Tp ch Ha hc, T. 41, s 2, Tr.

84 - 88, 2003

Kh nng in phn thu hi ch bng dung dch phc

cacbonat-ietylentriamin
n Ta son 30-9-2002
Nguyn Th Ph ng Thoa, Trn Vn Mn
i hc Khoa hc T nhin, i hc Quc gia Tp. H Ch Minh

Summary
Electrowinning processes of lead battery paste, compared to the thermal ones, are more
effective and environmental friendly. In this study we use diethylenetriamine (DETA) as a ligand
to dissolve lead carbonate in order to replace H2SiF6 and HBF4, which are toxic and corrosive
in the lead electodeposition. The complex solutions were electrolyzed in 4 hours with a cathode
of stainless steel and graphite anodes. In the various conditions of current density (from 5 to 30
mA/cm2), DETA concentration (150 - 180 g/L) and temperature (30 - 60oC) the current
efficiency of lead deposition was high. The cathode potential values were unchangeable during
the electrolysis. The decrease of precipitated lead mass per unit of cathode area by increasing
DETA concentration shows that metallic lead was formed by deposition of lead cations, which
have not been in the complex form.

I - Gii thiu
Trong cquy ch axit, cc tm l i cc cng
chc, t b ph hy c hc v& c th&nh phn n
nh trong sut qu trnh s dng (cha khong
5%Sb v& 95% Pb) nn d tch v& d ti sinh.
Ring phn cao ch c th&nh phn kh phc tp
v& thay i ty theo nh& sn xut, cch thc v&
thi gian s dng. Do vy vic ti ch cao
cquy kh khn hn.
Bng 1 trnh b&y th&nh phn ca cquy thi
sau khi tch v& phn loi theo nghin cu ca
hHng Engitec [1].

Bng 1: Th&nh phn khi l ng cc hp cht ha hc ch yu trong cquy ph thi

Th&nh phn, hp cht T l, % H&m l ng tng, %
Ch kim loi trong cc v& s n cc 25
PbSO4 50 - 60
PbO2 15 - 35
Cao ch PbO 5 - 10 38
Pb kim loi 2-5
Th&nh phn khc 2-4
V nha polypropylen 5
L cch nha, cao su cng 10
Dung dch H2SO4 22

84
 Theo kt qu phn tch ca chng ti th
th&nh phn cquy ch axit ph thi (loi 6V v&
12 V dng cho xe gn my ca x nghip
cquy ng Nai) gm: dung dch H2SO4 nng
2,34 mol/l (19,87%): 15,9%; v nha + dy
in + nt nha: 10,4%; ph kin kim loi (cu
ni, cht cc): 11,8%; s n cc: 23,3%; cao
ch: 27,2%; l cch PVC: 3,4%; cc th&nh phn
khc: 8%.
Hin nay thu hi ch t cao ch ph thi
c hai nhm ph ng php chnh. Mt l& kh
luyn bng cc cht kh m& thng dng nht l&
cacbon. Ng i ta trn than vi cc ph liu
cha ch v& nung nhit trn 600oC thu
c ch [2]. Vit Nam ph ng php n&y
c thc hin ch yu ti cc l th cng.
Nh c im ln nht ca nhm ph ng php
n&y l& gy nhim mi tr ng nng n do s
bc hi ch kim loi cng nh cc kh CO, SO2.
Ngo&i ra, sn phm thu c khng tinh khit
v& cn tip tc tinh ch. Nhm ph ng php th
hai l& in phn thu hi: ng i ta chuyn cc
hp cht cha ch trong cquy thi v dng tan
c ri in phn. u im chnh ca cc qu 06400-274.
trnh in phn l& cho php thu c ch c
tinh khit cao, p ng c cc i hi ca
cng nghip cquy, t gy nhim hn qu
trnh kh luyn.
Tr c y to dung dch in phn ch
th ng dng cht to phc H2SiF6 [3]. T
nhng nm 1990 nhiu ligand khc H c
ngh, th d Olper v& cc cng s H xy dng
cng ngh ti sinh ch t cao cquy bng cch
chuyn cao ch v dng ch sunphua ri ngm
tch trong dung dch Fe(BF4)3 thu c
Pb(BF4)2 ha tan, sau in phn thu hi ch
[4]. Nhng ligand cha flo c th b phn hy
khi in phn v& gy nhim mi tr ng. Do
gn y ng i ta H bt u th nghim vic tnh theo nh lut Faraday:
s dng mt s ligand hu c ha tan cc
mui ch [5, 6].
Trong t&i n&y chng ti b c u kho
st qu trnh in phn thu hi ch t dung dch
phc cacbonat ch - dietylentriamin (DETA).
II - Thc nghim
Dung dch in phn c ch to t cc
ha cht loi PA: ch cacbonat (PbCO3), axit
sunphuric (H2SO4), dietylentriamin v.v pha
trong n c ct. Tr c v& sau in phn kim tra
pH ca dung dch trn my pH Meter Corning
445, dn in o trn my Conductivity
Meter Jenway 4310.
Ngun in c cung cp bi my chnh
l u hiu BIELIT. Th tch in phn 120 ml.
Catot inox c kch th c 3,56 cm 1,95 cm
0,09 cm, c t cch u gia hai in cc
anot bng graphit, vi kch th c 6,11 cm
4,08 cm 0,51 cm. Khong cch gia anot v&
catot l& 6,22 cm. T l th tch dung dch trn
din tch catot v&o khong 12 ml/1 cm2. Tr c
mi ln in phn c catot v& anot c nh
bng bng giy nhm n mn P2000 ri
em ra sch bng x& phng, n c ri ra li
bng etanol loi b cc cht du m bm
trn in cc, sau sy kh ri cho v&o bnh
ht m. Khi l ng catot tr c v& sau in phn
xc nh bng cn phn tch hiu METTLER
TOLEDO. Th in cc catot c theo di so
vi in cc calomel bHo ha hiu PROLABO
Tin h&nh ba chui th nghim nh sau:
Chui mt dng thay i: in phn
dung dch (A) gm DETA 160 g/l, PbCO3 70
g/l, H2SO4 60 g/l, vi cc mt dng 5, 7,5,
10, 12,5, 15, 17,5, 20 v& 30 mA/cm2.
Chui nng DETA thay i: in phn
dung dch gm PbCO3 70 g/l, H2SO4 60 g/l, v&
DETA vi nng : 150, 160, 170, 180 v& 200
g/l ti mt dng i = 10 mA/cm2.
Chui nhit thay i: in phn dung
dch (A) ti cc nhit 30, 40, 50 v& 60oC vi
mt dng 20 mA/cm2.
L ng ch kt ta l thuyt (mPbLT) c
M .I .t
m PbLt = (1)
n.F
trong F = 96485 C; n l& s in t trao
i; I l& c ng dng in (A); t l& thi
gian in phn (giy).
Catot sau khi in phn c ngm ra
nhiu ln bng n c ct v& sy kh ri em cn
trn cn phn tch. Xc nh l ng ch kt ta
85
thc t (mPbTN) trn catod theo bin thin khi trnh in phn (trong khong 10 mV).
l ng catod tr c v& sau in phn.
T mPbLT v& mPbTN tnh c hiu sut dng: 0.690
m 0.685
H = PbTn

Ecatod, V
(2)
m PbLt 0.680
0.675
III - Kt qu v( bin lun 0.670
0 100 200 300
1. nh h ng ca mt dng i Thi gian, pht
Tin h&nh in phn trong 4 gi dung dch
c th&nh phn H2SO4 60 g/l; Pb 70 g/l; DETA Hnh 1: Bin thin th catot theo thi gian in
160 g/l (dung dch A); pH 10,03; dn in phn dung dch A
ring = 25,47 mS. Hnh 1 trnh b&y s thay Kt qu in phn dung dch A cc mt
i ca th catot theo thi gian in phn mt dng i thay i 5, 7,5, 10, 12,5, 15, 17,5, 20
dng i = 10 mA/cm2. Kt qu cho thy th v& 30 mA/cm2 c trnh b&y trong bng 2 v&
catot thay i khng ng k trong sut qu hnh 2.
Bng 2: nh h ng ca mt dng ln cc thng s ca qu trnh in phn dung dch A
(Scatot: din tch catot tip xc vi dung dch; mPb: khi l ng Pb kt ta trn 1 cm2 b mt catot)

i, Scatot, mPbLT, mPbTN, mPb, Hiu sut

Ec, V pH , mS
mA/cm2 cm2 g g g/cm2 dng, %
5,0 9,168 0,7088 0,7079 0,07721 99,87 0,681 10,01 25,90
7,5 9,360 1,0854 1,0438 0,11152 96,17 0,679 9,99 26,30
10,0 7,640 1,1801 1,1641 0,15237 98,64 0,678 9,99 26,40
12,5 8,022 1,5504 1,5372 0,19162 99,15 0,682 9,99 26,73
15,0 9,360 2,1688 2,1450 0,22917 98,90 0,684 9,98 27,13
17,5 9,360 2,5327 2,4801 0,26497 97,92 0,679 9,95 27,50
20,0 8,786 2,7170 2,6190 0,29809 96,39 0,681 9,95 27,30
30,0 7,640 3,5373 3,5192 0,45969 99,49 0,702 - 25,63

Kt qu trn hnh 2 cho thy khi l ng ch

Khi l ng ch kt ta

kt ta tng tuyn tnh theo mt dng i khi 0.5

trn 1 cm2 catot

mt dng tng t 5 n 30 mA/cm2. 0.4

Quan st lp ch kt ta nhn thy mt 0.3

dng nh hn 12,5 mA/cm2 lp ch kt ta sng 0.2

bng v& bm cht trn catot hn. mt 0.1
dng ln hn 12,5 mA/cm2, tuy khi l ng ch
0
kt ta nhiu hn nh ng sng bng khng 0 10 20 30 40
bng mt dng nh.
Mt dng, mA/cm2
Trn b mt anot thot nhiu bt kh do s
gii phng oxi t n c theo phn ng:
Hnh 2: Khi l ng ch kt ta trn 1 cm2 catot
+
2 H2O - 4 e O2 + 4 H theo mt dng

86
 pH dung dch sau in phn v& nhn thy u kh cao, trn 96%.
pH thay i khng ng k. iu n&y chng t
phc DETA hu nh khng b mt i trong qu 2. nh h ng ca nng DETA
trnh in phn. Kt qu thu c khi in phn mt
Hiu sut dng hi gim khi tng mt dng i = 10 mA/cm2 trong 4 gi dung dch
dng, iu n&y ph hp vi quy lut chung ca H2SO4 60 g/l; Pb 70 g/l; c nng DETA
qu trnh in phn. D vy ti tt c cc mt thay i t 150 n 200 g/l, c trnh b&y
dng H kho st, hiu sut dng t c trong bng 3 v& hnh 3.

Bng 3: nh h ng ca nng DETA ln cc thng s in phn

dung dch H2SO4 60 g/l; Pb2+ 70 g/l ti i = 10 mA/cm2
i, Scatot, mPbLT, mPbTN, mPb, Hiu sut
Ec, V pH , mS
mA/cm2 cm2 g g g/cm2 dng, %
150 9,550 1,4766 1,4663 0,1535 99,30 0,678 9,88 27,7
160 7,640 1,1801 1,1641 0,1524 98,64 0,678 9,99 26,4
170 9,750 1,5075 1,4810 0,1519 98,24 0,682 10,04 25,23
180 9,260 1,4472 1,3771 0,1487 95,16 0,686 10,11 24,17
200 9,168 1,4175 1,3439 0,1466 94,81 0,693 10,25 22,23

Hnh 4 cho thy l ng ch kt ta trn mt m khi nng ligand tng. iu n&y ph hp

n v din tch catot gim khi tng nng
DETA. iu n&y theo chng ti c th gii
thch bng s chuyn dch cn bng to phc:
Pb2+ + n DETA
Khi tng nng ligand, nng ion ch t
do gim m& chui th nghim in phn n&y
c thc hin mt dng thp (10
mA/cm2) l& vng kh ca ion ch t do. Khi
nng ligand tng nht ca dung dch in
phn tng cng khin cho hiu sut dng gim.
Khi l ng ch trn 1
vi quy lut chung v s chuyn dch v pha
m ca th cn bng EMZ+/M khi c s hin din
ca cht to phc.
[Pb(DETA)n]2+ 3. nh h ng ca ph gia gelatin
Cc th nghim in phn cho thy ch kim
loi kt ta ng u phn trong lng b mt
catot. Tuy nhin, do s phn b th khng u,
kt ta ch u tin din ra cc gc, cnh to ra
cc im li nhn. Mt in tch ln ti
nhng im li nhn dn ti kt ta ch s tp
trung pht trin nhanh hn ti , to hnh kt
ta dng phin l hoc nhnh cy. Hu qu l&

0.156
ch kt ta khng c dng tm c chc bm
cm2, g/cm2

0.154
0.152
trn b mt catot nh mong mun. khc
0.15 phc chng ti dng gelatin vi nng th
0.148 nghim l& 0,25%, 0,5% v& 1,0%. Kt qu cho
0.146 thy khng cn hin t ng kt ta dng phin
140 160 180 200
v& dng kim ti ra cnh catot. Trn to&n b mt
Nng DETA, % catot hin din lp kt ta mn chc v& d tch
bc. Tuy vy s c mt ca gelatin l&m dung
Hnh 3: Khi l ng ch kt ta trn 1cm2 catot dch km trong sut hn. Khi cho gelatin
theo nng DETA nng 1% khng ci thin thm cht l ng
ca lp kim loi kt ta. Do vy trong cc th
T bng 3 cng nhn thy, s chuyn dch nghim chng ti s dng ph gia gelatin vi
ca Ekt, th ti ch bt u kt ta, v pha nng 0,5%.

87
4. nh h ng ca nhit 30oC n 60oC. Kt qu in phn cho thy
H tin h&nh in phn dung dch A mt cc nhit khc nhau c trnh b&y trong
dng 20 mA/cm2 vi cc nhit thay i t bng 4.

Bng 4: nh h ng ca nhit ln cc thng s in phn dung dch A

(pH 10,03, 21,8 mS) ti mt dng i = 20 mA/cm2
Nhit mPb, Hiu sut , mS
Sc, cm2 mPbLt, g mPbTn, g Ec, V pH
, oC g/cm2 dng, % (sau p)
30 8,786 2,7170 2,6190 0,29809 96,39 0,681 9,95 -
40 8,022 2,4783 2,5011 0,31178 100,92 0,764 10,02 25,5
50 8,022 2,4783 2,4718 0,30813 99,74 0,712 10,04 24,8
60 8,022 2,4783 2,4299 0,30290 98,05 0,696 10,08 24,0

Theo l thuyt vic tng nhit l&m gim
nht ca dung dch v& tng chuyn ng
nhit ca ion v& l&m tng dn in ca dung
dch.
Thc nghim cho thy trong qu trnh in
phn nhit cao 50 - 60oC th in cc
khng tht n nh, bin i trong khong 20 -
30 mV. C s kt ta mt phn ca mui ch
trong dung dch v& pH ca dung dch tng sau
khi in phn, iu n&y c th do s bay hi
n c nhit cao.
IV - Kt lun
- Trong cc iu kin H kho st, hiu sut
dng ca qu trnh in kt ta ch cao, t trn
98%. Th catot n nh trong qu trnh in
phn.
- Trong khong bin thin ca mt dng
t 5 n 30 mA/cm2, tc kt ta ch t l
tuyn tnh vi mt dng.
- L ng ch kt ta trn mt n v din
tch catot thp inox gim khi tng nng
DETA t 150 n 200 g/l.
- Cht ph gia gelatin vi nng 0,5% ci
thin cht l ng lp ch kt ta: mn chc, bm
tt trn catot inox v& d tch bc sau phn ng.
- Khi tng nhit , qu trnh in phn xy ra
phc tp v& ch a c li gii thch c th.
Theo chng ti DETA ho&n to&n c kh
nng c s dng nh mt ligand trong qu
trnh in phn thu hi ch t bt cao ch ca
cquy ph thi. Tuy nhin rt cn c nhiu
nghin cu tip theo nhm ci thin iu kin
in phn v& tn thu ch.
T(i liu tham kho
1. K. Jobst, A. Grahl, M. Maccagni, M. Olper,
P. Scharf, R. Wagner, H. Warlimont:
Electrodeposited. J. of Power Sources 78, P.
73 - 78 (1999)
2. Beid-Charreton. US Patent number
5467365, Nov. 14 (1995).
3. D. Pletcher, F.C. Walsh. Industrial Electro-
chemistry, Chapman & Hall, Glasgow
(1993).
4. H. Warlimont, A. Grahl, M. Olper, M.
Maccagni: A Novel Concept To Produce
And Recycle Lighter Lead-Acid Batteries
For Automobiles, Proc. 3rd Int. Conf.
ECOMATERIALS, 99-102, (1997).
5. D. Felsher, J. A. Finch, P. A. Distin-
Electrowinning from copper-DETA complexes-
Canadian metallurgical quarterly, Vol. 39, No. 3,
P. 291 - 296 (2000).
6. Michael D. Gernon-Electrowinning of lead
- US Patent number 5520794, Oct. (1996).

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