ti

NGHIN CU XC TC MoO
3
/g-Al
2
O
3
BIN TNH BI
Co, Ni CHO PHN NG TNG HP BIO-HYDROFINED
DIESEL (BHD) T DU THC VT
GVHD: PGS.TS HUNH QUYN
SVTH : TIN TRNH
MSSV : 60902943
LP : HC09DK
TRNG I HC BCH KHOA TP.H CH MINH
KHOA K THUT HA HC
B MN KT CH BIN DU KH
LUN VN TT NGHIP
1
GII THIU
PHNG PHP NGHIN CU
KT QU V BN LUN
KT LUN V KIN NGH
NI DUNG
2
GII THIU
Nhu cu
nhin liu
ngy cng
tng
Du m
ngy
cng cn
kit
Nhin
liu sch,
ti to
3
Biodiesel t transester ha
n mn ng c
Gy ra lng mui than bm vo vi phun cao hn
D ng bng hoc c li khi thi tit lnh
Nng lng cung cp t hn diesel ng c yu
C th gy nhim: x phng, kim d, glyxerin, methanol
Qu trnh bo qun nhin liu biodiesel khng c lu
N
h

m
4
Bio Hydrofined Diesel
Sn phm qu trnh x l hydro (hidro processing)
Trn c s phn ng hydro ha v hydro craking
Nguyn liu l ngun du thc vt, m ng vt
Thnh phn khng cha oxy, ch yu l cc HC ging diesel khong
Sn phm c nhiu tnh cht vt tri: ch s cetan cao, nhit chy cao, kh thi sch...
5
C CH PHN NG
(3)
(4)
(1)
(2)
R
1
CH
2
CH
3
+ R
2
CH
2
CH
3
+ R
3
CH
2
CH
3
+ H
2
O (2)
R
1
COOCH
2
R
2
COOCH
R
3
COOCH
2
Xc tc
H
2
R
1
CH
3
+ R
2
CH
3
+ R
3
CH
3
+ CO
2
(3)
R
1
CH
3
+ R
2
CH
3
+ R
3
CH
3
+ H
2
O+ C
3
H
8
(4)
R
1
CH
3
+ R
2
CH
2
CH
3
+ R
3
CH
2
CH
3
+ CO
2
+ H
2
O (1)
6
R
1
COOCH
2
R
2
COOCH + H
2
BHD + H
2
O + CO
2
+
R
3
COOCH
2
Xc tc
H-OCO-C
n
H
2n+1
+ CH
3
CH
2
CH
3
C CH PHN NG
x, y, z: s lin kt pi
hydro ha
craking
7
Vin Du M UOP (M) a vo sn xut xng, diesel v olefin da trn
qu trnh hydrocracking s dng nguyn liu du m ng thc vt. Cc sn
phm bao gm green diesel hay BHD (Bio-Hydrofined Diesel, hoc Bio-
Hydrogenated Diesel), green gasoline v green olefin.
Cng ngh ch to nhin liu diesel sinh hc bng phng php x l hydro
cng c pht trin v thng mi ha quy m nh bi cng ty Neste
Oil ca Phn Lan v bi Nippon Oil ca Nht Bn. Cc bo co ca cc cng
ty ny cho thy BHD thu c c ch tiu cht lng rt tt, p ng tt cc
yu cu ca mt nhin liu s dng trong ng c diesel.
Nghin cu v ng dng BHD trn th gii
8
So snh cc ch tiu ca BHD vi FAME, disel thng thng
Cc ch tiu cht lng
Diesel thng
thng
Biodiesel
(FAME)
Green diesel
(BHD)
% Oxy 0
11 0
% NO
x
trong kh x
Mc c bn +10 0
Hm lng cht thm,% 412
0 0
Hm lng lu hunh, ppm <10
<10 <10
T trng, g/ml 0,84
0,883 0,78
Nhit chy, MJ/kg 43
38 44
im ng c,
o
C -5
-5 15 -30 10
im bt chy,
o
C
70 180 116
Thnh phn ct, 10 - 90% TT 200350
340355 265320
Ch s cetane 40
5065 7090
nht, mm
2
/s 3,7
5,5 4,1
Tnh n nh Tt
Mc c bn Tt
9
Bi Vn Ngc (2008), c thc hin ti Vin nghin cu Xc tc v Mi
trng, Cng ha Php, vi phn ng HDO trn cu t i din l
methoxyphenol, mt trong nhng cu t bn nht trong phn ng HDO.
Mc tiu nghin cu c nh hng cho vic ci thin Bio oil. Nghin
cu da vo nguyn l xc tc qu trnh HDS
H Lu Mnh Qun v cng s, Nghin cu bin tnh xc tc MoO
3
/g-
Al
2
O
3
bng Ni, Co s dng cho qu trnh hydro-deoxi ha (HDO)
Guaiacol (o-methoxy phenol) -PVPRO. nh hng ci thin bio-oil.
Nghin cu da vo nguyn l xc tc qu trnh HDS
Mt s nghin cu tiu biu v BHD Vit Nam
10
PHNG PHP NGHIN CU
Mc ch: Tng hp
xc tc CoMo/ g-Al
2
O
3
v NiMo/g-Al
2
O
3
bng
phng php tm.
o XRD mu xc tc.
Mc ch: Kho st hot
tnh xc tc. nh hng
ca nhit phn ng v
thi gian lu.
Phn ng tin hnh theo
m trong thit b cao p,
nhit cao.
Chng ct sn phm,
kim tra cc ch tiu
TNG HP XC TC TNG HP BHD
11
iu ch CoMo/-Al
2
O
3
iu ch NiMo/-Al
2
O
3
(NH
4
)
6
Mo
7
O
24
.4H
2
O
Ni(NO
3
)
2
.6H
2
O Co(NO
3
)
2
.6H
2
O
Ha tan trong nc
Tm dung dch ln cht
mang (Khuy u, 60
o
C,
qua m)
-Al
2
O
3
Sy 110
o
C, trong 10h
Nung 500
o
C, trong 3h
Xc tc
cn iu
ch
Quy trnh iu
ch xc tc
12
Tch xc tc
Thit b phn
ng cao p
Chng ct
Du u
nnh
Sn
phm
BHD
Xc tc
Quy trnh thc hin phn ng
13
KT QU V BN LUN
Nghin cu xc tc
Kho st hot tnh ca xc tc
nh hng ca nhit
nh hng ca thi gian phn ng
14
Kt qu o XRD mu CoMo/ g-Al
2
O
3
15
Kt qu o XRD mu NiMo/g-Al
2
O
3
16
Kho st hot tnh xc tc
Nguyn liu xc tc Sn phm sau tng hp
Hiu sut thu hi sn phm lng 75%
17
Kt qu GC-MS
Nguyn liu Sn phm
STT TN %
1 N-BUTANE 1,23
2 N-PENTANE 5,6
3 1-PENTENE 1,2
4 1-HEXENE 0,95
5 N-HEXANE 6,85
6 METHYLCYCLOPENTANE 1,65
7 2,4-HEXADIENE 1,07
8 N-HEPTANE 6,41
9 METHYLCYCLOHEXANE 1,67
10 TOLUENE 2,41
11 N-OCTANE 4,66
12 N-NONANE 3,22
13 N-DECANE 2,18
14 N-UNDECANE 1,75
15 N-DODECANE 1,85
16 N-TRIDECANE 1,41
17 N-TETRADECANE 0,69
18 N-PENTADECANE 1,09
STT Tn Cu trc %
1 Tetradecanoic acid (C14:0) 0,07
2 Hexadecanoic acid (C16:0) 11,77
3 Cis-Hexadecanoic acid (C16:1) 0,07
4 Octadecanoic acid (C18:0) 4,35
5 Trans-9- Octadecanoic acid (C18:1) 0,07
6 Cis-9- Octadecanoic acid (C18:1) 22,65
7 Trans-9,12- Octadecanoic acid (C18:2) 0,05
8 Cis-9,12- Octadecanoic acid (C18:2) 54,89
9 Eicosanoic acid (C20:0) 1,23
10 Octadecantrienoic acid (C18:3) 4,72
11 Cis-11-Eicosanoic acid (C20:1) 0,12
Thnh phn ch yu l cc
triglyceride ca C16, C18
C mt cc hp cht HC: ankan,
anken t C4 tr i
18
Kt qu khi dng xc tc CoMo/gAl
2
O
3
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
420
440
460
480
500
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00
N
h
i

0
C
% th tch
ng cong chng ct
0_Nguyn liu
1_Khng xc tc
2_CoMo khng hot ha
3_CoMo sau hot ha
Thng s M1 M2 M3
nht 2,8153 1,9675 1,9124
Ch s acid 55,6 59,3 54,5
Nhit chp chy 73 56 54
im ng c 5 <-10 <-10
Hmlng cn C,% 0,077 0,046 0,042
p sut 30 bar
Nhit 350
o
C
Thi gian 3h
Hmlng 1 %
19
Kt qu khi dng xc tc NiMo/gAl
2
O
3
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
420
440
460
480
500
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00
N
h
i

0
C
% th tch
ng cong chng ct
0_Nguyn liu
1_khng xc tc
NiMo khng hot ha
NiMo sau hot ha
Thng s M1 M2 M3
nht 2,8153 1,6721 1,6837
Ch s acid 55,6 57 62,8
Nhit chp chy 73 51 52
im ng c 5 <-10 <-10
Hmlng cn C,% 0,077 0,043 0,040
p sut 30 bar
Nhit 350
o
C
Thi gian 3h
Hmlng 1 %
20
KT QU GCMS khi thc hin vi 2 loi xc tc
0
2
4
6
8
10
12
14
16
18
20
%
Thnh phn ha hc ca BHD
CoMo/ Al2O3 NiMo/Al2O3
21
Kim tra mt s tnh cht sn phm khi dng 2 loi xc tc
Thng s CoMo/gAl
2
O
3
NiMo/gAl
2
O
3
nht 1,9675 1,6721
Ch s acid 59,3 57
Nhit chp chy
56 51
im ng c
<-10 <-10
Hm lng cn carbon
0,046 0,043
Hm lng HC %
76,62 69,78
Hm lng aromatic %
23,38 30,22
T trng (15
o
C)
0.83326 0.85658
Ch s cetane
52.42 44.64
22
xc tc sau phn ng
<200
o
C *200-350
o
C
*Sau 24h *sau 72h
>350
o
C
23
nh hng ca nhit
Thng s 250 300 350 400
nht 5,5896 2,2034 1,9675 1,7832
Ch s acid 180,6 64,2 59,3 51,3
p sut 30 bar
Thi gian 3h
Xc tc CoMo/gAl
2
O
3
Hmlng 1 %
24
0
50
100
150
200
250
300
350
400
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00
N
h
i

0
C
% Th tch
So snh 4 ng chng ct
1_250 C
2_300 C
3_350 C
4_400 C
nh hng ca thi gian phn ng
0
50
100
150
200
250
300
350
400
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00
N
h
i

,

t

o
C
% Th tch
So snh 4 ng chng ct
1h
2h
3h
4h
p sut 30 bar
Nhit 350
o
C
Xc tc CoMo/gAl
2
O
3
Hmlng 1 %
Thng s 1h 2h 3h 4h
nht 2,0054 1,9912 1,9675 1,8235
Ch s acid 76,1 43,7 59,3 51,4
25
KT LUN V KIN NGH
KT LUN
26
NGUYN LIU XC TC SN PHM PHN NG
Tng hp xc tc
cho qu trnh tng
hp BHD
Kim tra c tnh
cht s b ca xc
tc: kt tinh,
pha tn ti (ph
XRD)
Kho st c
thnh phn ha
hc (GC-MS)
Kho st c
thnh phn ha
hc (GC-MS)
Kho st c
tnh cht ha l
Kho st c
tnh cht ha l
ca sn phm
BHD
Nhit ,
350
o
C
Thi gian,
3h
L mt hng nghin cu va c ngha khoa hc, va c ngha thc tin cao ti
VN trong nh hng cho cng ngh sn xut nhin liu c ngun gc sinh hc.
KT LUN V KIN NGH
KIN NGH
27
Kho st tip cc yu t nh hng ti phn ng nh thay i p sut, % xc tc
So snh kt qu vi mt s nghin cu trc y khi s dng xc tc sunfua ha
Nghin cu su hn v c ch ca phn ng, pha hot tnh ca xc tc
Kho st phn ng tng hp BHD i vi xc tc CoMo, NiMo trn cc loi cht mang khc c
tnh acid yu hn hoc trung tnh nh TiO
2
, ZrO
2
, than hot tnh
Nghin cu kh nng ng dng sn xut biodiesel t cc ngun nguyn liu khc nh du ht
cao su, du thi, m c...nhng loi du thc vt khng c vai tr trong ngnh thc phm theo
phng php hydrocracking.
1. Jose, C.E., Electo, S.L., , Renewable and Sustainable Energy Reviews. 2009. 13 p. 1275-1287.
2. Murugesan, A., Umarani, C.,, Renewable and Sustainable Energy Reviews. 2009. 13 p. 653-662.
3. Apostolakou, A.A., Kookos, I.K., Marazioti, C., Angelopoulos, K.C.,, Fuel Processing Technology.
2009. 90 p. 1023-1031.
4. Sharma, Y.C., Singh, B., , Renewable and Sustainable Energy Reviews 2009. 13: p. 1646-1651.
5. Gerhard, K., in The Biodiesel Handbook. 2005, AOCS Press.
6. Quyt nh s 177/2007/QD-TTg ngy 20/11/2007 ca Th tng Chnh ph.
7. Stella, B., Aggeliki, K., Iacovos, A.V.,, Bioresource Technology. 2009. 100: p. 30363042.
8. U.S. Energy Information Administration (EIA). International Energy Outlook. 2013.
9. Nguyn Khoa Diu H, Tng quan nng lng Vit Nam Phng Kinh t, D bo v Qun l nhu
cu nng lng 2011.
10. ThS. Nguyn Anh Tun, Kin ngh gii php an ninh nng lng Vit Nam. B cng thng, 2012.
11. PGS-TSKH Lu Cm Lc, Cng ngh lc v ch bin du. 2010, Nh xut bn i hc Quc gia
TP.H Ch Minh. 384.

TI LIU THAM KHO

28
CHN THNH CM N
THY C V CC BN !
TRNG I HC BCH KHOA TP.H CH MINH
KHOA K THUT HA HC
B MN K THUT CH BIN DU KH
29
Ngun: Makoto Toba and al; Research Center for New Fuel an d Vehicle Technology
30
HN CH CA BIODIESEL TNG HP THEO PHNG PHP ESTER HO
31
32