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This document summarizes research on the solvent extraction of zirconium from nitric-hydrochloric acid solutions using tri-n-butyl phosphate (TBP) as the extractant. Key findings include:
1) TBP extracts zirconium and hafnium from mixtures of nitric, hydrochloric, and other inorganic acids with a separation factor exceeding extraction from individual acid solutions.
2) Extraction is highest from nitric-hydrochloric acid mixtures. Parameters affecting zirconium extraction, such as extractant concentration and acidity, were investigated.
3) Kerosene was used as the diluent to prevent decreased TBP extraction ability and accelerate phase separation compared to
This document summarizes research on the solvent extraction of zirconium from nitric-hydrochloric acid solutions using tri-n-butyl phosphate (TBP) as the extractant. Key findings include:
1) TBP extracts zirconium and hafnium from mixtures of nitric, hydrochloric, and other inorganic acids with a separation factor exceeding extraction from individual acid solutions.
2) Extraction is highest from nitric-hydrochloric acid mixtures. Parameters affecting zirconium extraction, such as extractant concentration and acidity, were investigated.
3) Kerosene was used as the diluent to prevent decreased TBP extraction ability and accelerate phase separation compared to
This document summarizes research on the solvent extraction of zirconium from nitric-hydrochloric acid solutions using tri-n-butyl phosphate (TBP) as the extractant. Key findings include:
1) TBP extracts zirconium and hafnium from mixtures of nitric, hydrochloric, and other inorganic acids with a separation factor exceeding extraction from individual acid solutions.
2) Extraction is highest from nitric-hydrochloric acid mixtures. Parameters affecting zirconium extraction, such as extractant concentration and acidity, were investigated.
3) Kerosene was used as the diluent to prevent decreased TBP extraction ability and accelerate phase separation compared to
Journal of Theoretical and Applied Physics, 3-3, 20-26 (2009)
Solvent extraction of zirconium from nitric-hydrochloric acid solutions using
TBP A. Sadigzadeh 1, , S. !hehrenama 1, " , #. Sho$ri 1 1 Nuclear Science & Technology Research Institute, Atomic energy organization of Iran, Tehran, Iran 2 Department of Chemical ngineering, Isfahan !ni"ersity of Technology, Isfahan, Iran Receied! "# Au$ust 200%&Accepted! 20 'cto(er 2009& Pu(lished! 20 )ece*(er 2009 A%stract +olent e,traction is a co**ercial *ethod for production of pure *aterials such as -irconiu* and hafniu* and their co*pounds fro* *ulti-co*ponent scru((er solution. /n the e,traction of -irconiu* and hafniu* salts fro* 01' 3 , 02l, 02l' 3 and 0 2 +' 3 into neutral or$anophosphorus co*pounds (1'P2) - such as tri(utyl phosphate (T4P)- in case usin$ *i,tures of inor$anic acids, 1'P2 e,tracts -irconiu* and hafniu* 5ith separation factor con- sidera(ly e,ceedin$ the correspondin$ alue for e,traction fro* solution of indiidual acids. A still hi$her separa- tion leel is o(tained 5hen usin$ *i,ture of acids, especially those of nitric-hydrochloric acids. /n this paper, the e,traction of -irconiu* fro* solution containin$ nitric-hydrochloric acids usin$ T4P in treated 6erosene as diluent has (een studied. The follo5in$ para*eters hae (een inesti$ated! effect of e,tractant, nitric-hydrochloric acids and -irconiu* concentrations, *i,in$ ti*e, acidification of or$anic phase, the or$anic&a7ueous phase ratio and te*- perature on the e,traction of -irconiu*. PACs& 36.20.0-8 36.20.0(8 36.20.1$ 'ey(ords# $irconium, %afnium, &traction, Tri'utylphosphate, Nitric(hy)rochloric aci) 1. )ntroduction 9irconiu* and hafniu* co-e,ist in nature, (ut in certain industry they *ust (e used alone. Thus, they hae to (e separated prior to their transfor*ation into pure *etals. +olent e,traction is a co**ercial *ethod for produc- tion of pure *aterials such as -irconiu* and hafniu* and their co*pounds fro* *ulti- co*ponent scru((er solution. :any or$anic e,tractants hae the a(ility to selectiely e,tract the ions dissoled in a dilute acid solution. )eter*ination of distri(ution factors of the ions present in the solution is, therefore, an i*portant para*eter in selection of the appropriate e,tractants. :any inesti$ations hae so far (een *ade on the solent e,traction of -irconiu* fro* a7ueous *edia containin$ sulfuric acid ;"-2<, hydrochloric acid ;3-6< and nitric acid ;3, 6-%<. A considera(ly 5ide section of e,tractants 5as contained esters. =aored esters in e,tractie *etal- lur$y rise fro* phosphoric acid and can (e diided to acidic and neutral esters ;"<. The e,traction of -irco- niu* and hafniu* salts fro* 01' 3 , 02l, 02l' 3 and 0 2 +' 3 into neutral or$anophosphorus co*pounds (1'P2) proceeds throu$h a solation *echanis* ;9<. As a neutral ester, tri(utyl phosphate (T4P) for*s >2orrespondin$ author! As$har sadi$-adeh8 ?-*ail! sadi$-adeh@yahoo.co* Tel! (A9%) 2" %%22"093 =a,! (A9%) 2" %%22"093 additional co*pounds 5ith *any *etallic nitrates, chlorides and thiocyanates. 2o*pared 5ith T4P, co*pounds 5ith *ore (ase phosphoryl $roup, PB', are (etter e,tractant than T4P. ?,tracta(ility increase 5ith follo5in$ arran$e*ent ;"0<! Phosphine C phosphinate C phosphonate C phosphate The e,traction *echanis* of 9r and 0f 5ith T4P inoles the hydrated 9r ion for*in$ a neutral *ole- cule and solate for*in$ at the a7ueous-or$anic inter- phase o5in$ to the coordination (ondin$ (et5een 9r and 0f ato*s and the o,y$en of the phosphoryl o,y- $en. 9irconiu* salts for* *ore sta(le T4P e,tracta- (le co*ple,es than do hafniu* salts ;3<. These co*- pounds the*seles are solu(le in T4P and therefore can (e efficiently e,tracted ;D<. /n $eneral, one should 6eep in *ind that the -ir- coniu* ions e,traction a(ility is stron$ly dependent on the nature of the initial co*pound. T4P e,tracts -irconiu* fro* sulfuric acid solutions only at hi$h concentrations of 0 2 +' 3 . The -irconiu* co*pounds e,traction a(ility aries as! nitrateC chlorideC sulfate C (ro*ide ;9<. /n so*e syste*s for control of $oernin$ che*i- stry of co*ple, for*ation reaction (et5een *etal and e,tractant, (ecause of e,tracta(le species for*ation in particular acidity, total concentration of hydro$en ion 5as 6ept in deter*ined ran$e ;3, "3-"#<. Accordin$ to :ailen 5or6 ;3<, (et5een e,istent species of 9r-e,tracta(le and ine,tracta(le in a7ueous solution, 9r A3 and 9r('0) A3 species are e,tracta(le. Also, in the case of 9r ion e,traction fro* nitric acid +adi$-adeh et al. Journal of Theoretical and Applied Physics, 3-3 (2009) *edia, other 9r species such as 09r(1' 3 ) # and 0 2 9r(1' 3 ) 6 hae (een su$$ested to (e e,tracta(le into T4P. /n this case, the 9r A3 ions predo*inate in solu- tions containin$ *ore than 3: 01' 3 . The chan$e in the *echanis* of -irconiu* e,traction into T4P in the hi$h acid concentration ran$e has (een confir*ed ;3, D, 9<. The partition of -irconiu* (/E) (et5een hydroch- loric acid solutions and solutions of tri-n-(utyl phos- phate (T4P) and of di-(2- ethylhe,yl)-phosphoric acid ()?0PA) in 6erosene has (een inesti$ated under different conditions. The effect of or$anic solent in the e,traction (y )?0PA has also (een e,a*ined ;#<. =ro* *i,tures of inor$anic acids, 1'P2 e,tracts -irconiu* and hafniu* 5ith separation factor consi- dera(ly e,ceedin$ the correspondin$ alue for e,trac- tion fro* solution of indiidual acids. /t has (een found that nitrate-fluoride, nitrate- chloride and nitrate- per chlorate co*ple, hae an enhanced e,tracta(ility. A still hi$her separation is o(tained 5hen usin$ *i,- ture of acids, especially those of nitric- hydrochloric acids. A sharp enhance*ent of -irconiu* e,tracta(ili- ty fro* hydrochloric acid 5ith addition of sulfuric acid has (een caused (y the dehydration action of sul- furic acid ;9<. Fan$ et al. ;"6< studied the e,traction of -irco- niu* fro* solutions of perchloric and nitric acid 5ith tri-n-(utyl phosphate (T4P) in 6erosene. Accordin$ to their results, 5hen the initial 02l' 3 concentration 5as less than 6 *ol&d* 3 , there 5as hardly any for5ard transfer of 9r(/E) into the or$anic phase, (ut 5hen the concentration 5ent up to % *ol&d* 3 , the percent e,- traction increased sharply until *ore than 90G e,trac- tion 5as reached. The effect of te*perature on e,traction reactions 5ith T4P can (e different under arious conditions $oerned on e,traction process. +o that, in e,traction of *oly(denu* fro* sulfuric acid and rhodiu* fro* hydrochloric acid *edias e,other*ic and endother*ic reactions happen respectiely ;2, "#<. As *entioned, the inesti$ation on *i,tures of neutral phosphorous esters and diluents can lead to discoer a *utual interaction. This inesti$ations indi- cated that *i,in$ of T4P and heptan, nonan and decan is acco*panied (y heat adsorption 5hereas its *i,in$ 5ith chlorofor* or car(on tetrachloride is an e,o- ther*ic reaction. /n the first case, heat adsorption is due to deco*position of T4P di**ers in hydrocar(on diluents 5hereas in the second case e,other*ic reac- tion is due to T4P co*(ination 5ith chlorinated hy- drocar(ons for the purpose of 22l 3 .2T4P and 202l 3 .T4P for*ation. These (onds decrease lar$ely effectie concentration of T4P in or$anic phase and e,traction concentration of diluted T4P 5ith chloro- for* and car(on tetrachloride. Also, accordin$ to our e,peri*ents, in e,traction syste*s containin$ T4P&22l 3 or 202l 3 , separation of a7ueous and or$an- ic phase needs fe5 *inutes. Therefore, 5e choose 6erosene as an unchlorinated hydrocar(on diluent to 3 +adi$-adeh et al. Journal of Theoretical and Applied Physics, 3-3 (2009) +olent e,traction of -irconiu* H Journal of Theoretical and Applied Physics, 3-3 (2009) preent the decrease of T4P e,traction a(ility and accelerate the separation of phases in this syste* ;"<. Ierosene as a refinin$ product of oil is for*ed (y co*ple, of unsaturated cyclic, aro*atic al6yl, and chain hydrocar(ons ;"<. The aro*atic co*pounds preent considera(ly the e,traction of heay *etals ;"2< . /n another research, s*all-an$le neutron scatter- in$ (+A1+) data for the tri-n-(utyl phosphate (T4P)- n-octane, 01'(3)- 9r(1'(3))(3) solent e,traction syste*, o(tained under a ariety of e,peri*ental con- ditions, hae (een interpreted usin$ the 4a,ter *odel for hard spheres 5ith surface adhesion ;%<. Ta$uchiJs *ethod ;"D< 5as used to deter*ine the opti*u* conditions for separation of -irconiu* fro* hafniu* (y solent e,traction. The e,peri*ental con- ditions 5ere studied for three different acids and T4P, )2?0PA or 2yane, 2D2 as e,tractant. The opti*u* e,traction of -irconiu* and opti*u* -irco- niu*&hafniu* separation 5as also achieed usin$ this co*(ination ;6<. /n this 5or6, the e,traction of -irconiu* fro* so- lution containin$ nitric-hydrochloric acids usin$ T4P in treated 6erosene as diluent has (een inesti$ated. 4ecause there are not sufficient reports on the e,trac- tion of -irconiu* fro* solution containin$ nitric- hydrochloric acids 5ith T4P. The follo5in$ para*eters hae (een aried! *i,- in$ ti*e, the e,tractant, nitric and hydrochloric acids and -irconiu* concentrations, acidification of or$anic phase, the or$anic&a7ueous phase ratio and te*pera- ture . ". *x+erimental 2.". Rea$ents and solutions The 6erosene, used as diluent in this study, 5as a co**ercial product. The or$anic phase 5as prepared (y dilutin$ T4P in 6erosene. 1itric acid (6#G) and hydrochloric acid (3 #G) 5as proided fro* :erc6, 9r2l 3 and 0f2l 3 5ere of analytical rea$ents $rade. )ou(ly distilled 5ater 5as used for preparin$ all the solutions. As a source of 9r(/E) and 0f(/E), 9r(0f)'2l 2 5as prepared (y dissolin$ 9r(0f)'2l 3 in deioni-ed 5ater. 9irconiu* tetrachloride in contact 5ith 5ater hydrolyses ery readily and for*s o,ychloride ;"3< 9r2l 3 A0 2 'K 9r'2l 2 A202l (") Therefore 5ith solation of -irconiu* tetrachlo- ride in 5ater, e,istence of hydrochloric acid is certain and its a*ount is related 5ith concentration of -irco- niu* n solution. 2.2. +olent e,traction procedure ?,traction e,peri*ents 5ere carried out usin$ *echanically a$itated techni7ue. The *i,ture 5as 3 3 a$itated (y an electro*otor 5ith a constant stirrin$ rate. After *i,in$ for # *in, the or$anic phase 5as separated fro* the a7ueous phase. The -irconiu* ion concentrations 5ere deter- *ined in a7ueous phase (y titration 5ith ?)TA and e*ployin$ ,ylenol oran$e as a rea$ent. The *etal ion concentrations in the or$anic phase 5ere calculated fro* the difference (et5een the *etal ion concentra- tions in the a7ueous phase (efore and after e,traction. The results are $enerally e,pressed as percenta$e *et- al e,traction. 3. ,esults and discussion /n this section the e,peri*ents perfor*ed on four different cases and the effect of i*portant para*eters are presented. a. The effect of or$anic phase para*eters such as percenta$e of e,tractant on e,traction of 9r. (. The effect of *ain a7ueous phase para*eters such as concentration of -irconiu*, nitric and hydrochloric acids, and e7uili(riu* hydro$en on e,traction process. c. The acidity of or$anic phase and its effect on -irconiu* e,traction. d. The effect of $oernin$ condition on *i,in$ *ediu* inolin$ te*perature, or$an- ic&a7ueou phase ratio on e,traction process. 3.". ?,traction reaction studies The e7uili(riu* e7uation of *etal ions e,traction fro* a7ueous solutions 5ith 12P2 as an e,tractant can (e descri(ed in the follo5in$ 5ay s+ (or$.) A*: (a7.) AaA (a7.) B;A a .: * .+ s < or$. (2) 5here + is the e,tractant, : is the anion or cation ion and A is any counter ion or other species that *ay (e present in the a7ueous phase. 3.2. ?ffect of arious para*eters on the e,traction of -irconiu* fro* acidic solutions The effect of contact ti*e, concentrations of e,- tractants, nitric and hydrochloric acids, 'r$an- ic&A7ueous ('&A) phase ratio, e7uili(riu* hydro$en ion and -irconiu* concentrations and acidification of or$anic phase on the e,traction of -irconiu* has (een inesti$ated and the results are reported in =i$s."-D. 3.2.". ?ffect of contact ti*e The e,traction e,peri*ents 5ere carried out for con- tact ti*es ran$in$ fro* 2 to "# *in. The operatin$ conditions of e,traction 5ere! ;02l< a7. B ;01'3< a7. B 3.6 :, ;9r A3 < B 62.#$&lit, ;01' 3 < or$. B".D :, ;T4P< B 2.2 : at roo* te*perature. The *etal e,traction percenta$e increases 5ith contact ti*e. The e,traction e7uili(riu* 5as esta(- lished after 2-3 *in (D6.#G for '&AB" and 93.%G for '&AB2.l#). 0o5eer, in all e,traction e,peri*ents a contact ti*e of # *in (D%.#G for '&AB" and 93.#G for '&AB2."#) 5as chosen for ensurin$ that the e7ui- li(riu* 5as reached. Accordin$ to these data, e,traction of -irconiu* (y T4P usin$ *i,er settlers doesnLt need the lon$ resident ti*e in *i,ers or $reat stirrin$ rate. Also, in the case of hafniu* e,traction, si*ilar to 9r, the e,- traction needed no lon$ ti*e. Therefore, *i,in$ ti*e can not (e a separation controllin$ factor. 4ut *i,in$ ti*e study is necessary for the calculation of e,tractor di*ensions. +o*e ti*es for safety of suita(le e,traction in each sta$e, $reater stirrin$ rate 5as selected. 'f course, this idea can (e ri$ht, (ut it has so*e pro(- le*s. /ncrease of stirrin$ rate can cause the for*ation of steady e*ulsion in the syste*. /n this case, fine droplets of a7ueous and or$anic phases *i$rate into other phase. This causes t5o pro(le*s8 "-ariation of '&A ratio8 2- due to different solu(ilities of 6erosene and T4P in 5ater and 5ater in the*, in lon$ ti*es, it can (e o(sered that the percenta$e of T4P aries in solent. Also, so*e ti*es part of enriched phase of hafniu* (output of a7ueous phase) fro* final sta$es of *i,er settlers Mas suspended dropletsM *ay *i$rate into for5ard sta$es or carried (y or$anic phase out of e,traction syste*. Thus, the decrease of stirrin$ rate in e,traction state lo5ers the a*ount of hafniu* in a7ueous production containin$ -irconiu* ions, after scru((in$ and strippin$ sta$es, fro* "%0 pp* to 0.2 pp*. 3.2.2. ?ffect of concentration of e,tractants /n the e,traction process, the increase of e,trac- tant concentration up to a certain point increases the distri(ution coefficient of -irconiu*. /ncrease of e,- tractant after this leel (threshold point) has no effect on e,traction percenta$e. 'f course, the situation of this threshold point aries 5ith different para*eters such as te*perature, a7ueous phase acidity, type of diluents and *etal ion concentration in a7ueous phase. /n this section, The e,tractant concentration in solent 5as aried and the effect on the e,traction ratio of -irconiu* fro* solution containin$ ;02l< a7. B3 :, ;01'3< a7. B3 :, ;9r A3 <B%0$&lit and '&AB" 5as studied at "6N"O2. The plot of ?G s. T4PG is sho5n in =i$. " and indicates the increase of e,traction percenta$e fro* 0 to 33.%G (y enhancin$ the e,tractant concentration fro* 0 to 60G, durin$ the e,traction process of -irco- niu*. 4eyond the declared e,tractant concentration of 60G, the a*ount of e,tracted 9r decreases to 30.#G. Therefore the solent concentration of 60G T4P is chosen for the (est e,traction of -irconiu*. Accordin$ to these data, the lo$ ;T4P< ersus lo$ ) 9r plot - ;T4P< B 0."%-2.2 : - is strai$ht lines. The alue of the slope is 0.6 and indicates one piece of T4P e,ists in e,tracta(le co*ple,. -ig. 1. TBP concentration effect on the extraction of zir- conium. )n this figure, the extractant concentration in solvent (as varied and the effect on the extraction ratio of zirconium from solution containing .#!l/a0. 1 3 2, .#34 3 /a0. 1 3 2, .5r 67 / 1 89g:lit and 4:A 1 1 (as stu- died at 1; < 1=!. 3.2.3. ?ffect of nitric and hydrochloric acids and hy- dro$en concentrations Accordin$ to the study on the effect of a 5ide ran$e of a7ueous phase acidities on -irconiu* e,trac- tion, little a*ounts of -irconiu* 5ere dissoled in 5ater. /t depends on the relation (et5een -irconiu* concentration and hydrochloric acid *olarity in feed solution. Therefore, 5ith dissolin$ $reat a*ounts of -irconiu*, lo5er *olarity of 02l is not pro(a(le. The effect of nitric and hydrochloric acid concen- trations ("-3 :) on the e,traction of "0 $&lit 9r(/E) has (een studied usin$ a solent syste* consistin$ of 60G ol. T4P in 6erosene. The e,traction of 9r(/E) 5as found to increase 5ith the increase in acid con- centrations. The results are presented in =i$s. 2 and 3. Accordin$ to these data, in the cases that the total hydro$en ion concentration -in a7ueous phase- is less than # :, the sensi(le e,traction 5onLt (e o(sered. This e,traction (ehaior is related to so*e para- *eters of syste* such as 6ind of diluents and e,is- tence of saltin$ out a$ents. +o that, in the e,traction syste* containin$ T4P&(utyl ether as solent and a7ueous phase containin$ nitric-hydrochloric acid and 2a2l 2 , for e,traction of 30-#0 $ 9r&lit fro* feed solu- tion containin$ total hydro$en ion concentration e7ual 3 :, ) 9r a(out "-".# 5as o(tained ;3<. Accordin$ to =i$s. 2 and 3, in ;0 A < tot. in a7. P D :, the e,traction procedure aries and the slope of ) 9r cures aries sharply. The sudden ariation of the e,traction procedure sho5s the chan$e of e,traction *echanis* (ecause of the chan$e in e,tracta(le spe- cies. -ig. ". *ffect of nitric and hydrochloric acid concentra- tions on the extraction of zirconium& .5r 76 / 1 19 g:lit, .TBP/ 1 "." 2, 4:A1 1, and tem+. 1 "9 < 1=!. -ig. 3. *ffect of .# 6 / on the extraction of zirconium& .5r 76 / 1 19 g:lit, .TBP/ 1 "." 2, 4:A1 1, and tem+. 1 "9 < 1 = ! . /n an industrial desi$n, 5e should pay attention to this point that input feed to e,traction unit for hain$ an econo*ic e,planation, a solution 5ith $reat con- centration of -irconiu*, a(out %0-90 $&lit *ust (e utili-ed. /n this case, due to relation (et5een 02l and 9r ion concentrations in feed solution, ?7. ", under the condition, %0- 90 $ 9r&lit, hydrochloric acid concentra- tion is appro,i*ately *ore than 3 :. =or access to re7uired *ini*u* ;0 A < tot. to accepta(le 9r e,traction - # :- nitric acid concentration *ust (e *ore than 2 :. Also, 5ith the increase of acidity up to ;0 A < tot .B D : - in feed sol. - separation factor falls sharply. Accordin$ to our e,peri*ents *ain controllin$ a$ent of e,traction and separation of -irconiu* and hafniu* process is nitric and hydrochloric acid con- centrations. The 5ei$ht of effect of each of the t5o affectin$ ele- *ents on the e,traction, the concentration of 01' 3 and 02l in a7ueous solution is inesti$ated 5ith the Ta$uchi statistical *ethod ;"D<. To e,a*ine t5o pa- ra*eters 5ith 3 leels, Ta$uchi proposes Q 9 array con- tainin$ 9 tests. =or replacin$ of results, 5e used the data e*ployed in =i$. 2. :ain factors and (ased conditions for this process are sho5n in ta(le". Ta%le 1. 2ain factors and their a++ointed levels. .5r 76 / 1 19 g:lit, .TBP/ 1 "." 2, 4:A 1 1, and tem+. 1 "9 < 1 =!. 2ain factors uni t >evel 1 >evel " >evel 3 ;01'3< *ol& lit 2 3 3 ;02l< *ol& lit 2 3 3 3.2.3. The effect of '&A phase ratio The operatin$ conditions used 5ere ;02l< a7. B 3 :, ;01' 3 < a7. B 3 :, ;9r A3 < B %0 $&lit, ;T4P< B 2.2 :, ;0 A < or$. B ".9# : and *i,in$ ti*eB # *in at"6 N " O2. The '&A phase ratio 5as aried (et5een "&2 and 3&". The results are sho5n in =i$. 3. The e,tracted *etal, percenta$e increased 5ith increasin$ the '&A phase ratio. The ariation of the phase ratio fro* "&2 to 3&" lead to an increase in the percenta$e of e,tracted *etal fro* 3#.#3 to 9#.2G. 4eyond ratio 3&", the phase ratio had little effect on the *etal e,traction. Therefore, this point 5as e,plained as a threshold point. -ig. 7. )nfluence of the 4:A +hase ratio on 5r extraction& .#!>/a0. 1 .#34 3 /a0. 1 3 2, .5r 76 / 1 89 g:lit, .TBP/ 1 "." 2, .#34 3 /org. 1 1.?@ 2, 4:A 1 1, mixing time 1 @ min and tem+.1 1; < 1 =!. The 4:A +hase ratio (as va- ried %et(een 1:" and 7:1. 2ertainly, the threshold point can ary under dif- ferent conditions (such as different concentrations of nitric and hydrochloric acids and -irconiu* in a7ueous phase, te*perature, e,tractant percenta$e and diluents). =or e,a*ple, in contactin$ of solution con- tainin$ ;02l< a7. B 3 :, ;01'3< a7. B 3 : and ;9r A3 < B "0 $&lit 5ith or$anic phase containin$ 60G T4P in 6ero- sene, for '&A ratio B "&", up to 9%G -irconiu* content 5as e,tracted. /n this case, increase of '&A ratio is not effectie and suita(le. 3.2.#. ?ffect of -irconiu* concentration The operatin$ conditions used 5ere ;02l< a7. B 3 :, ;01' 3 < a7. B 3 :, ;T4P< B 2.2 :, ;0 A < or$. B ".9# :, and *i,in$ ti*e B # *in at "6 N " O2 in this case in- crease of 9r concentration fro* # to 90 $r&lit causes a decrease in ) 9r fro* "".% to ". Therefore, relation of ) 9r and 9r concentration 5as follo5ed (y ?7. 3! ) 9r B 3R"0 -D R;9r A3 < 3 a7. -"0 -3 R;9r A3 < 3 a7. A 0.0"33;9r A3 < 2 a7. - 0.6903;9r A3 < a7. A"#.003 (3) =i$. # sho5s :c2a(e-Thiele plot ;"< for 9r(/E) e,traction. /n ;02l< a7. B 3 :, initial concentration of 9r in a7ueous solution can not (e *ore than "00 $r&lit. Therefore, this cure contained li*ited nu*(er of e7uili(riu* points. 2hoosin$ a special operatin$ line for e,traction process depends on so*e para*eters such as T4P content of or$anic phase and acid concentration in a7ueous phase. These para*eters effect on solents loadin$ capacity and e,traction a(ility of 9r ions. +o that for hain$ a suita(le e,traction fro* solution con- tainin$ 60 $ 9r&lit under *entioned operatin$ condi- tions, 5e can not e*ploy '&A B " condition. =or in this case e,tractant loadin$ capacity is fe5er than 60 $ 9r&lit. +o under this conditions *otion on e7uili(riu* cure is not possi(le. Shereas if 5e choose '&A B 2, een suita(le e,traction fro* solution containin$ %0 $ 9r&lit is possi(le. -ig. @. 2c!a%eAThiele +lot for 5r B)CD extraction. 3.2.6. ?ffect of te*perature The effect of te*perature on the e,traction of -ir- coniu* 5as studied (y chan$in$ te*perature (et5een "# O2 and 63 O2 at a constant T4P concentration. /t can (e seen fro* =i$. 6 that ) 9r increases 5ith te*- perature. -ig. ;. *ffect of the tem+erature on 5r extraction& .#!>/a0. 1 .#343/a0. 1 3 2, .5r 7 6 / 1 89 g:lit, .TBP/ 1 "." 2, .#343/org. 1 1.?@ 2, 4:A 1 1, and mix- ing time 1 @ min. /n =i$. 6, the slope of line is -2%0.9. Therefore, the apparent standard enthalpy of the e,traction reac- tion is #.3% 6J&$.*ol. +o the e,traction of -irconiu* fro* nitric- hydrochloric a7ueous *edia 5ith T4P is an endother*ic reaction. 4ut ariation of te*perature has no $reat effect on e,traction of -irconiu* (y T4P8 so that, 5ith increase of te*perature fro* "# O2 to 63 O2 percenta$e of e,traction 5as 2D.DG and 32G, re- spectiely. Shen loadin$ capacity of e,tractant approach to saturation point, the e,tractant does not hae sensi(le a(ility to e,traction of -irconiu* ions. /n this case, *i,in$ of this e,tractant 5ith a7ueous phase contain- in$ $reat concentration of -irconiu* (for e,a*ple solution containin$ ;0 A < tot. B 6 : and "00 $ 9r&lit). Sith increase of te*perature up to "0 O2 durin$ e,peri*ents, crystalli-ation of a7ueous phase *ay occur suddenly. 4ecause in this conditions, part of acid and 5ater e,tract into or$anic solent and e,trac- tion of -irconiu* does not happen. Therefore concen- tration of -irconiu* increases in a7ueous phase and su(se7uently sudden crystalli-ation due to increase of -irconiu* concentration and lac6 of te*perature hap- pens. 3.2.D. ?ffect of or$anic phase acidity The effect of nitric acid concentration in or$anic phase 5as inesti$ated 5ith contact of the acidic or- $anic phase 5ith a7ueous phase containin$ -irconiu* ion. )ecrease of (oth a7ueous and or$anic phase o- lu*e ariations is one of the reasons for acidified or- $anic phase in industrial e,traction processes of -irco- niu*, usin$ T4P. :ainly t5o features of acid e,traction (y phos- phorus esters such as T4P hae receied continuous attention. These are the capacity of esters to e,tract, or to dissole, acids 5ell oer an acid-to-ester ratio of unity, and the hydration of the acid in the or$anic so- lution. ?,traction of 01' 3 is dependent on (oth a7ueous phase acid and T4P concentrations ;3<. Ta%le ". *ffect of organic +hase acidity in extraction of zirconium and volume difference of a0ueous +hase& .#34 3 /a0. 1 .#!l/a0. 1 3 2 and .5r 76 / 1 89 g:lit and 4:A 1 1 at 1; < 1 O!. .#34 3 / org. , -inal vol. 4f a0. E*xtract ion of -inal acidity of 0. 0 " %. 3 3. 3 . ". 6 " 9. # 6. # . ". 9 " 9. # %. # . Accordin$ to the o(tained data, e,traction reac- tion rate of nitric acid (y T4P is fast. +o that, in *i,- in$ ti*e less than 0.# *inutes, the e,traction of acid is co*pleted. Therefore, in this case, acid e,traction did not need the lon$ residence ti*e or $reat stirrin$ rate in *i,ers. Also, (ased on the o(tained e7uili(riu* cure of nitric acid e,traction (y 60G T4P&6erosene, *ost concentrations e,tracted (y solent 5ere 2 : appro,- i*ately and to find a situation that consist *ore acid concentration in the or$anic phase is not possi(le (=i$. D). 'f course, this saturated point is related to te*per- ature, percenta$e of e,tractant and diluent type in the syste*. 4ased on these e,peri*ents, usin$ unacidified or- $anic phase for e,traction of -irconiu* under the con- dition *entioned a(oe, there is "0G deduction in a7ueous phase olu*e, (ut (y usin$ acidified or$anic phase, olu*e deduction reduces to 3G (Ta(le 2). Therefore, $enerally in all of the e,traction processes the '&A ratio 5as al*ost constant. -ig. F. *0uili%rium curve of #34 3 extraction %y TBP Ta%le 3. *xtraction of zirconium from a0. Phase in some stages %y unacidified solvent. .#34 3 /a0. 1 .#!l/a0. 1 3 2 and .5r 76 / 1 89 g:lit and 4:A 1 1 at 1; < 1O! St a g -ir st conc. -in al conc. -irst vol. of a0. -inal vol. of a0. " %0.0 60.2 # 0 3#.# 2 60.2 6".3 3 0 3D.3 3 6".3 63.6 3 0 2%.2 Accordin$ to the e,peri*ental data, (y usin$ un- acidified T4P for a fe5 sta$e e,tractions fro* the solution 5ith total acidity e7ual 6 :, after first sta$e of e,traction, a7ueous phase acidity decreases to 3.2 : (Ta(le 3). This is (ecause in the a7ueous total acidity under # :, there is no e,traction fro* a7ueous solution8 therefore, it ter*inates the -irconiu* e,trac- tion after the first sta$e. 0o5eer in each sta$e, e,traction of acid and 5a- ter happens. Therefore, olu*e of a7ueous phase de- creases in each sta$e. +o, the a7ueous phase acidity in each sta$e is reduced, e,traction does not happen and the concentration of -irconiu* in a7ueous phase de- creases due to its olu*e reduction and *ass constan- cy of -irconiu* in a7ueous phase. Therefore, in the industrial processes, acidifica- tion of or$anic phases due to control of '&A ratio and resort of suita(le e,traction of -irconiu* is necessary. 7. !onclusions Qi7uid-li7uid e,traction studies of 9r (/E) fro* solutions containin$ nitric-hydrochloric acids (y T4P&6erosene sho5ed that acid concentrations hae the *ost effect on the 9r e,traction. /n this case, there is no e,tracta(le -irconiu* and hafniu* species under the condition ;0 A < tot. B # : in a7ueous solution. Also, after ;0 A < B D : the *echanis* of e,traction reaction aries and increases sharply. Also, or$anic phase aci- dification is necessary for industrial processes. Ac- cordin$ to our data te*perature has poor effect on the aforesaid e,traction. ,eference ;"< =. 0a(ashi, ?,tractie :etallur$y, 2nd ?dition, Siley- E20, Tue(ec, ("993). ;2< Q. 9ou, 0ydro*etallur$y, @9, "93 ("99%). ;3< S. S. +chul-, J. ). 1aratil, 2R2 press /nc., ", ""9 ("9%D). ;3< =. Ull*an, Ull*anJs ?ncyclopedia of industrial che*istry, 6th ?dition, E20, 3?, 69D (2003). ;#< T. +ato, Analytica 2hi*ica Acta, @", "%3 ("9D0). ;6< :. Ta$hi-adeh, , R. Vhase*-adeh, , +. 1. Ashrafi-adeh, , I. +a(eryan, , :. Vhanadi :ara$heh, 0ydro*etallur$y, ?9, ""# (200%). ;D< A. I. :u6herWi, Analytical 2he*istry of 9irconiu* and 0afniu*, Per$a*on ',ford presses /nc., ("9D0). ;%< R. 2hiari-ia, :. P. Jensen, P. V. Ric6ert, 9. Iolari6, :. 4or6o5s6i, P. Thiya$araWan, Qan$*uir, "@, "0D% (2003). ;9< V. A. Fa$odin, '. A. +ine$ri(oa, in! T.2.Qo, :.0./. 4aird, 2. 0anson (?ds.), 0and(oo6 of +olent ?,traction, John Siley X +ons, 1e5 For6 ("9%3). ;"0< A. I. )e, +. :. Ihop6ar, R. A. 2hal*ers, +olent e,trac- tion of *etals, Ean 1ostrand, 1e5 For6 ("9D0). ;""< 0. F. Qee, +. V. Ii*, 0ydro*etallur$y, F3, 9" (2003). ;"2< V. Iordos6y, :. Eirni$, +olent ?,traction, 0en6el 2or- poration :/), Tucson Ari-ona ("99%). ;"3< R. 2alet6a, 2he*ic6e Qist, @8, 339 ("963). ;"3< 4. R. Reddy, J. R. Iu*ar, 0ydro*etallur$y, F7, "D3 (200#). ;"#< ?. Ieshaar- Ala*dari, +. I. +adrne-haad, 0ydro*etal- lur$y, @@, 32D (2000). ;"6< Y.J. Fan$, A.V. =ane, 2he*ical ?n$ineerin$ Journal, 88, 3# (2002). ;"D< J. Atony, =. J. Atony, Sor6 +tudy, @9, "3" (200").
Synthesis, Configuration, and Dehydration of Some 1-Alkyl - and Aralkyl-3-Methyl-4-O-Tolylpiperidin-4-Ols - AF Casy MA Iorio - J Chem Soc C 1970, 135 - DOI 10.1039 J39700000135