Tp ch Ha hc, T. 42 (1), Tr.

61 - 66, 2004

HIU NG TNG CNG CHIT CA CC NGUYN T T HIM nh (La, Pr, Nd, Sm, Eu) BNG HN HP TRIBUTYLPHOTPHAT V AXIT 2-ETYLHEXYL 2-ETYLHEXYL PHOTPHONIC T DUNG DCH AXIT NITRIC
n Ta son 19-5-2003 LU MINH I1, NG V MINH1, V QUANG MAI2
1

Vin Khoa hc v% Cng ngh Vit Nam 2 Tr,ng i hc S, phm Hu SUMMARY

The extraction of rare earth elements (La, Pr, Nd, Sm, Eu) by mixture of ntributylphosphate and 2-ethylhexyl 2-ethylhexyl phosphonic acid from nitric acid solutions has been developed. The influence of various factors such as the nitric acid concentrations, the n-tributylphosphate / 2-ethylhexyl 2-ethylhexyl phosphonic acid ratio,... on the Sk has been reported. The synergistic effects of rare earths has been investigated at the nitric acid concentration 0.2M; the formulation of complexes of rare earths with n-tributylphosphate and 2-ethylhexyl 2-ethylhexyl phosphonic acid has also been presented by using the IR, UV and raman analysis methods. I - M u Chit cc nguyn t t him (NTH) bng cc tc nhn tributylphotphat (TBP), triizoamylphotphat (TiAP), axit di-2-etylhexyl photphoric (HDEHP) t cc mi tr6ng nitric, tricloaxetic 8 6c nghin cu trong cc cng trnh [1 - 4]. Gn y c ch chit ca Ce(IV) vi axit 2-etylhexyl 2-etylhexyl photphonic (PC88A) trong mi tr6ng axit sunfuric cng 8 6c m t [5]. Trong bNi bo nNy, chng ti thng bo mt s kt qu chit cc NTH nhm nh (La, Pr, Nd, Sm, Eu) bng hn hp tributylphotphat (TBP) vN axit 2-etylhexyl 2-etylhexyl photphonic (PC88A) t dung dch axit nitric. II - PHN THC NGHIM 1. Ha cht - Cc dung dch mui nitrat t him 6c iu ch bng cch ha tan cc oxit t him t6ng ng c sch 99,9% trong HNO3 (PA). - Tc nhn chit lN TBP, sn phm ca h8ng BDH Chemicals Ltd Poole (Anh) c sch 98% vN PC88A (PA) lN sn phm ca h8ng Daihachi chemical Industry Co.Ltd (Nht) vN 6c dng trc tip khng qua x l lNm sch thm. - Dung mi pha lo8ng lN phn on du ha 6c ch6ng ct 170 - 210oC. - Cc loi ha cht khc nh6: HNO3, NaOH, DTPA, Arsenazo(III) u c sch PA. 61

2. Ph ng php chit Ph6ng php chit cc NTH bng cc tc nhn chit TBP, PC88A hoc hn hp TBP vN PC88A 6c tin hNnh trn phu chit c dung tch 20 ml. T l th tch ca pha n6c vN pha hu c lN 1 : 1. Thi gian chit vN phn pha lN 5 pht. Sau khi tch ring hai pha, nng NTH trong pha n6c vN pha hu c 6c xc nh bng ph6ng php chun vi dung dch chun DTPA (10-2 M) trong s c mt ca thuc th Arsenazo(III). III - KT QU V! THO LUN 1. nh h ng ca nng axit nitric cn bng n hiu ng tng c ng chit ca h TBP + PC88A Th nghim 6c tin hNnh vi nng ban u ca Nd3+ 0,1M, tc nhn chit 40% TBP + 40% PC88A - du ha. Nng axit nitric cn bng 6c thay i: 0,2M; 0,4M; 0,7M; 1M. Kt qu nghin cu nh h6ng ca nng axit nitric cn bng n h s c6ng chit Sk 6c trnh bNy bng 1. T bng 1, c th nhn thy trong phm vi nng 6c kho st ca axit nitric, h s tng c6ng chit ca NTH tng khi tng nng axit cn bng. thun tin chng ti chn nng [H+]cb = 0,2M cho nhng th nghim sau.

Bng 1: nh h6ng ca nng axit nitric cn bng n h s c6ng chit Sk [HNO3] cn bng Nd H s phn b D D (TBP) D (PC88A) D (TBP + PC88A) D (TBP) D (PC88A) D (TBP + PC88A) D (TBP) D (PC88A) D (TBP + PC88A) D (TBP) D (PC88A) D (TBP + PC88A) 0,005 0,170 0,350 0,019 0,090 0,256 0,029 0,022 0,150 0,031 0,001 0,099 Sk 0,30

0,2 M

0,4 M

0,37

0,7 M

0,47

1M

0,49

2. Hiu ng tng c ng chit Sk ca NTH nh bng hn hp TBP v2 PC88A Th nghim 6c tin hNnh vi nng ban u ca cc dung dch Ln(NO3)3 lN 0,1M, nng dung dch HNO3 cn bng 0,2M.

Bng 2: Hiu ng tng c6ng chit Sk ca NTH nh bng hn hp TBP vN PC88A NTH La D hoc Sk D (TBP) D (PC88A) D (TBP+PC88A) Sk 0,015 0,014 0,111 0,58 0,007 0,100 0,250 0,37 0,005 0,170 0,350 0,30 0,030 0,310 0,527 0,19 0,008 0,573 0,766 0,12 Pr Nd Sm Eu

Tc nhn chit lN hn hp 40% TBP + 40% PC88A - du ha. Kt qu thc nghim 6c trnh bNy trn bng 2. Bng 2 cho thy hiu ng tng c6ng chit gim dn t La n Eu. i vi h n tc nhn chit PC88A, qu trnh

chit theo c ch trao i ion nn cc NTH cui d8y c bn knh ion nh hn s to phc bn hn c h s phn b D ln hn; trong khi i vi h n tc nhn chit TBP to solvat c gi tr h s phn b D ni chung km hn.

62

3. nh h ng ca t l TBP/PC88A n h s tng c ng chit Sk ca cc NTH nh iu kin th nghim nh6 sau: nng ban u ca cc dung dch Ln(NO3)3 lN 0,1M, nng dung dch HNO3 cn bng 0,2 M. Tc nhn chit TBP + PC88A 6c pha lo8ng trong 20% du ho vi t l TBP/PC88A thay i: 1/9; 1/3; 2/3; 1/1; 3/2; 3/1; 9/1 (theo th tch). Kt qu thc nghim 6c trnh bNy trn hnh 1. T dng cc 6ng cong trn hnh 1, c th nhn thy t l TBP/PC88A nh h6ng n hiu ng tng c6ng chit kh mnh. Hiu ng c6ng chit cc i khi t l TBP/PC88A t 1 : 1. Cc NTH nh cui d8y c hiu ng tng c6ng chit nh hn cc NTH nh u d8y khi c cng t l TBP/PC88A. 4. ng ng nhit chit ca Nd trong h TBP + PC88A t mi tr ng axit nitric 6ng ng nhit chit lN i l6ng nh gi dung l6ng ca h chit, qua c th xc nh hiu sut ca qu trnh chit. Chng
3+] -2 -2, M [Ln3+ ]hc.10 ,M [Ln .10 hc

H s c6ngH chit S k chit S s c6 ng

0,6 0.6 0,5 0.5 0,4 0.4 0,3 0.3 0,2 0.2 0,1 0.1
0.0

La3+

Pr3+ Nd3+

-0,1 -0.1

1:9 1:3 2:3 1:1 3:2 3:1 9:1 Eu3+

TTBP/PC88A l TBP/PC88A T l

| Sm3+

Hnh 1: nh h6ng ca t l TBP/PC88A n Sk -0.2 ti 8 xy dng 6ng ng nhit chit ca Nd cho h 80% TBP+PC88A - du ha. Th nghim 6c tin hNnh t l ca TBP/PC88A lN 1 : 1. Kt qu 6c trnh bNy trn hnh 2. T hnh 2, c th nhn thy dung l6ng chit ca Nd ln nht khi tc nhn chit lN hn hp ca TBP vN PC88A.

60 60

Nd (40%TBP+40%PC88A)
50 50 40 40 30 30 20 20 10 10 0 0

Nd (40%TBP)

Nd(40%PC88A)

0 0

Hnh 2: 6ng ng nhit chit ca Nd h Ln3+ / (40%TBP + 40%PC88A) - du ha - HNO3 5. Xc nh kh nng to phc ca NTH vi cc tc nhn chit TBP, PC88A, hn hp TBP + PC88A bng ph hng ngoi, t ngoi v2 raman TBP vN PC88A c cng thc cu to nh6 sau: 63

Hnh 2: 6ng ng nhit chit ca Nd h Ln3+/(40%TBP+40%PC88A)-du ho-HNO

10 10

20 20

30 30

40 40

50 50

3+] 3+ [Ln .10, M ] .10. [Ln n

n

60 60

CH3(CH2)2CH2O P CH3(CH2)2CH2O

OCH2(CH2)2CH3

CH3(CH2)3CHCH2O C2H5 P

OH

CH3(CH2)3CHCH2O C2H5

TBP: tributylphotphat Trn ph hng ngoi ca PC88A, vng tn s cao, xut hin cc di hp th vng 2900 cm-1, cc di hp th nNy thuc dao ng ha tr ca cc nhm CH3, CH2. Di hp th 1657 cm-1 ng vi dao ng bin dng ca nhm OH. Di hp th 1196 cm-1 ca cc nhm P=O. Cc di hp th 1034 vN 984 cm-1 ca nhm P-O-C vN P-O-H. Trn ph hng ngoi ca Nd vi PC88A, c6ng vN tn s ca di hp th ng vi dao ng bin dng ca nhm OH vng tn s 1657 cm-1 thay i ng k (1667 cm-1). iu chng t proton ca nhm OH b tch ra vN nguyn t oxi s lin kt vi Nd to nn phc theo c ch trao i cation gia Nd vN PC88A.

PC88A: axit 2-etylhexyl 2-etylhexyl photphonic Di hp th ca nhm P=O 1196 cm-1 trong ph hng ngoi ca PC88A b gim v pha tn s thp trong qu trnh to phc do oxi ca nhm P=O t6ng tc vi Nd. Chnh s to phc nNy 8 lNm gim mt electron nguyn t photpho nn 8 lNm yu i lin kt P=O, dn n lNm gim tn s dao ng ha tr ca lin kt. Di hp th ca lin kt O-Nd vng tn s thp khng thy trn ph hng ngoi ca Nd vN PC88A nh6ng trn ph raman 8 thy xut hin vch ph 491,1 cm-1. Kt qu ph hng ngoi vN raman 8 chng t c s to phc xy ra theo c ch trao i cation gia Nd vN PC88A. Trn ph hng ngoi ca Nd vi TBP vN PC88A ta cng thy c s to phc t6ng t.

S sng (cm-1) Ph hng ngoi ca PC88A (ca PC88A)

S sng (cm-1)

Ph hng ngoi

3+ 3+ Ph hng ngoi ca (Nd + PC88A) (ca Nd + PC88A)

64

50000 50000

C6ng

Intensity (a.u.)

40000 40000

30000 30000

Dung mi pha lo 8 ng PC88A Nd 3+ +PC88A 491.1

20000 20000

10000 10000

0 0 200 400 600 800 1000 1200

200

400

600
Ph RAMAN

800

1000 1200 Wavenumber (cm -1 )-1 S sng (cm )

Ph raman Trn ph t ngoi ca Nd3+ vi TBP 8 chng t c s to phc v i vi ligan TBP xut hin cc i hp th 272 nm nh6ng khi to phc cc i nNy dch chuyn ln 299,5 nm. Trn ph t ngoi ca Nd3+ vi PC88A cng chng t c s to phc v i vi ligan
Ab4.5 Ab45 s 4.5 s 4.0

PC88A xut hin cc i hp th 263 nm nh6ng khi to phc cc i n N y dch chuyn ln 299 nm vN 353,2 nm. iu nNy 6c gii thch lN khi Nd3+ nh vNo oxi ca nhm OH lNm phn cc lin kt ca P=O nn xut hin 2 cc i trn.

Abs

40 4.0

0.4 0,4 0.4

Abs
299.0 299.0
3+ 3+ Nd +PC88A Nd +PC88A

3.5 35 3.5 3.0 30

3.0 2.5 25 2.5 2.0 20 2.0 1.5 15 1.5 1.0 10 1.0 0.5 5 0.5 0.0 0 0.0

0.3 0,3 0.3

Abs Abs

0.2 0,2 0.2

263.0 263.0

PC88A PC88A 353.2 353.2

nm 350 350 nm
350

0.1 0,1

272.0 272.0 299.5 299.5

250 250

3+ 3+ +TBP Nd Nd +TBP

0.1

TBP TBP

200
200

200

250
250

250

300
300

300

400

400

Ph t ngoi (Nd3++PC88A)

nm

400

450

450

500

450

500

0.0 0,0

0.0

500

250

300 300

300

350 350

350 nm

nm

nm

400 400 400

450 450 450

500 500 500

Ph t ngoi (Nd3++TBP) Ph t ngoi (Nd3+ TBP)

Ph t ngoi ca (Nd3+ + PC88A)

Ph t ngoi ca (Nd3+ + TBP)

65

IV - KT LUN Ln u tin 8 nghin cu kh nng chit cc NTH nh La, Pr, Nd, Sm, Eu bng hn hp tributylphotphat vN axit 2-etylhexyl 2-etylhexyl photphonic t dung dch axit nitric. 1. 8 kho st nh h6ng ca nng axit nitric cn bng (t 0,2 M n 1 M) n hiu ng c6ng chit Sk ca h (40%TBP + 40%PC88A) du ha trong mi tr6ng HNO3. Kt qu cho thy h s Sk xut hin tt c NTH nh vN khi tng [H+] th Sk tng theo. 2. 8 tin hNnh kho st h s tng c6ng chit Sk ca La, Pr, Nd, Sm, Eu ca h (40%TBP + 40%PC88A) - du ha. 3. 8 kho st nh h6ng ca t l TBP / PC88A n h s c6ng chit Sk ca cc NTH nh. Kt qu thc nghim cho thy t l TBP / PC88A 1 : 1 h s c6ng chit Sk cc i. 4. 8 thit lp 6ng ng nhit ca Nd vi TBP, PC88A vN hn hp (TBP + PC88A) t mi tr6ng axit nitric. Kt qu cho thy dung l6ng chit ln nht khi dng hn hp tc nhn chit TBP vN PC88A. 5. 8 xc nh 6c kh nng to phc ca

NTH vi cc tc nhn chit TBP, PC88A, hn hp TBP + PC88A bng ph hng ngoi, t ngoi vN raman. Cng trnh n%y ,c ho%n th%nh vi s h tr ca Ch,ng trnh nghin cu c bn trong lnh vc khoa hc t nhin. T!I LIU THAM KHO 1. L6u Minh i, ng V Minh, Phm Vn Hai. Tp ch Ha hc, T. 36, s 4, Tr. 62 66 (1998). 2. L6u Minh i, ng V Minh, V Vn Tn. Tp ch Ha hc, T. 37, s 4, Tr. 60 - 63 (1999). 3. V Vn Tn. Nghin cu tch phn chia t him M6ng Hum bng ph6ng php chit vi tributylphotphat, axit di-(2-etylhexyl) photphoric, Lun n Tin s Ha hc (2001). 4. John S. Preston & Anna C. du Preez. J. Chem. Tech. Biotechnol.,Vol. 61, P. 159 - 165 (1994). 5. L B Thun, HoNng Nhun, L6u Xun nh, V ng . Tp ch Ha hc, T. 40, s B, Tr. 116 - 122 (2002).

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