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