Tp ch Ha hc, T. 48 (4C) Tr.

8 - 12, 2010

NGHIN CU TNH CHT AXIT V XC TC CA DIATOMIT

AXIT HA BNG PHNG PHP LNG NG PHA HI (CVD)
n Ta son 12-7-2010
1

V TH MINH HNG , NGUYN TRUNG KIN2, NG TUYT PHNG2,

TRN TH KIM HOA2, V ANH TUN2
1

B mn Ha hc, Khoa H i cng, Trng i hc M a cht

2

Vin Ha hc, Vin Khoa hc v Cng ngh Vit Nam

ABSTRACT

Diatomite (Phu Yen) was successfully purified and acidified by Chemical Vapor
Deposition (CVD) method using evaporation of AlCl3 in N2 flow. The acidified diatomite
sample was characterized by FE-SEM, Temperature Programed Desorption of Ammonia
(NH3-TPD), Pyridine adsorbed FTIR. From characterization results, it revealed that by
acidification of diatomite, both Brnsted and Lewis sites were created. The sample was tested
in cracking of Bach Ho petroleum residue by using Micro Activity Test (MAT). In cracking of
Bach Ho petroleum residue, the sample exhibited a considerable activity (convertion of
21.46%). This can be explained by the contribution of both Brnsted and Lewis sites formed
in the acidified diatomite. In the distribution of products, high yield of LCO and HCO was
obtained.
I - M U
Cracking xc tc pha lu th (Fluid
Catalytic Cracking - FCC) l mt qu trnh
chuyn ha du m theo nhiu phn on khc
nhau thu c cc sn phm nh: kh kh,
LPG, gasoline, LCO, HCO, Xc tc cho qu
trnh chuyn ha ny gi l xc tc FCC, l h
xc tc bao gm pha hot ng - zeolit (ch yu
l zeolit Y, USY, REY chim 10-45%); pha nn
(oxit silic, oxit nhm, aluminosilicat, chim
55-90%)[1]. Pha nn ng vai tr quan trng
trong xc tc FCC, l mi trng pha long
phn tn pha hot ng, l cht ti nhit, cht h
tr khuch tn, Cht nn s dng trong xc
tc FCC thng khng c hot tnh xc tc hoc
hot tnh xc tc rt thp, nn n ch yu ng
vai tr l cht mang xc tc t c tc dng ph

tr hay hip ng xc tc vi pha hot ng.

Pha nn thng c cu trc xp, kch thc mao
qun ln, bn nhit cao nu ci thin c
hot tnh xc tc ca chng th s to ra c
mt h xc tc a mao qun l tng c tc
dng gi li cc kim loi nng gy ng c xc
tc nh V, Ni, Fe, mao qun ln. Cc phn
t ln, a vng c tin cracking trong mao
qun trung bnh (2-10nm) v tip tc cracking
trong mao qun nh ca zeolit [2].
Diatomit l trm tch cn c tn l
kizengua hay t to silic l khong st c sn
trong t nhin. Thnh phn ho hc ch yu ca
iatomit l SiO2 (50-96%), phn cn li l tp
cht Al2O3, Fe2O3, MgO, CaO Di y l
kt qu phn tch thnh phn ho hc ca
iatomit nguyn liu mt s vng khc nhau
trn th gii v Vit Nam[3 - 7].

Bng 1: Thnh phn ha hc ca iatomit

Thnh phn (% khi lng)
STT

Tn a im

SiO2

Al2O3

Fe2O3

MgO

CaO

Lomposc (M)

89,30

4,00

0,70

0,40

0,40

Inzenxki (Nga)

82,66

4,55

3,21

1,23

0,47

Nurnusxki(Acmeni)

95,11

0,15

0,23

0,20

0,60

Ph Yn (Vit Nam)

63

18

7,0

3,0

1,1

Da trn ngun diatomit (sn c Vit Nam) vi thnh phn ha hc, cu trc xp ph hp
chng ti tin hnh nghin cu hot ha diatomit (axit ha) bng phng php lng ng pha hi
(CVD-Chemical Vapor Deposition), s dng AlCl3 l ngun nhm.Tnh cht axit v xc tc ca
diatomit axit ha c nghin cu, kt qu c trnh by v tho lun trong bi bo ny.
II - THC NGHIM
1. Lm sch
Trc ht iatomit Ph Yn nguyn liu vi
thnh phn ha hc nh bng 1, s qua my
nghin ba v nghin bi thnh dng bt mn.
Tip theo bt ny s c nung 5000C trong
3-5h loi b cc tp cht hu c c trong
nguyn liu. iatomit Ph Yn sau khi loi
b cc tp cht hu c s thu c iatomit vi
b khung SiO2 vng chc, c cc mao qun
rng, din tch b mt ln, cu trc c bit xp,
bn v rt thch hp lm cht nn cho xc tc
FCC.

trong 3h trong dng kh He (hoc N2) ui

ht HCl, sau c trao i ion vi dung dch
NH4NO3 (2-3 ln) v nung 5500C trong 3h.

Hnh 1: S cy nguyn t Al vo khung

mng iatomit bng phng php CVD

2. Axit ha iatomit

3. Tnh cht axit

Vi mc ch lm cho cht nn cho xc tc

FCC cng c hot tnh xc tc c th tham
gia cracking s b cc phn t ln, chng ti
tin hnh axit ha iatomit bng cch s dng
phng php cy nguyn t nhm vo khung
mng SiO2 [8] to cc tm axit Bronsted v
Lewis, s thc nghim nh sau:

xc nh axit ca diatomit trc v

sau khi axit ha chng ti tin hnh o kh hp
ph amoniac theo chng trnh nhit (NH3TPD) v ph hng ngoi bin i fourier
(Pyridine FTIR) xc nh cng tm axit
v cc loi tm axit Brnsted v Lewis.

Phn ng c thc hin nhit trn

3750C nh mt l gia nhit hnh tr bn ngoi
ng phn ng. Phn ng c tin hnh trong
khong t 3h. v tip tc c nung 5500C

nh gi hot tnh xc tc ca vt liu

mao qun ln (iatomit axit ha Da) i vi
phn t ln, phc tp, chng ti tin hnh
phn ng cracking cn du Bch H (nhit

4. Hot tnh xc tc

si 360-5500C, nht (500C) 43,4 cSt) trn

thit b th hot tnh cng nghip MAT, ng
thi c phn tch bng GC-MS ti trung tm
du m, thnh ph H Ch Minh.
III - KT QU V THO LUN

iatomit Ph Yn sau khi c loi b cc

tp cht hu c v axit ha (Da) bng cch s
dng phng php cy nguyn t nhm vo
khung mng SiO2 to cc tm axit c chp
nh SEM nghin cu cu trc vt liu.

Hnh 2: nh SEM ca iatomit axit ha Da: A, trc khi axit ha; B, sau khi axit ha

1. Tnh cht axit

a) Phng php hp ph - gii hp ph
amoniac theo chng trnh nhit (TPDNH3):
Chng ti c trng axit ca cc mu
vt liu Da bng phng php hp ph - gii
hp ph amoniac theo chng trnh nhit
(TPD-NH3). i vi diatomit khng axit ha,
gin NH3 TPD ch c mt pic ln 150
1700C c trng cho cc tm axit yu. Trong
khi gin diatomit axit ha, ta thy tn ti 2
pic, pic nhit thp ng vi 170oC v pic
c trng 400 4500 C c cng ln. Hai
pic ny khng tch ri m xen ph ln nhau
chng t iatomit axit ha cng tn ti c tm
axit yu v tm axit mnh v c s phn b tm

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axit rng. T cc kt qu NH3 TPD, ta c th

khng nh trong diatomit axit ha mt lng
ln tm axit mnh c hnh thnh.
Da axit ha
0.09
0.08
0.07
Cng (a.u)

T hnh 2, ta thy iatomit axit ha Da c

cc dng nh hnh ng tr vi chiu di c 20
v ng knh c 10 hoc dng mnh (c 510) vi h l xp c ng knh t 0,5-0,8.
So vi diatomit khng axit ha, cu trc lng
ca diatomit axit ha b thay i, chng ch
yu tn ti dng mnh.

0.06

Da khng axit
ha

0.05
0.04
0.03
0.02
0.01
0
100

150

200

250

300

350

400

450

500

550

Nhit (C)

Hnh 3: Gin TPD-NH3 ca

iatomit axit ha Da
b) Phng php hp ph Pyridine FTIR
khng nh s tn ti ca tm axit
Brnsted (B) v Lewis(L) trong diatomit trc
v sau khi hot ha (axit ha) chng ti tin
hnh o hp ph pyridine trn diatomit bng
phng php ph hng ngoi bin i fourier
(Pyridine FTIR).

L
B

a
b

1700

1442.2

1587.7

1600

1500

d
1400

Wavenumbers (cm-1)

Hnh 4: Gin hp ph PyridineFTIR ca iatomit axit ha Da: a, gii hp 800C;

b, gii hp 1500C; c, gii hp 2500C; d, Diatomite khng axit ha
2. Hot tnh xc tc
nh gi hot tnh xc tc vt liu mao
qun ln (iatomit axit ha Da) i vi phn t
ln, phc tp, chng ti tin hnh phn ng
cracking cn du Bch H. iu kin trong
phn ng cracking cn du Bch H nh sau:
Lng xc tc l 4 gam, nhit phn ng l
4820C, t l xc tc/du l 3, thi gian phn ng
45 giy(s).
T bng 2, nu xt v chuyn ho cn
du Bch H trn cc xc tc th xc tc cng
nghip Arura-FCC c hot tnh cao (75,72%),
trong khi diatomit axit ha c hot tnh rt
ng k (21,46%).
Trong phn b sn phm, xc tc cng
nghip Arura-FCC cho sn phm ch yu l
xng, trong khi diatomit cho
sn phm ch yu l LCO v HCO vi lng
ng k.
Bng 2: Sn phm phn ng cracking cn du
Bch H
Sn phm
(% khi lng)
chuyn ha
H2

Xc tc
Arura
Da
-FCC
75.72
21.46
2.58
1.45

Cc
CH4 + C2H2 + C2H4
C3H8
C3H6
i-C4H10
n-C4H10
n-C4H8
i-C4H8 + C4 H6
Xng (25-216 0C)
LCO (216-360 0C)
HCO (>360 0C)

4.75
1.99
1.06
3.41
3.32
0.60
0.88
3.14
55.02
14.61
8.64

3.14
0.06
0.04
0.08
0.02
0.04
0.03
0.12
16.60
20.37
57.78

IV - KT LUN
Diatomite c axit ha thnh cng bng
phng php lng ng pha hi (CVD), cy
nguyn t nhm vo khung mng iatomit lm
tng axit ca diatomit. Lng tm axit
Brnsted v Lewis trong diatomit axit ha cng
tng so vi diatomit khng axit ha. iu ny
khng nh bi kt qu o pyridineFTIR.
Diatomit axit ha th hin hot tnh rt ng k
trong phn ng cracking cn du Bch H. Sn
phm ch yu thu c l LCO v HCO. Kt
qu ny ha hn tim nng ng dng ca
diatomit axit ha lm pha nn hot ng trong
xc tc FCC.
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Colorado, USA, 425, 412 397 (1994).

mesoporous materials from diatomite and

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