washing is used insiead of modem te€hnolo$/ like rhermal recompression technologv to product pure vacuum dried salt. The process of mechanical refining of sali generat€s thousands of lons €muent in fom of waste brine because recovery of this proces is 85 to 90% 1241. This emuenl dischdge in 1') the sea causes n osmotic shock ofthe living organisms (ecosystems) in the sea [16'17]. Cunent work ensues the formation of well shap€ py'arnidal crystals from the bittem of

salt processing industri€s and it is concluded that waste brine can be converted into well shap€ plaamidal crystals-

7.2 Suggestionst As biltem of salt industry can be ulilized fo. crystalliztion of pvramidal crystal so i! is reconnended to ulilize our develop method to conven this waste brine in to value add product thar is Fleur de Sel which is the most expensive salt of the world. Fleur d€ Sel ha3 growing market and replacing quickly aU olher flaky sak ftat arc available in the narket. By providing

150 CbnPo. t 7 pyramidal sali atreasonable price manufaclurefand consumer both can gel win

Unfodunalely this high concentrared brine 8lat can be used as a sources ot many usefirl product and also can be utilized bv removrng major impurities ,this brine is deposil back into the sea This process causes an osmotic shock ofrhe livingorsanisms (ecosvs|€ns) in the sea [17]The efluen! in the w6re is a heavily concentrared brine solution This discharged eflluent has the poGnrial lo kill organisms Although lhe brine solulion conlarn'ng naural ingredient of the sea water it may cause damage by it unnatuml concenhtion to marine population near outlel it Ir is imponafl 10 make rhe salt induslry friendiy lo env;onment, because could have very adve6e effect on the envircnment

Hollow capillarics of ssltt As we have d;scussed in chapter 7' a li1lle amol]nt ircn(III) can modiry morPholos/ in|o salt hollow sall capillaries more work should be done in ihe field as this hollow capillaries ofuniform size can

be used as a cadier of different nedicine or in replacement of capsules cover'

crystals make High solubilityt th€ 8rcat and rapid solubiiitv of pvramidal $em suitable for different applicadons where fdiest solubilitv is requircd l;kc

cheese manufacru ng The mentioned recommendarion for the use of fak) salt on the web si|e of Monon salt are given below and pvramidal crvstals are

suirable for aLl these sPplications

Cereals & Baked Goodsr lnstant hol breakfasl cereal' rcady-to-eal cereal, toppings for snack crack€rs, croutons and bread c.umbs' Dry Blends & Sessonings: Breading, batt€r' processed nixes, vegerable protein, soy flour/powder, oiyextmct powders' meat cures, tenderizers t5l ChaPier d 7

and Soups, Sauces & Dressings: Soups, sauces' gravies, po'Iable dressings

seasoning premixes Mea! Pouhry & Fish: Fish fillets, sausages, franks, bologna, frozen eggs' chill brines, narinades and s€rsoning premix condim€nts, Spreads & Proc€ssed Veg€tables: Ma€arine' mavonnaise'

Snack & Sweets: ChiPs, cr.ckers, ch€ese pufTs, popcom and nuts' instant cocotdrink mixes, chocolate syrup, coatings/cGme cenErs, gelatin' instant pudding/toppin8.

Rapid dissolving rate facilitates speed-up production and can save on going ro be manpower, a cost which is very high all around the world and

incrcas€ day by day in Pakistan too.

from Thc low bulk densily and large surface area difterentiare Fleur De Sel pvramidal crysBls with common cLrbic salt and any other grades ofsall. Thesc is e grear swface area cm be apPlied in liose aPplicaiion where salt requ'rcd 8

!o cure the food producl, tish curing, meel processing elc' It will reduce the co$s associsted with concenlrate disposal and' thercfore'

feduce ihe tokl cost of fresh salt production Ihe chemical composition of nalural pvramidal crvsrals and crvslallized bv thennal and conlrolled manner werc observed as nonnal comnon sea sah chemical composrlion.

l5l cl!@f 7

Soute ofoah.rt di.arab Tfi.s€ pyEridrl..yc.l tFcialy F!F!d ff@ toct sltt . !slt, Lle !5lt ed bit!.tn of sslt pmcrssitrg irduaEi.s arr nin€ral ric&, Otbe. thrn talte it c$ ur€ r! lt€ cdrii atrll sourc6 of vttudl€ ni!-d! lib ,c.ldun Ed E gBiuE .rd ir6. A c{qr€h6ivc lt|dy cd b€ dme s lbis ta?io to o9ldr di.Lty |Dd ncdicinal b.1lefits offu.. p$anidal ct)Btalt FLltr de S€l

t5l Chapter #8

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for the washing of solar salt)' l43l Philipp. de-F, Muchart. (A new process Th€ Second Symposiun on Sah (SECION Iv EVAPORATED)' held in Cleveland on sponsored by the Northem Ohio Geological Society, May 3-5,1965.

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tr€ah€nt process design) l4sl Harshrd M. P. (Factor for optimum brine Olin Corpontion Charleston, T€nnessee, USA, Sixlh lntemation Symposium on Salt 1983, Vol 2, page 515-31.

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seventh I47l J. Ulrich, M. IGruse' M.Steptnski, inr Pfoceeding Vol#2' (Elsevier' Symposium on Salt,Amsterdam, The Netherlands' 1993, (193)'pp H.Kakihara, H.R. H€rdyJ- Hosi, K.Tovokrua (eds), Amsterdan 209J12

160 I4SlBritish Pharmacopoeia (Intemational Edilion), vol I(HMSO, London, 2005), pp-604-605, Method 7647'14-5 l49f P. M .Synowiec and B. B'UJ'ikows|l.l. lnd.Eng Chen Res, 44,22'13- 228(2005). l50l Farhan Ullah Khan., Malld Mumt : and Toh3oen Ahmod(Pilot Plant srudy ro Urilize Waste Brine G€neiared by salt Industries) Jounat ot Basja & Apptie.r Sciences,2o12, 8, 3&A492

I51l Anlhony Scrutlon, (Laboratory Study of tho Crystalllzation of Sodium Chlorid€ From Brlno),R€search and Oevelopment Wainnington Laboralory, lmp€nal Chemical Induslry [d (Mond division), Nonhwich. Cheshir€ C W8 4DJ ,England. Fiflh Symposium on Salt.Page 383-395, Vol#2,[4ay 1980( [,lay 29 June 01,1979 Congress Cenlrum Hambulg, cermany).

[s2l Genrd oubibcn i.d Micn€l Virrd ( Phtsical .nd Chenical Ph€nohena A@onpdying Themsl Evaronrion ol Raw B nd. Foudh Symposium on Salt 't973

[53] Arulnd Kumar, V.P flohanda3, Rahol Sanghavi and P.K.cholh ( tonic inle€ctions or Calcium Surphare Oihyd€r,e in &ueous Sodjum Chtoride Soluton r Solubililies , densilies . Viscosities . Et€ctdc6t Conducrivities 6nd Sudace Tensions al 35oc).Joulnal of Solution Chemislry Vot.34, No.3 March 2005.

l6l of Salt deposils in [54] Yuin Jirqi, Huo Ctetrs/u, tnd Coi Keqin( Chsaderislics th. Dry Salr td

Salt volf I pas.l93' 194 (l9El).

t55lFarh'n Ullah Khsn (Slatus ofsodiun chloride available for industrial uses from different sources and areas of Paki$an) A thesis to tulfill requircment for M.Phil, Dept ofchemistry University ofKarachi 2fiX'

Third J56l Richsrd R.mitchell.(High raw brine purily from rock) The Symposium on Sall, sponsored by the Nonhern Ohio Geologicrl Societv,

was held in Cleveland on April 2l'24, 1969, The proce€dings wer€ edited

by Jon L. Rau and Louis F. Dellwig

ts4 G. a.sogglo rnd G.A.faok lron, Morton Sah Companv woodst@k (Oeteminalion Less Than PPM Calcium and Magnosium n lllonis€, of '/10 Sodlum Chloide). S€cond Symposium on Salt Page 225"238, Vol #2 1966 (May 3-5 1965 Clsvenland OH). ed'tod bv Jon L. Reu Pofe$or ot G@logv 3t KeDt stdte !lni@6ity, Kenl, ohio.

[58] M.Viard , J.M.Beyna (Parasitic crystalline occlusions in Solar Salt) Foudh International symposium of Salt

(Texas Bnn€ Corpolalion Housron rsgl Roaor-cn.Aeg c. florl.. c .M .smlih6v, i"i"", E. Mackinnon, Unl€d Ssll Coporation Houston Te'as) tTracs Metal Analvs6 of Aqncuhur€ Sah Produclt. Fourlh Svmposum oi sah iage 331-336. voill 19z4apd 8n2, 1973. Ast.oworld Holel Housbn Texas

t62 Chapt r # 8

Si Louis llissouri' (TBc€ MineralSalt 160l william H. Lynch, Hardy sallcompany, Svmposium on Salt Analysis with Atomic AbsotPtion SPectoPhotom€trv), Thid bv Jon L Rau Page 140149 Vol#2 1970 (Apdl22 24 l 969 Clsvenland OH) edited

DsFrttnent of Gonor.l scienc€6' 161l R Bult,Ar:o Nob€tCh€mic.b R6$arch on P.o.Bor 9!00,6E00 sBAhhem, The N.th.d.nds,(Hvpenation of chelatnn 8u wond chromatograPhy and ICP'OES fio ths dsiemination ol element in saltl' ) ['lGeerlmen 2000 sart symposium volume l? Page 1215-121€ Edited by Rob

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Tbe of impuriiies in rock el! l63lBlooEber& A., rNl L.detrburg,K.. 1959. Oallm@ 106' l p 54'59 $ld sall ud putin.d sdim chlorid€r J.El4loch'n soc . v no

Fldcularing ald sdinef,t'tion in Brbe [64t chu xln ( Analysis of F&to6 InllEncing bv sfd Puinotion) 9ri Inl.rutioMl Symposium oo Salt, vol # I Pag€ 130_134 Edited Zuolide,2009, Published by Gold wallPress

oPtinialion of bnne [6s] J.-H Schhldl wM€ierhofer' H Sch{aiser ( Ptoes of puificaiion .nd .vapondon for onbined c.vslalliadon ofNacl dd Na:SOr b, med fie mecbdical vapor rcconpEsion gd Incmtional SvnPosiu on Salt vol { I Page

2?-41. Editcd by sha znoliang,2009, tublish.d bv Oold w'll ?es

conslmption) 9'i l66lvltdlmir M sertiq ( Poce$ine ofslt for chemicol dd hunan 2009' litnadoMl Symposiun on Salt, vol *2, Page 1385'1402 Edited bv Sha Zuolims' Published b, Cold wall PE$.

t6l t61 Fu Yuhen& Liu Chrryhui ( Study on removal of high contenl of sulphate from brine wilh lime procest 9d Intemational Svmposium on Salt' vol. # I , Page 221-225. Edited by Sha Zuoliang,2009, Published bv Gold

168l Hong Zh€ng ( Seve.al Fado6 influ€ncin8 Flocculating Effect ofPAM in waste water Treatmeno Joumal Qinghai Environment, 2002 (12): 68-69.

169l Richrrd R,M. Project Engineer, Intemational Salt Company Clarks Summit, Pa. (Higher Raw Brine Purity ftom Rock Salr) Third Symposium on

Salt. Pase 155'61, Vol # 2, 1970 (Apil 22-24, 1969, Clevenland OH). lT0lAnthony Scrrtton(Laborarory Sludy of the Crystallization of Sodium Chloride fron Brine) fiffh international symposium on salt,May 29 - June 1, 1979 Hamburg, Gemany

[71] O. Raup, Brine mixingr an addilional mechanism for fomarion of basinevaporites, Am. Assoc. Petrol. ceol. Bull. 5a (12) (1970J 2U6-2259. lT2lDiet! DD, Elwell MR, Davis WE J.,Mei.henry EF.(Subchronic roxiciry of barium chloride dihydrate adminislered ro r.rs and mic€ in rhe drinking water). Division of Toxicrlo$/ Rese.rch and Testing, National Instirule of Environmental Heahh Sciences, Research Triangle Park. Nonh Carolina 27709.Fundam Appl Toxicol. 1992 Nov;19(4):527-37. l73l Ajeel SiDgh, Anik Sen, Bishwljit caoguly(Firsl principle srudy lowdds the influence of Cd2+ on rle morphology of sodium chlorideDoumal of Molecular Graphics and Modellins 28 (2010) 413-419.

164 Chrpter I 8

and P€rfection I74l RH, Do.emus, B,W. Roberi!, D. TntDboll,( Crosah Crystals), wiley,New Yorlq 1958, p.393.

Kenichi Krnura' t75l Noboru Iedt, tGhudinm Montri, Akivoshi Or.ki' and Youshihiro Sugi (Esl€rfication of Long-Chain Acid and Alcohols Catalyzed by Fenic Chloride Hexahydrate)' Ind EnS Chem' Res' 2008.47.8631-8618

jchi Akira S'lo' t?61 Noriski Kubotr, K€n Katrgiri, MasmK Yokota, grcwth Hiroshi )ashiro, IGzryoshi ltri. I impurit) enecr of iron I lllr on rhe of poslassium sulphst€ crystal in aqueous solution.Noumal of crysbl groMhl96( 1999) 156-163.1 l7?l Nori'ki Kubot! . J.W. Mullin (A kinetic model for crysral grotr4h from aqueous solutionin the presence of impurily), Joumal of Crysial Gro*ah 152 (1995) 203-208.

( lTSl N.Cabreri, D.A.Vormilyea, h : R.H.Dorenus €t tl (Eds.), Prefectio of crystal),Wiley, New York, 1958, pp.393-407.

165 Appendix 1A

166 Selection of Samnlins Material and Sites

As propos€d in the synopsis submined for this work, th€ nain objective ofthis work was to study of crystallization of prarnidal crysbls of sah as an allemale of natural crystallization which possible in odv hot summer davs with no whd Th€ naturally crysrallized pyranidal crystals of salt was first analvz€d to investigated their chemical conpositions to undeNt nd the ch€mistry of th€ brine solution and then ,the crystallization of p)ramidal crystals of sodium cl oride w€re attempted with lhe help of brine preParcd bv differcnt origin of salt having diff€rent chemical conpositions. For the success of work addition and subbaction of differ€nt chemical impuriti€s were applied with the help of sanmtion techriqu$ and brine purificaiion w3s also performed for lhe removal and balancing the major adon like sulphate and cations like calcium ed magnesium. The cryslallization of p)Talnidal crystals were observ€d th following malerials.

l- S€a Salt 2- Leke Salt 3- Rock Salt 4-Waste brine g€neded bv Sall Refineries.- 5- AR erade of NaCl ( wilh conbination of oters

l- Ser Salt

ln Pakistan tlere are seven sea salt works producing solar salt along with costal

area of Karachi dd Dhab€ji Sindh Pakistan. Two site were selected , one from Dhab€ji and other ftom costal area of Karachi for above mention€d work '

Ten Bndom samples were taken fton each site and analvzed for their chernical

t61 SEA SALT PROFILE (PSH): This salt works is situated adjacent to coas-tal arca of Dhab€ji Pakistan . Ten samples wcre collected ftom differed evapomtion ,ponds according to the information Provided bv the management of $lt works for setting the v€rity of salt having ditrerent chemical compositions, S-H-001,S-H-002, S-H'003,S'H-004 S-H-005' S-H-006 S-H'

007. s-H-008. s-H-009, s-H-o10.. SEA SALT PROIILE ( PSl0: PSK is relaied to Sea Salt works KhuNheed Salt that is situaled n€ar th€ coastal ar€a of Kamchi .Ten samples were collected from this site from different evaporation crysiallization pond provided infonnation of managem€nl of sall works S-K-001,S'K-002, S-K -

003,S-K-004. S-K-005, S-K-006, S-K-007, S'K-008,S-K-009 and S-K'o10'

2- Lake Salt- ln Pakislan more than 50 sah lake having size fron few Acr€s !o few thousad acfes are oPerated in the provence of Sind [55] For the purpos€ of crystatli?etion s€l€cted salt lak€ famous as Khipro SaIt thal

consisb offour small lakes.

LAKE SALT (PLIO: eLK) is siruated on rhe area of district Sanghar al Khipro. The salt is famous a! Khipro Sall. Sanples w€re collected ftom different Lakes.

3-Rock Solt r ROCK SALT PROFILE (PRI(r): The Kalabsgh mine sinratd at the

border olPunjab and khebor P.kthunkuh. In the west and east' the rang€

divides into seDarate nouniains tnass€s, or massifs West ofsakesar lhe

168 couse of ihe rang€ swings to the norlhwest, with low longitudinal rases. The Indus river br€6ks thmugh the ranges al Kalabagh' flowing between vertical cliffs inaccessible to communication The $unmits of tle sall mnge are slanling, hilly, and plateaulike. Tlfte samples were collecled form KalabaSh mine R-01 2, R'013 and R-01 4. ROCK SALT (PRIO: Th€ PMDC mine Vercha is situated is District

Klushab 17 km form Quaidabad Seven samples were collected form Verchamine R-00s, R-006,R-007, R008, R-009, R-0loand R-01 l.

4-MechaDicslly Proce$ Srlt rnd llv.stc brin€ g€nented bv Salt Refi!eri€s. Mechrnically proc€ss salt wer€ coll€ct€d ftom diITercd salt

manufactur€rs located in Kanchi Indusrial Are€, the nain purpose to

get lhese sanple ftom lhe salt producer wa! to ge! $e exact information ofthe origin ofp.ocess€d salt r!\r mate.ial Unfo.tunat€ly insGsd of modem technique like rccrysdlization usng thermal recompr€ssion fior making lhe sup€rior quality of salt like PUE Vacuun D.ied, the mechanical water washing to upgrade the salt is very common in the Pakistan. This process for up- gadstion process of sall gen€rat€s 10-15 % of

waste salt in form of concentrated brine solution. This brine solution has

more impurities be€ause lhe process is design for upgmding sah and ils r€move other impurilies of salt durinS lhe process and also concentrated

by the sodium chlorid€ itselt.

Raw salt is transported by truck form the harvesting area The next stage is washing *E sah in a conical tank by counter flow effect of the saturated brine

169 APPon lA

is purged outside The salt having a densiry of230 Be, de overflow ofthis unt to the hydro cvclones and then after having been washed, is pumPed as a slurry mills to nake the sal to dewatering conveyors which arc follow€d bv hvdro |o the fitst one' but wilh ready for rhe second washing siage which is similar last stage is the final different washing brine which is more clean The a moisture content of 4 0/o dewatering by wom scroll rype centrifuge to have Rotary Dryer for drying by weighi maximum . some of processors funher use

lhe producr up lo 0 lolo moi$ure level

rade of NrC!:

calcium Merck AR gmde NaCl, magnesium chloride , magnesium sulphate' chloride hexahvdrate' sulphate, potassiun chlo.ide and sodium sulphate, iron pr€Paring difierenr aluminum sulphate.( Al2(SOa)3 (|+| s)H2O) were us€d for

soltion to sludy lhe crystallization ofPvr.nidal crysills

SAMPLES: Rock Salt Salt' COLLECTION AND TREATMET OF 'Sea fton and Lak€ Salt samples were collected during the v€ar 2010-2011 lhe site for Sea Salt respective sarnpling locations. It wa! quite easy to select salt but il has sanpling but it was quite difficult to selecl the samples of sea works 'the qualiry mad€ possible with the help of man4ement of the Sea Salt ro lhe evapomlion of Sea Sak depends on lhe management ot brine feeding the nines ponds and seasonal variarion. Rock Salt sanPl€s wde coll€ded ftom of Rock Salr of Rock salt siruated in dilTerenl arcas of Punjab' All the samples

l?0 APP€IX lA

fiom dried were ftee liom blasting material Lake Salt samples were clllect€d 4 to 8 Inches' deoosits oflak€ Salt by digginS the surface of lhe Lak€ up to polv propvlene The Sea Salt ard Lake Salt ssmples were colle.ted in 25 Kg local market On bags with dense ploy ethylene as inn$ lin€r purchased from with the salt the sarnpling sites the sampling bags were rinsed twG ttiree times fill€d and s€aled. Samples were taken laboratory where samDles, lhen 'o at l10'c and moisture analyses w€re perfomed and elrtir€ $mples were dried store for further brine preParatrcn. For the Rock Salt sampl€s rninimum 2 kg piece of each Rock Salt w€re plov ethvlene Beforc collected in 25 Kg poly Propylen€ bags wilh clenl dense water and examined surfac€ of Rock Salt washed by double distilled deionized

dried in ov€n at I10"C. All the $nples were grinded to 8 mesh in the coa$e grander' Mixing of w€ighing for anv analvsis' Sround s.mple had been doing before

ANALYTICAL Tf, CHNIOUES: Salt sanples in screw capped bottles and dense Polvethvlene bags were study transferred lo laboral,ory and wer€ stalyzed for $e patameten under analyzed in th€ according ao the prcscribed pioc€dur€. All th€ parameten werc batch fonn. daximum wift in 7 davs of sanple collection' Following parameters were analyzed by tlle prescribed analltical t€chniques'

4.6.r./0 PURIIYaS!!e! using % Purity was estimat€d by volumetric analvsis bv Silver Nitmte Titration a mixtue of Polassium cbroma|e and dichromale mixture as indicatorl33,48,59]. l?l 4.6: !!!!AIES Sultute in salt sampl€s werc analyzed by grsvim€tric method. fte principal based on sulfat€ prccipitation in dilute HCI with BaCl, under contolled conditions to form BaSOl crystals of Miform size. Sulfare is precipitated as barillm sulfate in hydrocl oric acid medium by lhe addirion ofbarium chlonde. Tbe precipitation is canied out at boiling tenp€mturc and is digested and fih€red. Removal ofchloride is done by washing with hot water. lgnibd and w.iehed 6 BrSOa

Me!c!& Metals ion like Fe, Pb, Cr, ,Ni, Zn, and Cu wer€ analyzed by using Aromic Abso.ption Spectroscopy rnethod using Perkin-Elrner 3100 model( Analltical Methods Fo. AAS,I982)- Merals when bums on Ah-Cztlt flame $ey get excited by getting en€rgy of the sarne source (wav€ length by mean ofHollow

Cathode Lamp for each anallte). 'rhe ail1oun1 of en€rg/ absorbed is directly proportional ro rhe concentrarion of the anall€t59,60,6 I l. &4!g!rg_ By Flame enission SFctrophotometer

Calcium and Magnesium For the estimalion of calcium and Maq€sium d,< complex metic titration method is the method of choice for different reasons-

Amongst lhem is the saving oflim€, free form mechanical loss that is mther common in gravim.tric method of onalysis[.32,62,63]

172 REPORTING OF ANATYSIS:

- Scooe:

Analysis should b€ repon€d on a dry basis, if anslyses are on an as received sample conecrion should be mad€ by convening to a dry basis, Sodium Chloride Purity is detemin€d by subtradion the lolsl percentag€ of impurities from 100. Moisture $ould b€ reported as a sepamte value.

Procedure

4.7.21- Conven Sulfates to calcium sulfate and the unused calcium to calcium chlorid€ unless the sulfate in sample exceed! lhe quantity ne{essary to combine with the calcium. In this crse convert the calcium to calcium sulfate and lhe unused sulfate first !o nagnesiuh sulfate and the remaining sultatc if any to sodium sulAte. Conven th€ unused magn€sium to mag!€sium chloride.

4.7.22- Repon rock and solar sslt impurities to the thtud decimd placc and salt purity, by differ€nce to th€ second decimal place. 4.7.23. Repon evaporated salt impu.id* lo th€ third decimal place and salt 4.7.24 R€port purifi€d salt impurities to the four d€.imal place dd sslt purity by differcnc€ to the thiid deciinal place

WORK INSTRUCTION FOR

MATERTAL TESIING & REAGENT PREPARATION STANDARDS

CALCIIJM AS IMPURITY TN BRINE SllBgi

The following lesting standard developed by hpsr labodtorv should be u-,ed in atl testing fo. calcium pr€seni in brine as impurity

B!Eges!: EDTA solution 0.02N sodiurh hydmxide solution 20% pattern & reader indicator powder

Pipette out 25ml ofthe lested brine and add 75ml disrilled water.take 2ml

sodium hydroxide solution & add a pinch of pattem & r€ader indicator. A pink

colour is developed. titrate this with E.D.T.A solulion till a cl€ar blu€ colour

appea$ note th€ reading at this point. Mark lhis as !, Calculation:-

Calcium as ca (ppm) - va x n x meo0.o2oMconslitucnt) x 1000 x 1000 anount ofb.ine (ml)

v, =Volume ofEDTA used for calcium only N = Nomality of EDTA 25rnl =Volume pip€tte out frorn original solut'on

0.02004 = m€q ofcalcium

Rergenls prerrEtionr

EJ.T.A sla nda rd .olution(0.02 n l:

t74 weighr accurately 3 726gn of the disodiun s.lt of EDTA and make up to l000ml in l000ml volumetric nask bv disrilled warer' mark ftis solution as 0.02N EDTA solution.

Sodiun hvdmxide soldio 20%l weight accumtely 20gm of the sodium hvdroxide and make up to l00ml in l00nl volumetric flask by dislilled water .Ma* this solution as 2$loNaOH

Pcttor & re{der's iodicriort The dyestuff is rhoroughly mixed with 100 lirn€s i1s weight ofsodium sulphate

& lgm ofthe mixhrE is used in each tiration th€ indicator is not very stable in

Refrenc€: ASTM stan&rd tesl method for chemical

analysis of sodium chloride designation +534-98 publish€i F€bruary 1999.

WORK INSTRUCNON FOR MATERIAL TESTING &

REAGENT PREPAMTION STANDARDS

MAGNESSIUM A5 IMPURITY IN BRINE

SCOPE:The followins resrins sEroard d.\elopen b) hps, labodory should b. ued in

alltesling for nagnesiu presnl in bride a impuily,

REAGENT: E.D.T.A SOLUTION O.O2N AMMONIA BUFFER SOLUTION P"IO ERICHROME BLACK T INDICATOR POWDER PROCEDURE.. PiFtte o 25nl ofth€ tesled brine ald aild T5nldistilled w&r. buffer solution & apprcx 0.5s of black r indic.tor' A Pi*ish devclop€d. Titit lhis with EDTA sluion till a cled bluc mlou ar this point. Mdk lhb 6 vr CALCULATION:

MaS.siM s Mg(pprn) - lvFvn x N x Md0.0l2l6aconsdnFnt) x 1000 r 1000 volume ofbrine (mL)

Vr = Volne of edh ul.d for slcim + magnesiu N = No@alily of EDTA 25nL =VolM. pip€lie oul &om onginal $lulion 0-01216 - Meq of mgn6iM.

REAGENTS PREPMTIONT- ERICHROME BLACK T. INDICATORI Mir 05t of th. dry st!ff wilh 9Jg qt. pue sodiuD dJci.le E .D. T. A STANDARD SOLUTION(O.O2N): W€ight ac.urately 3.269 of rhe disodium salt of EDTA and mke up to 1000nL in

1000m1 volumetric ndk by disrilled wate.. (Mk this solution as 0.mN EDTA

AMMONIA BUFFER SOLUTION PHl0)r Dlssolved 67.59 oI amonium chloride in a 570 hL of a|motum hydroride dd make uPto 1omrnl

176 WORK INSTRUCTION FOR

MATERIAL TESTING &REAGENT

PREPARATION STANDARDS

BARITA4 IN BRINE SCOPB

'nE folovinS i6lin8 slldlrd slould b? us.d b ,ll ieting fo. blrid pltst in bdne 6 e

OUALITATTVE ANALYSIS:

REAGENTS:-

1l,l SULPHURIC ACID

PROCEDURE:- To 2.5n1 ofsivo bdne sdd 7.5n1 of distilled water md lmlofsulpluic acid ln,.ftr | 5miu1s lhe elution shorld trol be t|m oD6i.s@t th6 rhe compqison elution. CALCULATION! I|e samplc compli.s when ia tubidity is not morc inteffive thu that of tfic

REFRENCE lBritish pharmac.pcia 1993 volum€ i pag.604

REAGENT PREPARATION 9

1M SULPFURIC ACID :-

Ta*e 5.439h1 HZSO1 of98,08%o@ dd nalc into lootrrl volumerric fldk.

t71 WORKINSTRUCTION FOR

MATERIAL TESTING &

REAGENT PREPARATION STANDARDS

SUI-PHATE AS IMPURITY IN BRINE.

SCOPET

The following lesliis st nddd should b. Nd in all testing for sulphale p'esnt in briDe 4

Reagents; hy.b8hlori. ad.l dilute {n 1vlo bartln chloride slution m€thyl or.nge indi.ato! Procedure:- Take 25ml of biine dd add 75ml of diltilled wat€r . A.ld 0.1m1 of HCL 4N & ad.l 1d 2 drcps of this nethyl daryp tndi..to! heat the elution to boil & then add to thtu boiliry sohtion 10 to l2Dl of bdln chloride sohtion drcP by dtoP till i3 in slight exe3s, Continue to boil for { Dnuted, Nlow the solution to cool tiu trduld praipitates de folded. filte! lhe psipit te & wdh till is fre. fron chlcid6.dry the Prc.iPil.l6 at 105 to1l0.c, coEtandv for thirtv minut6. w1= weigtu of the bdiln slphatc in tm. wr= Anount of brine of the 3.mple in ml.

Badu'n sulphate - q/t6l|!@ 243.327 xw,

Mole.uld wetght of SO. . 969!y'mol. Moleculr weighl of BSO.' 233J! tnvnole

178 Apadir lB

Appendix 1B

t79 Appsdix IB

A brief introduction of brine purification

Brine purificalron has be€n considered as a key process to produce high quality ofsalt and one ofthe inportant factor !o ensue the quality offinal producr and smooth manufacturing op€mtion [64].Ihe ailn of brine purificalion is 10 ehninale or reduce the level of impurities or undesirable elements ofthe brine. Calciuh, magnesium and sulphate ar€ major impundes consid€r€d to be remove to get good qualig of brine , others impurities arc strontium, iron, poirssiun and bromine. Strontium and iron r€move by rhe sarne chemical thar werc use for the removal of calcium and magnesium process bur the renoval ofpoiassium and bromin€ ar€ performed by recrysiatlizarion [?01.

Brine Treatment fo. Fleur De Sel

Salt h not only use to give th€ iasre ou food, lh€ salt institute of the USA clatus more than 14000 ules of sali and every day a n€w applicarion is observed. The quality of salt is varied wilh the inpufities present .Many processes are €mployed ro purifi€d salt ro improve irs quality fo. making it suitable for desire applicarions. The conposirion of purified brine has an important impacl on the evapomtion pro€ess spccially on rhe salt quality[6j].

Sodirm Chloride rapidly dissotves in water. Wirh proper coniact berween wat€r and sah saruded brine is preparcd with in l0 min . The long€r conract tme is caused to increase the catcium suplhate sotubility in the wate{451. Calcium and magnesium are major impurides in salt and norma y renov€

180 Appendix 1B completely by many diff€rent m€thods, Othen najor impurilies a.re sulphat€' potassium and carbonate. Sodium carbonate is used to renove calcium's inpurities and maSnesim is removed by reacting with sodiun hydmxide or calciun hydroxide. badun chloride ,barium carbonate or calcium chloride act as a pr€cipitating agent for suplhate in rhe brine solution. Although brine treatment is not directly our topic bul before discussing the imporlanc€ ofbrine lreatnent for Fleur De Sel bdne, a brief introduction of brin€ purification is

All the reactions to remove inpurities ar€ s:tlightforwa.d. For study the impad of impurides, on crystallization of pyrmidal crystals, the brine purification was applied. Sodium carbonate , sodium hydroxid€ dd barium chloride w€re used to remove calicum, magnesium and sulphab Impuriti€s respectivelyl45,30,66l. The basic purpose to select above mentioned rejgenls was the common ions and to avoid addirion ofoth€rs unneces$ry impurities in lh€ brine solution t67,681 . For instane if we use c.lciun hydroxide insteed of sodiun hydroxide, it causes to increase of calciurn during the r€moval ofthe

The most common impurities of brine are compounds of calcium , magnesium and sulphate and ditrered t}?es of brine purifications ar€ applid io remove th€s€ impurities. The chemicat r€€genls for removing lhese inpurities in brine are few in nurnb€r. Followirg arc dcscription of lhe types which .ommonly select€d and their ph)Gical characteristics w€re defined. Various tesls were p€rformed in ofder to determine how these components affect crystallization, particularly panicle size and shape of pyramidal crystals.

l8l Append'x lB

SODA ASH ( Sodium Crrbomtc)

Anhydrous sodium carbonate ( NsrCOt or soda $h is used to r€move calcium panially salts by Fecipitation 6s calcium clrbonate. Magn€sium sslts are precipitat€d and do nol pr€cipitatc complelely with the us€ of caustic soda or line (CaO). Sod. {sh (NarCOt 3olutions at€ alkaline due to hvdtolvsis Sodl Ash is available in ligh! and dense fofin. The light sodr ssh dissolves faster

becaule ofthe smaller ahd lighter panicles, but th. denle form is pr€fen€d for

brine reatrnent as it has l€ss dust.

Soda Ash is slightly hygroscopic, and also r€act with CO, of th€ air under moist condition to produc€ sodium bi cfbonrte or sesquicartonate, Nalcr, NaHCO}2.HO, thes€ condilions sre caused some caking' when making soludons for chemical wet feed€B. the soda ash should always be added to th€

wat€r , never vice velsq as fonn.tion ofa hydrated ctke may csusc touble

CAUSTIC SODA N.OH) Causlic Soda is us€d !o pre.ipilate m.gnesium and lron salts fron brine. Alufilinum and other metals arc also r€moved duing sam€ process Caustic soda very quietly absorbs moislur€ fiom the air, be.omes sliPPery and individual panicles tus€ !oge$€r. Thereforc caustic loda is alwavs used in liquid form in chemical feed€r.

Brri'rm Chloride ( Brcl,)

Barium Chloride is used to remove sulphate ions ftom brine as a precipirat€ of insoluble bariutt sulphate. Two forms arE svail.ble ; the hydrsled cryslrl Bsclr.2HrO and the anhydrous BaCl, with sulPhate ion is rapid; howev€r lhe

lE2 APP€ ix lB carbonale is usually pr€fened due to its low€r cost, as BaCOs plus the fact lhat it removes calcium ions as well as sulphate ions in others applications

Rc|novrl of ImDuritiest

Cllcium Removah Calciun is present mostly as CaSOa and Caclr. It is ordinary removed to the limit of its solubility ss ca.rbonate bv treatinS the brine with soda ash' reactions in th€ mann€r are casol + Narcor ------cacor + Narso4

CaCl? + Narcor-- .... Cacor +2Nacl

sulphate' The rcactioo with Casoi leaves all the sulphale in the brine as sodium is bas€d The r€action is taken place slowly and fte accomplishm€nt of reaction ash is on the seuling time and exc4srive r€g€nl that is 08 8n excess soda in an hour used b€tter lhan 80% reaction occurs pmctically all is cornpleted

[45,69]. ash il takes several hours ofagitation lfwe use the theoretical amount ofsoda ' pr€cipihre' ro bring the rea€tion to th€ solubility end point of the CsCOr rapidlv However and excess amount ofsodium carbonate makes resction

Rcmovrl ofCrlcium offleur de sel brider was calculated The brine was taken in a container and the amount of calcium to brin€ by analyzing the brine volum€trically. Sodium carbonate was added place wiu stoichiometricslly, until the complel€ rmoval of calcium was taken l8l ApFndix iB vigoros agitation. After analyzing and io ensue conplete rcmovd of calcium in th€ brine, it was allowed to be settled for few hours. It precipilales a!

M.goesiun md Imn rtnovrl lr,lagnesiuin and Iron arc ordinarily pres€nt as MgCl, and Feclr altltouSh insoluble fenic oxide(Fero) may be in susp€nsion in a dirty brine . Mgclz and Feclr impuriti€s are rcmoved by adding caustic soda ( NaOH) or by hvdrate lime ( Ca (oH)r) . Lime is prefened in salt producing planr and caustic in Chlor- Alkali plants. Lime has lhe dissdvantage that it puts cslcium into lhe brine so requiring additional amo6t of soda ash for Imoval.

The reactions ar€ as follows.

MsCl, + 2NaOH ------Mc (OH), +2NaCl F€clr + 3NaOH ------Fe (oH)t, +3 NaCl MsCl, + Ca(OH)? ------Mg (OH), +cacl, 2Feclr + 3C.(OH)' ------2 Fc (OHL + 3CaCl,

Removrl oI Mqgn€sirn of tleur d€ Sel brine The brine was taken in a coftainer and the atnount of magnesium was

calculated by analyzing th€ brine solution volum€trically. Sodiutn hydroxide was added to brine sloichiometriclllv, until the conplec renoval of magnesiun wilh vigorous agitation. Aft€r analyzing ad to ensue @tnpl€te removal of nagnesium, brine was sllowed to b€ senled for fcw hours for

prccipitalion of ma$esium as magn€sium hydroxide.

lE4 ApFndix lB

Sulphste R€movcl

B.rite ( BaSOa) is hiel y insoluble nsking barium chlorid€ as an excelled is selection for removal phase for sulphal€ tr€atment process The barium salt commonly us€d for sulphate removal bv precipitltion include Ba ( OH)2'

BaCOr and Baclr.

NarSOa in brine is ordinarily due to Ee5on€nt of CaSO4 with Na,SOa wilh

NarCOr. The only common r€actions ar€ BaCl, and BaCO3'

Na:SO4 + Baclr ------BaSOI +2NaCl Na1SO4 + BaCOJ ----- BaSOr + Na:CO:

Renovrl oI Suph.le of fl€ur de 3.1 brine Brine was tr€al€d wilh barium chloride to removed sulphate as barium

sulphate. For this purpose brine wa! uken in a container end bariun chlorid€ was add€d until the complete removal of sulphate with stirring for dle

complete ard proper settling of fonn€d bariun sulphate, aluminum sulphate was used to settle insoluble impurities and a over niSht lime is I'ven to pr€cipitat€ all impurities. Brin€ wa! filt€red with 20 microns to r€mov€

susD€nded solid in case ofany. For the treatment of b.ine, the brine initiallv analyz€d for its chemical composilion lo find oul qudtified vrlues of rhe ions are being removed

Classical wet analysis were used to find out th€ amount ofcalcium, magnesium

lE5 Appendix lB and sulphale in brine and the stoichiomelric addition ofsodium ca.bonate, sodiun hydroxide and b3riun chloride w€re applied to removed calciun , magnesium and sulphate impurities [45].

t86 E E o f o- X NJ Table LO

Obseruations for Chemical analysis of bittern trom salt plant crystalllze by dlrect heating Direct Heating Brine of gittern

Calcium &/L Sulphate g/L at NaClc,/L 3ts 2.0O4 7.175 7453 60.8 3(,7 412 1.0s2 8.833 9.059 7200 35.6 314 s/2 0.951 9.314 4.301 9513 28.4 305 6/1 0.951 10.738 13.5('4 !1,266 30.2 715 !.2024 7.554 5.669 7456 85.5 300 a/s 1.3777 3.64 4.5144 72L3 44.5 E4 912 1.4024 7.27 4.256 5593 109.4 315 10/2 L72a 4.9L o.228 480 35-2 318 72/r 7.7 4.5144 53.6 313 t3l2 r.202 8.24 s.548 7244 51 306 r4lL 1.4529 4.t37 0.3192 u2 55.5 290 rsls 1.503 2.842 4014 3rz 16l2 0.9018 8.9 7.9U 8500 57 304 Tablell Obs€rvatlons for Chemical anall'sls of blttern from salt plant crystalll2e by direat heedng Dl.ect HeatinS Erine of Blttern

No. c.lcium&/t Sulphate&/L Pot.ssium ppm NaCl&fl- 5.294 3 0704 4747 38 301 1.002 8.63s 9.196 9lm 35.9 310 1.2024 6.6 5585 301 6..1@ 5lt1 30.7 2V2 o.476 lo.t2 roo5t 32.5 2!D 22/2 1.1177 11.o5 ,A50 55.'l 307 1.503 4,94 5,411 4021 5r1.1

1,.2024 5235

2Sl2 0.9013 4,69 9.1308 9418 25.4 312 26/2 4.3752 aa18 3os 0.9769 a.1a m.407 3436 28.6 314

Ahhah.liv t Table 12 observatons tor chehicar an.rvsis of c.vsta*r€d sart from bln€rn of sarr prant, crvstatred by dn€.i h€aang

Dir€d heating btttem of py.maidrl s.h crystats Ref Calcium % Sulphate% Magn€rium % Potassium ppm Bromine ppm NaCl% 317 o.15a o.761 o.1312 533 115 97.61 0.192 0.668 o.252 50{) 104_6 95.05 s/4 o.232 0.885 0.311 81a 59.8 95.27 613 o.262 0.5471 0.192 435 60-s 92.6a 716 0.128 0.4503 o.179 454 95.71 8n o.25 0.855 o.L92 927 69.4 92.65 72/3 o.072 0.385 0.15 426 96.8 95.42 13/4 0.104 o.407 o.17 593 9a.4 96.94 74/2 0.16 0.357 0.024 142 21.2 98.82 1s/5 0.168 0.489 0.o72 737 27.2 97.87 Table 13 Observatlons for Chemical analysis of crystallized salt fron, crystalll2ed by direct heatlnS

Dlrcct heatiry blttem of Pyramtdal salt crystat Ref No. c,lcium % 5ulphate% NaCl% \7/3 o.176 o.429 0.024 114 ral4 0.175 0.343 o.257 771 117.9 95.92

20/3 0.215 0.63s 0.136 424 68.1 95.59

2tl4 o.224 o.637 0.21, 914 104 95.9s

2214 0.216 0.843 o.262 890 70.1 95.57

23/4 o.2 0.54 0.04 637 67.8 97.06

o.216 o.423 o.24a 614 54.9 96.a7

25/4 o.l5 0.639 0.413 to54 50.1 95.15

26/4 0.208 0.55 o.257 654 85.5 97.75

2714 o.12 0_652 0.321 7aL 74 95.79 Table 14

Observation5 for Cli€mical analysis ot bltt€m brlne from salt plant , crystalllted by indlrect heatlng

Magnesium No. C€lcium &/t Sulphate €/t slL Aromine ppm NaC 6/L 3t6 2.O79L a319 6.945 7733 317 413 1.O27 8.589 8.876 7333 25.3 313 sIz 0.976 9.lE 9.0136 8240 22.1 312 1.O77 9.693 8.998 9253 28.8 304 1.3527 7.941 4.LL92 ao93 64.3 zw e/6 1.2773 4.S87 4.5444 7466 295 B13 1.3025 7.73 4.453 5266 59.2 310 1514 L6242 3.8 o.152 342 304 Table 15

Observatlons for Chemlcal analysis of the blttern brine from salt plant, crystallized by indirect heating

No. Calcium &/1" Sulphate g/L NaCl&/l- 7613 o.9769 6.955 6.3384 6942 308

$B !.3777 7.65 6.Oe|{! 6471 298

2U3 0.8265 9 8.8464 4500 34.1 299

22/3 0.7505 4_21 4.9456 4651 53.4 306

2313 1_152 5.93 5.9754 s212 314

2413 1.1022 7_54 5.7912 675A 2?.3 312

1.503 6.75 3.5472 8036 323

2513 0.9759 9.61 7.8124 8500 298

2713 \.1,2-72 9.53 7.94 8509 14.3 317 Table 15 obseruations for Chemlcal analysls of cJystalllred salt, crystalllzed by Indhect heatlnt Dlr€ct h€atln.€aun. blttemblnem of Pvrdmldllramldd s.ltsalt oastllicw3tll Ref No. Glcium% Sulphate% NaCl% 3Ia o.24 o.741 0.145 523 126.5 94.15 4ls 0.216 0.854 o.267 480 117.4 94.46 v5 o.224 0.7 0.252 60.5 94.45 614 0.16 0.648 0.291 a7z 52.L 92.12 0.184 0.873 o.17r) 500 92.67 ela o.064 0.316 0.126 4aa 72.6 95.17 BlS 0.064 0.303 0.15 573 91.5 95.51 t6/4 0.15 0.368 0.097 95.6 94.3 Table 17 Observatlons for Chemical analysls of cJystallized salt , crystallized by indirect headng Dlrect heatlry bittem of Pyramld.l s.lt crystats Ref No. C€lcium % Sulphate % NaCl% la/s o.144 0.41 0.215 1041 10!,.8 94.19

t9l3 0.184 o.442 0.107 442 57.1 96.18

2!S o.2 0.76 0.199 714 113.9 93.5

22/5 0.304 r.05 0.311 864 78.4 93.15

2315 o.1z 1.03 o.1q)8 475 74.5 94.42

24ls o.275 0.693 o.262 654 57.3 96.06

El5 o.2 o.674 o.47 11(D 92.42

2615 o.z o.674 0.199 763 74.7 94.79

2715 0.104 0.612 0.233 727 90.1 93.56 Table 18

100 hours observations fortheSea Salt brine

Iime in calcium g/L Sulphate&/L clt Nacl&/1, 0 1.503 4.aa 0.912 2072 105.3 322 ,.774 5.501 1.5808 3818 91.? 308 8 1.528 5.258 r.094 2508 95.9 295 12 1.624 s.472 o.9aa 2436 9a 324 15 '1.6032 4.839 1.(X88 2400 101.8 3ll 19 1.14 2400 72.4 298.8 24 1.7535 4.649 0.435 2290 u8.9 329 2A 1.7034 4.947 0.8816 2218 104.7 324 3Z 1.703 0.851 22ta 115.4 292.2 36 r.6242 1.4744 r636 108.2 295.2 40 2.2()44 5.48 0.4654 L925 90 305.39 44 2.O79 5.915 1.1704 2290 90.2 295 4a L.7034 6.229 1.054 1525 99 296 Table 19

100 hours observ.tion for the Sea Salt brine

Time in Calcium slL Sulphate&/l- AL ppm Nacls,/L 5.341 1.0336 273

1.503 5.7la 1.O33

1.2525

72 5.1,r2

0.3056

5,513 0r204

5.537 1.6112

7.6772

1.5352

1,3527 5,492

305.3 Table 20

100 hours sea sqlt obs€Bations Pyramldal sslt crysbls Ime in Calcium % Sulphate % MaSnesium % NaCl% 0 o.22 o.77 0.09 327 53.3 97.4 0.61 0.319 353 70 98.1 E o.70t4 o.57 o.1672 236 95.8 93.13 !2 o.2443 o.757 0.0243 200 o.2553 0.897 0.0388 52.4 96.8 19 0.90r8 0.883 o.0777 272 80.9 95.4 24 0.2883 o.92 o.0874 327 83.9 97.1 2a o.z@2 o.78 0.034 254 66.7 97-4 32 o.176 0.698 0.029 153 77.7 94.2 35 o.224 o.79 o.o29 127 54.4 98.2 40 0.2 0.803 0.063 109 81.9 97.6 o.144 o.574 0.043 r09 at.7 97.2 48 o.12 o.443 o.o72 lo9 84.7 94.4 Table 21

100 hours s€a salt obsedatlon Pyramidal s.lt cmtals

L27 351 94.1

363 55.7 93.2

96.4

r55I Table 22 chemi€arAnatysk of Lake satt Brine

Sulphate Bromide R.No Calcium g,/t ElL ElL ppln !.otassium NaCl A/l- 321.4

1B Jlo- 24 28 ,(505 1.2021 !2? 34 6.237 5.2712 ,153€ aai 1.22'E' 31 3B zl 2s3 36 1.1523 !4 48 300= 5.90 3907 1.1s23 621 5B 305 5.O1 301

6B

Ahhcn.liv t ^ Table 23

Chemlcal Analysis of pyramtdat .rystals .rystallize by lake salt

Sulphate S.No Calcium % % % NaCl% 0.1400 0.454 o_12 385 25.1 95.07 1B 0.140 o_531 0.3939 571 64.2 97.75 2A 0.158 0.537 o.2 628 44.7 97.rl8 2B o.29 1.115 0.15 615 69.2 95.11 o.232 0.842 0.0842 153 95.44 3B o_208 0.589 0.145 430 18.4 97.(A 0.251 o.717 0.\29 384 77.9 97.42 48 o.244 o.712 0.082 323 15.8 97.94 5A o.220 0.25 292 59.5 95.89 5B o.240 0.583 o.2l 75 52.4 96.03 0.200 0.613 0.15 400 48.4 97.93 58 o.237 0.583 0.091 422 51.0 98.2

A^^6n.liY t ^ Table 24

chemical analysis of Rock Salt brine

S.No Sodtum Calciun Magnesium Sulphat€ chloride s/L elL dL tur'

o-42 0.16 t.8 2E0 245 I o-52 0.28 2.4 3t7 947 2 o.72 0.39 3.72 lt2 l3l5 3 0.85 0.5 4.52 3r7 1350 0.95 o.62 4.79 318 l22a 5 0.95 0.65 4.42 ll8 a9 6 1.05 0.85 5.29 3t2 614 7 I 0.68 5.18 3t2 649 8 o.97 o.74 5.32 ll8 6t4 9 0.95 0.88 5.22 107 543 IO o.92 0.68 5.21 307 666

702 r a ^nnan.liY Table 25

chemical analysis ofcrystallized pyramidal crystals of Rock salt.

S-No sodiun CalciM Magnesium Sulphale o/" vo 0.032 0.019 0.166 9E.21 410 z 0.048 0.014 0.224 97.23 392 3 0.032 0.019 0.19 97.52 392 0.072 0.029 0.227 98.44 410 5 0.061 0.025 0.244 98.23 500 6 0.032 0.026 0.206 98.72 392 7 0.038 0.035 0.268 97.34 315 0.076 0.053 o.323 98.34 392 9 0.054 0.025 0.235 98.69 375 l0 0.054 0.025 0.268 97.51 .103 Appendix 2B

AbDendlx 2 B TABLE 26 CHEMICAL PARAMETERS OF SEA SALT ALONC WITH PROFILE(PSH)

Sampl€ Ca" Mg'* sol- NaCl CaSO. MsSO. NarSOa MgCl, No s-H-001 0.1282 o_8220 0.2125 1.9034 95.466 o.4357 1.9997 N.D 1.6383 s-H-002 0.2244 0.2480 0.1 '185 1.0640 98.4069 0.6581 N,D 0.4509 s-H-003 0.2000 0.1605 0.0625 0.6436 98.1241 0.5988 0.2770 N.D 0.4097 s-H-004 0.0962 o.1262 0.0375 0.4450 98.7857 0.3267 0.2687 N.D 0.2831 s-H-005 0.2048 0.1848 0.0875 't.0241 97.9648 0.6956 0.6635 N.D 0.1992 s-H-006 o.2444 0.1556 0.0687 0.7584 98.0856 0.8437 o.2043 N,D o.4479 s-H-007 0.2886 0.2246 0.1062 0.9505 98.705 0.9803 o.3243 N.D 0.6390 s-H-008 0.0401 0.1848 0.0650 0.3808 98.7176 o.1362 0.3567 N.D o.4414 s-H-009 0.2004 0.1265 0.0875 o.9241 97.7224 0.6807 0.5561 N.D 0.0573 s-H-010 0.2084 0.1411 o.0437 0.6753 94.4164 0.7079 0.2203 N,D 0.3785

205 TABLE2T

PROFILE (PSrK)' CHEMICAL PARAMETERS OF SEA SALT ALONC WIfi

Mgcl: NaCl CaSOa MgSOi Nazsoa Sample ca' Mg S04" No - 96.99 o.9527 0.M09 N,D 0.0718 s-K-oo'l 0.2805 o r69a o.1500 0.6761 o 8748 96.91 o.4762 o.6749 N,U s-K-002 0.1402 0.30E6 o.1575 '|.1532 97.55 0.9015 0.6479 N.D 0.3447 s-K-003 0.265/' nz1Aa o.1250 0.0691 '1.5330 97.03 1.4945 o.5995 s-K-004 o.4400 o.135U 0.0625 96.89 0.9510 0.3507 N,D o.5452 s-K-005 0.2800 0.2100 0.1000 oIt00 96.85 0.7078 o.6573 N.D 0.3179 s-K-o06 o.2044 0.1969 0.0925 0.4094 1.3000 96.62 o.7472 0.9482 N.U s-K-007 o.2200 0.3000 0.0875 '1.1410 0.7036 1 39t)L, 97.35 0.6793 N.L) s-K-008 0.2000 0.4100 0.0925 92.82 1.0528 0.3882 N,D o.o33l s-K'009 0.3100 o2400 o.1025 '1.0459 97 78 0.5095 1.2035 N.D s-K-010 0.1500 0.5100 0.0800 l.32UO

All the Values are in Percenr N.D = Less than Detectabl€ Limits TABLE28 CHEMICAL PARAMETERS OF LAI'E SALT ALONG WITH PROFILE(?LK)

MgSO. NarSOr Msch Sample Mg" sol' NaCl CaSO. No L-001 0.1763 0.'1167 312 0.94 97.031 N,D N,D 0.2016 L.002 o.1363 0.053 400 o.3327 98.499 o.463 0.0076 N,D L-003 o.328 0.126 625 1.08 96.291 1.1141 0.3682 0.1364 I-004 o.312 0.063 2fi 0.659 96.666 1.0598 0.1393 N.D N.O L-005 0.1523 0.1358 1812 1.338 95.885 o.7924 0.8714 N.D L-006 o.44 0.135 625 o.944 98.637 1.338 o.1277 N.D o.o21 L-007 0.1843 o.0424 250 o.7814 99.396 0.626 0.4081 N.D o.6994 L-008 0.232 0.2911 475 1.001 97.120 o.788 N.O L,009 0.4649 0.5593 1400 1.333 94.950 1.5791 0.5825 o.1172 N,D 0.1571 L-010 0_0392 0.0637 275 0.1875 99.250 o.1332 o.224 N.O L-01 I o.10d2 0.0962 275 0.46 98.699 0.3539 N.D L-012 0.104 0.096 275 0.388 97.650 0.3532 0.1738 L-013 o.2732 o.248 0.164 0.967 97.859 o.8424 0.4668 N.D N,D o.1477 L-014 o.'104 0.237 625 1.037 97.686 o.3525 0.987 All lhe Values are in P€rcedt N.D = Less than Det@table Limits

)o1 TABLEZg

wlTH PROFILE (PRKa) CHEMICAL PARAMETERS OF ROCK SALT ALONC

NaCI CaSOI MgSOa Na2SO4 MgCl? Sample Ca" Mg" K Soa'' No 0.3516 o.a374 N.D 0.0593 0.0710 0.1000 0.9891 97.9454 o.2014 R-01 o.2200 2.7095 N.D 0.1603 0.0486 o.1125 2A0A9 95.3101 0.5446 R-02 0.o144 1.0095 N.D 0.0633 0.0029 0.0812 0.8429 98.7296 o.2't51 #*+

TABLE 30 ALONG WITH PROFILE(PRV) CTIMICAL PARAT,GTERS OF R(rcK SALT

MgSOa Na2SOa MgCIt Mg" so.' NaCl Caso4 Sample ^-+ No o 104/ 0.0840 0.0881 N,D o!320 0 0170 0.0250 0.2035 99.4682 R-004 99.653 o.2711 0.0649 4.0906 N.O 0-0800 0.0131 n 2312 3.0100 R-O05 0.1960 1.5654 3€3S2 N.D o.o577 0.3161 o.3sUU 3.9a42 90.3'142 R-O06 o.7494 0.1683 0.5375 N.D R-007 o.2324 0.0340 o.2375 1.0549 0.6070 9A.9242 0.1 '1 14 o.o24l 0.7529 N.D R-OOE 0.0328 0.0049 0.0875 N,D 0.4803 99.2161 0.0652 o.o743 0.5545 R-009 0.0192 0.0150 0.1562 N,D 1.3219 a6.a47 4 o.4273 0.8554 R-010 0.1258 0.1 1 18 0.25s0

All lhe Valu€s are m Percenr N.D = tf,ss than Detectablc Limiis List ofluDllgc@

Tohi"n Ahnod(Pilot Pltnt study to l- F.th.n ull.h Khr|f' ta'Id llon 't 'nd E App ed ** ** t r. Ggt€tsd by Sall Indudi6) Jotttd of Sedc sc/orc€s, x12, 8, 3ES92

ll0 Jddtu'.rddt!^!4!!l!g Pilot Plant Study to Utillze Wastq grine Gen€Eted bY Salt lndust es

Fadan ULlah Khan, i,lajid Mumlazand Tehseen Ahm€d

Dep.nnnt ol cn nistv, Unitettt! at ra1cht KsnchiTs2To Pak6tan liiiii",i'. -i. do *t- r q "j.i".ii*Le*u.o".-rq'.*fu4b.'u

p to' i3 bgb 3'd L^q* crytrl - a *" a u'" p.." t stuutd'mi d.fij*r"- ..vlonrcnr ch.nq€. F I'E n.tu6r stutuGl11l qutritv 0l !'n bul as slntght PH rEran@ 6nd rhe up o'.daton or Rr'e 'mpm€d ch.llcng€ lho sudiv.Lol m.nne l € on t dsLlv saxniry qual'lv ol ha nB demand 'ndu5ln$ ul' ems tYP€ or *tr Er or@sse6 b 'nhd'€ To upgdd€ 3st qual'rv medan€Le6rl w'shing 6 iin"..t nowt,rer hundodr ol mev oher ue.d m.ny @ud'ee sn6@, chldcarbx a^d 'n p@t! Nr drv ar dife€il sboos and d*tLing Dv eiutuge .Doi*lon.. Th. *aihng 'mpd€s nod 9a 991 % Th' maior tlowniem$ols|lbulolsredu( trMEdes sll au.Ltv pobs ,i'i-*" -t' tn" *'""' slt rr€ doum m.ones'um 3urDh.t."t ad !ep.r.t€d lroh salt upgdoauon b'om'de L12l lJnbnunaierv 'nd 'i _ maring rtr 3uo€rbr 01o.s Ounns E uP E.daen Pl@s r0 15* or ccnn(w I'k. it ou.rr ot36[ Lre'e

r.,

Fbud 1: GrS D.b b' S.k P'dEA,d Pl@soB n P4Efill41 utlz€d and rcmovns najor impudt€r bul havng a densily of 23c Be (Baun6) lhe ov6riow or unlo un6to y ir is disposed off bac.k iilo 16 s.a w(houl lhe sal anor wa3h.d * ul iz5lion 15-151 this process €uses an osmol,! pumpad a3 a sur.y ro lhe hydro.cycones and lhoi lo shock or rhs riving oQansms (ecosyslems) i rho s6a deai.ing conveyors wlich aE bnowed by hydro Tri€ eflue ii irie w.gte € . h€aviry @ncsnrrar€d di5 ro ma[e $a sa( ready for ih. sBcond wssh ns dehaeed efiluenr hss th€ sbg. Th6 socond sbqe s simirar to the f6lonowilh polent. to krro.ganisms Ahoush be b ne soution brine which d ceaner llran rho cont3nmg nBtur.r oi rh pr.v'o6 b. ne The Last sbqe rhe iiar de*aterlns by 'g '.srcdLent wo.m scrcn type centdtugg to have manne popuraron near ou0el t45l rr s mpon ni ro or max'huh 4 0% by reighl lrTrel some preesto6 make rhe sa r indGtry fiiendry to en tudner use Robry tye. toi dryns rhe podud upro r cou d have very advece efiecr on rhe envnodnenr

2. PROCESS D€SCRIPTION 3, fiATERIAL AI{D HEIIIODS

Ra' eLt s kanspoded by tuck rrom ihe had.sr'ns arc: The nen slage G washins ol srrr pr@ossins uniB situated in sindh add aa|€hisrar oonka rank by counter frow 6lr.cl sal(atsd bln. Trbr.rr l@l. coht.ldoi ol uptd&d s.h in .mryrng 0F brin. volun.lic.ny. c.lcium hydDnd. M! .dded lo Mst b?li. .lolchio @npl.ia preoirraton ol hagiGium a3 maqnc6ium hydroxid.. n was ob..fr€d tlat som€ amount or q91 o.lolud turDhai6 also pE lpilll. d .t cl and rimlled solot liy or 6 duh 6u ph.ia Ln bnn. 8q R€eid s6. p.ft.m.d litt qen{€ 3iirin9, .. vi9@6 sbmng m.y inft$o dE *shg re ot m.sBr@ hydond. p1l f.mc cHdi'e sat ltilt€d .r co.suranl lo [email protected] od an i Afier .mrrzins and b .EU. @frpl€l€ €N.l ot m.g n*ium lron w.sL bdn6 sLr houre ijme @t giv.n b srution ro b€ snL€d. A lio Lmpofijes rce..n€d Efiru.n! md nEas unh ior vlr.L rv.Lr dowi inlo $6 bonom and th. cr..n a tEnsiarod inlo anothd cl.ti lank BeioB .nd Erl€r birc t€.tnenl bnn€ w.c $.lyzed ior ils chomlel @nr4trim (Table 3) rt e$ obsfled md in lh. ! mtisbt i'e$.d taNlerEd iattu s c.Ytterlz.bon.

'Ihe c.ll*Ed bdi. was ihnedi:it ry ir.hEpdr€d to the llDdalory iot luls€r dEmical analyde sd b n€ r.al'mt Tn. s.mpL$ #E.narrzod td rlr.ir demlcal cmpditlon or nalor en npu io!.uch r3 €lcom, magndLum rurphds potassum and bonid. and for $€ ansryt! of lar and brLn. 3.mpl€3 sLndsd p@du€8 Mr. 12.2. Crys|llhtttdr tt thod !.2. PcT6artun{ ol Brln. D6ns der povb!. t npddnft imp.cl oi u. &n .Mp€d pvlnid.l 0!rin9 many pcrioB .rpsim6nl5. i wE or th. crylr3rs. fte M.i. sLhl6 zo. ior conc..irstion or naqn.rlum rom on h6 cyslaL !h5p. crFEl qbtlh ws oas@d b.ir6n 5r5eo ll s€s v.g oasryed Lt wa! iol.d lh.l hlgh cd6nt.lion nol.d lh, dn.d h€atnq lron botb or nEgul.r py.amLda crysi.lr m.y cause lne lord.liM lr.guld drysbl gfwtl Dt w.c P and 3ometmes only crusl turmEtio. ws ob€.toed. Th. t€mpe6t(6 n tle Fn€ crysiallisr and r.3u bd srmo phendmenon was Ep.n d by S Inoue el a/ 16l lohalion of dllr.rcnt cryslalllzalion zon.s To d6r@me thB lsul a emar Bc.l6 piot pqer wEs Fina ry for rhe ol bfin€, pEcLpit ir6 or rrcb.rhent d$igned ior$€ utirE lis or*ctr bine mgmsium 6 masd.ium hyddld dimift or &.r€s. tf, @n@nt6rio^ o{ maoMium fd the dysL{a.ton ol ..diun c dde, 5x6 iter drinr$s $eel (3161) jscrc|€d dysl.nts sr d.cqn.d whid, e. .tbch€d *i$ geysF ttogh qp65 3.2.1. R.no6t ol u.gnslun and hot eater @r circur.l.d ior dnslad h€at t...t r Th. Msr€ brin€ wE. i.k n in a 150 L cyliidrcr (FEUG 2) 1 /aEl6 b'i.. w$ rlred n $s op€n tr6 rank. The amounl ot mEgn€lom {a3 €lculalod by Jd,.*.4!!44E?1!l!!!!--l! cN.trllis $d idr9.6tuE *.. minhli.d bv crru|lin! hol *.t.. i.trd. tE j..*.Ld crvtLlltd T.mpe€lrr. (5S5cC) k. .dlurt€d bv tf, e.v$. i.me d cdtoll€d iow ol clEuhllig hol s.Lr th. o6sdtd v@ br.n tu nD dv.rd&lbi of .q$re ptEm'dal sylbk ovdd|a.d Dvriid.l CMEB mE corbci.d.nd an€lrr.d lbr $.lr ch.mEl campoilior tlri4 (T.bL. 5) not d * s1,s2 .nd s3 1E bnm &!io. 6 .lro dlt4d thdulrloi nt' .r@rii. FGn hd, *$ lbd tum nf, bobm oftr ot cry.l3lliz.r to ruidtin rtin. l.vel h Fl€['.*!slE'.dPFm'd.|cry$!bm@oy (le.dtc.d.nt ol oy.dr.t

Ih€ r€mper.tur. tss m.inLiied .t 60oc but 5t lh. !m ro @lb.r ey.t 16 .nd t . esult ol lr.sh hd. ddilid Lmp€8tu6 [email protected] dghtv bul dudrg !l. wnob .rrdn6nl I M3 m.lnt.lmd in tF Enge ot 55' 6ot. T.hpe6n& wEs @idl6d bv n.i^t inin! $. nd ol d@hrid Ebr ih i-lot d mll ol c.v3t nar f by.dj6tjnq tF iffi or€.y..r Fdni6 orbrg. runb.D of ljnv .ucl.l w.s ob..B.d .! E rcsull ol .sireuon dunng c.llectih of cry3ltl! once in. n€hu. dtsbrri4td 2@ w o€*d, tE 8v!|.m losl L ml*ird. cclon aliiidon in .ny |!sn f. ob..N.d .s tho lomaijon of nresul4 notphology ot cryda!. crysblr o@ on th..uf€@ .. Inv€rl3qE. oyEmrd.r rh.F. 3.m cdnpolio, p+1, Ldp€€ttn .nd .i.th envlrc^Nnt w.E fE k.y Ed.E lo c$torr.d cry!Lll!.ton. In gme€l th. pyEhldEl cyst l. @ h. dysr ..d by dE biti.m ot .lt ind6!1.. our rt!. b hbh LEl ol nplal-s lik m.gmduh aid turphat which ds.d* $€ &rubrrrry ol eloiun in bnn. I t]€ m.ln @eon ol Ftqi. 2: ElForIy 0..i0d Jr@ Cl,rrlis t{ ftirm.id or h.!ur.r iwplEloay. Th. ..&hlly ol €ktum rulphalt In bdm ,E€.€d *h 0i i@ l^ dRESUITSA DD|aCUSSION

a ta .tsling p

rsor|rbno!'i'iClFh.n|

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