Tap chi khoa hgc trffdng Dgi hgc Quy NhOn TQP IV, sd 2 nam 2010<br />
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NGHIEN ClfU CHE TAO XUC xAC Ni-Mo/y-Al^O<br />
CHO P H A N ifNG HYDROTREATING<br />
<br />
LE VAN HI^U*. PHAN THI THUY TRANG^<br />
<br />
I.M6DAU<br />
Hidn nay, 6 nhiim moi trtfdng Id mpt vd'n d l ed'p bdch nhd't dang dtfdc todn nhan<br />
loai quan tdm. Cd rd't nhilu yd'u td ldm dnh htfdng dd'n moi trtfdng vd mpt trong nbtfng<br />
yd'u td quan ti-png dd la chd't Itfdng nhidn bdu dtfng cho dpng cd. Vide sdn xuat nhidn<br />
lieu sach bao gdm loai trtf cdc thanh phan cd hai trong nhidn bdu vd cac loai ca'u tii dpe<br />
hai ti-ong khdi tiidi cua dpng cd, ddc biet la ham Itfdng Itfu huynh, nitd, cdc oxit kim<br />
loai... trong nhidn lieu. Vi nd khdng chi lam dnh btfdng dd'n cha't Itfdng sdn pham, dnh<br />
htfdng dd'n dpng ed may mdc khi suf dung ma cdn cd tde dpng xd'u dd'n moi trtfdng vd stfc<br />
khoe cua eon ngtfdi. Mpt trong eac bidn phap de nang eao chd't Itfdng nhidn bdu la qua<br />
trinh bydrotreating vdi xuc tac Ni-Mo/Y-Al203. He xdc tde cho qua trinh ndy khong<br />
nhffng chi diing trong ede qua trinh chd' bid'n dau ma nd eon dtfdc tfng dung rpng rdi<br />
trong qua trinh xtf ly sdn pham long eua eong nghe chd' bid'n than da.<br />
2. T H U C N G H I E M<br />
<br />
2.1. Dung cu va hda chd't<br />
+ Chd't mang Y-AI2O3 dang bat tron (Phap).<br />
+ Mudi amoni polymolipdat (NH4)gMo,024.4H20 (Nga).<br />
+ Mudi niken nitrat Ni(N03)2.6H20 (Trung Qudc).<br />
+ Binh tam chdn khong, bdm but chan khong, tu sa'y, 16 nung,...<br />
2.2. Phvtdng phap nghidn cii'u<br />
Xuc tac Ni-Mo/Y-Al203 dtfdc tdng hdp bang pbtfdng phdp td'm cac pha boat dpng ldn<br />
chd't mang, lan Itfdt hai dung dich cac mudi (NRJ^Mop^^.AHp vd Ni(N03)2.6H20 ldn<br />
b l mat chd't mang Y-AI2O3. Qua binh ngdm tam cdc mudi ndy dtfdc tid'n bdnh nhilu lan,<br />
mdi lan tfng vdi tbi tich chd't long ldn nhd't ma chat mang y-AXp^ hd'p phu bdo boa. Sau<br />
mdi lan ngdm tam tid'n hanh sa'y vd nung d cdc nhiet dp khae nhau brong khodng thdi gian<br />
nha't dinh. Trtfdc kbitid'nbdnh phdn tfng, xuc tde dtfdc boat hda d dilu kidn ngbidn ctfu.<br />
2.3. Cac phiAftig phap xac dinh d^c triAig cua xuc tac<br />
Pbtfdng phdp TPR dtfdc tid'n bdnh trdn may Autochem II2902 Micromeritics tai<br />
phong tbi nghidm Ipc boa dau vd vdt lieu xuc tac, Dai hpc Bdch khoa Hd Npi.<br />
- Phd XRD cua cdc mau dtfdc chup trdn may PCM-Bruker D8 (Dtfc) tai Khoa<br />
Hoa hpc, Dai hpc Khoa hpc Ttf nhidn, Dai hpc Quo'e gia Hd Npi.<br />
12 Lfe VAN HI^U, PHAN THI THUY TRANG<br />
<br />
- Didn tich bl mdt dtfdc do bdng pbtfdng phdp BET trdn mdy Micromerictics ASAP<br />
2010 tai Phdng thi nghidm cdng ngh^ Ipc hda diu vd vdt li^u xdc tde, Dai hpc Bdch<br />
khoa Hd Ndi.<br />
Hinh dnh SEM vd EDS dtfdc chup trdn mdy Hitachi S4800 tai Phong tbi nghidm<br />
trpng did'm qudc gia vat lipu vd linh kidn difn tii, Vi^n Khoa hoc vdt bdu.<br />
Hinh dnh TEM dtfdc chup trdn mdy JEM 1010/JEOL(Nhat) tai Vidn v$ sinh dich<br />
te Trung tfdng.<br />
Pbtfdng phdp nghidn ctfu boat tinh xuc tde dtfdc tbtfc hidn d he phdn tfng vi ddng<br />
Microaetivity Test Unit MAT 5000 cda Zeton (Canada) vd hd thong phdn tfng dp suat<br />
eao ciia Vinci Technologies (Phdp), Trtfdng Dai hpc Bdch khoa Hd Npi.<br />
2.4. Cac phtfdhg phap danh gid chi tidu chd't \\i(fng cua nguydn li^u vd san ph^m<br />
- Pbtfdng phdp bu^'nb quang tia X (XRF-X Ray Fluorescence) xdc djnh bdm Itfdng<br />
Itfu huynh ciia nguydn bdu vd cdc mau sdn pham tai Trung tdm hda nghidm xdng dau<br />
quan dpi Ha N6i.<br />
- Pbtfdng phdp diim anilin xdc dinh hdm Itfdng bydrocacbon tiidm, pbtfdng phdp<br />
xac dinh dd sang ciia nhidn bdu ldng vd tinh ehi sd diesel cua nhidn bdu long dtfdc tiiifc<br />
bidn tai Phong tbi nghidm cdng nghe Ipc hda dau vd vat bdu xuc tde, Khoa Cong nghe<br />
hda bpe, Dai bpe Bach khoa Hd Npi.<br />
3. KET QUA VA THAO LUAN<br />
3.1. D$c triAig cua cha't mang va xuc tac<br />
3.1.1. Di$n tich be mgt rieng cua chat mang J-AiPj sff dung<br />
Bang pbtfdng phdp do hd'p phu vat ly, difa trdn dtfdng hd'p phu vd nhd hd'p phu<br />
nitd kd't hdp vdi pbtfdng trinh hd'p phu dang nhiet BET xdc dinh dtfdc didn tich b l mat<br />
ridng eiia Y-Al^O, Id 200,5641 mVg. Dtfdng kinh Id xd'p khoang 1(>4,1647A°. Kd't qua<br />
ndy cho thd'y y-Mp^ Id vat bdu khd xdp, b l mat ridng ttfdng ddi ldn tiuch hdp diing lam<br />
chat mang cho phdn tfng bydrotreating.<br />
3.1.2. Gian dd TPR cda xdc tac Ni-MotfAipp%mO-l2%MoOJ^Aip^<br />
Ttf kd't qud d dd tiii cho tha'y mlu<br />
Ni-Mo/Y-Al203 xud't hidn 4 pic kbii tai nhidt<br />
dp 180°C, 4060C, 542,3°C vd 598,2°C. Qud<br />
tiinh khuf bat dau tai nhidt dp khodng 150°C<br />
dien ra qud trinh khii Mo^ tiidnh Mo^+vd<br />
kd't thuc tai nhidt dp 598,2°C tfng vdi qud<br />
trinh khtf cua NiO, NiAip^. Pic khi^ tai<br />
nhidt dp la 406°C xud't bidn pic ddc tiiftig<br />
cho qua trinh khuf ciia pha NiMoO .<br />
Vdy chpn nhidt dp boat boa xdc tac<br />
cho qud trinh hydroti-eating id 400°C. r^ u i n?. A> TI^T> ^ - .<br />
Hinh 1. Gidn do TPR cua xuc tde Ni-Mo/^-Al 0<br />
NGHlfeN ctfu CH^ TAP XUC TAC Ni-Mo/y-AiPj CHO PHAN LfNG HYDROTREATING 13<br />
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3.1.3. Gian do nhieu XQ tiaX cua hf xdc tac Ni-Mo/y-Alflj<br />
A • •<br />
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2%NiO-12%Mo03/yAhO. S^'AiW^^<br />
I<br />
12%Mo03/iAhO: ,^^^^h^,<br />
<br />
/,<br />
.h.^<br />
Ai^YA<br />
V..u^\A.^*"^'<br />
70 80<br />
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Hinh 2. Gidn do nhieu xa tinh thi cua mdu y-AiPy 12%MoO/iAiPy 2%NiO-<br />
I2%Mo0^t{Aip^ (#); -^Aipy f ^ ) ; NiMoO^<br />
Phd XRD eiia mdu 12%Mo03 cho thd'y chi xud't bidn ede pie ddc trtfng cho<br />
Y-AI2O3 md khdng cd ede pic ddc trtfng cho M0O3. Dilu do chtfng td rang Mo phdn tan<br />
tdt trdn bl mat chd't mang bode kich thtfde tinh the M0O3 r^t be (d thi 4: Ty trgng vd chi sd diesel cda sdn phdm theo thdi gian khi %NiO thay ddi<br />
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Dd thi trdn cho tha'y tai gid tri 2%NiO cho chi sd diesel eao nha't. Dilu ndy pbii<br />
hdp vdi quy ludt bid'n ddi eua mat dp quang, diim anibn vd ty trpng. Thdng qua chi sd<br />
diesel biet dtfdc cdc thdnh phan eua bydrocacbon no nhtf parafinic vd naphtenic tdng<br />
ldn. Dilu dd chtfng to rang tai hdm Itfdng 2%NiO phdn tfng hydro boa xdy ra manh vd<br />
nang eao dtfdc chi sd diesel.<br />
Vdy cdc kd't qud trdn cho thay rang xuc tac Ni-Mo/Y-Al203 cho boat tinh tdt nhd't<br />
[ khi CO hdm Itfdng 12%Mo03 vd 2%NiO.<br />
4. KET LUAN<br />
Qua qud tiinh tdng hdp xtfc tde Ni-Mo/Y-Al203 vdi mue dich siJ dung cho qua trinh<br />
bydrotreating di ndng ed'p ede phan doan dau mo da. thu dtfdc mpt sd kd't qud sau:<br />
-I- Dilu chd' dtfdc xtfc tde Ni-Mo/Y-Al203 vdi bdm Itfdng NiO, M6O3 tiiay ddi vd<br />
tim ra dtfdc tiidnh pbIn tditfUciia no la 2%NiO vd 12%MoO,.<br />
+ Khdo sat dtfdc cdc ddc tiiTng boa ly eua cha't mang vd hd xuc tde 2%NiO-<br />
18 Lfe VAN m i u , PHAN THI THUY TRANG<br />
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12%Mo03/Y-Al203qua cdc kd't qud phdn tich TPR, XRD, SEM, EDS vd TEM. Qua do<br />
tao dtfdc pha NiMoO^ Id tiln chd't di tao ra pha NiMoS. Nhtf vdy, dd tdng hdp dtfdc xuc<br />
tde 2%NiO-12%Mo03/g-Al203 c6 boat tinh tdt cho qud trinh hydroti-eating.<br />
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TAI LifeU THAM KHAO<br />
[1] D. V. Ttfdng, D^ng hgc xiic tde, Trtfdng Dai hpc Bdch khoa Hd Npi, Nhd xua't bdn<br />
Khoa hoe vd Ky thudt (2006).<br />
[2] T. Kabe, A. Ishihara, W. Qian, Hydrodesulfurization and Hydrodenitrogenation<br />
Chemistry and Engineering, Kodansha Ltd, Tokyo (Japan), WILEY-VCH Verlag<br />
GmbH, Weinheim (Federal Republic of Germany), (1999).<br />
[3] M. A. Dominguez-Crespo, E.M.Aree-Estrada, A.M.Torres-Huerta, L.Diaz-Garcia,<br />
M. T. Cortez de la Paz, Support effects on bydrotreating activity of NiMo catalysts,<br />
Materials Characterization (2006).<br />
[4] L. Carolina, A. Jorge, S. R. Mohan, M. Gustavo, A comparative study on the effect of<br />
promoter content of hydrodesulfurization catalyst at different evaluation scales. Fuel<br />
86 (2007), 1232-1239.<br />
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SUMMARY<br />
RESEARCH ON THE PREPARATION OF NiMo/Y-AiPj CATALYSTS<br />
FOR HYDROTREATING REACTION<br />
<br />
Le Van Hieu. Phan Thi Thuy Trang<br />
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Hydrotreating catalysts are used to remove sulfur, niu-ogen and otiier contaminants<br />
from refinery feedstocks and petroleum products. NiMo catalysts supported on Y-Al 0,<br />
with different textural properties have been studied in the hydrotreating. The catalysts<br />
containing l-4%NiO and 8-12%Mo03 o" Y'Aip, were prepared by impregnation method<br />
The catalysts were characterized by BET, X-ray diffraction (XRD). TPR studies of the<br />
NiMo were analysed to correlate tiieir hydrotreating properties. TEM and SEM-EDS studies<br />
support the synergetie interaction between Ni sites and MoOx species. The results showed<br />
that NiMo/Y-Aip3 catalysts had grateful activity for tiie hydrotreating processes.<br />
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"Khoa H6a hoc, Tnfdng Dai hoc Bdch khoa Ha N6i<br />
•"Khoa H6a hoc, Tnrdng Dai hoc Quy Nhdn<br />
Ngay nhan bai: 05/02/2010; Ngay nhSn dSng: 12/03/2010.<br />
Tap chi khoa hgc trUdng Dgi hgc Quy NhOn Tgp IV, sd 2 ndm 2010<br />
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^ AP DUNG PHlTCfNG PHAP DAY HQC KIEN TAO-XUCfNG TAC<br />
DE REN LUY|:N KI NANG THIET KE KE HOACH BAI D ^ Y H 6 A HQC<br />
CHO SINH VIEN KHOA H 6 A HQC CAC TRl/dNG DAI HQC<br />
<br />
NGUYIN THI KIM ANH», DANG THI OANH"<br />
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^<br />
l.DAT VANDE<br />
Mue tidu ciia vide ddi mdi pbtfdng phdp day bpe d cdc trtfdng DHSP noi chung vd<br />
khoa Hoa bpe noi ridng la ddo tao sinh vidn sau ndy ra trtfdng trd thdnh nbtfng thay co<br />
gido ttfdng lai, ngodi vide trang bi cho sinh vidn (SV) nhffng Idd'n tbtfc ed bdn ve mon<br />
Hoa hpc con trang bi cho SV ede ki nang nghi: Mpt trong nhffng kl ndng nghi quan<br />
trpng la Id ndng day bpe. Nbtfhg tbtfc td' bien nay, d ede trtfdng phd thong nhilu giao<br />
vidn vd sinh vidn stf pham ndm cuo'i ebtfa nam dtfdc bdn chd't eua cac pbtfdng phap day<br />
bpe tich ctfc (day bpe theo li tiiuye't boat dpng, day bpe theo H thuyd't kid'n tao, stf pham<br />
ttfdng tac, day bpe theo b thuye't khdm phd,...) theo dung bdn chd't vd cae dinh htfdng<br />
ciia chung. Do vdy, vide td ehtfe cac boat dpng bpe tap eua bpe sinh can dung mtfc de<br />
the hidn dung net ddc thii vd phat buy tich ctfc cac pbtfdng phdp day bpe ndy.<br />
Trong ren luydn ki nang day hpc cho sinh vidn eo rat nhieu Id nang, vi du: Ddt<br />
va'n di eiia bdi gidng. Id nang bilu didn tbi nghidm kd't hdp vdi ldi noi ciia gido vidn,<br />
tdp thid't kd'bdi day (soan gido dn), dtf gid vd bid't each phdn tich mpt gid day ddng thdi<br />
tap gidng day mpt trich doan bdi day bode tid't bpe bp mdn,.... Tuy nhidn, trong cae Id<br />
nang day hpc can ren luydn cho sinh vidn trtfdng stf pham, theo chung toi vide bid't each<br />
phan tich mpt gid day vd thid't kd' kd' hoach bai bpe eo stf dung cae pbtfdng phap day bpe<br />
xac dinh Id quan trpng vd can thid't de tiitfc hidn vd ren cae Id ndng day bpe tie'p theo.<br />
Pbtfdng phdp day hpc kid'n tao-ttfdng tac Id mpt pbtfdng phdp tftf vidt trong vide<br />
ren ki ndng thid't kd' kd' hoach bdi day cho sinh vidn.<br />
2. NOI DUNG<br />
2.1. To chii'c cho sinh vidn nghidn cuTu cd sd li ludn ciia phtfdng phap d^y hpc kid'n<br />
t^o-ttfdng tac<br />
Cdn ctf vdo npi dung eiia phtfdng phap day bpe kid'n tao-ttfdng tac, sinh vidn cin<br />
ngbidn ctfu cd sd b ludn eiia pbtfdng phap vd trao ddi nhdm theo cac vd'n d l sau:<br />
a) Bdn chd't ciia phtfdng phdp kid'n tao-ttfdng tde, net ddc tiiii ciia pbtfdng phap,...<br />
(ndu va'n d l cho smb vidn thdo ludn, cdc npi dung ed ban vl pbtfdng phap can nam vffng).<br />
b) D l xud't cdc bidn phap de tim hieu cac kid'n tbtfc da cd ciia hpc sinh vl bai bpe<br />
(sinh vidn can xdc dinh cac kid'n tbtfc bdn quan dd'n bdi hpc da dtfdc hpc d trtfdng trung<br />
bpe cd sd, d cae cbtfdng trtfdc do, bai trtfdc do, d l xud't eac phid'u dilu ti-a, eac cdu hoi<br />
Idem tra mtfc dp nam cac idd'n tiitfc lidn quan dd'n bdi hpc ma bpe sinh da dtfdc hpc,...).<br />
NGUYIN THI KIM ANH, DANG THI OANH<br />
20<br />
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c) Dl xud't cdc bidn phdp dl tim hiiu cdc btfdng vl kid'n tbtfc hpc sinh mudn bi^t<br />
theo chu di cua bdi bpe vd cdc tdi lidu c6 tbi tim bilu npi dung cin thid't.<br />
d) Cdc mditiTTdnghpc tap cin chuan bi dl giiip hpc sinh ki^n tao ki^n tbtfc.<br />
Cbu£n bi cdc tbtf mue, tdi bdu tham khdo cho bdi day theo phtfdng phdp day hpc kien<br />
tao-ttfdng tde (vi du nhtf trang web hpc t$p); cdc kid'n tbtfc, ki ndng, thi nghidm, phtfdng<br />
tidn tnjfe quan, pbIn mim,...<br />
e) Dtf kid'n ede boat ddng bpe tdp (cbinb, chu y^u) cin td chtfc cho hpc sinh ti-ong<br />
mdt gid hpc hda bpe theo cdc dang bdi hpc thuyd't, dinh ludt; nguydn td vd chat; 6n tap,<br />
luydn tap; bdi tbifc bdnh vd cdc boat ddng hpc tap cin dtfdc td chtfc theo phtfdng phdp<br />
day bpe kid'n tao-ttfdng tde.<br />
2.2. Giang vidn tid'n hanh cho sinh vidn thao ludn nhdm<br />
Nbtfng bpe pbIn dp dung pbtfdng phdp day hpc ki^n tao-ttfdng tde gidp rdn luydn<br />
ki ndng thid't ke kd' hoach bdi day nhtf:<br />
- Hpc phan Pbtfdng phdp day bpe cu the (gidng day cdc cbtfdng mue d trtfdng phd<br />
tiidng) vd bpe phan Thi nghidm tbtfc bdnh pbtfdng phdp day hpc hda hpc. Dtfdc dp dung<br />
cho sinh vidn nam tbtf 3 trong vide thid't kd'tilebdoan bdi day.<br />
Hpc phan ren luydn nghidp vu stf phamti-ongday bpe hda hpc dtiiTdngphd<br />
thdng dtfdc dp dung cho sinh vidn ndm tbtf 4 trong vide thid't ke tid't hpc bode bdi day.<br />
Trong mdi td thtfdng gdm 16 dd'n 20 sinh vidn.<br />
De td ehtfe cho sinh vidn thdo ludn cdc vd'n dl trdn, chung toi dp dung thii thuat<br />
trong bpe tap ddng dang, bpe tap phdi hdp vd hpc tap hdp tde vd siJf dung ed'u tnic<br />
Jigsaw. Gidng vidntid'nhanh chia nhdm (mdi td cd 16 sinh vidn dtfdc chia thdnh 4 nhdm,<br />
mdi nhom cd 4 thdnh vidn) vd td chtfc cho sinh vidn gidi quyd't 4 vd'n di ndu ra theo cac<br />
btfdc ldm vide nhtf sau:<br />
HOAT DQNG Ctx G I A N G VIEN HOAT DQNG CUA SINH VIEN<br />
1. Thanh lap nhdm hdp tac mpt each ngau Tham gia vdo cdc nhdm vd phdn chia danh<br />
nhidn vd nhdm ndy gpi Id nbdmgd'c. sdeh tiieo sdtiitfttf 1, 2, 3,4.<br />
2. Phdt cho mdi thdnh vidn trong nhdm Cdc tiidnh vidn 1, 2, 3, 4 nhdn nhiem vu<br />
mpt vd'n dl thdo luan. Thdng bdo thdi vd ttf ngbidn ctfu npi dung vd'n dl dtfdc<br />
gian ddnh cho sinh vidn ttf nghidn ctfu. phdt.<br />
3. Thanh lap nhdm chuydn gia. Thdng Thdnh vidn ttf cdc nhdm khae nhau cd<br />
bdo thdi gian thdo luan trong nhdm chung chii dl gap nhau de thao luan trong<br />
chuydn gia. Lln Itfdt theo doi stf thdo mpt nhdm mdi.<br />
luan trong cdc nhdm de cd nhffng gdi y, Trong khi thdo ludn, cdc thdnh vidn trao<br />
dinh btfdng trpng tdm kid'n tbtfc cho cdc ddi vd tap luydn vl edch tiinh bay npi ,<br />
chuydn gia, giup dd sinh vidn vl npi dung ngbidn ctfu cho nhdm gd'c cda minh.<br />
dung pbtfdng phdp trinh bdy.<br />