Qu kh , hin ti v tng lai ca xc tc d

th

1.Gii thiu
Xc tc l mt lnh vc quan trng ca ha hc, vi hn 90%
cc qu trnh ha hc c s dng xc tc trong t nht 1 khu
no . Hin nay do cc vn mi trng, s c mt ca xc
tc thm ch cn quan trng hn trc y v to nn mt
trong nhng ngun chnh ci tin x hi ca chng ta. Mt
cuc kho st ca ngnh cng nghip M tit l rng doanh thu
hng nm t ha cht v sn xut nhin liu ng u tt c
cc ngnh cng nghip khc. Cuc kho st cng ch ra rng
hn 60% trong s 63 sn phm chnh v 90% ca qu trnh mi
t 1930-1980 c s tham gia ca xc tc trong , minh ha
vai tr quan trng ca lnh vc ny trong nhin liu v cc
ngnh cng nghip ha cht.
Bn nh gi ny l nhm trnh by mt s bi cnh lch s ca
xc tc v nhng thch thc ln m lnh vc ny phi i
mt trong na th k qua v n vn cn phi i mt trong
tng lai. Bn bo co ny ch hng n xc tac d th.
Mc ch ca chng ti trong bn tho ny l lm ni bt
nhng khm ph cht xc tc lin quan chnh v cc quy trnh
c pht trin hn ba th k qua. Lch s ca xc tc v s
ng gp ca n cho ngnh cng nghip ha hc c m t
rng ri trong vn hc. Chng ti d nh xem xt mt s bc
i lch s quan trng trong s pht trin ca xc tc v cc qu
trnh c s dng xc tc. V khng tho lun bia c hoc ln
men ru, n l th v nh li mt s quy trnh c, c tm
tt trong Bng 1.

Mt s cc quy trnh c pht trin p tr li vic lc

lng vn ti ch c xem nh nhng my ko ging nh
vic Chile d kin cm vn i vi dim tiu nh mt ngun
nitrat, th m thc y Haber v Bosch pht trin quy trnh cho
vic nh hnh ca nit kh quyn trong tng hp amoniac
(1909). Tng t nh vy, s cn thit cho mt th trn y
nng lng hn xng truyn cm hng cho tay ua v k s
c kh Php Eugne Houdry pht trin du axit (hydrocarbon),
qu trnh cracking (1930), v ti to xc tc v alkyl ha
(1940), iu ny cho php cc lc lng ng Minh s dng
mt ngun nhin liu mnh m cho my bay trong Th chin II.
Gn y hn, cc lc lng li xe nhng my ko thay i
v by gi ph hp hn vi mt chin lc nh hng th
trng, trong quy trnh n gin v t vn v vic s dng
nguyn liu r hn c a chung. T cui th k XX, cc mi
quan tm ca x hi cng tr thnh mt ng lc quan
trng mi , vi nghin cu chuyn su c dnh cho vic
chuyn i cc sn phm sn phm hu ch v x l tt
c cc loi cht thi cho vic bo tn v bo v mi trng.
Lut php nghim ngt hn c thnh lp m dn n
nghin cu v vt liu xc tc mi v cc quy trnh hiu qu
hn. C th hn, i vi vn mi trng,
hydrodesulfurization bt u vo nhng nm 1960 nh mt
phng php quan trng loi b lu hunh t nhin liu.
Hydrodesulfurization c kt qu gim ng k lng kh thi
ton cu ca cc oxit lu hunh, trong khi thnh tu ny lm
tng nhu cu i vi cc phn ng metan c chn lc (SMR) cho
vic sn xut H2 ; cht xc tc kim sot kh thi t pht trin
vo nm 1974 (oxy ha), 1978 (ba chiu), v trong nm 1990
(Pd ba chiu); gim xc tc chn lc NOx bi NH3 hoc N2H4
(SCR) cho in nh my vo nm 1980 bng cch s dng V,
W, v Ti oxit p thnh cc dng nguyn khi ; cht xc tc kim

sot kh thi ozone c pht trin bi Engelhard (nay BASF);

vic thay th CFCs bi HCFCs cho gim nng ozone
topospheric (l ozone), cc ph hy xc tc ca cc hp cht
hu c d bay hi t cc ngnh cng nghip tiu th sn phm;
sn xut thc phm v ha cht; s pht trin ca cc cht xc
tc kh thi oxy ha vo nm 1990 s dng ng c diesel mui
xeri nh ph gia; mt lot cc gii php s dng oxit kim loi
cho phn hy xc tc ca N2O (m kt qu trong mt gim
81% lng kh thi N2O t cc nh my axit adipic th gii); cc
pht trin cc cht xc tc lu tr NOx Pt-Rh-kim; s pht
trin ca Toyota Motor vo nm 1994; s pht trin ca ng c
diesel; cht xc tc loi b ht vo nm 2003; s pht trin ca
ur SCR cho vic kim sot kh thi NOx trong xe vo nm
2004; s pht trin loi b NOx trong n v regenerator FCC
trong nm 2007, v vv...
Cc nghin cu mi cng xut hin trong hai hoc ba thp
k qua thuc lc lng li xe coi nh "y" cho s pht trin
ca mt s hiu bit mc phn t chc nng xc tc, b mt
spectroscopies nhy cm, trong situ / operando c tnh k
thut, tnh ton khoa hc, ha hc lng t, phn t m hnh,
nhit ng hc v ng lc hc, phn ng v l phn ng m
hnh, thng lng cao sng lc cht xc tc v th nghim, v
vv. Ci tin ng k c thc hin tt c cc lnh vc, v
pht trin hn na nn tip tc trong tng lai.

2.Cht xc tc
K t thi c i, s pht trin v s dng cc vt liu c l mt
trong nhng mc tiu c bn ca th gii chng ta. Thi i,
thi k , thi i ng v st, c t tn sau
khi vt liu c bn c s dng bi con ngi xy dng cc
cng c ca h. vt liu khoa hc l hot ng hin i cung
cp nguyn liu cho vic ny nhu cu v tn, theo yu cu ca

cc tin b trong tt c cc lnh vc ca ngnh cng nghip v

cng ngh, vt liu mi cho s pht trin ca x hi.
T chc ha hc nguyn cht v ng dng (IUPAC) xc nh
mt cht xc tc nh "mt cht lm tng t l mt phn ng
m khng sa i cc tiu chun nng lng Gibbs tng th
thay i trong phn ng "[15]. Qu trnh ha hc ca tng tc
phn ng c gi l xc tc v cht xc tc va l mt cht
phn ng v sn phm ca phn ng, tc l, cc cht xc tc
c phc hi sau mi qui trnh xc tc. Hn na, cc cht xc
tc khng nh hng n thnh phn trng thi cn bng nhit
ng sau khi chm dt phn ng.
Qu trnh xc tc hiu qu hn yu cu phi ci tin trong
hot tnh xc tc v chn lc. C hai kha cnh c th c
ci thin bi thit k ph hp ca vt liu xc tc vi cu trc
mong mun v phn tn ca cc tm ang hot ng nh
mong mun. Vt liu nh zeolit, Alpo, sap, vt liu mao, PILC,
MOFs, vv... cung cp kh nng nh vy trong vn ny, vi
khu vc b mt tip xc ca cc cht xc tc c iu khin
rng ln nhng nhng ht mn nh khng c c. Hn na, mt
trong nhng ng dng quan trng nht ca cc cht xc tc rn
xp mi l l s thay th nguy hi vi mi trng, c tnh n
mn, kh khn ring v b cht xc tc ng nht (tc l
khong sn v axit Lewis, baz hu c v v c v cc hp cht
kim loi c hi) s dng trong qu trnh tng hp cht lng
pha ca s lng ln v tt ha cht (vide infra) [16]. C rt
nhiu cc h ca cc cht rn nh cht xc tc kim loi, oxit,
sulfide, cacbon, vv... nh vt liu ri hoc c h tr v mt s
h tr nhiu hn hoc t xc tc hot ng nh silica, nhm,
zirconia, titanic, ceria, cacbon, vv Nhng vt liu ny c th c
tnh cht ha hc c th, chng hn nh axit-baz hoc oxi ha
kh hoc hydro ha hoc hydro ha hoc oxy ha, v tnh
cht vt l nh xp, din tch b mt cao, chng hao mn,

nhit v(hoc) dn in, vv .Cc h ln nht tng ng vi

oxit bt c iu g zeolit, t st, vt liu mao, hn hp oxit l
cht xc tc hoc h tr. Trong s cc vt liu xp trnh by
mt s c tnh hp dn, c m t di y.

2.1.Zeolites
Trong cc lnh vc ha du, tng hp hu c, zeolit ng mt
vai tr quan trng trong th k XX. Zeolit l v c aluminosilicat
tinh th m cu trc bao gm mt mi lin kt ba chiu ca
TO4 t din (trong T thng l Si4 + v Al3 + nguyn t
tetrahedrally phi hp) lp rp vi nhau thng qua s chia s
ca cc nguyn t oxy to thnh cc tiu n v, trong
lp li to thnh mt mng v hn [17], bao gm ba chiu,
gp bn ln TO4tetrahedra kt ni vi nhau lin kt thng qua
T-O-T cu. Cc gc T-O-T l l tng 140 -150 v him khi
hn 180 . S tn ti ca Al trong mt cu trc Si hp thnh t
din b i 1 in tch m , iu ny i hi s tn ti ca cc
cation b, nm trong h thng xp.
Do , mt tnh nng th v ca zeolit l tnh linh hot ca cu
trc ca chng pht sinh t mt s lng ln cc phng thc
sa i v iu chnh tnh cht xc tc ca chng. Cc hot
ng xc tc c lin quan n s hin din ca trung tm hot
ng trong khun kh. Trung tm ny c th l axit, sc mnh
v s lng ca h (Bronsted, Lewis) c iu chnh theo
hng kim sot hoc trong qu trnh tng hp bng cch thay
th ng hnh ca nguyn t trung tm Si trong cc tm t din
trong mng tinh th zeolit, bi v d nguyn t ha tr ba nh
Al, B, Fe, Cr, Sb, As, hoc Ga, v cc nguyn t ha tr 4 nh
Ge, Ti, Zr, Hf hoc; v / hoc bi tng hp bao gm cc phng
thc lin quan n hi, s lng hi ha cht, trao i ion ca

cc cation k, s gim ca cc ion kim loi trao i vi mt

trng thi ha tr thp.
Mt khc bit c to ra gia cc cc zeolit mao qun nh,
va v ln.Trong trng hp ca zeolit mao qun nh, nh
zeolit A, tm SiO4 t din to thnh mt vng mi thnh vin
(10MR) vi ng knh mt 0,41 nm v trong trng hp ca
zeolit ln l chn lng, chng hn nh zeolite Y (Fig. 1), mt
khoang c ng knh 0,74 nm c hnh thnh bi mi hai
SiO4tetrahedra. Cc zeolit mao qun va, nh pentasil zeolit,
c cha mt vng mi thnh vin vi mt ng hnh elip ng
knh 0,55 0,56 nm. H thng cc khe v cc l trng trong
cc ry phn t ny sn xut cht rn vi cc khu vc b mt
v th tch mao qun ln , c kh nng hp th mt lng ln
hydrocacbon.
Zeolit c th c s dng nh cht hp th v l cht xc tc
trong mt s quy trnh xc tc. Cc bc t ph ln trong cht
xc tc zeolite pht sinh t qu trnh cracking cht xc tc lng
(FCC) cho bin du thnh nhin liu v ha cht. S b sung
ca zeolit (FAU v MFI) n st axit v cc cht xc tc cracking
aluminosilicate vo gia nm 1960 dn n mt s gia tng
mnh m trong chuyn i v xng du cho sn lng cng
nh vi s lng thp ca than cc v kh kh [18]. Cc cht
xc tc mi cho loi xng c ch s octan thp , ch yu l do
lng olefin ca chng thp hn [19-21]. Cc ch s octan tng
cng u FCC cht xc tc c gii thiu bi cc nh sn
xut cht xc tc Hoa K trong gia nhng nm 1970. Cht
xc tc Octane FCC bao gm hai thnh phn chnh, v cc
zeolit c th c s dng tng ch s octan ca xng. Cc
cng ty Chester [22] bo co rng, ngoi MFI (ZSM-5), cc
thnh vin khc ca gia nh MFI ca zeolit (MEL, ZSM-12, ZSM23, ZSM-35, ZSM-38) c kh nng tng ch s octan. Zeolit beta
(BEA) [23] v offretite (OFF) [24] c bo co sn xut

xng c ch s octan cao hn zeolit Y thng thng (FAU) v c

th s dng lm ph gia tng ch s octan.
Ct mc quan trng trong lnh vc ny c tm tt di y:
R. Milton (Union Carbide trong nm 1950), D. Breck, R. Barrer
v E. Flani-gen pht trin cc l trnh thng mi hu hiu i
vi zeolit khc nhau v
MeAPOs.
J. Rabo, lm vic ti Union Carbide, p dng vic s dng ca
zeolit
lc du (ng phn ha, 1959), trong khi C. Plank v E.
Rosinski ca Mobil Oil p dng zeolit cracking xc tc (1962)
cc phn phn on du nng.
P. Weisz v V. Frilette ca Mobil Oil pht trin khi nim (1960)
cht xc tc hnh chn lc, v W. Haag p dng hnh chn lc
cho vic sn xut ca cc cht thm.
G. Kerr ca Mobil Oil pht hin zeolit silica cao trong nm
1967 (ZSM-5,
sau ch nh l MFI) v th nghim cracking thng mi quy
m ln u tin c tin hnh vo nm 1983.
W. R. Grace pht hin ra s bay hi ca zeolite Y sn xut
zeolite Y cc k n nh (USY) trong nm 1969.
Mobil Oil pht trin cc vt liu mao qun loi silic
ch nh l MCM, HMS, vv vo cui nm 1990.
M. Taramasso, G. Perego, v B. Notari pht hin TS-1 (titan

silicalite-1 vi cc cu trc MFI), mt cht xc tc qu trnh oxy

ha chn lc
cho epoxy ha cc olefin, ti ENI-SNAM PROGETTI nm 1983.
UOP / HYDRO (1995) pht trin Sapo-34, mt ry phn t
phosphate silicoalumino p dng cho methanol to olefin
(qu trnh MTO).
Mt ti sn hp dn ca zeolit pht sinh t mng kch thc
mao qun phn t xp ca chng , cho php cc cht phn ng
nht nh xm nhp v cc sn phm d dng ri khi cc
mao qun hay khoang trng, hoc li b mc kt, hoc li
cc mao qun vi kh khn nu chng qu cng knh. Khi
nim ny, c chn lc hnh dng, i tin phong bi cc nh
khoa hc Mobil [25], c pht trin gii thch nhng
phn ng m khng tun theo lut c in ca nhit ng lc
hc v chu nh hng mnh bi kch thc ca cc mao qun
hay khoang trng tng i so vi kch thc ca cc cht
phn ng hoc sn phm phn t. Ph hp vi kch thc v
cu hnh ca phn ng phn t, v cc sn phm trung gian vi
hnh hc v tnh trng quanh co ca knh zeolite / h thng
khoang cung cp c s cho vic chn lc hnh dng c kim
sot. Cht xc tc chn lc hnh dng v phn tn trong zeolit
c xem xt trong mt s n phm [26-28]. Tuy nhin,
chn lc hnh dng trong zeolit t th hin thng qua: chn lc
cht phn ng, chn lc sn phm, chn lc qu trnh chuyn
i trng thi, kim sot giao thng phn t, vv..
Cc cht phn ng chn lc, kt qu trong vic loi tr cc
phn t qu ln khuch tn vo cc mao qun zeolite; mt
v d n gin l s mt nc ca ru. Trong zeolite mao qun
hp (CAA), n-butanol l mt nc, v isobutanol th khng.
Ngc li, nh mong i, isobutanol d b mt nc hn nbutanol qua NaX (trong c mao qun rng hn). Kt qu

trc y l d dng gii thch v c hai hnh thc c th nhp

NaX, nhng isobutanol cng knh b loi tr t CAA - chn lc
sn phm. Ngoi tr kch thc, li vo zeolit tinh th c th
gy tr ngi khi nh hng khng thun li mt cht phn ng
c gy ra bi hiu ng tnh in. Trong trng hp ny, s
lin kt ca mt trng tnh in zeolitic (vung gc vi mt
phng ca ca s) v mt lng cc phn t c th hn ch
nhp cnh ca lc y tnh in, m ch cho php cc phn t
nh c hnh thnh trong qu trnh phn ng khuch tn ra
khi cc mao qun zeolite. V d, trong ankyl ha toluen bng
methanol trn H-MFI, sn lng ca p-xylen tng ln v s
khuch tn ca cc p-xylen l ln hn nhiu so vi ca o- v mxylene (vide s h tng). Thm ch nu cc sn phm chnh ca
alkyl ha khng giu p-xylen, n thot ra nhanh hn t zeolite
cho php ng phn ha hn na cc o- v m-xylene v kt
qu trong tng sn lng ca p ng phn. Hn ch chn lc
qu trnh chuyn i trng thi xy ra khi cc phn ng c
ngn chn bi v trng thi chuyn tip tng ng s i hi
nhiu khng gian hn l c sn trong cc mao qun. iu khin
vo ra phn t [29] xy ra trong zeolit vi hai loi h thng
knh. Cc mi quan h gia chiu di ca phn t v kch thc
ca lng zeolite cng nh cc bin th trong cc dao ng phn
t [30] cng nh hng n hnh dng zeolite chn lc. Ngoi
cc yu t hnh hc, chn lc hnh dng c th th do nh
hng tnh in [31] l kt qu ca s tng tc gia in
trng ti cc ming mao qun v cc momen lng cc ca
phn t cht phn ng. Mt s tng tc nh vy c th c li
hoc c ch s khuch tn ca cc phn t cht phn ng vo
zeolite.
Hnh dng chn lc ca zeolit c th c sa i bng ion trao
i, loi nhm, nhng thay i trong khun kh t l Si / Al,
hoc bi bt k s sa i ny nh hng n kch thc mao

qun hoc hnh hc [32-45]. Hnh dng chn lc ca mt zeolite

thng c c trng bi "ch s hn ch," ca n m l t s
ca hng s tc cracking cho n-hexane v 3-methylpentane
[46]. Zeolit mao qun ln c ch s hn ch t hn 1; zeolit mao
qun va c hn ch s gia 1 v 12; zeolit mao qun nh c
hn ch s cao hn 12.
Hin tng hnh chn lc c minh ha trong hnh 2 cho s
tng hp ca 4,4-di-isopropyl-biphenyl v hp cht 2,6-diisopropyl-naphthalene c trung gian cho cc polyeste khc
hoc tinh th lng, bi ankyl ha naphthalene bi propylen trn
mordenite loi b nhm. Kch thc hp ca mordenite
(vng 10 cnh) zeolite ng h s hnh thnh ca cc ng phn
para t cng knh ca di-isopropyl naphthalene, tip theo l cc
ng phn ortho so vi cc ng phn meta, nh l d kin t
cn bng nhit ng khong 25:25:50 tng ng.
Mt kha cnh khc ca tnh cht zeolite l hiu ng gii hn,
nh pht trin bi E. Derouane [47-49], m ch n gin coi lc
van der Waals, tc l, b qua lc y Pauli, nh minh ha trong
hnh 3.
Derouane v cng s xut cc phng trnh sau y ca
nng lng van der Waals (W) ca mt phn t hnh cu ca
van der Waals bn knh (d) ch gii hn trong mt vi mao qun
hnh cu bn knh (a):
W (s) = - (C / 4d3) (1 - s / 2)-3 vi C = h / 2, ni alpha = e2/
m2 l phn cc ca mt nguyn t c xem nh mt momen
lng cc ng gi, dao ng mt tn s , v s l cong
b mt. iu ny tham s th hai, s = d / a, c th thay i
gia 0 v 1, ty thuc vo cc kch thc tng i ca cc
phn t gii hn v vi mao qun. Cc van der Waals lc l F =
(3C / 4d4 ) [(1 - s) / (1 s/2)4 . Trng hp rt tng ng vi mt
b mt phng (s = 0) v mt phn t vi kch thc ging nh

cc mao qun (s = 1); trng hp th hai ny c gi bi

Derouane v cc cng s nh mt "phn t ni" nn khuch tn
rt nhanh chng bi v chuyn ng ca n khng b cn tr bi
s tng tc ca n vi tng, nh b p bng lc van der
Waals . N cng a ra t phng trnh van der Waals do W s
= 1 = 8Ws = 0, c ngha l rng, theo m hnh ny, nng lng hp
ph do cc yu t van der Waals gii hn trong cc mao qun
zeolite c th ln n ln hn tng ng vi mt b mt phng
8 ln. Cc loi cc bin th ca W so vi s c th c tm thy
trong hnh 4.
H qu l, cc phn t trong cc mao qun c th tng tc
nhiu hoc t mnh m hn vi mi trng ca chng ty thuc
vo kch thc ca chng tng quan vi cc mao qun, v d,
90 kJ mol-1 cho p-xylen trong Sapo-11. Chng cng c th co
li vo cc mao qun, trong khi li zeolitic cng c th hi
co li khi hp ph, nh th hin bng XRD [50].
Hin nay, c hn 300 loi khc nhau ca cc khun zeolite c
bit, vi ch mt s t (BEA, FAU, MFI, MOR, sap-34) c ng
dng xc tc cng nghip quan trng; Tuy nhin, ngy cng
nhiu hn c ng dng trong sn xut cc ha cht tt. Mt
s nghin cu c m t di y minh ho cho tnh cht
ca chng.
Qu trnh tng hp axit adipic l mt v d th v. Qu trnh c
in (sn xut hng nm t 0,7 Mt, nng tt kh 25-40%) s
dng axit nitric l mt cht oxi ha vi s hnh thnh ca N2O,
m phi c ti oxy ha hn na axit nitric v l mt kh
nh knh quan trng. Mt qu trnh xc tc sau c pht
trin cho vic phn hy N2O. Tuy nhin, mt qu trnh s dng
cht xc tc Fe-MFI, c kh nng oxy ha benzen trc tip n
phenol [51-58] c pht hin ti Vin Boreskov ca xc tc
Novosibirsk, RU, v mt quy trnh c pht trin vi

Monsanto Co trong mt cng ty ngu nhin c gi l

SOLUTIA, nhng khng xut hin thng mi ha, theo hiu
bit ca chng ti. Qu trnh ny thn thin hn vi mi trng
v N2O c s dng thay v oxy oxy ha benzen phenol.
n cho qu trnh ny c trnh by trong hnh. 5.
Mt v d th v l phn ng Friedel-Crafts trn zeolit c tnh
axit. Vic cp n u tin ca axyl ha lin quan n sau
Al2Cl6method ca Friedel v Craft xut hin vo nm 1873
trong mt thng co s b bi Grucarevic v Merz [59], theo
bo co ca Olah trong mt nh gi lch s v ha hc FriedelCrafts [60,61] trn axyl ha kim loi xc tc ca cc hp cht
thm. Cc phn ng acyl ha Friedel-Crafts bao gm ch yu
ca sn xut ca mt xeton thm bng phn ng ca mt cht
nn thm vi mt thnh phn acyl trong s hin din ca mt
cht xc tc. nhiu giy t v cun sch c xut bn v
v bng sng ch c cp v ch ny, nh c tm tt
trong mt nh gi gn y [62]. Li ch trong cc nghin cu
acyl ha lc in t v trong vic ti u ha qu trnh chun b
c thc y bi nhng thc t ng k gi tr ca cc sn
phm xeton thm, to thnh quan trng trung gian trong dc
phm, nc hoa, hng thm, thuc nhum v cc ngnh cng
nghip ho cht nng nghip. Cc electrophin axyl ha c
xc tc bi axit Lewis (nh ZnCl2, AlCl3, FeCl3, SnCl4, v TiCl4)
hoc axit proton (nh HF hoc H2SO4). Tuy nhin, vic s dng
cc halogenua kim loi gy ra cc vn lin quan n qu
trnh thy phn ca phc hp, m kt qu trong vic mt cht
xc tc v th h ca mt lng ln cc dng cht thi c tnh
n mn. Nhng n lc ln c thc hin t c cc
mc tiu lm cho cc axit Lewis s dng khng ng nht cht
xc tc rn, trong zeolit axit c th. M t chi tit cc phn ng
Friedel-Crafts cho Arenes (v d, benzene, toluene, xylene), ete
thm (v d nh, anisol) vi anhydride acetic hoc axyl khc v

zeolit v trn t st, oxit kim loi, vv l a ra trong Ref. [60].

Vai tr ca cc hnh chn lc v kh hot tnh bi cc sn phm
v k nc so vi hydrophilicity cho zeolit c nhn mnh.
V d, acyl ha ca anisol hoc toluene vi anhydrit axetic c
thc hin trn BEA zeolite 90 C, thay th cc cht xc tc
AlCl3 c in m dn n nhiu mui trong nc thi, vn
n mn, chn lc thp v mt thi gian lu ngn ca cht
xc tc, nh tho lun. Khng ng, vic s dng H-BEA
zeolite dn n t hn 6 bc, t rn hn 10 ln v 100 ln x t
dung dch nc, ch yu l do cc hydrophilicity so vi k nc
ca zeolit, cho t nhiu cht phn ng cc, trong cho php
cc phn t cht phn ng nhp nhiu hoc t hn d dng
bn trong mao qun, trong khi cc phn t dung mi c ngn
chn xm nhp vo. Mc hp th tng i ca cc phn t
cht phn ng trong cc mao qun iu tit t l ca cc phn
ng bn trong cc mao qun , tc l, ty thuc vo t l hp
th tng i ca cc cht phn ng, v ngi ta nh vy,
la chn mt t l trong mi trng cht lng xung quanh cc
ht zeolite l khc nhau t m d kin t phn ng. V d, t
l ha hc 1:20 c th c la chn cho mt cho phn ng
toluene 1: 1 (cht phn ng khng cc) acyl ha bi anhydride
acetic (cht phn ng cc). iu ny tht c bit cho cc phn
ng pha kh vi zeolit rn, nhng cng cho phn ng pha lng
v zeolit rn, l mt quan trng kha cnh ca cc phn ng
ha hc tt trong zeolit, nh biu ha trong hnh. 6.
Mt v d th v lin quan n vic sn xut ca para-xylene (pxylen). Xylen, c bit l cc ng phn para, l hp cht c
nhu cu cao trong ngnh cng nghip ha hc hu c sn
xut polyethyleneterephtalate (PET) si, nha, nha, phim, vv
v p-xylen l mt cht ha hc trung gian trong qu trnh ny.
Cc ngun chnh ca Xylen l ct C8 sn xut bi ci cch xc
tc v cracking hi nc [65-68]. Tuy nhin, mt cch thun

tin tng cng sn xut p-xylen l bin i t c gi tr

metyl thm C7v C9 bi alkyl ha xc tc ca toluen vi
methanol theo sau s oxy ha(disproportionation) v ankyl ha
trans-(transalkylation) vi trimetyl benzen. Cc cht xc tc cho
nhng phn ng t cc acid Bronsted chung (H2SO4, H3PO4,
HF) axit Lewis (halogenua kim loi) v hn na rn axit
(Al2O3, SiO2-Al2O3, zeolit). N phi c lu , l h qu
ca vn mi trng, cc cht xc tc zeolite da trn hin
ang ng mt vai tr quan trng trong vic sn xut cc cht
thm alkyl. Nghin cu bo co trong cc ti liu m t mt lot
cc cht xc tc zeolitic ang hot ng trong cc ankyl ha
toluen vi methanol [36,38,39,69-78], toluene
disproportionation [79-84], transalkylation toluenTRIMETHYLBENZENE [85-89], v xylene ng phn ha [90-92].
Ni chung, cc tnh cht xc tc (c bit l s chn lc) v kh
hot tnh b mt ca zeolit trong nhng phn ng ph thuc rt
nhiu vo thin nhin, s v sc mnh ca cc axit trung tm
ca cht xc tc. V d, cc cht xc tc vi cc trang web c
tnh axit mnh c bo co l t chn lc v d dng v
hiu ho bi than cc [93 ]. S bin i ca axit v cu trc
ca zeolit (vi mao qun ln v trung bnh) c th c coi l
mt cch gim phn ng v ci thin chn lc p-xylen.
Hot ng cao v hnh dng chim u th chn lc c
quan st thy trn ZSM-5 [94-97], v cc phn ng l hiu qu
trn 450C. Cc ng phn p-chn lc cao ca ZSM5 sa i
c quy cho s khuch tn hn ch bn trong cc knh, tc l,
cc p-xylen, m nhanh chng khuch tn ra khi knh hp ,
c sn xut u tin. Mao qun zeolit ln vi cc h thng
knh gm 12 thnh vin, c bit l (mordenite) [98,99], cng
cni ln nh l cht xc tc hnh chn lc. Mc d kch thc
ca mao qun l quan trng i vi s chn lc para, hin
tng ny c quan st v zeolit ln l chn lng khi axit
c sa i bng cch thay th ng hnh hoc trao i ion

vi cc kim loi t him. Cc hnh thnh cc p-xylen cng b

iu tra v cc zeolite MCM-22 [100-102], c pht hin bi
Mobil, trong c mt tinh th c o cu trc [103]. N bao
gm hai h thng knh, c hai m c truy cp thng qua mt
vng 10 cnh ca s (10-MR). Mt h thng bao gm hai chiu,
cc knh truyn hnh sin vi 10-MR m ca, trong khi khc c
cha supercages ln bao gm 10-MR v 12-MR h vi mt
khng gian trng bn trong 0,71 0,71 1,82 nm. Nhng h
thng knh c lp ca nhau, v phn t khng th vt qua t
mt n khc trong tinh th ging nhau. Cc tnh cht xc tc,
chng hn nh hnh chn lc ca MCM-22, c chng minh
l trung gian gia 10-MR v 12-MR zeolit trong phn ng khc
nhau. Cc kt qu cho MCM-22 lm ni bt nh hng ca lng
v ca s trn chn lc hnh dng. Trong trng hp nh vy,
cc quan st thc nghim hnh chn lc c cho l do cc bin
i trong Si / Al v t l bn cht ca cc cation khun kh
thm. Toluen c b nhm ( Toluene disproportionation
dealuminated ) MCM-22 c tm thy xy ra ch yu
cc lng siu ln ca MCM-22 nhng khng phi trong knh 10MR ca MCM-22 nhit iu tra. Phn ca p-xylen l cao
hn so vi gi tr cn bng ca n v tip tc tng ln do b
nhm . p-Xylene c hnh thnh trong siu lng nh mt sn
phm chnh s c ng phn ha o- v m-xylene bi axit
khng ch trn b mt bn ngoi m cn trong 10-MR knh.
Nhng ci tin trong s chn lc para bi b nhm dn t c
ch hot ng ng phn ha; iu ny c th loi b khung Al
nguyn t ch yu trn b mt bn ngoi v bn trong knh 10MR so vi nhng th trong siu lng [102].
Nhiu phn ng ha hc tinh khc c pht trin bi
Corma, Garcia v cc i [2] ca h ti ITQ, Universidad de
Valencia, Ty Ban Nha. Nhng phn ng ny lin quan ch yu

n cc lnh vc ng dng ca zeolit trong xc tc, m trc

c gii hn kh ha phn ng.

2.2. AlPO4-n SAPO4-n, Me-AlPO4-n, Me-APSO4-n

Vo u nhng nm 1980, s pht hin ca mt gia nh mi
ca sng phn t c bo co ca cc nh nghin cu ti
Union Carbide. Wilson v cc cng s [104.105] m t cc vi
mao qun aluminophosphates chun b thy nhit t nhm, axit
photphoric v mt amin hoc mui amoni bc bn nh cc mu
hu c. Sn phm thnh phn cho cc ti liu ny l XR Al2O3
1,0 0,2 P2O5 yH2O, trong R l mt mu hu c nm
trong h thng mao qun tinh th. Cc vt liu kt tinh bao
gm xen k AlO2 v PO2 t din lin kt vi nhau thnh
(electrovalently) trung tnh, ba chiu khung c cu trc ph
thuc vo iu kin chun b. Nhng khun kh khng cha Al
O Al hoc P O P. C cu AlPO4-5 gm 4 v 6-phn t vng ni
vi nhau to thnh (unidimensional) knh hnh tr ca vng
12 cnh vi ng knh min ph ca khong 0,8 nm
[106,107,50,108,109]. Cc porosit ca cc cu trc c m t
bi cc nh nghin cu Union Carbide thay i t mao qun rt
nh (0,3 nm) mao qun tng i ln (0.8 nm). Bi v khung
AlPO4 l trung lp, chng khng c nng lc trao i ion. Chng
th hin s n nh nhit v thy nhit tt v c tnh xc tc
yu c tnh axit. S vng mt ca axit mnh hn ch vic p
dng nhng nguyn vt liu trong cracking xc tc. Bng cch
thay th ng hnh ca mt lot cc yu t vo. Khung AlPO4,
mt th h mi ca sng phn t tinh th c chun b
[110]. Cc yu t bao gm loi khung cation m phm vi t ha
tr I n V , nh Li, Be, B, Mg, Si, Ga, Ge, As, Ti, Mn, Fe, Co, v
Zn. Vic b sung silicon vi nhm v pht pho dn n
silicoaluminophosphate (Sapo) Sng phn t [111]. Cc cu
trc Sapo l hi thm nc v c axit thp n trung bnh,
ty thuc vo nng , silicon v cc kiu cu trc. Theo

Martens [112], thm ch cao SAPOs silic c hot tnh xc tc

thp hn so vi zeolit, USY nh vy. Sapo-37 l cht xc tc
cracking rt hot ng [113]. Mt s bng sng ch m t vic
s dng cc Sapo-5, sap-11, sap-37 v Sapo-40 trong s
octan cht xc tc FCC [114]. Vic thay th ng cu ca cc
ion kim loi vo khung AlPO4 kt qu trong kim loi
aluminophos-phates (MeAPO), trong khi s thay th ng hnh
ca kim loi ion vo SAPOs kt qu trong
silicoaluminophosphate kim loi khung-cng trnh (MeAPSOs).
Thuc tnh ca chng cng tng t nh ca Sng phn t m.
S n nh nhit v thy nhit ca MeAPSO l thp hn mt
cht so vi sng phn t AlPO4 v Sapo. MeAPSOs hin ra t
yu n mnh, ty thuc vo cc loi kim loi v cu trc
khung.

2.3. t st cha ct(PILCs)

t st cha ct (PILCs) c nghin cu t nm cui nhng
nm 1970 nh l vt liu vi xp vi kch thc mao qun ln
hn (0,4-2,0 nm, nhng khng u) v b cc m hn so vi
cc zeolit [115-117]. PILCs c xc nh l ng c vin tt cho
xc tc khng ng nht v kch thc l ca chng phn phi
kh rng v vn l ch yu trong phm vi vi mao qun xp [2].
Cc vt liu t st m c cu to cation ph cn bng kp
gia in tch m tm aluminosilicate. PILCs c chun b bi
sng tm t st, trao i ion cation vi [AlO4Al12 (OH) 24
(H2O)] 7+ tng hp oxo nhm, v nung vt liu to ra cc
tr ct oxit nhm bn trong cc tm t st. Kt qu l mt cao
cu trc xp vi din tch b mt ln ph hp vi tinh th cho
phn t sng, hp ph v xc tc [118]. PILC ging vt liu,
PCHs gi (cu trc d th t st xp) c chun b bng
cch s dng khun mu hot ng b mt trong cc tm t
st [119]. Cc PCHs c th iu khin, kch thc mao qun

ng u ca 1,4-2,2 nm v gi li cc c tnh ging nh cc

vt liu t st ban u.

2.4. Hydroxit hai lp (LDHs)

Hydroxit hai lp(LDHs), cn c gi l hydrotalcite nh hp
cht, l nhng hp cht ion dng tm m bao gm tch in
dng tm hydroxide vi hai lp in y cc anion v cc
phn t nc. Cu trc ca chng c lin kt vi rng cc
brucite khong thin nhin, Mg (OH) 2 [120.121]. Nhm ph
bin nht ca LDHs c th c biu din bi cng thc chung
[M2+1-xM3 +x (OH) 2] - [An- x / n mH2O], ni M2 + v M3 + l cation
kim loi ha tr 2,3 m chim tm bt din trong lp ch ca
tm hydroxide, v An- l mt lp xen anion m n b cho cc
in tch trn lp. in tch dng trn lp my ch pht sinh t
thay th ng hnh ca mt phn nh ca cc cation ha tr hai
vi cc cation ha tr ba. S kt hp Mg v Al c nghin
cu nhiu nht, vi mt lot cc t l Mg: Al v anion cc lp.

2.5. Khung hu c kim loi (MOFs)

Cc khung kim loi hu c, gi tt l MOFs, l vt liu mi
c pht hin khong 40 nm trc y bi cc nh khoa hc
polymer. S gia tng nhanh chng ca cc ti liu v chng bt
u ch khong 20 nm trc y [122.123]. tng hp ca h
tng ng vi cc phn ng ca cc nhm hu c v v c,
chng hn nh asenat, silicat, sunfat, pht pht, phosphonate,
vv iu ny phn ng c xy dng ln khung ba chiu hnh
thnh ca cc gc v c v hu c lin kt bi nhng lin kt
mnh. cc phn hu c bin i trong t nhin, chiu di v s
lng khng gian chim dng bi v n bao gm hoc axit
cacboxylic nhiu hoc t phn nhnh, amino khu phc hp, vv
Lch s ca MOFs c biu th trong hnh 7 v 8.

M t v cc cu trc v tm mao qun(porosites ) ca mt s

MOFs c minh ha trong hnh. 9-11 cho tnh ton din hn v
cc c tnh c th ca chng. Theo hnh. 11, mt s MOFs c
th m rng theo hp ph (th chuyn ng) hoc b bp mo,
c th dn trong c tnh khc nhau xc tc v ht bm [130135]. S hp ph c th c lm chm m khng bm; thuc
tnh ny c ngh bi Ferey v cc cng s. c s dng
cho vic phn phi chm mt loi thuc vo dng mu khi cy
mt ngi bnh, v d nh, cho bnh tiu ng [127].
i vi mt cch nhn xc tc xem c th phn bit ba kha
cnh ca thuc tnh MOFs lin quan n: (1) khun kh cc
nguyn t hay ion hot ng, (2) ng cc loi hot ng v
(3) tng hp sa i b sung. Hnh 12 cho thy kch thc
tng i khc nhau zeolit v MOFs so vi cc phn t hu c.
R rng l phn t ln c th xm nhp vo cc mao qun ln,
th m quan trng i vi mc ch xc tc, nu cu trc MOF
c b sung hoc c cc tm ang hot ng v by ra cc
nguyn t khung hoc cc cation kim loi kim loi c xm
nhp (Bng 2).
Garcia v cc cng s m t [131] vic s dng khung hu
c kim loi (MOFs) lm cht xc tc khng ng nht cho phn
ng oxy ha bng cch s dng hydroperoxides hoc oxy phn
t. Cc tc gi c gii hn mnh vo qu trnh oxy ha ca
cycloancan, qu trnh oxy ha ca tm benzylic, qu trnh oxy
ha ca cycloalkenes v oxy ha hiu kh ca ru, nhng
nhiu phn ng oxy ha hn c th c hnh dung v nghin
cu. Vic s dng cc MOFs l cht xc tc cho oxy ha i
xng cng c xem xt vi nhng nt c bit ca yu cu
oxy ha v cc li th ca vic c MOFs homo chiral.
Cc ng dng chnh ca MOFs quan tm: hp th, lu tr kh
t (H2, CO2, vv), tch kh, acid (Lewis; Bronsted), c bn, oxi

ha kh v xc tc i xng, chuyn i sinh khi,

biomimetism, enzyme, phn phi thuc, t tnh, quang phi
tuyn tnh, laser, cm bin, pht quang, vv. Trong xc tc, s n
nh nhit v lc l mt vn ln trong nhiu nm v hn
ch nghin cu, nhng by gi mt s h thng mi c
tuyn b l n nh ln n 500C. Cc MOFs c th khng thay
th zeolit trong lc du nhng cng cho ha hc tt di iu
kin phn ng nh nhng hn. c nhiu bi bo xut hin
cho mt s phn ng nh qu trnh oxy ha, Lewis kiu phn
ng ca cyanosilylation acetaldehyd [137], vv.
R rng l nghin cu xc tc vi MOFs l trong giai on u
ca h. chc chn l c th i vo cc vt liu phc tp hn
vi ligand hu c gia cc kim loi c th c hnh thnh bi
qu trnh chuyn i khu phc hp kim loi vi mt hoc hai
kim loi khong cch c kim sot. Loi nh vy ca vt liu
s cho php tng hp cc cht xc tc khng ng nht khng
ch da trn cc phc kim loi chuyn tip m cn bi s kt
hp ca tm n hoc a kim loi . Thit k ny c th dn
vt liu c mt hot ng xc tc tng t nh nhng g quan
st vi cc enzym.
Kh nng tng hp MOFs vi mt lng ln cc kim loi
chuyn tip c th c khai thc ch yu cho xc tc axit
Lewis, vi iu kin l cc kim loi c th xm nhp (ha tr c
sn) v c th chp nhn electron t cc cht phn ng. Ngoi
ra, cc hu c thnh phn ca MOFs cn h tr axit, baz, hoc
cp acid-base v nn cho php mt thc hin cc phn ng
lin tip. c th quan tm n cc ngnh cng nghip ha
cht trong khai thc MOFs nh cht xc tc d th. Cc v d
bao gm epoxit vng khu vi ru bi cacboxylat km, cc
phn ng ha hc tt nh Fries sp xp li, acylations, qu trnh
oxy ha alkylaromatic bng cobalt mui axit acetic, vv MOFs
cng cung cp mt s li ha nh cht xc tc i xng, mt

ch m khng th pht trin s dng zeolit. Tng hp bt

i xng thng xuyn c thc hnh trong tng hp cc loi
thuc, v nhng phn ng ny gn nh hon ton thc hin
bng cch s dng cht xc tc ng th t tin. Bng cch
s dng chiral ligand, mt s lng ln cc MOFs mi c th sn
sng v th nghim trong lnh vc ny. Xem xt s n gin ca
qu trnh tng hp MOFs v kh nng chi tr ca h, iu quan
trng l phi bit nu MOFs c th lm tt hn trong cc phn
ng quy m ln hoc bt i xng thay th t tin quy trnh
ng nht.
Cui cng, c mt nhu cu cho cc nghin cu l thuyt trong
lnh vc mi ny, h tr vic thit k cc MOFs v cung cp
hiu bit v tng tc ca cc cht v MOFs. Lm r c ch
phn ng, hnh hc ca cc trng thi bin i, v cc bc
kim sot trong c ch phn ng c th gip pht trin MOFs
trong mi thnh phn ng vai tr d kin, nh im xc tc
ca enzyme t nhin.

2.6. Hierarchical zeolites

Zeolit c sp xp v oxit mao qun va (alumina, titanic, vv)
nhn c s quan tm ngy cng tng v hiu sut ci
thin ca chng trong cc phn ng xc tc i vi zeolit thng
thng (vi mao qun hon ton) hoc oxit kim loi ph bin
[59.138.139]. Cc nguyn tc lin quan n vic to ra cc mao
qun va trong zeolite hoc trong bt k cc ht oxit kim loi.
Vt liu vi mao qun kt hp ny c tuyn b c li th so
vi cc vt liu chuyn vi hoc trung mao qun. Do cc phn
t cht phn ng c k vng khuch tn d dng hn [140]
trong cc mao qun t c cc hot ng tm ca zeolite.
Nhng vt liu ny cung cp s n nh nhit tt hn [141],
kim sot tt hn x l mt lng ln cc nguyn liu, t l
lc kim sot nhiu hn i vi mt hng s v dn dn pht

hnh cc thnh phn hot ng, v c nhiu kh nng ng gi

cc cht thi trong cc vi mao qun[142-144]. Vt liu xp khc
nhau kt hp vi m v trung mao qun, nh SBA-15, silic lc
gic mu (PHTS), mao qun nhm silicat (MAS), mao qun
silicat titan (MTS), UL-ZSM-5, v zeolit, c pht trin trong
vng vi nm qua. Cc vt liu ny c bn u c xy dng
t cc tin cht zeolite. xp nh trong cc vt liu mao vi
zeolite c th c to ra sau khi tng hp bi phng php x
l ha cht, bao gm c thy nhit, axit, baz, b silic/ b nhm
hoc phng php kt tinh [145.146], hoc khun mu [147149] hoc carbon da trn [150-153] phng php tip cn. B
silic trong cht c tnh kim tr thnh mt phng php
chun b ng dng rng ri iu chnh cc zeolit sa i v
ca s kt hp ti u ca phng php hiu qu v n gin.
X l kim cng l mt bc quan trng trong chin lc kt
hp vi sa i sau tng hp khc.

2.7. Vt liu carbon

Nano carbon (CNTs) to thnh mt lp xp vt liu. Chng
c nghin cu rng ri k t nhng vo nm 1991 [154].
CNTs c in t, c kh, xc tc, hp ph, v cc c tnh vn
chuyn rt c o, m lm cho chng th v cho mt lot cc
ng dng. ng nano carbon nhiu ngn (MWNTs) v cc ng
nano n ngn (SWNTs) nn c phn bit. Chng d dng
ch to v c th lm vic hoc nh l cht xc tc h tr,
bng cch by cc gc thuc ang hot ng trong mao qun,
hoc ci thin chuyn i hnh nh v lu tr nng lng
in (vide infra) [136,155-160]. Cc dng khc ca carbon
nanographitic cng c th chng minh c ha hn trong vic
pht trin nng lng ti to cc thit b nng lng. V d,
graphene, trong bao gm mt tm duy nht ca than ch,
c coi l mt hnh thc y ha hn ca carbon cho ng
dng k thut thit b v xc tc [161-165]. Mt khi lng

ng k ca ti liu dnh cho graphene v cc hnh thc khc

ca carbon, bao gm cc si nano graphitic, gi rng CNTs
l khng ch cc cu trc nano ha hn cho chuyn i hnh
nh hoc cc ng dng lu tr nng lng in. Cc tnh cht
vt l rt c o ca nano carbon c chng minh cho
mt lot cc thit b quang in cng nh cho pin Li-ion v t
in c ci thin.

2.8. Vt liu Mao qun trung bnh

Nhiu vt liu silica mao qun trung bnh c tng hp
trong nhng nm sau khi hot ng tin phong bng vic
nghin cu ca Mobil v gia nh M41S (MCM-41, MCM-48,
MCM-50) [166-168]. Vt liu mao qun trung bnh MCM-n c
tng hp bng cch s dng b mt nh tc nhn hng cu
trc v c th c c trng bi cc mao qun cng xc nh
cc kch c c th iu chnh trong khong gia 2 nm v 10 nm
v bi cc khu vc b mt ring gia 600 m2 g-1v 1300 m2g1
.Cc vt liu M41S i din nht l MCM-41 v MCM-48. MCM41 bao gm cc mao qun gi mt chiu thng xuyn trong
mt sp xp t ong, trong khi MCM-48 hin vt khi i xng
gm hai an xen nhau nhng khng kt ni ba chiu h thng
mao qun ca mao qun hnh tr. MCM-48 l kh khn hn
tng hp v cc vt liu cht lng cao thng c th c thu
c trong phm vi mao qun, kch thc gia 2 v 5 nm [169].
MCM-50 bao gm mt pha phn lp. Mt cch c lp, mt
nhm vt liu silic mao qun trung bnh vi cc c tnh tng
t nh ca MCM-41 c pht hin [170.171]; mt thnh vin
quan trng ca gia nh ny l FSM-16 [171]. quy m nh,
nhng vt liu c bn dng v nh hnh. Trong khi , cc
phm vi ng knh mao qun ca nguyn liu MCM-41 c
gii hn n 10 nm, a ra vt liu mao qun trung bnh vi
mao qun ng knh ln n khong 30 nm (SBA-15) c th
thu c s dng mt khi amphiphilic copolymer l mt mu

[172.173]. SBA-15 (tng t nh MCM-41) bao gm mt gi

hnh lc gic knh hnh tr; Tuy nhin, ty thuc vo cc chi tit
ca th tc tng hp, vt liu ny c th s hu vi mao qun
bt thng m kt ni cc knh ln cn [174.175]. Hn na,
mt lot cc mao qun trung bnh c tng hp, nh SBA1, SBA-2, SBA-12, SBA-16, HMS [176], MSU [177], KSW-2 [178180], TUD-1 [181], (PMOS) [182-184], mao qun nano carbon
vi cu trc trung bnh [CMK-1, CMK-3) [185.186]. Vt liu mao
qun trung bnh cha silic c bit trin lm hot tnh xc tc
thp v s vng mt ca cc tm hot ng, m thng i hi
cc nguyn t khc. V vy, mt trong nhng cc xu hng mi
trong lnh vc tng hp vt liu mao qun trung bnh l s kt
hp ca cc nguyn t khc c cng dng lm xc tc cc tm
ang hot ng. Quan tm nghin cu ng k hin ang tn
ti trong chun b v s dng cc nguyn t khc c cha mao
qun silic nh cht xc tc d th. Mt s th tc c bo co
cho s kt hp ca cc nguyn t khc m cng cho php cc
thit k ca cc cht xc tc vi cc tm ang hot ng nm
trn cao b mt bn trong c th xm nhp cc knh mao
qun. Cc th tc ny bao gm ngm tm [187-190], ghp
bng cht lng-rn phn ng [191-196], ghp bng phn ng
kh-rn [197], ghp bng rn rn phn ng [198.199], thay th
ng hnh [200-210], phn t cch tip cn thit k phn tn
[211-213] v mu phng php trao i ion [214.215]. Mc tiu
l tng hp vt liu xp c kh nng cha cc phn t cng
knh v do x l nguyn liu du m nng hn. V d, s ra
i ca Al vo khung silica a n axit sc mnh trung bnh
so vi nng axit ca zeolit bnh thng v gc lin kt Si O Al
ln hn. Cc ng dng ca vt liu nh vy trong ho du sau
c hn ch. Hin nay, nghin cu tp trung vo vic gii
thiu cc chc nng xc tc hot ng trong vng cc mao
qun trung bnh hoc ca cc ht nano kim loi hoc oxit. Kt
qu th v thu c; Tuy nhin, theo hiu bit ca chng ti,

cha c nghin cu no c sn xut mt t ph trong qu

trnh xc tc. Ti liu H-Al-MCM41 c s dng lm cht
xc tc cho s chuyn i ca mt lng ln cc cht nn trong
cc phn ng khc nhau nh cracking hydrocarbon,
hydrocracking v hydro isome ha, trng hp olefin, oligome
ha v ng phn ha, Friedel-Crafts cc ankyl thm v phenol
v axyl ha, acetylazations, Beckmann sp xp li,
glycosidation, hiu ng nghch o, v Prins . Mt s nh gi
v ti ny c cng b [2.216.217].
Kt qu th v cho cc vt liu kim loi mao qun trung bnh l
bo co lin quan n cc phn ng Fischer-Tropsch [218.219]
vi, hydro d sunfua ha [220-222], vic chuyn i methylcyclopentane [199.201], cc acyl ha ca phenol [223], cc naphthalene hydro ha [224], s hydro ca Arenes [225], hydro ha
cyclohexane [226], NO gim vi CO [227], cc acyl ha cc hp
cht thm [228], cc benzoylation ca benzen [229], cc Hon
i ca oct-1-ene [230], v s phn hy quang xc tc ca NO
[231], cc phn ng oxy ha [232.233] v k t tr i.

2.9. H thng xc tc d th a nng

Kt hp sc mnh tng hp cc hiu ng xut hin thi gian
gn y nh mt cch y ha hn tng hp hiu qu v
linh hot h thng xc tc d th. V d, nhiu nghin cu c
c thc hin trong na th k qua c nh cht xc tc
ng th v h tr vng chc tng hp xc tc d th [234],
c bit n kt qu trong tch d dng ca cht xc tc t
cc cht phn ng v sn phm. Ban u, cc trung tm hot
ng c thit k c i t mt b mt h tr gim
thiu h tr nh hng ph hoi trn tm xc tc v duy tr s
ng nht mi trng phc kim loi ca cc phi t vi mt
spacer di v tnh cht xc tc nh vy, [235]. Sau , n
c quan st thy rng h tr thm ch c th c mt s tc

dng c li trn cc cht xc tc ng nht [236] nh gii hn

[237] v cc hiu ng sc mnh tng hp [238-240]. Cht xc
tc nh chc v thm ch ba chc khng ng nht sau c
th c chun b v nghin cu v mt sc mnh tng hp
gia cc nhm a chc nng c th l pht trin trong khng
gian hn ch. Mt mc tiu quan trng hn na l c gng tng
hp cc cht xc tc d th vi tng cng sau khi cht xc tc
chiral c gii thiu vo gii hn khng gian. V d, Raja v
Thomas [241] ch ra rng, so vi cc sn phm gm thu
c trong ng nht xc tc, ci thin chn lc (ee% 5394%) trong bt i xng phn ng hir thu c sau khi chiral
phc RHI c gii thiu vo cc knh silic mao qun trung
bnh. ng v cc cng s[242] cng ch ra rng sau mt
cht xc tc 2 chc, 9-thiourea epiquinine, c thnh lp trong
cc knh ca silic mao qun trung bnh SBA-15, cht xc tc
khng ng nht trng by chn lc v ci tin chn lc
(92,5% v 99,2% chn lc ee so vi 83,8% v 93,2% chn lc
ee) trong bt i xng Friedel-Crafts phn ng gia indoles v
hp cht chc imin.
Cc hp cht c phn tng, vi hai chiu xen linh hot khu
vc, cng c ha hn h tr dng cho c nh cht xc tc
ng nht. V d, cc c nh ca khu phc hp ng trong t
st laponite c tm thy [243] tng ee t hu nh bng
khng gi tr ca. 40% trong phn ng ca metyl
phenyldiazoacetate vi C2H4OC2H4.
tng l ghp, neo hoc thether thc th hot ng xc
tc ti silica mao qun trung bnh. Nhng loi ny c th ging
hoc khc nhau m c th dn n nh chc, ba chc trong mao
qun. Li gn chng c th dn n tc dng hip ng i vi
mt s cht phn ng trong mt khng gian hn ch v m ra
mt lnh vc quan trng ca vic pht hin cc cht xc tc
mi, bng cch tn dng phm vi lin tc khong cch gia cc

nhm chc nng neo v cc tm thc cht hot ng trn cc

b mt h tr. Tc dng hip ng trong vng neo cht xc tc
nh chc, gia hai nhm chc nng neo, v gia cc nhm neo
v cc nhm hydroxyl trn rn b mt c s dng tng
hp cc cht xc tc a chc nng. Hy cng nhc nh rng tc
dng hip ng c s dng rng ri trong t nhin chng hn
nh cho cc enzyme m vi cc nhm chc nng gii hn c
th phn tch nhiu phn ng thun li vi hot ng cao v
tnh chn lc nhit phng gn [244].
3.

Ti nguyn nng lng

Hin nay, du m v kh t t nhin i din cho hn 60% ca

nng lng s cp cho 7 t ngi trn tri t. Than cng
cn l ngun nng lng quan trng, ch yu l chu . D
c s dng sn xut nng lng, giao thng vn ti, si
m hay lm ngun nguyn liu ha cht, mc tiu th du m,
kh t nhin v than d kin s tng trong tng lai gn, trong
khi pht trin cc ngun nng lng khc d kin s tng ln
nhanh chng sau khi mt pht trin chm trong 20 nm qua. S
gia tng ng k nhu cu nng lng trong vng hai mi nm
qua ch yu c p ng bng cch tng sn xut cc
ngun ha thch. Bi v tnh hnh ny, mt s chnh ph c
ph duyt lut mi nhm gim vic x kh CO2 bng cch
thc y vic s dng nng lng ti to ngun nng lng v
nhin liu sinh hc. Tng tiu th trn th gii vo nm 2005 l
13 triu tn (~87000 thng du), trong 81% n t cc ti
nguyn ha thch, nh th hin trong hnh 13.
Mi phn trm ca vic s dng nng lng trn th gii c
ngun gc t sinh khi, v 7% c ngun gc t nng lng ht
nhn. in ht nhn l mong mun min l cc ng v
uranium-235 ( 235U) c s dng. Tuy nhin, mt ngun cung
cp t hn hai mi nm ca U235 , Trong c th c phc

hi vi chi ph hp l, c sn. Khi vic cung cp 235 U s c

kit sc, sau n s l cn thit s dng l phn ng
ging. Tht khng may, cc sn phm ph ca phn ng ny l
rt nguy him phn t, plutoni-239,239Pu (238U 239Pu). Hn na
k t khi thm ha sau thm ha sng thn Nht Bn vo
nm 2011 v s sp ca cc nh my ht nhn
Fukushima, vic xy dng cc nh my ht nhn c hu
nh khng t cu hi ti nhiu quc gia, mc d ht nhn in
l khng CO2 v khng tiu dng ti nguyn ha thch.

3.1.Cc ngun ca du
Rt kh nh gi tr lng du chnh xc bi v n tng ng
vi cc c lng th l khu bo tn hin nay, l ngun ngu
nhin (thng thng v c bit nng nhc + bitum) tp trung
vo mt s lng hn ch ca cc nc (Saudi Arabia, vi 20%,
Iran, Iraq, v Venezuela; bn quc gia ny s hu 50% ca tr
lng th gii), vi 75% tp trung 11 quc gia. D tr hin
hnh tng ng vi khong 1000 Gbarrels.Do , khong 35
nm sn xut mc tiu th thc t, nhng t hn so vi du
c chit xut) v mt th thm 200 Gbarrels cho ngun ti
nguyn thng thng v 200-300 Gbarrels hn cho du siu
trng v bitum. Du c chit xut bng cch bm n gin
(20% sn lng th gii), bng cch tim nc (2/3 du sn
xut), hoc bng cch tim nc + ha cht hoc kh (khng
kh, CO2 hoc kh c sn xut (15%)). Nhng n lc khm
ph ti nguyn mi r rng l quan trng, v s thay th du
bng nng lng ti to l rt quan trng. Mt s khch hng
tim nng c th hin trong hnh 14.

3.2. Ton cnh kh thin nhin (NG)

Kh thin nhin cu thnh d tr ln nht ca cc ngun ti
nguyn ha thch. 11 nc chim 75% ngun ti nguyn kh t

trn th gii, vi 45% cho Nga, 28% i vi Iran, v 25% cho

Qatar. D tr hin nay c t 175-200 Tm3 (T = tera = 1012);
Tuy nhin, ln ti nguyn tn ti dng hydrat m-tan, nm ch
yu khu vc vng cc hoc trong din tch nc su. Kh t
nhin c th c s dng nh mt ngun nng lng (trong
nh my in hoc nh l mt h thng ngun si, v d),
nhng n cng c th c chuyn i thnh nhiu vt liu c
bn cho ha cht. Tuy nhin, hin nay, ch chuyn i sang kh
tng hp thng qua hi nc, oxy ho tng phn hoc oxy ha
nhit dng nh l cng nghip kh thi [246]. tt c bin i
trc tip, v d, methanol, dimethyl ether, formaldehyde, cht
thm, hoc olefin vn khng kh thi v mt kinh t. iu ny
thiu tnh kh thi l mt thch thc thc s cho trong tng lai,
mc d nhiu phng php c th qua qua 50 nm, bt
u vi s phn ng i-me ha trong nm 1970, khng thnh
cng thng mi. Cc phn ng chnh c th c tm tt di
y:
1.
2.
3.
4.
5.
6.

Reforming hi nc
Reforming CO2
Reforming nhit
Oxi ha tng phn c xc tc
Oxi ha ton phn
Phn ng Boudouard

Cc sn phm ha hc chnh t kh t nhin c tm tt trong

Bng 3.

3.3. Nhin liu sinh hc - mt ngun nguyn liu

v nng lng tng lai
Nhin liu sinh hc, tc l, tt c cc sn phm t thc vt (cy
trng, algaes, g, cht thi nng nghip vn ha, vv), ni ln
nh l mt ngun quan trng trong tng lai nng lng v ha
cht nguyn liu thay th, t nht l mt phn, than, du v

kh t t nhin. Ngun gc ca sinh khi t CO2 v nc di

photon nng lng mt tri v cht dip lc sn xut khi
lng ng ngun gc ca cellulose, hemicellulose, lignin,
v vn vn c bit n. Lignin to thnh mt trong ba thnh
phn chnh ca sinh khi ligno-cellulosic; hai thnh phn khc
bao gm cellulose v hemicellulose. Lignin l mt polymer v
nh hnh ba chiu bao gm cc cu trc phenylpropane
methoxylated. Trong vch t bo thc vt, lignin lp y cc
khong trng gia cellulose v Hemi-cellulose v hot ng nh
mt cht keo gi ma trn lignocellulose vi nhau. Lin kt
ngang vi cc polyme carbohydrate sau trao sc mnh v
cng h thng [245.247].
Trong nm 2005, hn 3% tng mc tiu th nng lng trong
Hoa K c cung cp bi sinh khi, v n gn y vt qua
nng lng thu in l cc ngun trong nc ln nht ca ti
to nng lng. Tng t nh vy, Lin minh chu u nhn
c khong 66% nng lng ti to t sinh khi, vt qua
tng s kt hp ng gp ca thy in, nng lng gi, nng
lng a nhit, nng lng mt tri v nng lng. Ngoi nng
lng, sn xut cc cht ha hc t sinh khi cng l iu cn
thit bi v n l ngun ti to duy nht ca nhin liu vn
chuyn cht lng.
Trong 30 nm qua, ba th h sn phm sinh khi ni ln
[248.249], c phn bit bi bn cht ca h. Trong khi ,
du l ngun gc ca nng lng trong th k XX, th k 21
c k vng s mang li ngun nng lng mi, ngun nng
lng c bit l ti to nh nng lng sinh hc [248].
Ba chin lc thc hin bnh n sinh khi c th c theo
sau [249]. Trong chin lc u tin, nhin liu sinh hc kh ha
kh tng hp hay lo ha theo nhit phn mt hn hp
ca cc phn t nh, c th c s dng sn xut ha cht

s dng cng ngh pht trin cho ngnh xng du nguyn liu.
Trong chin lc th hai, ct b rng ri ca cc nhm chc
nng c mt trn cc monome lignin sn xut cc hp cht
thm, nh phenol, benzene, toluen v xylen. Nhng ha cht
nn tng ny sau phn ng trong bc th hai s dng
cng ngh xc tc pht trin cho cc nh my lc du hin c
sn xut s lng ln v ha cht tt.Trong chin lc th
ba, sinh khi c chuyn i trc tip vi cc ha cht c gi
tr trong mt qu trnh mt ni, m i hi phi c cht xc tc
chn lc cao m loi b chc nng v cc mi lin kt. Chin
lc ny l thch hp nht cho vic sn xut ha cht tt vi
mt mc cao ca tnh nng, chng hn nh vanillin, m
ging vi cu trc lignin; Tuy nhin, cc phn t mc tiu phc
tp hn cng c th c sn xut vi thm ci tin trong cng
ngh xc tc. Tht vy, cch tip cn ny c th mang li rt
nhiu cc cht thm phc tp m khng phi l nu khng c
sn thng qua cc tuyn ng ha du thng thng. Bi v
khng c cc chin lc ny c k vng s mang li mt sn
phm duy nht trong cao nng sut, tch sn phm l mt
thnh phn quan trng ca mi qu trnh. Trong mi trng
hp, sau khi ch bin xc tc ca cc dng lignin, cc ha cht
hoc nhin liu phi c thanh ty, m r rng phi c a
vo ti khon trong cc nh gi ca mi trng tc ng ca
ton b qu trnh. Thnh phn t cellulose v hemicelluloses
sui c tch hp trong khun kh lignin, nhng cc mi tn
qu trnh c m t y khng cho r rng [245] - hnh 15.
S bin i ca cellulose, l thnh phn chnh ca cc nguyn
liu lignocellulose ti to di do nht v l khng n c, vo
ha cht v nhin liu thu ht c s ch ng k trong
nhng nm gn y. So vi cc ng chuyn i khc, chng
hn nh kh ha nhit cao v nhit phn v ln men
enzyme, mt nhit thp v tuyn ng xc tc chn lc

cho cc chuyn i cellulose trong, v d, mi trng nc,

thnh phn t nn tng, c th d dng chuyn i thnh gi
tr ha cht v nhin liu trong cc bc tip theo, l nhiu hn
mong mun. Glucose, polyol, axit hu c, v 5hydroxymethylfurfural (5-HMF) l tt c cc phn t nn tng
y ha hn. Mt s cht xc tc nh chc v h thng xc tc
c cha c axit i vi qu trnh thy phn -1,4-glycosidic
trong cellulose v kim loi ht nano cho s hydro hoc qu trnh
oxy ha ca monosaccharide polyol hoc axit hu c
c pht trin [250-256].
Mt s loi suy c th c rt ra gia th k XX nh my lc
du v cc nh my lc sing hc th k XXI. Trong bt u, cc
nh my lc du kh thc hin vi sn phm v kt hp cc
thnh phn ha hc v nng lng t. S pht trin ca cc nh
my lc du cn n lc ng k, ko di thp k tr thnh c
hiu qu cao, h thng tch hp tn ti ngy nay. Nhiu ngi
trong s nhng t ph cho php chuyn i ng ch ny
lin quan n nhng tin b trong xc tc. Tng t nh vy,
biorefineries hin ti, vn cn ang trong giai on trng nc
ca h, sn xut tng i t ha cht (ch yu l ethanol sinh
hc hoc cc loi du) vi t ha v hi nhp nng lng. Tng
t nh lch s ca
Nh my lc du kh, vi s pht trin ca cng ngh xc tc,
cc biorefinery c th tr thnh mt h thng hiu qu, tch hp
cao p ng cc yu cu ha v nhin liu ca th k XXI.
nhn ra h thng ny, ngoi vic chuyn i xc tc
cellulose v hemicellulose, phn lignin sinh khi nn c
chuyn i t mt sn phm cht thi-cht lng thp gi thp
vo mt cht lng cao, c gi tr cao cho s lng ln nguyn
liu v ha cht chuyn bi s pht trin ca cc cng ngh
xc tc thch hp. Cc chuyn i trc tip ca lignin thnh ha
cht c gi tr dng nh l nhiu kh khn hn so vi vic

chuyn i cellulose. Tuy nhin, iu ny chuyn i l rt quan

trng bi v lignin i din duy nht kh thi ngun nng lng
ti to sn xut cc hp cht thm m x hi hin nay ph
thuc.
C th kt lun rng sinh khi hin nay l ngun nng lng ti
to hng u trn th gii. Hn na, s ra i ca sinh khi
thnh h thng nng trnh by nhng thun li nht nh,
chng hn nh gim pht thi kh nh knh, bi v tng hp ca
n s dng CO2 v nc. Tuy nhin, vic huy ng ca n vn
trnh by nhiu thch thc lin quan n s cnh tranh gia s
dng v vic qun l cc ngun ti nguyn thin nhin ca a
phng (v d nh, nc, t, a dng sinh hc, t nng dn
v ti sn ring rng). Do , cng ngh lin quan nn c
cu trc ngun ti nguyn ny c pht trin c thc s
bn vng. Hai cng ngh tn ti cho vic sn xut cc nhin
liu thay th du diesel: methyl rau-du este (VOME) v cc loi
du thc vt hydrotreated (HVO). sau ny du, pha trn vi du
ha, bt u c s dng nh hng khng nhin liu.
Nng sut cy trng ph thuc vo bn cht ca cc Biosource,
cng chi tit
trong Bng 4. G l mt ngun quan trng cho lignin. vic sn
xut
v chuyn i g thnh nhin liu sinh hc c trnh by trong
Bng 5.
To nh du ht dng nh l c bit hiu qu (nng sut ca
70 t ha-1 v hiu qu nhin liu ca 14 toe ha-1), Trong khi ma
v c ci ng c nng sut cao (khong 70 ha t -1), Nhng
hiu qu nhin liu thp hn (khong 3 ha toe-1). so snh,
phn ln cc khc ngun sinh khi c nng sut t 10-20 t ha 1
v hiu qu ca 2-4 toe ha-1. Vic nui trng vi to sn xut

nhin liu sinh hc du, cellulose hoc hydro l min ph ca

nhiu hn ch trn cn. nh vy vi to c nui cy trong
photobioreactors v ch cn c gn gi vi nc, nh sng,
nhit v CO2. Vi to to thnh xu hng ph bin trong nghin
cu hin ti.
Trong tng lai, nng lng mt tri, a nhit, gi v c l ht
nhn cc nh my in c l s c s dng sn xut in;
sinh khi, kh thin nhin, than v du s c s dng cho
kh tng hp, ha cht, kh hydro s c s dng cho GTL v
hydroprocessing, v nh my lc du s c s dng sn
xut nhit, in, vn ti, v ha cht s lng ln (hp th
CO2).