Professional Documents
Culture Documents
VIIC
MC LC
M U
10
13
20
21
22
23
24
24
nh hng n nn kinh t
24
25
25
26
28
28
30
30
I.2.2 Vt liu hp ph du
30
31
31
31
32
32
33
33
35
36
38
39
39
39
40
II.5 NH GI KH NNG HP PH DU
40
40
42
43
43
47
50
52
53
55
III.4 NH GI KH NNG HP PH DU CA CC VT
LIU TRONG H DU - NC
56
57
57
59
60
60
61
62
64
64
65
IV.1 KT LUN
66
67
68
K HIU V VIT TT
PE: Polyetylen
PU: polyuretan
PP: polypropylene
PF: Phenol-formaldehyde
PS: Polystyren
PVA: Poly vinyl alcohol
CNTs: ng nano carbon
SWNTs: ng nano carbon n vch
MWNTs: ng nano carbon a vch
CNFs: si nano carbon
C-CNFs: si nano carbon pht trin trn m carbon
TG-DTA: Phng php phn tch nhit vi sai
FTIR: Phng php ph hng ngoi
SEM: Phng php knh hin vi in t qut
TEM: Phng php knh hin vi in t truyn qua
BET: Phng php ng nhit hp ph
PL: Hin tng pht sng quang ha
CVD: Phng php tng hp lng ng pha hi ha hc
LPG: Kh du m ha lng
C-CNTs (PF): vt liu c to bi CNTs, s dng cht kt dnh l polyme
PF, sau khi carbon ha
C-CNTs (PS): vt liu c to bi CNTs, s dng cht kt dnh l polyme
PS, sau khi carbon ha
C-CNTs (PVA): vt liu c to bi CNTs, s dng cht kt dnh l polyme
PVA, sau khi carbon ha.
C-CNFs: Si nano carbon pht trin trn m carbon
TM TT
Bng cch phi hp nhun nhuyn cc phng php ha hc (tng hp
lng ng pha hi ha hc, CVD) v cc phng php phn tch ha l hin
i (FTIR, BET, TEM, SEM, TG-DTA), chng ti tng hp thnh cng
cc vt liu mi trn c s nano carbon, bao gm ng nano carbon CNTs,
composit C-CNTs, si nano carbon pht trin trn m carbon C-CNFs v
xp CNTs. y l cc vt liu c b mt siu k nc, c kh nng hp ph
chn lc du trong h du nc. Cc vt liu C-CNTs, C-CNFs v xp
CNTs c hnh dng nh sn, khng phi dng bt nn c kh nng ng dng
thc tin rt cao. C th sp xp kh nng hp ph du trong h du nc
ca cc vt liu theo chiu gim dn nh sau: xp CNTs >>>>> CNTs > CCNFs > C-CNTs (PS) > C-CNTs (tm) >> than hot tnh. Bn cnh , vt
liu tm lc trn c s ng nano carbon CNTs c kh nng tch rt tt nc
v du trong h du nc.
M U
Trn du l s c xy ra trong qu trnh khai thc, lu tr, vn chuyn
v s dng du. S c ny khng ch nh hng tiu cc n nn kinh t m
cn gy nh hng nghim trng n mi trng sinh thi.
Cng vi tc pht trin kinh t cao, ti Vit Nam trong thi gian gn
y, cc ngnh cng nghip du kh cng ang pht trin mnh m. c tnh
mi nm chng ta tiu th khong 11 triu tn du v cc sn phm du.
Ngoi ra, Vit Nam cn nm trn tuyn ng hng hi quc t vn chuyn
du t Trung ng n Nht Bn vi lng du vn chuyn ln n 30 triu
tn/nm. iu c ngha l hng nhiu chc triu tn du ang c lu
thng trn lnh th Vit Nam mi nm v ko theo l nguy c xy ra cc s
c trn du l rt ln. Thc t cng cho thy cc s c trn du lin tip
xy ra t nhiu nm tr li y. V d, s c tu Neptune Aries nm 1994 ti
Thnh ph H Ch Minh, s c tu Formosa One nm 2001 ti tnh B Ra
Vng Tu, ba s c khc ti Thnh ph H Ch Minh nm 2003 v 2005,
trong s c nm 2005 rt nghim trng, s c tu M nh nm 2004 ti
min Bc v hng chc s c nh l khc trong c nc v trong ngnh Du
kh.
Cn c theo yu cu khch quan ca mt nn kinh t ang trn pht
trin c th nhn thy nguy c xy ra s c trn du ti Vit Nam chc chn
cn tip tc tng cao trong tng lai sp ti. Ngay trc mt, Vit Nam c
chin lc xy dng cc nh my lc du v iu ny s lm gia tng s vn
chuyn du th t nc ngoi vo Vit Nam. ng trc nguy c ny, vic
nghin cu cc cng ngh ng cu vi s c trn du l mt vn c tnh
cp bch v v cng quan trng.
Ngoi nhng phng php c hc nh s dng phao quy xa b, phao
quy trn b, s dng thit b kiu p v ht chn khng, cn nhiu cng
ngh x l s c trn du nh cng ngh phn tn ha hc, cng ngh
phn hy sinh hc, t ti ch hoc hp ph du m trong , phng php
hp ph c v l gii php thch hp nht v du c th c thu hi vi
nhng nh hng tiu cc ti thiu nht.
Phn ln cc cht hp ph hin ang c s dng x l s c trn
du nh t st, trn chu, len thy tinh u c kh nng hp ph rt thp.
Vt liu xp polyurethane c kh nng hp ph cao hn nhng li rt cng
knh v tnh tng thch v mt ha hc vi cc loi du khc nhau l cha
cao hoc khng x l trit c du.
Xut pht t vic nghin cu c tnh ca vt liu x l du trn chng
ti nhn thy, c th x l mt cch hiu qu vt du trn mt nc, vt
liu phi c 3 tnh cht quan trng sau y:
3
PHN I
TNG QUAN
D=k
, nm
(kN)
Armchair
Zigzag
Chiral
(a)
(b)
10
bn ko
gin di (%)
SWNT
13 - 53
16
Armchair SWNT
126.2
23.1
Zigzag SWNT
94.5
15.6 - 17.5
Chiral SWNT
MWNT
11 - 63 - 150
Inoc
0.38 - 1.55
15 - 50
Kevlar (o chng n)
3.6 - 3.8
2
12
(a)
(b)
13
14
16
19
20
23
26
27
(c)
(d)
31
32
34
PHN II
THC NGHIM
35
: Bnh kh
(2)
: p k
(3)
: Lu lng k
(4)
(5)
(6)
(7)
: Sc k kh
m 2 m1
100
m1
Trong : m2: khi lng mu CNTs sau khi tng hp, m1: khi lng
xc tc s dng.
Cc iu kin vn hnh to ra cc ng carbon nano c a ra
trong bng II.1.
Bng II.1: iu kin tng hp CNTs
iu kin tng hp
Gi tr
30 - 70
70 - 30
Nhit (C)
Vn tc cung cp kh (ml/pht)
630 740oC
48
37
Gi tr
20 30
80 70
Nhit (C)
680oC
Vn tc cung cp kh (ml/pht)
67
38
(N2) nhit 850 C trong thi gian 5h. Cui cng thu c vt
liu C-CNTs, k hiu C-CNTs (PF).
- Vi nha PS: cch lm tng t, vi hn hp gm 0,5g CNT
1,625g xp PS. Cho hn hp vo xy lanh n ra dng hnh tr.
Ct u tng on nh ri tin hnh v tay to cc vin hnh cu.
o
nhit 500 C trong thi gian 3h. Cui cng thu c vt liu CCNTs, k hiu C-CNTs (PS).
II.4 CH TO VT LIU XP CNTs
Vt liu xp CNTs c tng hp bng phng php CVD s dng cc
cht xc tc ferocen v 1,2-dichlotobenzen v ngun carbon. Bt ferrocen
c ha tan trong dichlorobenzene to dung dch c nng 0.06g/ml.
Dung dch ny c bm lin tc vo ng thch anh (2-inch) trong bung t
vi vn tc 0.13 ml/pht. Nhit phn ng c t nhit 860oC. Kh
mang l hn hp kh Ar v H2 c bm vo vi vn tc tng ng l
2000ml/pht v 300ml/pht. Tm thch anh 2 inch 1 inch c t trong
bung phn ng lm vt liu xp carbon pht trin ln. Vt liu xp
CNT sau 4 gi tng hp c ly t bn thch. dy ca vt liu t
khong 0.8 cm n 1 cm.
II.5 NH GI KH NNG HP PH DU
Trong th nghim ny du c dng l du thc vt v du diesel.
Khi lng ring ca du thc vt v du diesel ln lt l 0.9 g/cm3 v 0.84
g/cm3. Cho du loang trn b mt nc sau cho vt liu carbon vo hp
ph u. Kh nng hp ph ca du c tnh bng gi tr Q trong :
41
PHN III
KT QU V
THO LUN
42
Nhit : 650oC
Thi gian : 2h
Cht xc tc : Fe/-Al2O3
43
Cc yu t nh hng
X1, % V
X3, 0C
X2, cm/pht
Mc trn (+1)
70
670
Mc c s (0)
50
650
Mc di (-1)
30
630
20
20
+/- 1.682
+/- 1.682
+/- 1.682
Mc * (+/- 1.68)
33.64
3.364
33.64
1.5
1.0
0.5
0.0
-0.5
-1.0
-1.5
-2.0
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
600
500
LPG (%)
Hnh III.2. Lng CNTs to thnh khi xt tng tc gia nng LPG
(x1) v vn tc dng (x2)
44
M (%) = 572.9708-27.1572*x1+138.3164*x3-8.9059*x1*x1+1.25*x1*x3+26.4408*x3*x3
2.0
M (%) = 572.9708-27.1572*x1+138.3164*x3-8.9059*x1*x1+1.25*x1*x3+26.4408*x3*x3
1.5
NHIET DO (oC)
1.0
0.5
0.0
-0.5
-1.0
-1.5
-2.0
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
900
800
700
600
500
400
900
800
700
600
500
400
LPG (%)
Hnh III.3. Lng CNTs to thnh khi xt tng tc gia nng LPG
(x1) v nhit tng hp (x3)
HA.Hoang-TCC.Hoang - 3D Contour Plot (so lieu S1.sta 10v*17c)
M (%) = 563.9341-25.1599*x2+138.3164*x3+0.2527*x2*x2-23.75*x2*x3+28.53*x3*x3
2.0
M (%) = 563.9341-25.1599*x2+138.3164*x3+0.2527*x2*x2-23.75*x2*x3+28.53*x3*x3
1.5
NHIET DO (oC)
1.0
0.5
0.0
-0.5
-1.0
-1.5
-2.0
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
1100
1000
900
800
700
600
500
400
1100
1000
900
800
700
600
500
400
1225
1200
M (%)
1120
950
800
510
400
0
650
680
710
740
T (oC)
46
47
640 C trong vng 15h v 850 C trong vng 3h c tin hnh. Tuy nhin,
kt qu phn tch FTIR mu sau nung (hnh III.9) cho thy ti cc iu kin
trn PF vn cha b than ha ht. Thc vy, trn ph ca mu sau nung
850oC trong 3h vn thy xut hin cc pic 2921 cm-1 v 2851 cm-1, c
trng cho dao ng ko cng ca vng benzen.
48
Dao ng
ca
vng benzen
(a)
(b)
(c)
(a)
(b)
bn c
Vt liu
C-CNTs (PF)
C-CNTs (PS)
C-CNTs (PVA)
t yu cu
t yu cu
Khng t
Kt qu nh gi bn c hc ca 3 mu C-CNTs c iu ch
iu kin nung nu trn cho thy composite C-CNTs thu c t cht kt
dnh l nha PS v PS c bn c hc t yu cu s dng ca chng ti.
Composit C-CNTs trn c s s dng cht kt dnh l PVA c bn c hc
sau nung khng t yu cu nn chng ti khng nghin cu tip mu ny
na.
nh thu c t knh hin vi in t qut (SEM) ca composite CCNTs t nha PF c trnh by hnh III.12 cho thy rng vi phng i
50.000 ln v 100.000 ln, CNTs v carbon v nh hnh ca qu trnh phn
hy nha PF c mt mi lin kt cht ch, cc ng CNTs c bao bc, gn
kt vi nhau bi cc nguyn t carbon v nh hnh mi to ra hnh III.12 (a)
v III.12 (c). S gn kt ny c th l do qu trnh hnh thnh mng li
khng gian ca nha PF lm cho nhit phn hy ca n rt cao. Nh
bn c ca sn phm ny cao hn nhiu so vi vt liu thu c t nha PVA
v PS. phng i nh hn (10.000 ln) chng ta c th quan st mt
cch bao qut v s phn b ca CNTs. Kt qu c th hin trn hnh III.12
(b).
(a)
(b)
(c)
(b)
(c)
H
nh III.14. Xc nh gc thm t ca vt liu C-CNTs
Kt qu thu c t nghin cu ny cho php khng nh C-CNT l vt
liu c b mt siu k nc.
III.2 TNG HP V C TRNG TNH CHT CA C-CNFs
Carbon nano si iu ch theo phng php m t trong phn thc
nghim c ng knh khong vi chc nm v chiu di xp x 10 m. Cc
carbon nano si gn rt chc vi b mt ca m carbon. Hnh III.15 m t
hnh nh thu c t knh hin vi in t qut (SEM) ca cu to bn ngoi
v cu trc ca mu CNF sau khi c pht trin v nh hnh trn m
carbon.
s pht trin ca CNFs tun theo c ch TIP Growth (hnh III.16). Theo c
ch ny, cc nguyn t carbon to thnh nh s phn hy cc hydrocarbon s
c khuych tn vo bn trong cc tm hot tnh ca xc tc. Sau , chng
s bo ha cc tm xc tc v dn dn y cc tm xc tc tch khi b mt
cht mang v CNFs dn dn c to thnh.
54
55
liu l khc nhau. Khi khi lng ring ca du hay dung mi tng, Q tng
ln. iu ny l hon ton ph hp v gi tr Q c tnh bi t s gia khi
lng vt liu sau khi hp ph v trc khi hp ph. Do th tch xp ca vt
liu hp ph khng i, nn khi khi lng ring ca dung mi hoc du tng
ln, gi tr Q tng ln. Tuy nhin, do qu trnh hp ph cn ph thuc vo rt
nhiu yu t m mt trong s l kh nng tng tc gia cht hp ph v
cht b hp ph nn i khi t trng ca cht b hp ph, mc d cao hn (du
thc vt so vi du DO) nhng gi tr Q li khng cao hn (nh ch ra trong
hnh III.22).
57
H s Q
Ln 1
98,4
5,3
Ln 2
97,9
5,2
Ln 3
98,2
5,4
59
Ln 4
98,6
5,3
H s Q
Ln 1
98,4
58,3
Ln 2
99,0
58,2
Ln 3
98,6
58,9
Ln 4
98,9
58,9
Poly
stylen
(PS)
CNTs
Thng phn
ng
s 1
Toluen
Thng phn
ng
s 2
Kh
x
Kh N2
Thnh
phm
Nung
Kh x
Sy
To hnh
Dung dich
NiNO3
Kh x
Kh N2
Kh x
Sy
Nung
Thnh
phm
(2)
(3)
(1)
(2)
(2)
(1)
Kh LPG
(3)
Kh N2
(3)
Kh H2
(5)
Thnh phm
(4)
(1) : Bnh kh
(2) : Van iu chnh p sut
(3) : Van an ton
(4) : Tm m carbon x l
(5) : Bung t
Hnh III.26. S nguyn l qui trnh iu ch vt liu C-CNFs
Vi thit b qui m nh trn, c th thu c 400 kg vt liu CCNFs/nm.
III.6.3 xut quy trnh ch to vt liu xp CNTs
iu ch vt liu xp CNTs cn tin hnh quy trnh nh sau:
- Bt ferrocen c ha tan trong dichlorobenzene to dung dch c
nng 0.06 g/ml.
- Sau , dung dch ny c bm lin tc vo ng thch anh (6 cm)
trong bung t vi vn tc 0.13 ml/pht. Nhit phn ng l 860oC.
Kh mang l hn hp kh Ar v H2 c bm vo vi vn tc tng
ng l 2000 ml/pht v 300 ml/pht.
- Vt liu xp CNTs c pht trin ln trn tm thch anh (4 cm 3
cm) t trong ng phn ng.
- Vt liu xp CNTs c ly ra t tm thch anh sau 4 gi c khi
lng khong 0.5 g v khi lng ring khong 60 mg/cm3.
H thit b c qui m nh trn c th sn xut c 1 kg xp
CNTs/nm.
62
(2)
(2)
(3)
(1)
(3)
(1)
Kh H2
Kh Ar
(9)
Thnh phm
(8)
(9)
Thnh phm
(6)
(8)
(5)
(4)
(7)
(7)
63
64
PHN IV
KT LUN
V KIN NGH
65
IV.1 KT LUN
IV.1.1 Kt lun v ni dung khoa hc ca ti
ti hon thnh cc nhim v ng k, c th nh sau:
- ti u ha cc thng s ca qu trnh tng hp CNTs t kh
LPG: nng LPG l 31.2 %; vn tc dng kh trong h l 3.2
cm/pht v nhit tng hp l 710 oC. Vi cc iu kin ,
lng CNTs to thnh ln gp 72 ln so vi lng Fe c trong
xc tc.
- xc nh c iu kin thch hp x l nhit cc mu CCNTs (PF), C-CNTs (PS), C-CNTs (PVA) v c trng tnh cht
ca chng. la chn c cht kt dnh thch hp nht l
nha PS, va c iu kin carbon ha mm hn, va cho vt liu
c bn c hc thch hp.
- tng hp c vt liu CNF mang trn tm m carbon, vt
liu xp CNTs v c trng tnh cht ca cc vt liu.
- chng minh c tnh cht siu k nc ca vt liu nano
carbon v nghin cu kh nng hp ph du trong h du nc
ca chng. C th sp xp kh nng hp ph du ca cc vt liu
theo chiu gim dn nh sau: xp CNTs >>>>> CNTs > CNF >
C-CNTs (PS) > C-CNTs (tm) >> than hot tnh.
- thm d kh nng ng dng ca vt liu trong tch cht v x
l s c trn du
- xut qui trnh cng ngh qui m pilot ch to vt liu siu
k nc trn c s C-CNT ng dng x l s c trn du
IV.1.2 Kt lun v cc ni dung khc
ti thc hin vt ch tiu so vi ng k mt s ni dung sau:
Cng trnh cng b
1. Thu Ha Thi Vu, Thu Trang Thi Nguyen, Phuong Hoa Thi Nguyen,
Manh Hung Do, Hang Thi Au, Thanh Binh Nguyen, Dinh Lam
Nguyen, Jun Seo Park, Fabrication of photocatalytic composite of
multi-walled carbon nanotubes/TiO2 and its application for
desulfurization of diesel, Materials Research Bulletin (in press)
2011.
2. Vu Thi Thu Ha, Nguyen inh Lam, Nguyen Thi Thu Trang, Phan
The Anh, Au Th Hang, Preparation of micro/nano composites of
carbon nanostructure/TiO2 and CNT macroscopic shaping their
applications, Catalysis Communication (Revising) 2011.
66
o to
Tham gia o to 01 NCS v S dng Biogas cho ng c t
trong trong c ni dung ng dng c tnh siu k nc ca CNT lu
tr biogas (d kin bo v 2012).
IV.2 KIN NGH
Nhm tc gi ti kin ngh B Khoa hc cng ngh v B Cng
Thng tip tc cp kinh ph pht trin hng nghin cu lin quan n
vt liu CNTs, C-CNTs, C-CNF, c bit l vt liu xp CNTs cng nh ng
dng tch cht v hp ph chn lc du trong h du nc ca cc vt liu.
y l nhng loi vt liu mi vi rt nhiu tnh nng c bit u vit m
nhng vt liu thng thng khng p ng c.
Nhng nghin cu chuyn su, c tnh cht h thng v bi bn s gp
phn sm a nhng loi vt liu ny ng dng trn thc tin.
67
68
70
71