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B CNG THNG

VIN HA HC CNG NGHIP VIT NAM

VIIC

NGHIN CU CH TO VT LIU MI HP PH CHN LC DU


TRONG H DU NC C KH NNG NG DNG TRONG CC
QU TRNH TCH CHT V TRONG X L S C TRN DU
Thuc Nhim v nghin cu thng xuyn Phng Th nghim trng im
Cng ngh lc, ha du nm 2011

Ch nhim ti: PGS. TS. V Th Thu H


9015

H ni, thng 1/2012

MC LC
M U

PHN I. TNG QUAN

I.1 TNG QUAN TNH HNH NGHIN CU NC NGOI

I.1.1 Vt liu ng nano carbon

I.1.1.1 Cu trc ca ng nano carbon

I.1.1.2. Cc tnh cht c bit ca ng nano carbon

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I.1.1.3 Cc phng php tng hp ng nano carbon

13

I.1.1.4. Cc ng dng ca ng nano carbon

20

I.1.2. Si nano carbon

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I.1.3 Vt liu ng nano carbon pht trin trn m carbon

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I.1.4 Vt liu xp ng nano carbon

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I.1.5 ng dng cc vt liu hp ph trong s l s c trn du

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I.1.5.1 nh hng ca s c du trn

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nh hng n nn kinh t

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nh hng nghim trng n i sng sinh vt

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nh hng nghim trng n i sng con ngi

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I.1.5.2 Phn loi vt liu hp ph

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I.1.5.3. Yu cu k thut ca cc loi vt liu hp ph du

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I.1.6 ng dng cc vt liu siu k nc trong qu trnh tch cht

28

I.2 TNG QUAN TNH HNH NGHIN CU VIT NAM

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I.2.1 Vt liu ng nano carbon v si nano carbon

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I.2.2 Vt liu hp ph du

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I.2.3 S c trn du ti Vit Nam v bin php khc phc

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I.2.3.1 S c trn du tu Neptune Aries

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I.2.3.2 S c trn du Formosa One

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I.2.3.3 S c trn du tu Fortune Freighter

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I.2.3.4 S c trn du tu Hng Anh

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I.2.3.5 S c trn du tu Kasco Monrovia

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I.3 KT LUN TRN C S PHN TCH L THUYT

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PHN II. THC NGHIM

35

II.1 CH TO NG NANO CARBON (CNTs)

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II.2 CH TO SI NANO CARBON (CNF)

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II.3 CH TO VT LIU NG NANO CARBON PHT TRIN


TRN M CARBON (C-CNTs)

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II.3.1 Nguyn liu

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II.3.2 Qui trnh

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II.4 CH TO VT LIU XP T NG NANO CARBON (XP


CNTs)

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II.5 NH GI KH NNG HP PH DU

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II.6 THM D KH NNG TCH DU TRONG H DUNC

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PHN III. KT QU V THO LUN

42

III.1 NGHIN CU CNG NGH IU CH VT LIU NG


NANO CARBON PHT TRIN TRN M CARBON (C-CNTs)

43

III.1.1 Ti u ha qu trnh iu ch ng nano carbon

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III.1.2 Nghin cu tng hp vt liu ng nano carbon trn m


carbon (C-CNTs)

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III.1.3 c trng tnh cht ca vt liu ng nano carbon trn m


carbon (C-CNTs)

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III.1.4 Tnh cht siu k nc ca vt liu composite ng nano


carbon trn m carbon (C-CNTs)

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III.2 TNG HP V C TRNG TNH CHT CA SI NANO


CARBON (CNFs)

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III.3 TNG HP V C TRNG TNH CHT CA XP NG


NANO CARBON (XP CNTs)

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III.4 NH GI KH NNG HP PH DU CA CC VT
LIU TRONG H DU - NC

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III. 5 THM D KH NNG NG DNG CA VT LIU


TRONG QU TRNH TCH CHT V TRONG X L S C
TRN DU

57

III.5.1. Thm d kh nng ng dng vt liu trong qu trnh tch


cht

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III.5.2. Thm d kh nng ng dng vt liu trong x l s c trn


du

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III.6 XUT QUI TRNH CNG NGH CH TO VT LIU


SIU K NC T NANO CARBON QUI M PILOT

60

III.6.1 xut quy trnh cng ngh ch to ng nano carbon trn


m carbon (C-CNTs (PS))

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III.6.2 xut quy trnh ch to vt liu si nano carbon trn m


carbon (C-CNFs)

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III.6.3 xut quy trnh ch to vt liu xp ng nano carbon (xp


CNTs)

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III.6.4 nh hng ch to vt liu quy m cng nghip

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III. 6.5 nh gi s b hiu qu kinh t v ngha thc tin

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PHN IV. KT LUN V KIN NGH

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IV.1 KT LUN

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IV.2 KIN NGH

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TI LIU THAM KHO

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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

- Hp ph chn lc du trong h du nc, tc l phi c tnh cht k


nc, a du
- C khi lng ring nh c th ni ln mt nc
- C th chit c du khi vt liu ti s dng
p ng cc yu cu trn, vt liu trn c s nano carbon l mt
trong nhng ng c vin tt nht hin nay.
Nhng nghin cu thm d trong thi gian gn y ca nhm nghin
cu chng ti cho thy c th ch to c loi vt liu mi trn c s hn
hp C-CNTs (carbon v ng nano carbon) t cc ngun nguyn liu trong
nc c tnh nng hp ph du rt tt, rt thch hp cho vic x l s c trn
du v c bit, c th x l trit c cc vt du loang trn mt nc. Kt
hp cc phng php c hc vi phng php hp ph bng vt liu ny chc
chn s gip x l mt cch hiu qu s c trn du, mang li s trong sch
cho mi trng. Ngoi ra, vi tnh cht siu k nc v tnh cht hp ph
chn lc du trong h du nc, vt liu ny cn ha hn c nhiu ng dng
hn na trong cc qu trnh ha hc v x l mi trng.
V l do , ti t ra mc tiu nghin cu ch to vt liu mi trn
c s carbon-ng nano carbon (C-CNTs) c tnh cht siu k nc, c kh
nng hp ph chn lc du trong h du nc ng dng trong vic x l
du trn. C th l s nghin cu qui trnh cng ngh qui m phng th
nghim ch to vt liu siu k nc trn c s C-CNTs v nghin cu thm
d cc ng dng ca vt liu trong qu trnh tch cht v x l s c trn du.

PHN I
TNG QUAN

I.1 TNG QUAN TNH HNH NGHIN CU NC NGOI


I.1.1 Vt liu ng nano carbon CNTs
I.1.1.1 Cu trc ca CNTs
Cc ng nano carbon (Ting Anh: Carbon nanotube - CNTs) l cc
dng th hnh ca carbon.
ng nano l mt loi cu trc fullerene. ng nano c dng hnh tr,
ng knh c mt vi nanomet, di c th ln ti vi milimet, vi t nht
mt u khp kn c dng mt bn cu, cu trc buckyball. ng nano carbon
c cu trc rng, vi cc vch c to bi cc lp v carbon, c gi l
graphene. C hai loi ng nano carbon chnh: ng nano n vch (SWNT) v
ng nano a vch (MWNT) [11].

Hnh I.1. Cu trc fullerence


Bn cht ca lin kt trong ng nano carbon c gii thch bi ha
hc lng t, c th l s xen ph orbital. Lin kt ha hc ca cc ng nano
c cu thnh hon ton bi cc lin kt sp2, tng t vi than ch. Cu trc
lin kt ny, mnh hn cc lin kt sp3 trong kim cng, to ra nhng phn
t vi bn c bit. Cc ng nano thng thng t sp xp thnh cc "si
dy thng" c gi vi nhau bi lc Van der Waals. Di p sut cao, cc
ng nano c th trn vi nhau, trao i mt s lin kt sp2 cho lin kt sp3, c
kh nng to ra cc si dy khe, di khng gii hn thng qua lin kt
ng nano p sut cao.
Cu trc ca CNTs
Cu trc ca vt liu CNTs c c trng bi vc t Chiral, k hiu l
Cb. Vc t ny ch hng cun ca cc mng graphene v ln ng knh
ng (hnh I.2a).
Cb = na1 + ma2 = (n,m)
Trong , n v m l cc s nguyn.
a1v a2 l cc vc t n v ca mng graphene
Gc ca vc t Chiral :
Cos =
ng knh ng D c tnh theo cng thc sau:
6

D=k

, nm

(kN)

Hnh I.2. Vc t Chiral OA

Armchair

Zigzag

Chiral

Hnh I.3. Cc cu trc ca CNTs


Theo vc t Chiral, vt liu CNTs c cc cu trc khc nhau tng ng
vi cc cp ch s (n, m) khc nhau. Ba cu trc thng gp l: amchair,
zigzag v chiral tng ng vi cc cp ch s (n, n), (n, 0) v (n, m) (hnh
I.3).
Tuy nhin, y ch l cc cu trc l tng ca CNTs. Trn thc t, cu
trc CNTs bao gi cng tn ti cc khuyt tt, ty thuc vo cu trc hnh
hc v trng thi lai ha ca cc nguyn t carbon cu thnh nn CNTs.
Cu trc ca ng nano n vch v a vch c ch ra trn hnh I. 4.
ng nano n vch c th c xem l tm graphit di c dy mt nguyn
t, c cun li thnh mt hnh tr lin. Thng thng, cc ng c t l l/d
vo khong 1000, v th, chng c th c xem gn nh c cu trc mt
chiu. Hn na, mt SWNT gm hai min tch bit vi cc tnh cht l ha
khc nhau. Trc ht l thnh bn ca ng v th hai l u ng. Cu trc
khp kn l tng t hoc c xut pht t mt fullerece nh hn, nh C60.

(a)

(b)

Hnh I.4. Cu trc ca CNTs n thnh (a) v a thnh (b)


7

Cc nguyn t C sp xp theo hnh lc gic v ng gic hnh thnh cc


cu trc khp kn. C th xem xt cu trc ca CNTs da trn thuyt ca
Euler rng mi hai hnh ng gic l cn thit thu c mt cu trc lng
kn ch gm cc hnh lc gic v ng gic. S t hp ca mt hnh ng gic
v nm hnh lc gic xung quanh dn ti s un cong ca b mt thnh mt
cun kn. Vai tr th hai l vai tr c lp ca hnh ng gic l cc trng
thi m khong cch gia cc hnh ng gic lp fullerene l ln nht thu
c un cc b vi sc cng b mt nh nht, dn ti mt cu trc bn
vng hn. Cu trc nh nht bn vng m c th to ra theo cch ny l C60,
ln hn l C70, Mt c tnh khc l tt c cc fullerence bao gm mt
s chn cc nguyn t C bi v vic thm mt hnh lc gic vo cu trc ang
tn ti ngha l thm hai nguyn t C.
Mt cu trc khc, trong bao gm SWNTs l mt hnh tr. N c
sinh ra khi mt tm graphit c kch thc nht nh c cun theo mt
phng nht nh. Hai nguyn t trong lp graphene c la chn, trong
mt nguyn t ng vai tr l im mc. Tm s c cun cho ti khi hai
nguyn t trng nhau. Vecto t t nguyn t u tin hng ti nguyn t
khc c gi l vecto chiral v chiu di ca n bng vi chu vi ca ng
nano. Cc SWNTs vi cc vecto chiral khc nhau c cc tnh cht khng
ging nhau nh hot tnh quang hc, mnh c hc v tnh dn in.
SWNTs th hin cc tnh cht in khc bit so vi ng nano carbon a
tng. C th, rng vng cm c th thay i t 0 eV n 2 eV v dn
in c th l kim loi hay bn dn trong khi MWNTs c rng vng cm
bng khng tc dn in nh kim loi. SWNTs c s dng thu nh cc
linh kin in t, chng c th lm dy in cho dn in rt tt.
ng MWNTs gm nhiu lp than ch, c th c xem nh l mt tp
hp cc SWNTs ng trc vi ng knh khc nhau. Chiu di v ng
knh ca cc cu trc ny khc nhau nhiu so vi cc SWNTs v, tt nhin,
cc tnh cht ca chng cng rt khc nhau.C hai m hnh c s dng
m t MWNTs. M hnh th nht c tn gi l Russian doll, trong ,
MWNTs gm nhiu ng SWNTs n lng vo nhau. M hnh th hai gi l
Parchment, trong , MWNTs c m t nh mt tm graphite cun li.
Khong cch gia cc vch trong MWNTs tng ng khong cch cc lp
graphite trong cu trc than ch, xp x 3.4 .
Trong cc ng nano carbon a tng, ng nano carbon hai vch
(DWNT) c quan tm nhiu bi hnh thi hc v cc tnh cht rt ging vi
ng nano carbon n vch nhng in tr v tnh cht ha hc ca chng
c ci thin ng k. iu ny c bit quan trng khi s chc ha l cn
thit (ngha l ghp cc nhm chc ha hc ln b mt ca ng) thm cc
tnh cht mi cho CNT. i vi trng hp SWNT, s chc ha ng ha tr
s b gy mt s lin kt i C=C, li cc l trng trong cu trc ca ng
8

nano carbon v do thay i c hai tnh cht in v c ca chng. Trong


trng hp ng nano carbon 2 vch, ch c vch ngoi c bin tnh [12].
Khuyt tt (defect)
Cng ging nh cc vt liu khc, lun tn ti cc khuyt tt trong tinh
th hc nh hng n tnh cht ca vt liu, vt liu nano carbon cng khng
l ngoi l. Cc khuyt tt ny, c th xut hin trong qu trnh hnh thnh
khong trng nguyn t, hoc do s bin dng cc ch un v ch ni ca
ng nano, l kt qu ca vic thay th mt hnh lc gic bi hnh tht gic
hoc ng gic, dn n s sp xp li cc lin kt trong mng tinh th (hnh
I.5).

Hnh I.5. Cc khuyt tt trong CNTs


Do cu trc rt nh ca CNTs, bn ko ca ng ph thuc vo
bn ca cc on yu nht ca n, ni m lin kt yu nht quyt nh sc
bn ca c chui.
Cc khuyt tt tinh th hc cng nh hng n cc tnh cht in ca
ng. Ni chung, cc ch c khuyt tt th dn gim. Mt khuyt tt trong
kiu ng armchair c th gy ra vng bao quanh tr thnh bn dn, v
khong trng ca cc n nguyn t gy ra cc tnh cht t. Ngoi ra, cc
khuyt tt tinh th hc cng nh hng ln n cc tnh cht nhit ca ng,
chng hn nh cc khuyt tt dn n tn x phonon.
Trong mt s trng hp nht nh, cc khuyt tt c th c a vo
iu khin cu trc theo mun. Chng hn, vic a vo cc khuyt tt
cng c th dn ti cc cu trc mi khc nh nhnh ch Y (hnh I.6), nhnh
ch T hoc u mi SWNT. Cc khuyt tt ny s dn ti nhng cu trc c
bit c nhiu im khc bit, v thm ch, nhng tnh cht ny cn th v hn
cc dng nguyn bn ca chng [13].

Hnh I.6. Cu trc CNTs nhnh ch Y


9

I.1.1.2. Cc tnh cht c bit ca CNTs [14 - 16]


Hot tnh ha hc
Do s un cong b mt m CNTs c kh nng phn ng ha hc cao
hn so vi mt lp graphene. Hot tnh ca ng nano carbon lin quan trc
tip ti s chuyn orbitan pi v lm cho un cong tng ln. Do , s khc
bit cn phi c to ra gia thnh bn v cc u ca ng nano. Vi l do
tng t, ng knh ca mt ng nano nh hn s dn n hot tnh c
tng ln. S bin tnh CNTs bng cc cht c cng ha tr, hoc thnh bn
hoc hai u ng c chng minh l c th. V d, tan ca CNTs
trong cc dung mi khc nhau c th c iu chnh theo cch ny. Tuy vy,
vic kho st trc tip s thay th cht trn ng nano l kh khn do cc mu
nano ng dng th vn cha tinh khit.
Tnh dn in
Ph thuc vo vecto chiral ca chng, cc ng nano carbon c ng
knh nh hoc l cht bn dn hoc l c nh kim. S khc bit gia cc tnh
cht dn in l do cu trc phn t, lm cho cu trc min khc nhau v do
di min khc nhau. S khc nhau tnh dn din c th bt ngun t cc
tnh cht ca v graphene. in tr dn c xc nh bng c hc lng t
v c chng minh l ph thuc vo chiu di ca ng.
Hot tnh quang hc
Cc nghin cu l thuyt pht hin ra rng hot tnh quang hc ca
cc ng nano chiral bin mt nu cc ng nano tr nn ln hn.V vy, ngi
ta hy vng rng cc tnh cht vt l khc cng b chi phi bi cc thng s
ny. Cc tnh cht quang ca CNTs lin quan n s hp th, s pht quang
v ph tn x Raman ca n. Cc tnh cht ny cho php xc nh c im
cht lng ng nano carbon mt cch nhanh chng v chnh xc.
Hp th quang
Hp th quang trong CNTs khc vi hp th quang trong vt liu khi
3D thng thng bi c s hin din ca cc nh nhn (ng nano carbon c
cu trc 1D) thay v mt ngng hp th bi s tng hp th (trong trng thi
rn c cu trc 3D). Hp th trong ng nano bt u t s chuyn tip in t
t vng dn v2 n vng ha tr c2 hay t v1 n c1. S chuyn tip ny l
tng i nhanh v c th s dng nhn ra cc loi ng nano. Ch rng,
sc ca nh cng gim th nng lng cng tng v nhiu ng nano c cc
mc nng lng tng t E22, E11 v v th c s chng chp ng k trong
ph hp th.

10

Hnh I.7. Cu trc nng lng hp th quang ca CNTs


Phng php hp th quang thng c s dng xc nh cht
lng ca bt ng nano carbon.

Hnh I.8. Ph hp th quang t s phn tn ca SWNTs


S pht quang
Hin tng pht sng quang ha (PL) l mt trong nhng cng c quan
trng xc nh c im ca ng nano carbon. C ch ca hin tng pht
sng quang ha thng c m t nh sau: mt in t trong ng nano
carbon hp th nh sng kch thch t chuyn tip S22 to ra mt cp in tl trng. C in t v l trng nhanh chng nhy t trng thi c2 n c1 v t
v2 n v1. Sau chng ti hp thng qua mt qu trnh chuyn i nh sng
pht x t c1 n c2.
Tn x Raman
Ph tn x Raman c phn gii v nhy tt. Tn x Raman trong
SWNTs l cng hng, tc l ch nhng ng c d c mt rng vng
cm bng vi nng lng kch thch laser.
11

Hnh I.9. Ph Raman ca SWNTs


Cng ging nh ph PL, nng lng ca nh sng kch thch c th
c qut v vy m to ra c ph Raman. Ph ny cng cha cc c
im ni bt nhn ra ch s (n, m). Tri ngc vi ph PL, ph Raman pht
hin ra khng ch cht bn dn m cn nhn ra cc ng kim loi.
bn c hc
CNTs l loi vt liu bn nht, cng nht c bit n hin nay.
bn ny l kt qu ca lin kt ha tr sp2 c hnh thnh gia cc nguyn t
carbon. Vo nm 2000, ng nano carbon a tng c kim tra v c
c kt qu bn ko l 63 GPa. iu ny c hnh dung bng mt si
dy cp c tit din 1mm2 c th chu c lc cng 6422 kg. Khi lng
ring ca ng nano carbon rt thp vi khong 1,3 -1,4 g/cm3, l vt liu c
sc bn ring ln nht hin nay vi gi tr ln ti 48.000 kN.m/kg so vi
bn ca thp carbon cht lng cao l 154 kN.m/kg. Khi xem xt theo mt
tng th, CNTs tr nn rt mm do do chiu di ln hn nhiu so vi ng
knh. Do , cc hp cht ny thch hp cho cc ng dng trong cc vt liu
composite cn c tnh ng hng.
Bng 1.1. Tnh cht c hc ca CNTs vi cc cu trc khc nhau
Vt liu

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

Tnh cht siu k nc v a du


Vt liu k nc l vt liu c to ln t phn t khng phn cc v
do chng a cc dung mi khng phn cc v trung tnh. Cc phn t k
nc bao gm cc ankan, du, cht bo Cc phn t k nc thng cm
li vi nhau hnh thnh cc dng mixen trong nc. Khi cho git nc trn b
mt ca vt liu k nc ta s quan st thy gc tip xc b mt (c) ln. Vi
gc tip xc ln hn 150o vt liu l vt liu siu ky nc.

(a)

(b)

Hnh I.10. Hnh m phng gc tip xc (a)


v hnh nh git nc trn b mt ca vt liu siu k nc (b)
Vt liu nano carbon c cu thnh t cc phn t khng phn cc
nn bn cht ca chng c tnh k nc v a du. Hn na, din tch b
mt ring ln, xp cao lm cho chng c kh nng thm ht c mt
lng ln du.
I.1.1.3 Cc phng php tng hp CNTs [17 -19]
C ch mc
S to thnh cc ng nano v c ch mc ca n vn cha c bit
chnh xc v l mt ch gy nhiu tranh ci. C rt nhiu c ch c th tc
dng trong sut qu trnh to thnh ca CNTs. Mt trong s cc c ch bao
gm ba bc. Trc ht, cht u to thnh cc ng nano v cc
fullerence, C2, c to ra trn b mt ca cc ht xc tc kim loi. T cc ht
cacbua siu bn ny, carbon hnh que c to thnh nhanh chng. Th hai
c s graphit ha chm ca cc vch ca n. C ch ny da trn s quan st
ng ch ca n trn nh TEM.

13

Hnh I.11. C ch mc ca ng CNTs


C mt vi thuyt da trn c ch mc chi tit cho cc ng nano. Mt
thuyt cng nhn rng cc ht xc tc kim loi ang l lng hoc h tr
trn graphit hoc mt khc. Ngi ta on rng cc ht xc tc c hnh qu
cu hoc hnh qu l, trong trng hp s phn hy s xy ra ch trn mt na
b mt ( l mt cong thp hn vi cc ht hnh qu l). Carbon khuych tn
dc gradien nng v lng trn na i din, xung quanh v di chia i
ng knh. Tuy nhin, khng lng t chm ca bn cu, gii thch cho cc l
trng l c trng ca cc filament. Cho cc kim loi h tr, filament c th
to ra hoc bng s y (cn c bit n nh c s ca vic mc) trong
ng nano mc hng thng ra khi cc ht kim loi m vn gn vo , hoc
cc ht tho v chuyn ln u ca ng nano ang mc, c gn cho l mc
u. Ph thuc vo kch thc ca cc ht xc tc, SWNTs hoc MWNTs
mc.Trong s phng h quang in, nu khng xc tc trn graphit, MWNTs
s mc trn cc ht C2 c to thnh trong plasma.
Phng php phng in h quang
Ban u phng php ny c dng ch to fullerene C60, k t
sau khi khm ph ra CNTs th phng php ny c s dng ph bin nht
v c l l con ng d dng nht ch to CNTs. Tuy nhin, n l mt k
thut ch to hn hp nhiu thnh phn v yu cu tch cc ng nano ra khi
mui than v cc xc tc kim loi c mt trong sn phm th.
Phng php ny to ra cc ng thng qua s bc hi trong h quang
gia hai in cc l hai si carbon t i din sao cho ca hai si gn nh
chm nhau, cch nhau xp x 1 mm, trong mt bung kn, thng c lp
y bng kh tr (Heli, Argon) p sut thp (50 700 mbar).

14

Nhng kho st gn y ch ra rng cng c th to ra cc ng nano


trong nit lng bng phng php h quang in. Mt dng in mt chiu
c cng 50 - 100 A, t di dng mt hiu in th 20 V to ra nhit
cao ln ti 3000 4000 K phng gia hai in cc. Khi , kh gia hai in
cc than b ion ha tr thnh dn in. l plasma, v vy phng php ny
cn c tn l h quang plasma. S phng in lm bay hi mt trong s cc
si carbon v hnh thnh mt si nh kt t trn mt si khc.Hiu sut tng
hp CNTs ph thuc vo n nh v tnh ng nht ca mi trng plasma
gia hai in cc, nhit kt t to ra trn in cc carbon, mt dng, p
sut kh tr, hnh dng ca in cc, bung phn ng, Trong tt c cc loi
kh tr, heli cho kt qu to CNTs tt nht do n c kh nng ion ha cao.
Nhng hiu bit su hn v c ch mc thng qua vic o c ch ra
rng s phn b ng knh khc nhau ph thuc vo hn hp ca Heli v
Argon. Nhng hn hp ny c h s khuych tn khc nhau v dn nhit
khc nhau. Cc tnh cht ny nh hng ti tc khuych tn ca cc phn
t carbon v xc tc v tc lm mt, nh hng ti ng knh ca ng
nano trong qu trnh h quang. iu ny a n cu to ca ng l n lp
v mc trn cc ht kim loi vi cc kch thc khc nhau ph thuc vo tc
tt plasma v ngi ta cng nhn rng nhit , mt carbon v mt
xc tc kim loi nh hng ti s phn b ng knh ca ng nano.
Ty thuc vo chnh xc ca k thut, c th tuyn chn mc
SWNTs hoc MWNTs. Hai phng php tng hp khc bit c th c to
ra bng thit b phng in h quang. S thit b phng in h quang
c a ra hnh I.12.

Hnh I.12. S thit b phng in h quang


Trong iu kin ch to MWNTs ti u th qu trnh bay hi carbon
sinh ra mt lng nh mui than carbon v nh hnh v 70% carbon bc hi
t anot graphit sch lng ng ln trn b mt ca thanh graphit catot. iu
15

kin tng hp ti u l s dng in th mt chiu vi th 20 25 V, dng 50


100 A v p sut heli 500 mmHg. Phng in h quang l mt phng
php n gin cho CNTs cht lng cao v cu trc hon ho.
Tuy nhin, phng h quang in thng khng lin tc v khng n
nh nn bng phng php ny khng th to ra mt lng ln CNTs. CNTs
c to ra bm trn b mt catot v c sp xp khng theo mt quy tc
no c v dng chuyn ng l khng ng nht v in trng l khng
thun nht. Do , mt hi carbon v nhit cng khng ng nht, ht
nano carbon v cc tp cht bn lun cng tn ti vi ng nano. gii quyt
vn ny, ngi ta to ra nhng h h quang mi vi nhiu u th mi
v c hiu qu cao nh h quang plasma quay. y, lc ly tm gy ra bi
s quay to ra hin tng xoy v gia tc qu trnh bay hi ca nguyn t
carbon theo phng thng ng vi in cc anot. Hn na, qu trnh quay
lm cho s phng in vi c ng u v to ra plasma n nh. Bi vy
phng php ny lm tng th tch plasma v tng nhit plasma. Vi
tc quay l 5000 vng/ pht ti nhit 1025oC, hiu sut to CNTs l
60%. Hiu sut c th t ti 90% nu tc quay tng ln v nhit ln
t ti 1150oC.
Trong phng php h quang in, to MWNTs th khng cn s c
mt ca xc tc. Tuy nhin, to SWNTs, anot phi c cy xc tc, c
bit l cc xc tc kim loi. Cc xc tc kim loi thng c s dng ch
to SWNT bao gm mt s kim loi chuyn tip nh Fe, Co, Ni v mt s
kim loi t him nh Y, hoc Mo. SWNTs c th c to ra bng cch
phng in h quang qua in cc Fe-graphit trong mi trng kh Argon.
y, in cc anot chnh l cc h nh c to ra trn thanh graphit, c
lp y bi mt hn hp bt kim loi v bt graphit, cn catot l thanh
graphit sch. Cc b SWNTs th thng c ch to vi hn hp ca nhng
cht xc tc ny nh Fe/Ni hay Co/Ni.
Tm li, phng php phng in h quang to ra sn phm c cu
trc hon ho, nhng khng th iu khin c ng knh cng nh chiu
di ca CNTs.
Phng php bc bay laser (Ablation laser)
Vo nm 1995, nhm ca Smalley i hc Rice cng b s tng
hp ng carbon nano bng cch bc bay nh laser. Thit b ha hi bng
chm laser m nhm Smalley s dng c a ra trn hnh I.13. Laser xung
hoc laser lin tc c s dng ha hi graphit trong l ti nhit
1200oC. S khc nhau ch yu gia laser lin tc v laser xung, l vi
laser xung yu cu mt cng nh sng cao hn (100 kW/cm2 so vi 12
kW/cm2).

16

Hnh I.13. S thit b bc bay nh laser


Trong phng php ny, mt tm graphit dng lm bia b bc bay bi
bc x laser di p sut cao trong mi trng kh tr. MWNTs c to ra
trn bia graphit sch. Cht lng v hiu sut ca sn phm to ra ph thuc
vo nhit phn ng v 1200oC cht lng sn phm l tt nht. nhit
thp hn th cht lng sn phm gim v trong cu trc ca CNTs bt u
xut hin nhng sai hng. Trong phng php bc bay bng chm laser, nng
lng ca chm tia laser lm bay hi bia graphit c t trong l t bng
in nhit khong 1200oC. Lung kh Ar (p sut ~ 500 mmHg) thi hi
carbon t vng nhit cao v in cc lng ng bng ng c lm sch
bng nc. Nu dng bia graphit tinh khit ta s thu c MWNTs. Nu bia
c pha thm khong 1.2 % nguyn t Co/Ni vi khi lng Ni v Co bng
nhau s thu c SWNTs. Trong sn phm cn c cc dy nano to bi cc
SWNTs vi ng knh t 10 nm n 20 nm v di trn 100 m.
Gi tr trung bnh ca ng knh ng v mt phn b ng knh
ng ty thuc vo nhit tng hp v thnh phn xc tc. to SWNTs,
ngi ta cn dng phng php xung cc nhanh t laser in t t do (FEL)
hoc phng php xung laser lin tc.
L t c bm y kh heli hoc argon gi p sut 500 mmHg.
Mt lung hi cc nng hnh thnh, sau gin n v ngui mt cch nhanh
chng. Khi cc dng hi ngui i, cc nguyn t v phn t carbon nh nhanh
chng ngng t to ra cc b ln hn, c th bao gm c fullerene. Cc
cht xc tc cng bt u ngng t, nhng lc u chm hn, v ht cc b
carbon, ngn chng t hp thnh cu trc lng. Thm ch cc cht xc tc c
th m cc cu trc lng khi chng b ht ti . T cc b ban u ny, cc
phn t hnh ng mc thnh cc ng nano carbon n vch cho ti khi cc ht
xc tc tr nn qu to, hoc cho n khi cc iu kin lm lnh carbon
khng cn khuych tn qua hoc trn b mt ca cc ht xc tc. Cc ht
cng c th b bao bc nhiu bi lp carbon do chng khng th hp ph
hn na v cc ng nano ngng mc. Cc SWNTs to thnh trong trng hp
ny c b li vi nhau bi lc Van der Waals.
17

S bc bay laser gn ging phng php h quang in, do hn hp ti


u ca cht xc tc v kh nn l ging vi qu trnh phng in h quang.
iu ny c th do cc iu kin phn ng cn thit rt ging nhau v chc
chn cc phn ng xy ra vi c ch ging nhau.
Phng php bc bay bng laser l mt phng php c hiu qu cao
cho qu trnh tng hp b SWNTs vi vng phn b hp. Phng php ny
c u im l sn phm thu c c sch cao (trn 90%) so vi phng
php h quang in. Tuy nhin, y l phng php kh tn km v yu cu
ngun laser cng sut ln, in cc than c sch cao, lng sn phm to
ra t.
Phng php CVD (Chemical Vapour Deposition) [19 - 22]
Nguyn l chung
to lp ph bng cng ngh CVD, nguyn t cn ph c chuyn
thnh cc hp cht th kh, c hon nguyn tr li nh cc tc ng vt l,
ha hc xy ra vng ln cn b mt chi tit cn ph, nh lp ph c
hnh thnh. S qu trnh hnh thnh lp ph bng cng ngh CVD c
trnh by trn hnh I.14.

Hnh I.14. S cng ngh CVD


Tng hp CNTs bng phng php CVD
Phng php tng hp lng ng pha hi ha hc (CVD) l mt trong
nhng phng php lng ng mng ph bin nht. Khc vi hai phng
php phng in h quang v bc bay bng laze l nhm nhit cao (> 3000
K), thi gian phn ng ngn (s-ms), th phng php CVD li c nhit
trung bnh (700 - 1473K) v thi gian phn ng di tnh bng n v pht,
gi. Mt hn ch chnh ca hai phng php phng in h quang v bc bay
laze l CNTs c to ra khng ng u, sp xp hn n, c lp, khng
theo mt quy tc cho trc hoc khng c tnh nh hng trn b mt.
18

Nguyn tc: t mt ngun carbon trong mt pha kh v s dng mt


ngun nng lng, nh plasma hoc mt cun in tr gia nhit, truyn
nng lng sang phn t cha carbon th kh. Thng thng ngun carbon
th kh bao gm CH4, CO, C2H2. Ngun nng lng c s dng b gy
phn t thnh carbon nguyn t hot ng. Sau , carbon khuych tn thng
ti . dc gia nhit v c ph mt lp xc tc (thng l cc kim
loi chuyn tip u dy nh Ni, Fe hoc Co). CNTs s c to thnh nu
cc thng s thch hp c duy tr. Lin kt tri, cng nh vic iu khin v
tr theo kch thc nm, c th thu c bng vic s dng CVD. Vic iu
khin ng knh, cng nh tc mc ca CNTs cng c th c duy tr.
Xc tc kim loi thch hp c th u tin mc SWNTs hn l MWNTs.
S tng hp CNTs theo phng php CVD thc cht l mt qu trnh
hai bc bao gm bc chun b xc tc v bc tng hp CNTs. Thng
thng, xc tc c iu ch bng cch phun cc kim loi chuyn tip ln
v sau x l bng cch hoc l khc bng phng php ha hc hoc l
nhit cm ng cho s to thnh mm ca cc ht xc tc. Vic nhit dn
ti s hnh thnh dng b trn , t y CNTs s mc ln. Amoniac c th
c dng nh mt cht khc n mn. Nhit cho s tng hp CNTs bng
CVD thng trong khong 650 - 900oC. Hiu sut c trng cho phng
php CVD l xp x 30%.
C nhng nguyn l c bn cho qu trnh CVD. Trong thp k va
qua, nhng k thut khc nhau tng hp CNTs bng CVD pht trin,
nh CVD tng cng plasma, CVD nhit, CVD xc tc ancol, CVD h tr
gel kh v CVD c laze h tr,
Trong ti ny, chng ti s dng phng php CVD nhit ha hc
ch to CNTs.
Phng php CVD nhit ch to CNTs
Trong phng php ny, Fe, Ni, Co hoc l hp kim ca ba kim loi
lc u c lng ng trn . Sau khi c khc bng dung dch HF
long v nc ct, mu s c t trong mt ci thuyn bng thch anh.
Thuyn c t trong l phn ng CVD, v cc ht kim loi xc tc kch
thc nm c to thnh sau khi khc thm mt mng kim loi xc tc bng
kh NH3 nhit 750 10500C. Do CNTs mc trn cc ht xc tc mn ny
theo phng php tng hp CVD, vic hnh thnh cc ht xc tc mn l qu
trnh quan trng nht.
Khi CNTs mc trn mt mng xc tc Fe bng CVD nhit, ng knh
ca CNTs ph thuc vo chiu dy mng xc tc.Vi chiu dy mng l 13
nm, s phn b ng knh nm trong khong 30 - 40 nm. Khi chiu dy
mng ln ti 27 nm, th ng knh thu c s trong khong 100 200 nm,
v thu c MWNTs.

19

I.1.1.4. Cc ng dng ca CNTs [23]


Cc ng dng trong ngnh nng lng
CNTs c kh nng tch tr nng lng cao. Tc chuyn ti in t
t cc ny sang cc kia vi vt liu CNTs l rt nhanh. Do , hiu sut ca
cc pin nhin liu loi ny thng rt cao. Hai thnh phn c th tch tr in
ha trong CNTs l hidro v liti.
Do CNTs c cu trc dng tr rng v ng knh c nm nn vt liu
CNTs c th tch tr cht lng hoc cht kh trong li tr thng qua hiu ng
mao dn. Hp th ny c gi l hp th vt l. CNTs cng c th tch tr
hidro di dng ha hc (hp th nguyn t).
ng dng trong cc linh kin in t
- Thit b pht x in t trng: Yu cu chung l ngng th pht x
ca vt liu phi thp, mt dng phi c n nh cao, vt liu
pht x phi c ng knh nh c nano mt, cu trc tng i hon
ho, dn in cao, rng khe nng lng nh v n nh v mt
ha hc. Cc iu kin ny, vt liu CNTs p ng y . Hn na,
CNTs li tng i tr v mt ha hc nn c n nh v mt ha
hc rt cao.
- u d nano: Do tnh do dai v kh nng dn in ca CNTs c th s
dng lm cc u d in t trong knh hin vi AFM v STM.
- Cc ng dng sensor: Do tng tc ha hc cng nh c tnh tng
tc hay hp th c chn lc, ty theo yu cu ca tng ng dng.
Chng hn vi cc sensor xc nh nng cn cc thp s dng vt
liu CNTs th vt liu CNTs phi c bin i trc to cc
nhm COOH trn b mt. Cc nhm ny s tng tc vi phn t
etanol v gn cc phn t ny ln b mt CNTs, lm thay i dn
in ca vt liu hp th. T s thay i ny, nng cn c hp
th c th xc nh c.
- Vt liu t hp: y l ng dng ln nht c ngha quan trng, v vi
cc tnh cht tt ca CNTs khi tham gia vo vt liu composit s lm
cho tng tnh cht c nhit in ca cng c ln rt nhiu.
Mt hng ng dng khc cng ang c tp trung nghin cu l m
Crom gia cng vt liu CNTs. Vt liu CNTs c pha vo dung dch m.
Trong qu trnh m in ha, CNTs c xen ln vo trong lp m v nh v
mt cch ngu nhin trn lp m hoc ht tnh in (vi CNTs bin tnh). Kt
qu m cho thy cng tng r rt v lp m cng nhn hn.

20

I.1.2. Vt liu C-CNFs [24]


CNFs c cu trc nano hnh tr c to nn t nhng tm graphit hnh
nn c xp chng ln nhau. Cc lp graphit ny cun li thnh cc hnh tr
l cc ng nano carbon (hnh I.15).

Hnh I.15. Cu trc ca CNFs


CNFs dn in, dn nhit v c tnh cht c hc rt tt. Cc nghin cu
v vt liu nano composite gia cng bng nano carbon ch yu tp trung vo
cc hp cht composite to bi cc ng nano carbon. iu ny l do thc t
CNTs c t khuyt tt cu trc hn CNFs, dn ti cc c tnh tng th ca n
tt hn cng nh kch thc nh hn v mt thp hn. Tuy nhin, CNFs
li khng t v c th sn xut c vi hiu sut cao nn nhiu nghin cu
v kh nng ng dng cc vt liu ca n trn cc cht m khc nhau.
CNFs c cu trc hnh chn xp chng ln nhau l kt qu ca qu
trnh lng ng pha hi c s dng trong sn xut chng. Hiu qu cht
xc tc tng i thp dn ti cc khuyt tt trong cu trc micro ca CNFs,
yu cu cc x l c bit CNFs thu c cc thuc tnh mong mun. Mt
s phng php x l c s dng, trong bao gm x l bng axit, x
l nhit ( loi b cc khuyt tt), x l plasma (lm sch), v gn nhm
chc ln b mt (ci thin bm dnh b mt). Do t l kch thc cc chiu
ln v nng lng b mt cao (do ng knh c nano), CNFs c xu hng
kt t, dn n phn tn khng ng nht. Nhiu phng php c thc
hin nhm hn ch s kt t ca CNFs nh pha long cht nn vi cc dung
mi, kt hp trn c hc vi nh siu m.
Ngoi ra, do c dn in cao, CNFs c s dng nh cht n
ci thin tnh cht in ca vt liu tng hp cao phn t trong mt s
nghin cu.
Vt liu CNFs to ra trn m C l composite mi C-CNFs, y ha
hn to c s tip xc tt gia CNTs v vt liu nn. u im ca vt liu
CNFs to ra trn m C l CNFs v carbon c nhng thnh phn nguyn t
tng t nhau nn s c xu hng to lin kt tt hn gia chng, ng thi
khng cn phi to hnh cho sn phm. CNFs to ra trn m C c tnh cht
21

k nc, a du, tng t CNTs nn vt liu CNFs cng c ng dng


trong hp ph chn lc du trong h du nc.
I.1.3 Vt liu C-CNTs [25]
m rng kh nng ng dng ca CNTs trong cc lnh vc khc
nhau, CNTs thng c nh hnh dng ht hoc dng tm. Vic nh hnh
CNTs s lm cho qu trnh thu hi vt liu CNTs sau ng dng tr nn d
dng hn, ng thi, hn ch c nhng nguy c gy ra cho con ngi do
kch thc nano ca loi vt liu ny. Thng thng, qu trnh ny s dng
cc tc nhn kt dnh dng hu c. Sau khi x l nhit trong mi trng
khng c khng kh, cc tc nhn ny thng b phn hy, to ra sn phm d
bay hi v/hoc carbon (C). Lng C ny s cn li trn b mt ca vt liu
CNTs. V vy, trong ti ny, vt liu CNTs sau khi nh hnh c gi l
vt liu C-CNTs.
Cc phng php nh hnh dng ht bao gm: phng php gel ha d
th, phng php s dng tc nhn kt dnh.
Gel ha d th
CNTs c phn tn u trong cht gel ha, thng l alginate natri,
nh siu m, to dung dch huyn ph, c nht thch hp. Sau , nh
tng git hn hp huyn ph vo trong dung dch CaCl2 bo ha. Qu trnh
gel ha xy ra nhanh chng to lp mng bao bc cc git huyn ph. Tin
hnh nung phn hy hon ton cht gel ha s thu c sn phm l cc
ht cu CNTs.
y l phng php nh hnh kh n gin, c nhiu u vit, sn
phm to ra c tinh khit cao, v ng u, cc tnh cht c m bo
nh CNTs dng nguyn khai.
S dng tc nhn kt dnh [26 - 29]
Cc cht kt dnh thng c s dng l cc polyme PS, PF, PVA.
c nhiu ti ca nhiu tc gi nghin cu v composit trn c s CNTs, tuy
nhin ch dng mc xem CNTs nh l tc nhn gia cng tng
bn c cho vt liu polyme trong nn polyme ng vai tr mi trng
phn tn cho CNTs, v khng b nhit phn sau khi nh hnh. Vi cch lm
nh vy, tnh cht v din tch b mt ln ca CNTs khng c tn dng
mt cch trit . y, chng ti s dng polyme ging nh cht kt dnh,
lin kt cc ht CNTs li vi nhau. Bng cch ny khng nhng vn gi c
tnh cht v din tch b mt ln ca CNTs m cn to c dng hnh tr
hoc hnh cu, thun li hn cho qu trnh ng dng thc tin. i vi mi
loi nha khc nhau, phng php nh hnh cng khc nhau. Vi nha PVA,
qu trnh nh hnh c tin hnh bng cch nh tng git hn hp ng
nht vo mt trong cc dung dch cha ion tetraborate B(OH)4-, cn vi nha
PF v PS quy m phng th nghim c th s dng phng php v tay.
22

I.1.4 Vt liu xp CNTs [30 - 32]


Bt bin CNTs c pht minh bi cc nh khoa hc t i hc Bc
Kinh v i hc Thanh Hoa - Bc Kinh trong thi gian gn y. Nh c
nhng c tnh u vit nh mm do, kh nng hp ph cao, t trng thp,
dn in, bn nhit, bn trong cc mi trng khc nghit, xp CNTs ha hn
c nhiu ng dng nh sensor, mng lc, in cc, ... c bit, vt liu xp
CNTs c tnh cht siu k nc, u v c th ni ln mt nc (hnh I.16,
I.17) nn c kh nng hp ph tt du trong h du nc, rt thch hp vi
ng dng x l khu sau khi c s c trn du.
Xp CNTs c iu ch bng phng php CVD, vi ngun carbon
l 1,2-diclobenzen, trong s c mt cht xc tc Fe. Cc kt qu nghin cu
v kh nng hp ph du diesel ca sn phm cho thy dung lng hp ph
du ca xp CNTs l rt cao (Q = 143), cao hn nhiu so vi cc vt liu xp
khc (xp c ngun gc polyme Q < 40, cotton v loofah Q < 4, than hot
tnh Q 1). Mt u vit hn na ca cc xp CNTs l d dng thu hi trit
du nh phng php p c hc, ng thi c kh nng ti s dng cao.

Hnh I.16. c tnh xp ca vt liu xp CNTs

Hnh I.17. c tnh k nc u du ca vt liu xp CNTs

23

I.1.5 ng dng cc vt liu hp ph trong s l s c trn du


I.1.5.1 nh hng ca s c du trn [33]
Du trn l s gii phng hydrocarbon du m lng vo mi trng
do cc hot ng ca con ngi v gy ra nhim mi trng. Thut ng ny
thng cp n cc v du trn xy ra trong mi trng bin hoc sng.
Du c th bao gm nhiu loi khc nhau t du th, cc sn phm lc du
(nh xng hoc du diesel), bn cha du ca cc tu, du thi hoc cht thi
dnh du. Vic pht tn hoc thm ch hng nm c th dn sch. Du
cng c gii phng vo mi trng do r r t nhin t cc cu trc a
cht cha du di y bin. Hu ht cc v nhim du do con ngi u t
hot ng trn mt t, nhng cc vn ni tri c bit hng v cc hot
ng vn chuyn du trn bin.
Khi mt v trn du xy ra, du nhanh chng lan to trn mt nc.
Cc thnh phn ca du s kt hp vi cc thnh phn c trong nc, cng
vi cc iu kin v sng, gi, dng chys tri qua cc qu trnh bin i
khng mong mun nh: Qu trnh nh tng, qu trnh lng kt, qu trnh
oxy ha, qu trnh phn hy sinh hc Chnh nhng qu trnh ny lm
gim mt cch ng k cht lng nc, nh hng n mi trng sng ca
con ngi v sinh vt. ng thi, tc ng khng nh n nn kinh t ca cc
quc gia gnh chu s c ny.
nh hng n nn kinh t
Hi ng Nghin cu Quc gia Hoa K (NRC) a ra con s c on,
hng nm c khong 3,2 triu tn du lm nhim bin t cc ngun khc
nhau. Ngun nhim ln nht xut pht t cc c s cng nghip v dn c
th. Theo NRC, c khong 960.000 tn du nhim t ngun ny, chim
30%. ng hng th hai phi k n nhim do hot ng ca cc tu ch
du, 22%, sau l cc v tai nn tu ch du, 13%.
Nh trnh by trn, khi mi trng nc b nh hng nghim
trng s ko theo nhng tc ng khng nh n con ngi, sinh vt v nn
kinh t. Chng hn, nh hng kinh t do v trn du i vi ven b Vnh
M-hi-c bt u tng bc hin r. Trc tin, du trn gy nh
hng su xa i vi sinh thi ven b i Ty Dng ca M. Vng bin
rng hng nghn ki-l-mt vung trn Vnh M-hi-c b nhim, my chc
loi sinh vt bin v lc a nh cc loi c, chim, san h, ng vt c v v.v
b du th e do, mi trng sinh thi vng nc b nhim, c th t
nht phi mt 5 nm mi c th khi phc. Hn th na tc ng mnh
n ngnh du lch ven b Vnh M-hi-c.
Th hai, do v trn du, cng nghip du m, chim trn mt na tng
lng kinh t Vnh M-hi-c ng trc thch thc nghim trng. Tng
thng M -ba-ma trc tuyn b lnh cm khoan ging v thm d
24

trong 6 thng, n cui thng 6, khai thc du m ngoi khi ca M v


vy thit hi 135 triu USD.
Th ba, do nh hng ca trn du, ngh c trn Vnh M-hi-c chim
trn 20% th trng M cng b tc ng mnh. Hn 30% mt nc Vnh
M-hi-c cm nh bt c. Ngoi ra, ngnh vn ti bin cng b nh hng
ln bi pha hu quan phong to mt bin b nh hng ca du loang, phng
nga tu thuyn ra vo cng mang thm du trn.
U ban Bo v ti nguyn thin nhin M cng a ra cnh bo rng,
du trn pht tn nhiu cht c hi, mi ngi mt khi tip xc hoc ht
vo, c th s xut hin mt lot phn ng bt li, thm ch mc bnh ung
th, chi ph cha bnh tuyt i l mt chi tiu lu di v to ln.
nh hng nghim trng n i sng sinh vt
Cc chuyn gia nh gi, nng du trong nc t 0,1mg/l c th
gy cht cc loi sinh vt ph du; nh hng ln n con non v u trng ca
cc sinh vt y; du bm vo c th hoc sinh vt hp th qua qu trnh lc
nc lm gim gi tr s dng.
i vi chim bin, du thm t lng chim, lm mt tc dng bo v
thn nhit v chc nng ni trn mt nc. Nhim du, chim di chuyn kh
khn, phi di chuyn ch , thm ch b cht. Du cn nh hng n kh
nng n ca trng chim.
C - ngun li ln nht ca bin c nh gi l loi chu tc ng
tiu cc mnh m ca s c du trn: Du gy nhim mi trng lm c
cht hng lot do thiu oxy ha tan trong nc; du bm vo c lm gim gi
tr s dng do gy mi kh chu; du c th lm trng mt kh nng pht
trin, trng c th b ung, thi. nhim du cng lm bin i cn bng oxy,
gy ra c tnh tim tng trong h sinh thi, cn tr hot ng kinh t vng
ven bin
nh hng nghim trng n i sng con ngi
Nhng nghin cu v hu qu du trn i vi sc khe con ngi
cho thy con ngi b tn thng thn kinh, ngoi da, mt ming khi tip xc
vi hp cht hu c bay hi trong du. Nn nhn c th b ri lon nhn thc,
mt nh hng, suy yu t chi. Du cng gy nh hng ngn hn ti cc
chc nng ca thn, phi v gan.
Tm li, s c trn du ko theo nhng h qu to ln n mi
trng sng ca con ngi v sinh vt. gii quyt hu qu ca s c, cn
thit phi c s can thip ca cc nh khoa hc trong lnh vc vt liu v mi
trng nhm hn ch nhng thit hi n mc thp nht. ng thi, cc nh
chc trch phi c s kim sot cht ch trong cng tc phng nga s c.
nhiu nc trn th gii, khc phc s c trn du ngi ta
thng s dng cc bin php nh: c hc, sinh hc v ha hc.
25

i vi bin php c hc, trc tin du c quy gom, dn vo mt


v tr nht nh trnh b lan ra trn din rng. C th s dng phao ngn
quy khu vc du trn, ch thu gom x l. Sau khi du c quy, dng my
ht vng du ht du ln kho cha. Mt cng b rt mi t cc nh khoa hc
California v mt ci tin quan trng trong k thut lm sch du loang bin
l thit b tch vng du kiu mi c kh nng gom mt lng ln du,
gp 3 ln cc thit b c in. u im ca bin php ny l ngn chn, khng
ch v thu gom nhanh chng lng du trn ti hin trng. V vy, bin
php c hc c xem l tin quyt cho cng tc ng ph s c trn du ti
cc sng, cng, bin. Song, vic x l s c trn du bng phng php c
hc l khng trit , vt du vn cn li, s nh hng ti con ngi, mi
trng v sinh vt.
Bin php sinh hc bao gm vic s dng cc vi sinh vt phn gii du
nh vi khun, nm mc, nm men. Bin php ny ch c thc hin giai
on sau khi x l bng phng php c hc.
Bin php ha hc bao gm vic s dng cc cht phn tn, cc cht
ph nh tng ca h du - nc, cc cht keo t v cc cht hp ph du,
I.1.5.2 Phn loi vt liu hp ph [34 - 38]
Gn y, phng php ci tin cc vt liu hp ph tng kh nng
hp ph du v tng tnh k nc ang c ch trng nghin cu. Nhiu loi
vt liu mi c nghin cu nh:
Vt liu hp ph du hu c tng hp
Hin nay, vt liu hp ph du ch yu c ch to t cc loi polyme
hu c tng hp nh PP, PE, PU polyeste, polyamit, Copolyme khi trn c
s ca ankylstyren; polycacbodiimit, cc loi copolyme khi trn c s PP v
PE.
Cc loi vt liu hp ph du t polyme hu c tng hp c cc u v
nhc im chnh sau:
u im: nh v c t trng thp; khng hoc t ht nc; c tnh nng
c l cao; bn vi mi trng v ha cht; kh nng hp ph du cao; c
th sn xut cng nghip nn c sn trn th trng; d dng gia cng thnh
si v t d dng to thnh cc sn phm khc nhau nh cc loi phao,
gi, chn, khn, rt tin dng cho cng tc ng cu cc s c trn du;
Nhc im: gi thnh cao; khng b phn hy sinh hc, gy nhim
mi trng th cp nghim trng.
Vt liu hp ph du hu c ngun gc thin nhin
Cc sn phm v ph thi nng nghip nh cc loi si bng (bng vi,
bng go,), cc loi c bng, ru than bn, rm r, li ng, b ma, mn

26

ca, si g, mt s loi v cy v nhiu loi vt liu trn c s xenluloz bin


tnh khc.
Cc loi vt liu hp ph du hu c c ngun gc thin nhin k trn
cng c cc u im v nhc im chnh sau:
u im: gi thnh r, c ngun gc thin nhin v kh nng ti sinh
v tn, thn thin vi mi trng v c kh nng t phn hy sinh hc. Phn
ln cc loi vt liu hp ph du hu c c ngun gc thin nhin c cu trc
si nn c th d dng gia cng thnh si v t d dng to thnh cc sn
phm khc nhau nh cc loi phao, gi, chn, khn, tin dng cho cng tc
ng cu cc s c trn du.
Nhc im: kh nng ni km v c t trng cao, tnh u nc
(hydrophilicity) cao, tnh a du (hydrophobicity) thp v th vt liu c kh
nng hp ph du thp.
Vt liu hp ph du v c
Vt liu hp ph du v c gm cc loi khong st (vermiculite,
diatomite, perlite, ct thch anh, thch anh tinh th, silica, natri bicarbonat),
amberlite, khong st hu c, zeolite, si thy tinh, than ch, than hot tnh,
Cc u v nhc im chnh ca vt liu hp ph du v c k trn
nh sau:
u im: sn c, gi thnh r
Nhc im: c t trng cao, khng ti s dng c, ht nc, tnh
a du km v th vt liu c kh nng hp ph du thp; kh khn trong vn
chuyn v s dng v phn ln vt liu hp ph du v c u dng bt
hoc ht.
Trn th gii c rt nhiu nh khoa hc nghin cu ch to thnh
cng cc vt liu hp ph du. Tin s S. kathean, ging vin khng cng
ngh ca i hc AIMST Malaysia ch to thnh cng vt liu hp ph
du t bt v su ring vi kh nng hp ph du tng i tt; gp 30 -40
ln (Q= 30-40) so vi khi lng vt liu ban u [37]. Vt liu polyme nh
polypropylen, polyeste v polyuretan , cng c rt nhiu nh nghin
cu tng hp ch to v ng dng trong s c trn du. Kh nng hp ph
du ca cc ny cao hn so vi vt liu t thin nhin Q = 40-60 [31, 37]. Gi
thnh ca loi vt liu ny rt t khong 100USD/kg. Gn y cc nh khoa
hc Trung Quc (Xuchun Gui, Jinquan Wei, Kunli Wang) ch to thnh
cng vt liu xp CNTs c kh nng hp ph du rt cao (Q=143) cao hn
nhiu ln so vi cc vt liu xp khc. ng thi vt liu ny c u im
vt tri l c kh nng ti s dng nhiu ln do d dng thu hi du bng
phng php p c hc hoc t chy [31].

27

I.1.5.3. Yu cu k thut ca cc loi vt liu hp ph du [38]


c th tr thnh cc sn phm thng mi, cc loi vt liu hp ph
du cn phi p ng mt s yu cu k thut sau:
- Kh nng hp ph du cao v vn tc hp ph du nhanh v ht nc
thp;
- Kh nng lu du cao trong qu trnh vn chuyn;
- Kh nng thu hi du (nh hp ph) nhanh v bng nhng phng
php n gin nht c th;
- C cc tnh cht c l tt v c kh nng ti s dng nhiu ln;
- C t trng thp, kh nng ni cao trn mt nc;
- Chu c cc dung mi, ha cht thng dng;
- Khng b phn hy quang ha;
- Sn c v gi thnh r;
- p ng tiu chun v kh nng hp ph du trn 1kg vt liu hp ph
du nh sau:
9 Theo World Catalogue of Oil Spill Response Products,
1997/1998 [38], nu 1kg vt liu hp ph du hp ph c
khong di 5 kg du th vt liu hp ph du c xp loi km,
khng kinh t v khng c kh nng thnh sn phm thng mi
9 Nu 1kg vt liu hp ph du ht c khong 5-10 kg du th
vt liu hp ph du c xp loi kh, c kh nng thng mi;
9 Cn nu 1kg vt liu hp ph du ht c khong 10 kg du th
vt liu hp ph du c xp loi tt;
9 Theo tiu chun ca Nht Bn th vt liu hp ph du c chp
nhn nh mt mt hng thng mi th phi c kh nng hp ph
du t nht l 6 kg du trn 1kg vt liu hp ph du [40].
I.1.6 ng dng cc vt liu siu k nc trong qu trnh tch cht
Vt liu k nc c s dng loi b du t nc, x l s c trn
du v tch cc cht khng phn cc t cc hp cht phn cc nh tch nc
khi du, tch nc khi h nh tng du nc.
Cc loi vt liu k nc a du truyn thng l vt liu aerogel c
ch to bng cch trn t st vi polyme v nc v sau c lm ng
kh to ra vt liu siu nh vi xp khong 96% [41].
Zhongxin Xue v cng s [42] ch to tm li ph hydrogel PAM
c c tnh siu k nc v siu a du. Tm li ph PAM l vt liu c
ph ng thi mt li thp khng g c cu trc micro vi mt loi vt liu
hydrogel in hnh v thn thin vi mi trng, c cu trc nano,
28

polyacrylamide (PAM). c im ca n lm cho n tr thnh mt ng c


vin tt lm li chn lu gi du ti u ra ca nhng ng ng nc thi
cng nghip, trong cc v trn du, thit b lc nc nhim du; v tch du
c nht cao.Vt liu mi ny c th chn lc tch nc t hn hp du/
nc nh du thc vt, xng, du diesel, v thm ch c hn hp du th/
nc cho hiu qu lm sch t trn 99%.
Kangjian Tang v cng s [43] iu ch c mng boehmite
[AlO(OH)] t anodic alumina oxide (AAO), s dng xc tc ng. Mng
AlO(OH) c tnh cht siu k nc v siu a du vi cc gc tip xc vi
nc v du trn b mt ln lt l 152,8 v 0 .
Cc tc gi [44] a ra mt phng php ch to mt vt liu siu
k nc v siu a du thng qua cc lp ph composite oxit km trn mng
polydimethyl siloxane. Cc lp ph ny to ra b mt ca vt liu c gc tip
xc vi nc v du tng ng l gn 160 v nh hn 5.
Gn y, vt liu trn c s CNTs c c bit ch cho ng dng
ny. CNTs c s dng ch to b lc tch du v nc. Theo
Seunghyun Baik v cng s [45], b lc VAMWNT c tng hp bng cch
to MWNTs mc thng ng trn li thp khng g bng phng php lng
ng pha hi nhit ha hc, c th nghim tch ring cc lp du diesel
v nc. Kt qu thu c l cc ng nano hnh kim mc trn li vi cc l
xp kch thc micro kt hp vi nng lng b mt thp ca carbon lm
tng cng tnh cht siu k nc v siu a du ln hn 100 ln, gc tip
xc vi du v nc o c tng ng l 0o v 163o (hnh I.18).

(c)

(d)

Hnh I.18. B lc VAMWNT tch diesel (mu ) v nc (mu xanh)


(a) Gc tip xc vi nc (100 L, 163 4o),
(b) Hot ng ng hc ca git diesel,
(c) Diesel thm qua b lc mt cch chn lc,
(d) Bnh cha c o ngc v p sut thy tnh ca nc l 626.6 Pa
29

I.2 TNG QUAN TNH HNH NGHIN CU VIT NAM


I.2.1 Vt liu CNTs v CNFs
nc ta, vic sn xut CNTs cng c trin khai [1]. T nm
2003, CNTs c tng hp pht trin cc ng dng trong cc vt liu
composite, trong cc thit b tn nhit, hp th sng in t, thit b pht x
trng in t v u d qut. Hai c s u tin Vit Nam trin khai
sn xut CNTs vi quy m phng th nghim l Vin Khoa hc Vt liuVin Khoa hc v Cng ngh Vit Nam v Khu Cng ngh cao Si Gn. Ti
Vin Khoa hc Vt liu, CNTs c sn xut bng phng php CVD,
trung bnh mi ngy c th sn xut 100-300 gam bt CNTs, vi tinh khit
95%, vi chi ph sn xut thp hn nhiu so vi cc nc trn th gii, gi
tng ng vi gi ca Trung Quc, trong khi cht lng sn phm li tt
hn. Ti cc phng th nghim trong Khu Cng ngh cao Si Gn, cc nh
sn xut cng a ra mt phng php sn xut CNTs vi chi ph thp hn
gi nhp ngoi, i t ngun nguyn liu l b c ph v b ma. Nm 2009
sn lng CNTs t gn 2 tn.
V vt liu CNF, Vn nh Sn Th v cng s cng b cng trnh
nghin cu tng hp CNF dng bt da trn phn ng phn hy hydrocarbon
trn xc tc [2].
Nhm nghin cu ca chng ti trong nhiu nm qua tin hnh mt
s nghin cu lin quan n vic ch to CNTs t cc ngun carbon khc
nhau v bc u c nhng nghin cu v nh hnh vt liu CNTs [3 - 7].
Tuy nhin, y mi ch l cc nghin cu mang tnh cht thm d, cha c
tnh h thng.
I.2.2 Vt liu hp ph du
Trong nhng nm gn y, vt liu hp ph du c quan tm
nghin cu Vit Nam. Cc vt liu c trong t nhin nh rm r hoc cc
vt liu xp l nhng vt liu s ng nht c dng hp ph du, song
dung lng hp ph ca chng rt thp, nn t c hiu qu, ng thi khng
th loi b hon ton lp du nn ch ph hp vi vic x l s b.
Nhm tc gi thuc i hc S phm H Ni, i hc Bch khoa H
Ni v Vin Ha Hc, Vin Khoa hc v Cng ngh Vit Nam [8] tin
hnh ch to cc vt liu hp th du trn c s styren v lauryl metacrylat
bng phng php trng hp huyn ph. Kt qu th nghim cho thy, kh
nng hp ph toluen ca polyme khi t l St: LMA l 40:60 l thch hp. Khi
hm lng styren tng s lm tng khong h bn trong ca cu trc mng
khng khng gian 3 chiu ca polyme v vy lng du hp th tng. Nu
hm lng styren tng qu cao, kh nng co gin linh ng ca mng li
khng gian b cn tr dn ti kh nng hp ph du gim, ng thi tnh cht
ht du ca polyme ph thuc nhiu vo lng toluen trong du. Vic iu
30

chnh tuyt i cc yu t nh hng ti qu trnh trng hp l khng n


gin.
Nhm tc gi Cao Mnh Tng, Vin ng dng cng ngh [9] ch
to vt liu x l nhim du t cc nguyn liu l b ma, mn ca v tru.
Tuy vt liu ny gi thnh r, c tnh thn thin vi mi trng, nhng kh
nng hp ph du khng cao khong 10 n 12 (Q = 10 -12).
I.2.3 S c trn du ti Vit Nam v bin php khc phc [10]
Cng vi tc pht trin kinh t cao ca Vit Nam trong thi gian
gn y, cc ngnh cng nghip du kh cng ang pht trin mnh m. Sn
lng khai thc du th ca Vit Nam hin tng ln 20 triu tn/nm trong
khi nn kinh t pht trin y mnh nhu cu nng lng phc v cc hot
ng sn xut v lu thng. c tnh mi nm cc ngnh kinh t ca Vit
Nam 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 c vn chuyn qua cc tuyn ng
hng hi ny ln n 30 triu tn/nm.
Nh vy, hng chc triu tn du ang c lu thng trn lnh th
Vit Nam mi nm. iu ny to ra nguy c xy ra cc s c trn du rt ln.
Thc t cng cho thy, cc s c trn du lin tc xy t nhiu nm tr li
y.
I.2.3.1 S c trn du tu Neptune Aries
S c trn du tu Neptune Aries, xy ra ngy 3-10-1994 do tu
Neptune Aries m vo cu cng Ct Li, sng Si Gn, Tp. HCM. S c ny
lm trn hn 1600 tn du DO ra sng Si Gn v h thng cc sng
nhnh v knh rch trong khu vc ln cn cng Ct Li. Tng thit hi v mi
trng v kinh t x hi do hu qu ca s c c nh gi rt nghim
trng. Ch tu Neptune Aries bi thng 4,2 triu USD khc phc s
c v n b cho cc thit hi do s c gy ra. Theo thng k, s c trn du
tu Neptune Aries l s c c lng du trn ra ngoi mi trng ln nht
ti Vit Nam cho ti nay.
I.2.3.2 S c trn du Formosa One
S c trn du tu Formosa One xy ra ngy 7-9-2001 ti vnh Gnh
Ri tnh BR-VT. Do khng tun th ng cc ch dn ca cng v Vng Tu,
tu Formosa One m va vi tu Petrolimex 01 ang neo u trong vnh
Gnh Ri, lm trn 900 m3 (~ 750 tn ) du DO. Du trn nh hng
n ton b cc khu vc bi trc, mi Nghinh Phong, o Long Sn ca tnh
B Ra Vng Tu, gy thit hi nng n n cc hot ng nh bt v nui
trng thy sn, cc h rng phng h ven bin, cc bi tm du lch v sc
khe ngi dn a phng. Sau hn ba nm gii quyt khiu ni n b, ch

31

tu Formosa One bi thng hn 4 triu USD cho cc thit hi do s c


trn du gy ra.
Chnh quyn a phng nhanh chng trin khai nhiu bin php
khc phc nhm hn ch cc thit hi do du trn gy ra nh cnh bo y
n ngi dn a phng, trong c bit cho cc h lm ngnh ngh nui
trng thy sn, ng ca cc bi tm b nhim du, v huy ng cc lc lng
ca a phng thc hin cc bin php lm sch cc khu vc b nhim.
Mc d, cc bin php khc phc mang li nhiu hiu qu tch cc, nhng
do khu vc nhy cm cao nh rng ngp mn, cc bi nui trng thy sn,
cc bi tm khng c che chn v bo v kp thi, s c trn du tu
Formosa One vn gy ra thit hi nng n ti kinh t v mi trng ca tnh
B Ra Vng Tu.
I.2.3.3 S c trn du tu Fortune Freighter
S c trn du tu Fortune Freighter, xy ra ngy 12-1-2003 trn sng
Si Gn do va chm gia tu bin Fortune Freighter v on phng tin tu
ko ca tnh i An Giang. S c ny lm trn khong 300 tn du DO vo
mi trng. c tnh thit hi kinh t v mi trng ca s c khong hn 2
t ng.
Ngay sau khi s c xy ra 1 gi, cc t chc lin quan v cc c quan
chc nng huy ng lc lng n hin trng, trin khai cc phao quy
v my ht du ti khu vc xy ra s c. Kt thc cc cng tc ng cu s c,
lng du DO thu gom c l khong 170 tn, chim hn 36% lng du
trn ra ngoi.
I.2.3.4 S c trn du tu Hng Anh
S c trn du tu Hng Anh, xy ra ngy 20-3-2003 do tu Hng Anh
b m do sng ln trong khu vc vnh Gnh Ri, lm trn khong 100 tn
du DO nh hng trc tip n khu vc rng phng h Cn Gi v cc khu
vc nui trng thy sn ca Huyn Cn Gi. Tng thit hi v kinh t v mi
trng do s c gy ra c c tnh khong 23 t ng.
UBND Huyn Cn Gi nhanh chng t chc cu h cc thuyn vin
v thng bo cho cc c quan chc nng ca Tp. H Ch Minh. Sau khi nhn
c thng bo, cc lc lng ng cu trn a bn Tp.H Ch Minh v tnh
BR-VT bao gm X nghip Lin hip Trc vt Cu h (VISAL), Trung tm
ng cu S c Du trn quc gia khu vc pha nam, cng ty H t, cng ty
i Minh v cc c quan chc nng iu ng lc lng v phng tin
n khu vc s c. i th ln ca VISAL tin hnh bt kn cc np v van
ngn chn r r trong khi du ln nc c ht ngay ra ngoi. Cc n v
khc nh PVDrilling, Lin doanh Du kh Vietsovpetro (VSP), Cng ty i
Minh trin khai phao quy cng phi hp trong cng tc thu gom du.

32

n ngy 26-3-2003, tu Hng Anh c lm ni v a v cng


VISAL Vng Tu. Hot ng cu h chm dt lc 17h cng ngy. Tng
lng du v nc bm chuyn t trong tu ra ngoi l 567 tn.
I.2.3.5 S c trn du tu Kasco Monrovia
S c trn du tu Kasco Monrovia, xy ra ngy 21-1-2005 do tu
Kasco Monrovia m vo tr cng trong khi cp cng Saigon Petro trn sng
Si Gn, thnh ph H Ch Minh. Hn 500 tn du DO trn ra mi
trng. Tng thit hi c c tnh khong 15 t ng Vit Nam.
Ch mt gi sau khi s c xy ra, Cng ty i Minh, c s huy ng
ca S TN&MT Tp.HCM, trin khai lc lng gm 25 nhn vin, 4 tu
ng cu, cc tu v ca n ph tr, cc phao quy du, v cc my ht du n
hin trng s c. Cc lc lng khc nh i ng cu ca cng Saigon
Petro, S TN&MT, CSGT ng thy, Ban Qun l Khu ng sng u c
mt ngay ti hin trng gii quyt s c.
Mc d, cc lc lng ng cu c trin khai nhanh chng, nhng
do s c xy ra ng lc triu ln gn t nh, dng triu lm du phn
tn nhanh chng vo h thng knh rch chng cht trong khu vc, to iu
kin khng thun li cho cng tc thu gom du trn. n ngy 24-1-2005, cc
hot ng ng cu c chm dt, tu Kasco Monrovia c ko v cng
Nh B sa cha. Tng lng du thu c l khong 50 tn.
Thc tin ng cu cc s c nu trn cho thy hin cng tc ng cu
s c Vit Nam vn cha c pht trin mnh m mi ch ch yu l thu
gom n gin. Cc a phng ni xy ra s c cha c cc bin php bo v
sn sng cho cc khu vc nhy cm cng nh cc ngun li kinh t quan
trng. Chnh v vy, khi du khng th thu gom c do cc yu t t nhin
khng thun li (gi to, sng ln, v dng chy mnh), du nh hng trc
tip vo cc ngun li kinh t rt quan trng nh nui trng thy sn v du
lch, gy thit hi hng trm t ng. y thc s l mt bi hc cn c rt
kinh nghim nhm nng cao tng bc v hon thin nng lc cng tc ng
cu du trn ti Vit Nam.
I.3 KT LUN TRN C S PHN TCH L THUYT
Trn c s phn tch tng quan ti liu c th rt ra kt lun nh sau:
- C nhiu phng php khc nhau ch to CNTs, trong s ,
phng php phn hu xc tc cc kh cha carbon l phng php
c trin vng nht sn xut CNTs v CNFs nh chi ph sn xut
thp v hiu sut cao. Hn na, phng php ny tng i n
gin khi chuyn t phng th nghim sang p dng thc t.
- Vt liu nano carbon cn thit phi c to hnh dng c th
a vo ng dng thc tin. Phng php s dng cht kt dnh
33

polyme, m nh , sau khi x l nhit , s to ra composit CCNTs, ph hp vi mc ch nghin cu ca chng ti.


- Ty theo phng php iu ch, cn c th to c vt liu xp
CNTs, c nhiu tnh cht u vit hn so vi vt liu CNTs.
- S c trn du c nhiu kh nng xy ra t cc hot ng thm d,
khai thc du kh, cng nh t cc hot ng vn chuyn du v
hot ng hng hi. S c trn du nu xy ra s gy ra nhng thit
hi kinh t - x hi nng n, gy suy thoi mi trng nghim trng
m vic khc phc hu qu, phc hi li mi trng tn nhiu tin
ca v thi gian. Bn cnh cc cht hp ph hin ang c s dng
x l s c trn du nh t st, trn chu, len thy tinh, xp
polyurethane, vt liu trn c s nano carbon l mt trong nhng
ng c vin tt nht hin nay nh p ng c mi yu cu i hi
ca mt vt liu x l du trn nh: tnh cht k nc, a du, c
khi lng ring nh c th ni ln mt nc, c th chit c
du khi vt liu ti s dng.
- Vit Nam, ngoi cc kt qu nghin cu ca nhm tc gi ti,
cha c cng trnh cng b no lin quan n vic tng hp vt liu
C-CNTs, CNFs, xp CNTs v nghin cu cc ng dng ca chng
trong qu trnh tch cht v trong x l s c trn du.
V nhng l do , t c mc tiu ra ca nhim v, cn tp
trung nghin cu cc vn sau:
- K tha cc kt qu nghin cu ca nhm ti, trong ti ny,
chng ti s tin hnh nghin cu cng ngh iu ch vt liu mi
trn c s carbon-ng nano carbon (C-CNTs) c tnh cht siu k
nc c kh nng hp ph chn lc du trong h du-nc
- Nghin cu c trng cc tnh cht ca vt liu C-CNTs
- nh gi kh nng hp ph du ca vt liu C-CNTs trong h dunc
- Thm d kh nng ng dng ca vt liu trong qu trnh tch cht
v trong x l s c trn du
- xut qui trnh cng ngh ch to vt liu siu k nc C-CNTs
qui m pilot

34

PHN II
THC NGHIM

35

II.1 CH TO NG NANO CARBON (CNTs)


Mt s s liu c th trnh by trong phn thc nghim l s liu
trong qu trnh tin hnh kho st cc yu t, cha phi l cc s liu
ti u ha.
S nguyn l ca h thng tng hp carbon nano c th hin
trong hnh II.1.

Hnh II.1: S nguyn l ca phng php tng hp CNTs


bng phng php CVD
Trong :
(1)

: Bnh kh

(2)

: p k

(3)

: Lu lng k

(4)

: L nung c th iu khin c chng trnh nhit

(5)

: ng phn ng bng thch anh

(6)

: Thit b tch kh lng

(7)

: Sc k kh

Cc kh c s dng trong qu trnh tng hp CNTs l LPG, hydro v


nit.
CNTs c iu ch bng cch s dng xc tc Fe/-Al2O3 trong ,
cht mang -Al2O3 c iu ch trong phng th nghim, c din tch b mt
ring SBET = 403 m2/g. Cht mang c nghin v ry thu c cc ht c
36

kch thc 80 n 150 m. Xc tc c iu ch bng cch tm bi dung


dch Fe(NO3)3.9H2O. Sau , hn hp cht rn m s c sy 100oC trong
12h, ri nung 450oC trong 2 gi phn hy ht mui nitrat. Trc khi
c s dng cho phn ng tng hp carbon nano ng a thnh, xc tc c
kh. Hm lng st trong xc tc l 20% khi lng.
tng hp CNTs, trc ht, ly 0,2g xc tc Fe/-Al2O3 cho vo
thuyn s v t vo gia tm l nung. Sau khi kh xc tc bi hydro
550C trong 2 gi, cho LPG qua thit b vi vn tc dng kh v nhit n
nh. Sau 2h tng hp, CNTs hnh thnh s c lm ngui n nhit
phng ri c xc nh khi lng lm c s cho vic qui hoch thc
nghim v tnh ton ti u cc thng s tng hp.
Hiu qu ca qu trnh tng hp c nh gi bi s gia tng khi
lng ca mu CNTs sau khi tng hp (trong 2h) so vi khi lng xc tc
s dng, hay lng CNTs to thnh trn mt n v xc tc, trong 2 h (M,
%):
M (% ) =

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

Phn trm th tch LPG (%)

30 - 70

Phn trm th tch Hydro (%)

70 - 30

Nhit (C)
Vn tc cung cp kh (ml/pht)

630 740oC
48

Hnh II.2 chp h thit b tng hp vt liu CNTs v sn phm CNTs


trong ng phn ng.

37

Hnh II.2. Thit b tng hp CNTs bng phng php CVD


II.2 CH TO VT LIU C-CNFs
Si nano carbon c iu ch bng cch s dng xc tc Ni mang
trn m carbon. Trc khi s dng lm cht mang, m carbon c x l
trong dung dch axit 70C loi tt c cc tp cht v hot ha b mt.
Qu trnh phn tn cc tm hot tnh ln cht mang c tin hnh bng cch
tm dung dch NiNO3.6H2O ln trn cht mang. Sau hn hp c sy
1100C trong 12 gi, ri nung 450oC trong dng nit trong 2 gi. Oxit
nicken phn tn trn b mt ca cht mang c kh thnh nicken kim loi
bi hydro. Cc iu kin vn hnh to ra cc si nano carbon c a ra
trong bng II.2.
Bng II.2 : iu kin tng hp si nano carbon trn m carbon
iu kin tng hp

Gi tr

Phn trm th tch LPG (%)

20 30

Phn trm th tch Hydro (%)

80 70

Nhit (C)

680oC

Vn tc cung cp kh (ml/pht)

67

Cc vt liu carbon nano sau khi iu ch c c s dng trc


tip nh hnh m khng cn qua giai on tinh ch.
B mt ca vt liu c quan st bng phng php knh hin vi in
t SEM s dng my HITACHI S-4800 (Japan) v TEM, s dng my A
Tecnai - G2. Ph hng ngoi (IR) ca mu c ghi trn my TENSOR 37
BRUKER. Php o phn tch nhit TG-DTA c tin hnh trn my
Diamond TG/DTA Perkin Elmer. Cu trc xp ca vt liu c c trng
bng phng php ng nhit hp ph - nh hp ph nit trn my
Autometed BET sorptometer BET 201 A.

38

II.3 CH TO VT LIU C-CNTs


II.3.1 Nguyn liu
CNTs s dng c iu ch theo phng php CVD theo quy trnh
c m t trn. Polyvinyl alcohol thng mi PVA-217 c sn xut bi
tp on KURARAY (Malaysia) c s dng trc tip m khng chu bt
k mt s x l no. Nha Phenol-formaldehyde (PF) s dng c iu ch
trong phng th nghim di dng nha nhit rn Rezolic. Polystyren thng
mi c ha tan trong toluen n nng thch hp.
II.3.2 Qui trnh
Ba loi nha PVA, PF, PS c s dng lm tc nhn nh hnh cho
CNT, tuy nhin i vi mi loi nha khc nhau th phng php nh hnh
cng khc c th l: vi nha PVA c nh hnh dng cu bng cch nh
tng git mt vo trong dung dch c cha ion tetraborate B(OH)4 , trong khi
vi nha PF v PS c cho vo xy lanh n ra dng hnh tr v lm thnh
vin bng phng php v tay.
- Vi nha PVA: Hn hp ng nht gm PVA Anhydric maleic
(C4H2O3) CNT c chun b. Sau nh tng git hn hp trn
vo hn hp dung dch cha Na2B4O7 bo ha v Na2SO4 bo ha
ti pH 12 th PVA bt u gel ha mt ngoi mt cch nhanh
chng theo phng trnh sau :

- Khi tt c cc ht hnh cu n nh v hnh dng, vt liu c


ra nhiu ln bng nc ct v sau c nhit phn di mi
o
trng kh tr (N2) nhit 550 C trong 3h. Cui cng thu c
vt liu C-CNTs, k hiu C-CNTs (PVA).
- Vi nha PF: u tin, chun b hn hp ng nht gm 0,5g CNT
1,85g nha PF. 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
ng rn cc vin hnh cu nhit 150 C trong vng 30 pht
n nh hnh dng, ri em i nhit phn di mi trng kh tr
39

(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

Sn phm thu c c sy nhit 80 C trong vng 12h n


nh hnh dng, ri c nhit phn di mi trng kh tr (N2)
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 :

II.6 THM D KH NNG TCH DU TRONG H DU- NC


H lc du c thit k nh trong hnh v. Bnh trn c cha h dunc v c cnh khuy, trong nc c pha vi Kaliicromat c mu
phn bit vi u bn trn. Bnh di c ht chn khng. Du c lc
bi tm c cha carbon c kp gia hai bnh.
Tm lc cha carbon c iu ch bng phng php sau:
- X l CNTs nhit 7000C di dng kh He loi b ton b
nhm chc trn b mt, nhm lm tng thm kh nng k nc ca
CNTs.
- Phn tn CNTs trong toluen bng siu m
40

- Lc ht chn khng hn hp thu c trn tm lc bng Teflon


- Sy kh tm lc 1200C trong 2 h

Hnh II.3 Thit b lc nc trong h du-nc

41

PHN III
KT QU V
THO LUN

42

III.1 NGHIN CU CNG NGH IU CH VT LIU C-CNTs


III.1.1 Ti u ha qu trnh iu ch CNTs
Tin hnh tng hp CNTs theo qui trnh c m t trong phn thc
nghim, vi cc iu kin c th sau :
-

Ngun carbon : LPG (H2, N2)

Nhit : 650oC

Thi gian : 2h

Tc dng kh : 3,0 cm/pht

Cht xc tc : Fe/-Al2O3

iu kin ny, lng sn phm to thnh trn mt n v xc tc (M)


t gi tr 5,1. Kt qu c trng tnh cht cu trc t vi bng phng php
knh hin vi in t SEM v TEM ca CNTs thu c t thc nghim trn
c trnh by trong hnh III. 1.
Kt qu cho thy vt liu thu c l cc ng carbon nano, ng knh
ngoi t 10 - 30 nm, c ng u cao, khng c carbon v nh hnh.
Kt qu o din tch b mt ring BET cho thy b mt ring ca mu
CNTs l 152 m2/g. Kt qu ny hon ton ph hp vi cc kt qu c
cng b [32].

Hnh III.1. nh SEM v TEM mu CNTs tng hp 650oC


Nh vy, c th kt lun rng CNTs c tng hp thnh cng
cc iu kin nu trn. Tuy nhin qu trnh ch to CNTs c hiu qu, cn
phi ti u ha cc thng s. V th, trong nghin cu tip theo, 3 yu t gm
nng ca LPG (%), vn tc dng kh (cm/pht) v nhit tng hp (T
o
C) s c ti u ha. y l qui hoch thc nghim trc giao cp 2, vi 3
yu t nh hng (k = 3) v mc cc yu t (mc c s, mc trn, mc di,
mc *) c th hin bng III.1.

43

Hm mc tiu ca quy hoch ny l lng CNTs to thnh trn mt


n v xc tc trong 2h (M, %), nh c trnh by trong phn thc
nghim.
Bng III. 1- Mc cc yu t th nghim
Cc mc

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

Khong bin thin

20

20

Alpha (cnh tay n)

+/- 1.682

+/- 1.682

+/- 1.682

Mc * (+/- 1.68)

33.64

3.364

33.64

Kt qu nghin cu quy hoch thc nghim cho php chng ti th


hin cc tng tc cp i ca cc thng s lm vic n gi tr M, nh trong
cc hnh III.2, III.3, III.4.
HA.Hoang-TCC.Hoang-3D Contour Plot (so lieu S1.sta 10v*17c)
M (%) = 60 9.11 79 - 27 .157 2*x1 - 2 5.15 99 *x2 - 1 7.2 628 *x1*x1 + 3.7 5*x1 *x2 - 1 0.19 35 *x2*x2
2.0

1.5

VAN TOC (cm*min-1)

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

HA.Hoang-TCC.Hoang - 3D Contour Plot (so lieu S1.sta 10v*17c)

HA.Hoang-ND.Lam - 3D Surface Plot (so lieu S1.sta 10v*17c)

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)

HA.Hoang-ND.Lam - 3D Surface 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

VAN TOC (cm*min-1)

Hnh III.4. Lng CNTs to thnh khi xt tng tc gia vn tc dng


(x2) v nhit tng hp (x3)
Bn cnh , c th xc nh c phng trnh hi qui y nh
sau:
Y = 576.30 - 27.15x1 - 25.16x2 + 138.32x3+3.75x1x2+1.25x1x3 23.75x2x3 - 9.68x12 -2.61x22 + 25.67x32
(3.1)
gin n phng trnh hi qui, chng ti tin hnh kim tra mc
ngha ca cc h s ca phng trnh hi quy theo chun Student (tj), qua
h s b12, b13 v b22 b loi b. Phng trnh hi qui cn li nh sau:
Y = 576.30 - 27.15x1 - 25.16x2 + 138.32x3 - 23.75x2x3 - 9.68x12 +
(3.2)
25.67x32
T phng trnh hi quy ny, gi tr ti u ca nng LPG v vn tc
dng c xc nh, ln lt l: X1 = 31.2% v X2 = 3.2 cm/pht.
Trong khi , kt qu trong cc hnh III.3 v III.4 cho thy, khi nhit
tng, lng CNTs to thnh cng nhiu, c bit, khi nhit vt qu mc *
( 683.6oC), lng CNTs vn cn gia tng. iu chng t gi tr ti u ca
45

nhit nm ngoi vng kho st. Kt qu ny hon ton ph hp vi kt


qu thu c t phng trnh hi quy khi hai h s b3 v b33 (138.32 v
25.67) ca bin x3 (nhit ) u dng.
xc nh gi tr ti u ca yu t nhit cho qu trnh tng hp,
hai thc nghim thay i gi tr nhit (vi bc nhy 30oC), ti 2 gi tr ti
u ca nng LPG v vn tc dng va tm c, c tin hnh.
Lng CNTs to thnh ng vi cc gi tr nhit khc nhau c trnh by
trong hnh III.5.
1600

1225

1200

M (%)

1120
950

800

510
400

0
650

680

710

740

T (oC)

Hnh III.5. Lng CNTs to thnh ng vi cc gi tr ToC khc nhau


Kt qu trong hnh III.5 cho thy khi nhit l 710 oC, lng CNTs
to ra l ln nht, gp 12.25 ln so vi lng xc tc a vo ban u.
Nh vy, lng sn phm CNTs to ra nhiu nht (M % ---> max) khi
vng ti u ln cn xung quanh cc gi tr nng LPG l 31.2 %; vn tc
dng kh trong h l 3.2 cm/pht v nhit tng hp l 710 oC. Lc ,
lng CNTs to thnh ln gp 12.2 ln so vi lng xc tc Fe/- Al2O3 v
72 ln so vi xc tc tnh theo Fe.
Cc kt qu c trng tnh cht ca mu CNTs thu c iu kin
tng hp ti u cho thy mu c cu trc ca CNTs (hnh III. 6), c ng
u cao, ng knh ng nm trong khong 14 nm. Din tch b mt ring
BET ca mu c gi tr l 172 m2/g.

46

Hnh III.6. nh SEM v TEM mu CNT iu kin ti u:


T = 710oC, CLPG = 31.2%, VLPG = 3.2 cm/pht
Nh vy vi cc iu kin nu trn, vt liu CNTs c tng hp
vi cht lng cao v vi gi tr M cao nht.
III.1.2 Nghin cu tng hp vt liu C-CNTs
Trong cc thc nghim ny ba loi nha c chn lm cht kt dnh
cho CNTs, trong c hai loi nha nhit do l polyvinyl alcohol (PVA) v
polystyren (PS), mt loi nha nhit rn l phenol-formaldehyde (PF). Sau
thc nghim to dng cho CNTs, cc mu c x l nhit cao, khng
c mt oxy, nhm phn hy cc cht kt dnh polyme thnh cc hp cht d
bay hi v carbon (tm gi l qu trnh carbon ha). V vy vt liu c gi
l vt liu composite C-CNTs. Hnh III.7 l nh chp cc mu C-CNTs sau
khi c nh dng.

Hnh III.7. Vt liu trc khi nh hnh (CNTs) - a,


sau khi nh hnh dng vin (C-CNTs) - b v dng tm (C-CNTs) - c
V nhit v thi gian phn hy ca cc loi nha l khc nhau, cn
thit phi nghin cu chn c ch nung hp l cho tng loi. Phng
php phn tch nhit vi sai (TG/DTA), kt hp ph hng ngoi (FT-IR)
c s dng gii quyt vn ny.

47

Nh chng ta bit nha PF to thnh mng li khng gian khi


ng rn ng thi trong cu trc ca n c cha cc vng benzen rt bn, v
vy phn hy hon ton cn phi tin hnh nhit cao. iu ny c
lm sng t hn khi nghin cu qu trnh phn hy nhit ca mu bng
phng php TG/DTA. Trn gin trong hnh III.8 thy xut hin mt pic
ta nhit nhit 250oC, ng vi phn ng to lin kt ngang gia cc i
phn t ca PF mc trit hn. iu ny c th c gii thch l do
PF c tng hp trong phng th nghim nn c th phn ng polyme ha
xy ra cha hon ton. Phn ng ny loi ra mt phn t nc lm cho khi
lng ca mu gim xung t t. T 420oC nha PF bt u phn hy nhng
phi n 900oC mi phn hy hon ton v trong qu trnh ny c xut hin
o

mt pic thu nhit 640 C (ng vi qu trnh phn hy mnh nha).

Hnh III.8. Gin TG/DTA ca PFCNTs vi t v khi lng l 3 1


o

Nh vy, kt qu phn tch TG-DTA cho thy n 900 C nha PF mi


phn hy hon ton. Tuy nhin, trn thc t, i vi a s cc mu c mt
thnh phn no cn c phn hy, thay v phi x l nhit cao,
ngi ta c th x l mu nhit thp hn v lu trong thi gian di. p
dng trong trng hp ca C-CNTs (PF), cc thc nghim nung vt liu
o

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)

Hnh III.9. Ph FTIR ca 3 composites C-CNTs (PF)


(a): Sau khi ng rn 150oC, (b): Nung 640oC trong 15h,
(c): Nung 850oC trong 3h
o

Tng thi gian nung ln 5h ( 850 C), hu nh ton b lng PF c


mt trong mu b phn hy. iu ny c th hin r trn ph FTIR ca
mu trc v sau nung (hnh III.10). C th, trn ph ca mu sau nung
gn nh khng cn xut hin cc dao ng c trng ca vng benzene trong
o
nha PF na. T , c th kt lun rng 850 C, trong 5h, nha PF hu nh
b carbon ha hon ton.

(a)

(b)

Hnh III.10. Ph hng ngoi ca composite C-CNTs (PF)


(a) trc khi nung (sau khi ng rn 1500C)
(b) sau khi nung 850oC trong 5h
Vi cch lm tng t nh i vi cc mu C-CNTs (PF) trn c s
cht kt dnh l nha PF, tin hnh cc thc nghim xc nh ch nung
thch hp cho vt liu C-CNTs (PS) iu ch trn c s cht kt dnh l PS.
Kt qu phn tch nhit vi sai TG/DTA (hnh III.11) cho thy nha PS trong
49

mu C-CNTs (PS) c nhit phn hy thp hn nhiu so vi nha PF trong


mu C-CNTs (PF). 380oC, nha PS bt u phn hy v qu trnh kt thc
500oC sau 3h.

Hnh III.11. Gin TG/DTA ca PS CNTs ca composite PS-CNT


Cc kt qu nghin cu la chn ch nung i vi cc mu C-CNTs
(PVA) trn c s cht kt dnh l nha PVA, c tin hnh tng t nh
trn (khng ch ra y) cho thy qu trnh than ha ca PVA trong vt liu
din ra hon ton 5500C trong 3h.
Cc kt qu trn cho php chng ti xc lp ch nung hp l cho cc
loi nha, nh trnh by trong bng III.2.
Bng III.2: Ch nung thch hp cho cc loi nha

III.1.3 c trng tnh cht ca vt liu C-CNTs


Bng III.3 ch ra tnh cht c hc ca vt liu C-CNTs c ch to t
CNTs vi 3 loi polyme PF, PS, PVA theo ch nung thch hp nh nu
trong bng III.2.
50

Bng III.3 Tnh cht c hc ca vt liu


Tnh cht

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)

Hnh III.12. nh SEM ca composite C-CNTs (PF) nung 850oC, 5h


i vi composite C-CNTs (PS), kt qu thu c t nh SEM cho
thy, phng i 100.000 ln v 150.000 ln (hnh III.13 (a) v III.13 (c)),
hu nh khng thy c mt ca carbon v nh hnh to ra t qu trnh nhit
phn nha PS. y l mt thng tin cn phi c nghin cu chi tit hn
51

c th khng nh s chuyn ha hon ton carbon v nh hnh sang CNTs,


trong qu trnh nhit phn PS c th nh vo s c mt ca xc tc ln trong
CNTs. Ngoi ra, PS l mt polyme khng phn cc nn c th phn tn tt
CNTs hn l nha PF to iu kin d dng khi ng nht ha hn hp trc
khi nhit phn.
(a)

(b)

(c)

Hnh III.13. nh SEM ca composite C-CNTs trn c s nha


polystyrene nhit 500oC trong 3h
Kt qu nh gi din tch b mt ring BET v tnh cht xp ca vt
liu cho thy din tch b mt ring v th tch l xp ca cc vt liu C-CNT
(PS) v C-CNT (PF) thu c ln lt l 152 m2/g, 0.3 cm3/g v 130 m2/g,
0.4 cm3/g.
T kt qu c trng tnh cht ca vt liu, kt hp vi cc kt qu
c nu trong bng III.3 ta thy PS l loi nha thch hp nht sn xut
vt liu C-CNTs. Vi nhit nung thp (500oC) trong vng 3h, PS c
carbon ha hon ton thnh carbon. Hn na PS li l mt polyme phn cc
nn c kh nng phn tn tt CNTs to cho b mt vt liu ng u lm cho
din tch b mt ca vt liu khng thay i nhiu. iu c chng minh
bng nh SEM (hnh III.13).
Kt hp vi cc kt qu c nu trong bng III.3, nhn thy tng
hp vt liu C-CNTs, trong s hai cht kt dnh PF v PS, cht kt dnh PS l
thch hp hn c v ngoi vic c bn c hc t yu cu, PS cn c nhit
phn hy thp hn so vi nha PF.
III.1.4. Tnh cht siu k nc ca vt liu composite C-CNTs
Nh chng ta bit, b mt ngoi ca ng nano carbon c tnh cht
k nc. c tnh ny chnh l c s c th p dng loi vt liu t hp
ny trong lu tr kh, hp ph chn lc, tch cht. Theo s phn loi, mt vt
liu c b mt c xem l k nc khi gc thm t ca git nc ln hn
52

90 , cn vt liu c b mt c xem l siu k nc khi gc thm t ca


o
git nc ln hn 150 .
Thc nghim nghin cu tnh cht k nc ca vt liu C-CNTs c
thc hin trn tm C-CNTs. Sau khi chp nh ri xc nh gc thm t nh
s h tr ca phn mm Autocad, gc thm t trung bnh ca b mt vt liu
C-CNT c xc nh l xp x 162 , nh c trnh by hnh III.14.

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.

Hnh III.15. nh SEM ca b mt m C, CNFs trn C v CNFs


Trong cc ti liu tham kho, bng k thut chp nh bng knh hin vi
in t truyn qua phn gii cao (HR-TEM) ngi ta chng minh rng
53

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.

Hnh III.16. S pht trin ca CNF tun theo c ch TIP Growth


Kt qu nghin cu cu trc ca mu CNFs ca chng ti bng phng
php knh hin vi in t truyn qua (TEM) hnh III.17 cho thy r cc tm
xc tc Ni c y khi b mt ca cht mang v nh v u carbon nano
si.

Hnh III.17. nh TEM v s pht trin ca CNF trn tm hot tnh Ni


Thm vo , nh chp bng phng php knh hin vi in t qut
(SEM) ch compo (k thut chp cho php thu c cc nh SEM c
tng phn ln v th hin c mt in t v dn in ca vt liu)
cho thy r s c mt ca cc tiu phn Ni. Thc vy, cc tiu phn Ni c mt
in t v dn in ln chnh l cc im sng trn nh (hnh III.18)
cn cc vt ti l cc cm CNFs. y l ln u tin c ch TIP Growth hnh
thnh CNF c chng minh mt cch thnh cng bng phng php SEM.

54

Hnh III.18. nh SEM thu c ch compo ca vt liu CNF tng


hp trn xc tc 1% Ni/m carbon
III.3 TNG HP V C TRNG TNH CHT CA XP CNTs
Do thi gian c hn nn trong ni dung ny, chng ti ch tin hnh cc
nghin cu thm d v tng hp v nh gi tnh cht ca xp CNTs. Hnh
III.19 ch ra hnh nh ca ming xp CNT c tng hp bng phng php
CVD trong 4 gi.

Hnh III.19. Xp CNTs tng hp bng phng php CVD


Phng php SEM cho thy cu trc t vi ca vt liu xp CNT (hnh
III.20). T kt qu ca nh SEM ta thy kch thc trung bnh ca ng nano
carbon khong 14 nm. Cc ng nano carbon c sp xp chng ln nhau, to
ra cc l xp ln. Kt qu c trng tnh cht xp ca vt liu cho thy xp
CNTs tng hp c c din tch b mt ring 280 m2/g.

Hnh 3.20. SEM ca vt liu xp CNTs

55

III.4 NH GI KH NNG HP PH DU CA CC VT LIU


TRONG H DU - NC
Hnh III.21 ch ra kh nng hp ph du diesel (DO) v du thc vt
(thng phm) ca cc loi vt vt liu khc nhau: CNT-bt, C-CNT (PS), CCNFs, xp CNTs v than hot tnh ( so snh).
T kt qu ta thy kh nng hp ph du ca cc loi vt liu C-CNT
(PS), CNT-bt, CNFs ln hn rt nhiu so vi kh nng hp ph ca than
hot tnh. Hn na, ta cn thy s hp ph du ca CNT-bt ln hn so vi
vt liu CNT c nh hnh (C-CNT (PS) vin). iu ny hon ton hp
l v i vi hu ht cc loi vt liu, sau khi s dng cht kt dnh nh
hnh, tnh cht xp v din tch b mt ring ca mu thng b gim i do c
s co ngt b mt hoc s che ph cc l xp. iu ny lm cho kh nng
hp ph du ca vt liu b gim i. Vt liu xp CNTs c kh nng hp ph
du (DO v du thc vt) ln nht, gp 5 ln (QDO = 58,7 v QDu thc vt =
50,2) so vi CNTs bt (QDO = 13,4 v QDu thc vt = 11,5), chng t vt liu
ny c xp ln. Nh vy, i vi vt liu xp CNTs, du khng ch c
hp ph vo bn trong ng nano carbon m cn c hp ph rt nhiu
khong trng c to ra gia cc ng. V vy lng du hp ph c ln
hn rt nhiu so vi khi lng ca CNTs.
Do thi gian c hn nn chng ti cha c iu kin c trng tnh
cht mt cch h thng v iu chnh phng php ch to xp CNTs. Nhng
nghin cu su hn v loi vt liu th v ny s c thc hin trong cc
cng trnh tip theo.

Hnh III.21. Kh nng hp ph ca cc loi vt liu carbon


Hnh III.22 ch ra kh nng hp ph cc dung mi v cc loi du khc
nhau ca cc vt liu c nh hnh C-CNT (PS), C-CNFs, xp CNTs. T
hnh v ta thy kh nng hp ph dung mi, du khc nhau ca tng loi vt
56

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).

Hnh III.22. Kh nng hp ph dung mi, du ca cc vt liu nh hnh


III. 5 THM D KH NNG NG DNG CA VT LIU TRONG
QU TRNH TCH CHT V TRONG X L S C TRN DU
III.5.1. Thm d kh nng ng dng vt liu trong qu trnh tch cht
Mng lc tch cht, c iu ch theo phng php c m t
phn thc nghim, l 1 tm Teflon ph nano carbon, c tnh cht k nc v
a du. Tnh cht k nc ca mng c chng minh hnh III.23.

57

T nh chp, ta d dng nhn thy bng mt thng gc tip xc ca


nc vi b mt tm carbon ln hn 90o, chng t tm carbon l vt liu ky
nc.

Hnh III.23. Tnh k nc ca tm carbon


Kt qu nghin cu kh nng tch cht ca mng lc ph vt liu nano
carbon c th hin trong hnh III.24. Trong cc thc nghim ny, pha du
pha trn cn pha nc pha di, c cho thm kali dicromat (K2Cr2O7)
to mu cho d phn bit.
Trong qu trnh lc ht chn khng, hn hp c khuy trn u. V
tm lc nano carbon k nc, a du nn khi tm lc tip xc vi hn hp
du - nc, nc b y ra cn du c hp ph vo tm lc nano carbon v
nh lc ht chn khng nn du hp ph b ht xung pha di tm lc.
Kt qu l pha du v pha nc c tch ra d dng, trong , pha du i
qua tm lc xung bnh pha di cn nc li pha trn tm lc.
Th nghim va ri l mt th nghim c thit k minh chng mt
cch trc quan cho kh nng tch du v nc ra khi nhau. V vy, chng ti
thit k mu gi c t l th tch nc du tng i ln. Trong thc t,
c th nc ch ln mt lng nh trong du v cn thit phi c tch ra.
Vy trong trng hp ny, nc v du c d dng c tch khi nhau nh
tm lc nano carbon hay khng? tr li cu hi ny, chng ti thit k
th nghim th hai, trong , hm lng nc trong du l 5 % (dng nh
tng). Lp li th nghim trn ri xc nh hm lng nc trong du sau
khi tch nc.
Kt qu cho thy, lng nc cn li trong du l 0,9 %. iu
chng t, vt liu CNTs c kh nng rt tt nc ra khi du.
Tt nhin, kho st k vn ny cn cn phi tin hnh cc nghin
cu vi hm lng nc trong du khc nhau, nc phn tn trong cc dung
mi khc nhau, kch thc cc ht nc trong nh tng du khc nhau,
phng php iu ch tm lc CNTs khc nhau,
Tuy nhin, y l nhng kt qu bc u ht sc l th, m ra kh
nng ng dng thc tin ca vt liu trn c s CNTs.
58

Hnh III.24. Lc du trong h du nc ca tm carbon


III.5.2. Thm d kh nng ng dng vt liu trong x l s c trn du
Trong phn ny, chng ti tin hnh nghin cu kh nng thu hi du
v ti s dng vt liu sau khi hp ph. i tng c la chn nghin cu
l vt liu C-CNTs v xp CNTs. C hai vt liu u c hp ph du n
bo ha. Tip theo, vt liu C-CNTs bo ha du c gii hp bng cch gia
nhit v x l chn khng. Vt liu xp CNTs c gii hp bng cch p c
hc. Sau khi gii hp, vt liu c ti s dng. Thc nghim c lp i lp
li nhiu ln. Kt qu nghin cu c trnh by trong cc bng III.4 v III.5.
Bng III.4: Kh nng ng dng ca vt liu C-CNTs
S ln th nghim

Hiu sut thu hi du (%)

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

Bng III.5: Kh nng ng dng ca vt liu xp CNTs


S ln th nghim

Lng du thu hi (%)

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

Nh vy, qua cc th nghim thm d trn c th tm rt ra kt lun l


c hai loi vt liu u c kh nng cho thu hi du hp ph v c kh nng
ti s dng nhiu ln. iu chng t, cc vt liu ny u c kh nng ng
dng thc tin cao. Tt nhin, do y ch l nhng nghin cu thm d, nn
c th hng ti vic ng dng thc tin, s cn cn rt nhiu nghin cu
b sung.
III.6 XUT QUI TRNH CNG NGH CH TO VT LIU SIU
K NC C-CNTs QUI M PILOT
III.6.1 xut qui trnh cng ngh ch to C-CNTs (PS)
iu ch 0,1kg vt liu C-CNTs (PS) cn tin hnh quy trnh nh
sau (hnh III.24):
- To dung dch PS trong toluen bng cch khuy hn hp gm 0.325 kg
PS trong 4,062 kg toluen, trong 5 gi (hn hp A).
- Sau , cho 0,1 kg CNTs vo hn hp A ri khuy u n khi hn
hp tr nn ng nht (khong 3 gi).
- Tip theo, hn hp c to dng tm hoc dng vin bng my, sau
sy 80oC trong 12 gi n nh hnh dng, ri c nhit phn
o

di mi trng kh tr (N2) nhit 500 C trong thi gian 3gi.


Vi thit b qui m nh trn (nhng s dng 2 l sy), c th thu c
100 kg vt liu C-CNTs/nm.
III.6.2 xut quy trnh ch to vt liu C-CNFs
Quy trnh sn xut CNFs s dng xc tc Ni mang trn m carbon
gm cc bc sau:
- m carbon c x l trong dung dch axit 70C loi tt c cc
tp cht v hot ha b mt.
- Tm m carbon qua x l c tm dung dch NiNO3.6H2O.
60

- Hn hp c sy 1100C trong 12 gi, ri nung 450oC trong dng


nit trong 2 gi.

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

Hnh III.24 S nguyn l quy trnh iu ch vt liu C-CNTs (PS)


Dung dch
axit

Dung dich
NiNO3

Kh x

Kh N2
Kh x

Sy
Nung

Hnh III.25. S nguyn l quy trnh x l tm m carbon


Tip theo, t ming m carbon x l vo trong ng phn ng bng
thch anh. Sau khi kh xc tc bi hydro 550C trong 2 gi, cho LPG qua
thit b vi vn tc dng kh v nhit n nh. Sau khi tng hp xong, lm
61

Thnh
phm

ngui ng phn ng n nhit phng ri thu hi tm m carbon c cha


CNFs.

(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)

Hnh III.27. S nguyn l quy trnh iu ch vt liu xp CNTs (PS)


Trong
(1) : Bnh kh
(2) : Van iu chnh p sut
(3) : Van an ton
(4) : Thng cha dung mi Diclorobenzen
(5) : Thng phn ng
(6) Phu cho bt Ferocen
(7) Bm
(8) Bung t
(9) Tm thch anh

63

III.6.4 nh hng ch to vt liu quy m cng nghip


Vt liu nano siu k nc s c sn xut t LPG, ngun nhin liu sn c
Vit nam. iu ny s gp phn h gi thnh sn phm, ng thi ch ng c
ngun nguyn liu trong nc. Bn cnh , vt liu nano carbon ng dng cho
mc ch x l s c trn du khu sau khng i hi c sch tuyt i nh cc
ng dng trong vt l, ng thi hm lng nano carbon cng khng i hi qu
cao (hn 90% l tha mn). V vy chi ph cho sn xut nano carbon s c kh nng
cnh tranh vi cc loi vt liu khc. y l nhng u th gp phn rt ngn
khong cch t phng th nghim n quy m cng nghip ca loi vt liu ny.
III. 6.5 nh gi s b hiu qu kinh t v ngha thc tin
Nh trnh by cc phn trn, x l du trn bng cht hp ph thng l
qu trnh x l khu sau. c bit x l du trn bng vt liu nano siu k nc l
qu trnh x l tinh vi, thng c p dng lm sch s nhim nc bi du,
m cc phng php thng thng khc khng th thc hin c mt cch hiu
qu. Hn na, vt liu hp ph du trn c s nano carbon c kh nng hp ph du
cao hn nhiu so vi cc loi vt liu thng thng. Bn cnh , kh nng thu hi
du v ti s dng vt liu l rt ln. Ni tm li v hiu qu k thut vt liu siu
k nc trn c s nano carbon p ng c hu ht cc tiu chun i vi vt
liu hp ph du.
V hiu qu kinh t, nh cng phn tch trn, gi thnh ca vt liu
nano carbon hon ton c th cnh tranh vi gi thnh ca vt liu hp ph du
thng thng khc.
V mi trng, vic ng dng vt liu siu k nc x l khu sau cho s
c trn du s gp phn gim thiu nhim mi trng, lm trong sch mi trng
sinh thi ca vng nc b nhim du.

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

TI LIU THAM KHO


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