TP CH HA HC T.

53(3) 362-366 THNG 6 NM 2015

DOI: 10.15625/0866-7144.2015-00145

NGHIN CU TNG HP V C TRNG XC TC MgO, Co/SiO2

TRONG PHN NG FISCHER-TROPSCH P SUT THNG
V An1*, L Thi Sn1, Trn Thanh Phng1, o Quc Ty2, Hong Trng Ym2
1
Trung tm ng dng v Chuyn giao Cng ngh, Vin Du kh Vit Nam
2
Vin K thut Ha hc, Trng i hc Bch khoa H Ni
n Ta son 12-01-2015; Chp nhn ng 24-6-2015

Abstract
The catalyst samples MgO, 25 %Co/SiO2 with different content of MgO have been prepared by incipient wetness
impregnation method using Mg(NO3)2 solution and 25 %Co/SiO2 support. The catalyst was characterized by XRD,
BET, TPD CO and TPR-H2 methods and atalytic activity was determined by Fischer-Tropsch synthesis reaction at
ambient pressure. The obtained results show that the catalyst has the highest metal dispersal degree and reaction over
this catalyst gave a higher C5+ product distribution than that of 25 %Co/SiO2.
Keywords. Fischer-Tropsch synthesis, cobalt catalyst, promoter MgO.

1. GII THIU bit l loi vt liu SiO2 c phn b mao qun tp

Xc tc cho qu trnh Fischer-Tropsch (F-T)
hin nay cha thnh phn xc tc v cht xc tin
mang trn loi cht mang c din tch b mt ln.
Cht xc tc s dng trong qu trnh F-T ch yu l
Coban (Co) do c ca s hot ng vng nhit
200-250 C, hot tnh v chn lc cc sn phm
C5+ cao, hot tnh rt thp vi phn ng WGS, thch
hp vi nguyn liu c t l H2/CO t 2-2,3. Cc
loi cht xc tin thng thng l cc kim loi qu
nh Pt, Pd v Rh c b sung vi hm lng nh
lm gim kch thc ht Co trn b mt, cht xc
tin ny c th ng vai tr thc y hiu ng hydro
trn y. Ngoi ra, hot tnh ca xc tc Co trong
qu trnh F-T cn c b tr bi cc oxit kim loi
nh CeO, MnO, MgO, do s hnh thnh dng oxit
kim loi bn gia ranh gii ca cc ht Co v cht
mang hoc hnh thnh dng oxit kim loi tng i
tr vi qu trnh kh trn b mt cc ht coban oxit
to cc tm kim loi tch ri nhau gia cc oxit kim
loi xc tin, dn ti tng n nh ca cc ht Co
chng li s kt t trong sut qu trnh kh hoc ti
sinh xc tc [1-5].
i vi cht mang trong cc qu trnh F-T,
-Al2O3 c s dng ph bin nht. Tuy nhin,
cht mang ny c cha tm axit mnh do vy trong
phn sn phm ca phn ng c cha nhiu phn
on t C5-C11. nh hng u tin nhiu sn
phm nhin liu lng trong phn on C12+ nhiu
cht mang c s dng thay th -Al2O3 c
trung t 2-50 nm (MQTB). V vy trong nghin cu
ny, nhm tc gi tin hnh tng hp xc tc Co trn
cht mang SiO2 v s dng MgO nh l cht xc
tin cho qu trnh. Xc tc sau khi tng hp c
c trng bng cc phng php vt l xc nh
nh hng ca cht xc tin MgO n xc tc
Co/SiO2 thng qu nh gi s thay i thnh phn
pha, din tch b mt v phn b l xp, cc trng
thi kh ca oxit Co v c bit l mc phn tn
Co trn cht mang [6-9].
2. THC NGHIM
2.1. Tng hp xc tc
Xc tc MgO, 25 %Co/SiO2 c tng hp bng
phng php tm nhiu ln dung dch Mg(NO3)2 ln
cht mang 25 %Co/SiO2 c sy 110 C. Sau
khi tm mu c nung 550 C trong 4 gi vi
tc gia nhit 3 C/pht thu c xc tc MgO,
25 %Co/SiO2 vi cc hm lng 0,1, 0,2 v 0,4 %
MgO.
2.2. Phn tch c trng xc tc
2.2.1. Ph nhiu x tia X (XRD)
Ph XRD ch yu c s dng xc nh
trng thi pha tinh th coban trn b mt cht mang.
Cc trng thi tinh th ny lin quan mt thit n

362
TCHH, T. 53(3), 2015 V An v cng s
qu trnh kh cc dng coban trn b mt v trng trong 10 pht, v hp ph ha hc CO c tin
thi coban kim loi. Ph nhiu x Rnghen XRD hnh nhit 35 C.
ca mu nghin cu c ghi trn my Brucker D8
Advance (c) ti Phng th nghim Cng ngh Lc 2.3. Thit b tng hp F-T
Ha du v Vt liu Xc tc, trng HBK HN,
ng pht tia Rnghen bng Cu (c bc sng =
1,540 ); gc qut thay i t 5 n 70; bc qut
0,05 v tc qut 0,5 giy.

2.2.2. Hp ph/Nh hp ph nit (BET)

Phng php ny c s dng ch yu xc

nh s thay i din tch b mt v phn b mao
qun khi tm xc tc v oxit xc tin ln cht mang
SiO2. Cc ng ng nhit hp ph - nh hp ph
nit c o bng thit b Micromeritics ASAP
2010, v d liu thu c ti nhit ca nit lng,
77 K. Cc mu phn tch (0,2-0,3 g) c loi kh Hnh 1: Thit b phn ng kh tng hp
300 C qua m trong chn khng 10-6 Torr trc p sut thng
khi o. Din tch b mt c tnh ton t phng 1. FT-B01,2,3: Bnh kh CO, 8. FT-SH09: Thit b
trnh Brunauer Emmett Teller (o a im). H2, AR sinh hn nc lnh
2. FT-F04: Thit b iu 9. FT-T10: Bnh cha
2.2.3. Kh ha theo chng trnh nhit (TPR) chnh lu lng kh sn phm nng
3. FT-M05: Bnh trn kh CO 10.FT-T11: Bnh cha
Qu trnh chuyn trng thi ca oxit coban v v H2 sn phm nh
coban kim loi c xc nh bng phng php 4. FT-D06: Ct tch m xt 11. FT-T12: Bn cha
nc lnh -5 C
kh ha theo chng trnh nhit di dng kh
5. FT-D05: Ct tch m 12. FT-T13: Bm nc
H2. T qu trnh kh ha c th xc nh c hiu silicagel lm mt
qu ca qu trnh phn tn. Cc th nghim TPR 6. FT-R08: Thit b phn ng 13. FT-T13: Bm nc
c tin hnh trong mt thit b phn ng vi dng chnh tng p
hnh ch U lm bng quartz v c kt ni vi mt 7. FT-T15: Bn cha nc
detector dn nhit (TCD). Cc mu xc tc trc
tin c ra trong dng kh Ar ti 350 C loi Xc tc c t trong ng phn ng bng thp
b vt nc. Kh kh l hn hp 10 % H2/Ar c ng knh = 150 mm. Trc tin xc tc c x
np vo thng qua mt b iu khin lu lng l bng argon, sau nng nhit ln 550 C v
dng. Mu c gia nhit t 50 n 800 C vi tc c hot ho bng H2 vi lu lng 5 ml/pht
gia nhit l 10 C/pht. Lng mu a vo 0,2- trong khong 4 gi chuyn ht cc dng oxit
0,5 g. c bit by lnh by nc sinh ra trong coban v coban kim loi. Tip theo, h nhit xc
qu trnh kh. tc xung n nhit phn ng v a hn hp kh
H2, CO c chun b trc (vi t l c tnh
2.2.4. Hp ph xung CO (CO pulse chemisorption) ton ph hp) t bnh trn kh qua thit b lm kh
bng xt v silicagel vo thit b phn ng. Sn
Hp ph CO mt mt xc nh c cc i hp phm lng ca phn ng c ngng t nhit
ph CO mt nhit nht nh t d on -5 C phn tch lng kh. Sn phm ny c
vng nhit phn ng ti u. Mt khc, hp ph phn tch bng thit b GC-MS. Phn sn phm kh
CO cng cho bit dung lng hp ph t xc khng ngng t tip tc c a vo thit b ly
nh c phn tn kim loi trn b mt cht mu t ng sau c xc nh t l thnh phn
mang. Qu trnh hp ph xung CO c o bng bng GC-TCD.
my Micromeritics AutoChem II vi mt thit b
phn ng ch U lm bng quarzt, c kt ni vi 2.4. Thit b phn tch nguyn liu v sn phm
mt detector dn nhit (TCD). Trc khi hp ph
CO, cc xc tc c kh trong dng H2 400 C 2.4.1. Thit b phn tch thnh phn lng
trong 60 pht vi tc gia nhit 10 C/pht, lm
sch 405 C bng He. Lng mu a vo 0,2-0,5 My sc k GC-MS
g. Dng CO c a vo vi tc 15 ml/pht Kh mang: He, 1,5 ml/pht.

363
TCHH, T. 53(3), 2015 Nghin cu tng hp v c trng xc tc...
Ct: DB-5ms: 30 m 0,02 mm 0,25 m 300
290
Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Sample SiO2

Nhit injector: 250 C; split 80: 1 280

270
260

Nhit ct: 50 C gi trong 2 pht, tng nhit

250
240
230

ln 200 C vi tc 10 C /pht, gi 10 pht sau

220
210
200

tng ln 280 C vi tc 15 C /pht, gi nhit

190
180
170

Lin (Cps)
160

ny 2 pht. 150
140
130

Nhit transperline: 280 C 120

110
100

Detector: MS, ch scan.

90
80
70
60
50
40
30

2.4.2. Thit b phn tch thnh phn kh 20

10
0

20 30 40 50 60 70

2-Theta - Scale
File: Son VDK mau SiO2.raw - Type: 2Th/Th locked - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 10 s - 2-Theta: 20.000 - Theta: 10.000 - Chi: 0.0

My sc k GC-TCD
Nhit injector: 50 C (a)
Kh mang: He 1,2 ml/pht (2 bar) 60 0

Nhit ct: ng nhit 70 C gi trong 40 pht 50 0

Nhit Detector: 200 C 0,4%MgO, 25%Co/SiO2

Make up gas: He 20 ml/pht.
40 0

Lin (Cps)
30 0 0,2%MgO, 25%Co/SiO2
3. KT QU THO LUN
0,1%MgO, 25%Co/SiO2
20 0

3.1. c trng xc tc MgO, 25%Co/SiO2 10 0

Khc vi ph XRD ca cht mang SiO2 trn 20 30 40

2-Theta - Scale
50 60 70 80

F ile : So n m au 5% M n- 1% C e -1 0 % C o- Si O2 .ra w - T y pe : 2T h /T h l oc k e d - Sta rt: 20 .00 0 - En d: 8 0.0 00 - S te p : 0 .03 0 - Ste p tim e: 1 . s - T em p.: 2 5 C (R oo m ) - T im e S ta rte d: 1 3 s - 2 -T h e ta : 20 .00 0 - T he ta: 1

hnh 2a, ph XRD ca cc mu xc tc MgO, 25 F ile : So n m au 5% M n- 1% C e -2 5 % C o- Si O2 .ra w - T y pe : 2T h /T h l oc k e d - Sta rt: 20 .00 0 - En d: 8 0.0 00 - S te p : 0 .03 0 - Ste p tim e: 1 . s - T em p.: 2 5 C (R oo m ) - T im e S ta rte d: 1 3 s - 2 -T h e ta : 20 .00 0 - T he ta: 1
F ile : So n m au 5% M n- 1% C e -3 0 % C o- Si O2 .ra w - T y pe : 2T h /T h l oc k e d - Sta rt: 20 .09 0 - En d: 8 0.0 00 - S te p : 0 .03 0 - Ste p tim e: 1 . s - T em p.: 2 5 C (R oo m ) - T im e S ta rte d: 1 3 s - 2 -T h e ta : 20 .09 0 - T he ta: 1
00 -0 43 -1 0 03 (C ) - C ob al t O x id e - C o 3O 4 - Y: 3 3.4 2 % - d x b y : 1. - W L : 1.5 40 6 - C ub ic - a 8.0 84 00 - b 8.0 84 00 - c 8 .08 40 0 - alp h a 9 0.0 00 - b eta 9 0 .00 0 - g a m m a 90 .0 00 - F ac e- c en ter ed - F d -3m (2 27 ) - 8 - 5

%Co/SiO2 trn hnh 2b cho thy cc pc c trng

ca oxit Co3O4 cc gc qut 2: 310, 370, 450, 550, (b)
590, 650. Vi hm lng MgO c trong xc tc Hnh 2: Ph XRD mu SiO2 (a) v ph chng 0,1%,
25%Co/SiO2 t 0,2 n 0,4 % khi lng, ph XRD 0,2% v 0,4% MgO-25%Co/SiO2 (b)
ca cc mu cho thy khng c s khc bit v cc
nh c trng cng nh cng tn hiu. Bng 1: Kt qu phn tch b mt v kch thc
Bng 1 cho kt qu phn tch din tch b mt mao qun ca cc mu nghin cu
ring v phn b l xp ca cc mu xc tc SiO2;
25%Co/SiO2; 0,1 %MgO, 25 %Co/SiO2; 0,2 %MgO, Din tch
Kch thc
25%Co/SiO2; 0,4 %MgO, 25 %Co/SiO2 bng Mu b mt
mao qun ()
phng php o ng nhit hp ph N2. Kt qu t (m2/g)
bng 1 cho thy mu 25 %Co tm ln cht mang
SiO2 c s thay i ng k din tch b mt v phn SiO2 480 60
b l xp so vi cht mang SiO2 ban u. Tuy nhin,
khi thay i hm lng MgO t 0,2 n 0,4 % khi 25%Co/SiO2 465 52
lng, khng thy c s thay i r rt v din tch
b mt BET ca cc mu. Kt qu o phn b mao 0,1%MgO,
461 52
qun cho thy xc tc c kch thc mao qun trung 25%Co/SiO2
bnh [10]. 0,2%MgO,
462 52
Trong qu trnh phn ng kh tng hp thnh 25%Co/SiO2
nhin liu lng, hydro l cht tham gia phn ng 0,4%MgO,
trong pha kh, tn cng vo cc lin kt C-kim loi 460 52
25%Co/SiO2
sau qu trnh hp ph v phn ly CO. thc hin
c iu ny th CO phi c hp ph v phn ly Kt qu t bng 2 cho thy, hm lng MgO b
trn cc tm kim loi. Nh vy cng nhiu tm kim sung vo xc tc nh hng n phn tn kim
loi th kh nng hp ph CO cng ln tng ng loi. Khi thay i hm lng kim loi t 0,1 n 0,4
vi hiu sut chuyn ha cng cao. Bng phng % khi lng MgO, phn tn tng n 8,9 %
php hp ph xung CO c th nh gi s b c hm lng 0,2 %MgO sau gim xung. Tuy
hot tnh ca xc tc qua phn tn kim loi trn nhin, phn tn kim loi Co trn cc mu b sung
b mt cht mang. Kt qu o xung CO xc nh MgO u cao hn mu ban u. Nh vy, mu 0,2
phn tn kim loi c th hin qua bng 2. %MgO, 25 %Co/SiO2 c phn tn ln nht v

364
TCHH, T. 53(3), 2015 V An v cng s
c s dng nghin cu cc trng thi kh pic kh 4 nhit khc nhau. nhit kh 270
Coban trn b mt cng nh nh gi hot tnh xc C xut hin 1 pic kh c trng cho qu trnh
tc bng phn ng kh tng hp CO v H2 thnh chuyn trng thi Co2O3 trn b mt cht mang v
nhin liu lng. Co3O4. nh pic ny xut hin rt r chng t cc
ht oxit Co2O3 trng phn tn ng u. nh th
Bng 2: Kt qu o phn tn kim loi trn cc 2 tng ng vi nhit kh 312 C xut hin
mu xc tc MgO, 25 %Co/SiO2 khng r rng, pic ny c trng cho qu trnh
chuyn trng thi oxit Co2O3 v CoO trn b mt.
Mu phn tn kim loi (%) nh th 3 tng ng vi nhit kh 375 C tng
25 %Co/SiO2 6,8 ng vi qu trnh chuyn trng thi CoO v trng
0,1 %MgO, 25 thi Co kim loi. nh th 4 xut hin vng nhit
%Co/SiO2
7,6 khong 550 C n 600 C c trng cho qu
trnh chuyn trng thi Co-SiO2 v dng kim loi.
0,2 %MgO, 25 i vi gin kh TPR H2 mu 0,2 %MgO, 25
8,9
%Co/SiO2 %Co/SiO2 cc nh pic tng ng vi qu trnh kh
0,4 %MgO, 25 c s khc bit. Trn gin kh ca mu ny ch
7,4 xut hin 3 pic c trng 3 nhit khc nhau. Pic
%Co/SiO2
kh c trng cho qu trnh chuyn trng thi Co2O3
trn b mt cht mang v Co3O4 xut hin nhit
kh 270 C. nhit khong 300 C xut hin pic
kh c cng rt ln tng ng vi qu trnh
chuyn trng thi Co3O4 v Co kim loi trn b mt.
Kt qu trn gin kh cho thy khng phn bit
c cc trng thi kh Co+3 v Co+8/3 v Co+8/3 v
Co do hin tng che ph bi pic c cng ln
hn. Kt qu ny cng cho thy nhit kh cc
trng thi oxit coban v Co gim khong 75 C t
375 C xung 300 C chng t khi a thm cht
xc tin oxit kim loi MgO lm cho phn tn kim
loi trn b mt tt hn dn n lm gim nhit
kh.

3.2. Kt qu nh gi hot tnh xc tc bng phn

Hnh 3a: TPR H2 ca mu 25 %Co/SiO2 ng chuyn ha CO v H2

Phn ng kh tng hp CO v H2 bng xc tc

Hnh 3b: TPR H2 ca mu 0,2 %MgO, 25 %Co/SiO2
Qu trnh kh cc trng thi coban trn cht
mang v coban kim loi c th hin trn gin
kh TPR H2 trn hnh 3 (a v b). Gin kh TPR
H2 ca mu 25 %Co/SiO2 trn hnh 3a cho thy c 3
0,2 %MgO, 25 %Co/SiO2 c tin hnh vi cc
iu kin phn ng nh sau: nhit phn ng 210
C, tc khng gian kh gi 400-1, t l H2/CO =
2/1, thc hin phn ng trong 10 gi p sut
thng. Trc khi thc hin phn ng, xc tc c
hot ha trong dng kh H2 chuyn dng oxit
coban v dng coban kim loi nhit 450 C
trong 5 gi. Kt qu cho thy, xc tc 0,2 %MgO,
25 %Co/SiO2 cho chuyn ha CO, hiu sut C5+
v chn lc C5+ tng ng l 26,23 %, 19,21 %
v 72,97 % so vi 24,57 %; 15,87 % v 64,61 % trn
xc tc 25 %Co/SiO2. Nh vy, xc tc 0,2 %MgO,
25 %Co/SiO2 cho kt qu chuyn ha, hiu sut
v chn lc cao hn xc tc 25 %Co/SiO2. Phn
b sn phm khi thc hin phn ng chuyn ha CO
v H2 bng xc tc ny so vi xc tc 25 %Co/SiO2
c th hin trn hnh 4.
Kt qu cho thy sn phm hydrocacbon phn b
ch yu trong khong t C14-C21 v C22+. Kt qu so

365
TCHH, T. 53(3), 2015
snh cng cho thy, khng c s khc nhau v xu
hng phn b sn phm hydrocacbon gia hai loi
cht xc tc ny. Tuy nhin, xc tc 0,2 %MgO,
25 %Co/SiO2 c phn b sn phm C10+ cao hn xc
tc 25 %Co/SiO2.
Hnh 4: So snh phn b sn phm hydrocacbon trn
xc tc 25 %Co/SiO2 v xc tc 0,2 %MgO,
25 %Co/SiO2
4. KT LUN
tng hp c xc tc MgO, 25 %Co/SiO2
vi hm lng MgO thay i t 0,1; 0,2; 0,4 % khi
lng. Kt qu cho thy thnh phn pha, th tch l
xp cng nh phn b l xp, din tch b mt ca
xc tc khng thay i khi b sung MgO. Hm hm
lng cht xc tin MgO thay i t 0,1 n 0,4 %
khi lng lm tng phn tn Co trn b mt
cht mang so vi mu cha dng cht xc tin. Kt
qu cng cho thy vi hm lng cht xc tin MgO
0,2 % khi lng, xc tc tng hp cho phn tn
ti u.
Kt qu c trng xc tc bng phn ng chuyn
ha CO v H2 trn xc tc 0,2 %MgO, 25 %Co/SiO2
cho chuyn ha sn phm, hiu sut C5+ v
chn lc C5+ tng ng ng l 26,23 %, 19,21 % v
72,97 % cao hn so vi mu xc tc 25 %Co/SiO2.
ng thi kt qu so snh phn b sn phm trn hai
loi xc tc c v khng c cht xc tin MgO cho
thy khng c s khc nhau v xu hng phn b
sn phm hydrocacbon. Tuy nhin, xc tc
Lin h: V An
Trung tm ng dng v Chuyn giao Cng ngh
Vin Du kh Vit Nam
Tng 2, ta nh Vin Du kh Vit Nam
173 Trung Knh, Yn Ha, Cu Giy H Ni
E-mail: anv@vpi.pvn.vn.
Nghin cu tng hp v c trng xc tc...
0,2 %MgO, 25 %Co/SiO2 c phn b sn phm C10+
ln hn xc tc 25 %Co/SiO2.
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