DAI HOC
QUOC GIA HA NQI
TRl/OfNG DAI
HOC
KHOA HQC iV NHIEN
DE
TAI
NGHIEN
CUtJ
KHOA HQC DAC
BI?T
CAP DAI
HQC QUOC GIA
NGHI
EN
Ciru
CHE TAG VAT LIEU HAP
PHV
SET
HUtJ
CO
(ORGANOCLAYS) TREN CO
SOf NGUON
NGUYEN LIEU
BENTONIT VA
iTNG
DUNG DE
XlT
LY CAC CHAT
HUU
CO
l.Tendetai:
Tilng
Viet:
"Nghien
ciru chi tao vat lieu
hdpphu
set
hitu
ca (organoclays) tren ca so
nguSn nguyen lieu bentonite va
vmg
dung di
xic ly cdc
chat
hiru
ca doc hgi trong
nirac"
Tilng
Anh:
''Development
of organoclays based on bentonite and their use in the
treatment of hazardous organic chemicals in water and
wastewater''
2.
Chu tri de tai: PGS.TS.
Nguyin
Van Noi, Khoa Hoa hoc, Truang DHKHTN
3.
Cac can bo
tham
lieu set huu ca va ung dung trong qua trinh xu ly cac nguon nuac bi 6 nhiem cac chat
huu ca doc hai. Buae dau nghien cuu xay dung qui
trinh
cong nghe su dung set hiru ca
de tach
loai
cac chat huu ca doc hai trong cac nguon nuac bi 6 nhiem.
6. Tom tat noi dung nghien
cihi
cua de tai va ket qua dat
dvac.
- Noi dung
+
Che tao va xac dinh cau true cua vat lieu set
hiju
ca
+ Khao sat kha nang xu ly cua vat lieu che tao
duge
-
Phuong
phdp nghien ciru:
+ Nghien cuu
sir
hinh thanh set huu ca nha qua trinh trao doi ion cua bentonite
vai cation huu ca dang
[(CH3)3NR]".
Cau true
ciia
set Huu ca dugc xac dinh
bang cac phuong phap XRD,
+ So cu nhan dugc dao tao trong
khuon kho
de tai: 3
- So
thac sT
dugc dao tao trong khuon kho de tai: 1
- Da cong bo 01 bdo cdo tai Hoi nghi Khoa hoc quoc te,
01
bdo ado tai Hoi nghi Khoa
hoc Truang DHKHTN, 02 bdi bdo trong pham vi thuc hien de tai.
7.
Tinh
hinh
kinh
phi
cua de
tai:
- Tong kinh phi dugc
cip
60.000.000 dong
- Da chi theo dung noi dung hgp dong : 60.000.000
d6ng
XAC NHAN GUA KHOA
GHU TRI DE TAI
PGS.TS.
Trinh
Ngoc Ghau
PGS.TS.
Nguyen Van
N^i
5. Objectives and contents:
- Development of organoclays by modifying bentonite with HDTMA and
TIOT
-Characterization of organoclay structure by
XRD,
Thermal analysis, IR and SEM
methods
s
- Sorption of some textile dyes such as direct dye, acid dye and reactive dye on Na-
bentonite, HDTMA-bentonite and
HDTMA-TIOT-bentonite
was investigated
- Application of organoclays in the treatment of wastewater from Duong Noi textile
handicraft village in Ha Dong town.
6. Project results
Research results
- Sorption materials-organoclays received from chemical modification of bentonite
by HDTMA and TIOT
- Organoclays were successfully applied in the treatment of wastewater from Duong
Noi textile handicraft village.
Publication
- 01 scientific report on the international Symposium (the third
ISAMAP
in Korea)
- 01 report on the scientific conference of Hanoi University of Science
- 02 papers
Education results
Graduated Students (MS): 1
Undergraduated Students (BS): 3
MO
cac loai pham nhugm.
O
nuac ta, viee nghien
cuu,
ung dung set huu ca chu yeu trong
llnh virc dlu
khi;
set hiru ca da dugc nghien cuu thanh cong de pha dung dich khoan goe dau. Tuy nhien,
viee ung dung set
hiJu
ca trong xu ly nuac thai moi chi
a nhijmg
buae ban
ddu.
D^
tai
nghien cuu dugc xay
dung'nham
tan dung nguon khoang set bentonit re
ti^n,
c6 tru
lugng
Ian
lam vat lieu xu ly cac chat huu ca doe hai, dac biet la hoa
ch4t
det nhugm,
trong nuac thai mot each hieu qua. Viee nghien cuu che tao vat lieu
hip
phu set huu
ca tren ca so bentonit bien tinh va ung dung trong xu ly nuac thai nganh det nhugm c6
Ngoai ra trong bentonit con mot so khoang
khae
nhu caolinit, mica, canxit,
thach
anh,
cac muoi kiem
Thanh phan hoa Hgc cua montmorillonit, ngoai hai nguyen to kim loai chinh la
Si va
Al
con c6 cac nguyen to khae nhu Fe, Ca, Mg,
Ti,
K, Na Ty
le
AI2O3:
Si02
nam trong khoang
1:2
den
1:4.
Bentonit dugc
chia
thanh hai loai:
- Bentonit truang no eo thanh phan chinh la montmorillonit Na, hay con ggi la
Bentonit natri. Khi bao hoa nuac bentonit natri eo the truang no den 20
Ian.
- Bentonit khong truang no c6 thanh phan chinh la montmorilonit canxi, con ggi
la bentonit canxi.
7 7.2.
Cau
true
th^
montmorillonit duge cau tao tu hai mang tu dien
k^t
vai mot mang bat dien a giua. Giua
cac lap cau true la cac cation trao
d6i
va nuac hydrat. Khoang each giua cac lap trong
ciu
true
ca ban cua Montmorillonit la 9,6
A°.
Khoang each do bi thay doi nhieu hay it
tuy
thugc
vao
s6
lugng, ban chat cation trao doi va lugng nuac hap thu,
thuong len
tai
15A°.
Khoang each nay c6 the tang den
40A°
khi cac cation bi thay the boi ion v6 ca
phan
cue,
cac
phire
ca kim, polyme v6 ca, cac phan tu huu ca. Ducri day la so do cau
true
khong gian mang
va/hoac
dugc thay the bang cation
khae.
M""
.n
H2O
Lap set
Cation kim loai bi hidrat hoa
Lap set
Hinh
6: Sa do cau
true
khong gian
ciia
Montmorillonite
1.1.3. Cdc tinh chat
cia
set bentonit
[5]
a. Tinh chat trao doi cation
Nhu da trinh bay trong phan truae, trong mang cau
true
cua montmorillonit thuong
xay ra
sir
thay the dong
Huih
cua cac cation. Ket qua cua su thay
thi
nay la xuit hien cac
tH6
cua cac cation theo trat tu sau:
H"
>
Al^"
>
Ca^"
>
Mg^"^
>
K""
>
NHU"
> Na"
Dung lugng trao doi cation CEC (cation exchange capacity) dugc dinh
nghia
la
t6ng s6
cation trao doi tren mot dan vi
kh6i
lugng set, thong thuong dugc tinh bang
mili
duang lugng gam (meq) tren
lOOg
set kho.
Vi tri trao doi ben ngoai
Vi tri trao doi ben trong
o
0
o
b. Tinh chat truang na
Trucmg no la mot trong
nhiing
tinh chat dac trung cua khoang set. Khi tiep xuc
vai nuac hoae moi truang khong khi am set bi truang no, the tich eo the tang len 15-20
Ian
so vai the tich kho ban dau. Trong qua trinh truang na, nuac xam nhap vao va dugc
giu
lai
trong khoang khong gian
giira
cac phien set. Lugng nuac hip phu nay phu thugc
rat nhieu vao kha nang hydrat hoa cua cac cation. Kha nang hydrat Hoa cua cac cation
tang theo thu tu sau:
Li"
> Na" >
NH4^
> K" >
Mg^"
>
Ca^"
>
Al^"
> H"
KicH
thuae, Hinh dang cua cac cation giua cac lap cung anh Huong den kha nang
Hydrat hoa va truang no set. Cac cation c6 ban kinh hydrat hoa
Ian
se lam cho khoang
each
hiru
eo phan
cue.
Doi vai cac chat dang cation thi
bentonit hap phu chung theo eo che trao doi cation.
Sir
hap phu trao doi nay phu thuoc
vao dien tich, hinh dang, kich thuoc cua cation trao doi va dung lugng trao doi cation
cua khoang set. Cac chat huu eo phan
cue
c6 kich thuoc va khoi lugng nho bi hap phu
bang each lien ket true tiep vai cac cation trao doi nam giua cac lap hoae
lien kk
vai
cac cation do qua cau
H2O.
Con chat huu ca phan cue eo kich thuoc va khoi lugng
Ian,
lien ket
true
tiep vai oxi day cua tu dien trong mang
luai
tinh the bing
lire
Van
der Wall.
1.2. Vat lieu hap phu set
hihi
ca
(Organoclay)
giua cac lop
philn
set
(dooi)
tang len ma con lam cho set co tinh
chat ua dau. Khi do, set se co kha nang truong no va phan tan
duqc
trong cac dung
moi huu
CO
khae nhau.
10
Hinh
8. Mo hinh cau
true
cua set
hiru
ca
Khae
vai cac hgp chat huu co phan cue, cation huu ca thay the cac cation v6 co
nam giua hai phien set va lien ket chat che vai be mat phien set. Su
tuong
tac nay ggi
la hap phu trao doi, nguyen tu
nito eiia
cac amin gan chat vao be mat phien set, con
duoi hydrocabon se thay the vi tri cac phan tu nuac da bi hap phu tu truoc nam song
song hoae vuong goe vai be mat phien set. Lugng cation
Hun
co trao doi co the
do do su hip phu chu
ylu
la
su hap phu mao quan.
- Khi R la cac alkyl mach dai thi vat lieu la set huu co eo ai
lire Ion
vai chit huu
CO
(Organophilic Organoclay). Vat
Heu
nay co tinh ky nuac va ai
lire
vai cac chit
hiru
CO
cao Hon Han, the hien a he so phan bo Kow > 104. Voi su co mat
eiia
nhom alkyl
mach dai nay thi be mat hap phu cua vat lieu se co ciu
true
khong gian 3
chi^u,
do do
su Hap phu se duge quyet dinh chinh la do ai
lire
cua nhom alkyl voi eac chit huu co.
Set hiru ca dugc ung dung trong nhieu
linh
vue khae nhau. Trong cong nghiep
dau khi, set
chat co phan tu lugng
Ion.
Nho dac diem do,
set huu eo co the ung dung de lam vat lieu xu ly nuac nhiem cac hgp chat huu co doc
hai voi moi truang.
CHue
nang lam sach nuac diu tien phai ke den la tach loai eac hgp
chat Huu
CO
doc Hai eo do tan thap trong nuac, dac biet la diu, creozol, PAHs va PCBs.
Mot so tai lieu nghien cuu chi ra rang, tham chi kha nang Hap phu
ciia
set huu co con
vugt xa than Hoat tinh. Mot he thong
xii
ly nuac 6 nhiem dau va hgp chat BTEX
(benzen - toluen -
etylbenzen
-
xylen),
dat hieu qua tot la khi he thong su dung ket hgp
set huu
co/than
hoat tinh, vi set huu co co kha nang hap phu tot Hon doi voi nhom hgp
chat toluene, xylenes, trong khi do than Hoat tinh se xu ly tot benzen [8,10,12].
12
PHAN II: CAC
PrnTCfNG
PHAP NGHIEN
CUtJ
goc mot buae quet 0.03°.
2.3.
Phuong
phap pho hong ngoai
Phuong phap pho hong ngoai IR dung de phan tich cac dac diem va cac lien ket
giira cac nguyen to trong mang luai tinh the. Trong dai buae song 400-4000em"', pho
hong ngoai cho biet
nhimg
dao dong lien ket trong mang cau true cua montmorillonit.
Dam pho hap thu
ciia
dao dong bien dang Si-0' trong tu dien
Si04
nam trong khoang
420-470 cm"'. Dam pho
dac'trung
cho lien ket
Al-0
trong bat dien nam xung quanh 815
em"'.
Nhom OH" trong mang luai dugc dac trung boi dam pho nam xung quanh 3600
cm"'.
Pho hong ngoai
ciia
bentonit va set hiru co dugc do tren thiet bi IR
Nicolet-Model
Nexus 670.
2.4.
Phuong
phap phan
TG/DSG-SETARAM, Khoa Hoa hgc,
vdi
cac
dilu
kien sau:
- Khoang nhiet do
30-800°C
13
-
Toe
do gia nhiet: 10
C/phiit
2.5.
Phuong
phap kinh hien vi dien tu quet (SEM)
Kinh hien vi dien tu quet la thiet bi nghien cuu cau tnic be mat
ciia
mau. Do
phan giai
eiia
kinh co the dat dugc
10'^
-
10*"^nm,
do pHong dai 1cm
hem
gap nhieu
Ian
so voi kinh hien vi quang hgc. Nguyen tac
ciia
xac
djnh
nong do pham nhuom
Khi
chieu
mot dong sang qua dung dich thi dung dich do se hap thu chgn
Ige
mot so tia sang tuy theo
mail
sac
ciia
cac chat trong dung dich co nong do xac dinh.
Theo dinh
luat
Buger-Lamber-Beer ta e6:
A
=
\g^
= kb
A : Do hap thu quang cua dung dich
k
:
He so hap thu
b : Chieu day cuvet dung dung dich
He so Hap thu k con phu thugc vao nong do dung dich:
k=eC
e : He so khong phu thugc vao nong do
Do do ta eo:
A
=
Gia tri COD duge xac dinh thong qua viee do mat do quang tren may do COD
Merck Nova 30.
15
PHAN
IH:
THVC
NGHIEM,
KET QUA VA THAO
LUAN
3.1 Lam giau bentonit
aJTrao
doi vai
Na^:
Bentonit tho dugc ray lay co Hat
<0.15mm
roi dugc trao doi vai ion Na", thi
nghiem nhu sau: can khoang set va
NaHC03
vao eoc, them nuac eat roi khuay cho set
phan tan deu trong nuac, giam toe do khuay va duy tri trong 12
gio.
Ty le
NaHC03/bentonit la
3/100
theo khoi lugng. Lge gan va nia khoang set tai pH trung tinh.
b)Tdch bo hat tho:
Bentonit Di Linh-Lam Dong, ngoai thanh phan khoang chinh la monmorillonit
con chua nhieu loai khoang khae. Cac khoang vat di kem gom c6 caolinit, thach anh,
fenspat,
clorit, gatit Montmorillonit tap trung
ciia
bentonit truae va sau khi lam giau dugc trinh bay a bang
1.
Bang 1: Do truomg no va dung lugng trao doi cation CEC
ciia
bentonit truae va sau
khi lam giau
Vat lieu
Bentonite chua lam giau
Bentonite da lam giau
Do truong na
(ml/g)
trong
nuo-c
2.75
7.5
CEC
(mg/lOOg)
51.0
70.0
TIT
ket qua tren cho thay, bentonit sau khi lam giau eo do truang no va dung
lugng trao doi cation (CEC) tang len dang ke.
16
3.2 . Che tao set
hihi
ca
3.2.1.
Chi tao set
hitu
diing
(g)
CEC: dung
lugng ^^o ^^i
cation
ciia
bentonit (meq/g)
MW:
khoi lugng
moi
amin bac bon -HDTMA (364.46
g/mol)
X: khoi lugng khoang set bentonit (g)
- Tien hanh phan
ung
Nho tir tir dung dich HDTMA tir pheu chiet vao Hon hgp
huyen
phii.
Dieu chinh toe do nho gigt sao cho chuyen het dung dich amin vao Hon
hgp phan ung trong khoang thai gian la 1 gia. Hon Hgp tiep tuc dugc khuay va giir
nhiet do
a 60-70*^C
trong 2 gio. Ngimg cap nhiet va khuay Hon hgp phan ung trong
12
gia de phan ung xay ra Hoan toan.
Lge,
nia san pham bang
nuoe
nong cho toi khi loai bo hoan toan ion
CI'
Wio
den khoi lugng khong doi a nhiet do
70^C.
3.3.
Khao sat kha nang ung dung vat lieu hap phu set
hihi
ca de xu ly
nude
thai
det
nhu9m
.3.3.1.
KItdo
sat kha nang hap phu cda vat lieu thu
duxrc
tren mau
nir&c
pha
tir
pham
nhuom
De khao sat kha nang hap phu cua vat lieu thu dugc
chiing
toi tien hanh khao
sat kha nang Hap phu
eiia
vat lieu doi voi mau pha. Loai pham nhugm dugc
lira
chgn la
pham nhugm true tiep mau do; pham nhugm cation mau xanh va pham nhugm axit
3.3.2. Khao sat kha nang
hdpphu
cda vat lieu thu
dirac
trin mau
nw&c
thai lay tit
thuc dia
Mau nuoe thai dugc lay tai dong thai ra tir be nhugm
ciia
cong ty
Trach
nhiem
hiru Han thuomg mai det may Tin Thanh, thugc lang La Ca, xa Duang Noi, Ha Dong.
Tien hanh
xii
ly bang vat lieu hap phu che tao duge qua eac thi nghiem sau:
- Lay 100ml dung dich nuac thai
chira
pham nhugm khuay voi mot lugng xac
dinh vat lieu hap phu trong 3 gia.
- Lge bo phan chat ran roi xac dinh gia tri COD con lai va quan sat
sir
thay
doi mau nuoe thai.
3.4. Ket qua va thao
luan
3.4.1.
Kit qua nghiin
ciru
hgp
voi ket qua phan tich cau tnic qua pho X-ray, dieu do khang dinh goc amin bac bon da
duge dinh vi trong cau tnic cua bentonit.
Ket qua phan tich nhiet cho thay ham lugng nuac trong bentonit ban dau va set
huu
CO chenh
lech kha
Ian.
Trong bentonit-Na ban dau la 6,74% thi ham lugng nuac
trong set hiru co la rat nho
1,23%),
va bi giai phong a vimg nhiet do thap
hem
lOO^C.
Dieu nay cho thay vat lieu set Hiru co eo tinh ki nuoe cao
hem
bentonit.
Den khoang nhiet do tren
520^C
thi ham lugng mau mat di a set hiru co la
17,78%),
trong do co ca lugng am va lugng mat di do su phan
hiiy
cua phin hiru co. Tir
do
CO
the tinh dugc lugng Hiiu ca trong set hiru co chiem khoang 16,55%.
19
Do truang na trong Toluen
So lieu ve do truong no
bien tinh ciing dugc duge tang len.
Tir ket qua phan tich pho nhieu xa tia X cho thay khoang each eo ban eac lap
set da tang tir
15,23A°
len
37,00A°.
Khoang each nay tang len dang ke la co so cho
viee tao mao quan eo duang kinh
Ion.
Tren pho hong ngoai xuat hien pie img voi
buae
song 1475,18 cm"' dae trung
cho lien ket
=C-N ciia
amin bac bon. Cac pic
ling
voi buae song 2926,71 cm"' va
2855,15 cm"' dac trung cho lien ket
= CH2
va -
CH3.
Nhu vay co
th^
khing dinh nhom
amin bac bon da duge dinh vi tren be mat lap set.
Pho phan tich nhiet cho thay lugng am
ciia
vat lieu khoang 2,5 % irng vai nhiet
do
97,90*^C.
nhuom.
3.3.3.1.
Ket qua khao sat kha nang
hdpphu
cua vat lieu bentonit-Na vd vat lieu set
hiru ca bentonit-HDTMA
D6
danh gia kha nang hap phu
eiia
timg loai vat lieu, tien Hanh hoi quy cac gia tri
thuc
n^em
theo cac phucmg trinh hap phu ding nhiet Langmuir va Freundlich, thu
dugc cac gia tri dac trung nhu sau:
Bang 3: Kk qua khao sat kha nang hip phu
ciia
vat lieu bentonit-Na
Pham nhugm
Vang cation
Xanh cation
Do phan tan
Xanh true tiep
Tim axit
Hoi qui theo mo hinh
Langmuir
qmax(nig/g)
1263,9
855,5
581,5
1,28
4: Ket qua khao sat kha nang hap phu
ciia
vat lieu set
hiJu
co bentonit-HDTMA
Pham nhugm
Xanh cation
Do phan tan
Xanh true tiep
Tim axit
Hoi qui theo mo hinh
Langmuir
qmax (mg/g)
626,84
347,17
224,55
242,49
R^
0,900
0,900
0,878
0,953
Hoi qui theo mo hinh
Freundlich
K
47,23
0,74
106,30
62,12
1/n
chii
yeu la hap phu vat
ly. Vi vay, khi khoang each lap trong set HiJu co tang thi su hap phu ciing tang len.
Tir cac ket qua thuc nghiem tren mau pham nhugm axit mau tim, co the nhan
thiy tai trgng hap phu cue dai
eiia
set hiru co co giam so voi bentonit - Na, dieu nay
cho thiy viee gan ket goc
hiJu
co vao vat lieu nay khong lam tang hieu suat tach loai
chit 6 nhiem. Hay noi each khae,
dii
van eo kha nang hap phu pham nhugm tir nuoe
thai,
nhung loai vat lieu nay khong to ra c6 uu the noi trgi.
Viee nghien cim che tao vat lieu hap phu set hiru co HDTMA - bentonite tren
CO
so bentonit bien tinh da khae pHuc dugc nhuge diem
ciia
bentonite
-
Na trong viee
img dung trong xir ly nuac thai nganh det nhugm (nang tai trgng hap phu doi voi pham
nhugm true
tilp
tir
l,28mg/l
len
224,55mg/l),
dieu nay co y nghia thuc tien
1,36
KPHD
Nong
d9
sau xir
Iy(nig/1)
d pH 7.5
94,85
83,05
10,59
KPHD
KPHD
KPHD
Nong do sau
\\x
ly(mg/l)
d pH 9.5
95,91
84,72
83,66
0,51
0,43
0,27
22
Bang 6
.
Ket qua khao sat vai pham vang cation
Nong
dg
trudc
1,50
KPHD
Nong
d9
sau xir
ly(mg/l)
d pH 9.5
279,00
207,78
162,41
9,87
4,24
1,68
KPHD
Cac ket qua thu duge cho thay d dieu kien khao sat, set hiru co hap phu pham
xanh cation d pH=7,5 tot Hon d moi truong kiem (pH=9,5) va axit
(pH=4,4).
O
pH=7,5,
vai 50ml dung dich pham xanh cation c6 nong do dau khoang 800mg/l thi
chi can 0,lg set hiru ca la co the xu ly gan nhu hoan toan.
Tuong tu , doi vdi dung dich pham vang cation ket qua thu duge ciing chi ra
kha nang hap phu cua set hiru co che tao dugc doi vdi loai pham mau nay cung rat tot
va kha nang Hap phu d
pH=7,5
ciing tot Hon d d moi truong kiem
(pH=9,5)
va axit
(pH=4,4).
3.3.4. Khao sat kha nang
Khoi lugng vat
lieu (g)
0.05
0.1
0.15
0.2
0.25
0.3
Bentonite - Na
COD eon lai
(mg/1)
202.25
192.25
187.25
169.75
169.75
139.75
pH
8.23
8.27
8.25
8.26
8.29
8.29
Bentonit-HDTMA
COD eon lai
(mg/1)
164.75
52.25
39.75
hiru ca bentonit-HDTMA-TiOT
Ket qua xii ly nude thai det nhugm lang nghe Duong Noi - Ha Dong - Ha
Tay duge trinh bay d bang 8 va 9 .
Bang
8.
Gia tri COD sau khi
xii
ly nude thai vdi vat lieu set hiru eo bentonit-
HDTMA-TiOT
Lirgng
set
htru co'(g)
0,025
0,050
0,.100
COD dau vao
961,5
961,5
961,5
COD sau khi xu ly
329,0
'
301,5
204,0
24
Bang 9: Bang gia tri
ciia
COD sau khi
xii
ly nude thai vdi bentonit-HDTMA-TiOT d
thai thi tir gia tri COD ban diu 961,5 mg/1 da giam xudng con 204 mg/1, dat hieu qua
xii
ly tach loai COD la tren
78%)
Dieu nay
chimg
to bentonit-HDTMA-TiOT dieu che
ducfc CO
kha nang img dung tot vao thuc te.
25
Copyright: Tài liệu đại học ©