TP CH KHOA HC V CNG NGH, I HC NNG - S 4(39).

2010

XC NH CC THNG S CHNH CHO QU TRNH TNG HP

TIO2 C NANO T ILMENIT HU BNG PHNG PHP THY
NHIT S DNG KOH V H2C2O4
DETERMINATION OF KEY PARAMETERS FOR SYNTHESIZING NANOSCALE
TIO2 FROM HUES ILMENITE BY HYDROTHERMAL
METHOD USING KOH AND H2C2O4

Hong Th Cc, Hunh Th Hng Thm,

H Vit Thng, Phm Cm Nam
Trng i hc Bch khoa, i hc Nng

Vn Quang
Cty CP Khong sn t Qung Chu Lai,
Ni Thnh Qung Nam.

TM TT
TiO2 kch thc c nano bao gm pha anatase v rutile c tng hp bng cch
phn hy tinh qung ilmenite Hu trong dung dch KOH, sau dung dch bn thu c cho
phn ng vi H2C2O4 theo c ch ngh bi Liu (Int. J. Miner. Proces. 2006; 81; 7984) cng
nh Nayl v Aly (Hydrometallurgy 2009; 97; 86-93). Khng ch cc yu t nh hng n qu
trnh phn hy bao gm kch thc ht ilmenite (74-105m), nng KOH (70%) v H2C2O4
(80%), t l khi lng KOH vi ilmenite (5/1), thi gian phn ng (3 gi), nhit v thi gian
nung, chng ti thu c TiO2 vi dng hnh cu, kch thc ht nh hn 50nm.
ABSTR ACT
Nanoscale-TiO2 including anatase and rutile type is obtained by decomposing Hues
ilmenite using KOH. The obtained mixture paste then reacts with H2C2O4 based on the
mechanism proposed by Liu (Int. J. Miner. Proces. 2006; 81; 7984) and Nayl and Aly
(Hydrometallurgy 2009; 97; 86-93). Manipulating the factors that affect the synthesis process
such as the size of ilmenite particles (74-105 m), the concentration of KOH (70% in weight)
and H2C2O4 (80%), alkali-to-ilmenite mass ratios (5/1), time of reaction (3h), temperature and
time of annealing, we obtained the TiO2 powder with the size of grain less than 50nm.

1. Gii thiu
Titanium oxite (TiO2) c p dng rng ri trong sn xut giy, sn, nha, cao
su, gm, dt v m phm[1] c bit hin nay c s quan tm ng k trong
nghin cu tng hp v ng dng TiO2 vi kch thc c nano trong lnh vc xc tc
quang ho.[2] TiO2 dng bt vi kch thc c nano l l cht xc tc quang ha hiu
qu s dng trong qu trnh x l ngun nc thi b nhim bi cc cht hu c.
Nhiu nghin cu xc nhn rng TiO2 vi kch thc 10 nm s c hiu ng quang
ha cao v nhng ng dng ca n nh vic ph ln cc vt liu xp c meso cng nh
cc lnh vc c quan tm nghin cu v p dng. [3]
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TP CH KHOA HC V CNG NGH, I HC NNG - S 4(39).2010

Thng thng, iu ch TiO2 thng s dng sulfuric acid [4] hay

hydrochloric acid vi nng cao (>90%) phn ng vi qung ilmenite (FeO.TiO2)
giai on u tin. C ch qu trnh c din t theo cc phn ng sau:[5]
FeTiO3 + 2H2SO4 TiOSO4 + FeSO4 + 2H2O

(1)

FeTiO3 + 6HCl TiCl4 + FeCl2 + 3H2O

(2)

Tuy nhin, tm kim phng php hiu qu tinh luyn v t nhim mi

trng l mt trong nhng nhim v cn t ra. Gn y thay th phng php acid
v to ra tinh th TiO2 kch thc c nano, phng php kim c nhiu tc gi quan
tm nghin cu. Qu trnh phn hy ilmenite bng kim c th thc hin p sut
thng [6,7] nhm to ra cc tinh th TiO2 nano dng hnh cu.
Mc ch ca bi bo ny nhm xc nh cc thng s chnh cho qu trnh tng
hp TiO2 kch thc c nano da trn phng php thy nhit bng KOH ti p sut
thng da trn quy trnh xut nm 2006 ca Liu v nhm tc gi [6], sau Aly v
cng s [7] p dng thnh cng gn y trn mu ilmenite ti Egypt. Trong nghin
cu ny, ilmenite Hu c phn hy bng dung dch KOH vi nng cao sau
phn ng vi H2C2O4. Cc kt qu nghin cu c thc hin trn cc thit b phn tch
hin i nh hunh quang tia X (XRF), ph hng ngoi chuyn i (FT-IR), knh hin
vi in t qut (SEM) v phng php nhiu x tia X (XRD).
2. Nguyn liu v phng php nghin cu
2.1. Nguyn liu
Qung ilmenite vi khi lng 500g cung cp bi cng ty TNHH Khong Sn
Tha Thin Hu c gia cng nghin, sng v chn kch thc ht phn b nm trong
gii hn t 105 74m. ng thi so snh nh gi kch thc v hnh dng ca sn
phm thu c chng ti s dng TiO2 kch thc nano ca hng Merck i chng.
Tinh th KOH v H2C2O4 thng mi ca Trung Quc, c ln lt pha thnh
dung dch KOH 70% v H2C2O4 80% (khi lng).
2.2. Thit b
Thnh phn ha ca ilmenite, TiO2 ca hng Merck v sn phm c phn tch
bng phng php hunh quang tia X (XRF) ti Trung tm Phn tch Phn loi Hng
ha Xut khu Nhp khu min Trung.
nh gi cu trc b mt ca sn phm thu c thng qua phn tch knh hin
vi in t qut (SEM) trn my S-4800, Hitachi High-Technologies ti phng th
nghim trng im v Vt liu v Linh kin in t-Vin Khoa hc Vt liu, Vit Nam.
Xc nh thnh phn pha ca sn phm bng phng php nhiu x tia X (XRD)
ti Trng i hc Khoa hc T nhin, i hc Quc gia H Ni.
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TP CH KHOA HC V CNG NGH, I HC NNG - S 4(39).2010

3. Kt qu nghin cu v tho lun

3.1. Thnh phn ha ca nguyn liu
Ilmenite Hu: Bng 1 trnh by kt qu phn tch xc nh thnh phn ha ca
tinh qung ilmenite Hu bng XRF, cho thy rng hm lng TiO2 thu c tng thch
vi kt qu phn tch ICP-MS [4]. Tuy nhin hm lng FeO theo phng php XRF
cho gi tr thp hn (4%) vi kt qu ca cng trnh k trn v hm lng SiO2 ch cao
hn khong 2%. Nh vy, c th kt lun rng phng php o XRF cho cc gi tr
trong gii hn hon ton tin cy c. Vi kt qu trn cho thy hm lng ch yu
trong tinh qung ilmenite Hu l TiO2 v SiO2. So snh vi phn tch nhiu x tia X
trong cng trnh nghin cu gn y [4] cho thy thnh phn pha ch yu c kho
st l FeO.TiO2 v mt lng nh rutile v anatase.
TiO2 Merck: Mu TiO2 c phn tch vi thnh phn TiO2 nm dng khong
anatase chim 98.9 % khi lng (tng ng vi kt qu phn tch ca hng Merck,
99%). Hm lng khng ng k (<0.5% khi lng) cc oxide bao gm SiO2, K2O,
P2O5, CaO, ZrO2 c pht hin cng vi 0.02% FeO. Kt qu phn tch cu trc b
mt ca mu TiO2 c nano c cho trn Hnh 2 vi phn b kch thc c ht TiO2
trong mu Merck t 50nm n 250nm.
Bng 1. Thnh phn ha hc ca ilmenite

Oxide

TiO2

FeO

SiO2

MnO

Al2O3 Cr2O3

Ilmenite Hu

53.61

37.16

2.65

2.56

2.45

TiO2 Merck

98.90

0.02

0.46

MgO

P2O5

ZrO2

0.81

0.20

0.18

0.11

0.25

0.03

3.2. Tng hp TiO2 kch thc c nano t tinh qung ilmenite bng phng php
kim
Theo c ch tinh luyn TiO2 t tinh qung ilmenite bng cch phn hy trong
dung dch KOH m c v sau tip tc phn ng vi H2C2O4 theo quy trnh ca
Liu, Aly v cng s[6,7]. Qu trnh thc hin hai giai on, bao gm:
Giai on 1: Qu trnh phn hy ilmenite bng KOH
Phn ng ca FeTiO3 (thnh phn chnh trong ilmenite) vi KOH nng cao
c m t nh sau:
3FeTiO3 + 4KOH K4Ti3O8 + 3FeO + 2H2O
Nng KOH, thi gian, nhit phn ng v t l ilmenite v dung dch KOH
l cc yu t chnh nh hng n qu trnh. Trong qu trnh thc hin, chng ti khng
ch cc yu t nh hng trn trong gii hn: kch thc ht ilmenite 105 - 74m, nng
KOH, 70%, thi gian khuy trong 3h, t l KOH: ilmenite = 5:1, v nhit phn
ng 130 -1500C.
Giai on 2: Qu trnh chit tch TiO2 bng H2C2O4
32

(3)

TP CH KHOA HC V CNG NGH, I HC NNG - S 4(39).2010

Sn phm ca phn ng trn dng bt nho c ra bng nc ct tch

cc tp cht sau tc dng vi H2C2O4 to ra Ti(OH)2(C2O4)22- v FeC2O4 theo
phn ng:
K4Ti3O8 +8H2C2O4 3H2Ti(OH)2(C2O4)2 + 2K2C2O4 +2H2O

(4)

K2C2O4 + FeO + H2O FeC2O4 + 2KOH

(5)

Chng ti s dng nng oxalic acid 80%, thi gian phn ng 3 gi ti nhit
100 - 1500C nhm phn ng xy ra tt nht vi kt qu l s to thnh
H2Ti(OH)2(C2O4)2. Sau mu c lc, ra bng nc nng v dung dch em un
si thu c dung dch keo v c em i sy v nung 6500C - 7000C trong 3 gi.
Mu thu c c ra bng HCl ln cui, sau bng nc ct, cui cng em i sy
110-1200C.
Do nhng hn ch trong iu kin thc nghim, trong cng trnh ny chng ti
cha cp n hiu sut thu hi TiO2 m ch quan tm n cc tnh cht ca sn phm
cui cng. Kt qu phn tch thnh phn ha bng XRF ca mu da trn quy trnh cho
thy hm lng TiO2 trong mu thu c nm trong khong 89-93%, vi hm lng
FeO nm trong khong 0.3 n 0.7%, phn cn li gm mt t SiO2 v cc oxide khc.
iu ny chng t qu trnh phn hy tch FeO trong ilmenite bng KOH c thc
hin trit ti iu kin kho st.
Kt qu phn tch SEM cho thy cc ht TiO2 thu c bng quy trnh nu trn
c trnh by . Quan st nh SEM thu c cho mu c nung 650 - 7000C vi
thi gian lu 3 gi cho thy kch thc TiO2 pht trin n 50nm. Kch thc ht TiO2
ca mu nhn c pht trin tng i ng u hn khi so snh vi mu TiO2 ca
hng Merck Hnh 2.

Hnh 1. SEM ca mu TiO2 c tch t ilmenite nung ti 650- 7000C lu 3 gi

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TP CH KHOA HC V CNG NGH, I HC NNG - S 4(39).2010

Hnh 2. SEM ca mu TiO2 (Merck)

khng nh thnh phn pha ca sn phm thu c, chng ti tin hnh phn
tch XRD trn mu, kt qu th hin Hnh 3.
Faculty of Chemistry, VNU, D8 ADVANCE-Bruker - Mau 01
d=3.246

800

700

600

d=1.688

400
d=2.486

Lin (Cps)

500

d=1.892

d=2.054

d=2.297

100

d=2.959

d=3.515

200

d=1.624

d=2.188

300

0
20

30

40

50

2-Theta - Scale
File: NamDN Mau01.raw - Type: Locked Coupled - Start: 20.000 - End: 60.000 - Step: 0.020 - Step time: 0.3 s - Temp.: 25 C (Room) - Time Started: 4 s - 2-Theta: 20.000 - Theta: 10.000 - Chi: 0.00
00-021-1272 (*) - Anatase, syn - TiO2 - Y: 7.41 % - d x by: 1. - WL: 1.5406 - Tetragonal - a 3.78520 - b 3.78520 - c 9.51390 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - I41/amd (141) - 4 00-021-1276 (*) - Rutile, syn - TiO2 - Y: 86.06 % - d x by: 1. - WL: 1.5406 - Tetragonal - a 4.59330 - b 4.59330 - c 2.95920 - alpha 90.000 - beta 90.000 - gamma 90.000 - Primitive - P42/mnm (136) - 2 - 62.4

Hnh 3. XRD ca mu thu c nung 650-7000C trong 3h

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TP CH KHOA HC V CNG NGH, I HC NNG - S 4(39).2010

4. Kt lun
Vi nhng nghin cu ban u cho kt lun rng c th s dng KOH thay th
H2SO4 hay HCl phn hy qung ilmenite, sau cho phn ng vi H2C2O4 nhn
c cc tinh th TiO2 bao gm khong rutile v anatase. Trong quy trnh tng hp, cc
phn ng ha hc c thc hin gm hai giai on vi cc thng s nh hng c
khng ch nh sau:
- Giai on phn hy ilmenite bng KOH to ra K4Ti3O8 v FeO c th s dng
nng KOH 70% khi lng, thi gian phn ng trong 3h v t l KOH: ilmenite Hu
l 5:1.
- Giai on phn ng vi H2C2O4 to H2Ti(OH)2(C2O4)2, nng cn thit cho
H2C2O4 l 80% khi lng, thi gian phn ng 3h trong khong nhit 100-1500C.
Keo t dung dch, lc v nung 650-7000C, kt qu thu c cc ht TiO2 hnh cu
vi kch thc ht tinh th nh hn 50nm bao gm c hai khong rutile v anatase.
ti tip tc hng pht trin theo hng xc nh thng s thc nghim
thc hin qu trnh thu c TiO2 vi hiu sut cao nht. ng thi kho st nhit
nung cn thit thu c sn phm vi hm lng khong anatase cao hn nhm cho
cc mc ch xc tc quang hc. Hng ng dng ph TiO2 ln cc vt liu c l xp
mao qun to ra vt liu xc tc quang ha cho cc qu trnh x l nc thi s c
cp trong cc cng trnh tip theo.
* Cng trnh ny l mt phn kt qu ca ti nghin cu cp b 2010-2011
do PCN lm ch nhim ti.
TI LIU THAM KHO
[1] M. Wang, K-D. Woo, I-Y. Kim, W. Ki, Z. Sui, Separation of Fe3+ during
hydrolysis of TiO2+ by addition of EDTA, Hydrometallurgy 89 (2007) 319322.
[2] A. Fujishima, X. Zhang, D. A. Tryk, TiO2 photocatalysis and related surface
phenomena; Surface Science Reports 63 (2008) 515-582.
[3] M. Anpo, M. Takeuchi, The design and development of highly reactive titanium
oxide photocatalysts operating under visible light irradiation, Journal of Catalysis
216 (2003) 505516.
[4] [4] Trn Minh Ngc, Nghin cu iu ch TiO2 dng anatase kch thc nano t
tinh qung ilmenite Tha Thin Hu, Lun vn Thc s, 2008.
[5] B. Liang, C. Li, C. G. Zhang, Y. K. Zhang, Leaching kinetics of Panzhihua
ilmenite in sulfuric acid, Hydrometallurgy 76 (2005) 173179.
[6] Y. Liu, T. Qi, J. Chu, Q. Tong, Y. Zhang, Decomposition of ilmenite by
concentrated KOH solution under atmospheric pressure, International Journal of
Mineral Processing, 81, (2006) 7984.
[7] (a) A.A. Nayl, N.S. Awwad, H.F. Aly, Kinetics of acid leaching of ilmenite
decomposed by KOH: Part 2., Journal of Hazardous Materials 168 (2009), 793799. (b) A. A. Nayl, H.F. Aly, Acid leaching of ilmenite decomposed by KOH,
Hydrometallurgy 97 (2009) 86-93.
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