TAP CH PHAT TRIEN KH&CN, TAP 11, SO 08 - 2008

NGHIN CU KH NNG HP PH V TRAO I ION CA X DA V

V TRU BIN TNH
L Thanh Hng (1), Phm Thnh Qun (1), L Minh Tm (1), Nguyn Xun Thm (2)
(1)Trng i Hc Bch Khoa, HQG-HCM
(2)Vin Cng Ngh Ha Hc TpHCM
1. GII THIU
Cng vi s gia tng cc hot ng cng nghip l vic sn sinh cc cht thi nguy hi, tc
ng tiu cc trc tip n sc khe con ngi v h sinh thi. Cc hot ng khai thc m, cng
nghip thuc da, cng nghip in t, m in, lc ha du hay cng ngh dt nhum to ra
cc ngun nhim chnh cha cc kim loi nng c hi nh Cu, Pb, Ni, Cd, As, Hg[1,4].
Nhng kim loi ny c lin quan trc tip n cc bin i gen, ung th cng nh nh hng
nghim trng n mi trng [1,2]. i vi nhng nc ang pht trin nh Vit Nam, qui m
cng nghip ch yu mc va v nh, vic x l nc thi gp nhiu kh khn do chi ph x l
cao, kh nng u t thp [3,4]. Cc ph phm nng nghip do c nghin cu nhiu s
dng trong vic x l nc v chng c cc u im l gi thnh r, l vt liu c th ti to c
v thnh phn chnh ca chng cha cc polymer d bin tnh v c tnh cht hp ph hoc/v
trao i ion cao [1,2,3].
Cc vt liu lignocelluloses nh mn ca, x da, tru, v cc loi u, b ma c
nghin cu cho thy c kh nng tch cc kim loi nng ha tan trong nc nh vo cu trc
nhiu l xp v thnh phn gm cc polymer nh cellulose, hemicelluloses, pectin, lignin v
protein. Cc polymer ny c th hp ph nhiu loi cht tan c bit l cc ion kim loi ha tr
hai. Cc hp cht polyphenol nh tannin, lignin trong g c cho l nhng thnh phn hot
ng c th hp ph cc kim loi nng. Reddad (2002) [8]cho rng cc v tr anionic phenolic
trong lignin c i lc mnh i vi cc kim loi nng. Mykola (1999) [9] cng chng t rng cc
nhm acid galacturonic trong peptin l nhng v tr lin kt mnh vi cc cation.
Cc nhm hydroxyl trn cellulose cng ng mt vai tr quan trng trong kh nng trao i
ion ca cc lignocelluloses. Bn thn cc nhm ny c kh nng trao i yu v lin kt OH y
phn cc cha mnh. Nhiu bin php bin tnh c cng b nh oxy ha cc nhm
hydroxyl thnh cc nhm chc acid hoc sulfo ha bng acid sulfuric.
Gn y nht l phng php ester ha cellulose bng acid citric. James D. Mc Sweeny
(2006) dng acid citric hot ha g Aspen [5], Wayne E. Marshall (2006) dng acid citric hot
ha v u nnh u nhn thy mt s gia tng ng k kh nng tch loi cc ion kim loi tan
trong nc [6]. Qu trnh hot ha bao gm cc bc ngm vt liu trong dung dch acid citric
bo ha sau sy kh, cc phn t acid citric khi s thm su vo cc mao qun ca vt liu.
Tip theo nung nhit khong 120oC trong 8 gi [7]. Acid citric u tin s chuyn thnh
dng anhydric, tip theo l phn ng ester ha xy ra gia anhydric acid v cc nhm hydroxyl
ca cellulose. Ti v tr phn ng nh vy xut hin hai nhm chc acid (t acid citric) c kh
nng trao i ion. Nu tng nhit hoc ko di thi gian phn ng, qu trnh ester ha c th
tip tc xy ra i vi cc nhm acid cn li ca acid citric lm gim kh nng trao i ion (Hnh
1) [5].

Science & Technology Development, Vol 11, No.08 - 2008

Hnh 1. Ester ha cellulose bng acid citric

So vi cc bin php bin tnh cellulose trc , phng php s dng acid citric c nhiu
u im nh iu kin phn ng n gin, tc nhn acid khng c hi, gi thnh khng cao.
Phng php ny c nhiu tc gi khc ng dng rt hiu qu cho cc ph phm nng nghip
l cc loi vt liu xp d dng cho acid citric ngm vo bn trong. Tuy nhin i vi mt s g
cng, bin php ny cho hiu qu khng cao.
Vi mc tiu tm kim mt loi ph phm nng nghip c kh nng x l hiu qu cc cation
cng nh anion, trong nhng nghin cu ban u ny chng ti chn hai sn phm ph trong
nng nghip ph bin ng bng song Cu Long l x da v v tru kho st kh nng tch
ion kim loi ra khi nc ca chng. Qu trnh bin tnh bng acid citric cng c p dng
xem xt hiu qu ca n trn hai vt liu trn.
2. THC NGHIM
2.1. Nguyn vt liu v phng php
2.1.1. Nguyn vt liu ha cht nghin cu
Ha cht dng trong th nghim l NiCl2.6H2O, CdCl2.H2O, Zeolit A, Dimethylglyoxim v
Dithizon dng PA ca Merck; nha cationit ca M. Cc dung mi CHCl3, CCl4, acid citric ca
Shanou Xilong (Trung Quc) v nc ct mt ln. Cc ha cht c pha trong cc dung mi
thch hp to cc dung dch c nng xc nh v khng qua x l g thm. X da Bn Tre,
tru Tin Giang c s dng trong nghin cu ny.
2.1.2. Qu trnh hot ha
X da v v tru c ra sch bng nc thy cc x l tp c hc. 200 g vt liu kh
c ngm vo 2,5 lt dung dch acid citric bo ha trong 48 gi. Sau , x da v tru c ly
ra khi dung dch acid citric, kh t nhin iu kin phng th nghim. Cc vt liu ny c
sy 60oC trong 5 gi, v hot ha 120oC trong 8 gi. Vt liu sau khi hot ha c ngm
ra bng 5 lt nc ct trong 4 gi, lp li qu trnh ny 3 ln nhm ra ht acid citric d. Sau
sy li 60oC trong 6 gi, bo qun trong cc bao plastic.
i vi nhm khng hot ha, 200 gam vt liu c ngm vi 5 lt nc ct trong 4 gi, lp
li qu trnh ny 3 ln tng t i vi nhm vt liu c hot ha loi cc tp cht c trong x
da v tru.
2.1.3. Thit b nghin cu
Phn ng c thc hin trong thit b Jatest gm 6 h thng khuy hot ng cng ch .
Nng cation c xc nh bng phng php so mu trn my Genesis 20 (Anh Quc).
dn in ring v pH cc dung dch c o bng my o dn WTW LF330 v my o pH
Cyberscan 510 (Anh Quc). i vi mu cha ng thi Ni2+ v Cd2+, nng ca chng c
xc nh bng phng php AAS trn my Perkin Elmer 3300.
2.2.M t th nghim

TAP CH PHAT TRIEN KH&CN, TAP 11, SO 08 - 2008

Cn chnh xc 2 g vt liu bng cn phn tch cho vo bercher 250ml. Thm 200ml dung dch
cha kim loi c nng xc nh, o nhanh dn in ring v pH ban u ca h. Thc hin
phn ng trong 60 pht, c nh ch khuy bng my Jatest cho tt c cc th nghim. Lc
nhanh, o dn v pH sau phn ng. Dung dch qua lc c pha long n nng thch hp
xc nh nng Ni2+ (o hp thu ca mu bc sng 375nm, ng chun C(ppm) =
1,7804A 0,01039; R2 = 0,9993) v xc nh nng Cd2+ (bc sng 520nm, ng chun
C(ppm) = 1,321A 0,0312; R2 = 0,9913). T tnh dung lng x l (lng cation x l trn 1
g vt liu, mg/g) v hiu sut tch loi cation (%) ca x da v tru. So snh vi cc vt liu
tng ng khng hot ha v cc loi trao i ion thng dng l nha cationit v zeolit A. Mi th
nghim c lp li 2 ln, kt qu c nh gi trn gi tr trung bnh.
3. KT QU V THO LUN
3.1.Kho st s thay i pH, dn ca dung dch Ni2+ v Cd2+
Nh nu trong phn gii thiu, kh nng tch loi ion kim loi ra khi dung dch nc l
do s hp ph hoc/v s trao i ion ca cc polymer c trong thnh phn ca ph phm nng
nghip. Nu s trao i ion c xy ra, hai ion H+ s thay th cho mt ion kim loi ha tr hai, kt
qu s lm gim pH ng thi tng dn in ring (S/cm) ca dung dch. Kho st s thay
i pH v dn in ca hai dung dch Ni2+ v Cd2+ khi ngm trong tru v x da c v khng
c hot ha bng acid citric (Bng 1, 2, 3, 4) u nhn thy pH dung dch gim ng thi dn
in ring tng. Mc thay i pH v trn cc dung dch ngm trong vt liu c hat ha bng
acid citric ln hn so vi dung dch ngm trong vt liu khng hot ha. Nh vy khi cha hot
ha c s trao i ion xy ra v qu trnh ny c tng cng i vi vt liu hot ha.
Bng 1. pH dung dch Nickel trc v sau x l
2+

[Ni ],
ppm
100
50
10
5
1

Nha
cationit
pH0
4,52
4,64
4,75
4,86
5,01

pH1
3,34
4,00
4,58
4,78
4,91

Zeolit A
pH0
6,55
6,75
6,93
7,17
7,15

pH1
5,41
5,85
6,08
6,36
6,55

X da
khng
hot ha
pH0
pH1
5,32
4,69
5,89
5,23
6,03
5,46
6,55
5,94
6,67
6,03

X da
hot ha
pH0
6,25
6,35
6,53
7,01
7,05

pH1
5,25
5,21
5,66
6,42
6,82

Tru
hot ha
pH0
5,20
5,41
5,53
5,65
5,70

pH1
4,40
4,75
4,90
5,41
5,48

Bng 2. dn dung dch Nickel trc v sau x l

[Ni2+] ppm

Nha
cationit
0,
1,
S/cm

100
50
10
5
1
[Ni2+] ppm
100
50
10

S/cm

92,30
149,82
50,65
79,72
19,54
29,83
18,01
27,02
16,32
24,14
X da khng
hot ha
0,
1,

Zeolit A
0,

1,

S/cm

S/cm

102,51
168,30
60,12
95,34
34,56
51,43
15,21
22,48
10,12
12,93
Tru
hot ha
0,
1,

X da
hot ha
0,
1,
S/cm

S/cm

107,10 175,78
50,45
76,81
21,90
32,58
17,65
25,44
12,17
17,50
Tru Khng
hot ha
0,
1,

S/cm

S/cm

S/cm

S/cm

S/cm

S/cm

85,55
38,14
25,55

133,86
57,10
35,51

82,51
40,12
14,56

131,25
61,32
21,64

78,14
36,55
12,11

114,73
51,83
16,13

Tru
Khng
hot ha
pH0
pH1
5,69
5,00
5,88
5,25
5,97
5,52
6,35
6,01
6,37
6,01

Science & Technology Development, Vol 11, No.08 - 2008

5
1

20,14
19,52

27,11
25,22

10,21
10,12

14,32
12,95

8,96
7,56

11,52
9,34

Bng 3. pH dung dch Cadmium trc v sau x l

Nha
cationit

2+

[Cd ]
ppm
100
50
10
5
1

pH0
5,54
5,61
5,71
5,75
6,85

pH1
3,94
4,66
5,29
5,47
6,66

pH0
5,87
6,25
6,75
6,89
7,33

pH1
4,31
5,23
5,76
6,40
7,10

X da
khng
hot ha
pH0
pH1
5,02
3,70
5,33
4,54
5,67
4,84
6,11
5,29
6,25
6,11

X da
hot ha

Zeolit A

pH0
4,26
4,52
4,70
4,86
5,01

pH1
3,12
3,78
3,96
4,21
4,82

Tru
hot ha
pH0
4,40
4,99
5,15
5,32
5,96

pH1
3,28
4,30
4,96
5,16
5,79

Tru
Khng
hot ha
pH0
pH1
5,40
4,14
5,49
4,22
5,64
5,48
5,82
5,69
5,96
5,79

Bng 4. dn dung dch Cadmium trc v sau x l

[Cd2+] ppm
100
50
10
5
1
2+

[Cd ] ppm
100
50
10
5
1

Nha
cationit

Zeolit A

0, S/cm
1, S/cm
50,6
72,57
30,5
39,67
13,5
16,79
12,95
15,61
10,87
12,92
X da khng
hot ha
0, S/cm
1, S/cm
52,17
65,29
35,36
42,54
18,97
22,39
11,32
12,68
9,12
10,07

0, S/cm
46,5
30,25
10,01
9,87
8,96

1, S/cm
62,11
40,32
13,22
12,50
11,28

Tru
hot ha
0, S/cm
1, S/cm
59,35
80,87
45,35
61,46
24,83
32,56
20,55
26,16
18,21
22,60

X da
hot ha
0, S/cm
1, S/cm
75,91
114,05
50,29
72,72
22,4
31,28
18,52
24,77
14,68
19,05
Tru Khng
hot ha
0, S/cm 1, S/cm
49,39
63,59
31,35
40,30
14,83
18,95
10,55
13,36
9,21
10,44

Nng dung dch ban u cng nh hng rt nhiu n s thay i trn. Nng dung
dch cng cao th tng dn in ring v gim pH cng ln.
3.2.Kho st kh nng hp ph hoc/v trao i ion Ni2+, Cd2+
Kh nng x l ion kim loi ca x da v tru c kho st trn hai dung dch m phng l
dung dch Ni2+ v Cd2+ cc nng khc nhau. Kt qu c so snh vi cc loi nha trao i
ion thng dng v zeolite A.
Bng 5. Hiu sut (%) x l Ni2+

Bng 6. Dung lng (mg/g) x l Ni2+

C, ppm

100

50

10

C, ppm

100

50

10

Cationit

89,21

79,84

65,62

Cationit

49,60

22,46

3,78

Zeolit A

91,23

86,23

71,51

Zeolit A

55,65

25,55

3,93

X da

63,51

58,42

45,96

X da

31,75

14,60

2,29

X da*

90,22

83,24

49,73

X da*

54,11

25,81

2,48

Tru

45,21

39,40

32,17

Tru

22,60

9,86

1,60

TAP CH PHAT TRIEN KH&CN, TAP 11, SO 08 - 2008

Tru*
Hiu sut
(%)
100
90
80
70
60
50
40
30
0
20

78,41

59,63

32,59

39,21

14,90

1,63

Cationit

mg/g
50

Zeolit A

40

X da

30

X da

X da*

20

X da*

Cationit

Tru

Zeolit A

Tru

10

Tru*

Tru*

40

60

100 [Ni2+], ppm

80

20

40

60

100 [Ni 2+], ppm

80

Hnh 2. Hiu sut x l Nickel

Hnh 3. Dung lng x l Nickel

Bng 7. Hiu sut x l (%) Cd2+

Bng 8. Dung lng (mg/g) x l Cd2+

C, ppm

100

50

10

C, ppm

100

50

10

Cationit

82,46

69,37

59,11

Cationit

41,23

17,34

2,95

Zeolit A

77,56

68,52

58,93

Zeolit A

38,78

17,13

2,94

X da

50,23

40,98

32,15

X da

25,11

10,24

1,60

X da*

81,24

70,36

60,88

X da*

40,62

17,59

3,04

Tru

40,12

35,21

23,17

Tru

20,06

8,80

1,15

Tru*

68,41

61,35

51,55

Tru*

34,20

15,33

2,57

Hiu sut
%

mg/g
Cationit

80

Zeolit A
X da

60

X da*

40

Tru
Tru*

20
0

Tru*

20

40

60

80

2+

100 [Cd ], ppm

Hnh 4. Hiu sut x l Cadmium

90
80
70
60
50

Cationit
Zeolit A
X da
X da*

40
30
20
10
0

Tru
Tru*

20

40

60

80

2+

100 [Cd ], ppm

Hnh 5. Dung lng x l Cadmium

(* tng ng vi vt liu c hot ha)

T s liu thu c trong cc bng 5-8, mt s nhn xt c th c rt ra nh sau:
- X da sau khi hot ha c kh nng hp ph/trao i ion rt cao ngang bng vi nha trao
i ion hoc zeolite A. Hiu sut x l Ni2+ t 90,22% v 83,24% tng ng vi nng Ni2+ l
100 ppm v 50 ppm, ngang vi zeolite A. Hiu sut x l Cd2+ hai nng trn l 81,21% v
70,36%, ngang vi nha trao i ion. Dung lng x l mt ln cng tng ng nha trao i
ion v zeolite A.
- Kh nng hp ph/trao i ion Ni2+ v Cd2+ ca tru hot ha thp hn so vi x da hot
ha. Hiu sut x l Ni2+ v Cd2+ nng 100 ppm v 50 ppm tng ng l 78,41%; 59,63%
v 68,41%; 61,35%.

Science & Technology Development, Vol 11, No.08 - 2008

- X da v tru khng hot ha vn c kh nng hp ph/trao i ion Ni2+ v Cd2+. Tuy hiu
sut x l ca x da khng hot ha (63,51% i vi Ni2+ nng 100 ppm) thp hn so vi x
da c hot ha nhng nguyn liu ny rt phong ph v rt r nn 63,51% vn l mt s
liu rt c ngha.
- Qu trnh hot ha bng acid citric c hiu qu r rt lm tng hiu sut x l ln khong
30% (63,51% 90,22% i vi x da v 45,21% 78,41% i vi tru). Kh nng x l ca
tru km hn so vi x da c th do kh nng hp ph ban u kn hn, v hm lng thp cc
polymer c tc dng hp ph nh lignin, tannin. Tuy nhin kh nng trao i ion vn tng
ng x da v vy sau khi hot ha cc nhm OH, tng hiu sut l 30% ging nh x da.
- Cc s liu thu c nng cc ion l 10 ppm c s st gim r rt hiu sut x l ca
c x da v tru. Chng ti cho rng c l phng php so mu s dng vng nng thp
khng chnh xc v s dng phng php AAS kim tra li kt qu nng cc ion l 10
ppm. Kt qu cho thy hiu sut nng 10 ppm thc cht vn cao nh vng nng cao.
Bng 9. Kt qu x l dung dch Ni2+ v Cd2+ nng 10 ppm bng phng php AAS
X da hot ha
V tru hot ha
Ni2+ ,%

88,92

68,89

Cd2+ ,%

81,46

63,03

4. KT LUN
Kt qu kho st cho thy hai loi ph phm nng nghip l x da v tru c kh nng hp
ph/trao i ion Ni2+ v Cd2+ vi hiu sut kh cao (50 60% i vi x da v 40 45% i
vi tru).
Vic hot ha x da v tru bng acid citric c tc dng nng cao r rt hiu sut x l ion
Ni2+ v Cd2+, lm tng hiu sut c hai ln khong 30%. Hiu sut ny khng thay i nhiu khi
thay i nng ion kim loi trong dung dch.
Kh nng hp ph/trao i ion r rng ph thuc nhiu vo bn cht cu trc ca nguyn liu.
Cn c nhng nghin cu thm v cu trc (b mt ring) v thnh phn (thnh phn cc
polymer) nguyn liu hiu r nguyn nhn gip x da c kh nng hp ph/trao i ion tt
hn tru. Trn c s c th nh hng nhanh chng loa nguyn liu no c kh nng hp
ph/trao i ion tt nht.

TAP CH PHAT TRIEN KH&CN, TAP 11, SO 08 - 2008

TI LIU THAM KHO

[1]. N. A. Adesola Babarinde1, J. Oyebamiji.Babalola and R. Adebowale Sanni, Biosorption
of lead ions from aqueous solution by maize leaf, Ibadan, Nigeria (2006).
[2]. James S. Han, Stormwater filtration of toxic heavy metal ions using lignocellulosic
materials selection process, fiberization, chemical modification, and mat formation,
U.S. Department of Agriculture, Forest Service, USA, (1999).
[3]. J.C Igwe , E.C.Nwokennaya and A.A. Abia, The role of pH in heavy metal
detoxification by biosorption from aqueous solutions containing chelating agents,
P.M.B 2000 Uturu, Abia State Nigeria (2005).
[4]. Jame W.Patterson, Industrial Wastewater Treatment Technology, second edition,
Butterworth Heinemann, Boston London Singapore Sedney Toronto
Wellington (1985).
[5]. James D. Mc Sweeny, Roger M. Rowell, Soo-Hong Min, Effect of Citric Acid
Modification of Aspen Wood on Sorption of Copper Ion, Journal of Natural Fibers, Vol.
3(1) (2006).
[6]. Wayne E. Marshall, Dual-functional ion exchange resins from agricultural by-products,
US Patent Issued on August 29, 2006, United States Patent 7098327, (2006).
[7]. Wayne E. Marshall et al, Enhanced Metal Adsorption by Soybean Hulls Modified with
Citric Acid, Bioresource Technology, vol. 69, pp. 263-268 (1999).
[8]. Reddad, Z., C. Gerente, Y. Andres, M.C. Ralet, J. F. Thibault, and P. L. Cloirec, Ni(II)
and Cu(II) binding properties of native and modified sugar beet pulp. Carbohydrate
Polymers 49: 23-31. (2002).
[9]. Mykola, T. K., L. A. Kupchik, and B.K. Veisoc, Evaluation of pectin binding of heavy
metal ions in aqueous solutions. Chemosphere, 38(11): 2591-2596. (1999).