Nang Cap Nhien Lieu

Tiu lun Nng cp nhin liu GVHD: PGS.TS.
Nguyn Hng Lin

HVTH: Nhm 4-13BKTHH1-2 2

LI M U
Ngy nay, du m tr thnh ngun nng lng quan trng nht trn ton
th gii vi khong 65-70% nng lng s dng i t du m. Tuy nhin, theo
tnh ton ca cc chuyn gia th vi tc tiu th nh hin nay v tr lng du
m hin c, ngun nng lng ny c th s dn cn kit sau khong 40-50 nm
na. Bn cnh , nhu cu s dng nng lng du m vn khng ngng tng ln
cng vi s lng cc phng tin giao thng vn ti. Vn nhim mi trng
t kh thi ng c theo cng ngy cng tr nn nhc nhi. Do vy, bn cnh
nghin cu tm ra cc ngun nng lng mi thay th mt cch ph hp, cn
c cc gii php nng cp nhin liu nhm bt kp cc loi ng c ngy cng
hin i, tit kim nhin liu v quan trng nht l p ng yu cu v vn
gim pht thi nhim mi trng.
S c mt lu hunh trong nhin liu nh hng xu n cc ch tiu kinh t-
k thut cng nh mi trng, chng hn: lm gim hiu sut s dng nhin liu;
mi mn ng c; gy ma axit khi c pht thi vo khng kh di dng kh
SO
x
, lm gim hiu qu x l ca b chuyn i xc tc Do , gim hm
lng lu hunh trong nhin liu n mc thp nht p ng yu cu v mi
trng m vn ph hp vi ch tiu kinh t - k thut l mt trong nhng hng i
quan trng trong nghin cu trong nng cp nhin liu.
Trong cng ngh lc ha du, qu trnh Hydrodesunfua ha (HDS) c s
dng ph bin x l lu hunh. l qu trnh nhm tch loi S ra khi hp
cht cha lu hunh bng H
2
, c mt ca cht xc tc. Tuy nhin, vi qu trnh
ny, kh lu hunh su xung di 50 ppm c bit l di 5 pmm phi s
dng cng ngh HDS c bit vi xc tc hot tnh cao, iu kin khc nghit v
kh m bo khng lm gim tr s octan khi kh lu hunh su trong xng.
Do vy, c rt nhiu cc nghin cu v ang c thc hin nhm kh lu
hunh sau trong nhin liu vi nhiu h xc tc khc nhau, trn c s khc phc
cc nhc im trn. y, bi tiu lun ny xin c trnh by trn c s tm
hiu mt nghin cu mi c thc hin gn y: Kh lu hunh su trong
xng s dng zeolit trao i ion: Cu(I)- v Ag(I)-beta.

Tiu lun Nng cp nhin liu GVHD: PGS.TS. Nguyn Hng Lin

MC LC
LI M U .................................................................................................... 2
PHN 1. GII THIU CHUNG ....................................................................... 4
PHN 2. THC NGHIM................................................................................ 7
2.1. Nguyn liu v thuc th ..................................................................... 7
2.2. iu ch cht hp ph .......................................................................... 7
2.3. c trng ca cc cht hp ph .......................................................... 8
2.4. Hp ph lp c nh v qu trnh ti sinh ........................................... 8
2.5. Phn tch hm lng lu hunh tng .................................................. 9
PHN 3. KT QU V THO LUN........................................................... 10
3.1. c trng ca cc cht hp ph ........................................................ 10
3.2. Kh lu hunh vi lp xc tc c nh ............................................. 12
3.3 Ti sinh cht hp ph ......................................................................... 17
PHN 4. KT LUN ...................................................................................... 19
TI LIU THAM KHO ............................................................................... 20


PHN 1. GII THIU CHUNG
Kh lu hunh su trong cc nhin liu ng c nhn c nhiu s quan
tm ca cc quc gia trn ton th gii, cc yu cu k thut c quy nh
nghim ngt hn i vi lu hunh trong nhin liu xut pht t cc vn mi
trng. Trung Quc, qui nh cc nh my lc du phi gim hm lng lu
hunh trong du diezel v xng xung di 15 ppm vo nm 2010. S quan tm
i vi cc loi nhin liu c hm lng lu hunh cc thp cng c thc y
trong cc ng dng pin nhin liu. Bi v cc hp cht lu hunh hu c trong
nhin liu hydrocarbon lng gy ng c vi cc cht xc tc c s dng trong
x l nhin liu (nh trong qu trnh reforming xc tc hay trong chuyn ha hi
nc trong h thng pin nhin liu) v cc cht xc tc in cc trong cc ngn
ca pin nhin liu.
Nh vy, hm lng lu hunh c th chp nhn c i vi pin nhin liu
v nguyn liu reforming l di 1 ppm v thch hp hn l di 0,01 ppm. Qu
trnh kh lu hunh bng Hydro (HDS) l qu trnh rt hiu qu trong vic loi b
cc hp cht cha lu hunh trong nhin liu, c ng dng rng ri trn ton
th gii. Trong qu trnh ny, cc iu kin tin hnh rt khc nghit nh nhit
v p sut cao, tiu th hydro cao. Hin nay, yu cu hm lng lu hunh cc
thp i vi nhin liu ngy cng kht khe. iu ny ch c th t c bng
cch s dng qu trnh HDS v iu kin phn ng nghim ngt nh tng kch
thc thit b phn ng, v lu lng hydro. Di nhng iu kin ny, nhiu
olefin v cc hp cht thm c trong xng c bo ha, iu ny lm gim ng
k ch s octan, ngay c i vi cc ng c thng thng. c nhng s quan
tm ln n vic pht trin mt phng php mi kh cc hp cht lu hunh
t nhin liu lng cho cc ng dng pin nhin liu. S hp ph c chn lc loi
b hp cht lu hunh l mt th thch, khi chng cng tn ti vi nng cao
hydrocacbon thm trong xng. Kh lu hunh su trn nhiu cht hp ph ging
nh hn hp oxit bin tnh, than hot tnh, khong st v zeolit c nghin
cu. Trong s ny, cc cht hp ph trn c s zeolit c coi nh nhng vt
liu y ha hn cho vic loi b lu hunh trong xng.
Wardencki c bo co trc v mt cht hp ph hiu qu nhiu hp
cht lu hunh khc nhau t dung dch n-heptan trn zeolit 13X v mt s tc gi
nghin cu s hp ph cc hp cht thiophen trn zeolit ZSM-5.


Gn y, mt s cng trnh nghin cu ca Weitkamp, Garcia, v Chica
bo co mt s tc ng tiu cc (nh qu trnh oligome ha cc hp cht
thiophen) cho thy qu trnh kh lu hunh trn xc tc ZSM-5 khng ph hp
loi b cc cht dn xut cha lu hunh ca cc hydrocarbon . qu trnh ti
sinh c d dng nn trnh qu trnh oligome ha. Gn y, nhiu cng trnh
c thc hin i vi qu trnh hp ph thiophen trn zeolit faujaxit c trao
i cc ion kim loi khc nhau. Cht hp ph Cu(I) Y ca Yang v cc cng s c
kh nng loi b thiophen trong nhin liu bi phc vi nng lu hunh
tng di 1 ppm. Song v cc cng s tin hnh mt cuc kho st c ch s
dng hp cht lu hunh c v khng c h thng da trn cht hp ph zeolit
Y . iu ny cho thy cc hp cht lu hunh c hp ph trn Ce-Y zeolit qua
hp ph trc tip (SM) hn l qua mt phc . Laborde - Boutet kho st s hp
ph cnh tranh gia thiophen v cc hp cht thm trn cht hp ph kim Y v
X, sau kt lun rng bn cht ca zeolit c nh hng ln n s hp
ph/tng tc hp ph v kh lu hunh chn lc.
i vi mt vt liu hp ph tt, khng ch c kh nng hp ph v chn lc
cao, kh nng nh hp ph ca n nhm cho php ti sinh cng rt quan trng.
Gn y, mt s phng php ci thin tnh chn lc v kh nng kh lu
hunh thng a cht mang c din tch b mt BET cao (nh than hot tnh
hoc cc vt liu mao qun tm halogenua kim loi) hoc cation kim loi chuyn
tip (bao gm Ag
+
, Cu
+
, Ni
2+
v Ce
2+
) vo zeolit.
Bng cch s dng SBA -15 v than hot tnh nh cc cht mang, Wang
pht trin hai loi cht hp ph da trn c s Pd, c kh nng hp ph lu hunh
cao hn so vi Cu(I) Y. Tuy nhin, ch cn 70% v 48 % kh nng x l lu
hunh tng ng i vi cht hp ph PdCl
2
/AC v PdCl
2
/SBA-15 sau khi ti
sinh nhit.
Trong cng trnh nghin cu ny, zeolit beta l mt h thng mao qun rng
ba chiu bao gm 12 nhm vng v t l Si/Al c th iu chnh trong mt phm
vi rng. Do , zeolite beta c th kim sot d dng tm hot ng v s n nh
nhit cao c li cho s hp ph v ti sinh, do n c th c cng nhn l mt
vt liu quan trng cho vic s dng trong qu trnh hp ph lu hunh. Nhiu
nghin cu cho thy rng c nhiu tm hot ng trn Fe-BEA hn Fe-ZSM-5
trong vic kh N
2
O.


Nghin cu ny c thc hin lm sng t mt s vn v cc cht hp
ph zeolit beta trao i Cu(I), Ag(I) c iu ch theo phng php SSIE,
hng ti vic kh trc tip lu hunh t cc hp cht thiophen.
Cc th nghim khc c thc hin trn cc thit b kh lu hunh cho xng
mu v xng FCC thc t s dng vt liu hp ph tng c nh trong iu kin
thng. Hiu sut kh lu hunh nh hng bi nhiu yu t nh cc cation kim
loi trao i khc nhau, hm lng ca cc cation kim loi trn zeolite beta, t l
SiO
2
/Al
2
O
3
ca zeolit. Cui cng, qu trnh ti sinh cc cht hp ph zeolite beta
Cu(I), Ag(I) cng c nghin cu. Kt qu cho thy kh nng x l lu
hunh ca cc cht hp ph zeolit beta Cu(I), Ag (I) tng ng l 0,239 mmol S/g
v 0,237 mmol S/g. C hai cht hp ph u cn khong 95% kh nng kh lu
hunh sau 9 ln ti sinh.


PHN 2. THC NGHIM
2.1. Nguyn liu v thuc th
Cc hp cht lu hunh bn nhit, thiophene (99,9%) v benzothiophen
(95%), c sn xut bi hng Aldrich. Zeolite beta c s dng nh mt
nguyn liu u, c tng hp trong phng th nghim. Cyclohexan (99%), s
dng lm dung dch xng mu, v cc ha cht khc c s dng trong cc
phng php phn tch c xut s t Trung Quc.
2.2. iu ch cht hp ph
Cc nguyn liu u s dng trong nghin cu ny l cc zeolit beta Na vi t
l SiO
2
/Al
2
O
3
khc nhau (8, 12, 25, 30, 60, v 80), c kch thc ht trong khong
200-300 nm. Dng amoni ca zeolit beta t c bng cch trao i 10 g Na-beta
vi 150 ml dung dch NH
4
Cl 1 M ti 383

K hai ln trong 1 gi. Tip theo, NH4-
beta c nung 773

K vi thi gian 4 gi trong khng kh. Sau , thu c cc
H-beta v bo qun trong mt ci hp kh trc khi iu ch Cu(I) - v Ag(I)-
beta bng cch trao i ion. Cc phng php khc nhau c s dng cho vic
iu ch zeolit trao i kim loi chuyn tip nh nhng cht xc tc. Bao gm cc
qu trnh trao i ion trong dung dch nc thng thng; k thut trao i ion
trng thi rn (SSIE); phng php thng hoa hoc lng ng pha hi ha hc.
Ni chung, phng php trao i ion trng thi rn c nhng u im sau: (i)
cho php iu khin hm lng kim loi trao i; (ii) cho php trao i trc tip
cation kim loi m khng cn s c mt ca phc kim loi t qu trnh trao i
ion trong nc; (iii) c th ti sinh ngay p sut thng; (iv) c th to thm
mt s tm hot ng so vi phng php trao i ion trong dung dch nc; (v)
cho php iu khin kch thc ca tinh th.
Nhiu kt qu nghin cu cho thy rng xc tc zeolit trao i ion kim loi
c iu ch theo phng php SSIE hnh thnh nhiu tm hot ng hn so vi
phng php trao i trong dung dch nc trong qu trnh xc tc nht nh. Do
, phng php trao i ion (SSIE) trng thi rn c s dng y iu
ch C (I) v Ag(I) beta nh cc cht hp ph loi b cc hp cht lu hunh
hu c t xng. Mt qu trnh in hnh l: 5g zeolit H-beta c trn vi mt
lng CuCl kh, sau hn hp c chuyn sang mt thit b phn ng thch
anh.


Tip theo, hn hp CuCl/beta c cho tip xc vi nit kh vi tc dng
50 ml/pht v tc nng nhit l 10 K/pht t nhit mi trng n 623 K v
gi nhit ny trong 2 h, v sau gi 873 K trong 6 h trong mi trng kh
nit tinh khit.
T l CuCl/zeolit theo khi lng tng ng l 10%, 15%, 20%, 25%, 30%.
Tt c cc mu c lm mt t t n nhit phng trong mi trng nit kh
v sau bo qun trong mt hp kh trc khi s dng. Mt dy cc mu Ag(I)-
beta zeolit vi cc t l AgNO
3
/zeolit theo khi lng t 10 % n 30% cng
c iu ch theo mt qu trnh SSIE tng t trong iu kin khng kh tnh.
2.3. c trng ca cc cht hp ph
Cc phng php phn tch b mt v th tch mao qun c s dng xc
nh cc c trng ca cht hp ph. Cu trc tinh th ca cht hp ph c c
trng thng qua nhiu x tia X (XRD) bng cch s dng nhiu x Rigaku XRD-
6000 vi bc x CuK ( = 0,154 nm, in p 40 kV v dng in 30 mA), gc
qut 2 nm trong gii hn t 5
o
n 40
o
, tng dn 2
o
/ln. Din tch b mt ring
v th tch mao qun ca cc cht hp ph c o bng thit b hp ph vt l
ASAP 2010 s dng kh Nit hp ph/gii hp ph. Din tch b mt ring
c tnh bng phng php Brunauer-Emmett-Teller (BET ). Mu c loi b
khng kh qua m 673 K n p sut chn khng trc khi o. Quang ph
hng ngoi IR hp ph pyridin c s dng kho st bn cht ca cc tm
axit. Ph ca cc mu c ghi li trn my o MAGNA-IR 560 FT-IR (Hng
Nicolet CO, USA) vi phn gii 2 cm
-1
s dng lt bn dn KBr. Khong 10
mg mi mu c p thnh mt lt bn dn c ng knh 13mm. u tin, t
cc lt bn dn ny vo mt cuvet 350 C trong 2 gi. Sau , cc mu c
lm mt n nhit phng v ph hng ngoi c ghi li. Cc pyridin tinh
khit c a vo bung hng ngoi cho n khi cht hp ph bo ha. Cui
cng, gii hp ph pyridin c thc hin tng bc nhit cao di p sut
10
-2
Pa v ph c ghi li.
2.4. Hp ph lp c nh v qu trnh ti sinh
Qu trnh th nghim c thc hin trong mt thit b phn ng thch anh
kiu ng c ng knh trong l 6 mm v chiu cao ct phn ng l 250 mm.
Nhit c o bng mt cp nhit in Chromel/Alumel c c nh trung
tm ca ct cht hp ph. Mt bm nh lng c s dng xng mu vo
lp hp ph.

Theo khuyn co ca Yang v cc cng s, qu trnh phn ng c thc hin
nh sau mt gam cht hp ph c gai nhit n 450
o
C trong mi trng kh
heli. Kh heli ban u c a qua mt ct lc phn t 3A loi b m nu
c trc khi i qua ct hp ph. Thi gian hot ha l hn 18 gi cho tt c cc
cht hp ph, tr khi c yu cu khc. Trong nghin cu ny, xng mu c
chun b vi 200 ppm hm lng lu hunh tng (thiophen 150 ppm v
benzothiophen 50 ppm) trong cyclohexan. Hm lng lu hunh tng trong xng
mu c phn tch bng cch s dng mt vi sc k.
Qu trnh kh lu hunh c bt u bng cch a xng mu vo thit b
phn ng lp vt liu c nh cha 1 g cht hp ph, khng gian cn li ca ct
c in y bng thy tinh. Tc khng gian th tch i vi qu trnh kh
lu hunh trong bi bo ny c c nh ti 60 h
-1
. u vo v u ra c
phn tch c c nhng biu ng cong v tnh ton kh nng hp ph.
Khi cht hp ph zeolit t n im bo ha, bm vn chuyn xng c ng
li. Mu xng thc t vi hm lng lu hunh khong 200 ppm c cung cp
bi Nh my lc du Lan Chu ca Petrochina. Qu trnh ti sinh cc cht hp
ph c thc hin trong dng Nit kh 623 K trong hn 6 gi vi tc
khng gian th tch 2400 h
-1
. Qu trnh ny c lp i lp li 9 ln v kh nng
kh lu hunh ca cht hp ph ti sinh c kim tra.
2.5. Phn tch hm lng lu hunh tng
Tng nng lu hunh trong cc mu chun, xng mu c xc nh bng
mt thit b phn tch hm lng lu hunh LC-4 Microcoulometry. Thit b c
hiu chnh trong phng th nghim ti ba cp hm lng lu hunh khc nhau: 0-
10 ppm, 10-50 ppm v 50-300 ppm s dng benzothiophen (BT) trong n-octan
nh mt dung mi hiu chun v cc biu hiu chun tuyn tnh thu c cho
mi khong hiu chun. ng tuyn tnh ca mi biu hiu chun trong mi
phm vi cng c kim tra cho bng cch s dng mu chun cha lu hunh.
Gii hn pht hin ca my phn tch hm lng lu hunh tng nm trong iu
kin lm vic bnh thng l 0,1 ppm.


PHN 3. KT QU V THO LUN
3.1. c trng ca cc cht hp ph
u tin, gii hn lng ion kim loi trao i vi H- beta zeolit c xc nh
theo l thuyt theo phng php sau. Zeolit Na-beta vi t l SiO
2
/Al
2
O
3
l 30,
thnh phn tinh th l Na
7
[Al
7
Si
57
O
128
]. Sau hai ln trao i ion NH
+
4
v nung,
lng Na
+
trong zeolit beta gim i 93% vi thnh phn l H
6.5
Na
0.5
[Al
7
Si
57
O
128
].
Nh vy, cation kim loi c trao i trng thi rn l 95%. Chng hn nh
CuCl, lng trao i theo l thuyt l 0.144 g trn mi gam zeolit Na-beta. Lng
AgNO
3
trao i cng c xc nh theo phng php tng t.
Phng php nhiu x tia X cho php kim tra kt tinh ca cc cht hp
ph Cu-beta v Ag-beta v nhng thng tin v dng tn ti c th ca cc oxit
kim loi nu c sau khi trao i theo phng php SSEI. Nh vy, hm lng kim
loi trao i ti u cng c th c xc nh nh ph XRD. Hnh 3.1 v 3.2 l
ph XRD ca Cu-beta v Ag-beta. Kt qu cho thy phng php SSIE khng nh
hng n cu trc ca zeolit, ph hp vi M-ZSM-5 trao i ion kim loi chuyn
tip theo phng php SSIE. kt tinh ca Cu(I)-beta v Ag(I)-beta gim nh
theo s tng hm lng ca ng hoc bc trn zeolit do cc khuyt tt khung
mng li gy ra bi cc ion kim loi sau khi mang ln. Vi quy trnh iu ch
Cu-beta, m bo thu c cht hp ph Cu-beta bng phng php SSIE l
Cu(I)-beta m khng b oxy ha thnh Cu(II), ton b qu trnh phi t trong mi
trng kh tr l nit. Mu c th tc thi tip xc vi khng kh trong qu trnh
o ph nhiu x tia X, do n c th kh trnh khi to thnh Cu(II), nhng
trc s dng trong qu trnh kh lu hunh Cu(II) c kh ti ch trong dng
(in situ) v Cu(I) trong mi trng kh tr. Nh c th thy trn hnh hnh 3.1,
nhiu x ti 2 bng 28,6
o
l do tinh th CuCl v cng ca n tng ln cng
vi s gia tng t l CuCl/H beta. Hm lng CuCl ti u theo zeolit l 15% khi
lng.
Cc ph nhiu x thu c (hnh 3.2) cho thy c mt pha ph ti 2 bng
38,1
o
biu th s c mt ca lng nh Ag
2
O khi lng AgNO
3
trao i vt qu
15%. Abuzeid v cc cng s nghin cu pha Ag
2
O trong Ag-ZSM-5 bng
phng php nhiu x tia X (in situ) trong sut qu trnh nung t nhit mi
trng ti 350
o
C. Kt qu cho thy cc peak ca Ag
2
O gim vi vic nhit
tng. iu ny cho thy cc oxit bc phn ng vi cc tm axit Btonsted. Ngoi
ra, cng peak ca AgO
2
tng khi nhit gim ti nhit mi trng cho
thy s tri ngc ca qu trnh ny.

Hnh 3.1. Ph XRD ca Cu(I)-beta vi t l CuCl/zeolit khc nhau.
a) 0%; b) 10%; c) 15%; d) 20%; e) 25%; f) 30%.

Hnh 3.2. Ph XRD ca Ag(I)-beta vi t l AgNO
3
/zeolit khc nhau.
Khi t l CuCl/beta hoc AgNO
3
/beta zeolit vt qu 15%, CuCl hoc Ag
2
O
tinh th c th tn ti trong cc knh mao qun/b mt ca zeolit v iu ny
nh hng ti c trng cu trc v hiu sut kh lu hunh (nguyn nhn gim
hiu sut kh S).
bng 3.1, din tch b mt ring BET v th tch mao qun ca cht hp ph
Cu(I) v Ag(I) gim nh vi s gia tng qu trnh trao i ion kim loi trong
zeolit H-beta.

2 /
C
n
g

/

c
p
s

2 /
C
n
g

/

c
p
s


Bng 3.1. Mt s c trng cu trc ca zeolit H-beta v zeolit beta trao i
ion kim loi vi hm lng khc nhau
Mu
Hm lng cation
(%)
Din tch b mt ring
BET (m
2
/g)
Th tch mao qun
(cm
3
/g)
H-beta
*

Cu(I)-beta
*

Ag(I)-beta
*

0
10
15
20
25
30
10
15
20
25
30
587
564
543
529
489
476
560
551
517
496
482
0,386
0,367
0,359
0,357
0,313
0,302
0,361
0,355
0,335
0,329
0,316

* T l SiO
2
/Al
2
O
3
ca zeolit beta l 25.
3.2. Kh lu hunh vi lp xc tc c nh
Trong nghin cu ny, tnh hp ph kh lu hunh ln u tin c thc
hin trong xng mu trn cc Na-, Cu(I)- v Ag(I)-beta zeolit. Kt qu cho thy
Na-beta zeolit khng hiu qu loi b lu hunh, ch c 20% lu hunh c
kh trong khi Cu(I)- v Ag(I)-beta tng ng l 92% v 87%. V vy, cc cation
kim loi Cu(I), Ag(I) trn zeolit ng mt vai tr quan trng trong vic kh lu
hunh hp ph. Nghin cu ny tp trung vo vic kho st kh lu hunh trn
cc vt liu hp ph Cu(I)- v Ag(I)-beta zeolit dng lp c nh.
Hnh 3.3 cho thy cc kt qu kh lu hunh trong xng mu c cha 200
ppm lu hunh trn Cu(I)- v Ag(I)-beta zeolit. Kh nng x l ca Cu(I)-beta v
Ag(I)-beta tng ng l 0,239 mmol S/g v 0,237 mmol S/g. Vi 1 g Cu(I)- hoc
Ag(I)-beta, tng ng khong 46 v 42 ml xng mu c x l vi hm lng
lu hunh gim mnh t 200 ppm xung di 1 ppm.


Hnh 3.3. Kh nng kh lu hunh trong xng mu trn Cu(I)- v Ag(I)-beta
zeolit nhit v p sut mi trng.
i vi qu trnh kh lu hunh trong xng, cc tc gi bo co kh nng
hp ph mang tnh x l ca Cu(I) Y-zeolit cp lu hunh 0,28 ppm l 0,14
mmol S/g. Mc d c tc ng ca phng php phn tch nh lng lu hunh
cp ppm trong nhin liu lng kh lu hunh khi hm lng lu hunh tng
trong phm vi nh (chng hn <10 ppm). Mt nghin cu gn y cho thy ion Cu
+, Ag +trong Cu-trao i Y (Ag-trao i Y) zeolit c hot tnh trong vic loi b
cc hp cht lu hunh thiophen bi phc . Trong nghin cu ny, axit ca
zeolit beta bao gm c tm Bronsted v Lewis khng nhng thay i sau khi trao
i Cu+ v Ag+ theo phng php SSIE m cn c nh hng n hiu sut kh
lu hunh.
Bng 3.2 cho thy lng axit Bronsted v Lewis ca H-beta cng vi Cu(I)-
v Ag(I)- beta. Ni chung, zeolit dng H c coi l c tnh axit v axit s
gim khi cc proton (H+) c trao i vi cc cation kim loi. C th thy rng
Cu(I)- v Ag(I)-zeolit beta c axit Bronsted thp so vi H-beta v axit
Lewis cao hn so vi H-beta. axit Bronsted gim tng ng l 93,5% vi
Cu(I)- v 89,2% Ag(I)-beta so vi H-beta. axit Lewis tng ln Cu(I)- v
Ag(I)-beta khng ng ngc nhin v cc cation kim loi l cht nhn in t.
iu ny hon ton ph hp i vi cc cng trnh trc y thc hin trn nhiu
zeolit trao i cation kim loi. Do axit Lewis cao hn to iu kin thun
li cho Cu(I)- v Ag(I)-beta i vi qu trnh hp ph lu hunh thiophen bi
l cc cu t cho in t.

Th tch xng mu (ml)
H
m

l
n
g

S

s
a
u

x

(
p
p
m
)


Bng 3.2. axit ca Cu-, Ag-beta zeolit iu ch theo phng php SSIE
Mu
Nhit
gii hp
(K)
Axit
Bronsted
(mol.mg
-1
)
Axit Lewis
(mol.mg
-1
)
Lng
trao i*
(%)
Bronsted/Lewis
H-beta

Cu(I)-beta

Ag(I)-beta

473
623
473
623
473
623
0,501
0,204
0,017
0,029
0,016
0,060
0.113
0,058
0,221
0,044
0,268
0,038
-

93,5%

89,2%

4,12

0,17

0,25

* Lng trao i (%) = [(axit Bronsted ca H-beta) (axit Bronsted ca M(I)-
beta)] / [axit Bronsted ca H-beta].
Kh nng hp ph hay dung lng hp ph lu hunh ca H-beta v Cu(I)-,
Ag(I)-beta c so snh thy r hn nh hng ca cc cation trong zeolite
beta n kh nng hp ph lu hunh. Nh c th thy trong hnh 3.4, kh nng
x l ca H-beta l 0,156 mmol S/g trong xng mu, kh nng kh lu hunh ca
Cu(I) v Ag (I) zeolit beta rt gn nhau v kh nng x l tng thm khong 0,08
mmol S/g so vi H-beta.

Hnh 3.4. nh hng ca Cu(I) v Ag(I) n dung lng hp ph lu hunh.
Ghi ch: iu kin hp ph: SV = 60h
-1
(L), nhit v p sut mi trng.

Thnh phn cation kim loi (%)

D
u
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g

l
n
g

h
p

p
h

(
m
m
o
l

S
/
g
)


Vi cc iu kin th nghim hin ti, H beta zeolit khng trao i kim loi
cng hp ph mt s hp cht lu hunh. iu ny cho thy axit ca zeolit
cng gp phn hp ph v kh lu hunh t cc hp cht lu hunh hu c. C
th, axit Lewis tng v tng tc gia Cu(I) v Ag(I) vi cc hp cht lu
hunh thiophen c th c nh hng ln n qu trnh kh lu hunh, iu ny
hon ton ph hp vi cc bo co gn y v mt s cht hp ph trn c s
zeolit. Hn na, cc thuc tnh khc ca cc cht hp ph, chng hn nh th tch
l xp, kt tinh tng i, hm lng cc cation kim loi trao i cng nh
hng n kh nng hp ph lu hunh. Kt qu kh lu hunh (Hnh 4) cho thy
kh nng hp ph c ci thin bi s hin din ca Cu(I) v Ag(I) trong cht
hp ph. Tuy nhin, kt qu x l vi cc mu c hm lng khc nhau ca
Cu(I)- v Ag(I) trn zeolit ch ra rng hm lng kim loi ti u l khong 15%
khi lng. iu ny c th c gii thch l do hai qu trnh cnh tranh sau
y: c s gia tng cc tm hp ph khi cc thnh phn cha Cu tng ln trong
phm vi nh(trong khong di 15% khi lng).
Tuy nhin vi s gia tng mui ng (vt hn 15% trng lng) th cc cm
tinh th kim loi c th lm kt cc knh mao qun ca cht hp ph v phong ta
cc tm hot tnh dn n gim din tch b mt ring v th tch l xp, iu ny
ph hp vi kt qu o ph nhiu x tia X v hp ph vt l BET. Cui cng, iu
ny bt u chim u th v lm gim kh nng x l thiophen vi s gia tng
hm lng Cu. Vi s gia tng thnh phn nhm trong khung tinh th zeolit, cc
cation kim loi b tr in tch cn phi c tng ln. Do , s lng cation
trao i Cu(I) v Ag (I) v cc tm hot tnh hp ph lu hunh c th c kim
sot/ci thin bng cch iu chnh t l SiO
2
/Al
2
O
3
ca zeolit. Trong thc t, kh
nng kh lu hunh ca cht hp ph ph thuc vo mt s yu t nh cation kim
loi trao i, tnh cht cu trc vi mao qun, tnh axit-baz c lin quan n t l
SiO
2
/Al
2
O
3
trong khung.
S c mt ca cc tng tc axit-baz trong qu trnh kh lu hunh t cc
hp cht thiophen bng zeolit vi t l SiO
2
/Al
2
O
3
khc nhau c bo co gn
y. Kt qu thu c (trn hnh 3.5), bng cch s dng zeolite beta vi t l
SiO
2
/Al
2
O
3
l 8, 12, 25, 30, 60 v 80, cho thy kh nng x l ca cht hp ph
lc u tng theo s gia tng t l SiO
2
/Al
2
O
3
, v sau gim khi t l
SiO
2
/Al
2
O
3
vt qu mt gi tr nht nh . Kt qu thc nghim ch ra rng
axit v s lng cation trao i trong zeolit gim vi s gia tng t l SiO
2
/Al
2
O
3
,
mc d din tch b mt ring BET v th tch mao qun tng ln.

Hnh 3.5. nh hng ca t l SiO
2
/Al
2
O
3
ca zeolit n dung lng hp ph.
Ghi ch: iu kin hp ph: SV = 60h
-1
(L), nhit v p sut mi trng,
thnh phn cation kim loi 15%.
Nh vy zeolit vi t l SiO
2
/Al
2
O
3
l 8 th kh nng hp ph lu hunh thp
hn vi t l SiO
2
/Al
2
O
3
l 12-30 do din tch b mt ring BET v th tch mao
qun nh hn.
Do , t l SiO
2
/Al
2
O
3
ti u ca cc cht hp ph nm trong phm vi t 10
n 30. Sau khi hp ph bo ha, t l S/Cu v t l S/Ag trn cht hp ph l
0,33 v 0,36, mc d cc tm hot tnh khc cng tham gia vo qu trnh kh lu
hunh. V vy, mt trong nhng thch thc v kh lu hunh su bng hp ph
l ci thin hiu sut s dng ca cc cation kim loi trao i v chn lc hp
ph.
Ngoi ra, vi zeolit c hm lng Al cao (v d zeolit Y), c th trao i
nhiu cation kim loi hn. Tuy nhin, s n nh nhit v thy nhit ca cht hp
ph nn c xem xt, c bit l khi s dng thng xuyn. Zeolit Y c tnh axit
vi t l Si/Al thp c th mt phn b sp cu trc khi tip xc vi hi m ngay
c nhit phng. Nh chng ta bit, t l Si/Al cng cao, cu trc ca
zeolit cng n nh. Th nghim hp ph lu hunh vi xng FCC thc t trn
Cu(I) v Ag(I)-beta zeolit c thc hin. Vi 1 g cht hp ph Cu(I)- hoc
Ag(I)-beta, tng ng 30 ml v 22 ml xng FCC thc t c th c x l vi
hm lng lu hunh gim t 200 ppm xung di 1 ppm. Nh vy, kh nng x
l tng ng l 0.168 mmol S/g v 0.145 mmol S/g (hnh 3.6). Vic gim kh
nng kh lu hunh trong xng FCC thc t l bng chng ca mt s hp th
cnh tranh t cc olefin v hp cht thm.
D
u
n
g

l
n
g

h
p

p
h

(
m
m
o
l

S
/
g
)


Hnh 3.6. th biu din dung lng hp ph S trong xng FCC thc t ca
Cu(I)-beta v Ag(I)-beta zeolit iu kin mi trng.
i vi c thiophen v cc hp cht thm, m my in t ca n c th d
dng thu ht vo cc tm axit trn cht hp ph. Ngoi ra, thiophen cn c cc
electron khng lin kt m khng phi l m my in t, trong cc electron
trong obitan sp2 vung gc vi cc obitan p. Cc electron ny to cc lin kt b
sung cho cc phn t thiophen. C s khc bit v kh nng kh lu hunh vi
xng FCC thc t, iu ny c th l do cc thuc tnh axit-baz khc nhau hoc
phn b in tch khung c th thay i tng tc hp ph thiophen v cc hp
cht khng no ln trn Cu(I)- v Ag(I)-beta zeolit. Cc nghin cu tip theo ang
c tin hnh nhm so snh kh nng hp ph cc hp cht lu hunh v
hydrocarbon khng no trn cht hp ph.
3.3 Ti sinh cht hp ph
Mt trong nhng vn kh khn v qu trnh hp ph kh lu hunh l ti
sinh cc zeolit hp ph. Ni chung, c hai k thut ti sinh cht hp ph l x l
nhit v dng dung mi ra gii. Cht hp ph trn c s silica thng c ti
sinh bng cch ra dung mi nhit mi trng, nhng vic loi b dung mi
sau khi ra gii thng rt kh khn. V vy, dung mi ra gii ch ph hp vi
nhng trng hp nht nh nh nhng vt liu nhy cm vi nhit . Trong
nghin cu ny,x l nhit c la chn v cc cht hp ph c ti sinh bi
mt dng N
2
ti 623 K vi thi gian t nht l 6 h. S c mt ca kh tr thun li
cho vic kh Cu
2+
v Cu
+
trong sut qu trnh ti sinh. T l mt khi lng ca
cht hp ph ti sinh l di 1%.
Th tch mu xng FCC thc t (ml)
T
h
n
h

p
h
n

l
u

h
u
n
h

(
g
/
g
)


Phn tch ph nhiu x tia X ca cc cht hp ph sau 9 ln ti sinh cho thy
cu trc ca zeolit khng b nh hng bi qu trnh x l nhit. Kh nng kh
lu hunh ca cc cht hp ph ti sinh c kim tra mt cch cn thn, v mi
lin h gia s ln ti sinh vi kh nng x l (so vi cht hp ph mi) c
minh ha trn hnh 3.7.

Hnh 3.7. nh hng ca s ln ti sinh n dung lng hp ph
(so vi cht hp ph mi).
Nh vy, kh nng x l ca cc cht hp ph gim trong khong 5% sau ln
ti sinh u tin v gim nh dn dn qua 8 ln ti sinh tip theo. Do , iu ny
c th c hiu rng cc hp cht lu hunh hp ph trn cht hp ph trn c
s zeolit beta c th d dng c loi b bi qu trnh x l nhit do h thng
m cc knh mao qun 3 chiu. Cc tm hot tnh v cu trc ca cht hp ph
da trn zeolit beta c tnh n nh nhit tt hn. c bo co v kh nng x l
lu hunh ca PdCl
2
mang trn than hot tnh l cao hn so vi cc cht hp ph
Cu-, ng nh d on khi tnh ton obitan phn t. Nhng PdCl
2
/AC ch c th
phc hi khong 70% kh nng kh lu hunh so vi cht hp ph mi.

Ln ti sinh
D
u
n
g

l
n
g

h
p

p
h

s
a
u

t
i

s
i
n
h

(
%
)


PHN 4. KT LUN
Cc cht hp ph rn Cu(I)- v Ag(I)-beta zeolit c iu ch thnh thnh
cng theo phng php trao i ion trng thi rn (SSIE). Cc tnh cht ha l
ca cc cht hp ph thu c cho thy kt tinh, din tch b mt ring BET v
th tch mao qun gim vi s gia tng hm lng cation kim loi trao i trn
khung, nhng axit Lewis tng dn ln. Hm lng ti u ca Cu(I) v Ag(I)
trao i vi zeolit beta nn c khong 15% khi lng. T l SiO
2
/Al
2
O
3
ti u
ca zeolit beta l 10-30, iu ny c nh hng n hiu sut kh lu hunh.
Qu trnh th nghim x l lu hunh s dng cht hp ph Cu(I)- v Ag(I)-
beta zeolit c thc hin trn xng mu v xng FCC thc t vi m hnh lp vt
liu hp ph c nh. Kh lu hunh su trong xng mu xung di 1 ppm c
th thc hin iu kin mi trng. Ngoi tr phc , kh nng kh lu hunh
ph thuc vo mt s yu t nh tng tc axit-baz, c bit l axit Lewis trn
khung, tnh cht ca zeolit. i vi hp ph lu hunh trong xng mu, kh nng
x l ca Cu(I)- v Ag(I)-beta zeolit tng ng l 0,239 mmol S/g v 0,237 mmol
S/g.
Cc cht hp ph c ti sinh tt v kh nng x l sau 9 ln ti sinh ch
gim trn di 5% so vi cht hp ph ban u. i vi xng thc t, kh nng
kh lu hunh gim khong 30% so vi xng mu, do s hp ph cnh tranh gia
cc thiophen v hydrocarbon khng no trong xng thc t. Ni chung, Cu(I)- v
Ag(I)-beta zeolit c th l cht hp ph thch hp cho qu trnh kh lu hunh su
trong xng iu kin mi trng. Cc nghin cu tip theo cn ci thin hn
na kh nng hp ph lu hunh v chn lc hp ph nhm kh lu hunh su
trong xng thc t.


TI LIU THAM KHO
1. Y. Gong, T. Dou, S. Kang, Q. Li, Y. Hu, Deep desulfurization of gasoline
using ion-exchange zeolites: Cu(I)- and Ag(I)-beta, Fuel Processing
Technology 90 (p.122129), 2009.
2. inh Th Ng, Nguyn Khnh Diu Hng, Ha hc du m v kh, Nh
xut bn Khoa hc v K thut, 2010.
3. http://xangdau.net/tu-van/goc-ky-thuat-va-tu-van/10-ly-do-su-dung-nhien-
lieu-co-luu-huynh-thap-21458.html

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