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"'•""? ARAB REPUBLIC OF EGYPT >,* 4 ATOMIC ENERGY .ESTABLISHMENT

'- - \,f < ?, i ' '. 'NUCLEAR,CUEM1STBY DEPARTMENT " -

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X We regret that some of the pages in the microfiche copy of this report may not be up to the proper legibility standards/even though the best possible copy was used for preparing the master fiche. A.R.E.A.S.E./Rep,- 288

A1AB M3PUBT.TC OF MYPT ATOMTC ENERGY ESTABLISHMENT NUCLEAR DEPARTMENT

IITGH GRACE FROM WASTE BITTERN

B7

T.S0*SY.-YAMANI, MoYoPAlAK? »

and S0L,ISAAC

1979

SCIENTIFIC INFORMATION DIVISION ATOMIC ENERGY POST OFFICE

CAIRO?AoRoEo - i -

CONTENTS

Page

Ani* TRACT ...... o...... ««....««».«.<>(>..s. * 1

INTRODUCTION. „ „ o 0 u . u. o. »...... 1 EXPERIMENTAL. „.. o 1 RESULTS AND MSCUWON. 2 a) qtudy on physical and Chemical propertiea of the Bitterns.... 2 b) precipitation with : 2 Effect of Magnesium Concentrations G

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ABSTRACT \ ( The pr«di*cti«n of high grade »agnesiit for nuclear purposes fr«» sea vater by use of both aqueous and gaseoua wni.onia has been descri­ bed. The effect of precipitating conditions on the settling rate and » u^nc-sium recovery, was thoroughly examined, Aauuonia gas approach -was recou'tuended and justified. INTRODUCTION The demand of magnasiunu anefyhl.or alloy Is steadily irAcrf"&K»Bing owing to ffidcnicg the circle •©# their industrial applications

In the Older-H&H and MurcpuXe type rettcio,ro y »agne:uujfc and xife r alloys particularly fcagraox AL 80J uv-gnox A lsP fc'f-2.r *»d M?-Jhfe are used extensively aepclad materials,.

Most of the processes woed'to obtain the fl,eiaJ. rely upon magnesia preparation ao imteirmediate otep in magnKeiura production^ Due to the shortage in reserves'of magnesium ores in generalp sxirs- ction of magnesium was mostly^ achieved from sea watair „ Most of ire* approaches reported involved the treatment of eea -"rater or bittern by lime^ "*v'j burnt dolomite ' and electrolysis^ " "*', Liquid- liquid extraction was attempted more recently on laboratory scale " \ Pew informations were patented on magnesium extraction by aqueous aromoniaj ' '. It is the aim of the"'present 'investigation to carry out a systematic economic study on magnesia extraction from saline water by both aqueous and gaseous aaaionia whereby an i&proved method was suggested for production of high grade aa&gneaia0

' EXPERIMENTAL

Bittern samples used were obtained by evaporation of aea water (Ajiexandriaj 4®Be) by> solar energy in huge ponds whereby crystalline sodium chloride is deposited} the mother liquor (waste bittern) which is usually rejected (by draining again to

the sea)?ia used as the starting material in this study. Viscosity and density measurements of the bittern saasples were conducted by ©Oittv«n« tional method„ C» was detenoined complexowetricaliy using Murezid® indicator whereas Mg w-as determined either ,co3spleyometricaily wzih Eriochrome Bl&c& T(in absence of C**-) or by difference (in prfiS«?Biffie of O) between Mg + Ca as determined complesoaietrically with Hrioisfarcase a -

Black T indicator and ca **« determined with Murexirie indicator, Sulphuton vrd al*?o dettrotinet* coiupleyc-nietrical ly by «c»r 7!<«p1 * '*nd liriochrott'' fUck Tj carbonate*f litrfoetricaMr uHinr neihyl re* indicutor;totttl httlid*p by t'ol'iurd'* method1 , The offee* of pre- cipHutiop condition* WUA checked by chewical unulvHCM. Mapupsiun recovery van determined by taking ivliquntfi cf th'- nlurrjof. before rettling* treating with pel, neutral izinp, vith uu.tioniu then Kitkinft' ap to volume and Biagm'si'Sis IP thru determined (ia an uliqout) couplero»»ctrically »s u>enlion<:d above, ^ettlinfl r&tf wap dete­ rmined by flhul»iri{r the slurry in a stoppered iLeusuring cylinder (f(«5 cm) and noting the level occupied by the aeltiliair precipitate utter various periods, while using a slurry of 300 ai.

u) Study on physical and Chemical properties of the Bittern:

The variation of density tend viscosity of different bittern samples vit.h the chemical composition of their constituent element*] was esu- tkiT»od by evaporation of the initial bittern, then cooling to rooit tenperuture ( '" 33°C)| results are represented in Table(l). it is evident that increasing the bittern density enhances n.arlieclly both the viscosity »nd tho total hnlides content while iuhibit* the sulphates, carbonates> and &eta.l*. Tt is worthy c-etiticninr that higher vi?cof»iticp ( ". « centipoiees) are not beneficially uned due to ("•conondc reasons, eptiaoE' B-agnefiuui recovery i« achieved at about 370Be' whereby the niajority of impurities are discarded.

b) precipitation with Am&onia Solution:

The influence of various precipitating conditions on both the nettling rate (-vhich is used an a criterion for the effectivenepp of filterability) and odt^neniuio recovery, in piven below; the concentration of ABBonit solution used was 24 voliuse % and data are presented in Table (>>). «" 3 "

Table (l) The variation of Tjenuity and viscosity of Bittern Samples vith their Chemical Composition, density Viscosity Mg++ Ca++ SO. Total co P Alkali 4£ a °Pe' (Centipo­ (M) (M) (M) Halides 00 Metals ises) (M) (M)

24.2 1,3 1.23 1.20 0,30 6.7 0.02 5.10

W.l 1.5 1,61 0.60 n034 6.0 0.04 4,50 28,1 2,0 1.73 0o04 0„35 5c2 0.09 3,00 29 <. 2 2.5 2„06 o.oi 0o46 5*3 0„l4 2»53 31,7 2.8 2.55 m 0o44 5.6 0,19 1.80 33.o 3,2 2.08 ~ 0.29 8.2 0.21 1,60 34,3 3.8 3.09 - 0,2ft 8o4 n.nl o.m

35,0 3.2 3.*3 - 0*26 P„5 „ «v0» 36.8 5.8 3.91 - 0.25 8.8 - „ 37,9 3.9 4.73 ~ 0.05 io„i - - 38 A 6.5 •5.U - - 10.1 - „ • 39 Complete Crystal liLaatio n - 4 -

Table (2)

precipitating Conditions of vith AamtOQia. iig Concn. Temp, nate of Stirring y'inal Settling Mg (g/l) ,c Addit xon f^ate ftate *}ecovory (cai3/»in.) (r„p.m„) pH (cro/oiin.) (#)

11.5 0.25 95.0 23 0.17 95.2 34.5 27 25 1000 10.4 0.10 95.6 56.5 0.02 96.0 69.0 0.01 96.2 90 0,01 96.8

26 0.27 96.0 40 0.30 96.5 11.5 55 20 500 10.0 0.48 97.0 70 0.61 97.5

10.2 0.24 45.0 15 0.26 45.7 45 of\ 20 250 S.9 0.28 45.7 25 o„u 45.9 60 0.0R 46.0 immediately 0.06 46.5

100 0.2 96.5 250 2.4 96.2 11.5 26 20 500 10.0 2.7 96.3 750 2.4 96.5 1000 1.9 96.2 - s --

Con. Table (2)

Mg Concn. Temp. Rate of gtirring Final Settling Mg, 1 (g/ ) er, Addition Rate . pH Rate Recorei-y (cm /rain.) , (r.p.aa.) (cnj/min.) -(#)

8.7 0.04 81.1 8.9 0.25 45.1 Ho5 26 20 500 9.1 0.30 60,2 9,7 0.32 87,5 9.9 0,45 93.4 10 „o 0,36 97,0

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Effect of Magnesium Concentration:

Settling rate and recovery- of magnesium *»» examined as a function ot magnesium concentration in the bittern (11.5-90 g/l Mg)j aamplea uaed were obtained from concentrated bittern (37'B«') by appropriate dilutions with aea water (4*Be'). T* *• revealed that for higher eon- contrationa ( \.90 g/l Mg)» the precipitate ia ao compact and bed does not settle. Optimal data are developed arouad 11.5 g/l magaeaium whereoy good settling rates are obtained.

Temperature:

The increase of temperature of precipitation, raises appreciably the settling rate and slightly, magnesium recovery. The ambient tem­ perature ( ^ 25*) is advised to be used. pate of Addition: Insignificant influence of the rate of ammonia addition on magnesium recovery, ia observed. Settling rate -was shown to be improved markedly with riae of addition rate upto about 20 cm /mia. then decreaaea aharply afterwards. Optimum values are hence achieved at about 20 «•> /min.

Effect of Stirrings Although recovery remains nearly unaffected with riae of the stirring speed, the aettling rate is considerably improved with agita­ tion upto about 500 r.p.m. then decreaaea gradually afterwards. Moderate stirring ia hence required for attaining beat results.

Final pHj Increase in pH leads to a pronounced riae in recovery and gives also a marked improvement in settling rate. Recovery was raised by more than 3-fold while settling rate by 9-fold, wiAh increase of pH from 8.7 to 10. Optimum pH ia hence adopted around 10.

Summing up, it could be inferred from the above observations that optimal precipitation conditions (96$ recovery* 2.7 cm/min. settling rate and 98$ purity), are the following: n-agncsium concentration in M 7 IM

the hi&teanss 1165 g/1 > 4eaop«r«.*ur®a 25*? ro-te o£ *»&<•»£* ttddlikm* 20

CB. /roin0; wod*r*te siiffrifflg (500 »".puw.) and PH should b« adjured ut fcpproxiaifttaly 10. c) precipitation with G^atoua Annoain* Concerning ainimonittcgttflsi th* *f£eet of various p«Mr*n>*t«r» oia both the settling rate «nd r*«"?v»ry *rt gxvea &a f*bJ» {$)<> Effect of magnftaiuai COttcemtr»ti«ms TJacre*»ing the magnesium content dimininhas coa*iderabl y both the nettling rein and recovery* At higher cone eat ratio an ( ,.56 g/l Kg/? clogging &t tho mouth of the bubbler occurs due to higher rate of preci­ pitation. Best results ore attained at about 11,5 g/1 Ug« *i}ate of A)G3B)onia Injections It is evident from Table (3), Mat increasing the flo*"r«to of ammonia injection leads to a alight rise in magnesium recovery (ahouit l„7%) vhilc the settling rate i.a increased by about 2- foldj optimal duta o-re tiua rccoamendod ot «>bout 1„5 or 2 I/sain,, Tjepth of Injections Increasing tho depth of injection (distaace between the nurtttee of the nolation &n

solution &s UIBO due to exothermic aajwonifc di»soXutionc Injection depths between lo and 15 cm are required for obtaining better results,,

Geometry 6f th© Containers

Tn order to examine the iaf liaemse «f the *0tttaia*r geeoafttry, precipitation V*B conducted by use ©f Pftlirae solution of 1X„5 g/l Mgj

flov-rate of fHBn>onia of 2 l/»in, and depth of injection ®f 5 caic 8

Table (3) Ff*«eipit&tiiig Cottditiotli of Magnesium Hydroxide with Araonia aa«

Ug concn. n

11.* 0.25 95.5 23 0.27 00.8 31 2.0 10 0.10 85.2 44 0.02 80.2 56 o.oi 79.4

• 0.0 0.13 04.3 0.6 0.13 95.5 0.9 0.20 90.0 11.5 1.2 10 0.20 95.0 1.5 0.22 95.5 2.0 0.27 05.6

2.5 2.1 91.5 5.0 2.28 93.5 T.5 2.36 94.0 11.5 2.0 12.0 2.38 94.6 15.0 2.24 94.7 19.0 0.30 95.5 ~ 9 - while varying the ratio of the container to the bubbler »t 5 , 7 and 9f the corresponding nettling rates were 0.26» 0.25 and 0.20 cu/min, while the recoveries being 94.3 9 92.1 and 90$ 9 respectively. It c»uld be i»f«rred that as the $ af the container increases; recovery ef magnesium gradually decreases due to larger surface area exposed. Settling rate decreases slightly with rise of centainer ff? presumably due te uneffi- oient bubble stirring effeet.

Conclusion g

From the abeve study involving treatment of bittern with g*.««««iaj ft»in«nia9 optical data (95$ recovery 9 2.1 m/min„ settling irate »»d 99.9$ purity),; *re the ftllewings magnesium «on

OD9 using a container whose $ $>*•/. 5-fold that of the bubble 3 final pH of precipitati** was generally «n«eutmtered at -^Z 0o4§ ««i»

F*r an easier equipment handling and for eeonamic rtnetsie, pr»&es~ sing of bittern with ammonia gas (which is recycled) was the approach mostly receBwended for production ef high grade magnesia (99.9$) that could bo obtained by calcination of the precipitated liydroxid<&0 Justification of using oononia gap method was ascertained by ape«str»- graphic analysis,conducted on magnesia produced. It was proved that high grade magnesia obtained by gaseous assonia contained only traces of potapsiiun and 100 Pftn boron. Since borons has a high detriment*! effect on the nuclear properties ef magnesia; further studies are needed to reduce the boron content to \ \ pps in nr&er to agree with the nuclear specifications! this is beyond the scope of the present investigation,, - 10 -

ACKNOWLEDGEMENT

The authors -iri*h to exprees their gratitude to Dr.P.A. El-Fekey, for hiB kind endearour, aad to Dr. F. Abow El-Nour, for spectrographs analyses conducted. - 11 -

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