Options for Treatment of Sodium Sulphate Containing Effluents

215

Options for Treatment of Sodium Sulphate Containing Effluents

J. Pradhan, M.K. Ghosh, T. Subbaiah and S. Anand
Regional Research Laboratory, Bhubaneswar-751 013

ABSTRACT: Sodium sulphate containing li uid e!!luents can be treated in two ways " to reco#er sodium sulphate crystals as well as to con#ert sodium sulphate to sodium hydro$ide% &n the present in#estigation electrochemical splitting o! sodium sulphate to con#ert it into sodium hydro$ide has been studied in detail #arying current density, temperature and sodium sulphate concentration in the electrolyte% 'he optimum conditions !or obtaining higher current e!!iciency and lower energy consumption are(current density )00 *+m) , sodium sulphate concentration in catholyte, 110 to 130 g+L and temperature , 50-.% Salting out method to produce sodium sulphate crystals using methanol, acetone and mi$ture o! methanol and acetone has also been in#estigated% &t has been obser#ed that a ueous solution o! methanol gi#es best results with respect to the nature o! sodium sulphate crystals and !iltration properties%

1. INTRODUCTION Sodium sulphate is produced in large uantities as a byproduct during manu!acture o! cellulose !rom al/ali solutions using sulphuric acid as the precipitant% *lso in many hydrometallugical industries sodium hydro$ide is used either !or p0 ad1ustment or !or neutrali2ing the sol#ents during sol#ent e$traction steps generating !inal e!!luents containing substantial amount o! sodium sulphate% 3n the one hand the reco#ery o! acids and al/ali !rom salts is highly desirable to minimi2e chemical consumption by their reuse and e!!luent treatment costs% 3n the other hand, the industrial demand !or sodium sulphate is decreasing% 4lectrohydrolysis o! sodium sulphate to con#ert into sodium hydro$ide and sulphuric acid has been /nown !or many years 5Stender and Seera/, 16357% Later it has been the sub1ect o! many in#estigators 5Radd and 3ertle, 16738 9:rissen and Simmroc/, 16618 ;artin, 16638 0ol2e et al, 166<7% ;any inorganic salts are produced industrially !rom a ueous solutions% 'he !inal production step in#ol#es the crystalli2ation o! the salt !rom a ueous solutions% *ddition o! organic sol#ents to an a ueous solution can reduce the solubility o! some inorganic solutes% Based on this principle some interesting separation methods !or the reco#ery o! salts !rom wastes and other e!!luents ha#e been proposed% 4#en though

relati#ely large amounts o! sol#ents are re uired in the systems it was proposed that sol#ent could be reco#ered by distillation% &n the present in#estigation in order to de#elop a process !or treating sodium sulphate solutions the !ollowing three options were studied, 5i7 4lectro-chemical decomposition to obtain =a30 5ii7 Salting out techni ue !or producing sodium sulphate crystals% 5iii7 Lime boil to obtain =a30 2. EX ERI!ENT"# 2.1 Ele$tro$hemi$al De$omosition E%periments 'he electrochemical e$periments were carried out in a cell made o! >erspe$% &t consisted o! ) compartments o! e ual dimensions o! 300 ml% 'wo compartments were separated by a neutral polypropylene thin membrane% 'he temperature was maintained by operating the cell in a thermostatically controlled water bath 5Sis/in 9?L*B3 @>.7 and current was controlled by a recti!ier 5*plab 7)51, Regulated A. >ower supply7% Auring each set di!!erence in =a)S3< concentration between catholyte and anolyte

energ( $onsumption. 01h/0g $urrent effi$ien$(.8

216 concentration was maintained at )0 g+L with catholyte concentration being the higher% &n all e$periments >b-Sb anode and stainless steel cathode o! sur!ace area ))%5 cm) 5each7 were used% 'he cell #oltage was measured by connecting a #oltmeter to the anode and the cathode in the two compartment cell% 'he cathodic current e!!iciency was measured by analy2ing the =a30 !ormed a!ter ) hours at the cathode compartment% 2.2 E%perimental ro$edure for Salting Out Studies Bnown uantities o! the sodium sulphate solution were stirred !or desired time with methanol or acetone% 'he phases were allowed to e ulibrate% Sodium sulphate crystallises out% 'he product was !iltered dried and weighed% 2.& De$omposition '( #ime )oil 'he e$periments were carried out by ta/ing 100 ml o! sodium sulphate solution and predetermined uantities o! lime slurry was added% 'he contents were heated in a 300 mL closed reactor% Sodium hydro$ide was analysed in the !iltrate% &. RESU#TS "ND DISCUSSION &.1 Ele$tro$hemi$al De$omposition of Na2SO* Effe t of Current 'ensit! 'he current density was #aried !rom )00 to <50 *+m) and the results are shown in 'able 1% 'he

Mineral Pro essing Te hnolog! "MPT #$$%&

results on e!!ect o! current density on energy consumption and current e!!iciency are shown in Cigures 1 and ) respecti#ely% &t is obser#ed that with increase o! current density cell #oltage increases resulting in enhancement o! energy consumption and )00 *+m) current density has resulted in higher current e!!iciency%
, * 2 + 1++ 2++ &++ *++ -++
2 $urrent densit(. "/m

23g. 14 Effect of current density on energy consumption

1++ 77+ 66+ 51++ 2++ &++ *++ -++
2 $urrent densit(. "/m

2ig. 24 Effect of current density on current efficiency

Ta'le 14 Effect of current density on decomposition of of sodium sulphate. Conditions: temp. ambient, catholyte 90g/L Na2 !", anolyte #0 g/L Na2 !"
(o $ 2 & " % C') "A*m#& 200 2%0 2#% &#% "%0 EC)) "K al*+g of (aO,& 2.9# &.#$ &.#" ".$& %.09 CE".& 90.$# '$.2% '0.#$ '$.2& #9.02 C/-"/olt& ".0 ".% ".% %.0 (.0 (aO, 0ormed "g& $.2$ $.&( $."9 2.0" 2.&(

C)* current density, EC ** energy consumption, CE+ current efficiency, C,+ + cell -oltage,

Effe t of Cathol!te Con entration

'he concentration o! sodium sulphate in the catholyte was #aried !rom 50 to 150 g+L while its

Options for Treatment of Sodium Sulphate Containing Effluents

217
66 6, 6* 62 6+ 56 5, + -+ 1++ 1-+ 2++ sodium sulphate. g/l

concentration in the anolyte was #aried !rom 30 to 130 g+L 5always maintaining )0 g+L less in the anolyte7% &t was obser#ed that at sodium sulphate concentration o! 110 to 130 g+L in the catholyte, higher current e!!iciency and lower cell #oltage were obtained whereas at a concentration o! 50-70 g+L low current e!!iciency was recorded% 'he results o! these studies are shown in !igures 3 and < and 'able )%

2ig. &4 Effect of Na2 !" concentration in the catholyte on current efficiency

Ta'le 24 Effect of sodium sulphate concentration in catholyte and anolyte on current efficiency. Conditions: Current density 2#% ./m2, temp. ambient, current /0.(2 ., time 2 h
Anol!te (a#SO1, "g*2& &0 %0 #0 90 $$0 $&0

(o. $ 2 & " % (

Cathol!te (a#SO1, "g*2& %0 #0 90 $$0 $&0 $%0

$urrent effi$ien$(. 8

CE) . #'.$ #'.$ '0.# '(.% '(.% '&.%

EC)) K3h*+g of (aO, (.'( %.$% &.#" &."9 &."9 &.($

C/"/& '.0 (.0 ".% ".% ".% %.0

(aO, formed, g $."% $."% $."9 $.(0 $.(0 $.%"

CE* current efficiency, EC** energy consumption, C,+ cell -oltage

Ta'le &4 Effect of temperature on sodium sulphate decomposition. Conditions: .nolyte Na2 !" #0 g/L, catholyte Na2 !" 90 g/L, Current 0.(2 ., Current density 2#% ./m2
S.(. $ 2 & " Temp. o C &0 "0 %0 (0 CE) . '0.#$ '(."' '(."' '(."' &.#" &."9 &.$ &.$ EC)), K3h*+g of (aO, ".% ".% " ".0 C/-, /olts Mass of (aO, formed, g $."9 $.(0 $.(0 $.(0

CE* current efficiency, EC** energy consumption, C,+ cell -oltage

Effe t of Temperature

218 'emperature was #aried between 30 and D0o.% Eith increase o! temperature !rom 30 to <0o., current e!!iciency increased !rom F0%7G to FD%<FG and abo#e <0o. there is no #ariation in the current e!!iciency% But the increase in temperature resulted in more !ormation o! al/ali at lower energy consumption and cell #oltage% 'he results are gi#en in 'able 3 and Cigures 5 and D%
energ( $onsumption. 01h/0g 6 , * 2 + + -+ 1++ 1-+ 2++ sodium sulphate. g/l

Mineral Pro essing Te hnolog! "MPT #$$%&

&.2 Re$o9er( of Sodium Sulphate '( Salting Out 'he present wor/ is also de#oted to reco#er sodium sulphate !rom a ueous synthetic solutions o! methanol or acetone% 'he data has been generated to e$plore the possibility o! utili2ing the techni ue !or reco#ering sodium sulphate% Preparation of (a#SO1 Solution and Mi4tures of (a#SO1, C,5O, and ,#O Solutions o! di!!erent compositions with .0330, 0)3, =a)S3< were made% .0330 was added to salt solution while the contents were being stirred and the stirring was continued !or 5 min% 'he contents were /ept !or )0 min% to achie#e phase e uilibrium% 'he contents were then !iltered and /ept at 110o. till constant weight was obser#ed% Crom this data weight wise composition o! three constituents !or saturated solutions were obtained% Salting out of (a#SO1 b! C,5O, 'hree concentrations o! sodium sulphate #i2, 6)%D<, )1D and )<7 g+L were used as the stoc/ solutions% &n order to generate the ternary diagram the re uired uantities o! these solutions were mi$ed with methanol% 'he results obtained !or a typical solution o! 6)%D< g+L =a)S3< are gi#en in 'able <%

2ig. *4 Effect of Na2 !" concentration in the catholyte on energy consumption

8 $urrent effi$ien$( 7* 7+ 6, 62 56 + 2+ *+ tem perature ,+
.+

6+

2ig. -4 Effect of temperature on current efficiency Ta'le *4 )istribution of components at e0uilibrium and 1 precipitation of Na2 !"
S.(. $. 2. &. ". %. (. #. '. 9. ,# O "6ol& '".# ##.#2 (9.'" (2.%9 %"."2 "%.&2 %&.02 2&.9( $2.& C,5O, "6ol& #."% $%.09 2&.(9 &&.0% "&.$$ %&.'& (".#2 #%.9& '#.(' .(a#SO1 in soln. #.'% #.$9 (."# ".&( 2."# 0.'% 0.2( 0.$$ 0.$" . (a#SO1 pptd. 0 0 2edissol-es 2".' %0.9# #9.' 92.09 9%.2 9(.'%

Options for Treatment of Sodium Sulphate Containing Effluents

* energ( $onsumption. 01h/0g &.& 2.2&*-o temperature. C ,-

219 case o! acetone when compared to methanol% *lso in the case o! acetone the nature o! sodium sulphate that separates out is li/e a gel and !ilters #ery slowly% &.& De$omposition of Sodium Sulphate 1ith #ime Lime boil method is one o! the means to regenerate ammonia !rom ammonium sulphate solutions 5Sarangi et al%, )00<7 % *ttempts were made to crac/ sodium sulphate by boiling with calcium o$ide+calcium hydro$ide% 'he chemical reaction should be,
=a)S3< H .a3 H 0)3 .aS3< H ) =a30

2ig. ,4 Effect of temperature on energy consumption

Salting out (a#SO1 b! A etone *cetone was used as the sol#ent !or salting out sodium sulphate as this sol#ent has the ad#antage o! low boiling point and conse uently lower energy re uirement !or sol#ent distillation% 'he e$perimental details and the Gage o! sodium sulphate precipitation is shown in 'ables 5% &t is obser#ed that !or the same amount o! sol#ent less G age o! precipitation is obser#ed in

%%%517

* number o! e$periments were carried out to generate sodium hydro$ide by crac/ing it with lime% &n each e$periment 100 ml o! solution containing 100 g+L sodium sulphate was heated at temperatures ranging between F0 to 100o. with < to 10 g o! lime !or 1 to ) h% Sodium hydro$ide !ormation under the studied range o! parameters was negligible%

Ta'le -4 3t.1 distribution of components at e0uilibrium and 1 precipitation of Na2 !"

S. (o. $. 2. &. ". %. (. #. '. 9. .,#O '".# ##.9" #$.$9 (&.2# %".&# "%.$# &".'" 2&.9% $2.&& .C,5COC,5 #." $%.&9 2".$" &&.&' "&.0& %&.%& (".2$ #%.(' '#.(( .(a#SO1 in soln. #.'% (.(# ".(# &.&% 2.( $.& 0.9% 0.&# 0.0$ 29.& "2.' "'." (9.2 #0.% '&.# 9'.9 . (a#SO1 pptd. 0 #.% (

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Mineral Pro essing Te hnolog! "MPT #$$%&

*. CONC#USIONS 'he electro-chemical splitting techni ue is a #iable process to produce sodium hydro$ide !rom sodium sulphate% 'he optimum conditions !or obtaining higher current e!!iciency and lower energy consumption are as !ollows,current density )00 *+m), sodium sulphate in the catholyte 110 to 130 g+L, temperature 50o.% Regenration o! organic sol#ent limits the application o! salting out techi ue !or sodium sulphate reco#ery% -. "C:NO;#ED<E!ENT 'he authors are than/!ul to Airector, >ro!% B%B% ;ishra, RRL5B7, !or his /ind permission to present this paper in ;>'-)007% RE2ERENCES
I1J 0ol2e, S%, 9:rissen, 9, Cischer, .% and Bal#elage, 0%, 0ydrogen consuming anodes !or energy sa#ing in sodium sulphate electrolysis% .hemical 4ngineering and 'echnology, 175D7, 3F)-F6 5166<7% I)J 9:rissen, 9% and Simmroc/, B%0%, 'he beha#iour o! ion e$change membranes in electrolysis and electrodialysis o! sodium sulphate% 9ournal o! *pplied 4lectrochemistry, )15107, FD6-F7D 516617% I3J ;artin, *%A%, 4lectrochemical production o! sodium hydro$ide and sul!uric acid !rom acidi!ied sodium sul!ate, ?S >atent =o% 5)30776 516637% I<J Radd, C%9% and 3ertle, A%0%, 4lectrolytic cell and process !or electroly2ing sodium sulphate, ?S >atent =o% 3,607,D5< 516737% I5J Sarangi, B%, Rout, =%.%, Subbaiah, '%, *nand, S% and Aas, R%>%, 3ptions !or reco#ery o! ammonia+ ammonium sulphate !rom synthetically prepared e!!luent streams, 49;> K 4>, <537,)3<-)<3 5)00<7% IDJ Stender, E%E% and Seera/ &%9%, 4lectrolysis o! a ueous solutions o! al/ali sul!ates, 'ransactions o! 'he 4lectrochemical Society, DF, <63-5)0516357%