Professional Documents
Culture Documents
TRNG I HC S PHM
---------------------
LUN VN THC S HA HC
I HC THI NGUYN
TRNG I HC S PHM
---------------------
MC LC
Mc lc
Danh mc cc bng
Danh mc cc hnh v, th
M u .................................................................................... 1
Chng 1: TNG QUAN ...................................................................... 3
1.1 Gii thiu v phng php hp ph .................................. 3
1.1.1. Cc khi nim ............................................................. 3
1.1.2. Cc m hnh c bn ca qu trnh hp ph ................... 5
1.1.2.1. M hnh ng hc hp ph ................................ 5
1.1.2.2. Cc m hnh hp ph ng nhit ........................ 6
1.2. Gii thiu v VLHP v lc ................................................ 9
1.2.1. Nng sut v sn lng lc .......................................... 9
1.2.2. Thnh phn chnh ca v lc........................................ 10
1.2.3. Mt s hng nghin cu s dng ph phm nng nghip
lm VLHP ............................................................................................... 11
1.3. Phng php ph hp th nguyn t ............................... 12
1.3.1. S xut hin ph hp th nguyn t ............................. 12
1.3.2. Cng ca vch ph hp th nguyn t .................. 13
1.4. S lc v mt s kim loi nng........................................ 14
1.4.1. Tnh trng ngun nc b nhim kim loi nng .......... 14
1.4.2. Tc dng sinh ha ca kim loi nng i vi con ngi v
mi trng .............................................................................................. 15
1.4.3.
, crom,
http://www.lrc-tnu.edu.vn
http://www.lrc-tnu.edu.vn
DANH MC CC BNG
Bng 1.1: Din bin sn xut lc Vit Nam ........................................... ..10
Bng 1.2: Thnh phn v lc ................................................................... ..10
Bng 1.3: Gi tr gii hn nng cc cht nhim trong nc thi cng
nghip .................................................................................................... ..19
Bng 2.1: iu kin o ph hp th nguyn t c ngn la ca mt s kim
loi......................................................................................................... ..23
Bng 2.2: S ph thuc ca mt quang vo nng Cd(II) ................. ..24
Bng 2.3: S ph thuc ca mt quang vo nng Cr(VI) ................. ..24
Bng 2.4: S ph thuc ca mt quang vo nng Cu(II) .................. ..25
Bng 2.5: S ph thuc ca mt quang vo nng Mn(II) ................. ..25
Bng 2.6: S ph thuc ca mt quang vo nng Ni(II) .................. ..25
Bng 2.7: S ph thuc ca mt quang vo nng Pb(II) .................. ..26
Bng 2.8: nh hng ca pH n s hp ph Cd(II) ................................ ..27
Bng 2.9: nh hng ca pH n s hp ph Cr(VI) ............................... ..27
Bng 2.10: nh hng ca pH n s hp ph Cu(II) .............................. ..28
Bng 2.11: nh hng ca pH n s hp ph Mn(II).............................. ..29
Bng 2.12: nh hng ca pH n s hp ph Ni(II) ............................... ..29
Bng 2.13: nh hng ca pH n s hp ph Pb(II) ............................... ..30
Bng 2.14: nh hng ca thi gian n s hp ph Cd(II), Cr(VI), Cu(II),
Mn(II), Ni(II) v Pb(II) ca VLHP .......................................................... ..33
Bng 2.15: nh hng ca nng ion kim loi n s hp ph Cd(II) v
Cr(VI) ca VLHP ................................................................................... ..35
Bng 2.16: nh hng ca nng ion kim loi n s hp ph Cu(II) v
Mn(II) ca VLHP ................................................................................... ..36
Bng 2.17: nh hng ca nng ion kim loi n s hp ph Ni(II) v
Pb(II) ca VLHP .................................................................................... ..38
Bng 2.18: Kt qu tch loi Ni(II) khi nc thi ca nh my
quc phng............................................................................................. ..41
http://www.lrc-tnu.edu.vn
DANH MC CC HNH
Hnh 2.1: Ph IR ca nguyn liu ............................................................ ..22
Hnh 2.2: Ph IR ca VLHP .................................................................... ..22
Hnh 2.3: nh chp SEM ca nguyn liu ............................................... ..23
Hnh 2.4: nh chp SEM ca VLHP ....................................................... ..23
Hnh 2.5: ng chun xc nh nng Cd(II) ...................................... ..24
Hnh 2.6: ng chun xc nh nng Cr(VI) ..................................... ..24
Hnh 2.7: ng chun xc nh nng Cu(II) ...................................... ..25
Hnh 2.8: ng chun xc nh nng Mn(II) ..................................... ..25
Hnh 2.9: ng chun xc nh nng Ni(II) ...................................... ..25
Hnh 2.10: ng chun xc nh nng Pb(II) .................................... ..26
Hnh 2.11: nh hng ca pH n s hp ph Cd(II) ............................... ..27
Hnh 2.12: nh hng ca pH n s hp ph Cr(VI) .............................. ..27
Hnh 2.13: nh hng ca pH n s hp ph Cu(II) ............................... ..28
Hnh 2.14: nh hng ca pH n s hp ph Mn(II) .............................. ..29
Hnh 2.15: nh hng ca pH n s hp ph Ni(II) ............................... ..29
Hnh 2.16: nh hng ca pH n s hp ph Pb(II) ............................... ..30
Hnh 2.17: nh hng ca thi gian n s hp ph Cd(II), Cr(VI), Cu(II),
Mn(II), Ni(II) v Pb(II) ca VLHP .......................................................... ..32
Hnh 2.18: ng ng nhit hp ph Langmuir ca VLHP i
vi Cd(II)... ............................................................................................ ..35
Hnh 2.19: ng ng nhit hp ph Langmuir dng tuyn tnh ca VLHP
i vi Cd(II) ......................................................................................... ..35
Hnh 2.20: ng ng nhit hp ph Langmuir ca VLHP i
vi Cr(VI) .............................................................................................. ..36
http://www.lrc-tnu.edu.vn
http://www.lrc-tnu.edu.vn
M u
Hin nay, th gii ang rung hi chung bo ng v thc trng nhim
mi trng ton cu.
Nm trong bi cnh chung ca th gii, mi trng Vit Nam cng ang
xung cp cc b. Nguyn nhn chnh dn n nhim mi trng l do
ngun nc thi, kh thi,.. ca cc khu cng nghip, khu ch xut,Cc
ngun nc thi ny u cha nhiu ion kim loi nng nh: Cu(II), Mn(II),
Pb(II), nhng trc khi a ra ngoi mi trng hu ht cha c x l
hoc x l s b, do vy gy nhim mi trng, c bit l mi trng
nc.
c nhiu phng php c p dng nhm tch loi cc ion kim loi
nng khi mi trng nc, nh: phng php ha l (phng php hp ph,
phng php trao i ion,), phng php sinh hc, phng php ha
hc,Trong , phng php hp ph c p dng rng ri v cho kt qu
rt kh thi [12]. Mt trong nhng vt liu s dng hp ph kim loi ang
c nhiu ngi quan tm l cc ph phm nng nghip, nh: v tru, b
ma, li ng,.[15] [17] [19]. Hng nghin cu ny c nhiu u im l s
dng nguyn liu r tin, d kim, khng lm ngun nc b nhim thm.
Mt khc
vic ch to vt liu hp ph (VLHP) nhm
n
.
Do , chng ti chn ti: Nghin cu kh nng hp ph mt s ion
http://www.lrc-tnu.edu.vn
2
Mc tiu
- Nghin cu cc yu t nh hng n s hp ph (pH, thi gian,
nng ion kim loi).
- Th nghim kh nng hp ph ca v lc vi mt kim loi.
Nhim v nghin cu
- Ch to vt liu hp ph t v lc.
- Kho st mt s c im b mt ca v lc (bng ph IR v nh chp
SEM).
- Kho st nh hng ca cc yu t: pH, thi gian, nng ca ion kim
loi n s hp ph trn.
- X l ngun nc thi ca khu cng nghip, khu ch xut.
Phng php nghin cu
- Kt hp k thut phng th nghim v cc phng php ho l ch
to v kho st c im b mt v lc trc v sau khi hot ho.
- nh lng cc ion kim loi bng phng php hp th nguyn t.
http://www.lrc-tnu.edu.vn
.
-
).
.
.
,l
,l
n [6] [11].
http://www.lrc-tnu.edu.vn
4
.
G
vi
.
.
:
.
-
:c
.
-P
:l
[2].
.
pha mang (
[6][11].
http://www.lrc-tnu.edu.vn
5
.
[11].
Dung lng hp ph c tnh theo cng thc:
q
(1.1)
:
q: d
(mg/g).
V: t
(l).
(g).
Co: n
(mg/l).
Ccb: n
(mg/l)
Hiu sut hp ph
Hiu sut hp ph l t s gia nng dung dch b hp ph v nng
dung dch ban u.
H
(Co Ccb )
.100
Co
1.1.2.
(1.2)
.
1.1.2.1.
:
-
.
.
http://www.lrc-tnu.edu.vn
6
-
th
.
[1].
:
v
dx
dt
(1.3)
gian:
V
dx
dt
(C0
Ccb )
k (qmax
(1.4)
q)
:
x: nng cht b hp ph (mg/l)
t: thi gian (giy)
:h
Co: n
(mg/l).
Ccb
k: h
q: dun
qmax: d
(mg/l)
.
(mg/g).
(mg/g).
1.1.2.2 .
C
http://www.lrc-tnu.edu.vn
.
V
th
: p
Langmuir,[6] [11].
M hnh
Henry
Phng trnh
y: l
:
a = K. P
(1.5)
:
K: h
a: l
P
(mol/g)
(mmHg)
[11].
M hnh
Freundlich
[10].
s
q
k . C cbn
:
(1.6)
http://www.lrc-tnu.edu.vn
8
Hoc dng phng trnh ng thng:
lg q
1
lg Ccb
n
lg k
(1.7)
:
k: h
n: h
[11].
M hnh
:
Langmuir c dng:
q
q max
b.Ccb
1 b.Ccb
(1.8)
:
q: d
(mg/g)
qmax: dung l
(mg/g)
b:
uir
.Ccb <<
= qmax.b.Ccb
.Ccb >>
= qmax
.
.
1
qmax
Ccb
1
qmax .b
(1.9)
http://www.lrc-tnu.edu.vn
9
1.2. Gii thiu v VLHP v lc
1.2.1. Nng sut v sn lng lc
Lc l cy cng nghip ngn ngy, c pht hin v gieo trng t
khong 500 nm nay, gi tr kinh t ca lc c ch khong 250 nm tr
li y.
Cy lc c gi tr kinh t cao v c nhiu cng dng, c bit c
dng lm thc phm, trong cng nghip thc phm, trong k ngh, trong
trng trt,
Ph phm ca cy lc gm: kh du, v ht v thn l.
Thn v l cy lc c th dng lm thc n cho gia sc v cc loi phn
bn c gi tr tng ng phn chung
Cho n th k XIX u th k XX, trn th gii, lc l cy h u c
din tch ln nht, hin nay ng hng th hai trong s cc cy ly du thc
vt (v din tch v sn lng) vi din tch gieo trng vo khong 20
triu ha/nm, sn lng vo khong 25.5
21
26 triu tn.
http://www.lrc-tnu.edu.vn
10
Bng 1.1: Din bin sn sut lc Vit Nam
Nm
Sn lng (tn)
2001
244 600
14.84
363 100
2002
246 700
16.23
400 400
2003
246 800
16.46
406 200
2004
258 700
17.44
451 100
2005
260 000
17.42
453 000
2006
246 700
18.70
462 500
2007
254 600
19.80
505 000
1.2.2.
V ht chim khong 25
4.2
2.6
18.5
1.8
0.2
0.5
http://www.lrc-tnu.edu.vn
11
: xenluloz, hemixenlu
l gluxit,
.
.
Xenluloz: l
-glucoz [C6H7O2(OH)3]n
0,7 g/l
(II)
31
[17].
http://www.lrc-tnu.edu.vn
12
my thi ra, c bit l cc vng t, ngun nc b nhim ion kim loi v
v ca c lc c th loi b 95% ion ng khi nc thi cng nghip trong
khi mn ca ca cy thng ch loi b c 44%. C th t c hiu qu
cao nht nu nc c tnh axit yu trong khi nhit li t c tc ng n
hiu sut tch loi ion kim loi [26].
:c
ion
3PO4
0.39 mmol/g
[15].
http://www.lrc-tnu.edu.vn
13
trng thi hi t do, nu ta chiu mt chm sng c bc sng xc nh vo
m hi nguyn t th cc nguyn t t do s hp th cc bc x c bc
sng nht nh ng ng vi nhng tia bc x m n pht ra trong qu trnh
pht x ca n. Lc ny nguyn t nhn nng lng ca cc tia bc x
chiu vo v chuyn ln trng thi kch thch c nng lng cao hn trng
thi c bn.
Qu trnh c gi l qu trnh hp th nng lng ca nguyn t t
do trng thi hi v to ra ph hp th nguyn t ca nguyn t [8][14].
1.3.2. Cng ca vch ph hp th nguyn t [8]
Trong vng nng C nh ca cht phn tch, mi quan h gia cng
vch ph hp th v nng N ca nguyn t trong m hi cng tun
theo nh lut Lambe Bear:
I I o .e
( K . N .L)
(1.10)
Trong :
Io: cng chm sng chiu vo m hi nguyn t
I: cng chm sng ra khi m hi nguyn t
K : h s hp th nguyn t ca vch ph tn s
L: b dy lp hp ph
Gi A l mt quang hay tt nguyn t ca chm tia sng cng
Io sau khi qua mi trng hp th. A c tnh bi cng thc:
A
lg
Io
2.303 K .N . L
I
(1.11)
http://www.lrc-tnu.edu.vn
14
Trong mt php o ph hp th nguyn t, gi tr L khng i nn A
ph thuc vo nng C
A = a . Cb
(1.12)
Trong :
a: hng s thc nghim, ph thuc vo tt c cc iu kin ha
hi v nguyn t ha mu
b: hng s bn cht, ph thuc vo tng vch ph ca tng
nguyn t (0 < b 1)
- vng nng C nh lun tm c gi tr Co b bt u bng 1, khi
mi quan h gia A v C l s ph thuc tuyn tnh.
- vng nng Cx > Co, 0 < b < 1, mi quan h gia A v C l khng
tuyn tnh.
1.4. S lc v mt s kim loi nng
1.4.1.
.
c
,
3
http://www.lrc-tnu.edu.vn
15
[1] [4].
1.4.2.
loi
-SH. -SCH3
[5].
1.4.3.
cc
mangan, niken v ch
1.4.3.1.
Trong thin nhin, cadimi l nguyn t t ph bin v thng tn ti
trong cc khong vt. Gn mt na lng cadimi hng nm trn th gii dng
m thp, phn cn li dng ch to hp kim, lm pin kh v acquy.
Cadi
i
i
,
cadi
[4] [10].
http://www.lrc-tnu.edu.vn
16
1.4.3.2.
rom
[10].
.
(VI). Cr(III) t c hn nhiu so vi Cr(VI). Vi hm lng
nh Cr(III) rt cn cho c th, trong khi Cr(VI) li rt c v nguy him.
c th
.
,
i,...[4].
1.4.3.3.
ng l kim loi mu , dn in v dn nhit tt, kh nng chy, c
phn b rng ri trong t nhin v l nguyn t quan trng.
Hp kim ca ng d ch ho c hc v bn vi ho cht. Trong cng
nghip, ng l kim loi mu quan trng nht, c dng ch yu trong cng
nghip in, ngnh thuc da, cng nghip nhum, y hc,
ng c mt lng b trong thc vt v ng vt. Trong c th ngi,
ng c trong thnh phn ca mt s protein, enzym v tp trung ch yu
http://www.lrc-tnu.edu.vn
17
gan. S thiu ng gy ra thiu mu. Khi c th b nhim c ng c th gy
mt s bnh v thn kinh, gan, thn, lng ln hp th qua ng tiu ho c
th gy t vong [10].
1.4.3.4.
Mangan l kim loi mu trng bc, cng, kh nng chy.
Trong t nhin mangan l nguyn t tng i ph bin, ng hng th
ba trong cc kim loi chuyn tip. Gn 95% mangan c dng ch to
thp trong ngnh luyn kim.
Mangan l nguyn t vi lng trong c th sng. Ion mangan l cht hot
ho mt s enzim xc tin mt s qu trnh to cht dip lc, to mu v sn
xut khng th nng cao sc khng ca c th. S tip xc nhiu vi bi
mangan lm suy nhc h thn kinh v tuyn gip trng [10].
1.4.3.5.
ken
c mu trng bc, d rn, d dt mng, c ng dng
rng ri trong cng nghip luyn kim, m in, sn xut thu tinh, gm, s.
Niken c trong huyt tng ngi,
, trong thu
.
a
.
Niken c th gy cc bnh v da, tng kh nng mc bnh ng th ng
h hp,
http://www.lrc-tnu.edu.vn
18
protein c
.C
b nhim n
[4].
1.4.3.6
,...
v cc hp cht ca ch u rt c. Ch
, h
,t
th,...
.
can
[4] [10].
1.4.4.
[1] [27]
TCVN 5945:2005
cng nghip nh sau:
http://www.lrc-tnu.edu.vn
19
Bng 1.3: Gi tr gii hn nng cc cht nhim trong nc thi
cng nghip
Gi tr gii hn
STT Nguyn t
n v
A
Ch
mg/l
0.1
0.5
1.0
Cadimi
mg/l
0.005
0.010
0.500
Crom (VI)
mg/l
0.05
0.10
0.50
ng
mg/l
2.0
2.0
5.0
Niken
mg/l
0.2
0.5
2.0
Mangan
mg/l
0.5
1.0
5.0
:
Nc thi cng nghip c gi tr cc thng s v nng cc
cht nhim bng hoc nh hn gi tr qui nh trong ct A c th vo cc
vc nc thng c dng lm ngun nc cho mc ch sinh hot.
Nc thi cng nghip c gi tr cc thng s v nng cc
cht nhim ln hn gi tr qui nh trong ct A nhng nh hn hoc bng
gi tr qui nh trong ct B th c vo cc vc nc nhn thi khc, nh:
cc vc nc dng giao thng, thy li ti tiu cho trng trt, nui trng
thy hi sn,tr cc thy vc qui nh ct A.
Nc thi cng nghip c gi tr cc thng s v nng cc
cht nhim ln hn gi tr quy nh trong ct B nhng khng vt qu
gi tr qui nh trong ct C ch c php thi vo cc ni c qui nh
(nh h cha nc thi c xy ring, cng dn n nh my x l nc
thi tp trung,)
http://www.lrc-tnu.edu.vn
20
2.1.1. Thit b
- My nghin bi (Nga)
- My quang ph hng ngoi IR Prestige-21 Shimadzu (Nht)
- My khuy IKA Labortechnik (c)
- My o pH Precisa 900 (Thy S)
- T sy Jeio tech (Hn Quc)
- My hp th nguyn t Thermo (Anh)
-
,c
.
Nc ct hai ln
Natri hiroxit
NaOH
Axit xitric
C6H8O7.H2O
Axit nitric
HNO3
Cadimi nitrat
Cd(NO3)2.4H2O
Kali icromat
K2Cr2O7
ng nitrat
Cu(NO3)2.3H2O
Mangan(II) nitrat
Mn(NO3)2.6H2O
Niken nitrat
Ni(NO3)2.6H2O
Ch(II) nitrat
Pb(NO3)2
http://www.lrc-tnu.edu.vn
21
2.2. Ch to VLHP t nguyn liu v lc
2.2.1. Quy trnh ch to VLHP t nguyn liu v lc
V lc nguyn liu c nghin nh bng my nghin bi. Ly 25g
nguyn liu cho vo cc cha 500ml dung dch NaOH 0.1M, khuy u
trong 120 pht, lc ly phn b rn, ra sch bng nc ct n mi trng
trung tnh, sy kh 85-90oC. Sau , phn b rn tip tc c cho vo cc
cha 150ml dung dch axit xitric 0.6M khuy trong 30 pht, lc ly b rn,
sy 50oC trong 24 gi, nng nhit ln 120oC trong 90 pht. Cui cng,
ra bng nc ct nng ti mi trng trung tnh v sy kh 85-90oC, thu
c VLHP [23].
2.2.2. Kt qu kho st mt s c im b mt ca VLHP
Nguyn liu v lc ban u c x l bng NaOH loi b cc
pigmen mu v cc hp cht hu c d ha tan, tip tc c este ha bng
axit xitric. Kt qu ca qu trnh x l c th hin trn ph hng ngoi
(IR) thng s dch chuyn ca nhm cacbonyl t vng s sng 1737.86 cm -1
n vng s sng 1728.22 cm-1, rng v c cng mnh hn (hnh 2.1 v
hnh 2.2).
Tin hnh chp nh knh hin vi in t qut (SEM) ca nguyn liu ban
u v VLHP, quan st thy VLHP c xp cao hn v din tch b mt ln
hn r rt (hnh 2.3 v hnh 2.4).
http://www.lrc-tnu.edu.vn
22
http://www.lrc-tnu.edu.vn
23
Cng
n
HCL
Chiu
cao
n
(mm)
Tc
dng kh
(ml/pht)
Khong
tuyn
tnh
(mg/l)
STT
Nguyn
t
Bc
sng
(nm)
Cd
228.8
0.5
50%Imax
7.0
1.2
0.05
2.5
Cr
357.9
0.5
100%Imax
8.0
1.4
0.2
10.0
Cu
324.8
0.5
75%Imax
7.0
1.1
0.05
2.5
Mn
279.5
0.2
75%Imax
7.0
1.0
0.05
4.0
Ni
232.0
0.1
75%Imax
7.0
0.9
0.1
8.0
Pb
217.0
0.5
75%Imax
7.0
1.1
0.1
10.0
http://www.lrc-tnu.edu.vn
24
Pha cc dung dch cc ion kim loi nng Cd(II), Cr(VI), Cu(II), Mn(II),
Ni(II) v Pb(II) vi nng khc nhau t dung dch chun nng 1000
mg/l, thm vo mt th tch xc nh dung dch HNO3 10% nng
HNO3 l 1%. Pha dung dch HNO3 1% lm mu trng. Tin hnh o mt
quang (A) ca tng dung dch. Dng th biu din s ph thuc ca mt
quang vo nng ion kim loi. Kt qu thu c th hin cc bng 2.2,
2.3, 2.4, 2.5, 2.6, 2.7 v cc hnh 2.5, 2.6, 2.7, 2.8, 2.9, 2.10.
Bng 2.2: S ph thuc ca
y = 0.0921x + 0.0024
R2 = 0.9996
0.25
0.20
Tn mu
C (mg/l)
Mu trng
0.00
0.0030
STD 1
0.05
0.0080
0.05
STD 2
0.10
0.0120
0.00
0.00
0.15
0.10
0.50
1.00
1.50
2.00
2.50
3.00
Nng (mg/l)
STD 3
1.00
0.0910
STD 4
2.50
0.2340
y = 0.0165x + 0.003
R2 = 0.9995
Mu trng
C (mg/l)
0.00
A
0.0010
STD 1
0.50
0.0120
STD 2
1.00
0.0210
0.14
Mt quang
Tn mu
0.16
0.12
0.10
0.08
0.06
0.04
0.02
STD 3
5.00
0.0860
STD 4
8.00
0.1350
0.00
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
Nng (mg/l)
http://www.lrc-tnu.edu.vn
25
Phng trnh tuyn tnh s ph thuc ca mt quang vo nng
Cr(VI) l y = 0.0165x + 0.003
Bng 2.4: S ph thuc ca
y = 0.0209x + 0.0018
R2 = 0.9997
0.06
C (mg/l)
Mu trng
0.00
0.0020
STD 1
0.10
0.0040
STD 2
1.00
0.0220
STD 3
2.00
0.0440
STD 4
2.50
0.0540
Mt quang
0.05
Tn mu
0.04
0.03
0.02
0.01
0
0.00
0.50
1.00
1.50
2.00
2.50
3.00
Nng (mg/l)
y = 0.0825x - 0.0025
R2 = 0.9998
0.35
Tn mu
C (mg/l)
Mu trng
0.00
-0.0020
STD 1
0.05
0.0020
STD 2
1.00
0.0770
STD 3
2.00
0.1650
STD 4
4.00
0.3270
Mt quang
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
Nng (mg/l)
http://www.lrc-tnu.edu.vn
26
Bng 2.6: S ph thuc ca
y = 0.0288x - 0.0025
R2 = 0.9997
0.25
0.20
C (mg/l)
Mu trng
0.00
-0.002
STD 1
0.50
0.012
0.05
STD 2
1.00
0.025
0.00
0.00
Mt quang
Tn mu
0.15
0.10
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
Nng (mg/l)
STD 3
5.00
0.144
STD 4
7.00
0.198
Mu trng
0.00
-0.0020
STD 1
0.50
0.0060
STD 2
1.00
0.0130
STD 3
5.00
0.0720
STD 4
10.00
0.1450
0.14
Mt quang
Tn mu
y = 0.0147x - 0.0016
R2 = 1
0.16
0.12
0.10
0.08
0.06
0.04
0.02
0.00
0.00
Nng (mg/l)
http://www.lrc-tnu.edu.vn
27
trong khong 1.00 n 6.00 bng dung dch NaOH long v dung dch HNO3
long (cc ha cht ny c s dng iu chnh pH ca dung dch trong
cc th nghim tip theo). Xc nh nng ion kim loi Co ca cc dung dch
bng phng php hp th nguyn t. Cho vo mi bnh 1g VLHP. Khuy
dung dch bng my khuy vi tc khuy 250 vng/pht (tc khuy ny
c duy tr tin hnh cc th nghim tip theo), nhit phng . Thi
gian khuy i vi cc dung dch Cd(II) l 30 pht, cc dung dch Cr(VI) l
50 pht, cc dung dch Cu(II) l 30 pht, cc dung dch Mn(II) l 80 pht, cc
dung dch Ni(II) l 70 pht v cc dung dch Pb(II) l 50 pht. Lc b b rn,
xc nh nng cn li ca ion kim loi trong cc dung dch sau hp ph
bng phng php hp th nguyn t. Kt qu th hin qua cc bng 2.8, 2.9,
2.10, 2.11, 2.12, 2.13 v cc hnh 2.11, 2.12, 2.13, 2.14, 2.15, 2.16.
Bng 2.8: nh hng ca pH
n s hp ph Cd(II)
4.00
Cc thng s hp ph
Co
Ccb
3.00
q (mg/g)
pH
3.50
2.50
2.00
1.50
1.00
99.84
95.85
0.20
2.00
103.82 47.82
2.80
3.00
98.13
32.68
3.27
4.00
100.00 29.70
3.52
5.00
99.30
27.21
3.60
6.00
99.22
29.49
3.49
hp ph Cd(II)
1.00
0.50
0.00
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
pH
Nhn xt:
Trong khong pH kho st (1.00 6.00), khong pH s hp ph ca
VLHP i vi Cd(II) tt nht l 4.00 6.00.
http://www.lrc-tnu.edu.vn
28
4.50
4.00
3.50
q (mg/g)
2.50
2.00
1.50
1.00
0.50
0.00
0.00
2.00
4.00
6.00
8.00
10.00
12.00
pH
4.50
n s hp ph Cu(II)
4.00
Co
Ccb
(mg/l)
(mg/l)
(mg/g)
1.00
102.63
100.09
0.13
2.00
105.81
74.88
1.55
3.00
101.01
34.61
3.32
4.00
100.98
17.76
4.16
5.00
101.00
17.80
4.16
3.50
q (mg/g)
Cc thng s hp ph
pH
3.00
3.00
2.50
2.00
1.50
1.00
0.50
0.00
0.00
1.00
2.00
3.00
4.00
5.00
6.00
pH
Nhn xt:
Trong khong pH kho st (1.00 6.00), khong pH s hp ph ca
VLHP i vi Cr(VI) tt nht l 1.00 2.00.
http://www.lrc-tnu.edu.vn
29
Trong khong pH kho st (1.00 5.00), khong pH s hp ph ca
VLHP i vi Cu(II) tt nht l 4.00 5.00.
Bng 2.11: nh hng ca pH n
2.50
s hp ph Mn(II)
pH
Co
Ccb
(mg/l)
(mg/l)
(mg/g)
1.00
98.32
98.15
0.01
2.00
98.54
92.27
0.31
3.00
98.98
70.63
1.42
4.00
99.01
64.31
1.74
5.00
99.41
58.44
2.05
6.00
98.67
56.45
2.11
2.00
q (mg/g)
Cc thng s hp ph
1.50
1.00
0.50
0.00
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
pH
Nhn xt:
Trong khong pH kho st (1.00 6.00), khong pH s hp ph ca
VLHP i vi Mn(II) tt nht l 5.00 6.00.
Bng 2.12: nh hng ca pH n
2.50
s hp ph Ni(II)
2.00
pH
Co
Ccb
(mg/l)
(mg/l)
(mg/g)
1.00
102.89
101.20
0.08
2.00
102.89
74.53
1.42
3.00
102.89
62.34
2.03
4.00
102.89
60.10
2.14
5.00
102.89
60.00
2.14
6.00
102.89
59.89
2.15
q (mg/g)
Cc thng s hp ph
1.50
1.00
0.50
0.00
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
pH
http://www.lrc-tnu.edu.vn
30
s hp ph Ni(II)
Nhn xt:
Trong khong pH kho st (1.00 6.00), khong pH s hp ph ca
VLHP i vi Ni(II) tt nht l 4.00 6.00.
Bng 2.13: nh hng ca pH
6.00
n s hp ph Pb(II)
Cc thng s hp ph
pH
Co
Ccb
q (mg/g)
5.00
4.00
3.00
(mg/l)
(mg/l) (mg/g)
1.00
98.23
18.23
4.00
1.00
2.00
98.78
1.83
4.85
0.00
0.00
3.00
99.40
1.43
4.90
4.00
100.00
1.32
4.89
5.00
99.03
1.36
4.88
6.00
98.75
1.32
4.87
2.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
pH
Nhn xt:
Trong khong pH kho st (1.00 6.00), khong pH s hp ph ca
VLHP i vi Pb(II) tt nht l 2.00 6.00.
Nhn xt chung:
- Mi trng pH cng cao dung lng hp ph ca VLHP i vi cc
cation kim loi cng tng, v dung lng hp ph gim khi pH gim. iu
c gii thch: trong mi trng axit mnh, cc phn t ca c cht hp ph
v cht b hp ph c tch in dng v bi vy lc tng tc l lc y
tnh in. Hn na, nng ion H+ hin ti cao nn trong hn hp phn ng
cnh tranh vi cation kim loi trong s hp ph, kt qu l lm gim s hp
http://www.lrc-tnu.edu.vn
31
ph cation kim loi. Tng t, pH tng, nng ion H+ gim, trong khi nng
cation kim loi gn nh khng i v bi vy s hp ph cation kim loi
c th gii thch ging s trao i phn ng H+ - M2+ (M: kim loi) [21].
- i vi s hp ph anion kim loi Cr2O72-, hiu sut hp ph tng khi
gim pH ca dung dch. Theo chng ti iu c th c gii thch:
Trong dung dch icromat lun tn ti cn bng:
2CrO42- + 2H+ Cr2O72- + H2O
Trong mi trng axit, cn bng trn chuyn dch sang phi, lm tng
nng Cr2O72-, khi s hp ph Cr(VI) ch yu l s hp ph Cr2O72-. Xt
v khi lng Cr(VI) b hp ph th mt anion Cr2O72- tng ng vi hai
anion CrO42-. Mt khc, xt v nh hng ca hiu ng khng gian th s hp
ph mt anion Cr2O72- thun li hn so vi s hp ph hai anion CrO42-. Nh
vy, khi nng Cr2O72- trong dung dch ln hn nng CrO42- th lng
Cr(VI) b hp ph cng cao.
2.3.3. Kho st thi gian t cn bng hp ph ca VLHP i vi Cd(II),
Cr(VI), Cu(II), Mn(II), Ni(II) v Pb(II)
Ly cc bnh nn dung tch 100ml cha 50ml dung dch cc ion kim loi
Cd(II), Cr(VI), Cu(II), Mn(II), Ni(II) v Pb(II) ring bit, vi nng ban u
ca cc ion Cd(II), Cr(VI), Cu(II), Mn(II), Ni(II) v Pb(II) tng ng bng
103.60 mg/l, 107.47 mg/l, 103.52 mg/l, 183.71 mg/l, 343.86 mg/l v 98.75
mg/l. iu chnh pH ca cc dung dch cha mi ion kim loi n gi tr nm
trong khong pH tt nht cho s hp ph kho st (2.3.2). C th: cc
dung dch Cd(II) c pH bng 5.00, cc dung dch Cr(VI) c pH bng 1.00, cc
dung dch Cu(II) c pH bng 4.50, cc dung dch Mn(II) c pH bng 5.00, cc
dung dch Ni(II) c pH bng 5.00, cc dung dch Pb(II) c pH bng 4.50. Cho
1g VLHP vo mi dung dch trn. Khuy mi dung dch bng my khuy
http://www.lrc-tnu.edu.vn
32
trong cc khong thi gian 5, 10, 20, 40, 60, 70, 80, 120 (pht), nhit
phng. Lc b b rn, xc nh nng ca ion kim loi trong cc dung dch
sau hp ph bng phng php hp th nguyn t. Kt qu c th hin
bng 2.14 v hnh 2.17.
400.00
Nng (mg/l)
350.00
300.00
Cd(II)
250.00
Cr(VI)
200.00
Cu(II)
Mn(II)
150.00
Ni(II)
100.00
Pb(II)
50.00
0.00
0.00
20.00
40.00
60.00
80.00
http://www.lrc-tnu.edu.vn
32
Thi gian
khuy
(pht)
Cd(II)
Cr(VI)
Cu(II)
Co
Ccb
Co
Ccb
103.6
80.20
107.47
70.53
103.52 21.08
10
103.6
36.98
107.47
48.23
103.52 19.93
20
103.6
34.03
107.47
29.30
103.52 18.02
40
103.6
34.19
107.47
24.50
103.52 17.81
60
103.6
34.08
107.47
24.49
103.52 17.76
70
107.47
24.52
103.52 17.79
80
107.47
24.48
120
Thi gian
khuy
(pht)
Mn(II)
Co
Ccb
Co
Ni(II)
Co
Ccb
Pb(II)
Ccb
Co
Ccb
250.32
95.75
2.32
10
229.70
95.75
1.90
20
230.16
95.75
1.72
40
220.02
95.75
1.54
60
207.76
95.75
1.48
70
207.89
95.75
1.54
80
208.01
95.75
1.54
120
183.71 133.78
http://www.lrc-tnu.edu.vn
33
Bng 2.14: nh hng ca thi gian n s hp ph Cd(II), Cr(VI), Cu(II), Mn(II), Ni(II) v Pb(II)
ca VLHP
Nng (mg/l)
Thi gian
khuy
Cd(II)
Cr(VI)
Cu(II)
Mn(II)
Ni(II)
Pb(II)
(pht)
Co
Ccb
Co
Ccb
Co
Ccb
103.6
80.20
107.47
70.53
103.52
21.08
2.32
10
103.6
36.98
107.47
48.23
103.52
19.93
1.90
20
103.6
34.03
107.47
29.30
103.52
18.02
1.72
40
103.6
34.19
107.47
24.50
103.52
17.81
1.54
60
103.6
34.08
107.47
24.49
103.52
17.76
1.48
70
107.47
24.52
103.52
17.79
1.54
80
107.47
24.48
1.54
120
183.71 133.78
Co
http://www.lrc-tnu.edu.vn
Ccb
Co
Ccb
Co
Ccb
34
2.3.4. Kho st dung lng hp ph cc i ca VLHP i vi Cd(II),
Cr(VI), Cu(II), Mn(II), Ni(II) v Pb(II)
Ly cc bnh nn dung tch 100ml cha 50ml dung dch tng ion kim
loi vi cc nng ban u khc nhau v c iu chnh n mi trng
pH ti u cho tng ion kim loi kho st (2.3.2). C th: cc dung dch
Cd(II) c pH bng 5.00, cc dung dch Cr(VI) c pH bng 1.00, cc dung
dch Cu(II) c pH bng 4.50, cc dung dch Mn(II) c pH bng 5.00, cc
dung dch Ni(II) c pH bng 5.00, cc dung d ch Pb(II) c pH bng 4.50.
Cho vo mi bnh 1g VLHP. Kho st qu trnh hp ph trong khong thi
gian t cn bng hp ph i vi tng ion kim loi kho st (2.3.3). C
th: thi gian khuy i vi cc dung dch Cd(II) l 30 pht, cc dung dch
Cr(VI) l 50 pht, cc dung dch Cu(II) l 30 pht, cc dung dch Mn(II) l
80 pht, cc dung dch Ni(II) l 70 pht v cc dung dch Pb(II) l 50 pht.
Xc nh nng C o ca ion kim loi trong cc dung dch ban u v nng
Ccb ca ion kim loi trong dung dch sau hp ph theo phng php hp
th nguyn t. Tnh dung lng hp ph ca VLHP i vi tng ion kim
loi theo cng thc (1.1).
Kt qu th hin cc bng 2.15, 2.16, 2.17, v cc hnh 2.18, 2.19, 2.20,
2.21, 2.22, 2.23, 2.24, 2.25, 2.26, 2.27, 2.28, 2.29.
http://www.lrc-tnu.edu.vn
35
Bng 2.15: nh hng ca nng ion kim loi n s hp ph
Cd(II) v Cr(II) ca VLHP
Cd(II)
Co
Ccb
Cr(VI)
q
Ccb/q
Co
Ccb
Ccb/q
(g/l)
26.23
2.33
1.19
1.95
10.48
2.10
0.42
5.01
35.05
4.90
1.51
3.25
25.42
7.00
0.92
7.60
68.98
14.06
2.75
5.12
50.13
12.13
1.90
6.39
87.42
23.14
3.21
7.20
100.04
37.44
3.13
13.13
129.48
48.73
4.04
5.01
20.12
173.25
79.98
4.66
6.40
41.04
280.03 170.00
5.50
6.72
69.48
413.63 287.64
6.30
7.00
94.32
7.00
R2 = 0.9905
y = 0.1524x + 3.3996
R2 = 0.992
50.00
6.00
40.00
C cb/q (g/l)
q (mg/g)
5.00
4.00
3.00
2.00
30.00
20.00
10.00
1.00
0.00
0.00
Ccb (mg/l)
0.00
0.00
Ccb (mg/l)
hp ph Langmuir ca VLHP
hp ph Langmuir
i vi Cd(II)
http://www.lrc-tnu.edu.vn
36
R2 = 0.9814
8.00
7.00
C cb /q (g/l)
q (mg/g)
6.00
5.00
4.00
3.00
2.00
1.00
0.00
-1.000.00
y = 0.1342x + 6.0593
100.00
R2 = 0.9987
90.00
80.00
70.00
60.00
50.00
40.00
30.00
20.00
10.00
0.00
0.00 100.00 200.00 300.00 400.00 500.00 600.00 700.00
Ccb (mg/l)
Ccb (mg/l)
hp ph Langmuir ca VLHP
hp ph Langmuir
i vi Cr(VI)
Ccb
Mn(II)
q
Ccb/q
Co
Ccb
(g/l)
(mg/l) (mg/l)
Ccb/q
(mg/g)
(g/l)
5.58
0.22
0.27
0.81
24.69
9.72
0.75
12.99
8.11
0.16
0.40
0.40
36.18
18.00
0.91
19.80
28.50
1.15
1.37
0.84
61.26
32.45
1.44
22.53
54.05
3.40
2.53
1.34
96.85
59.45
1.87
31.79
108.84
19.00
4.49
4.23
144.58 100.98
2.18
46.32
192.70
64.90
6.39
10.16
192.30 144.30
2.40
60.13
290.20 150.00
7.01
21.40
256.91 204.71
2.61
78.43
399.76 248.09
7.58
32.71
333.77 280.00
2.69
104.15
http://www.lrc-tnu.edu.vn
37
R2 = 0.9835
7.00
35.00
6.00
30.00
5.00
4.00
3.00
25.00
20.00
15.00
2.00
10.00
1.00
5.00
0.00
-1.000.00
50.00
100.00
y = 0.1304x + 1.0478
R2 = 0.9973
40.00
C cb/q (g/l)
q (mg/g)
8.00
150.00
200.00
250.00
0.00
0.00
300.00
50.00
250.00 300.00
Ccb (mg/l)
Ccb (mg/l)
hp ph Langmuir ca VLHP
hp ph Langmuir
i vi Cu(II)
R2 = 0.9889
3.00
100.00
C cb/q (g/l)
q (mg/g)
2.50
2.00
1.50
1.00
80.00
60.00
40.00
20.00
0.50
0.00
0.00
y = 0.3287x + 12.108
R2 = 0.9985
120.00
50.00
100.00
150.00
200.00
250.00
300.00
Ccb (mg/l)
0.00
0.00
50.00
Ccb (mg/l)
hp ph Langmuir ca VLHP
hp ph nhit Langmuir
i vi Mn(II)
http://www.lrc-tnu.edu.vn
38
Bng 2.17: nh hng ca nng ion kim loi n s hp ph
Ni(II) v Pb(II) ca VLHP
Ni(II)
Co
(mg/l)
Ccb
Cf/q
Co
Ccb
(mg/l)
Ccb/q
25.15
3.89
1.06
3.66
47.34
0.11
2.36
0.05
34.58
8.92
1.28
6.95
100.51
1.01
4.97
0.20
51.63
15.56
1.80
8.63
188.00
4.65
10.00
0.47
80.13
31.29
2.44
12.81
408.55
43.66
20.89
2.09
114.13 56.91
2.86
19.89
616.03
123.09
24.65
4.99
154.02 90.02
3.20
28.13
806.48
244.44
28.10
8.70
216.00 150.00
3.30
30.78
12.31
270.01 206.45
3.18
31.92
17.59
4.00
70.00
R2 = 0.9532
3.50
60.00
3.00
50.00
C cb/q (g/l)
q (mg/g)
Pb(II)
2.50
2.00
1.50
40.00
30.00
1.00
20.00
0.50
10.00
0.00
0.00
50.00
100.00
150.00
200.00
250.00
Ccb (mg/l)
y = 0.2909x + 3.3394
R2 = 0.9972
0.00
0.00
50.00
100.00
150.00
200.00
250.00
Ccb (mg/l)
hp ph Langmuir ca VLHP
hp ph Langmuir
i vi Ni(II)
http://www.lrc-tnu.edu.vn
39
R2 = 0.9704
y = 0.0309x + 0.5179
R2 = 0.9952
20.00
30.00
17.50
25.00
15.00
C cb /q (g/l)
q (mg/g)
35.00
20.00
15.00
10.00
12.50
10.00
7.50
5.00
5.00
0.00
0.00
-5.00
2.50
100.00
200.00
300.00
400.00
500.00
600.00
0.00
0.00
Ccb (mg/l)
Ccb (mg/l)
hp ph Langmuir ca VLHP
hp ph Langmuir
i vi Pb(II)
http://www.lrc-tnu.edu.vn
40
http://www.lrc-tnu.edu.vn
41
VLHP. Xc nh nng Ccb1 v Ccb2 ca Ni(II) trong cc dung dch sau hp
ph bng phng php hp th nguyn t.
Hiu sut hp ph c tnh ton theo cng thc (1.2). Kt qu thu c
th hin bng 2.18.
Bng 2.18: Kt qu tch loi Ni(II) khi nc thi ca nh my
quc phng
Co (mg/l)
Ccb1 (mg/l)
H1 (%)
Ccb2 (mg/l)
H2 (%)
1.76
0.378
78.56
0.159
90.97
Nhn xt:
Sau khi hp ph ln mt hiu sut hp ph t 78.56% v nng Ni(II)
trong dung dch t tiu chu
,...Khi hp ph ln hai hiu sut hp ph t ti 90.97% v nng Ni(II)
http://www.lrc-tnu.edu.vn
42
KT LUN
.
3. kho st c mt s yu t nh hng n s hp ph ca VLHP
i vi Cd(II), Cr(VI), Cu(II), Mn(II), Ni(II) v Pb(II). Cc kt qu thu c:
- Trong khong pH kho st (1.00
10.00), khong pH s hp ph
6.00
2.00
5.00
6.00
6.00
6.00
70 pht
http://www.lrc-tnu.edu.vn
43
Cr(VI): thi gian t cn bng hp ph l 40 pht
80 pht
70 pht
120 pht
80 pht
80 pht
http://www.lrc-tnu.edu.vn
44
Ti Nguyn
(2002),
, Nxb
3. Tr
.
(2003
.
(1999),
,
(2002),
ti
7. PP Koroxtelev (1974), Chun b dung dch cho phn tch ha hc, Ngi
dch: Nguyn Trng Biu, Mai Hu ua, Nguyn Vit Hu, L Ngc Khnh,
Trn Thanh Sn, Mai Vn Thanh, Nxb Khoa hc v k thut, H Ni.
8. Phm Lun (1998), Phng php phn tch ph nguyn t, Nxb i hc
Quc gia H Ni.
9. on Th Thanh Nhn (1996), Gio trnh cy cng nghip, Nxb Nng
nghip H Ni.
10. Hong Nhm (2003), Ho hc v c, tp 3, Nxb Gio dc.
http://www.lrc-tnu.edu.vn
45
(2004),
2,
pp. 205-208.
20. W.E. Marshall., L.H. Wartelle., D.E. Boler, M.M. Johns., C.A. Toles.
(1999), Enhanced metal adsorption by soybean hulls modified with citric
acid, Bioresource Technology 69, pp. 263-268.
http://www.lrc-tnu.edu.vn
46
http://www.lrc-tnu.edu.vn