Xuc Tac Quang Hoa Di The

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cc
MC LC (?)
5 C s ca xc tc d th 1
5.1 Cc giai on c bn trong xc tc d th 1
5.2 ng hc v c ch cc phn ng xc tc d th 4
5.2.1 Vai tr ca hp ph trong xc tc d th 4
Quan h hp ph v ng hc xc tc 6
Phng trnh Freudlich 6
Phng trnh Langmuir 6
5.2.2 ng hc v m hnh phn ng 8
5.2.3 Cc c ch phn ng pha kh 10
5.2.3.1 C ch LangmuirHinshelwood (1921) 10
5.2.3.2 C ch EleyRideal (1943) 12
5.3 Cc l thuyt ( tng) v xc tc d th 16
5.3.1 Kha cnh nng lng v quan h vi hot tnh xc tc 16
5.3.2 Vai tr ca yu t khng gian 30
5.3.3 Yu t in t 41
Xc tc xi ho kh 41
Xc tc Axid/Baz (Xc tc ion) 41
5.3.3.1 Kim loi 43
5.3.3.2 Xc tc lng kim (bimetallic) 48
5.3.3.3 Xc tc bn dn 53
Mi quan h gia cu to v tnh cht bn dn 54
Pha tp tng dn ca bn dn 55
Hp ph ho hc trn bn dn 57
Hp ph xi 58
Hp ph hyr 58
Trng hp TiO
2
58
Phn ng trn b mt bn dn 58
Trng hp xc tc xi ho 58
Cc dy hot tnh 60
Cc v d la chn xc tc: 60
Phn ng phn hu N
2
O 60
Xt phn ng xi ho CO trn bn dn 61
Phn ng phn hu etanol 62
Phn ng hyr ho etylen 63
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Cht mang 64
5.3.3.4 Cht cch in: Xc tc axit v xc tc baz 66
Tnh axit b mt 66
Xc tc baz rn 73
5.4 Tnh cht xc tc trong thc t 79
5.4.1 Cc yu t nh hng n cc tnh cht xc tc 79
5.4.2 Xc tc trn cht mang 80
Vai tr ca cht mang: 81
Chc nng ca cht mang: 81
Cht mang dn ti tnh a chc: 86
Hiu ng SMSI 86
Phn ng hyr ho axeton thnh isopropanol: 86
5.4.3 Cc cht xc tin 88
5.4.4 Cht c ch 92
5.5 S mt hot tnh v S ti hot ho 94
5.5.1 S u c xc tc 95
5.5.2 S u c trong xc tc kim loi 96
5.5.3 S u c xc tc xit bn dn 98
5.5.4 S u c xc tc axit 98
5.5.5 Cc sn phm phn r (deposit) bm trn b mt xc tc 98
5.5.6 Cc qu trnh nhit v s thiu kt 100
5.5.7 Tn tht xc tc qua pha kh 101
M hnh s mt hot tnh 102
M hnh da trn hp ph Langmuir 102
Ti sinh xc tc 103
5.6 Cc c trng xc tc d th 105
5.6.1 Xc nh cc c trng vt l v ho l 106
5.6.2 c trng ho hc v c trng b mt 111
Phng php phn ng theo chng trnh nhit 112
Hin vi in t truyn qua (TEM) 113
Nhiu x in t nng lng thp(Low-Energy Electron Diffraction(LEED)) 114
Ph hng ngoi (IR) 114
Ph in t phn tch ho hc (Elec/ Spectr. for Chem. Analysis= ESCA) 115
Ph in t Auger - Auger Electron Spectroscopy (AES) 116
Ph bn ph ion - Ion Scattering Spectroscopy (ISS) 117
ii
Khi ph ion th cp (Secondary Ion Mass Spectrometry = SIMS) 117
Ti liu sch gio khoa v xc tc d th v ho l b mt 122
iii
DANH MC BNG
Bng 5-1 So snh cc bc trong phn ng ng th v d th 3
Bng 5.2 So snh hp ph vt l v hp ph ho hc 5
Bng 5-3 Mt s v d hp ph ho hc 5
Bng 5.4 Phn loi kim loi theo kh nng hp ph ho hc 17
Bng 5-5 Hp ph ho hc CO trn kim loi chuyn tip 22
Bng 5.6 Ph IR ca CO hp ph trn cc xc tc Ni trn cht mang 23
Bng 5-7 Cc vng hp th IR ca phc etylen 23
Bng 5-8 So snh hot tnh xc tc kim loi chuyn tip trong mt s phn ng 25
Bng 5-9 Cu trc v khong cch mng kim loi (khong cch ti nguyn t bn cnh gn nht o
bng nm) 31
Bng 5-10 Phn loi cc phn ng xc tc bi kim loi 34
Bng 5-11 Hiu ng khng gian trong mt s phn ng 34
Bng 5-12 Hp ph v hyr ho etylen trn cc b mt niken 35
Bng 5-13 Hot tnh cc mt tinh th Fe khc nhau trong phn ng tng hp NH
3
36
Bng 5-14 Phn loi xc tc rn 42
Bng 5-15 Hot tnh xc tc so snh ca cc kim loi 48
Bng 5-16. Cc xc tc lng kim v cc qu trnh cng nghip tng ng 48
Bng 5-17 Hyr ho etylaxetat etanol trn xc tc Rh/Sn-SiO
2
49
Bng 5-18 Hyr ho crotonalehit trn xc tc Pt 49
Bng 5-19 Hyr ho dn xut ca pyridin vi xc tc lng kim mang trn Al
2
O
3
51
Bng 5-20 Bin tnh xc tc nhm Pt bng kim loi th hai 51
Bng 5-21 Nng lng kch thch bt in t ca mt s vt liu 53
Bng 5.22 Tnh cht ca mt s xit bn dn 55
Bng 5.23 Phn loi cc xit kim loi theo tnh cht in t 56
Bng 5.24 xi ho CO trn xc tc bn dn 62
Bng 5-25 Phn hu etanol trn xc tc xit bn dn 63
Bng 5-26 Phn ng trn xc tc trn cht mang 64
Bng 5.27 Phn loi xc tc A/B d th 62
Bng 5.28 Hiu qu ca Al
2
O
3
vi axit khc nhau trong phn ng loi nc etanol 71
Bng 5.29 axit ca cc vt liu xit hn hp 72
Bng 5.30 Xc tc axit trong mt s phn ng (xp theo s tng axit) 73
Bng 5.31 Cc cht mang xc tc cng nghip, tnh cht v ng dng 80
Bng 5-32 La chn cht mang xc tc 81
Bng 5.33 Hyr phn trn xc tc Ni trn cc cht mang khc nhau (10% Ni) 83
Bng 5.34 ehyr ho xyclohexan thnh benzen trn xt Pt/cht mang 773K 84
Bng 5.35 Hy ho CO trn xc tc Pd vi cc cht mang khc nhau 84
Bng 5.36 Hot tnh tng i ca Rh trn cc xit trong phn ng hyr ho CO 84
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Bng 5.37 nh hng ca cht mang n sn phm hyr ho CO trn Rh 85
Bng 5.38 Xc tc Cu trn cc loi xit trong phn ng hyr ho CO 85
Bng 5.39 Hiu ng SMSI trong phn ng hyr ho axeton thnh isopropanol trn xc tc Pt vi
cc cht mang khc nhau 87
Bng 5.40 Cc v d v cc cht xc tin trong xc tc cng nghip ` 89
Bng 5-41 Nguyn nhn mt hot tnh ca mt s xc tc cng nghip
Bng 5-42 Cc cht c v c ch xc tc 96
Bng 5-43 Chuyn ho nafta trn xc tc 0,6%Pt /Al
2
O
3
, s mt hot tnh v ti sinh 101
Bng 5-44 Din tch b mt ring ca mt s xc tc v vt liu mang 110
Bng 5-45 Hp ph ho hc c trng b mt kim loi 111
ii
DANH MC HNH
Hnh 5-1 Cc bc c bn trong phn ng xc tc d th vi xc tc rn xp 1
Hnh 5-2 Din bin nng theo v tr trong trng hp phn ng xy ra trong vng khuch tn
ngoi (a), khuch tn trong l (b), v ng hc 2
Hnh. 5-3 S ph thuc ln tc thc t, r
eff
vo i lng nhit nghch 3
Hnh 5-4 ng hp ph ng nhit (isotherm) Langmuir 6
Hnh 5-5 S c ch LangmuirHinshelwood 10
Hnh 5-6 Cc trng hp ca phn ng lng phn t pha kh theo c ch L-H 11
Hnh 5-7 C ch EleyRideal 12
Hnh 5-8. S ph thuc tc phn ng vo nng cht A trong phn ng pha kh lng phn t
theo c ch EleyRideal 13
Hnh. 5-9 Din bin ca phn ng pha kh A
g
P
g
16
Hnh 5-10 Hp ph ho hc hay s hnh thnh phc etylen - b mt Pt 19
Hnh 5-11 S thay i th nng ca h H
2
hp ph trn Ni 19
Hnh 5-12 C ch hp ph phn li ca H
2
trn b mt Ni 20
Hnh 5.13 Quan h hot tnh so snh ca cc kim loi trong phn ng phn hu axit foocmic vi
nhit hnh thnh foocmat kim loi 24
Hnh 5.14 Quan h hot tnh v nhit hp ph trong tng hp amnic 24
Hnh 5.15 Quan h gia entalpy hp ph ho hc trung bnh ca hyr v v tr ca nguyn t
trong bng tun hon 26
Hnh 5.16 Cc mt phng tinh th trong mng lp phng v ch s Miller tng ng 31
Hnh 5-17 S cc nguyn t xung quanh v ho tr t do ca cc nguyn t b mt Ni ng vi cu
trc fcc 32
Hnh 5.18 M hnh b mt tinh th (BASF, Ludwigshafen, Germany) 33
Hnh 5.19 Quan h tc phn ng v khong cch kim loikim loi trong xc tc hyr ho
etylen 35
Hnh 5.20 Phn ng xi ho CO trn b mt Pt 37
Hnh 5-21 Hp ph v phn hu axetonitril trn b mt Ni 38
Hnh 5-22 Qu trnh truyn in t 42
Hnh 5-23 Mt in t 3d v cng thot
o
ca cc kim loi chu k 4 43
Hnh 5-24 Thuyt vng: s thay i mc Fermi khi hp ph: 44
Hnh 5-25 Hot tnh xc tc trong phn ng CO + H
2
CH
4
trn cc kim loi 44
Hnh 5-26 Quan h hot tnh xc tc trong phn ng hyr ho etylen v c trng d 45
Hnh 5-27 Quan h i lng hp ph hyr trn xc tc hp kim CuNi v thnh phn 46
Hnh 5-28. Hot tnh ring ca hp kim CuNi trong phn ng ehyr ho xyclohexan v hyr
phn etan thnh metan 316
o
C 47
Hnh 5-29 Bn dn thc v hin tng kch thch to in tch 53
Hnh 5-30 Bn dn v hot ng ca chng theo kiu: 54
Hnh 5-31 Hot tnh so snh ca cc xit trong phn ng phn hu N
2
O 61
Hnh 5.32 Cc tm axit trn b mt xit nhm Al
2
O
3
67
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Hnh 5-33 C ch phn ng ehyrat ho etanol trn nhm oxit 71
Hnh 5-34 Cc tnh cht quan trng nht ca xc tc cng nghip 79
Hnh 5.35 M hnh hyr ho axeton trn Pt/TiO
2
v hiu ng SMSI 87
Hnh 5-36 S tc ng ca K trong hp ph phn li N
2
trn xc tc Fe 90
Hnh 5-37 Cc kiu gim hot tnh 95
Hnh 5-38 Cc c ch lm gim hot tnh xc tc (M = kim loi) 95
Hnh 5-39 S cc ho qua con ng ehyr ho 99
Hnh 5-40 S mt hot tnh trong cc qu trnh chuyn ho (reforming) xc tc 99
Hnh 5-41 Din bin hot tnh trong qu trnh phn ng, trc v sau ti sinh 103
Hnh 5-42 S cc phng php nghin cu xc tc 106
Hnh 5-43 ng ng nhit hp ph vt l ??????
Hnh 5-44 My o hp ph (Phng th nghim Xc tc, FH Mannheim, c) 111
Hnh 5-45 Ph TPD ca amoniac gii hp t zeolit 112
Hnh 5-46 Nguyn l thit b gii hp ph theo chng trnh nhit (temperature programmed
reduction TPR) 112
nh AMI 114
Hnh 5-47 Tp hp cc tinh th platin trong xc tc Pt/graphit: nh lng bng ph XPS (hnh
gia hng trn), hnh nh TEM (hng di) (BASF, Ludwigshafen, c) 114
Hnh 5-48 My ph ESCA (BASF, Ludwigshafen, c) 116
Hnh 5-49 Ph ESCA ca xc tc Ag/Al
2
O
3
116
Hnh 5-50 Ph ISS ca xc tc bc trc v sau s dng trong phn ng xi ho etylen 117
Hnh 5-46 So snh khoa hc b mt vi xc tc cng nghip 119????
ii
DANH MC CC S
S 5.1 C ch hyr ho alken 26
S 5.2 C ch hyr ho chn lc axetylen 27
S 5.3 C ch phn ng xi ho 59
S 5.4 Hyr ho etylen trn xc tc ZnO 63
S 5.5 Phn ng reforming n-hexan trn xc tc Pt/Al
2
O
3
86
S 5.6 Phn ng reforming metan vi CO
2
trn xc tc Rh/Al
2
O
3
88
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5 C s ca xc tc d th
5.1 Cc giai on c bn trong xc tc d th
Bn thn phn ng xc tc d th l kt qu ca nhiu qu trnh l hc cng nh ho hc k
tip nhau. Trong nhiu ti liu ngi ta gi y l c ch v m ca phn ng xc tc d
th. C ch ny bao gm 7 bc k tip nhau.
Xt phn ng pha kh A + XT P + XT, ta c cc bc: (1) phn t cht phn ng A
khuch tn t th tch phn ng (kh, lng), qua lp mng kh st b mt xc tc rn ti l
xp; (2) A khuch tn trong l ti tm hot ng trn b mt xc tc (rn); (3) A hp ph
trn tm hot ng; (4) A thc hin phn ng chuyn ho thnh sn phm P; (5) P gii hp
khi b mt xc tc v (6) P thc hin qu trnh khuch tn ngc ra khi l v (7) P ra
khi l mng kh b mt, ngc vi A bc (1), gii phng b mt cho chu trnh chuyn
ho tip theo. Trong trng hp xc tc c h l xp rt nh, khi cc phn t A hoc P
khng th chuyn ng t do nh trong pha kh, chng gn nh phi b trong khe hp
khi thc hin qu trnh xc tc. Khi bc (2) v (6) ng vai tr rt quan trng, phn
bit hai qu trnh khuch tn i khi ngi ta gi l l khuch tn ngoi v khuch tn
trong (l) [T20, T26]. Cc qu trnh va nu c m t trn hnh 5.1. Khi xem xt ng
hc phn ng xc tc d th ta phi lu n quy tc: giai on chm nht l giai on
quyt nh vn tc ton b qu trnh.
Hnh 5-1 Cc bc c bn trong phn ng xc tc d th vi xc tc rn xp
Trong xc tc d th bn thn phn ng ho hc (bc 4) l quan trng nhng giai on
hp ph (bc 3, 5) cng rt quan trng v khng th tch ri khi (4). Trong trng hp
vn tc bn thn phn ng ho hc chm hn, giai quyt nh vn tc l bc (4), khi ta
ni phn ng xy ra trong vng ng hc, ng hc khi l ng hc vi m. Trng hp
ngc li, khi vn tc phn ng ln, vn tc khuch tn vn chuyn cht nh ta ni
phn ng xy ra trong vng khuych tn, ng hc trong trng hp ny l ng hc v
1
m. Nh vy, phng trnh ng hc ca ton b qu trnh s th hin tc ca qu trnh
chm nht.
Cc yu t nh hng n tc thc t ca phn ng, r
eff
, c nhiu, l bn cht b mt
phn cch pha, xp v cu trc h l xp, tc chuyn khi trn lp b mt, v tt
nhin l bn cht xc tc. Nu phn ng xy ra trong vng khuch tn th cc s liu ng
hc s th hin quy lut ca qu trnh chuyn khi vt l, khi ta khng thu c thng
tin chnh xc v bn thn phn ng ho hc. Nh vy, nu ta mun nh gi ng c ch
phn ng th cn m bo rng phn ng trong iu kin nghin cu phi xy ra vng
ng hc.
V d, ta c th loi b yu t khuch tn mng bng cch tng tc dng kh. Nu
khuch tn trong l xp chm, ta c th gim kch thc ht xc tc gim ng i ca
phn t cht phn ng, iu ny phi c thc hin cho ti khi yu t khuch tn trong
ht nh hng.
thy r cc iu nu, ta xem xt gin nng cht phn ng - v tr xc nh
nng theo chiu i vo tm ht xc tc (hnh 5.2).
Hnh 5-2 Din bin nng theo v tr trong trng hp phn ng xy ra trong vng khuch tn
ngoi (a), khuch tn trong l (b), v ng hc
Theo hnh 5.2 ta c cc trng hp sau:
a) Khuch tn ngoi (trn lp mng tip xc kh/rn) hoc khuch tn trong l xp l giai
on quyt nh: y l trng hp tc phn ng ho hc rt nhanh so vi khuch tn;
cht khuych tn vo bao nhiu s chuyn ho ht by nhiu.
b) Khuch tn trong l giai on quyt nh: tc phn ng nhanh hn so vi khuch tn
trong l nhng chm hn so vi khuch tn ngoi; cht khuch tn vo ti tm hot ng
bao nhiu s chuyn ho ht by nhiu, tc s th hin tc khuch tn trong.
c) Vng ng hc: tc phn ng chm so vi c hai dng khuch tn.
Khi thay i nhit phn ng tc phn ng thay i theo quy lut nh (H. 5-3).
2
Hnh. 5-3 S ph thuc ln tc thc t, r
eff
vo i lng nhit nghch
Trong vng ng hc tc phn ng tng nhanh khi nhit tng, nng lng hot ho
xc nh theo Arrhenius s l nng lng hot ho ca bn thn phn ng, tng t nh
trng hp phn ng ng th. Trong vng khuych tn trong, tc qu trnh cng tng
theo nhit v tun theo phng trnh Arrhenius, tuy nhin dc s thp hn, khi
phn xc tc thc s hot tnh s gim. Khi tng nhit vn tc qu trnh s tng nhng
tng chm hn vng ng hc Trong vng khuych tn ngoi (cn gi l khuych tn
mng) tc , reff, tng khi tng nhit phn ng nhng s tng chm hn na. Tng
ng nng lng hot ho trong min ng hc cao nht v nng lng hot ho trong vng
khuych tn ngoi s thp nht tnh theo phng trnh Arrhenius.
Trong thc t, cc phng trnh ton hc ca ton b qu trnh xc tc d th s kh phc
tp v ng thi phi tnh ti c cc qu trnh vt l (khuych tn) v cc qu trnh ho hc
(hp ph-chuyn ho), ngoi ra cn tnh ti c nhit phn ng v cc qu trnh truyn nhit.
Trong nhiu trng hp do m hnh ton hc rt phc tp v phi gii bng cc phng
php s. Cc phn ng ng th v d th c bn thng gp c nu v so snh trong
Bng 5-1. Ta thy s c mt s iu tng ng.
Bng 5-1 So snh cc bc trong phn ng ng th v d th
ng th D th
-
Hnh thnh cc v tr trng trong khng gian
phc
To phc vi cc phn t nh nh H
2
, CO
Phn ng cng-xi ho, hnh thnh lin kt
Phn ng cng v chuyn ho vng meta; cc
tng tc i nhn hoc i in t
Phn ng tch-kh, loi tr ( -elimination)
Khuych tn cht phn ng ti tm b mt xc
tc rn
Hp ph vt l
Hp ph ho hc
Phn ng chuyn ho trn b mt
Qu trnh gii hp, khuych tn ngc
3
5.2 ng hc v c ch cc phn ng xc tc d th [T20, T32]
Hiu bit v ng hc rt quan trng trong xc tc d th v nhng l do sau:
1) Khi c phng trnh ng hc ngha l bit bc phn ng i vi tng cht phn
ng hay sn phm ta s tm c c ch phn ng. Khi c c ch phn ng ta c c s
khoa hc ti u ho xc tc, iu m hin nay ch yu c lm bng thc nghim
rt tn km.
2) Bn thn cc thng s bn phn ng, cc thng s hnh hc, cu trc ca ht xc tc
c lin h cht ch vi bc phn ng v cc thng s nhit ng ca phn ng.
3) Khi kho st s ph thuc ca tc phn ng vo nhit s thu c nng lng
hot ho, gi tr ca i lng ny l bng chng v giai on no s quyt nh vn
tc ton b qu trnh phn ng.
Nh bit, qu trnh hp ph v cc thng s hp ph l thnh phn khng tch ri ca
ng hc phn ng xc tc d th, v vy tip theo ta s xem xt yu t hp ph trong ng
hc ca cc phn ng trn xc tc d th.
5.2.1 Vai tr ca hp ph trong xc tc d th [T42, T43]
Trc ht cn phn bit hai qu trnh hp ph vt l v hp ph ho hc.
Hp ph vt l l h qu tng tc gia cc phn t trn b mt cht rn vi cc phn t
trong pha kh hoc lng nh cc lc van der Waals, khi lng nhit to ra trong qu
trnh hp ph xp x gi tr i lng nhit ho hi ca cht b hp ph.
Trong hp ph ho hc s hnh thnh lin kt gia cc phn t cht b hp ph v cc
nguyn t b mt xc tc. trng thi b hp ph cc phn t cht phn ng tr nn hot
ng hn, nhit hp ph trong trng hp ny xp x nhit phn ng ho hc. V d: nhit
hp ph ca xi trn carbon l xp x 330 kJ/mol, ngha l xp x nhit ca phn ng t
chy carbon (394 kJ/mol).
iu ny khng c ngha l cht hp ph mnh s l xc tc tt. Trong thc t, mc d
khng c hp ph th khng c xc tc nhng khng phi cht hp ph no cng s l cht
xc tc, l v phn ng xc tc mang tnh c th, trong khi hp ph th khng. Nh vy
c th ni hp ph l iu kin cn nhng cha . iu th hai cn lu l phi phn bit
r kh nng hp ph (tc l 1 gam hoc 1 m
2
cht rn s hp ph c bao nhiu phn t
cht b hp ph) v tc (ng hc) hp ph.
C hai dng hp ph u to nhit, v vy khi nhit tng cn bng hp ph s dch
chuyn v pha gii phng cht b hp ph. Hp ph vt l l qu trnh rt nhanh, cn bng
s thit lp nhanh ngay c nhit thp. Hp ph ho hc, tng t nh phn ng ho
hc, thng c nng lng hot ho cao, tc hp ph s tng khi nhit tng.
V kha cnh p sut, tc c hai dng hp ph tng ng bin vi p sut. Hp ph ho
hc ch xy ra i vi cc phn t cht b hp ph lp st b mt rn (hp ph n lp),
4
ngc li hp ph vt l c th dn n hp ph a lp. Bng 5.2 tng hp cc so snh
hai dng hp ph ny.
Bng 5.2 So snh hp ph vt l v hp ph ho hc
Hp ph vt l Hp ph ho hc
Nguyn nhn lc van der Waals
khng c trao i in t
lin kt ng ho tr/lc culon
c trao i in t
Cht hp ph tt c cht rn mt s cht rn
Cht b hp ph tt c kh nhit < nhit ti
hn, phn t khng thay i
mt s kh c kh nng phn ng,
phn li thnh nguyn t, ion, gc
t do
Khong nhit thp thng cao
Nhit hp ph nh, xp x nhit nng chy (~
10 kJ/mol), lun dng
ln, xp x nhit phn ng (~
80-200 kJ/mol), thng dng
Tc rt cao rt ph thuc nhit
Nng lng hot ho thp thng cao (tr khi khng cn hot
ho)
Lp ph b mt a lp n lp
Mc thun nghch rt cao thng thun nghch
ng dng o din tch b mt, kch thc l
xp
o nng b mt v ng hc, o
tc hp ph v gii hp, xc
nh bn cht tm hot ng
Bn cht b mt nh hng mnh m n hp ph. Trong hp ph vt l s nguyn t b
mt ni chung l quan trng nhng trong hp ph ho hc bn cht b mt mi l quan
trng. V d, hyr hp ph ho hc trn niken nhng khng hp ph trn xit nhm, xi
hp ph trn carbon nhng khng hp ph trn MgO. Mt s v d hp ph ho hc c
nu trong bng 5-3.
Bng 5-3 Mt s v d hp ph ho hc
H Nhit hp ph, kJ/mol Nng lng hot ho, kJ/mol
H
2
trn graphit
CO trn Cr
2
O
3
N
2
trn Fe (xc tin Al
2
O
3
, K
2
O)
CO trn Pd
H
2
trn W
189
38 63
147
72 76
84 - 315
25
0,8 3
67
9,6 38,0
42 105
Hnh dng b mt, cu trc b mt cng quan trng trong hp ph ho hc. V d, nhng
phn b mt g gh (gc, cnh) v cc khuyt tt b mt s ng vai tr quan trng. c
bit, nhng phn tri ln thng cha cc nguyn t c cc ho tr d thng ng vai tr
cc tm hot ng. V d trong phn ng cracking cumene, nng tm hot ng tnh
c l 3,6*10
19
/g xc tc hoc 1,2*10
17
/m
2
b mt xc tc.
Tng kt li, cc yu t sau s nh hng mnh ti ng hc xc tc:
1) Hp ph l bc i trc bn thn phn ng xc tc d th (XTDT).
5
2) Phn ng XTDT bao gm hp ph ho hc, y l qu trnh c trng v l phn
ng gia phn t cht phn ng v b mt xc tc.
3) B mt xc tc khng ng nht, ch mt phn nh cc nguyn t b mt l tham
gia phn ng, y l cc tm hot ng.
Sau y ta s xem xt cc quy lut hp ph v vai tr ca hp ph trong ng hc xc tc
[15,T32].
Quan h hp ph v ng hc xc tc
Phng trnh Freudlich
Thng cn bng hp ph c biu din bng cc phng trnh kinh nghim. Phng
trnh Freundlich (Pt. 5-1) l mt dng thng gp.
n
A F A
p a C
(5.1)
C
A
= nng cht b hp ph A trn b mt
p
A
= p sut ring phn ca A trong iu kin cn bng
a
F
= h s thc nghim, c trng cho h hp ph-b hp ph nh
n = l s nm gia 0 v 1
Phng trnh Langmuir
Quan h gia C
A
v p
A
cng c m t bng phng trnh vi hai hng s l phng trnh
Langmuir (Pt. 5-2).
A
A
A
bp
bp
C C
+

1
(5.2)
C
= hp ph cc i
b = hng s cn bng hp ph = k
ad
/k
dead
ng biu din quan h C
A
p
A
nhit constant c dng nh (H. 5-4): C
A
tng dn v
tim cn C
ng vi hp ph n lp (mononuclear coverage) trn b mt. ng cong

trong H. 5-4 c gi l ng hp ph ng nhit hay iosotherm.
H. 5-4 ng hp ph ng nhit (isotherm) Langmuir
Dung lng hp ph n lp
c
h
e
p
h
max
Dung lng hp ph n lp
c
h
e
p
h
max
6
Khi b hoc p
A
ln pt. chuyn thnh dng CA = C
, ngha l hp ph t gi tr n lp, ffy

l trng hp phng trnh Freundlich c n = 0. Khi p
A
hoc b c gi tr rt nh phng
trnh 5-2 c dng nh phng trnh Freundlich vi n = 1 (Pt. 5-3).
A A
bp C C

(5.3)
cc gi tr b hoc p
A
trung gian ta c trng hp ca phng trnh Freundlich vi n= 0
1.
p dng phng trnh Langmuir cho trng hp hp ph ho hc vi gi thit l b mt
ng nht v mt nng lng, khi entalpy hp ph s khng ph thuc vo mc che
ph b mt bi phn t cht A k hiu l
A
.
Xt phn ng gia A pha kh vi b mt F pha rn ta c:
A(g) + F(s) AF(s) (5.4)
Khi ta vit c cn bng:
A F
AF
A
p C
C
K
(5.5)
C
AF
= nng A trn cc tm hot ng b mt trn mt n v b mt
C
F
= nng cc tm hot ng trn mt n v b mt
Khi (1
A
) l phn b mt t do, ta c:
C
AF
=
A

C
F
= (1
A
)
Nh vy Pt.5-5 chuyn thnh Pt.5-6:
( )
A A
A
A
p
K
1
(5.6)
T y tm c biu thc ca
A
(Pt.5-7):
A A
A A
A
p K
p K
+
(5.7)
Tip theo ta xy dng quan h gia cc i lng hp ph vi phng trnh tc phn
ng xc tc d th nh sau.
Xt phn ng n gin A C vi gi thit l A hp ph v khng phn licn C khng hp
ph. Khi tc chuyn ho A ch ph thuc vo phn A b hp ph, ta c:
A A
A A
A
A
p K
p kK
k
dt
dp
+

1
(5.8)
Xt cc trng hp sau:
7
1) Nu K
A
hoc p
A
rt nh, khi K
A
p
A
<< 1, vy
A
~ K
A
p
A
ngha l phn ng c dng
bc mt theo A. y l trng hp mc che ph thp hay hp ph yu.
2) Nu K
A
hoc p
A
c gi tr ln, khi K
A
p
A
>> 1, ta c dp
A
/dt = k ngha l
A
= 1, hp
ph l cc i v tc phn ng khng ph thuc vo p
A
, phn ng l bc zero theo A.
Nu hai iu kin bin u khng ph hp, khi bc phn ng theo A phi c gi tr gia
0 v 1. Nu c th theo di c phn ng vng p sut (nng ) rng, khi ta s
thy khi p sut gim dn th bc phn ng s tin ti mt v khi p sut tng dn bc phn
ng s gim dn ti khng.
3) Trng hp thng gp hn l trng hp c hai cht phn ng hay hp ph hn
hp. Ta xt trng hp ny vi gi thit hai kh A v B s cnh tranh chim ch cc
tm t do, khi phn b mt t do s bng (1
A

B
), khi ta c phng trnh 5-9
v 5-10 biu din mc che ph b mt bi mi tc nhn phn ng:
B B A A
A A
A
p K p K
p K
+ +
(5.9)
B B A A
B B
B
p K p K
p K
+ +
(5.10)
4) Mt s cht hp ph phn li, v d qu trnh sau:
(AA)(g) + F(s) AF(s) (5.11)
Khi ta c biu thc tng ng:
A A
A A
A
p K
p K
+
(5.12)
Cc qu trnh khc cng xem xt tng t, cc biu thc dn ra y c s dng khi
thit lp phng trnh tc phn ng xc tc d th ng thi l c s d bo c ch
phn ng [2].
5.2.2 ng hc v m hnh phn ng [8, T26]
thit k c thit b phn ng cn xy ng c phng trnh tc , r, v s ph
thuc ca tc vo cc thng s lin quan n phn ng. lm r iu ny cn phn
bit ng hc vi m v ng hc v m. Khi xem xt mi quan h tc ca bn thn phn
ng ho hc v nng cc cht tham gia, nhit , xc tc ta c ng hc vi m. Nu
xem xt s ph thuc tc chung ca qu trnh vo cc yu t cng ngh nh chuyn
khi v truyn nhit ta c ng hc v m.
Theo phng trnh tc 1-2, tc phn ng ph thuc vo nng ca cc cht phn
ng v c nng xc tc. Nh bit, phng trnh tc ch mang tnh hnh thc, ch
da vo phng trnh ny ta vn cha r c ch phn ng. hiu c ch cn phn bit r
phn t s (s ht tham gia vo phn ng c bn) v bc phn ng. .
8
Ta cng nhn thy nhiu trng hp m ta khng th gn cho bc phn ng (s m ca
nng trong phng trnh tc ) mt gi tr c th. iu ny thng gp trong phn ng
xc tc d th. Trong xc tc d th tc phn ng chuyn ho A c th c tnh cho
mt n v b mt ring S ca xc tc (m
2
/(g) hoc kg) thay v chia cho th tch nh phn
ng ng th nh Pt.1-2 (Pt.5-13).
( )
1 2
,
* * * ,
1

s m kg kmol C kf
dt
dn
S
r
A
A
S A
(5.13)
Thng dng hn l dng khi nim tc phn ng c gy ra bi mt g (kg) xc tc,
khi ta phi chia tc chuyn ho cho khi lng xc tc, m
cat
v thu c r
eff
- tc
phn ng thc (Pt.5-14):
( )
1 1
,
* * ,
1

s kg kmol C kf
dt
dn
m
r
A
A
cat
eff A
(5.14)
Cn lu , tc phn ng thc trong xc tc d th ngoi vic ph thuc vo nng cht
phn ng, nhit phn ng nh phn ng ng th cn ph thuc vo cc thng s ng
hc v m nh b mt phn cch pha, c ht, t khi, xp, cu trc h l xp v tc
khuych tn.
Ta s thit lp biu thc tc cho phn ng xc tc d th pha kh sau [T20, T26]:
A + B C
Trc ht vit cc phng trnh tc cho tt c cc thnh phn c mt (lu : trong phn
ng ng th khng c cu t C):
c
C
b
B
a
A
p p kp r
(5.15)
y r l tc tnh cho mt n v khi lng xc tc v k l hng s vn tc c th
nguyn ph thuc vo bc phn ng a, b, v c. Thng thng cc s m ny khc mt. S
xut hin ca p
C
l do sn phm c th chim ch trn xc tc do cha kp gii hp ph
hoc gii hp ph km.
M hnh hnh thc ny thng khng tnh n s thay i ca cc s m (bc phn ng)
khi thay i nhit , p sut, v vy ch c ngha trong khong hp nhit v p sut.
V vy ngha thc t l khng ln.
c m hnh tt hn ta cn xt n yu t hp ph, gii hp ph v s tham gia ca cc
thnh phn phn ng. Khi phng trnh tc phi cha p sut ring phn ca mi
thnh phn trong hn hp phn ng. Khi phng trnh tc cha ba yu t: (1) yu t
ng hc (kinetic term) cha cc i lng nng (p sut ring phn); (ii) yu t ng
lc thc y qu trnh (driving force) hay l khong cch n cn bng; (iii) yu t cn tr
(resistance term) (Pt.5-16):
9
( ) ( )
( )
n
e f f
te r m c e r e s i s
fo r c e d r i v i n g t e r m k i n e t i c
r
_ ta n
_ _
(5.16)
S m (bc) n thng c gi tr 1 hoc 2 v ph thuc vo s tm hot ng tham gia phn
ng giai on quyt nh vn tc. Yu t cn tr (resistance term) thng l cc yu t
lin quan n hp ph ho hc.
Cc yu t trong Pt.5-16 cha cc thng tin v hp ph i vi cc thnh phn phn ng.
xy dng phng trnh tc y cn xc nh mi quan h gia vn tc vi nng
, nhit , p sut, v cn bit c ch. Trong phn ln cc trng hp n gin ho
ngi ta kim sot giai on chm nht giai on quyt nh vn tc l [2]. Khi ,
phng trnh tc cha cc yu t quyt nh vn tc quan trng nht. i vi phn ng
bt thun nghch, khi yu t chuyn khi quyt nh ta thng gp dng Pt.5-17:
n
A eff
kp r
(5.17)
hoc vi phn ng A + B R + S ta s c:
( )
n
R R A A
B A
eff
p K p K
p kp
r
+ +
1
(5.18)
Cc phng trnh tc kiu Pt.5-17 v 5-18 c xy dng trn c s l thuyt v tm
hot ng. c phng trnh chi tit hn, m t c c c ch phn ng s tn nhiu
chi ph v cng sc, trong thc t sn xut ngi ta ch cn nhng thng tin phc v
cng tc thit k bn phn ng.
5.2.3 Cc c ch phn ng pha kh [15, 34, T35]
Trong phn ny ta xem xt phn ng xc tc lng phn t pha kh. Phn ng c dng:
AG + BG CG (5-19)
C hai c ch. Ta xem xt ln lt.
5.2.3.1 C ch LangmuirHinshelwood (1921)
Trn c s gi thit l hai cht phn ng A, B hp ph ng thi nhng trn hai loi tm
khc nhau, to hai trng thi trung gian b mt khng phn li, tip theo phn ng gia hai
cht trung gian to sn phm, sau l gii hp ph sn phm C. Ta c s Hnh 5-5:
A
G
+ * A* v
B
G
+ * B*
A* + B* C* + *
C* C + *
C khuch tn vo th tch, gii
phng tm hot ng *
10
Hnh 5-5 S c ch LangmuirHinshelwood
Nh vy, y l qu trnh nhiu bc v bc no cng c th l giai on quyt nh vn
tc, tuy nhin thng giai on phn ng ho hc gia hai cht trung gian l giai on
chm nht. Nh vy tc phn ng, trng hp hai cht cng hp ph ho hc trn hai
loi tm khc nhau, c xc nh theo phng trnh sau:
( )
2
1
B B A A
B B A A
B A
A
eff
p K p K
p K p kK
k
dt
dp
r
+ +

(5.20)
Cc iu kin bin ca biu thc ny l:
1) Trng hp c hai cht phn ng u hp ph yu, khi c KA v KB<<1 (pt.5-20) tr
thnh reff = kpA pB v k = kKAKB. Phn ng c dng bc mt vi mi cht phn ng,
bc phn ng chung = 1 + 1 =2.
2) Trng hp A hp ph yu nhng B hp ph mnh, y l iu kin ng vi KA << 1
<< KB v biu thc tc c dng
r
eff
= kp
A
/p
B

trong k=kK
A
/K
B
.
Bc phn ng theo A bng 1 v bng -1 theo B.
Xt trng hp p
B
= constant.
1) Nu p
A
rt nh, tch K
A
p
A
trong mu s ca phng trnh 5-20 nu so vi (1 + K
B
p
B
) th
qu nh, c th b qua nn phng trnh s c dng:
A
B B
B B
A A eff
p k
p K
p K
p kK r '
1

+
Nh vy l tc t l thun vi p
A
hay phn ng l bc 1 theo A.
2) Tc phn ng t cc i khi
A
=
B
hay K
A
p
A
= K
B
p
B
.
3) Khi gi tr p
A
rt ln, biu thc (1 + K
B
p
B
) trong mu s 5-20 s rt nh so vi K
A
p
A
, v
phng trnh 5-20 s c dng:
11
Hnh 5-6 Cc trng hp ca phn ng lng phn t pha kh theo c ch L-H
A A A
eff
p p K
k
r
1 ' '

Nh vy bc phn ng theo A l 1. H.5-6 m t cc trng hp ny [15].
Khi nng A thp, phn b mt b che ph bi A l
A
nh, v tt c cc phn t b hp
ph vi B. Khi che ph
A
tc phn ng tng v tng ti maximum khi b mt c
che ph bi A bng b mt b che ph bi B (tc l
A
=
B
). Khi A tip tc tng phn A
che ph s tng, khi phn B s gim, khi kh nng phn ng gia A v B hp ph s
gim. Khi ta ni b mt b khng ch bi A.
C ch LangmuirHinshelwood p dng c cho mt s phn ng, v d:
1) Oxi ho CO trn xc tc Pt
2CO + O
2
2CO
2
2) Tng hp metanol t kh tng hp, xc tc ZnO
CO + 2H2 CH
3
OH
3) Hyr ho etylen trn xc tc Cu
C
2
H
4
+ H
2
C
2
H
6
4) Kh N
2
O bng H
2
trn xc tc Pt hoc Au
N
2
O + H
2
N
2
+ H
2
O
5) Oxi ho etylen thnh axetalehit trn xc tc Pd
CH
2
=CH
2
+ O
2
CH
3
CHO
5.2.3.2 C ch EleyRideal (1943) 12
Theo c ch E-R mt trong hai cht phn ng, v d A hp ph ho hc, khi A
*
l sn
phm b mt s phn ng vi cht cn li, B t pha kh, k hiu B
G
. Kt qu phn ng l
to sn phm C
*
b hp ph. C ch EleyRideal c m t trn Hnh 5-7. Bc tip theo
l qu trnh gii hp sn phm khi b mt. S phn ng vit nh sau:
A
G
+ * A*
A* + B
G
C*
C* C + *
C khuch tn vo th tch, gii
phng tm hot ng *
Hnh 5-7 C ch EleyRideal
12
Trong trng hp ny phn b mt b che ph bi A (
A
) ng vai tr quyt nh, khi
ly
A
t ng nhit Langmuir (Pt.5-7) ta c:
B
A A
A A
B A eff
p
p K
p K
k p k r
+

1
(5.21)
T y, ta thy phn ng l bc nht theo B, theo A ta c quan h r
eff
- p
A
c dng ng
Langmuir (H.5.8) khi coi p
B
l hng s.
Hnh 5-8. S ph thuc tc phn ng vo nng
cht A trong phn ng pha kh lng phn t theo c ch EleyRideal
Mt s phn ng sau tun theo c ch EleyRideal:
1) xi ho etylen thnh oxit etylen:
Trong phn ng cng nghip ny xi hp ph phn ng vi etylen t pha kh to xit
etylen. ng thi xi hp ph phn li thnh xi nguyn t rt hot ng (hp ph phn li),
khi s xy ra phn ng oxi ho hon ton hu c ti CO
2
v H
2
O, y l phn ng ph
khng mong mun.
2) Kh CO
2
bng H
2
:
CO
2
,
g
+ H
2
* H
2
O + CO
3) xi ho amonic trn xc tc Pt:
2NH
3
+ 3/2O
2
* N
2
+ 3H
2
O
4) Hyr ho cyclohexen:
5) Hyr ho chn lc axetylen trn xc tc Ni hoc Fe:
HCCH + H
2
* H
2
C=CH
2
13
Hai c ch nu l tng i d hiu. Trong thc t chng ta s bt ti hng trm c ch
vi cc phng trnh tc tng ng khc nhau. S hiu bit v c ch l iu kin tin
quyt ta c th xy dng c cc phng trnh tc phn nh y cc bin s m
n ph thuc.
Tt nhin, trong thc t khng th tnh ht mi giai on, khi ngi ta phi s dng
php gn ng l tnh cho giai on quyt nh vn tc. Trong phn ln cc trng hp
phi s dng cc phng trnh thc nghim v a vo nhng thng s quyt nh vn tc
quan trng nht l .
Cc m hnh ton m t ng hc phn ng cn c xy dng trn c s thng k s liu
y cho php chn c m hnh gn thc t v tin vy nht, tuy nhin s liu thc
nghim thng i hi l rt ln.
14
5.3 Cc l thuyt ( tng) v xc tc d th
5.3.1 Kha cnh nng lng v quan h vi hot tnh xc tc [8, T38]
(1) thc hin phn ng phn t phi tin v tm hot ng, hp ph ln v chuyn sang
trng thi trung gian hot ng. nh vy xc tc phi hp ph ho hc i vi t nht mt
trong hai cht phn ng. Cng hp ph khi s ng vai tr quyt nh: nu qu
mnh hay qu yu u gim hot tnh xc tc, lc tng tc (o qua lng nhit hp ph)
cn va phi. y l yu t ph hp v mt nng lng.
(2) Nh nu bc hp ph l khng th thiu trong xc tc d th. Khi nghin cu
hp ph ho hc v nhit hp ph s em li nhiu thng tin hu ch v c ch tc ng
ca xc tc d th [10]. Cc tm hot ng trn b mt xc tc c coi l cc nguyn t
cn d ho tr hay thiu in t, v vy n c kh nng lin kt vi cc phn t cht b hp
ph, s thay i mt in t lm yu i cc lin kt trong phn t cht b hp ph, lm
n d phn ng hn. Hnh 5.9 l bc tranh so snh phn ng xc tc vi phn ng khng
xc tc v kha cnh nng lng.
Hnh. 5-9 Din bin ca phn ng pha kh A
g
P
g
Ea,0 = nng lng hot ho ca phn ng pha kh khng xc tc
Ea,1 = nng lng hot ho thc
Ea,2 = nng lng hot ho biu kin
Z1 = trng thi chuyn tip trong phn ng khng xc tc
Z2 = trng thi chuyn tip trong phn ng xc tc d th (hp cht b mt)
HR = thay i entalpy (hiu ng nhit) ca phn ng
Trong hnh 5.9 ta thy c ba phn ng c bn ng vi ba nh nng lng. y, ta cng
phn bit nng lng hot ho thc v nng lng hot ho biu kin. Nng lng hot
ho biu kin tnh t trng thi ban u ca cht phn ng, nng lng hot ho biu kin
tnh t trng thi hp ph ho hc, y chnh l nng lng hot ho xc tc, i lng
quan trng hn trong ho xc tc.
To phn ng
khng xc tc
phn ng
b mt c
xc tc
To phn ng
khng xc tc
phn ng
b mt c
xc tc
15
Trong mt s trng hp sn phm hoc hp cht trung gian hp ph qu mnh, khi
qu trnh gii hp tip theo s kh khn, khi ta c hin tng xc tc b u c bi sn
phm hoc trng thi trung gian, xc tc s mt hot tnh.
(3) thit lp c c ch phn ng ta cn hiu r cc trng thi trung gian. Trong nhiu
trng hp vn ny ch c xem xt mt cch nh tnh.
i vi xc tc kim loi, trng thi trung gian c nghin cu mnh m nht, cc l
thuyt tng ng cng hon chnh nht. Nhiu mi quan h c thit lp. V d, s
hp ph ca cc hydrocarbon trn kim loi tun theo quy lut:
Dy axetylen > cc ien > cc alken > cc alkan
Cc cht phn cc > Cc cht khng phn cc
Vi cc kh n gin mnh ca cc lin kt hp ph ho hc trn phn ln cc kim loi
tun theo dy:
O
2
> C
2
H
2
> C
2
H
4
> CO > H
2
> CO
2
> N
2
Khi so cc kim loi vi nhau th bn lin kt hp ph ho hc i vi cc loi kh trn
rt khc nhau, l v cu trc in t ca cc kim loi rt khc nhau. Ngay t nhng nm
1950 ngi ta thit lp c bng phn loi cc kim loi theo nhm v kh nng hp
ph ho hc ca chng i vi nhiu loi kh [T20]. Bng 5.4 cho thy 37 kim loi c
chia thnh 7 lp theo hng gim dn hot tnh hp ph ho hc.
Bng 5.4 Phn loi kim loi theo kh nng hp ph ho hc [T20]
Kim loi, nhm kim loi
Kh
O
2
C
2
H
2
C
2
H
4
CO H
2
CO
2
N
2
(A) Ti, Zr, Hf,V, Nb,Ta, Cr,
Mo,W, Fe, Ru, Os
+ + + + + + +
(B1) Ni, Co + + + + + +

(B2) Rh, Pd, Pt, Ir + + + + +

(B3) Mn, Cu + + + +
t
(C) Al, Au + + + +

(D) Li, Na, K + +

(E) Mg, Ag, Zn, Cd, In, Si,
Ge, Sn, Pb, As, Sb, Bi
+

+ hp ph ho hc mnh ; yu ; khng hp ph
Theo bng 5.4, tr vi trng hp th nhm kim loi chuyn tip c hot tnh hp ph cao
nht. Trong mt chu k, quy tc chung l hot tnh s tng khi tng th t nguyn t, t
maximum gn gia chu k sau gim dn. Cc kim loi lp A c kh nng hp ph tt
c cc loi kh, k c nit l kh kh hp ph, kh hot ho nht.
16
Lp E c hot tnh km nht, chng ch c hot tnh i vi xi l kh d hot ho nht.
Cc lp trung gian c kh nng hot ho tt t O
2
ti CO hoc H
2
.
Nhng kim loi c kh nng hp ph vi nhiu loi kh s c phn bit tip theo thng
qua cc thng s:
H s hp ph l i lng phn nh lc hp ph
Kh nng trao i kh ang trng thi b hp ph ny vi kh khc
Nhit hp ph
nh lng qu trnh hp ph thng ngi ta o th tch kh b hp ph p sut 10
-3
bar nhit phng. Trong mt s trng hp sch ca kim loi nh hng n s xp
hng kim loi. V d, ng sch k thut hp ph hyr km, tuy nhin ng tnh khit
hon ton khng hp ph hyr.
(4) Trt t ni trn lin quan n cu trc in t ca cc nguyn t kim loi. Cc kim loi
lp A l thuc nhm 4 n 8 trong cc chu k, lp B1 cha cc kim loi khng qu nhm 9
v 10; v lp B2 l nhm cc kim loi qu. Lp B3 cha mangan v ng, y l hai
nguyn t thuc chu k kim loi chuyn tip u tin c tnh bt thng. Cc kim loi cn
li thuc cc lp C, D, v E l cc kim loi ng trc hoc ng sau cc kim loi chuyn
tip cng chu k.
R rng, cu trc in t ca kim loi c lin h vi hot tnhxc tc. Cc kim loi chuyn
tip c cc orbital d c lp y in t mt phn, chng l nhng xc tc tt. Do cc
orbital d cha bo ho chng c tim nng lin kt vi cc phn t cht phn ng, ngha l
chng c kh nng hot ho hay l xc tc. Trong khi cc kim loi chuyn tip hot ng
c 1 hoc vi in t d cha ghp i lp in t th cc nguyn t thuc cc phn nhm
chnh cng chu k ch c cc in t s hoc p cha ghp i, chng l cc kim loi hp ph
ho hc yu. Nh vy quy tc chung l in t d cha ghp i l cn thit m bo
s tng tc vi cc phn t b hp ph (hay cc phn t cht phn ng).
Nhn chung s hnh thnh trng thi chuyn tip s gim nng lng hot ho. i vi cc
kh hot ng nh CO v O
2
, cc trng thi chuyn tip khng phi lc no cng cn thit
hn na chng c th c hot ho bi phn ln kim loi.
Tip theo ta s xem xt s hnh thnh lin kt di nh sng ca nhit ng hc. Qu trnh
hp ph l qu trnh to nhit, trong qu trnh ny s hnh thnh cc lin kt mnh gia cc
nguyn t kim loi b mt v cc phn t cht b hp ph. ng thi vi s hnh thnh cc
lin kt hp ph s bc t do ca phn t kh s gim, iu ny c ngha l entropy S gim
hay bin thin S m. y l qu trnh t din bin, v vy bin thin nng lng t do
Gibbs phi m:
G = H T S (5.22)
17
Thng thng entropy thay i khng ln, cn bin thin entalpy hp ph H th ph
thuc mnh nht vo tng tc gia cc phn t b hp ph v b mt xc tc. Thng c
hai dng hp ph ho hc c bn [T35]:
Hp ph phn t, khi cc lin kt trong phn t cht b hp ph khng b b gy
Hp ph phn li, khi lin kt trong phn t b hp ph b b gy, khi cht b hp
ph s phn thnh cc ht nh hn hp ph trn b mt xc tc
Thng hp ph phn t xy ra khi phn t cht b hp ph c cc lin kt kp hoc cp
in t t do. V d trng hp b mt platin, cc ng ng etylen s cho ti hai in t
t mt lin kt i hnh thnh hai lin kt vi cc nguyn t Pt b mt. Sn phm
l cc orbital lai ho sp
3
ng vi phc t din b mt (Hnh 5.10).
Hnh 5-10 Hp ph ho hc hay s hnh thnh phc etylen - b mt Pt
V d th hai: s u c xc tc Ni bi cc hp cht lu hunh:
Hp ph phn li s xy ra khi lin kt trong phn t cht b hp ph l lin kt n, v d
trng hp hp ph H
2
. Nu phn t H
2
hp ph trn, v d, xc tc Ni. Khi gin
nng lng ng i ca phn ng s c dng (Hnh 5-11) [10, T43].
Hnh 5-11 S thay i th nng ca h H
2
hp ph trn Ni
ng 1: hp ph vt l (0,32 nm, HP = 4 kJ/mol)
ng 2: hp ph ho hc (0,16 nm, HC = 46 kJ/mol)
18
Dng th ny c l sn phm ca hai ng cong: ng bn (No1) phi biu din vi
nhit hp ph nh, HP = 4 kJ/mol. Tuy nhin tip theo H
2
tri qua qu trnh hp ph
ho hc vi HC = 46 kJ/mol ln hn nhiu (No2). Trong qu trnh ny lin kt HH b
b gy, hyr tn ti trn b mt di dng nguyn t H, hn thnh lin kt NiH.
Nh vy trng thi hp ph hyr ho hc c nng lng thp nht nhng ng gn b mt
nht (im B). M t ny ng vi phng trnh
H
2
(g) + Ni HNi
Lu l hai lin kt NiH hnh thnh cho mt phn t H
2
hp ph. Nh vy hp ph phn
li lun to s lin kt nhiu hn trng hp hp ph phn t, v mt nhit qu trnh na
lun to nhit v nhit ph v lin kt (E
D H2
= 218 kJ/mol)) ln hn nhit hp ph. Bin
thin entropy trong qu trnh ny = 68 J(mol H)
1
K
1
[T22]. Vy bin thin nng lng t
do Gibb bng (Pt.):
G = 46 + (300*0,068) = 25,6 kJ/mol (5-22)
Xc sut phn ng ny rt cao. Theo hnh ny th u tin H
2
hp ph vt l trn Ni, sau
hp ph phn li thnh nguyn t. Qu trnh ny c m t trn Hnh 5-12.
Hnh 5-12 C ch hp ph phn li ca H
2
trn b mt Ni
C ch hot ho hyr v alken trong xc tc d th c nhiu v d tng ng vi xc tc
ng th.
Khi hyr ho alken phc b mt c hnh thnh trc ht nh s cho - nhn in t
v s hnh thnh phc , tip theo l s hnh thnh phc phn li:
Trong trng hp alken c nhm allyl (v d: propen) qu trnh to phc b mt nh sau:
Vi xc tc xit ta c cc trng thi trung gian sau:
19
Etylen c th hp ph phn t nhit thp hn nhit phng, nhit cao n phn
li to phc etylidyn c dng:
Hp ph phn li H
2
cng c th thc hin trn b mt cc xc tc xit. V d, trn b mt
ZnO hyr to lin kt hyrua, ZnH, khi bn cnh s xut hin proton (Pt.5.25) [T39].
(5.25)
y chnh l phn ng hot ho H
2
trong sn xut metanol t hn hp Syngas (CO + H
2
):
CO + 2H
2
CH
3
OH
Qu trnh hp ph phn li c th c thc hin trn xc tc axit Brnsted, v d MgO
(Pt.5-26) [35].
(5.26)
Trn b mt kim loi CO th hin cc trng thi hp ph khc nhau, n c th c cu trc
thng, dng cu ni, phc a tm:
Trng thi hp ph c th ph thuc vo bn cht kim loi, mc che ph, kh nng
chuyn t dng ny sang dng khc (Pt.5.27).
(5.27)
Khi hp ph ho hc CO c th nm trng thi phn t hoc b phn li, iu ny ph
thuc vo cu trc in t ca kim loi (Bng 5.5).
20
Bng 5-5 Hp ph ho hc CO trn kim loi chuyn tip [T20]
Hp ph phn li Lp in t ngoi Hp ph phn t
Fe 3d
6
Ni 3d
8
Cu 3d
10
Mo 4d
4
Ru 4d
6
5060 kJ/mol
Ti, Mn, Cr Re 5d
5
Pd 4d
8
400 kJ/mol
140170 kJ/mol, Pt 5d
8
Cn lu l cc nguyn t lp b mt khng phi lc no cng ging cc nguyn t
trong th tch. V d, ngi ta chng minh c rng tt c cc xit Cu(II) hp ph CO
t pha kh nhng ion Cu
2+
hon ton khng tng tc vi CO. l do lp xit b mt coa
cc tm Cu
+
c th tng tc vi CO to phc b mt.
Ngoi cc yu t bn cht ho hc lin quan n yu t nng lng kh nng to phc cn
ph thuc vo cc yu t hnh hc. V d, trn b mt Ni phng CO b hp ph s tn ti
trng thi phn t, tuy nhin cc khim khuyt tinh th dng bc thang phn t CO hp
ph s b phn li. Hin tng ny cng ph bin v tr cc kiu khim khuyt tinh th
khc (bc thang, gc, cnh).
Nit l kh c cu trc in t gn CO cng hp ph trn nhiu kim loi. TRong trng
hp ny c th s dng thuyt orbital phn t. Khi tin gn b mt kim loi, cc in t
ca lin kt N
2
s chuyn sang cc orbital d trng ca kim loi, kim loi s ng gp tr li
vo lin kt * trong cc orbital ca N
2
, iu ny s lm yu lin kt trong phn t N
2
.
y chnh l giai on hot ho N
2
trong xc tc tng hp amnic. Nh vy c ch phn
ng N
2
+ H
2
s bt u t bc hp ph phn t i vi N
2
, tip theo s l phn li N
2
v
iu ny s quyt nh thnh cng ca xc tc trong phn ng.
Cc hp cht cha xy nh alcol cng tham gia hp ph phn li, v d hp ph metanol
(kh) trn xc tc xit molybden (Pt.5.28), y chnh l giai on hot ho trong cc phn
ng xi ho. xit hoc xit hn hp c th l cc xc tc xi ho - kh (Mc 5.3.3).
Trng thi b hp ph ny ca cc cht phn ng c th c suy ra t s thay i ca ph
IR, iu ny tng t nh trong xc tc ng th [28]. Cc dng phc thng v phc cu
ni ca CO trn b mt cht rn cng c th phn bit c nh ph IR, v d trn xc tc
Pd rn ghi nhn c hai trng thi vi cc vng hp th phn bit kh r:
Vt liu mang cng nh hng n ph hp th ca CO.
21
Vi xc tc Pt rn mang trn SiO
2
v mang trn Al
2
O
3
ngi ta chng minh c l t
l hai dng phc thng v dng cu ni ca CO s cao hn nu cht mang l SiO
2
. iu
ny c ngha l vt liu mang cng nh hng ti mnh ca tng tc hp ph. iu
ny th hin trong thc t l vi Ni/SiO
2
th SiO
2
nh hng yu n tnh cht ca Ni
nhng cht mang Al
2
O
3
v TiO
2
th nh hng mnh. Cc trng thi hp ph ca CO trn
cc xc tc Ni c tng kt trong Bng 5.6 [T37].
Bng 5.6 Ph IR ca CO hp ph trn cc xc tc Ni trn cht mang
Vng hp th [cm
1
] Cng Cu trc
1915 mnh
2035 mnh
1963 trung bnh
2057 trung bnh
2082 yu
Ph IR ca nhiu hydrocarbon trn b mt kim loi cng tng ng vi cc phc cha
cc phi t v kim loi tng ng, v d phc ca phc etylen (Bng 5-7). Hin tng yu
i ca lin kt C=C u c ghi nhn cho c xc tc rn v xc tc dng th (lu l
vng hp th ca etylen kh (khng hot ho) c vng hp th IR 1640 cm
-1
).
Bng 5-7 Cc vng hp th IR ca phc etylen
Xc tc rn Pd/SiO
2 So vi phc : Pd(C
2
H
4
)
CH2
[cm
1
]
2980 2952
C=C
[cm
1
]
1510 1502
Phng php: c lp matrix Pd trong hn hp C
2
H
4
/Xe = 1:100, 15K, chn khng siu cao
Trong trng hp hot ho nit ph IR ca phc b mt cng c ghi nhn trc c khi
ngi ta c th tng hp c phc cha N
2
so snh.
Trong phn ng phn hu axit foocmic, mt phn ng m hnh trong xc tc d th, ph IR
cng l cng c hu hiu xc nh c ch phn ng. Trn b mt xc tc kim loi bng
ph IR ngi ta ghi nhn c s hnh thnh phc foocmat b mt v s chuyn ho
thnh H
2
v CO
2
(Pt.5.29):
22
(5.29)
Hnh 5.13 Quan h hot tnh so snh ca cc kim loi trong phn ng phn hu axit foocmic vi
nhit hnh thnh foocmat kim loi [T20]
Trn Hnh 5.13 hot tnh xc tc, trc y, c th hin bng nhit m ti phn ng
t chuyn ho quy c, ngha l nu T nh ta c hot tnh cao, ta thy r mi quan h
kiu ni la: nhit hnh thnh foocmat qu ln hoc qu nh u dn ti hot tnh km,
cc kim loi nhm Pt vi nhit hnh thnh foocmat va phi l cc xc tc ti u trong
phn ng ny.
Hnh 5.14 Quan h hot tnh v nhit hp ph trong tng hp amnic
Ngoi i lng nhit hnh thnh, xy dng mi quan h bn cht xc tc hot tnh
xc tc, cc thng s nhit ng khc cng c quan tm, v d nhit hp ph hay gii
hp ph. Rt nhiu cc th kiu ni la c th bt gp trong cc nghin cu cng b.
Mt v d c in nhng vi mt i tng rt quan trng l xc tc tng hp amnic.
Hnh 5.14 cho ta bc tranh ca dy kim loi chuyn tip u tin chu k 4.
23
Cc kim loi pha tri nh ni hp ph mnh N
2
trong khi cc kim loi bn phi hp
ph yu. nh ni chnh l v tr ca Fe, l xc tc tng hp amnic tt nht hin nay v
cha c g thay th c.
Tng t nh vy ta thy c mi lin h gia cu trc in t ca kim loi hay l v tr ca
chng trong bng tun hon vi hot tnh ca kim loi trong cc phn ng khc (Table 5-
8).
Bng 5-8 So snh hot tnh xc tc kim loi chuyn tip trong mt s phn ng [T22]
No Phn ng Kim loi v tc phn ng so snh
1
2
3
Hyr ho etylen (xc tc kim
loi)
Hyr e sulphua ho
ibezotiophen (xc tc MeS
X
)
Hyr phn CH
3
NH
2
thnh
metan (xc tc kim loi)
Nb
0,5
Cr
0,95
Mo
2
Tc
13
Re
0, 008
Fe
15
Ru
100
Os
0,9
Co
100
Rh
26
Ir
100
Ni
36
Pd
3
Pt
11
Cu
1,2
Au
0,5
Cc xc tc tt nht in m, mu .
Hot tnh xc tc cao nht ng vi cc xc tc kim loi chuyn tip c t 6 n 8 in t d,
y l minh chng ca yu t in t trong xc tc. Cht phn ng v xc tc phi p ng
cc iu kin: hp ph nhanh, lin kt hp ph ho hc phi va mnh lu tr c
nng trng thi trung gian cao nhng phi cho php ti cu trc lin kt. Do nhiu yu
cu rt khc nhau nn xc tc phi iu ho c cc yu cu ny.
Ni chung, nu xt hng trong Bng 5-8, lc hp ph ho hc gim dn theo chiu t tri
sang phi. Pha tri bng lin kt hp ph ho hc qu mnh, n mc cc trng thi hp
ph tip theo kh thay i, iu ny c ngha l phn ng kh xy ra hay xy ra chm.
cui bng, pha bn phi hp ph yu dn ti phn che ph b mt nh nn tc cng
nh, ngoi ra hp ph yu cng ng ngha tc dng hot ho yu ca xc tc i vi
cht phn ng..
gii thch hot tnh xc tc ngi ta hay s dng mt i lng nhit ng l nhit hp
ph. Trong trng hp khng c thng tin v i lng ny c th dng cc i lng sau:
Nhit gii hp ph
Nhit hnh thnh trng thi trung gian
Tn s giao ng ph IR ca lin kt kim loi cht b hp ph, v.v...
iu ny cho thy vai tr ca cc nguyn t b mt v l minh chng b xung quan im
rng cc nguyn t b mt khc cc nguyn t trong th tch.
Hnh 5.15 m t hp ph hyr. Khi i t nhm 4 n nhm 6 entalpy hp ph ho hc
tng , sau s gim. i vi cc nhm 810 nhit hp ph ho hc gn constant [T20].
Trong mi chu k thng c mt nguyn t bt thng, v d mangan, iu ny c quy
cho trng thi d
5
ngha l cc orbital d c lp y mt na.
24
Hnh 5.15 Quan h gia entalpy hp ph ho hc trung bnh ca hyr v v tr ca nguyn t
trong bng tun hon [T20]
iu c bit i vi Zr l nhit hnh thnh ZrH
2
= 163 kJ/mol ng bng nhit hp ph
H
2
trn Zr. Quy lut tng t cng ghi nhn c vi cc kh khc nh N
2
, CO, v CO
2
.
Trong cc phn ng cng nghip cc quy lut trn c th hin nh sau. Phn ng hyr
ho ni i C=C rt thng gp, phn ng mu (model) nghin cu xc tc hyr ho
l phn ng H
2
+ H
2
C=CH
2
[22]. ng gp chnh trong lnh vc ny l do cc cng trnh
ca Balandin v Horiuti, Polanyi [30].
Thng thng xc tc hyr ho l cc kim loi chuyn tip, hot tnh ca chng c xp
theo dy sau:
Ru, Rh, Pd, Os, Ir, Pt> Fe, Co, Ni>Ta, W, Cr~Cu
S 5.1 C ch hyr ho alken [32]
Nh vy, ta thy u bng l cc kim loi nhm Pt, tuy nhin ta thy hnh nh bc tranh
khng ging bc tranh hp ph hyr trn, l v trong phn ng H
2
+ H
2
C=CH
2
cn
phi ng thi hot ho c H
2
ln C=C. Mt s c ch phn ng c xut, sau y l
mt trong s (S 5.1) [32].
25
Theo s ny phn t alken trng thi hp ph tng tc ln lt vi hai nguyn t
hy b mt (nguyn t H hnh thnh do hp ph ho hc mnh). Trong bc 3, xut
hin trng thi hyr ho bn phn (hemihydrogenated), l gc etyl. Tip theo l bc 4
to etan v gii hp ph etan (khng nu trong s ) v gii phng tm hot ng xc
tc quay li chu trnh.
Cc nghin cu v hp ph H
2
nh trao i H
2
/D
2
, ph IR cho thy H
2
c mt s trng thi
hp ph, v d i vi Pt ta c hai trng thi:
Hw = H hp ph yu (weakly bound)
Hs = H hp ph mnh (strongly bound)
Ta c th phn bit nguyn t H hp ph yu nm trng thi to lin kt vung gc vi
mt phng Pt v nguyn t H hp ph mnh nm gia hai nguyn t Pt bng ph IR. Ngoi
ra ta cng bt gp c trng thi phn t H
2
hp ph. Tng t nh cc phc/trng thi trung
gian dng hyrua trong xc tc d th nu ta c trng thi phc [IrHCl
2
(PR
3
)
3
] v
[IrH
2
Cl(PR
3
)
3
] trong xc tc ng th.
Trong xc tc ng th phn t hyr tham gia phn ng cng xi ho vi tm kim loi
ca phc, b ng li to nguyn t hyr v th hai v tr Cl
-
trong phc to phc cha
hai nguyn t H (dihydrido complex), cc nguyn t H s ln lt chuyn sng olefin
trong phc thc hin phn ng hyr ho. Tnh tng t gia c ch phn ng xc tc
ng th v d th ny cng c th hin i vi xc tc Rh vi v d l phc
[RhCl(PPh
3
)
3
] ng th v Rh d th trn than hot trong phn ng hyr ho.
S 5.2 C ch hyr ho chn lc axetylen [T20]
Xc tc palladi rt quan trng trong cc phn ng hyr ho chn lc. V d trong sn xut
alken cn loi b axetylen v cc tp cht khc. C ch phn ng hyr ho chn lc i
vi C C cho trong S 5.2. Theo S 5.2 ta li gp sn phm hyr ho bn phn l
gc vinyl, n y c hai kh nng, mt l cng mt nguyn t hy to etylen hoc phn
26
ng tip to etan. chn lc ca qu trnh rt ph thuc vo xc tc v iu kin phn
ng. Ta c th d bo chn lc s gim nu tng p sut hyr v gim nhit . Ring
Pd c chn lc tuyt i vi cc hp cht axetylen theo hng to etylen. iu ny
c gii thch l do Pd hp ph phn li rt mnh H
2
ngay c p sut H
2
thp. y chnh
l giai on quyt nh vn tc trong nhiu phn ng hyr ho.
Mt phn ng mu khc cng c giai on quyt nh vn tc l giai on hp ph phn li
hyr l phn ng trao i H
2
/D
2
trong cchydrocarbon. Dy hot thu c nh sau:
Rh > Pd > Pt > Ni > Fe > W > Cr
y l mt trong nhng phng php tt nht nh dng trng thi hp ph trung gian
trn b mt kim loi. Cht phn ng mu l CH
4
, trong trng thi hp ph trung gian l
nhm CH
2
, vi C
2
H
6
, trng thi hp ph l alkyl/alkene thay nhau thit lp trn b mt xc
tc kim loi.
27
5.3.2 Vai tr ca yu t khng gian [T22, T37]
Bn cnh yu t nng lng v yu t lin quan l cu trc in t, yu t khng gian cng
ng vai tr rt quan trng [32]. Ngoi ra xp, cu trc h xp v b mt ring cng cn
tnh n. Yu t khng gian trong xc tc d th c ngha l phn t hp ph s nh hng
chnh xc ln cc nguyn t b mt. y chnh l cc nguyn t ng vai tr cc tm hp
ph v trong nhiu trng hp ng thi l tm xc tc.
Ngay t 1929 Balandin xut thuyt a v (multiplet theory), theo tm xc tc phi
ng vi cu trc vt liu xc tc v c hnh hc xc nh. Nu ta cho rng khi phn t cht
phn ng qu ln n c th hp ph trn mt tm hot ng n im (single-point
adsorption) th n s c th hp ph trn mt tm a v (multipoint adsorption), khi ta s
thy ngay vai tr quan trng ca yu t hnh hc ca b mt xc tc trong bc hp
ph/hot ho phn t cht phn ng. Balandin a ra khi nim nguyn l tng ng hnh
hc (geometric correspondence) gia phn t cht phn ng v cc nguyn t b mt ca
xc tc rn. Nguyn l ny phn no tng t nguyn l cha-kho (key/keyhole) trong
xc tc enzymatic, theo phn t c cht no phi c hnh dng ph hp hon ton vi
men y l men s xc tc cho phn ng ca c cht nu, iu ny gii thch chn lc
tuyt i ca cc xc tc men, iu m hu nh khng gp trong xc tc d th.
Khi pht trin nguyn l ny cho xc tc rn ta hiu rng cc tm hot ng chnh l cc
nguyn t b mt c cc ho tr d hoc khim khuyt in t (xem thm mc 5.3.3).
Chnh v vy, cc phng php nghin cu b mt cht rn quy m nguyn t ng vai
tr quyt nh hiu r c ch phn ng xc tc d th. Khi cha c thng tin v cu trc
b mt ta buc phi s dng cc thng tin chung v kiu mng tinh th, khong cch
nguyn t xc nh yu t hnh hc, iu ny trong thc t t khi mang li thnh cng
[T40], v vy khng nn ch i nhiu cc thng tin dng ny.
Mt trong nhng d bo u tin ca thuyt a v l mi tng quan gia khong cch
gia tm hai nguyn t kim loi tnh t cc c trng mng vi qu trnh hp ph ho hc
ca phn t cht phn ng c hai nguyn t. Khi s ny sinh tranh lun l vi khong
cch ln gia cc nguyn t to tm hot ng th phn t cht phn ng dng AB phi
phn li mi c th hp ph ho hc, trong khi vi cc mng tun theo nguyn l sp xp
c kht th cc lc y c th gy kh cho qu trnh hp ph ho hc. . iu ny c th
hin trn c s v d qu trnh kh hyr ho xyclohexan.
Nh ta thy ch c cc nguyn t vi khong cch gia cc nguyn t nm gia 0,248 v
0,277 nm c kh nng xc tc phn ng kh hyr ho xyclohexan. Bng 5.9 cho ta danh
mc cc thng s mng ca mt s kim loi thng gp trong xc tc.
Ta nhn thy trong s cc kim loi nu ch c cc kim loi c cu trc sp xp c kht,
ngha l cc kim loi c c mt nguyn t b mt cao nht c hot tnh xc tc, chng l
cc nguyn t sau:
Loi fcc: t Pt n Ni
28
Loi hcp: t Os n Co
Bng 5-9 Cu trc v khong cch mng trong kim loi (khong cch ti nguyn t gn nht o
bng nm) [T40]
Loi mng tinh th
Lp phng tm khi (bcc) Lp phng tm mt (fcc) Su mt c xp kht (hcp)
Ta
W
Mo
V
-Cr
-Fe
0,286
0,272
0,272
0,260
0,246
0,248
Ce
Ag
Au
Al
Pt
*
Pd
*
Ir
*
Rh
*
Cu
*
-Co
*
Ni
*
0,366
0,288
0,288
0,286
0,276
0,274
0,270
0,268
0,256
0,252
0,248
Mg
Zr
Cd
Ti
Os
*
Zn
*
Ru
*
-Co
*
Be
0,320
0,312
0,298
0,292
0,270
0,266
0,266
0,252
0,224
* Cc kim loi c kh nng xc tc phn ng kh hydro ho xyclohexan
Trong thc t, dng nh phn ln cc xc tc tt nht l cc kim loi c cu trc fcc.
Trong nghin cu c bn, nh lng nh hng ca yu t hnh hc iu kin tin
quyt l kim loi phi sch, cu trc b mt phi xc nh. V vy, ngi ta thng dng
cc n tinh th cho cc nghin cu loi ny. Vi n tinh th cc nguyn t b mt s c
trt t theo hai hng.
Trong tinh th hc, phn loi cc mt phng ngi ta dng cc ch s Miller. Cc ch s
ny ni ln mt phng trong mt t bo c bn c chn bi trc tinh th no v bao
nhiu trc. Cc ch s s ni ln di on a, b, v c m mt phng cn xem xt ct cc
trc to ox, oy, oz v c ghi di dng nghch o gi tr s ca trc (H.5.16).
Hnh 5.16 Cc mt phng tinh th trong mng lp phng v ch s Miller tng ng
B mt tinh th ca t bo dng lp phng ct 1 trc tinh th s c ch s (100). B mt
ca lng tr ct hai trc ca h lp phng s l (110). B mt bt din ct ba trc to
khong cch a, b, c u nhau nh (H. 5-16) l (111).
29
Nhiu xc tc c cu trc fcc. Trt t sp xp ca cc nguyn t trong cc b mt Miller
khc nhau c m t trong Hnh 5-17. ng thi s cc nguyn t xung quanh v cc ho
tr t do ca cc nguyn t b mt ca Ni cng c ch r [T33]. S ho tr t do cao nht
trong hnh l 5 ng vi cc b mt lng tr.
n tinh th ca nhiu kim loi chuyn tip kch thc vi cm c th nui c, sau
ngi ta ct sao cho mt phng cn nghin cu c phi ra ngoi. Nhng b mt n tinh
th nh vy s c xc nh cc c trng cu trc bng cc phng php ph b mt
hin i, sau chng c dng cho hp ph bng cc cht kh nh CO, N
2
O, O
2
, v
hydrocarbon, khi cc trng thi hp ph s c ghi nhn, cc kiu cng nh cc c
trng ca cc lin kt hp ph s c xc nh bng cc phng php ph tng ng.
Hnh 5-17 S cc nguyn t xung quanh v s cc ho tr t do ca cc nguyn t b mt Ni ng
vi cu trc fcc
Tt nhin, trong thc t cc n tinh th khng c ng dng lm xc tc, vai tr ca chng
chnh l cho php nh lng s khc bit ca cc qu trnh xy ra trn cc b mt khc
nhau, y chnh l bc tranh trong cc a tinh th thc t [18]. Xc tc cng nghip thng
l cc a tinh th d chng c th rt phn tn, chng s phn b ngu nhin v khi cc
30
mt phng b mt s l bt k. Hn na cc a tinh th thc thng cha cc khim khuyt.
phn tn ca xc tc (s ht/cm3) v din tch b mt ring thng quan h ng bin.
Hnh 5.18 cho thy cc khim khuyt tinh th, v d b mt tinh th c th to bc thang,
b mt tinh th c th c cc nguyn t li ra, thiu nguyn t, trt t nguyn t b lch ...
Lu , cc b mt bc thang ca cc mt c mt nguyn t cao nh mt (111) v (110)
c chiu cao bng kch thc nguyn t. V d mt (557) ca Pt c mt bc thang ca b
mt (111) ni vi mt n nguyn t (001). Cc b mt gp ghnh kiu bc thang nh vy
c th c trng bng cc phng php ph b mt hng mnh. Rt l l cc b mt dng
bc ny kh bn trong iu kin phn ng [32]. c bit l cc tinh th c ng knh ln
hn 10 nm c cc mt vi ch s Miller cao, c cc khim khuyt lch mng thng c th
nhn thy di hin vi in t qut.
Hnh 5.18 M hnh b mt tinh th (BASF, Ludwigshafen, Germany)
Nhng ht gy ra tnh xc tc (cc tm hot ng) l cc nguyn t hoc nhm nguyn t
b mt, hot tnh hp ph ho hc ca chng rt ph thuc vo phn tn. Thc t, thc
o hot tnh TON c p dng i vi mt nguyn t (Mc 1.2) [26].
Do yu t khng gian khng phi l tin quyt cho mi trng hp trong phn ng xc tc
d th, ngi ta phn bit hai trng hp: cc phn ng nhy cu trc v khng nhy cu
trc. Trng hp u l trng hp hot tnh ph thuc cu trc cc nguyn t b mt,
trng hp sau ch ph thuc vo s lng cc nguyn t b mt. Bng 5.10 phn loi hai
nhm phn ng ny thng qua cc tc ng khc nhau.
Bng 5.11 l danh mc cc phn ng gp trong cng nghip thuc c hai loi. S phn loi
tuyt i thc t l khng th, cc v d sau s ch r iu ny. Trong khi phn ng hyr
ho etylen trn xc tc Ni l nhy cu trc th phn ng ny trn Pt tinh th, Pt dng phoi
mng, trn xc tc trn cht mang li chy vi tc v nng lng hot ho gn nh l
31
hng s. Cc phn ng trn xc tc ri thuc loi khng nhy cu trc. p sut thng
cc b mt Pt(111) v Rh(111) u c che ph bi lp n phn t etylidin C
2
H
3
hp
ph ho hc rt mnh.
Bng 5-10 Phn loi cc phn ng xc tc bi kim loi [T24]
Loi phn ng
Cc hiu ng v nh hng ca chng
cu
trc
kh nng to
hp kim
kh nng b
u c xt
s kim loi
s nguyn t
to 1 tm h
Khng nhy cu trc - km va mt s 1 hoc 2
Nhy cu trc va ln rt nng rt nhiu nhiu
Bng 5-11 Hiu ng khng gian trong mt s phn ng
Cc phn ng nhy cu trc Cc phn ng khng nhy cu trc
Hyr phn:
Etan (Ni)
Metylxyclopentan (Pt)
Xyclohexan (Pt)
Hyr ho:
Benzen (Ni)
Etylen (Ni)
ng phn ho:
Isobutan, hexan (Pt)
Vng ho:
Hexan, heptan (Pt)
Tng hp amonic (Fe)
Metan ho
M vng: xyclopropan (Pt)
Hyr ho: benzen (Pt), xeton
ehyr ho: xyclohexan (Pt)
xi ho CO
xi ho etylen thnh etylen oxit (Ag)
Phn ng hyresulfur ho trn xc tc Mo l khng nhy cu trc, tuy nhin trn xc tc
Re li thuc loi nhy cu trc. xi ho etylen trn xc tc Ag khng nhy cu trc. Trong
trng hp ny nguyn nhn c quy cho tc dng bin i b mt ca xi lm cc
nguyn t b mt ging nhau.
Xt phn ng hyr ho etylen trn xc tc Ni. Etylen hp ph trn Ni di dng phn t,
nht l khi c mt hyr. Cc nghin cu v ph cho thy ni i ca etylen c b gy
v to hai lin kt vi hai nguyn t Ni gn nhau, kt qu l to cu trc etan. Lin kt
ny tt nhin khng qu mnh cc bc khc ca phn ng c th tip din.
Vi b mt Ni c ch s Miller nh, hai lin kt NiNi vi di 0,25 v 0,35 nm c ghi
nhn. Cc thng tin t ph LEED tm tt trong Bng 5.12 [T19, T23].
32
Ta c th gii thch cc kt qu trn nh sau: Vi khong cch NiNi = 0,25 nm, gc Ni
CC tnh c = 105
o
. y l gi tr gn vi 109
o
l gc trong ca t din, khi ta s c
hp ph ho hc mnh i vi etylen trn mt (111). Nu khong cch NiNi = 0,35 nm,
gc NiCC tnh c = 123
o
, khi hp ph ho hc s km hn, vi cu hnh ny cc
phn t etylen b ko cng v do sn sng b hyr ho.
Bng 5-12 Hp ph v hyr ho etylen trn cc b mt niken [T23]
Khong cch
NiNi, nm
B mt Gc NiCC Loi lin kt
Hiu ng xc
tc
0,25 (111) 105
o
mnh, n nh thp
0,35 (100), (110) 123
o
yu Cao
Cch thc bin lun nh th c th c p dng i vi cc kim loi khc. V d, mt
(100) ca cc kim loi c nguyn t ln hn Ni (nh Pd, Pt v Fe) s th hin tnh hp ph
ho hc yu hn, iu ny cng s ng vi kim loi vi khong cch MM nh hn Ni
nh Ta. Hnh 5-19 cho thy tc so snh trong phn ng hyr ho etylen hydrogenation
cng c dng ni la khi xp theo khong cch MM.
Hnh 5.19 Quan h tc phn ng v khong cch gia nguyn t nguyn t ca kim loi trong
phn ng hyr ho etylen [T35]
Khi khong cch MM rt ln, kh nng thc hin hp ph C=C trn hai im l khng
th, v vy xc tc hyr ho etylen cn c khong cch MM va phi. y chnh l
trng hp Ri vi kch thc gia hai nguyn t l 0,375 nm, tuy nhin bn cnh yu t
khng gian cn yu t nng lng (entalpy hp ph) nn cn xem xt ng b c hai yu
t.
Trong thc t cng c nhiu phn ng u tin mt mt tinh th no . V d, mt (111)
trong cc kim loi c cu trc fcc v hcp thng rt hot ng. iu ny th hin rt r
trong trng hp xc tc Fe trong tng hp amnic. Phn ng tng hp amnic l phn
ng nhy cu trc c trng, mt (111) hot ng nht c hot tnh cao hn mt (110) ti
440 ln (Bng 5-13) [T35]. Trong phn ng phn hu axit foocmic mt (111) mnh hn 3
ln so vi (110) hoc (100).
33
Bng 5-13 Hot tnh cc mt tinh th Fe khc nhau trong phn ng tng hp NH
3
[T35]
Mt Hot tnh so snh
110 1
100 21
111 440
Trong phn ng hyr ho benzen v ehyr ho xyclohexan, tm xc tc cn c 6 im
(nguyn t). Khi cc lin kt C=C m ra hp ph ho hc s c thc hin bng cch to
cc lin kt . Khi b mt (111) l thch hp nht.
Trong trng hp xi ho CO [4], cc nghin cu bng ph LEED cho thy vi xc tc Pd
th CO hp ph to lp hp ph n phn t c cu trc trt t. Cc phn t CO hp ph
khng phn li trn t nht hai nguyn t Pd. Ph IR ca CO hp ph trn mt Pd (111) cho
thy bc sng hp th cc i ph thuc vo mc che ph b mt. mc hp ph
thp khi 0,18, vng hp th (CO) yu c ghi nhn s sng = 1823 cm
-1
. Kt
lun cc nghin cu ny l: phn t CO hp ph trn tm 3 nguyn t Pd, iu ny lm
yu lin kt CO:
Khi che ph tng, s nguyn t Pd t do trn b mt gim, khi CO hp ph trn tm
hai nguyn t di dng phc cu ni, khi lin kt CO s bn hn. Cu trc bn ny s
tip tc th hin cho ti khi CO ph kn b mt xc tc. Nh vy, tu iu kin CO c th
hp ph trn tm hai hay ba im (nguyn t). Tuy nhin, ta cn quan tm n tc nhn
phn ng th hai l xi. Khi xt hp ph ca hn hp hai kh ta c hai kh nng:
Hp ph tp th: c hai loi nguyn t cng hp ph v phn b u trn b mt
Hp ph cnh tranh: hai kh cnh tranh ch hp ph, khi mi loi kh khi hp
ph s to trt t cho ring mnh
Khi hp ph cnh tranh, xc tc s u tin hp ph O2. Gi s ta a xc tc vo kh
quyn xi, xi s hp ph phn li to xi nguyn t trn b mt. Nu a CO vo nhit
phng s xy ra phn ng rt nhanh theo c ch EleyRideal (Pt.5-30).
O* + CO CO
2
nhanh (5.30)
Nu cho xc tc vo CO trc, cho xi vo sau th phn ng s khng xy ra (Pt.5.31).
CO* + O2 CO
2
(5.31)
34
Nu cho Pd hp ph CO mt phn ri a vo kh quyn O2, khi O
2
s hp ph ln cc
v tr t do trn b mt v to thnh cu trc ca ring mnh. Khi , phn ng s xy ra
bin vng, ni CO hp ph tip cn c vi O hp ph, trng hp ny phn ng xy ra
chm v tun theo c ch LangmuirHinshelwood (Pt.5.32).
CO* + O* CO
2
chm (5.32)
Nh vy phn ng xy ra hay khng ph thuc vo phn ng nhanh (Pt.5.30), iu ny l
c th khi ta a xc tc vo hn hp CO + O
2
. nhit thp CO cnh tranh b mt v
lm chm phn ng. Tuy nhin khi tng nhit ln trn 100
o
C, CO s gii hp mt phn,
phn O
2
hp ph ho hc tng ln, phn ng s xy ra nhanh hn, t max khong xung
quanh 200
o
C, sau tc li gim dn khi tng nhit . y l phn ng khng nhy
cu trc, tc nh nhau trn mi b mt Pd [32].
Trn xc tc Pt phn ng ny cng c quy lut tng t [T36]. CO cng hp ph khng
phn li, che ph do hp ph CO cng gim nhanh khi tng nhit (H.5-20a). Thi
gian tn ti ca CO trn b mt thay i tng ng nh sau:
Nhit phng
150
o
C ~ 1 s
400
o
C ~ 10
4
s
Phn t O
2
lc u hp ph ln Pt to cu trc kiu peroxit, cu trc ny s phn li to xi
nguyn t v to nhit mnh (H.5.20b). V phn t O
2
cn vi nguyn t b mt hp ph
nn hin tng bo ho xy ra kh nhanh.
Hnh 5.20 Phn ng xi ho CO trn b mt Pt
mc che ph do CO thp xi cng hp ph v phn ng s xy ra theo c ch
LangmuirHinshelwood gia cc phn t b hp ph vi nhau. Sn phm CO
2
hp ph yu
nn nhanh chng gii hp v i vo pha kh (H.5-20c). Tng t nh trng hp xc tc
Pd: s khng xy ra phn ng gia CO hp ph v O
2
pha kh.
Xc tc Pt ng vai tr rt quan trng trong cc phn ng yu cu hot ho hyr v
hydrocarbon (v d: phn ng hyr ho, ehyr ho, hyr phn). Trong nhiu trng
hp cc v tr bc thang, lch mng trn b mt ng vai tr quan trng trong xc tc. Ph
b mt LEED hin i cho php xc nh cc nguyn t cc v tr ch bit ny. V d,
vi mt Pt (557) xc nh c 2,5*10
14
nguyn t v tr bc thang/1 cm
2
, vi mt
(679) o c 2,3*10
14
nguyn t v tr bc thang v 7*10
13
nguyn t lch
mng/1cm
2
[32]. ghi nhn rng O
2
v H
2
khng hp ph trn b mt (100) v (111)
35
phng, tuy nhin s hp ph trn cc v tr bc thang. B mt (111) cng khng c hot tnh
trong phn ng ehyr ho xyclohexan. c bit trong phn ng hyr phn xyclohexan
thnh n-hexan ghi nhn s ph thuc rt mnh ca hot tnh vo mt cc nguyn t
v tr bc thang v lch mng. Cc nguyn t v tr lch mng c hot tnh cao hn cc
nguyn t bc thang mt bc. Trn c s bn phc trung gian v hot tnh xc tc c
th phn thnh 3 loi nguyn t Pt:
Cc nguyn t b mt bo ho: hot tnh km
Cc nguyn t v tr bc thang: hot ng hn, xc tc hot ho CH v HH
Cc nguyn t lch mng km bo ho: hot tnh cao, nht l i vi lin kt CC
Cc nguyn t v tr bc thang v lch mng hot ho cc lin kt CH v CC nhng
chng khng b che ph bi carbon (cok), v vy chng khng b mt hot tnh do hin
tng cok ho. Ngi ta cho rng khi cok xut hin chng s b ho hi do hyr ho.
Cc nghin cu tng t cng c tin hnh vi etylen v CO. Ngi ta cng ghi nhn
c l cc nguyn t v tr bc thang c hot tnh cao hn nhiu cc nguyn t trn b
mt phng. Trn c s ph IR ghi nhn c cc trng thi hp ph ho hc sau ca CO
trn xc tc Pt:
(CO)
bc thang: 2066 cm
1
, che ph thp, lin kt CO yu
(CO)
b mt: 2090 cm
1
, che ph ln
V d khc v vai tr ca v tr bc thang l qu trnh hp ph v phn hu axetonitril trn
xc tc Ni (H.5.21) [11].
Hnh 5-21 Hp ph v phn hu axetonitril trn b mt Ni [11]
Nh ta thy trn mt phng (111) lin kt axetonitrilb mt yu v thun nghch (H.5-
21a). 90
o
C cc phn t gii hp, ch c khong 12% s phn t l tham gia phn ng
lm gy lin kt CN to cc mnh C v N trn b mt. Trn mt (110) c mt cc
nguyn t bc thang cao 90% cc phn t hp ph phn li 110
o
C. l do trong trng
hp mt phng ngang nhm CH
3
khng lin kt vi b mt (H.5-21a), khi phn ng
khng xy ra. Trong trng hp phn t hp ph c s tham gia ca cc nguyn t bc
thang (H.5-21b, c) hai u phn t phn ng c ko cng v s ph hu lin kt CN s
xy ra.
36
Nh nu, cu trc b mt xc tc quy m nguyn t c nh hng ln n hot tnh
xc tc cng nh chn lc trong phn ng xc tc d th. Nh vy, hot tnh xc tc,
chn lc, ngoi bn cht kim loi to nn b mt xc tc, cn ph thuc vo t l s
nguyn t b mt so vi tng, t l s nguyn t nm v tr bc thang, cc gc cnh ...
Khoa hc hin nay m t kh tt tng nguyn t c lp, tuy nhin rt kh m t xc tc
thc do cc tm xc tc thng l cc tp hp nguyn t, c phn b kch thc, hnh th
a dng v cn tng tc vi b mt vt liu mang [20].
Tuy nhin, c th o c phn tn ca kim loi (t l s phn nguyn kim loi phi ra
b mt trn tng kim loi). Trong trng hp cc kim loi qu ngi ta o bng hp ph
vi H
2
hoc CO. Cc nguyn t gc s c trng cho xc tc c phn tn cao, cc phn
t bc thang c trng cho xc tc c phn tn va phi, khi phn tn thp ta hay
gp cc nguyn t b mt phng.
i vi cc ht xc tc Pd phn b u trn cht mang thu c nhng thng tin sau:
C ht Pd 4 10 nm
B mt ring ca Pd 9,5 m
2
/g
phn tn 21%
Din tch b mt theo BET 500 m
2
/g
Xc tc thng mi cha kim loi qu thng ch cha 0,11 %, phn tn thng t 40
ti gn 100 %, c ht c th t ti 14 nm [T41].
Quy lut chung l khi tng din tch b mt xc tc th hot tnh tng. Tuy nhin nhiu
phn ng cn ph thuc vo cu trc b mt, khi s khng ghi nhn c s ph thuc
tuyn tnh gia hot tnh v b mt, trong mt s trng hp chn lc gim khi din
tch b mt tng.
B mt ca vt liu mang cng ng vai tr quan trng. Cc phn ng nh hyr ho,
hyresulfua ho v hyrenitrogen ho u tin b mt ln, trong khi cc phn ng
xi ho chn lc nh epoxi ho olefin khng cn b mt ln gim thiu phn ng ph.
Trong nghin cu xc tc cc phng php c trng b mt c bit quan trng thit
lp quan h cu trc xc tc v din bin phn ng xc tc. y chnh l cng c c bn
ti u ho ch to xc tc.
37
5.3.3 Yu t in t [29, L33]
Yu t in t trong xc tc lin quan n mi tng quan gia cu trc in t ca bn
thn cht rn vi cc tnh cht ho l lin quan v hot tnh - chn lc ca xc tc.
Cu hi ch yu l: mi lin h gia hot tnh xc tc v cc yu t hnh hc v tnh cht
in t ca cht rn?
Vo nhng nm 1960 yu t in t c nghin cu mnh, mc d nhiu quy lut c
pht hin song quy tc chung cho mi xc tc, mi phn ng vn cha hnh thnh. Nhiu
quy lut ng cho h xc tc - phn ng ny li khng th p dng cho h phn ng khc.
V vy ta cn xem xt theo loi phn ng v loi xc tc.
Xc tc xi ho kh [T34]
y l nhm xc tc c dn in, ht dn l cc in t linh ng hoc l trng, chng
l kim loi hay bn dn. Cc phn ng sau thuc loi ny:
Hyr ho alken, aromat v cc ni i
Hyr ho CO v CO
2
thnh metan
Tng hp amoniac
Tng hp hyrocarbon v alcoh t hn hp kh tng hp
Oxi ho hydrocarbon, SO
2
, NH
3
v.v.
ehyro ho cc hp cht hu c
Phn hu axit formic
Polymer ho hyrocarbon
i vi cht phn ng c ch thng bt u t phn ng ng li trng thi hp ph, to
gc t do vi s tham gia ca xc tc (Pt.5-33). Phn ng ny dn ti s hnh thnh cc
gc t do nh s trao i in t:
Cat.
+ A : R A : Cat. + R
(5-33)
Cc xc tc cho cc trng hp ny l kim loi, bn dn (thng l cc xit kim
loichuyn tip c kh nng thay i trng thi xi ho) v cc phc, ion kim loi chuyn
tip. Cc kim loi trong mi trng xi ho thng b ph bi lp xit c tnh bn dn nn
cng c th c coi l cht bn dn.
Xc tc Axid/Baz (Xc tc ion)
Cc xc tc ny khng c in t linh ng, chng l cc cht cch in. nhit cao,
tnh cch in c th b mt mt phn. Khc vi xc tc xi ho kh, xc tc ion khng c
kh nng ng li m thc hin phn ng d li:
A : Cat. A
+
+ :Cat.
hoc
A : Cat. A:
+ Cat.+ (5.34)
38
V mt nng lng d li khng thun li bng s ng li. Cc phn ng sau thuc loi ny:
Thu phn
Hp nc v loi nc
Polymer ho v trng ngng
Cracking
Alkyl ho
Isomer ho
Phn ng bt cn xng (disproportionation)
Cc phn ng loi ny km theo s hnh thnh cc hp cht ion trung gian, xc tc l cc
axit hoc baz rn nh Al
2
O
3
hoc CaO v c bit l cc xit hn hp kiu aluminosilicat,
Al
2
O
3
/SiO
2
, v MgO/SiO
2
. y cc hiu ng in t c s dng hiu qu gii thch
cc hin tng tng hot tnh xc tc cng nh u c. V vy, ngi ta phn loi xc tc
theo tnh dn in nh trong Bng 5-14.
Bng 5-14 Phn loi xc tc rn
Cht dn in Bn dn Cch in
dn,

1
cm
1
10
6
10
4
10
3
10
9
, tng khi
tng T
10
9
10
20
S chuyn in t Trao i e gia kim
loi/cht b hp ph
Trao i e T cao

V d Kim loi, ch yu l KL
chuyn tip v hp kim
kim (Si, Ge v);
Cc xit khng t
lng v sulfua
(ZnO,Cu
2
O, NiO, ZnS,
Ni
2
S
3
....)
Cc oxit t lng
(Al
2
O
3
, SiO
2
, B
2
O
3
,
MgO, SiO
2
/MgO,
SiO
2
/Al
2
O
3
), mui,
axit rn
V s trao i in t gia cht phn ng v xc tc:
Hnh 5-22 Qu trnh truyn in t
Cht phn ng (b hp ph) c phn loi nh sau:
Phn ng nhn (acceptor reactions): in t chy t xc tc n cht phn ng; khi
cht b hp ph l acceptor (v d trng hp cht phn ng l cht c i lc
in t cao; y l cc phn ng vi b mt c xi linh ng.
39
Phn ng cho (donor reactions): in t chuyn t cht phn ng ln xc tc (v d:
cht phn ng c kh nng cho in t, l cc cht kh c nng lng ion ho
nh; phn ng khi H
2
hoc CO linh ng trn b mt.
V mt hnh nh iu ny c th c m t nh Hnh 5.22.
5.3.3.1 Kim loi [T27, T35]
Vi cc kim loi v hp kim ngi ta thit lp c cc mi lin h gia cc tnh cht in
t tp th v hot tnh xc tc. Hai l thuyt thng dng y l thuyt vng v thuyt
ho tr ca Pauling.
Trong kim loi cc in t ho tr thng nm cc orbital s hoc d. Cc nguyn t thuc
cc phn nhm chnh vi in t s l cc cht dn incho in t c trng, chng c
kh nng hnh thnh lin kt mnh vi cc cht nhn in t nh S hoc O; khi s to
thnh cc sulphua hoc xit bn vng trn b mt. Khi kim loi nh mt tnh cht ban
u ca chng v v vy chng khng th hin tnh xc tc. Ngc li, cc kim loi chuyn
tip vi cc in t d l xc tc tt. Chng xc tc cho c phn ng xi ho ln kh.
Theo thuyt vng, kim loi dn in c nh s dch chuyn ca cc in t () hoc l
trng (+) (xem Hnh 5-23).
Hnh 5-23 Mt in t 3d v cng thot
o
ca cc kim loi chu k 4
Trong bng tun hon cc nguyn t, nu xp theo hng, i t tri sang phi cc nguyn t
s c s in t d tng dn. Theo thuyt vng, cht rn c hai vng nng lng, l vng
dn v vng ho tr, gia hai vng l vng cm, khng c in t y. Th nng ca cc
40
in t trong cht rn c c trng bi mc Fermi, v phn mnh mc Fermi ng vi th
in ho ca in t v l trng 0 K.
V tr ca mc Fermi th hin v tr ng vi mt in t cao nht?. Nng lng cn
bt in t t mc Fermi vo chn khng c gi l cng thot,
o
(Hnh 5-24a). Vi
cc kim loi nhm d, cng thot mc xung quanh 4eV ngha l vng sng UV. Cc
orbital d cha lp y hoc l trng l c tim nng to lin kt vi cht b hp ph. Mc
Fermi cng thp th hp ph cng mnh.
Hnh 5-24 Thuyt vng: s thay i mc Fermi khi hp ph:
a) khng c hp ph; b) cht hp ph nhn e (acceptor); c) cht hp ph cho e (donor)
E
F,0
= Mc Fermi; E
F
= Nng lng Fermi
Khi cha hp ph, in t trong kim loi phn b vng ho tr v vng dn. Mc Fermi
ng vi E
F,0
nh trn hnh 5.24a. Khi hp ph donor hoc acceptor, nng lng vt rn s
thay i nh th no?
Trn b mt, cc in t hoc l trng s to lin kt b mt vi phn t cht b hp ph,
khi bn lin kt to thnh s ph thuc vo v tr ca mc Fermi. Cc acceptor (nhn
in t, v d: O
2
) lm gim mt in t ca vng dn ca kim loi, h qu l mc
Fermi h xung gi tr E
F
v lm tng cng thot
A
>

o
(Hnh 5-24b). Cc cht cho,
donor (v d: H
2
, CO, C
2
H
4
) cho in t vo vng dn ca kim loi, khi cng thot gim
dn ti
A
<

o
(Hnh 5-24c).
Cc kim loi thng c vng cm hp nn cc in t ho tr di chuyn tng i t do
tham gia to lin kt, tuy nhin trong cc kim loi nhm d ch c nhng orbital trng mi
c kh nng ny. Thc nghim chng minh l c tn ti mt mi lin h gia s in t
d hay s orbital d cn trng vi hot tnh xc tc. Thc t cho thy, trong mt chu k, cc
kim loi u tri ca dy (t in t d) s hp ph mnh, nhit hp ph gim dn khi i t
tri sang phi dy nguyn t, khi , i vi cc phn t cht b hp ph, th s hp ph
phn li s gim dn.
Xt phn ng c th l phn ng hyr ho CO trn cc kim loi khc nhau. Hnh 5-25 cho
thy khi in y ca cc orbital d tng dn th hot tnh tng, t cc i Co v sau
gim dn. th dng ny c gi l th hnh ni la c gii thch bng hiu
ng in t nh trn [38].
41
Hnh 5-25 Hot tnh xc tc trong phn ng CO + H
2
CH
4
trn cc kim loi khc nhau
Ngoi mc in y ca ca cc d-orbital, cn c th dng cc khi nim trong thuyt
lin kt ho tr ca cc kim loi: lin kt gia kim loi vi phn t b hp ph c to
thnh bi cc in t d cha gp i. Phn ng gp ca cc in t d ca kim loi vo s
hnh thnh lin kt ho tr gia phn t b hp ph vi kim loi c gi l phn trm c
trng d, c xut bi Pauling, ngi xut phn loi 3 loi lin kt do orbital d:
Orbital d to lin kt ng ho tr di dng lin kt lai ho dsp
Lin kt do d-orbital t do ca kim loi
Lin kt do d-orbital ca nguyn t
Phn trm c trng d, k hiu c tnh bng Phng trnh 5-35.
S in t d to lin kt x 100
= (5.35)
S in t lin kt + s orbital kim loi
i vi Ni i lng = 40 %, ca Ru v Rh l cao nht (50 %).
Hnh 5-26 cho thy gia c trng d v hot tnh xc tc trong phn ng hyr ho etylen
c mi quan h tuyn tnh [T20]. Tuy nhin quan h ny (H.5-26) khng hon ton l do
yu t in t. Theo Pauling, c trng d ca lin kt kim loi tng khi hng s mng
gim. V vy, bn cnh yu t in t th yu t hnh hc cng ng vai tr quyt nh.
Hnh 5-26 Quan h gia hot tnh xc tc trong phn ng hyr ho etylen vi c trng d ca cc
kim loi
42
Mc lp y in t ca cc d orbital nh hng mnh n kh nng hp ph ho hc
ca kim loi. Khi to hp kim t kim loi A hot tnh bng kim loi B c hoc khng c
hot tnh, hp kim AB c th c hot tnh cao hn hay km hn so vi hot tnh ca kim
loi A ban u. iu ny thy r trong trng hp cc kim loi nhm 810 trong bng tun
hon, y l nhm cc kim loi c hot tnh cao trong cc phn ng hyr v ehyr ho.
Khi hp kim ho cc kim loi c hot tnh ny vi cc kim loi khng c hot tnh hyr
ho thuc nhm 11 nh Cu, Ag, v Au dn n tng lp y cc d-orbital ca cc kim
loi gc v lm gim hot tnh xc tc hyr ho. Trong trng hp xc tc hp kim hai
thnh phn, ghi nhn c hin tng cc nguyn t ng tp trung ln b mt, y l
hin tng tch pha, thng gp trong hp kim. Khi o hp ph H
2
trn xc tc hp kim ta
s thy r hin tng ny. Ngi ta nghin cu cc xc tc hp kim Cu/Ni, Cu/Pt v
Cu/Pd trong phn ng hyr ho etylen. Khi tng hm lng Cu, mc Fermi s nng ln
lm gim i lc hp ph vi hyr v h qu l gim tc phn ng. Ngc li nu hp
kim ho Ni bng Fe hot tnh s tng.
Hiu ng tng t cng c ghi nhn i vi mt s phn ng cho in t khc, v d:
phn ng phn hu axit formic v phn hu metanol. Vi phn ng phn hu hyr peroxit
li ghi nhn hiu ng ngc li. Khi s hp kim ho bng Cu, tng ng vi s nng
mc Fermi li tng vn tc phn ng. iu ny c cho l do trong c ch phn ng, giai
on chm nht (quyt nh vn tc phn ng) l phn ng nhn in t dn ti s hnh
thnh ion O
-
hoc OH
-
.
Trong trng hp hp kim Cu/Ni chng minh c l Cu tp trung ln b mt hp kim
trong khong thnh phn rng (1895 % Ni). iu ny th hin r khi nghin cu hp ph
hyr (Hnh 5-27).
Hnh 5-27 Quan h i lng hp ph hyr trn xc tc hp kim CuNi v thnh phn
Cc hp kim Ni/Cu c chn lc c bit, iu ny thy r trong phn ng hyr phn
etan thnh metan (Pt. 5-36) v ehyr ho xyclohexan thnh benzen (Pt. 5-37).
C
2
H
6
+ H
2
2CH
4
(5-36)
C
6
H
12
C
6
H
6
+ 3H
2
(5-37)
43
Theo Hnh 5-28 tc hyr phn etan gim 3 bc khi thm 5%Cu vo Ni. iu ny l do
phn li lin kt CC, ti thiu hai nguyn t Ni gn nhau phi tham gia vo tc ng
ny. Khi thm cc nguyn t Cu, lu l Cu c xu th tp trung ln b mt, chng s lm
gim cc cp NiNi, cc yu t xc tc c bn, iu ny gim mnh hot tnh xc tc.
Hnh 5-28. Hot tnh ring ca hp kim CuNi trong phn ng ehyr ho xyclohexan v hyr
phn etan thnh metan 316
o
C
Ngc li, tc phn ng ehyr ho xyclohexan li tng nh khi hp kim ho Ni bng
mt lng nh Cu, khi tng tip hm lng Cu, tc n nh v gim t ngt khi hm
lng Cu rt cao (Hnh 5-28). Cc hiu ng ny thng gp khi dng cc xc tc hp kim
khc nh Pd/Ni, Pd/Ru v Pd/Pt, chng u c hot tnh cao hn kim loi Pd trong phn
ng ehyr ho xyclohexan.
Hiu ng hp kim ho ny c ng dng trong cng nghip. V d, sn xut alken
t alkan dng xc tc ehyr ho Ru/Os trn cht mang, phn ng ph l hyr phn nh
trn, nu b xung mt lng nh Cu vo hp kim trn, hot tnh hyr phn gim mnh,
khi s thu c nhiu alken hn. y l xc tc mang trn cht mang c din tch b
mt ln (~300 m
2
/g), xc tc l nhng ht tinh th hn hp nh, c kch thc nh hn 5
(bimetallic clusters). Khi b xung Cu, cc nguyn t Cu s tp trung trn b mt Ru, lm
gim hot tnh hyr phn nh trng hp xc tc Ni trn.
Tuy nhin, thuyt vng cng c mt s gii hn. Do ch gii hn yu t in t, v c khi
b xung yu t hnh hc, y vn khng c thng tin v kiu lin kt v cc trng thi b
mt. V d, hin tng to phc b mt (hp ph ho hc) c th khng dn ti s thay i
in tr khng c xem xt. c bit trong trng hp hp kim, s trao i in t,
tng tc gia phn t b hp ph vi b mt kim loi chc chn b nh hng bi yu t
khng gian, tuy nhin nhiu khi d kin thc nghim vn khng th gii thch c.
V vy, la chn xc tc kim loi vn da theo mt s quy tc kinh nghim sau [T40]:
1) Kim loi c th xc tc cho cc phn ng hyr ho, isomer ho v xi ho.
2) Trong cc phn ng c s tham gia ca hyr (mt mnh hoc cng hyrocarbon),
ta c dy hot tnh sau:
44
Ru, Rh, Pd, Os, Ir, Pt>Fe, Co, Ni,>Ta, W, Cr~Cu
3) Pd l kim lai rt hot tnh v thng chn lc. Pd c th huyr ho ni i chn
lc trong khi khng ng n cc nhm chc khc.
4) Trong mt s trng hp hot tnh xc tc lin quan n c trng d trong lin kt
kim loi, tuy nhin iu ny khng phi ng cho mi trng hp.
5) Trong mt s trng hp ta c th thy quan h gia hng s mng kim loi vi
hot tnh xc tc.
6) Cc kim loi sau bn trong mi trng xi v lu hunh:
Rh Pd Ag
Ir Pt Pd
7) Hot tnh ca kim loi gim theo dy:
(W-Mo) > Rh > Ni > Co > Fe
Mi phn ng thng c mt dy hot tnh kim loi ring, ta c th tra cu trong cc ti
liu chuyn kho (Bng 5-15). Cc dy ny khng ging nhau, thm ch mu thun, v vy
khng nn p dng tu tin dy hot tnh ny cho phn ng khc.
Bng 5-15 Hot tnh xc tc so snh ca cc kim loi [T33, T40, T41]
Hyr ho olefin
Hyr ha etylen
Hyr phn
Hyr ho axetylen
Hyr ho vng thm
ehyr ho
Isomer ni i ca alken
Hyrat ho
Rh > Ru > Pd > Pt > Ir Ni > Co > Fe > Re Cu
Rh, Ru > Pd > Pt > Ni > Co, Ir > Fe > Cu
Rh Ni Co Fe > Pd > Pt
Pd > Pt > Ni, Rh > Fe, Cu, Co, Ir, Ru > Os
Pt > Rh > Ru > Ni > Pd > Co > Fe
Rh > Pt > Pd > Ni > Co Fe
Fe Ni Rh > Pd > Ru > Os > Pt > Ir Cu
Pt > Rh > Pd Ni W Fe
5.3.3.2 Xc tc lng kim (bimetallic catalysts)
Trong cng nghip c nhiu xc tc lng kim, cc v d cho trong Bng 5-16.
Bng 5-16. Cc xc tc lng kim v cc qu trnh cng nghip tng ng
Xc tc Qu trnh
Ni/Cu-SiO
2
Pd/Fe-SiO
2
Rh, Ru, Ni+Sn
Rh/Mo-SiO
2
hoc Al
2
O
3
Ni/Sn; Rh/Sn
Pt/Sn
Hyr ho vng thm v olefin mch di sn xut dung mi
Hyr ho 2.4-dinitrotoluen thnh 2.4-diaminotoluen (qua 2-nitro-4-
aminotoluen v 2-amino-4-nitrotoluen)
Hyr ho ester thnh axit hoc alcol
Hyr ho CO v CO
2
thnh metanol v dimetyleter
Hyr ho etylaxetat thnh etanol
ehyr ho v cracking alkan
45
Sau y l mt s phn ng trn xc tc lng kim. V d: phn ng hyr ho etylaxetat
thnh etanol trn xc tc Rh/Sn-SiO
2
(Bng 5-17). Khi hm lng Sn tng ta thu c cc
kt qu trong Bng 5-17 [40].
Bng 5-17 Hyr ho etylaxetat etanol trn xc tc Rh/Sn-SiO
2
[40]
543K, H
2
/etylaxetat = 9:1, 50 bar, bn phn ng kiu ng dng vi phn
* Thi gian phn ng ko di, to thnh dietyleter v axetaldehit
Khi hm lng Sn, cc kt qu trn c l gii nh sau:
Cc nguyn t Rh b mt b c lp bi cc nguyn t Sn, iu ny dn ti
Kh nng hp ph ho hc ca xc tc i vi CO v H
2
gim mnh
Ph IR: xc tc Rh/Sn-SiO
2
c nhm carbonyl 2000 cm
1
E
a
: Rh/SiO
2
= 75,2 kJ/mol; Rh/Sn-SiO
2
= 46 kJ/mol
Tnh cht in t ca Sn mt in t ca Rh
C ch phn ng th hin Phng trnh 5-38.
(5-38)
Phn ng hyr ho chn lc crotonaldehit c nghin cu vi cc xc tc Pt. Cc kt
qu c tng hp trong Bng 5-18.
Bng 5-18 Hyr ho crotonalehit trn xc tc Pt [42]
46
353 K, chuyn ho < 10%, 1 bar, bnh phn ng dng ng, hm lng kim loi 5,07,2%
Cc kt lun l:
Hyr ho C=O tt nht trn Pt-TiOx v Pt-GaOx, vi xc tc lng kim l Pt-Sn v
Pt-Ni
Hyr ho C=C c thc hin trn kim loi sch
Xc tc lng kim Pt/Sn c ng dng trong nhiu qu trnh ehyr ho. Cht mang tt
nht l alumina, ZnAl
2
O
4
hoc MgAl
2
O
4
. nh hng ca Sn v cht mang c xc nh.
Tm tt nh sau.
nh hng ca Sn:
Sn l xc tin ca Pt, tng c ba tnh cht quan trng nht l hot tnh, chn lc
v n nh
Hiu ng in t: vi hm lng Sn < 15% cc orbital d c lp y in t
5d; khi s t cc ho hn, t hyr phn lin kt C-C hn
Hiu ng tp hp (Ensemble effect): phn ng ehyr ho yu cu tp hp Pt nh
hn ( phn tn ca Pt cao hn); khi Sn phn tn cc nguyn t Pt, hnh thnh
nhiu tp hp Pt nh hn.
nh hng ca cht mang:
To tnh axit b mt
n nh xc tc di tc ng ca nhit trong phn ng v trong qu trnh ti sinh
n nh kch thc cc tm xc tc, nht l cc ht Pt trng thi phn tn cao
C th tng tc ho hc vi cc cht xc tin
To h l xp ph hp
Sau y l v d v hiu ng xc tin ca Rh trong vic tng chn lc trong phn ng
hyr ho dn xut ca pyridin trn xc tc lng kim [41]. T Bng 5-19 ta thy s thay
i t l kim loi s dn ti thay i chn lc trong phn ng (Pt.5-39).
47
(5-39)
Bng 5-19 Hyr ho dn xut ca pyridin vi xc tc lng kim mang trn Al
2
O
3
[41]
Khi to hp kim vi kim loi khng hot tnh c th thay i mnh chn lc bng cch
tng tc phn ng cn v hn ch phn ng khng mong mun. V d, khi thm Sn vo Pd
ta thu c xc tc loi b axetylen trong dng etylen (hyr ho chn lc axetylen). Zn,
Pb, Ag v Au cng c tc dng tng t [T41]. Khi thm Au khng hot ng vo xc tc
Pd, tc phn ng gia H
2
v O
2
tng ln ti 50 bc. Nu thm Au vo Pt hot tnh xc
tc Pt isomer ho n-hexan tng 10 bc. Hin tng ny c quy cho hiu ng widening
lm tng khong cch gia cc nguyn t PtPt khi nguyn t Au ln chen vo mng Pt.
Cc v d v hiu ng cho thm i vi xc tc Pt s dng trong cng nghip c tm tt
trong Bng 5-20 [T23].
48
Bng 5-20 Bin tnh xc tc nhm Pt bng kim loi th hai [T23]
Base metal
Additive Reaction Effect of additive
Pt
5 20% Rh ammonia oxidation
increased NO yield,
lower Pt losses
Ag Au ethylene oxidation higher selectivity of
ethylene oxide formation
Ag 10 % Au cumene oxidation increased rate of
formation of cumene
hydroperoxide
Pt
Ge, Sn, In, Ga dehydrogenation and
hydrocracking of alkanes
increased lifetime due to
lower carbon deposition
Pt
Sn + Re
dehydrocyclization and
aromatization of alkanes
increased catalyst
activity and stability
Pt
Pb, Cu
dehydrocyclization and
aromatization of alkanes
effectivity of
aromatization
Pt, Pd, Ir
Au oxidative
dehydrogenation of
alkanes, n-butene to
butadiene, methanol to
formaldehyde
improved selectivity
Ir
Au (Ag, Cu)
hydroforming of alkanes
and cycloalkanes
high aromatics yield
above 500 C
Pd Sn, Zn, Pb selective hydrogenation
of alkynes to alkenes
Trong cc nghin cu gn y, cc xc tc lng kim, nht l trn c s Pd cng c
nghin k trong phn ng hyr ho chn lc cc alehit no v cha no, cc c ch phn
ng cng c xc nh [T32]. Dy hot tnh ca cc kim loi nhm 810 trong phn
ng hyr ho crotonalehit c xc nh nh sau:
Ir, Co < Rh < Ni < Pt <Pd
Trong trng hp hyr ho n-butyraldehit thnh butanol ta c dy ngc li. C hai phn
ng thuc loi phn ng mt tm v c bc quyt nh tc l phn ng to cht trung
gian hyr ho bn phn. C ch hai phn ng ny c coi l nh sau;
1) Hyr ho alken bng phn ng cng phi t i nhn (nucleophilic ligand):
(5-40)
Nh vy, kim loi th hai phi c tnh cho in t tng tnh i nhn.
2) Hyr ho nhm carbonyl bng phn ng cng phi t i in t (electrophilic
ligand):
49
(5-41)
Kim loi th hai phi c tnh nhn in t tng tnh i in t ca xc tc
Qu trnh hyr ho lin kt i trong crotonalehit to butyralehit xy ra rt m trn
xc tc Pd/Al
2
O
3
(Pt. 5-40). Cc tc nhn cho thm nh kim loi Fe, Sn v Pb khng c tc
dng ng k. Tuy nhin, chng li tng tc cho qu trnh hyr ho nhm carbonyl ca
butyralehit theo (Pt.5-41). l do cc cht cho thm l cc cht nhn in t, khi
chng tng chn lc cho phn ng vi nhm carbonyl.
Tuy nhin, trong cc ti liu nghin cu c th thy Fe, Sn, Pb li c tnh cho in t, iu
ny c th chng minh bng ph IR. y l v d cho thy tnh c th ca cc l thuyt
xc tc, v khoa hc xc tc vn mang nhiu tnh gi thit.
50
5.3.3.3 Xc tc bn dn [16, 35, T27]
Cht bn dn l nhm cc cht rn phi kim c cu trc in t khc kim loi. Thuyt vng
c s dng kh tt gii thch tnh xc tc ca nhm bn dn.
Trong tinh th bn dn c hai vng phn bit r: vng nng lng thp cha cc in t
ho tr (vng ho tr VB) v vng nng lng cao cha cc in t dn (vng dn CB).
Trong iu kin thng cc in t ch c tr vng ho tr, khi cht bn dn khng
dn in. Nu vng dn c in t lp tc n tr thnh cht dn in.
Gia hai vng khng c orbital in t c th c tr nn gi l vng cm, c rng
(eV) no . Ngi ta phn bit bn dn thc hay i- (intrinsic), bn dn loi n, hay loi p
[T27]. Trong bn dn loi i in t c sinh ra khi di tc dng ca nhit hoc bc x
in t s thot ra khi nguyn t cha n nhy ln CB, li mt l trng (Hnh 5.29).
Hin tng quang in l mt v d.
Hnh 5-29 Bn dn thc v hin tng kch thch to in tch
Nu nng lng kch thch ln hn hoc bng b rng vng cm, in t s nhy t vng
ho tr ln mt orbital trng vng dn, ng thi li mt l trng mang in dng
vng ho tr. B rng vng cm c tnh t mc nng lng thp nht ca CB ti mc
nng lng cao nht ca VB. Bng 5.21 cho ta gi tr b rng vng cm ca mt s vt
liu.
Bng 5-21 Nng lng kch thch bt in t ca mt s vt liu
Cht / Nguyn t
Nng lng kch thch , eV (H.5.29)
C (kim cng)
Si
Ge
Sn (xm)
5,2
1,09
0,6
0,08
Phn cc in t c th nhy ln CB nh chuyn ng nhit c th tnh qua phn b
Boltzmann exp( /2kT). Trong xc tc bn dn loi i rt t gp; ta gp ch yu l bn dn
loi n v loi p. Thng chng l cc xit hoc sulphua khng t lng. Thng thng
dn ca chng thp nhng c th tng bng cc tc nhn bin tnh thch hp.
51
Gi thit trong tinh th bn dn xut hin cc nguyn t cho in t hay donor, y l
nhng nguyn t d mt in t khi un nng. Cc in t ny s nm vng cm, ngay
di CB, v vy chng ch cn mt nng lng Ei ti thiu l c th nhy ln CB (Hnh
5.30a). Nh vy l trng chnh l nguyn t donor va mt in t, khi chng ta c
trng hp dn c gy ra bi in t hay dn loi n (n = negative).
Hnh 5-30 Bn dn v hot ng ca chng theo kiu:
a) bn dn loi n; b) bn dn loi p
Trng hp ngc li nu ta a vo mng cc nguyn t c tnh thu in t (acceptor).
Khi n s ly in t t VB (Hnh 5-30b). Khi nhit tng, in t t VB s b nguyn
t nhn ko ra khi VB, li mt l trng dng trong VB. Khi dn c gy ra
bi s chuyn dch ca cc l trng dng hay dn loi p (p = positive), trong trng
hp ny nng lng ion ho Ei cng thp. Trong bn dn tn ti mc Fermi, lun nm
trong vng cm. y l mc nng lng ng vi th in ho nm khong gia mc
nng lng lp y cao nht v mc nng lng khng lp y thp nht. Mc Fermi c
o bng cc phng php ph, n c gi tr ln i vi bn dn loi n v nh i vi bn
dn loi p. Hnh 5.30 cn cho thy cng thot in t
A
.
Mi quan h gia cu to v tnh cht bn dn
Nh nu bn dn ng vai tr quan trng trong k thut ni chung v xc tc ni ring.
Khi tng nhit , mng tinh th xit c xu th hoc l hp ph hoc l thot xi.
(1) Vi bn dn loi n, v d ZnO qu trnh thot xi c m t bng Pt.5.42 v 5.43.
2Zn
2+
O
2
[2Zn
2+
+ O
2
+ 2e]2(Zn
+
) + O
2
(5.42)
2Zn
2+
2O
2
[2Zn
2+
+ O
2
+ 4e]2(Zn
o
) + O
2
(5.43)
Trong trng hp ny ZnO c tnh bn dn l nh s xt hin ca ht (Zn
+
) v (Zn) nm
trong mng xit. Hai phn ng trn c th c thc hin hoc l bng cch nng nhit
hoc l bng phn ng kh vi H
2
, CO, hoc hyrocarbon nhit phng. Cc ht (Zn
+
)
v (Zn) nm trong mng xit khi c tnh cho in t trung ho in tch chung. Cc
in t t do (quasifree) ny thot ra lm cho mng trung ho v in tch. Khi cng
thc phn t ca ZnO tr nn khng t lng Zn
1+x
O.
Nu cho ZnO hp ph xi, dn s gim v O
2
c tnh nhn in t (Pt.5.44):
52
(Zn
+
) + O
2
Zn
2+
O
2
(5.44)
Trng hp hp ph hyr, y l cht cho electron, v vy dn ca ZnO s tng do
phn ng:
(Zn
+
)O
2
+ H
2
Zn
2+
+ OH
(5.45)
(2) i vi cc bn dn loi p, v d NiO, s hp ph xi c thc hin theo Pt.5.46:
4Ni
2+
+ O
2
4Ni
3+
+ 2O
2
(5.46)
Khi nhn thm phn t O
2
vo mng, O
2
nhn 4 in t t Ni
2+
v s hnh thnh 4Ni
3+
tng ng vi bn l trng (h
+
), khi dn tng nh s dch chuyn theo nguyn l
chy tip sc ca cc l trng theo cc nt mng.
Khi cng thc ca NiO hay cc bn dn loi p c dng Ni
1x
O. Cc kim loi c oxit l
bn dn loi p phi d thay i ho tr khi trng thi xit. l cc xit ca kim loi
chuyn tip trng thi ho tr thp nh Ni
2+
, Co
2+
, Cu
+
, khi hp ph xi chng d dng
chuyn thnh cc l trng Ni
3+
, Co
3+
, Cu
2+
. Ngc li, cc xit bn dn loi n phi l cc
xit kim loi bnh thng tn ti ho tr cao nht, v d: ZnO, TiO
2
,V
2
O
5
, MoO
3
, Fe
2
O
3
.
trng thi ban u dn in ca c xit loi n ln loi p u thp. tng dn ca
chng ngi ta dng k thut pha tp.
Pha tp tng dn ca bn dn
Nu ta c bn dn loi p, tng dn ta cn tng mt l trng. t c iu ny
c th cho thm vo mng cc xit ca kim loi c ho tr thp hn. V d, khi mng Ni
2+
trong mng NiO c thay bng Li
+
, ta thy in tch tng ca mng s m do trong mng
s d ion O
2
, b in tch m d ny Ni
2+
phi xi ho ln Ni
3+
, khi mt l trng
s tng, dn in s tng. Nu thm ion ho tr ln hn 2+, v d Cr
3+
ta c hiu ng
ngc li: mng tr nn d in tch + v s tm cch tr v trung tnh bng cch nhn in
t t bn ngoi, in t s trung ho l trng h
+
lm gim mt ht dn h
+
v dn.
Trong trng hp bn dn loi n, v d ZnO, ta c bc tranh ngc li: cht cho thm nu
l cc xit c ho tr cao hn Zn
2+
, v d: Ga
2
O
3
, Cr
2
O
3
, hoc Al
2
O
3
s tng dn, nu l
Li
2
O s gim dn. Thng thng cc cht cho thm ch khong 1%. Tng kt v cc
tnh cht ca cc xit bn dn c nu trong Bng 5.22.
Bng 5.22 Tnh cht ca mt s xit bn dn
Loi n Loi p
Cc xit vi ion trong mng
Cc xit c khim khuyt mng
Ht mang in (kiu dn in)
Thm M2
I
O
Thm M2
III
O3
Hp ph O2, N2O
Hp ph H2, CO
ZnO, CdO
TiO2, ThO2, CeO2
in t
gim dn
tng dn
gim dn
tng dn
UO2
Cu2O, NiO, FeO
l trng h
+
tng dn
gim dn
tng dn
gim dn
53
C mt s phng php kho st tnh cht ca cc loi vt liu ny. V d, o dn theo
nhit ; khi ta s bit mc ca hiu ng bn dn v cc mc nng lng. C th o
cc tnh cht quang in, quang in t v lin h vi dn, cng thot.
Trong thc t, cc kt qu o c th rt mu thun. Cn lu n tp cht, v d ZnO c
th cha cc tp nh Zn, Zn
+
, kh nng hp ph cc kh lm thay i dn. Cn to iu
kin c lp mu khi o. Tuy nhin cc tnh cht th tch chung nh dn, nng lng ion
ho, dn, cng thot rt kh lin h vi hot tnh xc tc. l do hot tnh xc tc ch
xc nh bi lp nguyn t b mt.
Bng 5.23 phn loi cc xit quan trng nht theo tnh cht in t ca chng.
Bng 5.23 Phn loi cc xit kim loi theo tnh cht in t
Loi n Loi p Loi i (intrinsic) Cch in
xit ca cc nhm chnh
ZnO, GeO
2
, CdO, HgO, SnO
2
,
As
2
O
5
, Sb
2
O
5
, PbO
2
, Bi
2
O
5
,
Al
2
O
3
( nhit cao)
xit kim loi chuyn tip
Sc
2
O
3
, TiO
2
, V
2
O
5
, Fe
2
O
3
,
ZrO
2
, Nb
2
O
5
, MoO
3
, Ta
2
O
5
,
HfO
2
, WO
3
, UO
3
NiO, Cr
2
O
3
, MnO,
FeO, CoO, Cu
2
O,
Ag
2
O, PtO
Fe
3
O
4
, Co
3
O
4
, CuO BeO, B
2
O
3
, MgO,
Al
2
O
3
, SiO
2
, P
2
O
5
,
CaO, SrO, BaO
Nh vy, tng t nh trng hp xc tc kim loi, lin h gia cu trc in t v tnh
xc tc kh thit lp. S dng quan h ny thng mang tnh cc b, hay dn n mu
thun, v d:
1) xit v sulfua kim loi chuyn tip l cc xc tc mnh, chn lc cao, c vai tr ht
sc ln trong cng nghip. Theo thuyt in t nhiu bn dn khc cng c th l xc tc
tt, ng thi tnh cht bn dn cng d dng thay i bng cch pha tp. Tuy nhin thc t
khng nh vy, trong ho hc yu t c th lun phi tnh ti.
2) Khi bin tnh bng cht cho thm dn thay i rt mnh, tuy nhin trong phn ln cc
trng hp hot tnh xc tc khng thay i nh mong i.
Trong thc t thc nghim nh hng theo l thuyt vn l con ng la chn xc tc tt
nht cho mt phn ng c th, trong xc tc hu nh khng gp trng hp xc tc cng
nghip no c ng dng m khng qua th nghim. Hn na cc kt qu nghin cu
quy m phng th nghim cho php hiu r hn cc yu t quyt nh vn tc, y s l c
s hon thin, nng cp xc tc.
Hin nay, cc xc tc xit, trong phn ln l vt liu bn dn c tim nng ci tin rt
ln qua con ng thay i cc tnh cht in t nh k thut pha tp, nh c th to ra
nhng xc tc xit r tin nhng c th thay th c cc kim loi qu him, l trng
hp xc tc x l kh thi chn lc (qu trnh SCR) v xc tc i ho chn lc metanol
thnh formaldehit..
54
Hp ph ho hc trn bn dn
Cc kh c tnh kh nh H
2
, CO c tnh hp ph ho hc rt mnh, thc cht l phn ng
kh, trong nhiu trng hp l bt thun nghch. Sau hp ph CO, un nng mu s thu
c CO
2
+ H
2
O. Trng hp hp ph H
2
, phn ng theo phng trnh (5.46), trong
bc hp ph ho hc l phn ng ng li to H nguyn t b mt:
M
2+
+ O
2
+ HH HM
+
+ OH
(5.46)
Khi tng nhit hyroxyl ion chuyn ho thnh hi nc thot ra v li mt l trng
anion, cc cation kim loi s b kh vi s lng tng ng, i khi ti kim loi.
Hp ph H
2
v CO th hin rt mnh trn bn dn loi n, vi bn dn loi p hp ph cc
kh ny s yu hn. Trong qu trnh hp ph ho hc mnh ny cc in t t do hoc cc
l trng (h
+
) s tham gia to lin kt hp ph. iu ny dn n s thay i in tch ca
cc tm hp ph v h qu l in tch ca phn t b hp ph. Khi in tch b mt thay
i, n mt mc no n s cn tr qu trnh hp ph tip theo. Khi , nu o nhit
hp ph theo che ph b mt ta s thy lng nhit pht ra trn n v b mt s gim
dn, khi ng ng nhit hp ph s ngy cng xa ng Langmuir.
CO bt u hp ph ho hc bng tng tc vi ion kim loi b mt, trong nhiu trng
hp phn ng ny dn ti s kh kim loi:
CO .... Me
2+
+ O
2
M + CO
2
(5.47)
Khi xi hp ph trn bn dn loi n, in t s chy t mc donor-cho ca cht hp ph
hnh thnh ion O
v O
2
. Khi , b mt s phn cc v mang in m, iu ny s cn tr

hp ph xi tip theo. Hin tng ny, xi hp ph trn bn dn loi n, c gi hin
tng t c ch. Nu bn dn loi n, v d ZnO c cng thc chnh xc theo t lng th
hin tng ny khng xy ra. Khi mng ca n n thiu O, n s hp ph mt lng O
b s khim khuyt anion trong mng v xi ho phc hi cc ion Zn
2+
.
Cc kim loi c thin hng hp ph xi l cc kim loi c 5, 7, 8 hoc 10 in t d. Trt
t hot tnh sp xp nh sau:
Cu
+
Ag
+
> Pt
2+
> Mn
2+
> Rh
2+
> Ir
2+
> Co
2+
> Hg
2
2+
ng vi chng l cc xit bn dn loi p nh Cu
2
O, Ag
2
O, MnO v PtO, y l cc xc tc
hot ho xi tt.
Vi cc xit bn dn loi n, ion kim loi c 1, 2 hoc 5 in t d cng hp ph tt xi.
Hot tnh c xp theo th t sau:
V
5+
> Mo
6+
> W
6+
> Cr
3+
> Nb
5+
> Ti
4+
> Mo
4+
Tng ng cc bn dn loi n nh V
2
O
5
, MoO
3
, WO
3
, Cr
2
O
3
, v TiO
2
l cc xc tc xi
ho tt.
Hp ph xi
55
Nh nu, khi bn dn loi p hp ph xi, che ph b mt rt cao v km theo s hnh
thnh cc ion O
2
v O
2
. Trong trng hp NiO ion Ni

2+
s xi ho thnh Ni
3+
, nhit hp
ph gn nh l hng s, cn b mt c lp y dn ti bo ho bi O
2
:
2Ni
2+
+ O
2
2(O
Ni
3+
) (5.49)
Hp ph hyr
H
2
hp ph d li trn tm hai nguyn t ca ZnO, khi s hnh thnh cp donor cho v
acceptor - nhn. Ht hyrua H
b mt rt hot ng, qu trnh m t nh sau:

Cr
2
O
3
c th phn li H
2
bng hai bc, bc mt l d li tng t ZnO trn:
(5.50)
Hai l:
(5.51)
Trng hp TiO
2
TiO
2
vi khim khuyt anion (khuyt tinh th v tr O) c nghin cu kh k, cc kt
qa tng kt nh sau [17, 35]:
H
2
hp ph phn li trn tm Ti
O
2
hp ph phn li v lm y v tr O trng
CO hp ph phn t trn nguyn t Ti nm cnh l trng O
CO
2
phn ng vi ion O
2-
to carbonat b mt; khim khuyt O
2
khng nh hng
Cc phn ng tm tt y l c s xem xt c ch cc qu trnh xc tc bn dn.
Phn ng trn b mt bn dn [T20, T40]
Trng hp xc tc xi ho
Phn ng xi ho bao gm cc bc:
1) To lin kt gia xc tc v cht phn ng cn xi ho (v d: hyrcarbon) thng qua
hp ph ho hc.
2) Hp ph ho hc vi xi.
3) Chuyn in t t cht cn xi ho ti cht nhn l O
2
thng qua xc tc.
4) Tng tc gia cc ion, gc t do hoc gc ion hnh thnh t cht phn ng vi ion O
-
,
O
2-
to sn phm trung gian/hoc sn phm.
56
5) Sp xp li cht trung gian nu c.
6) Gii hp ph sn phm.
Yu cu u tin l xc tc phi to c lin kt vi cht phn ng (cht cho e). Cc xit
bn dn loi p c xu th hp ph mnh xi hn loi n s l xc tc tt cho qu trnh ny.
Tuy nhin, hot tnh v chn lc kh song hnh, thc t l p km chn lc hn n trong
phn ng xi ho. Cc xc tc bn dn loi p thng xi ho hon ton cht hu c ti
CO
2
v H
2
O, trong khi bn dn loi n c th xi ho ti hp cht trung gian no .
T l xi trn hyrocarbon hp ph trn xit bn dn loi p thng ln v kh kim sot,
iu ny thng dn ti phn ng xi ho/t chy hon ton. Vi bn dn loi n t l ny
nh nn phn ng thng dng sn phm trung gian, ngoi ra iu khin chn lc
th cc cht bin tnh l cng c thch hp. Tuy nhin, trong thc t cc oxit c loi n ln
loi p u khng phi xc tc xi ho chn lc tt. V l , ng dng chng trong xi ho
chn lc l hn ch, sau y l mt s v d bin t.
C th bin tnh xc tc xi ho trn c s bn dn. S thay i chn lc c gii thch
da trn:
S thay i m in
Th ion ho
Lc lin kt Ob mt xc tc, kh nng ly xi t mng
C ch phn ng xi ho/kh thng c quy v c ch hai bc; qu trnh xi ho
phn t X c cho l tun theo mt trong hai qu trnh hai bc nh sau (S 5.3):
A O
2(G)
O
+ O
sn phm
B X
+ O
mng
sn phm + khuyt tt mng
O
2(G)
+ khuyt tt mng O
mng
S 5.3 C ch phn ng xi ho [T22]
Trng hp A: O
2
hp ph nhanh hn X, khi X* hp ph phn ng vi xi d. Qu
trnh tip tc ti sn phm cui l carbon ioxit v nc.
Trng hp B: X hp ph tng tc vi xi trong mng tinh th. y l trng hp xi
ho chn lc ti sn phm trung gian, sn phm trung gian c th l cc hp cht carbonyl,
cc cht xi ho khng hon ton. C ch xc tc chn lc c xut bi Marsvan
Krevelen, trong xc tc l mng cha cation vi lp d trng hoc lp y, v d:
Mo
6+
V
5+
Sb
5+
Sn
4+
4d
0
3d
0
4d
10
4d
10
57
xit kim loi trng thi xi ho cao thng sn sng cho xi mng, v hnh thc l ion
O
2-
. Xc tc xi ho thng gp nht l V
2
O
5
. Tc phn ng rt ph thuc vo s lng
lin kt V=O trn b mt, iu ny c kim chng trong cc phn ng xi ho H
2
,
CO, etylen, buten, butadien, v xylen. Giai on quyt nh tc phn ng l bc
chuyn V
V
thnh V
IV
(Pt.5.52). y cng l trng hp pphn ng xi ho metanol thnh
formaldehit trn xc tc MoO
3
, trong trng hp ny l s lin kt Mo=O.
(5.52)
Cc xit kim loi, nht l kim loi chuyn tipc th thc hin cc phn ng xi ho,
ehyr ho, ecarboxylat ho, ecarbonylat ho, b gy lin kt CC. Xem thm[32,
T41].
Cc dy hot tnh
xi ho H
2
khi d xi:
Co
3
O
4
> CuO > MnO > NiO > Fe
2
O
3
> ZnO > Cr
2
O
3
> V
2
O
5
> TiO
2
46 55 59 59 63 100 76 76 Ea [kJ/mol]
xi ho amnic:
Co
3
O
4
> MnO
2
> Cr
2
O
3
> CuO > NiO > Fe
2
O
3
> ZnO > TiO
2

Trong c hai phn ng trn giai on quyt nh tc l giai on hp ph phn li xi.
Cc phn ng xi ho hon ton hu c t ng dng cng nghip, tr lnh vc x l mi
trng mi ni.
Cc phn ng xi ho chn lc c ngha thc t ln hn:
xi ho propen to acrolein:
MoO
3
> Sb
2
O
5
> V
2
O
5
> TiO
2
= Fe
2
O
3
> SiO
2
> WO
3
.Al
2
O
3

xi ho benzen thnh anhydric maleic:
V
2
O
5
> Cr
2
O
3
> MoO
3
> Co
2
O
3

xi ho imer ho ng vng propen thnh 1,5-hexadien v benzen:
ZnO > Bi
2
O
3
> In
2
O
3
> SnO
2
> Ga
2
O
3
> CdO
Cc dy v d nu cho thy mt kt lun l: cho ti u th k 21 khng c quy lut
chung cho mi phn ng, mi phn ng phi t chn ly xc tc trn c s hiu bit c ch
phn ng v c ch hot ng ca xc tc bit. Tip theo l thc nghim.
Cc v d su cho thy cch thc la chn xc tc:
Phn ng phn hu N
2
O:
2N
2
O 2N
2
+ O
2
(5.53)
58
C ch nh sau:
N
2
O + e
N
2
+ O
ads (5.54)
O
ads + N
2
O N
2
+ O
2
+ e (5.55)
Bc chuyn in t qua xc tc l bc quyt nh vn tc; ngoi ra xc tc phi l cht
hp ph xi tt ( to O
ads mt trong Pt.5.55). Qu trnh chuyn electron t O
hp ph
ch c th hin thc nu mc Fermi b mt xc tc thp hn nng lng ion ho ca O
hp
ph. y l trng hp ca bn dn loi p. Dy hot tnh xc tc cho phn ng ny c
xy dng trn c s nh gi nhit bt u qu trnh phn hu. Xc tc c th c chia
thnh 3 nhm (Hnh 5.31). ng nh d on, cc bn dn loi p thuc nhm hot tnh cao
nht, nhm th hai l xit cch in, bn dn loi n km hot tnh nht.
Hnh 5-31 Hot tnh so snh ca cc xit trong phn ng phn hu N
2
O [5]
Sau khi chn c nhm tin cht kh d hn c cn phi lm r nh hng ca cc yu t
nh phn tn, tp cht, s v loi tm hot ng ... V d, chn NiO. Ta thy ngay t
trn, tnh bn dn loi p s mnh ln nu b xung tp cht, th nghim cho dy sau [T35]:
(NiO + 2% LiO
2
) > NiO >> (NiO + 2% Cr
2
O
3
)
Nh vy cht cho thm loi p tng hot tnh xc tc, loi n gim hot tnh.
Phn ng vi cht cho e cng c xc nh l bc quyt nh tc phn ng trong
cc phn ng vi xc tc bn dn loi n.
Xt phn ng xi ho CO trn bn dn
59
Phn ng xi ho CO (Pt.5.56) c nghin cu k cho c hai loi xc tc NiO loi p v
ZnO loi n (Bng 5.24).
Bng 5.24 xi ho CO trn xc tc bn dn
Xc tc E
a
, kJ/mol
1 NiO (loi p)
+ Cr
2
O
3
+ LiO
2
63
80
50
2 ZnO (loi n)
+ Ga
2
O
3
+ LiO
2
118
84
134
2CO + O
2
2CO
2
(5.56)
Theo bng kt qu v nh d bo bn dn loi p c nng lng hot ho thp hn ngha l
hot tnh cao hn. Mi cht cho thm m tng tnh bn dn loi p u dn ti kt qu tt
hn, v vy LiO
2
tng hot tnh ca NiO, cn Cr
2
O
3
th ngc li.
Cc kt qu ny c th d bo c. ng hc hnh thc cho thy phn ng l bc mt
theo CO, v vy giai on quyt nh vn tc l phn ng hp ph ho hc CO hay l phn
ng vi cht cho in t:
CO + [+] CO
+
ads (5.57)
Qu trnh hp ph ho hc ca O
2
(Pt.5.58), phn ng vi cht nhn iin t l phn ng
nhanh, tc t l thun vi p sut xi:
1/2O
2
O
ads + [+] (5.58)

Giai on cui cng l phn ng gia hai ht b hp ph theo c ch Langmuir
Hinshelwood:
COads+ + O
ads CO
2,g
(5.59)
Trn c s c ch phn ng vnh gi giai on quyt nh tc ta thy ngay, vi phn
ng (5.57) th p sut CO cao, mt l trng ln s tng tc giai on ny ng thi
tng tc ton b qu trnh. Vi ZnO l bn dn loi n v nguyn tc l cht cho in t
s khng hp vi qu trnh cng yu cu tng tc vi cht cho in t (Pt.5.57), v vy s
l t nhin khi ZnO km hot tnh so vi NiO. Tuy nhin khi tng tnh n bng cch cho
thm Ga
2
O
3
ta thy thay v gim hot tnh th hot tnh li tng. iu ny dn ti suy lun
l trong trng hp ny phn ng vi cht nhn in t (O
2
) li quyt nh vn tc. Kim
tra cho thy qu nhin vn tc phn ng ph thuc t l thun vo p sut xi, ngha l
phn ng (5.58) l quyt nh tc . V d ny cho thy, c ch phn ng c th thay i
khi thay i xc tc. iu ny li thm mt minh chng cho tnh c th ca xc tc.
Phn ng phn hu etanol
60
Phn ng phn hu etanol c th xy ra theo nhiu hng, y xt hai hng, tu vo
xc tc c th (A) ehyr ho to thnh axetaldehit hoc (B) ehyrat ho to thnh
etylen. Bng 5.25 tng quan cc kt qu nghin cu [T35].
CH
3
CHO + H
2
(A)
C
2
H
5
OH
H
2
C=CH
2
+ H
2
O (B) (5.60)
Bng 5-25 Phn hu etanol trn xc tc xit bn dn
Catalyst
Hiu sut phn r etanol [%]
CH
3
CHO + H
2
C
2
H
4
+ H
2
O
-Al
2
O
3
Cr
2
O
3
TiO
2
ZrO
2
Fe
2
O
3
ZnO
Hng tng c trng n
1,5
9
37
55
86
95
98,5
91
63
45
14
5
Cc kt qu y c gii thch nh sau. Khi i theo chiu mi tn theo hng tng c
trng n (cho in t) ca xc tc phn ng tng theo hng ehyr ho, y l hng
tng mc Fermi, tng kh nng cho in t ca xc tc, xu th ny hon ton ngc vi xu
th kh nc.
Phn ng hyr ho etylen
Phn ng hyr ho etylen trn xc tc ZnO xung quanh 100
o
C c nghin cu k bng
ph IR. Tm hot tnh l tm hai nguyn t, cp ZnO. Cc th nghim hp ph cho thy
tm hp ph nh cao hn b mt rn [T24]. ZnO thc hin qu trnh hp ph phn li H
2
theo kiu d li, to hyrua. Cc nguyn t H hp ph ho hc khi lin kt vi O b mt c
th chuyn vo to lin kt vi O trong mng (S 5.4).
S 5.4 Hyr ho etylen trn xc tc ZnO
Cht phn ng etylen cng hp ph trn O bng hp ph vt l, sau + H bn cnh v
chuyn sang trng thi hp ph ho hc phc etylenyl trn Zn. Khi hai v tr cnh nhau
61
c gc H v etylenyl s xy ra phn ng gia hai ht hp ph to etan. Tip theo l gii hp
sn phm. Trong phn ng ny H s dch chuyn t O n tm Zn.
Trong cng nghip ngi ta thng ch trng cc xc tc xit hn hp. V d hn hp ca
cc xit Fe, Co, Ni, Cu v Zn vi cc xit Cr, Mo, v W. Khi ta s c cromit, molybdat,
v volphramat (tungstat). Trong cng nghip cc phn ng sau s dng xc tc hn hp:
xi ho metanol thnh formaldehit: Fe/Mo, Fe/W
Hyr ho chn lc v ehyr ho: Cu/Cr
esulfua ho, enitrogen ho, v eoxygen ho: Co/Mo, Ni/Mo
Tng hp metanol: Zn/Cr, Zn/Cu
Chuyn ho CO: Fe/Cr
Trong qu trnh tng hp metanol CuI c phn tn trn nn ZnO. ng s hp ph ho
hc vi CO, cn ZnO hp ph hyr. Hyr hp ph phn li s phn ng vi CO trng
thi hp ph to ht trung gian =CHOH, tip theo l bc + H to metanol.
Cr
2
O
3
/Al
2
O
3
l xc tc trong phn ng ehyr ho butan thnh buten v butadien.
Khi b xung xit kim loi kim, xc tc ny c th dng cho phn ng vng-thm ho n-
alkan. Trong xc tc ny Al
2
O
3
va l cht mang, va l pha hot ng di dng pha hn
hp vi crom oxit. Tm hot ng l cc ion Cr
2+
v Cr
3+
[T41].
Cht mang
Cc xit bn dn cn lm cht mang xc tc. Ngay c khi xit khng c hot tnh trong
phn ng, nhng khi mang pha xc tc ln chng h tr xc tc rt r. V d, Ni v Ag
thng mang ln Al
2
O
3
bng k thut phn hu pha kh (chemical vapor-phase deposition =
CVD). Xc tc dng ny c tnh cht nh b li nh hng dng in t t cht mang qua
kim loi ti cht phn ng (Eq. 5-61). Vi xc tc loi ny cc phn ng vi cht nhn
in t l rt ph hp.
e e
Al
2
O
3
Ni Cht phn ng/nhn in t (5.61)
(pha tp loi n)
Ngoi suy rng ra, ta thy vi cht phn ng l cht cho th xc tc trn khng tt, khi
cn thay th bn dn loi n bng bn dn loi p hoc dng Al
2
O
3
pha tp loi p. Khi cht
mang s ht in t. Vn ny s quay li mc 5.4. Mt s xc tc cng nghip loi
ny c cho trong Bng 5-26.
Bng 5-26 Phn ng trn xc tc trn cht mang
Phn ng Xc tc
Phn hu axit foocmic
Hyr ho etylen
Hyr ho aldehit
Ni/Al
2
O
3
,

Ag/C
Ni/ZnO
Pd/C
62
Tng kt li nh sau [T40]:
1) Cc xit kim loi chuyn tip xc tc cc phn ng xi ho v ehyr ho.
2) Mt s xit c nhiu trng thi xi ho ni chung l xc tc xi ho tim nng .
3) Kim loi kim n nh trng thi xi ho cao, axit, trng thi xi ho thp.
4) Hot tnh v chn lc thng nghch nhau trong xi ho xc tc.
5) Cc xit kim loi c cu trc in t d
0
hoc d
10
c chn lc cao.
6) Hot tnh xc tc lin quan ti:
cng lin kt xi b mt
nhit hnh thnh xit kim loi
s nguyn t O trong oxit
kh nng c xi trong mng
7) Trong cc phn ng xi ho H
2
, CO, v hydrocarbon hot tnh xc tc lin quan n
nng lng lin kt xi b mt:
Co
3
O
4
> MnO
2
> NiO > CuO > Cr
2
O
3
> Fe
2
O
3
> ZnO > V
2
O
5
> TiO
2
> Sc
2
O
3
hiu r c ch phn ng xc tc tnh cht in t chung l khng . Cn phi xem xt
ng b vi cc yu t hnh hc b mt, s tng ng cu trc in t b mt v cht phn
ng ... V vy y v mt l lun cn nhiu vic lm.
63
5.3.3.4 Cht cch in: Xc tc axit v xc tc baz [T24, T39, T41]
Xc tc nhm ny t ph bin hn, kh nng tham gia phn ng xi ho kh km, t nht l
nhit thp. xit rn kh ca cc nguyn t chu k ba Na
2
O, MgO, Al
2
O
3
, SiO
2
v
P2O5 l cc cht cch in, chng c tnh cht t baz ti lng tnh v axit. Cc xit ca
cc nguyn t ca cc chu k khc cng tng t.
Do rt kh lin h tnh xc tc vi tnh cht in t, nht l trng hp cc cht cch in,
khi ta phi s dng cc tnh cht khc. Trong trng hp ny tnh axit/baz l ph hp.
Cc cht cch in nh Al
2
O
3
, aluminosilicat, SiO
2
/MgO, silicagel, phosphat dng AlPO
4
,
v cc loi st hot tnh l nhng xc tc thng gp. Tt c cc cht rn ny u c cc
tm axit b mt.
Mt nhm xc tc axit rt hot ng v ph bin l aluminosilicat tinh th l zeolit l xc
tc ch lc trong cng nghip lc du. Ngc li, xc tc baz rn c rt t ng dng. Cc
xc tc A/B bit c lit k trong Bng 5.27.
Bng 5.27 Phn loi xc tc A/B d th [T41]
Xc tc axit rn Xc tc baz
1. Oxit nh Al
2
O
3
, SiO
2
, TeO
2
2. Oxit hn hp nh Al
2
O
3
/SiO
2
, MgO/SiO
2
,
ZrO
2
/SiO
2
, cc heteropolyaxit
3. Cc axit khong (H
3
PO
4
, H
2
SO
4
) trn cht
mang rn xp
4. Cc cht trao i cation
5. Cc mui ca cc axit cha O; cc phosphat
kim loi nng, cc sulfat, tungstat
6. Halogenua ca cc kim loi ho tr ba (v d:
AlCl
3
) trn cht mang xp
7. Cc zeolit ( dng H)
8. Cc siu axit: ZrO
2
hoc TiO
2
tm H
2
SO
4
1. Oxit, hyroxit, v amit cc kim loi kimm
v kim th (k c cht mang)
2. Cc cht trao i anion
3. Cc mui kim loi kim, kim th vi cc
axit yu nh cacbonat, carbua, nitrua, silicat
v.v...)
4. Cc siu baz: MgO pha Na
Tnh axit b mt
Cc xc tc axit rn ng vai tr quan trng trong cng nghip. l cc phn ng
dehyrat ho alcol, hyrat ho olefin, cc qu trnh, v polymer ho olefin. Sau y ta xem
xt bn cht cc tm axit trn b mt rn.
C hai loi tm axit: (1) tm Brnsted (protic proton) v (2) tm Lewis (nonprotic
khng proton). Cc tm Brnsted s cho proton b mt, cn tm Lewis nhn cp in t,
ngha l lin kt vi cc ht nucleophil.
Xt v d v vai tr ca cc tm Brnsted v Lewis trn c s nhm oxit Al
2
O
3
. Nhm oxit
cha cc phn t H
2
O lin kt, lng nc lin kt ph thuc vo nhit . Oxit nhm mi
kt ta cha y nc b mt nhit di 100
o
C. Khi cc nhm OH c kh nng
phn li v ng vai tr tm Brnsted. nhit trn 150
o
C cc nhm OH bt u mt
nc do phn ng:
64
OH + OH H
2
O + O
Phn ng ehydroxyl ho ko mt s nguyn t Al t lp cn b mt ln, y chnh l cc
tm axit Lewis. 400
o
C cc xit nhm b mt khi ehydroxyl ho s th hin tnh axit
Lewis nh cc l trng phi tr (ion Al
3+
), khi cc ion O
2-
ng vai tr tm baz Lewis.
Nh vy b mt xit nhm s c c tm Brnsted ln tm Lewis (H.5.32).
Hnh 5.32 Cc tm axit trn b mt xit nhm Al
2
O
3
nhit trn 900
o
C Al
2
O
3
mt hon ton cc nhm OH b mt, khi n ch c tnh
axit baz Lewis.
Trong thc t ngi ta chng minh c rng cc tm axit Brnsted ng vai tr quan
trng trong cc phn ng polymer ho olefin, cracking cumen, v phn ng bt i ho
(disproportionation) toluen thnh benzen v xylen. Cn tm axit Lewis c cho l ng
vai tr chnh trong phn ng phn hu isobutan [32].
Tnh axit baz rn v c bn tng t axit baz trong pha lng. V vy phng trnh
Brnsted vn p dng y. So vi pha lng, phn taxit b mt khng phn li, phng
trnh Brnsted c dng:
lg k = lg a + H
o
(5.62)
trong k l hng s tc phn ng xc tc, l mc chuyn proton ( <1), a l
hng s cho mi loi phn ng, H
o
l hm logarit nng axit Hammett, - y l thc o
kh nng cho proton.
Hm axit H
o
cho ta thng tin v cc tm axit b mt. nh lng n ngi ta dng
phng php chun bng baz vi cc ch th chuyn dng, t gi tr H
o
c th so snh
mnh yu vi axit sulfuric.
Phng cch u tin c ngh n c trng tnh axit (nh tnh v nh lng cc
tm axit) l s dng cc baz chun . V bn cht, phng php ny khng c g khc
vi phng php chun axit baz thng thng, ngha l chun axit bng baz vi
s c mt cht ch th c kh nng thay i mu khi mi trng chuyn t axit sang baz.
C th quan st s i mu ca cht ch th bng mt thng hay bng quang k.
Lc axit c th c xc nh bng kh nng ca axit cho proton trung ho mt baz:
BH
+
B + H
+

65
Ta c cn bng:

+
+
BH
B
H
a
a
a a
K

trong ,
i
a
l hot ca cu t i,- khi

+ +
+
BH BH
B B
H
a
C f
C f
a K
trong , f
i
l h s hot ca cu t i.
Theo nh ngha,

,
_

+ +
+
BH BH
B B
H
a a
C f
C f
a K pK log log
v

+ +
+

,
_

BH
B
BH
B
H
a
C
C
f
f
a pK log log
S hng u ca biu thc trn y c gi l hm axit v c Hammett t tn l hm
H
o
Hm Hammett:

,
_

+
+
BH
B
H
o
f
f
a H log
Hm H
o
khng ch ph thuc vo kh nng cho proton ca dung dch m cn ph thuc vo
bn cht ca baz B na. Hammet s dng cc baz, v d, n-butylamin, lm cho t
s f
B
/f
BH
+
gn nh khng i v nhn c nhng s liu t tng thch cho mt dy cc
tm axit c lc khc nhau ng vi cc baz c lc khc nhau, ngha l i mu nhng
mi trng khc nhau hay l i mu cc cht ch th khc nhau. Theo nh ngha trn y,
trong dung dch long ga tr ca H
o
xp x bng gi tr ca pH; axit cng cao th gi tr
ca hm Hammett cng m. V d, trong mi trng HClO
4
hoc H
2
SO
4
m c hm
Hammett c gi tr 10.
Cc cht ch th Hammett ch cho php xc nh axit chung, v chng tc dng vi c
cc tm Bronsted v tm Lewis, cn xc nh cc tm Bronsted phi s dng cc cht
ch th dnh ring cho tng tc vi proton (ch th Hirschler k hiu l H
R
) l cc
arylmetanol. Tm axit lm chuyn mu cht ch th c pK
a
cng nh th lc ca n cng
mnh. Nh vy, bng phng php chun c th xc nh c mt dy cc tm axit c
mnh khc nhau nu chng tn ti trn b mt. Cn lng baz n-butylamin tiu hao,
tnh bng mili ng lng cho mi gam cht xc tc (meq/g), l nng ca cc tm axit
c lc tng ng. S chun c tin hnh trong dung mi hu c, v d, benzen.
66
Trc khi tin hnh chun , cht xc tc c to ht vi kch thc 0,5 1,2 mm v
c x l chn khng nhit 500
o
C. Di y l bng m t mt s cht ch th
thng c s dng.
Phng php chun , d c tin hnh trn cc mu cht rn c x l trong iu
kin chn khng v nhit cao, qu trnh chun vn ch c tin hnh nhit
thng trong mi trng kh tr (v d trong bung cha kh nit), cho nn c th coi cc
s liu thc nghim nh vy khng tng hp vi iu kin tin hnh phn ng xc tc.
khc phc nhc im ny phng php hp ph cc baz, nh amoniac, pyriin, quinolin
hoc trimetylamin, c p dng trong vic xc nh s lng v lc cc tm axit trn
b mt cht xc tc. Tu theo bn cht ca baz c s dng m k thut thc nghim
ca phng php phi c tin hnh mt cch thch hp.
Cht ch th Mu ca dng baz Mu ca dng axit pK
a
Ch th H
o
Metyl Vng +4,8
p-imetylaminoazo- Vng +3,3
benzen
Benzalaxetophenon Khng mu Vng -5,6
Antraquinon Khng mu Vng -8,2
Ch th H
R
Triphenylmetanol Khng mu Vng -6,6
iphenylmetanol Khng mu Vng -13,3
Amnic thng c s dng xc nh axit ca cc cht xc tc (aluminosilicat v
nh hnh v zeolit) bng cch cho amoniac hp ph sau gii hp cc nhit khc
nhau t thp ln cao. Phng php ny vi nhng quy trnh thao tc khc nhau, k c gii
hp theo chng trnh nhit (TPD), ngi ta c th xc nh khng nhng s lng cc
tm axit ng vi cc nhit gii hp khc nhau (tc cng l ng vi cc tm vi lc axit
khc nhau) m c nng lng gii hp amnic t cc tm axit c lc khc nhau.ph
Cc phng php nh lng axit khc c th l bt k, v d hp ph ho hc (nh
vi amnic va nu), khi ta thu c tng cc tm axit Brnsted v Lewis, cc baz
dng y l amonic, quinolin, pyridin. Ph hng ngoi cng c th dng nh lng
tm axit Brnsted. Khi cho pyridin (py) hp ph ln xc tc ta c th ng thi xc nh
c c hai loi tm axit: py ly H
+
ca tm Brnsted (Pt.5.63), to lin kt cho-nhn vi
tm Lewis (Pt.5.64). Hai hp cht b mt ny c bc sng c trng rt xa nhau nn d
phn bit.
67
Xt SiO
2
: so vi Al
2
O
3
, tm Lewis khng xut hin, l v cc nhm OH trn b mt
SiO
2
lin kt rt mnh, khi ta ch quan st c cc tm Brnsted, tuy nhin chng l
cc tm axit yu, xp x axit axetic.
Mt dng axit/baz rn hay gp l aluminosilicat: y l cc xc tc cracking ch lc
trong cng nghip. S hnh thnh aluminosilicat c th hnh dung nh sau. Gi thit ta c
mng khng gian ca xit silic ho tr bn, by gi thay nguyn t Si trong mng bng
nguyn t Al ho tr ba. Do ho tr (3+) ht Al dng nh ng vai tr ht m trong mng,
khi trung ho in tch m ny, ht Al cn mt in tch dng. Nu in tch ny l
H
+
, khi ta c axit mnh (Pt.5.65).
(5.65)
axit ca xc tc ny c xc nh bng phng php chun axit-baz bng cc
baz vi cc mnh khc nhau hoc o bng ph IR sau khi cho hp ph cc baz hu
c khi nh quinolin hoc amonic. Ph ESR cng l cng c tt kho st trng thi ca
cc cht b hp ph ny.
So vi Al
2
O
3
, aluminosilicat th hin tnh axit Brnsted mnh m hn, l do s phn li
ca cc phn t nc b mt (Pt.5.66).
(5.66)
Theo Pt.5.66, tm Al s hnh thnh lin kt th t nh cp in t ca anion hydroxit, khi
proton c th tng tc vi nguyn t O bn cnh, khi ta s c tm Brnsted mnh.
Ht Si
4+
v nguyn tc l dng hn Al
3+
s ko in t v lm yu lin kt OH, iu ny
s lm tng axit. Thc nghim cho thy axit s mnh nht khi Al thay th mt phn
Si ng vi hm lng Al
2
O
3
vo khong 30%. Tng t nh vy ta c bc tranh gii thch
s hp ph ho hc ca amonic trn cc tm Brnsted (Pt.5.67):
(5.67)
Tng t, c th gii thch hin tng axit Brnsted tng mnh khi cho aluminosilicat
hp ph HCl (Pt.5.68).
68
(5.68)
Bng 5.28 Hiu qu ca Al
2
O
3
vi axit khc nhau trong phn ng loi nc etanol [7]
axit
(*)
so snh 175
o
C SiO
2
, % Na
2
O,% chuyn ho,%
chn lc
C(cok),
%
Etylen Ete
0,021
0,046
0,060
0,02
0,01
0,13
0,25
0,06
0,03
66,1
98,8
85,7
25,3
99,2
89,2
70,1
0,2
0,1
0,1
0,2
0,5
(*)
mmol NH
3
/g Al
2
O
3
Phn ng ehydrat ho - loi nc thng c thc hin trn xc tc axit rn, v d phn
ng loi nc ca cc alcool thnh eter v xeton. Xc tc tt cho phn ng loi ny l
Al
2
O
3
bin tnh c axit khc nhau (Bng 5.28).
Cc xit nhm thng mi thng cha tp cht, thng gp nht l SiO
2
and Na
2
O. Cc
tp cht ny nhy cm i vi chn lc v hiu sut i vi etylen. C ch phn ng
bao gm s tham gia ca c hai loi tm axit v baz (H.5.33).
Hnh 5-33 C ch phn ng ehyrat ho etanol trn nhm oxit
Trong trng hp ny tp cht SiO
2
tng axit, Na
2
O tng baz.
axit so snh c nh gi bng phng php hp ph amonic. S c mt ca
SiO
2
hoc Na
2
O lm thay i cn bng gia cc tm axit Brnsted, gia cc tm axit
baz Lewis. Xc tc c axit trung bnh c hot tnh cng nh chn lc theo etylen
cao nht. Xc tc c hm lng Na
2
O cao s tt hn cho phn ng to eter.
Mt vn trong xc tc cng nghip l s to thnh cok, trong nhiu trng hp s che
ph tm hot ng, gim hot tnh xc tc. Thng thng, xc tc giu SiO
2
hn ( axits
cao hn) s to cok mnh hn. l do phn ng to cation carbenium mnh hn, khi
chng s ghp i-polymer ho v to cc lp cok bm ln b mt, khi hot tnh
cng nh chn lc ca xc tc u gim.
Ngi ta cng chng minh c rng cc tm Brnsted trung bnh l tc nhn chnh ca
phn ng ehydrat ho ion, cn tm axit Lewis do Al
3+
khng tham gia phn ng. Bng
chng l khi u c xc tc bng mt lng nh baz, v d NH
3
hoc pyridin cng
khng c ch phn ng. gii thch s hnh thnh eter trn Al
2
O
3
ngi ta s dng c
69
ch LangmuirHinshelwood, khi hai phn t alcol s hp ph trn hai tm cnh nhau v
hnh thnh hai phn t hp ph cnh nhau, v d mt to alkoxit OC
2
H
5
v phn t th
th hai to lin kt hyr, sau chng s tng tc vi nhau.
(5.69)
Tng t nh vy, s hp ph ho hc ca olefin trn aluminosilicat cng c thc hin
theo c ch ny (Pt.5.33). Theo Pt.5.69, phn t olefin ng thi hp ph trn hai tm
axit/baz, l nhm hydroxyl b mt v O trong mng, l nh s tng ng hnh hc.
Xc tc axit trn c s aluminosilicat l xc tc quan trng trong cng nghip, trong cng
nghip lc du y l xc tc cracking ch lc. Phn ng bt u bng tng tc gia cc
tm axit Brnsted vi alken, khi H
+
s gn vo lin kt C=C hnh thnh carbenium
ion trng thi hp ph ho hc (Pt.5.70).
(5.70)
Khi mch hydrocarbon di b b gy, iu ny s dn ti cc qu trnh ng phn ho,
polymer ho v alkyl ho v s hnh thnh cc hydrocarbon thm. Phn ng kiu ny cng
thng gp trong xc tc ng th khi s dng xc tc axit Lewis (BF
3
, AlCl
3
) thc y
trao i proton .
Trong nhiu phn ng ngi ta ghi nhn c s tng quan gia axit ca mt loi xc
tc no vi hot tnh xc tc. V d, trong phn ng polymer ho olefin s hnh thnh
cok ph thuc vo axit v tun theo dy sau [T40]:
SiO
2
/Al
2
O
3
> SiO
2
/MgO>SiO
2
>> -Al
2
O
3
> TiO
2
> ZrO
2
> MgAl
2
O
4
> UO
2
> CaO ~ MgO
axit
Bng 5.29 axit ca cc vt liu xit hn hp [T41]
Thnh phn A B [A], % B mt ring, m
2
/g axit, H
o
Al
2
O
3
SiO
2
ZrO
2
SiO
2
Ga
2
O
3
SiO
2
BeO SiO
2
MgO SiO
2
Y
2
O
3
SiO
2
La
2
O
3
SiO
2
94
88
92,5
85
70
92,5
92,5
270
448
90
110
450
118
80
8,2 (~H
2
SO
4
90%)
8,2 7,2
8,2 7,2
6,4
6,4
5,6 (~H
2
SO
4
71%)
5,6 3,2
70
Bng 5.30 Xc tc axit trong mt s phn ng (xp theo s tng axit) [T33]
Xc tc axit
ng phn ho n-pentan
(Pt/cht mang); T phn ng
(
o
C)
Polymer ho
propylen 200
o
C
Cracking n-heptan
(
o
C) v chuyn ho
10%
-Al
2
O
3
SiO
2
ZrO
2
TiO
2
Al
2
O
3
, S
r
nh
Al
2
O
3
, S
r
ln
Al
2
O
3
, clo ho
Al
2
O
3
/MgO
Heteropolyaxit
Al
2
O
3
flo ho
Aluminosilicat
Zeolit trao i ion
H
3
PO
4
/cht mang rn
AlCl3, HCl/Al
2
O
3

KH
KH
KH
KH
500
450
430
400
Khng bn
380
360
260
-
120
0
0
0
0
< 1
0 5
10 20
20 30
70 80
> 80
> 90
> 95
90 95
100
KH
KH
KH
KH
KH
490
475
460
Khng bn
420
410
350
Khng bn
100
Thc t cho thy axit s mnh ln khi xc tc cha hai xit c s phi tr khc nhau
hoc s xi ho khc nhau. Cc xc tc xit hn hp c ph hot tnh rng c lit k
trong Bng 5.29. axit c so snh vi cc axit khong thng thng. u im ca xc
tc axit rn l n nh nhit, khi ta c th p dng chng cc qu trnh i hi nhit
cao. Tng t vi phn ng ng phn ho, polymer ho, v cracking ngi ta cng
khng nh nh hng ca axit (Bng 5.30).
Xc tc baz rn [16]
Xc tc baz d th t gp hn, chng ch c vi ng dng cng nghip. Cc xc tc quan
trng nht l cc hp cht/xit kim loi kim v kim th. xit manh c nghin cu k
nht [35]. Trn b mt xit kim th nc b phn li rt nhanh to cc ion hyroxyl b
mt (Pt.5-71).
(5.71)
Cp ion trn b mt MgO cng c th thc hin qu trnh d li i vi HX tng t tm
axit Brnsted (Pt.5.72), axetylen, axetic axit, v alcol (Pt.5.73).
71
S d li i vi alcol dn ti ht RO v H
+
gii thch ti sao oxit kim loi kim th l xc
tc tt cho qu trnh eydr ho alcol. Xc tc ehyr ho th hin mnh hn khi nng
nhit , khi lc kim ca MgO tng. MgO trng thi kh ht nhm hyroxyl b mt
khi tng nhit l baz mnh n mc c th bt proton khi cc tm axit Brnsted yu.
Hin tng d li trn MgO cn c ghi nhn c i vi H
2
.
Trn xit kim th buten hp ph v chuyn thnh metylallylanion (CH
3
CH=CHCH
).
Carbanion ny l trng thi trung gian trong ng phn ho ni i ca buten. S hp
ph xy ra mnh hn trn CaO ( baz ln hn) so vi MgO. Khi hot ho CaO 700
900
o
C ta nhn c baz Lewis mnh nht, y l xc tc ti u trong phn ng ng
phn ho thnh 2-buten.
xit manh l dung mi tt cho cc ion kim loi chuyn tip 3d. V d, cc ion Co
2+
v
Ni
2+
phn tn rt tt trn MgO. Cc lin kt ng ho tr cationanion lm gim baz
ca xit, khi chng tr nn mm hn. Trong phn ng hyr ho CO, cc xc tc
Co/MgO, v Ni/MgO c hiu sut cao hn i vi cc sn phm C2 v C3 so vi Co, Ni
trn Al
2
O
3
. Trong phn ng ehyr ho alcol, ion Co
2+
cng tng chn lc.
Cc xit kim, kim th cng l xc tc tt cho phn ng ehydrohalogen ho cc alkyl
halogen nhit 100250
o
C. S loi b HHal xut pht t phn ng E2 rt chn lc. Ta
c dy chn lc trong phn ng tch loi trans sau:
SrO CaO > MgO > Al
2
O
3

Dy ny cng trng vi dy so snh baz ca cc oxit.
Trong mt vi trng hp cc xit MgO, CaO, v BaO hot ho nhit cao cn c
dng hyr ho cc alken v dien.
Phn ng benzaldehit trn xit hot ho to sn phm benzyl benzoat (Pt.5.74, phn ng
Tischchenko):
(5.74)
Dy xc tc xp theo hot tnh nh sau:
BaO >> SrO >> CaO > MgO
Xc tc baz c hot tnh cao nht l cc kim loi kim mang trn xit nhm. V d, xc
tc 5%Na/Al
2
O
3
chuyn ho hon ton 1-buten thnh 2-buten ngay 20
o
C. Cc olefin
mch di hn cng ng phn ho tt trn cc xc tc loi ny.
72
Trong s cc phn ng th phn ng ghp i metan rt c quan tm. Xc tc Li
2
CO
3
bin tnh bng MgO c hiu qu cao nht. chn lc theo etylen v etan t c kh
tt.
Mc d c mt s kh nng, song ng dng tht s trong cng nghip ch c vi qu trnh,
v d:
Trng ngng axeton thnh iaxeto alcol trn xc tc Ba(OH)
2
hoc Ca(OH)
2
trn
cht mang.
Bt i ho metylcyclopenten thnh metylcyclopentadien v metylcyclopentan trn
xc tc Na
imer ho propen thnh 2-metylpenten trn xc tc kim loi kim/cht mang
Alkyl ho mch nhnh ca toluen trn xc tc Na/Al
2
O
3
Polymer ho butadien trn xc tc Na
73
5.4 Tnh cht xc tc trong thc t
5.4.1 Cc yu t nh hng n cc tnh cht xc tc
Xc tc l mt i tng a ngnh, nghin cu xc tc i hi kin sthc tng hp. Khi
ni n xc tc, u tin ngi ta ni n hot tnh. Hot tnh cao cho php gim dung
tch bn phn ng, gim thi gian phn ng, mm ho iu kin phn ng, tng nng
sut, gim gi thnh. Tnh cht th hai l chn lc. Trong nhiu trng hp chn lc
cn quan trng hn hot tnh. Th ba l thi gian lm vic ca xc tc hay cn gi l thi
gian sng. Khi cho xc tc vo bn phn ng, iu kin phn ng khc nghit n s mt
dn hai tnh cht quan trng nht l hot tnh v chn lc, khi phi thay xc tc hoc
hot ho li xc tc hay cn gi l ti sinh. R rng l thi gian sng ca xc tc cng cao
cng tt. Cui cng l kh nng ti sinh, m bo xc tc lm vic lu di n cn phi
ti sinh c v d dng ti sinh. Trong iu kin phn ng thc t, xc tc cn phi c
hnh dng, kch thc ht sao cho gim thiu nh hng ca yu t khuch tn. Tng kt
li cc tnh cht quan trng nht ca xc tc ta c Hnh 5.34.
Hnh 5-34 Cc tnh cht quan trng nht ca xc tc cng nghip
Xc tc c nghin cu, sn xut nhm phc v mt qu trnh c th, ngha l mt phn
ng no trong mt thit b phn ng vi cu hnh bit trc, iu kin phn ng d bo
c. V vy, chng phi p ng ng thi nhiu iu kin:
Hot tnh/n v th tch phn ng cao
chn lc i vi sn phm nh cao
bn i vi cc tc nhn lm gim hot tnh
Ti sinh c v ti sinh d dng
Cht lng n nh t m ny n m khc
THI GIAN
SNG
N NH
HH, C HC
NHIT
HNH DNG
KCH THC
CHN LC
HOT TNH
XC TC
D TH
XC TC
D TH
THI GIAN
SNG
N NH
HH, C HC
NHIT
HNH DNG
KCH THC
CHN LC
HOT TNH
XC TC
D TH
XC TC
D TH
74
Bn trong mi trng phn ng: nhit (gy nt, bit dng), dng kh (gy mi
mn), hi hoc H
2
O (sn phm hay mi trng phn ng)
Bn c hc: chu nn (vi xc tc trong ct); chu co dn (do thay i nhit )
Hiu qu xc tc ph thuc vo nhiu yu t nh:
Pha hot ng (bn cht: kim loi, oxit; dng tinh th, hnh thi hc )
Cht mang (bn cht, cu trc xp, kh nng tng tc, to phc )
Mi trng phn ng (dung mi, cc cht tan trong dung mi, pH ...)
Cc cht cho thm bin tnh (v c, hu c, to phc)
Cht c ch
hiu r xc tc cn c hiu bit y v cu to xc tc, c v mt ho hc ln kha
cnh vt l. Nh nu tnh cht ca xc tc c th thay i c thng qua thay i cc
yu t thnh phn, b mt ... tu yu cu t ra.
5.4.2 Xc tc trn cht mang [T32, T35]
y l nhm xc tc c khi lng ln nht, c bit trong hai ngnh tiu th nhiu nht l
lc-ho du v cng nghip ho cht.
Xc tc trn cht mang l loi xc tc m pha hot ng (quyt nh tnh xc tc, nh kim
loi, xit, thng chim phn nh, thm ch rt nh (khi xc tc l kim loi qu)) c gn
ln nn vt liu rn, xp, thng c b mt pht trin, thng l tr trong mi trng phn
ng. Cc vt liu mang thng c sn xut di dng vin, mnh, xuyn, tr, cu.
Cc cht mang thng gp nht l Al
2
O
3
, SiO
2
, MgO, TiO
2
, ZrO
2
, aluminosilicat, zeolit,
than hot tnh, v gm. Bng 5.31 cho danh mc cc cht mang thng gp.
Bng 5.31 Cc cht mang xc tc cng nghip, tnh cht v ng dng
Cht mang Din tch b mt ring, m
2
/g ng dng
xit nhm
- Al2O3
- Al2O3
-
Aluminosilicat
Silica, SiO2
Titania, TiO2
Than hot tnh
Gm corund
iatomit
160 300
5 10
180
200 1000
40 200
600 1200
0,5 1
200
Cracking, hyr ho, ehyr ho, metathesis
Hyr ho chn lc axetylen, xy ho chn lc
(etylen xit)
Cracking, ehyrat ho, isome ho, amni-oxi
ho
Polyme ho, hyr ho, xi ho, kh NOx (qu
trnh SCR)
TiO2/SiO2 xi ho xylen -> anhyric phtalic,
V2O5/TiO2 xi ho chn lc
Vinyl ho axetylen, hyr ho chn lc (kloi
qu, tng hp hu c tinh vi)
xi ho chn lc (etylen oxit, anhyric maleic t
benzen, phtalic t o-xylen )
Hyr ho
75
t st
Zeolit
Monolit tm cordierit
50 300
300 600

Hyr ho, trng ngng
Lc du, xc tc hai chc, xc tc tng hp huc
c
Xc tc kh thi t, vt liu mang cu trc
Vai tr ca cht mang:
H gi thnh: Pha xc tc nhiu khi l kim loi qu, t (nhm Pt), tn dng b
mt cn phn tn chng trn vt liu c b mt ln. Khi chng chim t trong rt
nh trong khi xc tc. V d, xc tc hyr ho cc aromat rt tt l Rh, Re v Ru
thng ch c vi ti 0,5% khi lng trn cht mang Al2O3 hoc than hot tnh.
Tng hot tnh: Nh phn tn cao xc tc c hot tnh cao, khi xc tc s
cho php thc hin phn ng iu kin t khc nghit hn, thit b nh hn, em
li nng sut cao hn, h gi thnh sn phm cng nh u t.
Tng chn lc: tng hiu sut, gim pht thi, gim chi ph tinh ch, gim tiu
hao nguyn liu, nng lng.
Tng kh nng ti hot ho: ko di tui th xc tc, gim chi ph xc tc.
t c tt c cc mc tiu trn, sau khi xc nh c thnh phn pha xc tc ph
hp, cn la chn c vt liu mang ti u. Vt liu mang ti u l vt liu p ng cc
yu cu ca qu trnh p dng, c v mt ho hc ln v mt vt l (Bng 5-32).
Chc nng ca cht mang:
C nh pha xc tc
Phn tn pha xc tc
n nh pha xc tc
Tng din tch b mt xc tc
Bng 5-32 La chn cht mang xc tc [T40]
Cc yu cu v mt vt l Cc yu cu v mt ho hoc
B mt ring ln (hot tnh, phn b pha xtc)
xp (chuyn khi, truyn nhit)
Hnh dng v kch thc ht (khuych tn trong,
gim tn tht p)
n nh c hc (mi mn, va p)
n nh nhit (tng bn xc tc, tng kh nng
ti sinh)
T khi (t l pha hot tnh/th tch phn ng)
Pha long tc ng nhit do phn ng
Tng kh nng tch (xc tc bt)
Hot tnh ring (tnh nhit pht ra)
Tng tc vi pha xc tc ( chn lc, xc tc
hai chc)
n nh hot tnh xc tc (chng thiu kt, u
c)
Tr i vi dung mi, cht phn ng
76
Chc nng chnh ca cht mang l tng din tch pha xc tc hot ng. Nhn chung hot
tnh xc tc d th tng khi tng din tch b mt pha xc tc, tuy nhin khng phi lc no
cng gp quan h tng tuyn tnh, l do cn s ph thuc vo cu trc pha b mt. Mt
khc, chn lc thng gim khi b mt tng. Quy tc chung l, cc xc tc hot ho
hyr (hyr ho, hyr ho kh sulfua, hyr ho kh nit) i hi cht mang c b mt
ln, cn xc tc xi ho chn lc (v, d epoxi ho olefin) yu cu b mt thp hn ch
cc phn ng ph.
Chn c cht mang ph hp vi xc tc v phn ng c th l rt quan trng v trong
nhiu trng hp cht mang nh hng mnh n hot tnh cng nh chn lc ca xc
tc. Bn cht phn ng s quyt nh la chn cht mang.
Nu ta chn cht c b mt ln, v d, than hot tnh lm cht mang, khi pha xc tc
kim loi s tn ti trn b mt cht mang di dng cc tinh th nh c lp nhau, b dy
ca cc tinh th ny ch vi nguyn t, khi b mt tip xc s rt ln.
Trong cc phn ng theo m pha lng thng dng xc tc dng bt, cn phn ng trong
pha kh, hoc pha lng nhng trong thit b chy lin tc (kiu lc nh git) thng dng
xc tc dng vin, hoc khi rng.
H l xp ca cht mang cng ng vai tr ln, l v n s nh hng n qu trnh vn
chuyn cht phn ng (hoc sn phm) do khuch tn vo (v ra) cc l ti (v ri) cc
tm hot ng. Ngoi ra, kch thc l xp cng quyt nh kh nng s dng b mt c
nh cc tm hot ng.
p ng cc i hi rt khc nhau ca thc t ng dng, cc vt liu mang xc tc
thng mi, v d nh alumina, than hot thng c nhiu loi, p ng khong rng v
kch thc ht, din tch b mt ring cng nh phn b l xp rt khc nhau.
chn cht mang cn lm r iu kin phn ng. u tin phi bit phn ng xy ra
trong dung mi no, trc ht cht mang phi bn, tr i vi dung mi trong iu kin
phn ng. Tu vo yu cu ca phn ng, xc tc c th mang t (v d, 0,3%Pt/Al
2
O
3
,
15%Ni/Al
2
O
3
) hoc nhiu pha xc tc (v d, 70%Ni/Al
2
O
3
, Fe/Al
2
O
3
).
Trong xc tc trn cht mang, khng phi lc no cht mang cng m bo s phn tn
xc tc tt; s phn tn ngoi yu t b mt cn ph thuc vo hng lot cc yu t ho l
quyt nh tng tc pha xc tc - cht mang khc nh:
Cc hiu ng in t: in t c th trao i to lin kt ho hc
Cc lc hp ph (v d: lc van der Waal)
S hnh thnh trng thi kh ca cht mang trn b mt
S hnh thnh cc pha mi trn b mt
Cc hiu ng in t nu trong mc 5.3.3; iu ny ph thuc nhiu vo tnh cht bn
dn loi n hay loi p ca vt liu mang. Tng tc vi cht mang c th lm yu kh nng
hot ho ca v suy ra hiu qu ca xc tc, tuy nhin li gim s dch chuyn v co cm
77
ca pha xc tc. Trong nhng nm cui, cc nh hng do tng tc mnh gia pha xc
tc kim loi v cht mang (strong metalsupport interaction = SMSI) ngy cng c quan
tm [18]. u tin, nm 1978 khi nim ny c dng gii thch hin tng hp ph
ho hc ca H
2
v CO trn xc tc kim loi nhm Pt trn cht mang TiO
2
. Khi xc tc ny
c a vo mi trng kh nhit cao vi H
2
(400
o
C), sau s thy hp ph H
2
,
CO, v NO gim mnh. Hiu ng ny cng thy trong cc phn ng tng hp hu c: cc
kim loi nhm platin mang trn TiO
2
thay i mnh hot tnh v chn lc trong phn
ng hyr ho CO. Sau y l mt s v d thc t v vai tr ca SMSI:
Cc qu trnh hyr ho l lnh vc ng dng c in nht v rng ri nht ca xc tc trn
cht mang. Cc kim loi xc tc thng dng l Co, Cu, Ni, Pd, Pt, Re, Rh, Ru, v Ag.
Tuy nhin cng c mt s xc tc c hiu. Phn ln cc xc tc l kim loi phn tn rt
mn trn cc cht mang nh than hot tnh, Al
2
O
3
, aluminosilicat, zeolit, kieselguhr, hoc
cc mui tr nh BaSO
4
[22]. V d xc tc hyr ho chn lc clonitrobenzen (Pt.5.75).
(5.75)
Thng thng, hyr ho cc hp cht nitro ngi ta dng xc tc palladi, tuy nhin Pd
cng xc tc rt tt phn ng kh hyrclo, iu ny dn ti s hnh thnh anilin. tng
chn lc theo hng (5.75) cn xc tc Pt/C c chn lc cao theo hng to o-
cloanilin m khng nh hng ti tc hyr ho.
Trong phn ng ehyr ho cc ng ng ca xyclohexanon (Pt.5.76) thng dng xc
tc Pd/than hot tnh. Khi tng trt t ca pha kim loi, xc tc tng phn tn v v
vy tng bn nhit. Khi nhit tng xy ra qu trnh co cm cc ht xc tc, tng kch
thc ht lm gim hot tnh xc tc.
(5.76)
Trong phn ng hyr phn etan thng dng xc tc Ni trn cht mang. y l xc tc
c dng chng minh mi quan h gia phn tn ca pha xc tc (din tch b mt
ring ca cht mang) vi hot tnh xc tc (Bng 5.33). Trn thc t Ni phn tn trn SiO2
tt hn trn Al2O3, ng thi cng nh hng n dng tinh th Ni. Ngoi ra cn lu
n nh hng ca cc tm axit trn nhm xit, cc tm ny dn n s hnh thnh lp ph
do cc ho mnh hn dn ti gim hot tnh xc tc.
Bng 5.33 Hyr phn trn xc tc Ni trn cc cht mang khc nhau (10% Ni) [T35]
Xc tc Tc , mol m
-2
h
-1
.10
6
SiO2
Al2O3
151
57
78
SiO2/Al2O3 7
Phn ng ehyr ho xyclohexan thnh benzen li chu nh hng ca cc yu t in t
(Bng 5.34). Khi i t TiO
2
ti SiO
2
hot tnh xc tc gim dn, iu ny c quy cho s
gim yu t bn dn loi n ca vt liu mang xc tc. Thng thng xit bn dn loi n
yu l cc cht mang tt nht cho phn ng ny. y, cht bn dn loi n mnh nh ZnO,
mc d c mt in t cao hn TiO
2
li hon ton khng c hot tnh.
Bng 5.34 ehyr ho xyclohexan thnh benzen trn xt Pt/cht mang 773K [T28]
Xc tc Benzen, %
Pt/ZnO
Pt/TiO
2
Pt/Al
2
O
3
Pt/MgO
Pt/SiO
2
-
76,1
59,8
32,3
23,1
Phn ng rt quan trng l hyr ho CO c nghin cu kh nhiu. Sau y l mt s
kt qu, tuy nhin chng i khi mu thun [T28]. i vi phn ng tng hp metanol xc
tc Pd trn La2O3, MgO v ZnO c hot tnh v chn lc cao, tuy nhin cng Pd trn
cht mang l TiO
2
v ZrO
2
li thin v phn ng to metan (Bng 5.35). Nu cht mang c
tnh axit, v d Al2O3 xc tc s c thin hng to dimetyl eter. Tuy nhin trong nghin
cu ny tc gi khng cp n nh hng ca phn tn pha xc tc.
Bng 5.35 Hy ho CO trn xc tc Pd vi cc cht mang khc nhau [T28]
Xc tc
chn lc, %
CH
3
OH H
3
COCH
3
CH
4
C
2+
Pd bt
Pd/MgO
Pd/ZnO
Pd/Al
2
O
3
Pd/La
2
O
3
Pd/SiO
2
Pd/TiO
2
Pd/ZrO
2
75,0
98,4
99,8
33,2
99,0
91,6
44,1
74,7
0
1,2
0
62,7
0
0
8,6
0,5
8,8
0,3
0,1
3,3
0,5
1,5
42,1
22,3
16,2
0,2
0,2
0,8
0,5
0,2
5,2
2,5
Bng 5.36 Hot tnh tng i ca Rh trn cc xit trong phn ng hyr ho CO[T28]
Cht mang Hot tnh tng i
TiO
2
MgO
Al
2
O
3
CeO
2
SiO
2
100
10
5
3
1
79
Phn ng hyr ho CO cng chu nh hng ca thnh phn cht mang v phn tn
pha xc tc kim loi. Chng hn, vi cc kim loi nhm cc Nhm 810, phn tn km
s thun li cho phn ng hnh thnh hyrocarbon, phn tn cao s thun li cho s
hnh thnh cc hp cht hu c cha xi. Hot tnh so snh trong phn ng hyr ho CO
ca xc tc Rh trn cc loi cht mang c tng kt trong bng 5.36. Cc kt qu ny ph
hp vi kt qu nghin cu hp ph ho hc H
2
trn cc tm Rh.
Mt nghin cu khc v Rh cho thy, trng thi xi ho ca Rh ph thuc vo cc dng
hp ph ho hc ca CO v iu ny lin quan n phn b cc dng sn phm (phn ng
gia CO v H
2
thng dn n hai nhm sn phm nh Pt.5.77):
Rh/xit
CO + H
2
HC cha O + HC (5.57)
Nu hp ph ho hc dn ti phn li CO th sn phm s l hydrocarbon, nu hp ph
khng phn li th dn ti sn phm l cc hp cht cha xi, v d alcol (Bng 5.37).
Bng 5.37 nh hng ca cht mang n sn phm hyr ho CO trn Rh [T22]
Xc tc Pha hot ng Dng hp ph CO Sn phm
Rh/SiO
2
Rh/ZrO
2
Rh/ZnO
Rh/La
2
O
3
Rh(0)
Rh(0)
Rh(1)
Rh(1)
Phn li
Phn li/
Khng phn li
Khng phn li
CH
x
42% etanol
12% metanol
32% metan
94% metanol
Vi xc tc Cu/cht mang, s khc bit v hot tnh trong phn ng hyr ho CO (Bng
5.38) c gii thch bng hiu ng in t quyt nh tng tc ca Cu vi cht mang
[13]. Vi cc xit bn dn loi p nh Cr2O3 v ZrO2, y l cc xit c work functions
ln hn Cu kim loi, hot tnh xc tc s ln hn hot tnh ca Cu kim loi. l do khi
in t s chy t cht mang v cc ht xc tc Cu. Vi cht mang l cht cch in
nh SiO2 v Al2O3, hot tnh xc tc s xp x hot tnh ca Cu kim loiv khng c s b
xung in t. Trong trng hp cht mang l cc xit l bn dn loi n, in t s chy t
cc ht xc tc v cht mang, y l cc trng hp TiO2 v MgO, khi hot tnh xc tc
s km so vi hot tnh ca Cu kim loi.
Bng 5.38 Xc tc Cu trn cc loi xit trong phn ng hyr ho CO [13]
Xc tc
Work function ca
cht mangm eV
TON.10
3
theo CO
a)
Loi bn dn
(cht mang)
5%Cu/ZrO
2
5%Cu/Cr
2
O
3
5%Cu/graphit
5%Cu/ZnO
20%Cu/Al
2
O
3
20%Cu/SiO
2
5,0
5,8
4,8
4,6
-
-
0,41
0,24
0,04
0,03
0,01
P
p
n ( kim)
n
cht cch in
cht cch in
80
5%Cu/TiO
2
5%Cu/MgO
Cu kim loi
3,0
3,5
4,55
0,02
0,01
0,01
0,02
n
n
kim loi
a) TON = mol CO/nguyn t kim loi b mt_s; H2/CO = 3; tc dng 60 mL/min, p sut
thng, 275
o
C; c ht ca pha xc tc nh nhau.
Cht mang dn ti tnh a chc:
V d v kh nng cht mang b xung chc nng cho xc tc l xc tc Pt/Al
2
O
3
. Pt xc tc
cho phn ng ehyr ho napten to cc hp cht vng thm (aromat), khng xc tc
cho phn ng isomer ho hoc vng ho n-alkan. Tuy nhin khi mang ln Al2O3 c tnh
axit n s c c hai chc nng, v d phn ng reforming n-hexan nh s 5.5 [T20]:
S 5.5 Phn ng reforming n-hexan trn xc tc Pt/Al
2
O
3
Bn thn Pt cng nh Al
2
O
3
khng isomer ho alkan. Tuy nhin, cc tm axit ca Al
2
O
3
c
th isomer ho n-alken, sau s hyr ho thnh isoalkan nh Pt. hot ho xc tc
ngi ta b xung clo t c axit theo yu cu.
Hiu ng SMSI [18]:
Trong phn ng hyr ho CO trn xc tc Pt/TiO
2
, khi thc hin qu trnh kh nhit
cao TON tng 100 ln. Khi nghin cu hp ph ho hc, c hai cht u l CO v H
2
u
gim kh nng hp ph trn xc tc kh nhit cao, mc d khng ghi nhn c s
co cm cc ht xc tc do nhit . Tuy nhin, ghi nhn c s kh mt phn cht
mang thnh TiOx, v cc ht cht b kh ny ph ln mt phn b mt Pt. iu c bit
l mc d hot tnh tng nhng nng lng hot ho o c cng tng thay v gim [37].
Phn ng hyr ho axeton thnh isopropanol:
Phn ng hyr ho axeton thnh isopropanol l phn ng mu nghin cu qu trnh
hyr ho xeton (Pt.5.78):
(5.78)
Cc php o ng hc trn xc tc Pt vi ht khc nhau cho thy kch thc ht Pt
khng nh hng n hot tnh xc tc. Trn cht mang tr SiO
2
gi tr TON gn nh l
constant trong khong kch thc ht Pt = 21000 nm; iu ny c ngha phn ng thuc
81
loi khng nhy cu trc. Trn cht mang TiO
2
, gi tr TON tng ti 500 ln sau khi kh
nhit cao (Bng 5.39).
Bng 5.39 Hiu ng SMSI trong phn ng hyr ho axeton thnh isopropanol trn xc tc Pt vi
cc cht mang khc nhau [37]
Xc tc TON.10
2
, s
-1
E
a
, kJ/mol
Pt/SiO
2
Pt/ -Al
2
O
3
Pt/TiO
2
(LTR)
Pt/TiO
2
(HTR)
~ 1,1
2,4
~ 2,8
~ 565
67 t 2,5
78
67 t 2,9
67 t 8,3
iu kin phn ng: 303K, 0,1 MPa, H2 /axeton = 3,06; LTR = kh nhit thp, HTR = kh
nhit cao.
Phn ng ny c cho l tun theo c ch LangmuirHinshelwood, theo c hp ph
cnh tranh gia phn t axeton v nguyn t hyr, trong hp ph axeton l ch yu.
Hiu ng SMSI c gii thch l do nguyn t O ca nhm carbonyl c hot ho mnh
hn trong trng hp xc tc Pt n thun. Trong trng hp kh TiO
2
nhit cao,
nguyn t xi hp ph c bit mnh trn cc tm Ti
3+
mi kh ph trn ht Pt (H.5.35).
Hnh 5.35 M hnh hyr ho axeton trn Pt/TiO
2
v hiu ng SMSI [37]
Hiu ng SMSI cng ghi nhn c trong phn ng hyr ho crotonaldehit, trong
trng hp ny chn lc thay i rt mnh. Vi cc xc tc Pt/SiO
2
v Pt/Al
2
O
3
phn
ng dn ti sn phm l butyraldehit hoc butanol tng ng; trong khi vi xc tc
Pt/TiO
2
chn lc theo crotyl alcol khng no t ti 37%.
Mt v d khc l phn ng reforming metan vi CO
2
to hn hp kh tng hp
(Pt.5.79). Phn ng ny ph hp tch tr nng lng mt tri di dng nng lng ho
hc [14].
CH
4
+ CO
2
2CO + 2H
2
(5.79)
Xc tc l Rh(0,2%), cht mang l gm c ch to di dng khi t ong xp, ph mt
lp Al
2
O
3
. C ch phn ng c coi l bao gm:
82
Al
2
O
3
nh tnh axit s xc tc qu trnh to cation CH
3
+
. nhit cao, xit nhm
s c tnh cht ca bn dn loi n.
Khi CO
2
hp ph n s nhn in t t bn dn loi n, ng thi s cho in t i
vi bn dn loi p (tnh lng tnh kiu Lewis).
Kim loi c mang ln bn dn loi n s nhn in t v mt in t trn n
tng.
Hiu ng SMSI tng lin kt kim loi - cht mang. Mi lin kt ny c th c tnh
ion dn ti cc tnh cht hnh hc s thay i.
T hp cc hin tng nu dn ti s bin i theo s 5.6. u tin metan hp ph
v phn li, mt H. Phn t CO
2
s phn ng vi mnh CH
3
+
bng hai cch: mt l t pha
kh, hoc l do phn t CO
2
b hp ph trn tm Rh bn cnh. Trong trng thi hp ph
in t s chy t cht mang bn dn loi n qua Rh ti cht phn ng v c nhn bi c
hai cht phn ng. Cc in t ca CO
2
tn cng mnh metan b kh H, ng thi CO s
hnh thnh. Cui cng H tch ra, gii hp v to H
2
.
S 5.6 Phn ng reforming metan vi CO
2
trn xc tc Rh/Al
2
O
3
[14]
Tng tc kim loi - cht mang cng c ghi nhn i vi cc xit phn nhm chnh nh
SiO
2
, Al
2
O
3
v MgO, nhng cht thng c coi l tr v mt ho hc. Tng tc kim
loi - cht mang mnh cng c thy vi hng loi kim loi nhm 810 v cht mang
carbon. Cc trng thi cacbua ca Pd, Ni v s chuyn ho carbon bc cc vi tinh th kim
loi c chng minh [18].
5.4.3 Cc cht xc tin [39]
Xc tin l nhng cht bn thn khng phi l xc tc nhng khi i vi cht xc tc n
lm tng hot tnh xc tc. Thng cht xc tin ch chim vi phn trm. Bn cht hin
tng xc tin cn cha c lm r. Hin nay c coi l c bn loi xc tin:
Xc tin cu trc tng chn lc nh thay i cu trc b mt theo hng u
tin phn ng mong mun. y l loi xc tin quan trng nht v n tc ng trc
tip n cc tng tc b mt xc tc.
Xc tin in t thay i tnh cht in t ca xc tc, t y s thay i i lc
xc tc vi cht phn ng.
83
Xc tin n nh t chc c nhim v n nh hnh thi b mt, ngn cn s tng
kch thc ht lm gim hot tnh xc tc, gim tc ng ca nhit d, tng n
nhit.
Xc tin chng c bo v xc tc khi tc ng tiu cc ca cc cht c c th
t nguyn liu cng nh l sn phm ca phn ng ph.
Xc tc c th ch c mt pha hot ng nhng vi cht xc tin. Thng thng pha hot
ng chim phn ln khi lng, thng l trn 75%. Bn thn cc xc tin c th c ng
thi hai hay hn kh nng nn phn loi xc tin khng nn tuyt i ho. Tuy khng phi
l xc tc song xc tin ng vai tr quan trng trong xc tc, chng thay i cc tnh cht
ca xc tc nh hot tnh, chn lc, bn. Tuy nhin phn ln cc loi xc tin vn
phi tm bng con ng thc nghim, nhiu khi mang tnh may ri, ch c s t cht xc
tin c d bo mt cch khoa hc. Sau y l v d mt s cht xc tin trong xc tc
cng nghip (Bng 5.40).
Bng 5.40 Cc v d v cc cht xc tin trong xc tc cng nghip [T41]
Xc tc (ng dng) Cht xc tin Chc nng
Al
2
O
3
(cht mang v xc tc) SiO
2
, ZrO
2
, P Tng n nh nhit
K
2
O Gim cok ho
HCl Tng axit
MgO n nh kch thc, hnh thi
SiO
2
/Al
2
O
3
(xc tc cracking, cht mang) Pt Tng xi ho CO
Pt/Al
2
O
3
(xc tc reforming) Re Gim hyr phn v thiu kt
MoO
3
/Al
2
O
3
(xc tc x l bng H
2
, HDS, HDN)) Ni, Co Tng hyr phn C-S v C-N
P, B Tng phn tn MoO
3
Ni/gm (chuyn ho hi nc) K
2
O Gim cok ho
Cu/ZnO/Al
2
O
3
(chuyn ho nhit thp) ZnO Gim thiu kt Cu
Fe
3
O
4
(tng hp amnic) K
2
O Cho e
-
, tng phn li N
2
Al
2
O
3
n nh cu trc
Ag (xc tc tng hp OE) Kim loi kim Tng chn lc, gim thiu kt,
n nh trng thi xi ho
Xc tin cu trc tc ng n hot tnh xc tc thng qua mt s c ch. Xt phn ng
thm vng ho alkan trn xc tc Pt, y l phn ng thc hin theo c ch phn li khng
chn lc dn ti s hnh thnh cok, ph gia Sn s gim hin tng ny. Hin tng ny
c quy cho hiu ng tp hp (ensemble effect) cc nguyn t Pt, hiu ng ny cng
c pht hin vi cc ph gia l hyroxit kim loi kim v kim th trn xc tc Rh trong
phn ng tng hp metanol t hn hp CO/H
2
v phn ng hyrformyl ho etylen. ghi
nhn c rng thng qua hiu ng tp hp cht cho thm che ph cc tm hot ng
chu trch nhim thc hin phn ng phn li CO to cok. C hai phn ng nu thc hin
trn cc tm l cc tp hp b mt nh, v vy cht xc tin lm tng hiu sut tng hp
metanol v phn ng cng CO vo alken.
84
Xc tin cng c th n nh nguyn t ca tm xc tc trng thi ho tr cn thit. V d
l tc dng ca clo i vi bc trong phn ng xi ho chn lc etylen to etylen oxit
(EO). Thay v b kh v Ag
o
ghi nhn c trng thi xit-clorua bc trn b mt. y
l phn ng gia nguyn t O c tnh electrophilic vi ni i C=C ca etylen giu in t.
Trong iu kin phn ng, Xc tin xezi n nh pha hot tnh ny di dng phc b mt
dng .
Mt v d na v xc tin n nh cu trc l vai tr ca Al
2
O
3
trong xc tc tng hp
amonic. Mt thi gian di ngi ta coi vai tr ca Al
2
O
3
l chng hin tng co cm cc
ht xc tc Fe trng thi kh, tuy nhin gn y pht hin ra l Al
2
O
3
tc ng tch
cc n s hnh thnh mt Fe(111) c hot tnh cao nht.
Xc tin in t c xem xt trn c s mt xc tin thng gp l K. K
2
O thng c
thm vo xc tc hyr ho CO v tng hp amonic. Bn thn K
+
l ht rt dng, khi c
mt cnh tm kim loi hot ng n ko in t v pha nguyn t kim loi v t y s
truyn cho cht b hp ph/phn ng. Bng cch ny s to iu kin lin kt N
2
vi xc
tc thng qua s trao i in t vi orbital * ca cht b hp ph. Hnh 5.36 m t qu
trnh hot ho nit trn xc tc Fe tng hp amnic.
Hnh 5-36 S tc ng ca K trong hp ph phn li N
2
trn xc tc Fe
Bng cch nu cht xc tin K tng tc phn ng tng hp amnic. Trong th
nghim hp ph N
2
trn cc mt Fe(100) v (110) t hot tnh hn ghi nhn rng ch mt
lng nh K cho thm tng nhit hp ph N
2
ln 16 kJ/mol v tng tc phn li N
2
ln
300 ln. y l bng chng rng trong phn ng N
2
+ H
2
th bc hot ho N
2
l bc
quyt nh tc chung ca phn ng. Trong thc t xc tc Fe thng mi thng cha
khong 1,8 mol% K.
Tnh thc y s cho in t ca K ph thuc vo mc che ph cc ht xc tc bi K,
ngha l ph thuc vo hm lng xc tin, iu ny c chng minh bng cch o nhit
hp ph ca K trn b mt kim loi chuyn tip. mc che ph thp, gi tr nhit hp
ph o c bng khong 250 kJ/mol, i lng ny ng vi nng lng ion ho hon
ton nguyn t K. Khi tng che ph, s phn cc mt phn cc ht K dn ti s trung
85
ho in tch. Khi che ph = 50 %, nhit hp ph gim mnh, cn gn 97 kJ/mol,
ng vi nhit thng hoa ca K kim loi. Khi K r rng l khng phi ion.
Cc hiu ng tng t cng c ghi nhn trong phn ng hyr ho CO trn xc tc Pt,
Ni v Ru. K tng hot tnh v chn lc i vi phn ng to C
2+
-hyrcarbon, iu thy
c th d bo nu hp ph phn li CO c thc hin d dng. Bng chng ca iu ny l
khi c mt K, CO s gii hp ph nhit cao hn 100200 K v nhit ca hp ph ho
hc tng ln 2050 kJ/mol. Ph dao ng cho thy khi tng che ph bi K, tn s dao
ng ca CO 1875 v 2120 cm
1
( = 0) gim ti 1565 cm
1
( = 0,6). Nh vy K
gim trt t ca lin kt CO t 2 ti 1,5, khi CO hp ph d phn li hn. Bng chng
l vi xc tc Rh p sut ring ca CO thp CO hp ph phn t nhng khi thm xc tin
K n s hp ph phn li.
Ngoi vic tng cng kh nng trao i in t xc tin loi ny cn c kh nng trc
tip to lin kt vi cht b hp ph. y l v d cc ion kim loi kim trong phn ng
tng hp metanol trn xc tc Cu. NaOH v KOH c th phn ng vi CO iu kin
kh mm to format, tip theo format s phn ng vi H hp ph phn li to metanol.
Hin tng xc tin to lin kt cng gp trong phn ng metan ho xc tc. Cc phn t
nc hnh thnh trong phn ng s hp ph trn cc tm hot ng v lm chng mt hot
tnh, khi cn ko chng ra bng cc hp cht thiu in t theo (Pt. 5.80).
MO
x1
+ H
2
O MOx + H
2
(5.80)
Khi H
2
to thnh s d gii hp hn. Cc xit kim loi d kh l xc tin thuc loi ny,
trong s cc xit kim loi, hot tnh trong phn ng (5.80) c xp theo dy:
UO
2
/U
3
O
8
> MoO
2
/MoO
3
> WO
2
/WO
3
> PrO
3
/Pr
4
O
10
> Ce
2
O
3
/CeO
2
> CrO
2
/Cr
2
O
3

Nh vy cht xc tin tt nht s l UO
2
.
Mt cht xc tin khc l K
2
SO
4
trong phn ng xi ho metanol thnh formaldehit trn
xc tc V
2
O
5
. Vi khi lng khong 1020% K
2
SO
4
tng rt mnh hot tnh v chn
lc t 85 ln 97%. Trong trng hp ny K cng thc y qu trnh cho VO
x
in t, lm
yu lin kt V=O v tng tc phn ng.
Vi xc tin n nh t chc chng s c tc dng vi c cht mang ln pha xc tc. V
d cht mang c tnh axit l xit nhm, n c th tn ti di nhiu dng th hnh (cc
pha) khc nhau. Pha Al
2
O
3
thng dng nht l pha -Al
2
O
3
. Pha ny c cu trc spinel
khim khuyt, b mt ln, c axit nht nh, c kh nng to dung dch rn vi cc xit
kim loi chuyn tip nh NiO v CoO. nhit trn 900
o
C -Al
2
O
3
chuyn pha thnh
pha -Al
2
O
3
c cu trc hexagonal v b mt nh. Hin tng nhit cao c th gp
trong qu trnh hot ho-ti sinh xc tc. Thm ch nhit thp cng c th xy ra s
chuyn pha nhng chm, khi xc tc s mt dn hot tnh. Khi b xung mt lng nh
(12%) cht xc tin l SiO
2
hoc ZrO
2
vo -Al
2
O
3
s dch chuyn nhit chuyn pha
ln cao hn, bng cch s tng n nh nhit ca cht mang/xc tc.
86
Xc tin chng c c th khng ch cc phn ng khng mong mun, v d s to cok.
S to cok thng xy ra trn cc tm axit Brnsted di dng phn ng cracking, tip
theo s l phn ng polymer ho, cng xc tc bi tm axit, to polymer dng (CH
x
)
n
che ph b mt tm xc tc, ngn cht phn ng vo cc l xp. loi cok ngi ta
thng dng k thut nng nhit v t cok trong khng kh, khi nhit tng cc b
c th lm xc tc mt hot tnh do hin tng co cm. gim hot tnh ca cc tm axit
to cok ngi ta dng kim, thng l cc hp cht kim loi kim. V d K
2
CO
3
s c
cho vo khi ch to xc tc v s gim thiu kh nng cok ho ca Al
2
O
3
.
Trong phn ng reforming hi nc i vi phn on naphta, kali tng hot tnh phn
ng C + H
2
O. Tuy nhin khi s hnh thnh KOH c th thng hoa v mt tc dng. Khi
ngi ta dng aluminosilicat kali. Trong iu kin c hi nc v CO
2
n s phn hu
thnh K
2
CO
3
v KOH mc khng ch phn ng to cok. S cho thm ny tng
thi gian sng ca xc tc ln ti 45 nm [T35].
Xt phn ng hyresulfur xc tc. y l mt qu trnh quan trng trong ho du v
sn xut phn m. Xc tc l CoMo/Al
2
O
3
. Phn ng xy ra nh Pt. 5.81:
+H2 +H2
RS R= R (5.81)
H2S
Phn ng hyr ph n lin kt CS c ni bng phn ng hyr ho alken to thnh.
Cht mang xc tc l -Al
2
O
3
c b mt ln (~ 250 m
2
/g). Cht cho thm l 1% SiO
2
ng
vai tr cht n nh t chc. Mui cobalt v molybden c tm ln cht mang v nung
phn hu to cc oxit nh MoO
3
, CoO, Co
3
O
4
, v CoAl
2
O
4
. Tin cht quan trng to
xc tc l MoO
3
, chuyn thnh pha hot ng cn sulfua ho to cc vi tinh th MoS
2
c cha cc ion Co
2+
. Cc tm hot ng CoMoS s hot ho hyr thc hin phn
ng kh sulfur. y Co ng vai tr xc tin cu trc v ng thi lm tng phn tn
ca cc ht sulfua pha hot ng.
i vi cc nguyn liu du nng xc tc cn cha cht cho thm K v P trung ho cc
tm axit, gim s to cok, tng phn tn ca pha molybden. V d ny, mc d dng
n gin ho, cho thy phc tp ca trong quan h gia cc thnh phn xc tc: pha xc
tc, cht mang, cht xc tin v khi lng cng vic cn phi lm a xc tc vo ng
dng cng nghip.
5.4.4 Cht c ch
Cht c ch l nhng cht lm gim hot tnh xc tc, thng thng l do chng tng tc
vi xc tc. V d:
Xc tc Pt hoc Pd mang trn CaCO
3
, khi pha Pb (xc tc Lindlar) pha xc tc s
tng tc vi Pb, gim hot tnh. Khi gim hot tnh hyr ho xc tc tr thnh
xc tc hyr ho chn lc lin kt ba C C thnh lin kt i C=C (Pt. 5.82):
Pt+Pb/CaCO3
87
RC CH + H
2
RC=CH (5.82)
100150
o
C
Cc dung dch aprotic: tng tc vi xc tc thng qua s to thnh lin kt H,
cnh tranh tng tc vi cc phn t cht phn ng.
Cc cht c cu trc tng t c cht S trong xc tc enzym.
Cht c ch qu mnh s tr thnh cht c, v d: S tng tc vi xc tc hyr
ho Ni. Nu liu lng S nh Ni mt bt hot tnh v tr thnh xc tc hyr ho
chn lc C C tng t xc tc Lindlar nhng hot tnh km hn, cn nhit cao
hn (200250
o
C), lng H
2
S pha vo l 1 ppm so vi cht phn ng.
88
5.5 S mt hot tnh v S ti hot ho [6]
Xc tc c thi gian lm vic gii hn. C loi mt hot tnh sau vi pht, c loi lm vic
hng chc nm. iu ny rt quan trng trong cng nghip v thi gian lm vic cng di
hiu qu kinh t cng ln. Xc tc gim hot tnh do nhiu nguyn nhn, v d do:
Cc tm hot ng b che lp
Do cc phn ng ho hc, cc tc ng nhit, vt l hot tnh b mt
Bng 5-41 tng quan nguyn nhn suy gim hot tnh ca mt s xc tc cng nghip.
Bng 5-41 Nguyn nhn mt hot tnh ca mt s xc tc cng nghip
Phn ng
iu kin
phn ng
Xc tc
Thi gian
sng, nm
Nguyn nhn
mt hot tnh
Tng hp amnic
N
2
+3H
2
2NH
3
450-550
o
C
200-500 bar
Fe/K
2
O/Al
2
O
3
5-10 Thiu kt chm
Metan ho
CO+3H
2
CH
4
+H
2
O
250-350
o
C
30 bar
Ni/Al
2
O
3
5-10 B u c t
t do S, As
Tng hp metanol
CO+2H
2
CH
3
OH
200-300
o
C
50-100 bar
Cu/Zn/Al
2
O
3
2-8 Thiu kt chm
Hydrodesulfua ho du
nh
300-400
o
C
35-70 bar
CoS/MoS
2
/Al
2
O
3
0,5-1 Phn hu
sulfua
xi ho amonic
2NH
3
+2,5O
2
NO+3H
2
O
800-900
o
C
1-10 bar
li Pt 0,1-0,5 Mt Pt, u
c
Cracking xc tc 500-600
o
C
2-3 bar
Zeolit 0,000002 to cc
xi ho benzen->MA
C
6
H
6
+O
2
C
4
H
2
O
3
350
o
C
1 bar
V
2
O
5
/MoO
2
/Al
2
O
3
1-2 to pha V
khng hot
ng
Hnh 5-37 Cc kiu gim hot tnh [8]
Hin tng xc tc mt dn hot tnh, i khi c gi l lo ho, c th hin di dng
biu thc m t s suy gim hot tnh theo thi gian. Hot tnh xc tc a l t l gia tc
89
phn ng xc tc thi im phn ng t v tc phn ng thi im bt u phn
ng (t = 0; Pt.5-83).
( )
( )
( ) 0
t r
t r
t a
(5-83)
Trong qu trnh phn ng hot tnh xc tc gim, cc kiu thng gp nh Hnh 5-37.
S mt hot tnh khng ch gim hot tnh, ng ngha vi nng sut, ca xc tc m nhiu
khi cn gim c chn lc. Chnh v vy, ngi ta lun tm cch ngn nga hin tng
ny v khi n xy ra ti mc no th ti sinh xc tc, ngha l tc ng xc tc tr
li cng gn hot ban u cng tt. Ti sinh xc tc c th c tin hnh tng m hoc
lin tc in-situ khi xc tc ang trng thi lm vic trong bn phn ng.
Hnh 5-38 Cc c ch lm gim hot tnh xc tc (M = kim loi) [8]
y ta s trnh by v cc c ch lm gim hot tnh xc tc v cc phng php ti sinh
xc tc [T35].
C bn nguyn nhn lm gim hot tnh xc tc, l do:
Xc tc b u c. Cc cht c ph bin l H
2
S, Pb, Hg, S, P
Cc sn phm phn ra che ph b mt (v d: s to cc)
Cc qu trnh nhit thiu kt do nhit cao lm gim b mt hot ng
S mt mt pha hot ng do bay hi, mn c hc (v d: trong phn ng vi CO
trn xc tc kim loi, kim loi b bay hi do to thnh phc carbonyl vi CO)
Cc c ch ny c m t trn Hnh 5-38. Ta s xem xt cc hin tng ny sau hn.
5.5.1 S u c xc tc
S u c xc tc v bn cht l phn ng ho hc gia cht c vi pha hot ng, c
th l vi cc tm hp ph. Khi tm hot ng s mt kh nng hot ho cht phn ng.
Hiu ng u c rt mnh ngay c khi nng cht c rt nh, iu ny ng vi thc t
l s tm hot ng trn b mt l mt con s gii hn v khng ln.
Thut ng cht c xc tc thng p dng i vi nhng cht khng tham gia phn ng ta
mun nhng li tng tc (thng l) bt thun nghch vi xc tc. Cn sn phm bn thn
90
phn ng xc tc khi khuych tn chm ra khi b mt cng s lm gim tc phn ng
nhng khi ta gi l hin tng c ch.
C ch u c v c ch ca mt s cht c nu Bng 5-42. Sau y l nhng cht
c ph bin nht i vi cc xc tc quan trng nht, l cc kim loi, bn dn, cc axit
rn khng dn in.
Bng 5-42 Cc cht c v c ch xc tc [T41]
Qu trnh Xc tc Cht c, c ch xc tc Kiu tc ng
Tng hp amnic
Hyr ho
Cracking xc tc
xi ho amnic
xi ho SO
2
Tng hp etylen oxit
Fe
Ni, Pt, Pd, Cu
Aluminosilicat
Pt/Rh
V
2
O
5
/K
2
S
2
O
7
Ag
S, Se, Te, P, hc As, Hal
O
2
, H
2
O, NO
CO
2
CO
S, Se, Te, P, hc As, Hal
Hg, hc Pb
O
2
CO
amin, H
2
O, porphyrin ca
Ni, Fe, V
cc
P, As, hc Sb, Pb, Zn, Cd, Bi
r
Hp cht As
Hp cht halogenua
cht c: hp ph hh
hoc tng tc ho hc.
cht c nh: xi ho b
mt Fe, kh c nhng b
thiu kt.
c ch: trung ho xc tin
kim.
u c v c ch: hp
ph ho hc mnh,
chuyn ho thnh CH
4
,
tng cng thiu kt.
cht c: hp ph hh
hoc tng tc ho hc.
cht c: to hp kim.
cht c: to xit b mt
to phc carbonyl vi.
c ch:che ph tm hot
ng.
cht c:che ph tm
hot ng.
cht c: hp kim ho,
lm rn si xt.
phn hu NH
3
.
c ch cht c; to
hp cht
c ch: tng chn lc
5.5.2 S u c trong xc tc kim loi
Cc xc tc kim loi rt nhy cm vi mt s cht c, thng l tp cht trong hn hp
phn ng, ngay c khi chng c nng thp. Cc xc tc kim loi hot ng c l nh
cc orbital d c s dng to lin kt hp ph vi cht phn ng. .
C th chia cc cht c xc tc thnh ba nhm:
Cc ion phi kim
Cc ion kim loi
Cc phn t cha bo ho
91
C th l cc ion ca cc nguyn t nhm 15 (N, P, As, Sb, Bi) v 16 (O, S, Se, Te) l cc
cht c mnh. c tnh ph thuc vo s c mt ca cp in t t do trong phn t cht
b hp ph. Nu cp in t ny c mt, n s c kh nng to lin kt cho-nhn v tr
thnh cht c.
Cht c: H
2
S, tiophen, NH
3
, PH
3
, AsH
3
Cht khng c: SO
4
2-
, NH
4
+
, PO
4
3-
, AsO
4
3-
, cc sulfon (R-S(=O)(=O)-R')
i vi cc ion kim loi c tnh ph thuc vo s in t d. Cc kim loi c orbital d
trng nh kim loi kim, kim th v cc kim loi c t hn 3 in t d l khng c, v d
i c tc Pt:
Cht c: Zn
2+
, Cd
2+
, Hg
2+
, In
2+
, Tl
+
, Sn
2+
, Pb
2+
, Cu
+
, Cu
2+
, Fe
2+
, Mn
2+
, Ni
2+
, v.v
Khng c: Na
+
, Be
2+
, Mg
2+
, Al
3+
, La
3+
, Ce
3+
, Zr
4+
, Cr
2+
, Cr
3+
Cc kim loi hp ph mnh cc kh nh CO v olefin. Nu chng hp ph bt thun nghch
trn xc tc chng tr thnh cht c. Nu chng phn hu th xc tc c gii c, khi
iu ny s dn n to cc.
Do tng tc trong hp ph ho hc c mnh yu khc nhau ta s ch i nhiu hin
tng khc nhau xy ra trong phn ng hyr ho cc phn t cha bo ho. Hin tng
c ch do s c mt ca phn t khng no cnh tranh c th lm cho phn ng hyr ho
chm li t cht t cho ti dng hon ton. V d, xc tc hyr ho Pt v Ni b u c
bi CO hoc CN
-
, hoc trong trng hp hyr ho xyclohexen chng b u c khi c
mt mt lng nh sn phm l benzen.
Cc halogen v hp cht N bay hi l cc cht c yu, chng gim i cht hot tnh xc
tc do hp ph thun nghch v xc tc d dng phc hi hot tnh.
Hin tng u c c th l thun nghch hoc bt thun nghch. V d, S nhit thp
u c xc tc Ni bt thun nghch, do xc tc metan ho khng ti sinh c ngay c
khi x l bng H
2
. Tuy nhin nhit cao S c th c loi b bng phn ng hyr ho
v x l hi nc, khi xc tc Ni trong phn ng chuyn ho hi nc (steam
reforming) li l xc tc bn vi cht c S.
chng c ta c cc phng php sau:
Lm sch nguyn liu bng x l ho cht (t; c th to tp khc)
X l nguyn liu bng xc tc (rt hiu qu i vi cht c hu c)
Lm sch nguyn liu bng hp ph (v d: dng ZnO hp ph cc hp cht Strong
chuyn ho kh t nhin, ng dng m Ph M)
Mt gii php chng c khc l dng cc cht xc tin. V d, S u c xc tc Ni
nhng khi c mt cromit ng s t c v Cu
2+
tng tc thay Ni to sulfua.
a ra quy trnh chng c cn hiu rt r c ch b u c ca xc tc.
92
5.5.3 S u c xc tc xit bn dn
Bn cht phn ng trn xc tc bn dn l s cho nhn in t qua cc tm nhn cho trn
b mt bn dn nn bt c phn t no cn tr qu trnh ny s l cht c xc tc. V d
phn t b hp ph mnh trn b mt xc tc l cht c. Tuy nhin hin tng ny khng
lin quan trc tip n bn cht xc tc bn dn. C th ni ti nhng nm u 2000 vn
cha c l thuyt c th v vn ny. Nhn chung xc tc bn dn bn vi cht l, thay
i hot tnh xc tc bn dn ti mc ghi nhn c lng cht l phi l vi phn trm.
5.5.4 S u c xc tc axit
Hin tng u c xc tc axit d hiu hn bn dn nhiu. Khi tm axit b trung ho
chng mt tnh axit ngha l mt hot tnh, vy cc kim loi kim, kim th v xit ca
chng, v bt k cht no c tnh baz u l cht c, nht l baz hu c. Tuy nhin, cc
kim loi kim v kim th thng c thm vo iu khin tnh axit ca xc tc,
chng thng khng c mt trong nguyn liu u. Ngc li cc baz hu c, v d cc
hp cht N thng gp trong nguyn liu du th. Thng thng 2535 % cc hp cht N
trong du m c tnh baz.
c ca baz hu c ph thuc trc tip vo tnh baz ca chng. V d: pyridin,
quinolin, amin v indol l baz, trong khi pyrrol v carbazol khng c tnh baz. Cc
cht c ny c th x l bng hyr ho, ng thi qu trnh ny cng x l S v nhiu
kim loi nng khc.
i khi ngi ta cn u c mt phn, l trng hp gim hot tnh xc tc tng
chn lc. V d: trong phn ng chuyn ho xc tc trn xc tc Ni ngi ta cho vo vi
ppm H
2
S. So vi Pt xc tc Ni c hot tnh hyr phn cao hn, iu ny dn ti s cc
ho v to cc sn phm kh. Khi cho H
2
S vo, S s hp ph chn lc ln cc tm c hot
tnh hyr phn cao nht, khi chn lc theo hng phn ng isomer ho cn thit s
tng, phn ng ph gim.
Hin tng u c mt phn c nghin cu nhiu trong phng th nghim. V d, xc
tc Pd u c mt phn bi Pb (xc tc Lindlar), S, hoc quinolin c dng hyr
ho chn lc cc hp cht axetylen thnh cis-olefin. Mt ng dng khc l s loi b vt
phenylaxetylen ( mc 200 300 ppm) khi styren bng hyr ho chn lc.
Trong phn ng Rosenmund reaction (Pt.5-84), phn ng hyr ho RCOCl loi b HCl
to aldehit:
O O

RCCl + H
2
RCH + HCl (5.84)
Xc tc l Pd (5 % Pd/BaSO4) c u c bng cc hp cht cha S nh quinolin,
tioure, hoc tiophen s chng c phn ng hyr ho alehit.
5.5.5 Cc sn phm phn r (deposit) bm trn b mt xc tc
93
Khi cht hu c hp ph trn tm hot ng, polime ho v phn r chng to lp ph
dng polymer trn b mt xc tc thng c gi l cc, iu ny nhiu khi dn ti s
mt hot tnh ca xc tc. l v trong nhiu phn ng chuyn ho ca hydrocarbon,
phn ng ph hay gp l polymer ho. Khi cc sn phm ph ny lp y cc l xp, xc
tc s mt hot tnh v phn t cht phn ng khng th khuch tn vo cc tm b mt
bn trong. nhit cao (trn 200
o
C) cc hp cht polymer ny b nhit phn mt hyr
(ehyr ho) to carbon, khi ta c cchtj hoc lp cc trn b mt, qu trnh ny gi l
cc ho (coking). Cc xc tc c tnh axit hoc xc tc hyr/ehyr ho l nhng cht
hay b cc ho. Coking thng xy ra trn cc tm axit ca xc tc hoc cht mang zeolit
v aluminosilicat. Kh nng b cc ho ph thuc trc tip vo axit ca vt liu.
Nhng cht c kh nng to cc nhiu nht l cc tin cht c tnh thm v cc olefin,
chng thng c mt trong nguyn liu u hoc hnh thnh trong qu trnh phn ng di
dng sn phm trung gian hoc sn phm ph. Trong xc tc lc-ho du, khi thm 510%
zeolit vo xc tc cracking v nh hnh, hot tnh tng ln vi bc, ng thi s cc ho
gim mnh. y l mt v d na v chn lc hnh hc ca xc tc zeolit, trong do
kch thc ln cc hp cht trung gian to cc khng chui c vo l zeolit (xem 7.3.1).
Trn cc xc tc ehyr ho (kim loi, oxit, sulfua), lp cc hnh thnh theo cc con
ng khc so vi s b gy mch hyrcarbon trn xc tc axit. Phn ng ln lt qua
cc bc ehyr ho, hyr phn s to cc ht C
x
. Cc ht ny rt hot ng, chng tp
hp li to cu trc kiu cacbua hoc ging graphit (pseudo-graphite). Khi c mt xc
tc axit cc ht C
x
s dch chuyn t tm ehyr ho ca kim loi ti tm axit trn vt liu
mang v chuyn ho tip ti nh trn tm axit (H.5-39).
Hnh 5-39 S cc ho qua con ng ehyr ho
Hnh 5-40 S mt hot tnh trong cc qu trnh chuyn ho (reforming) xc tc [T35]
94
C ch cc ho qua phn ng ehyr ho thng gp trong chuyn ho xc tc,
hyresulfua ho, trn xc tc kim loi khi kim loi b nhim bn bi nguyn liu u. V
d xc tc Pt/Al
2
O
3
(H.5.40). trnh hin tng ny ngi ta dng xc tc lng kim, v
d khi thm Re vo xc tc Pt n nh ca xc tc t tnh bng tun tng ln hng nm
(Hnh 5-40). Reni c ch qu trnh coking v c s co cm cc ht xc tc (sintering), iu
ny ko di thi gian lm vic ca xc tc v gim chi ph ti hot ho. Ngoi nh hng
ca yu t cht cho thm, p sut H
2
cng ng vai tr nht nh.
Cc tp kim loi trong nguyn liu u cng ng vai tr trong phn ng hyresulfua
ho v hyrenitrogen ho. Du th thng cha cc kim loi nng di dng phc
porphyrin mc ppm: Fe ( 150 ppm), Ni ( 50 ppm) v V ( 100 ppm). Cc porphyrin
u tin hp ph trn Al
2
O
3
v aluminosilicat sau phn hu c phn hu li ht kim
loi. Nikel l hot tnh cao nht y. Khi ti sinh xc tc cc kim loi b xi ho v cc
xit mi hnh thnh s l cc tc nhn xi ho mnh (v d: V2O5). Cc xit kim loi ny
c mt s hiu ng m: chng che ph tm hot ng, chng c hot tnh cao v kh nng
to cc cao. V vy tch loi kim loi l mt qu trnh quan trng trong lc du. C th p
dng cc qu trnh sau: hp ph porphyrin, hyr ho v gn kim loi ln Al
2
O
3
. Mt
phng php khc l s dng cht cho thm. V d: khi thm Sb cc kim loi nng s to
hp kim v gn trn cht mang di cc dng khc nhau.
Nh vy chng coking ta c th tng p sut ring phn ca hyr hoc trung ho mt
phn tnh axit.
Khi cc hnh thnh, hot tnh gim ngi ta s ti sinh xc tc bng qu trnh t c
kim sot. Trong cc l cracking cng nghip kiu phn ng trn lp m gi si xc tc
s tun hon lin tc gia hai khoang phn ng v ti sinh. Trong bung ti sinh lp cc s
c t chy bng xi to CO
2
, nhit to ra trong phn ng t chy c s dng
t nng l phn ng chnh v qu trnh cracking thu nhit i cht.
5.5.6 Cc qu trnh nhit v s thiu kt
nhit cao cn lu hai qu trnh: chuyn pha v thiu kt.
nhit cao qu trnh chuyn pha ca c pha hot ng ln cht mang rt hay xy ra. V
d -Al
2
O
3
b mt ln tr thnh -Al
2
O
3
b mt nh dn ti gim hot tnh. Mt v d
khc l s chuyn pha ca TiO
2
dng anatase thnh rutile trong xc tc V
2
O
5
/TiO
2
/corundum trong phn ng xi ho o-xylen thnh phthalic anhydric.
Thiu kt l hin tng thng gp trong luyn kim v k thut gm. Trong xc tc n
cng ph bin. Nguyn nhn l do xc tc thng c cu trc xp, b mt ln nh vy
nng lng b mt rt ln lm cu trc qu phn tn khng bn, s co cm li khi thiu kt
l con ng tt yu gim nng lng b mt, nhit thiu kt thng ch mc 1/3
n nhit nng chy ca vt liu khi. S thiu kt lm tng kch thc ht, tng
tip xc gia cc ht. C mt s trng hp thiu kt mnh ln nu nguyn t b mt to
hp cht bay hi, v d: xc tc Cu to CuCl
2
bay hi khi c mt clo. H qu chnh ca
95
hin tng thiu kt l s suy gim din tch b mt v suy ra l hot tnh xc tc. Khi
chn lc cng c th thay i. S thay i s xy ra mnh trong trng hp ca phn
ng nhy cu trc. Cc nghin cu c bn v thiu kt hay c thc hin vi xc tc
Pt/Al
2
O
3
c phn tn cao.
Cc nghin cu vi phn ng chuyn ho naphtha, trong vai tr ca ti sinh th hin rt
r. Cc d liu Bng 5-43 cho thy trong qu trnh ti sinh bng cch t chy cc th
kch thc ht xc tc tng, iu ny th hin s gim u s liu v hp ph H
2
. Cc
nghin cu vi phn ng mu cn ch ra rng chn lc cng thay i. C th l, khi
tng kch thc ht xc tc s hnh thnh cc hp cht thm nh qu trnh ehyr v
vng ho gim tng ng, phn ng isomer ho tng, cn hot tnh hyrocracking gn nh
khng i.
Bng 5-43 Chuyn ho nafta trn xc tc 0,6%Pt /Al
2
O
3
, s mt hot tnh v ti sinh [T35]
Trng thi xc tc Lng H
2
hp ph, cm
3
/g xc tc
Mi
B cc ho, 1 ngy (1%C)
Ti sinh
B cc ho, 1 ngy (1%C)
Ti sinh
B cc ho, 5 ngy (2,5%C)
Ti sinh
0.242
0,054
0,191
0,057
0,134
0,033
0,097
Mt v d khc l phn ng tng hp etylen xit. Khi b mt xc tc Ag gim, hot tnh
gim tng ng, cng ti sinh qu trnh gim ny cng mnh.
V d cui l phn ng kh chn lc xit nit trn xc tc xit vanadi [20]. Xc tc l
V
2
O
5
mang trn cht mang TiO
2
(anatas). nhit trn 350
o
C b mt anatas gim, iu
ny dn ti s ti cu trc ca ht vanadi pentoxit, lc ny tr nn qu nhiu trn b
mt, cc tinh th V
2
O
5
dng si mc ln rt r di hin vi in t. H qu l phn ng
khng mong mun s xy ra mnh hn, c th l s hnh thnh N
2
O tng. tng n
nh nhit chng li hin tng trn ngi ta thm vo xc tc cc cht n nh nhit nh
sulfate hoc bin tnh pha hot ng bng xit volfram.
Nhn chung cc phng php chng thiu kt c th l:
Cho thm cht n nh pha hot ng bng cch phn tn u trn b mt cht mang, v
d xc tc Ni c th c n nh nh Cr
2
O
3
.
Ti phn tn li cc ht kim loi, v d: vi xc tc reforming Pt/Al
2
O
3
th x l bng clo
to PtCl
2
bay hi ri li hp ph v phn hu thnh Pt trn cht mang Al
2
O
3
.
5.5.7 Tn tht xc tc qua pha kh
96
Mt tc ng nhit na l nhit cao dn ti s bay hi mt s thnh phn xc tc v vi
xc tc quan trng nht l tn tht pha hot ng. iu ny xy ra vi c cc thnh phn
c coi l d bay hi (v d: P
2
O
5
trong H
3
PO
4
/silica gel, HgCl
2
/than hot) ln cc thnh
phn vn c kh bay hi do tng tc ca kim loi vi mi trng thnh cc xit, clorua
hoc nht l carbonyl bay hi. V d trong qu trnh xi ho amnic trn xc tc Pt/Rh
dng li (qu trnh Ostwald sn xut axit nitric) Pt xc tc phn ng vi xi pha kh to
thnh PtO
2
bay hi. Khi s thy xut hin cc ht Pt xp mc trn b mt xc tc Pt/Rh.
iu ny c th ngn chn bng cch cho thm cc xit t him.
Trong cc phn ng hyr ho trn xc tc cha Mo nhit qu cao trong qu trnh ti
sinh ti nhng im nng khu vc s xut hin MoO
3
, xit trn 800
o
C s bay hi, khi
pha hot ng s mt v tng ng l xc tc s gim hot tnh.
Tng t l v d v xc tc Ni trong phn ng metan ho i vi hn hp kh tng hp.
Nu nhit lp xc tc xung thp hn 150
o
C xc tc s b tiu hao do s hnh thnh
niken tetracarbonyl bay hi v c c tnh cao.
M hnh s mt hot tnh
m t qu trnh mt hot tnh cn da trn cc c ch, v c ch khc nhau nn ta s c
nhiu m hnh.
M hnh da trn hp ph Langmuir
Gi s tng s tm hot ng, Z
tot
, gim dn theo thi gian lm vic t do b u c bi
tp cht trong nguyn liu. p dng ng hc Langmuir ta vit c phng trnh tc
phn ng:
1 1
1 1
1 1
1 1
'
1 1 p k
p k
p k
k K Z k
r
tot s
+
(5-85)
Tc gim hot tnh r
d
c xc nh nh s gim hot tnh theo thi gian:
' dt
da
r
d

(5-86)
Trong m hnh ny c th coi r
d
chnh l tc mt cc tm hot tnh. r
d
ph thuc vo
nhit , hot tnh xc tc a, nng tc nhn lm gim hot tnh C
d
v nng lng hot
ho ca qu trnh E
d
:
( )
( )
d
RT E
d d
C a f e k r
d
, .
/
0 ,

(5.87)
Gi tr nng lng hot ho rt cao, v d 290 kJ/mol c xc nh cho phn ng
chuyn ho heptan trn xc tc Pt/Al
2
O
3
.
V mt nh lng tc mt hot tnh thng c th hin di dng hm m:
m
d
n
d d
C a k
dt
da
r
'
(5.88)
97
Nu khng c cht c, ta c m = 0. Trong qu trnh s dng s xut hin s gim hot
tnh do thiu kt. Trng hp n gin nht ta c n = 1, khi Pt.5-88 tr thnh:
a k
dt
da
r
d d

'
(5.89)
Ly tch phn Pt.5.89 t t = 0 ti t ta c:
( )
'
0 '
'
t k
t
d
e a t a

(5.90)
V a(t = 0) = 1, ta thu c:
( )
'
'
t k
d
e t a

(5.91)
Hm exponent dng ny cng c dng m t hin tng u c bng cch t nng
cht c bng hng s. V d l phn ng hyr ho etylen trn xc tc Cu (cht c l
CO) v phn ng ehyr ho alkan trn xc tc Cr/Al
2
O
3
.
Vi qu trnh cc thiu kt s gim hot tnh tun theo phng trnh bc hai, ta c:
2
a k r
d d

(5.92)
Ly tch phn ta c:
( )
' 1
1
'
t k
t a
d
+
(5.89)
V d ng dng ca lut hyperbol ny l qu trnh ehyr ho xyclohexan trn xc tc
Pt/Al
2
O
3
v hyr ho isobuten trn xc tc Ni.
Ti sinh xc tc
Hot tnh xc tc thay i theo thi gian nh trong Hnh 5.41. Theo thi gian hot tnh
gim dn, dng th s ph thuc vo iu kin phn ng v ng hc s gim hot tnh.
u tin ta th tc ng lm chm tc gim hot tnh bng cch thay i iu kin
lm vic ca xc tc (v d: tng nhit , gim p sut trong cc phn ng hyr ho).
Hnh 5-41 Din bin hot tnh trong qu trnh phn ng, trc v sau ti sinh
S mt hot tnh c th xy ra nhanh hoc chm. V d trong phn ng x l naphta bng
hyr, xc tc c th lm vic vi nm, cn trong phn ng cracking xc tc mt hot tnh
98
sau vi pht. Trong mi trng hp khi xc tc gim hot tnh n mc cho php th ta
phi ti sinh (hot ho li) xc tc, hoc thay xc tc. Trong thc t rt kh c th t c
hot tnh ban u v lun c nhng tc nhn gy mt hot tnh vnh cu khng th phc
hi.
Khi ti sinh khng c ngha kinh t th ngi ta thay hon ton khi lng xc tc.
99
5.6 Cc c trng xc tc d th [3, 28]
Trong nghin cu xc tc d th, cn lm r mi quan h gia ba yu t sau: (1) cc c
trng xc tc, c v kha cnh vt l ln ho hc, (2) cc tnh cht ng dng, y l hot
tnh xc tc, chn lc v thi gian sng ca xc tc, iu kin ti sinh (nu c) (3)
phng php iu ch xc tc. Cc phng php cn p dng y rt nhiu, kh c
phng th nghim no c , k c cc nc giu c, v vy ngi nghin cu cn c
hiu bit cng y cng tt v mt l lun, cng nh v kh nng ca cc phng th
nghim xung quanh, v bit phi hp vi ng nghip t kt qu ti a. Cc phng
php nghin cu c th l rt c in cng nh rt hin i, tuy nhin ng qu h thp gi
tr ca cc phng php c in cng nh qu cao cc phng php hin i [33].
Cc tnh cht vt l ca xc tc rn l th tch l xp, phn b l xp theo kch thc, b
mt ring theo BET, nhiu khi cn ch c bn c hc nh chu mi mn khi cc
vin xc tc s dng trong h phn ng tng si.
Hnh 5-42 S cc phng php nghin cu xc tc
Cc c trng ho hc l thnh phn nguyn t, cc mc cu trc, c bit l cu trc pha,
cc c trng ca lp b mt. Ta s thy, khi i t b mt vo su th tch ca vin xc tc,
thnh phn ho hc cng nh cu trc c th thay i. Ngoi ra, cn phi nh lng c
cc thnh phn cho thm (cc cht xc tin/tr xc tc, cc cht lm chm), cc sn phm
phn hu/lng ng trn b mt xc tc, cc tc nhn gy c, cc hp cht trung gian ....
Khong trc nhng nm 1970 hp ph ho hc l phng php c nht cho php nh
gi lp nguyn t b mt. Sau trn th trng bt u xut hin cc phng php ph
in-situ v ph b mt hin i cho php nh lng cu trc cng nh thnh phn ho hc
b mt, k c mt s trng thi trung gian, iu ny m ra vin cnh cho con ngi ngy
cng hiu r bn cht ca qu trnh xc tc, t cc quy lut xc tc d th s c hon
ng hc
T chc:
BET, SEM,
xp Hg
c trng
c l
Thnh phn
ho hc:
AAS, ICP,
RFA
Ph.tch
b mt:
ESCA,SIMS,
TEM,SEM,
microprobe
Phn tch pha:
Nhiu x tia X
phn tn
KL qu:
Hp ph CO
Ph.php
nhit:
TG,DTA,DCS
TPR, TPD,
TPO
XC TC
D TH
ng hc
T chc:
BET, SEM,
xp Hg
c trng
c l
Thnh phn
ho hc:
AAS, ICP,
RFA
Ph.tch
b mt:
ESCA,SIMS,
TEM,SEM,
microprobe
Phn tch pha:
Nhiu x tia X
phn tn
KL qu:
Hp ph CO
Ph.php
nhit:
TG,DTA,DCS
TPR, TPD,
TPO
XC TC
D TH
100
thin hn [21]. Ni dung mc ny l gii thiu cc phng php nghin cu c trng xc
tc cng nh vt liu rn, trnh by v kh nng cng nh gii hn ca mi phng php.
Hnh 5-42 cho ta bc tranh ngn gn v cc phng php ny.
5.6.1 Xc nh cc c trng vt l v ho l [T41]
Cc c trng vt l chnh ca vt liu xc tc l:
Hnh thi hc: li lm ca b mt, hnh hc cc cu trc trn b mt
xp: phn th tch l xp trong vin xc tc
Cu trc: ch yu l cu trc h l xp (kch thc l, phn b l theo kch thc,
hnh dng l)
Mt c trng rt quan trng l nhng l xuyn qua ton th tch ht t mt ny ti mt kia
ca vin xc tc. Phng php xc nh phn b l xp theo kch thc thng dng nht
l phng php nn p thu ngn (mercury porosimetry), phng php ny cho php o
c cc l xp t kch thc trung bnh (mesopores) c ng knh l nm trong khong
125 nm ti cc l ln (macropores) c kch thc ng knh trn 25 nm. Nguyn l ca
phng php l o th tch ca lng thu ngn chui vo l xp khi tng dn p sut. T
y tnh c bn knh l xp theo phng trnh 5-94:
p
r
p
cos 2
(5.94)
y: p = p sut
= sc cng b mt ca Hg lng
= gc thm t Hg/vt liu nghin cu rn
rp = bn knh l hnh tr
Thng thng p sut p dng nm trong khong 0,1200 MPa ng vi kch thc l l
3,757500 nm. Trong thc t l xp thng khng c dng tr nh mong mun, nh vy
nu tnh theo phng trnh 5-94, cc kt qu s c khc bit so vi thc, khi s cn
kim tra bng nhng phng php o trc tip hn nh hin vi.
Cc d kin thu c bng phng php nn thu ngn c bit quan trng i vi nhng
xc tc vin phi lm vic trong iu kin khi khuch tn ng vai tr quyt nh vn tc
qu trnh. Cu trc l ln l yu t quan trng nht quyt nh kh nng quay vng xc tc
cng nh thi gian lm vic ca xc tc, yu t ny c th hiu chnh trong qu trnh sn
xut.
i vi bn thn phn ng chuyn ho th h l xp loi trung bnh v loi nh (meso- v
micropore) l yu t quyt nh. Cc i lng th tch l, kch thc l, v phn b l
trong vt liu microporous c xc nh bng phng php hp ph kh p sut tng
i (p/p
o
) thp (p
o
l p sut hi bo ho). Phng php ny da trn hin tng ngng t
hi b hp ph trong l mao qun. tnh phn b l xp cn xy dng c ng hp
101
ph v gii hp ph ng nhit, khi s thu c vng tr c trng cho hin tng
ngng t mao qun. T y tnh c kch thc l theo phng trnh Kelvin (Pt.5-95):
p o
r RT
V
p
p cos 2
ln
(5.95)
y: V = th tch mol cht b hp ph
= sc cng b mt ca cht b hp ph lng
= gc thm t b hp ph/vt liu nghin cu rn
rp = bn knh l hnh tr
(V hnh . ng tr)
P/P
o

V d vt liu micropor l zeolit v mt s loi than hot tnh. Trong trng hp vt liu
loi ny nu s dng phng php BET o din tch b mt c th dn ti sai s ln do
ngng t mao qun. Din tch b mt ring A
S
(o bng m
2
/g) xc tc hoc vt liu
mangc o bng phng php BET. tnh c A
S
cn xc nh th tch kh b hp
ph (thng dng N
2
) ng vi b mt hp ph n phn t. ng ng nhit hp ph
thng c dng nh Hnh 5-43.
102
Hnh 5-43 ng ng nhit hp ph vt l
Trong Hnh 5-43 trc tung l th tch kh b hp ph, trc honh l p sut tng i ca
cht b hp ph p/p
o
( p = p sut hi b hp ph, p
o
= p sut hi bo ho). p sut tng
i nh lp b hp ph n phn t tun theo phng trnh Langmuir (Pt.5-96):
( )
( ) [ ]
o
o
M
p p K
p p K
V
V
/ 1
/
+
(5.96)
V
M
= th tch lp n phn t
K = hng s
Tuy nhin, cc gi tr ln hn p/p
o
= 0,1 s xut hin hp ph a lp. M hnh hin
tng hp ph a lp c pht trin bi Brunauer, Emmett, v Teller vi phng trnh
BET (Pt.5-97) [T35]:
( ) ( ) [ ]
o o M
p p c p p
cp
V
V
/ 1 1 +
(5.97)
c l hng s cha nhit hp ph v ngng t v l hng s i vi mt nhm cht nh
(v d: oxit, kim loi) vi gi tr thng trn 100.
Phng trnh 5-97 c p dng cc gi tr p/p
o
nh hn 0,3, trn gi tr ny s b nhiu
bi hin tng ngng t mao qun, bt u t cc mao qun c ng knh nh nht, sau
lan dn ra cc mao qun trung bnh khi p/p
o
tin ti 1. Dng phng trnh (5-97) tnh
trc tip V
M
l khng thc t v phi c gi tr c chnh xc. Ngi ta thng tuyn tnh ho
phng trnh (5-97), khi ta c phng trnh (5-98) d x l hn:
( )
( )
( )
c V
p p
c V
c
p p V
p
M
o
M o
1
/
1
+
(5.98)
Trong c = exp[(E
1
E
L
)/RT]
E
1
= nhit hp ph ca lp b hp ph th nht (tng tc K-R)
E
L
= nhit hp ph ca lp th hai tr ln = nhit ho lng ca hi b hp ph.
Khi dng th vi trc tung l p/V(p
o
p) v trc honh l p/p
o
, trong vng 0,05 <
p/p
o
< 0,35 th l ng thng, ct trc tung ti I, c dc bng A, ta c th xc nh
c hai hng s ng thi l V
M
v c.
103
T th ta c h phng trnh:
A = (c 1)/V
M
c = 1/V
M
1/V
M
c 1/V
M
I V
M
= 1/(A + I)
I = 1/V
M
c = 1/(1/(A+I)I) = A/(I+A) c = 1 + A/I
S
BET, tot
(m
2
) = V
M
N /V ( = din tch b mt b chim ch bi 1 phn t cht b hp ph)
S
BET
(m
2
/g) = S
BET, tot
/a (a = khi lng cht hp ph)
V d 1:
Tnh S
BET
ca hn hp beton ho rn bng hp ph hi nc 97 C. Kt qu x l
theo BET thu uc: A = 24,20; I = 0,33; cho
H2O
= 0,114 nm
2
. Ta tnh c S
BET
= 156
m
2
/g.
Tuy nhin tnh S
BET
thng s dng cc loi cht b hp ph m phn t khng (hoc t)
b bin dng khi ho lng, l cc kh tr hoc N
2
lm cht b hp ph, qu trnh hp ph
c thc hin nhit gn nhit N
2
lng (- 195,79
o
C),
N2
= 0,16 nm
2
.
Khi bit din tch b mt BET v b mt xc nh bng phng php nn thu ngn ta c
th nh lng c din tch b mt l nh (micropore). Bng 5-44 cho ta gi tr b mt
ring ca mt s vt liu xc tc thng gp.
Bng 5-44 Din tch b mt ring ca mt s xc tc v vt liu mang
Xc tc hoc cht mang B mt ring, m
2
/g
Zeolit ZH trong cracking
Than hot tnh
Silica gel
Aluminosilicat
Al
2
O
3
Ni/Al
2
O
3
(xc tc hyr ho)
CoMo/Al
2
O
3
(xc tc hyresulfua ho)
Fe-K
2
O-Al
2
O
3
(xc tc tng hp amnic)
V
2
O
5
(xc tc xi ho bn phn)
Kim loi qu/Al
2
O
3

Si Pt (xc tc xi ho amnic)
1000
200-2000
200-700
200-500
50-350
250
200-300
10
1
0-10
0,01
Din tch b mt ring (A
S
hoc S
r
) l mt trong nhng c trng quan trng bc nht ca
cht hp ph, xc tc v vt liu mang, tuy nhin khng phi lc no ta cng c mi tng
quan t l thun gia A
S
v hot tnh xc tc, nht l trong trng hp xc tc mang trn
vt liu mang. Trng hp cn xc nh phn b mt hot ng ny cn s dng phng
php hp ph ho hc. o hp ph ho hc vi cc cht kh ph hp nh H
2
, O
2
, CO, NO
v N
2
O nhit phng hoc cao hn ta c th xc nh c phn b mt tng tc vi
chng l cc tm xc tc hot ng ng vi cc cht phn ng tng ng (H.5-44).
La chn kh cho hp ph ho hc ph thuc vo pha xc tc (Bng 5-45).
104
Hnh 5-44 My o hp ph (Phng th nghim Xc tc, FH Mannheim, c)
Bng 5-45 Hp ph ho hc c trng b mt kim loi
Cht b hp ph Kim loi T,
o
C u im Nhc im
H
2
Pt, Pd
Ni
0-20
78
195
hp ph hh phn li
hp trn cht mang t
hp vl rt t, ng lng
c th to hyrua
nhy tp cht
CO Pt, Pd
Ni, Fe, Co
0-25
78
195
khng tan trong th tch hp ph vl T nh
bc cu v lin kt
thng, hoc to phc
carbonyl hoc phn li
O
2
Pt, Ni
Ag
Cu
25
200
195
hp ph t trn cht mang xit hp ph vl T nh, c
th c xi ho
N
2
O Cu, Ag 25 hp ph t trn cht mang xit,
hu nh khng xi ho
o rt kh (pp th
tch)
Bng 5-45 cng lit k cc u v nhc im ca mi loi kh, rt kh tm c loi kh
c trng cho mi kim loi, v vy, phng php ny p dng tt cho xc tc mt kim loi
nhng kh p dng cho xc tc a kim.
Phng php chun b mt c th p dng xc nh Pt v Pd trn vt liu mang.
Phng php ny da trn hin tng hp ph phn li ca H2 hoc O2, sau nh lng
lng O2 hoc H2, tng ng tng tc vi H
2
hoc O
2
b hp ph ho hc. Vn ca
phng php ny l c ch phn ng cn cha r. Khi bit lng cht b hp ph (nh
lng qua lng cht phn ng) ta tnh c lng pha xc tc kim loi hot ng (nu
bit ng lng cc phn ng tng ng), t y kt hp vi b mt BET c th tnh
c phn tn ca pha xc tc. Th tch kh b hp ph s ng vi b mt hot ng. S
nguyn t kim loi hot ng tnh cho 1 gam xc tc cho ta mc phn tn. Thng
thng s nguyn t kim loi b mt t l thun vi s tm hot ng. Khi bit phn tn
s so snh c hot tnh xc tc trn c s tnh cho 1 n v b mt kim loi hot ng.
chng mc no , hp ph ho hc cng c th p dng cho xc tc xit [33].
Phng php gii hp ph nhit theo chng trnh nhit (Temperature-
programmed desorption-TPD) [43, 44]
105
Khi ta s dng cc cht b hp ph l NH
3
, H
2
, CO hoc CO
2
. T cc gi tr gii hp ph
ta thu c mt s thng tin gi tr. Trong th nghim TPD ta theo di lng cht b hp
ph gii hp ra khi tng dn nhit theo chng trnh t sn, thng l tng tuyn tnh.
TPD cho php xc nh cc trng thi hp ph v ng hc gii hp. V mt nh tnh d
kin TPD rt d hiu: nhit gii hp cng cao ngha l cht b hp ph tng tc vi b
mt ca i tng nghin cu cng mnh. Trn ng cong (ph) TPD din tch di cc
pic gii hp ng vi lng cht b hp ph hay l b mt b hp ph, khi t ph TPD ta
tnh c:
Th tch lp b hp ph
S ph thuc ca lng b hp ph vo nhit
S bin i ca xc tc (v d: b thiu kt, gim b mt) khi nng nhit trong
kh tr
nh lng tnh axit, v d ca zeolit, nu dng cht b hp ph l amoniac
Cc phn t cht b hp ph ho hc s lin kt vi nguyn t b mt, cng ca lin
kt ny ph thuc v bn cht cp tng tc. V d, amoniac s tng tc rt mnh vi b
mt c cc tm axit, rt yu nu b mt c tnh baz. Hnh 5-45 cho thy ph TPD ca
amoniac gii hp t zeolit H-ZSM-5 (axit mnh).
Hnh 5-45 Ph TPD ca amoniac gii hp t zeolit [43]
Trn ph TPD c hai pic gii hp, mt pic ng vi vng nhit thp (LT), pic kia ng
vi vng nhit cao (HT). Pic LT ng vi lng NH
3
gii hp t cc tm axit yu hoc
cc tm khng axit do cht mang l silicalit. Peak nhit cao (HT) ng vi amoniac gii
hp t cc tm axit mnh c trng cho zeolit. mnh ca cc tm ny ph thuc vo
nhit gii hp. Tuy nhin phng php ny khng cho php phn bit tm axit l loi
Lewis hay Brnsted.
5.6.2 c trng ho hc v c trng b mt
Thnh phn xc tc l yu t c bit quan trng, nht l cc pha, cc hp cht b mt.
Ngoi ra cng s rt c ch nu ta nh lng c lng cht/pha xc tc trn b mt v
106
trong th tch. Cc thng tin khc cn c l tng tc gia pha hot ng v cht mang,
gia cc tm hot ng vi nhau. Cc hin tng nu c nh lng nh cc phng
php ph hin i. V xc tc d th l hin tng b mt, v vy cc phng php c
trng b mt ng vai tr quyt nh hiu bit bn cht xc tc [28].
B mt xc tc, hp cht b mt, cc nguyn t hay tp hp nguyn t kim loi phn tn
trn b mt, trng thi cc phn t b hp ph trn b mt c nghin cu bng cc loi
ph nh ph electron, ph ion, hin vi phn tch, v hng lot phng php khc [12, 33].
Ta s xem xt ln lt cc phng php nghin cu thnh phn ho hc ca b mt xc tc
v cht mang, xc nh mi tng quan gia cu trc vt liu v hot tnh xc tc. Tt
nhin nhng nghin cu ny i hi cc cng c nghin cu c phn gii rt cao. Thng
thng xc tc d th rt kh c cu trc, thnh phn ng nht, v vy phng php ly
mu, chun b mu v s la chn phng php ph hp cng quan trng khng km bn
thn cng c.
Phng php phn ng theo chng trnh nhit [44, 45]
Phn ng theo chng trnh nhit (temperature-programmed reaction) l cc k thut s
dng phn ng ho hc c tin hnh v theo di khi tng nhit tuyn tnh theo thi
gian. C mt s phn ng, l kh theo chng trnh nhit (temperature-programmed
reductionTPR), oxi ho (TPO), v sulfua ho (TPS). Thit b nghin cu bao gm: ng
ng xc tc c t trong l t nng theo chng trnh, nu xc tc l xit n s c
t trong dng kh tr, thng l Ar hoc N
2
cha vi % H
2
. Hm lng H
2
trong dng kh
ra c phn tch lin tc, khi lng H
2
tiu th cho phn ng vi xc tc xit c xc
nh theo nhit phn ng. Thng thng tc nng nhit i vi ng phn ng c
t trc bng h vi in t nm trong khong 0,120
o
C/min. Nguyn l h thng c m
t nh Hnh 5-46.
Hnh 5-46 Nguyn l thit b phn ng (kh) theo chng trnh nhit (temperature programmed
reduction TPR) [45]
S kh xc tc c th theo di bng phng php TPR. Tng ca lng H
2
tiu th tng
ng lng xi phn ng.
107
Cc xc tc x l hyr v d nh xc tc hydrodesulfurization (HDS), l Mo hoc W (xc
tin bi Co hoc Ni) trn cht mang xit nhm hot ng c trong mi trng sulfua. Cc
xc tc ban u c ch to di dng xit, s phi hot ho bng hn hp H2S v H2.
Qu trnh sulfua ho c th kho st bng TPS.
Tng t (v ngc li) nh TPR k thut TPO s c dng nh lng trng thi kh
ca xc tc. Chnh v s tng t ny trn mt my c th thc hin c hai k thut. Nu
phi hp vi gii hp CO theo chng trnh nhit (TPD) ta c TPR/TPD cho php
chun nh lng cc lin kt kim loi cha bo ho, hin tng thng xy ra khi x
l bng TPR/TPO.
nh AMI
Hin vi in t truyn qua (TEM)
TEM cho php xc nh hnh dng, kch thc ht kim loi trn cht mang cng nh khng
cht mang vi phn gii gn nguyn t [27]. Hin vi in t truyn qua qut (scanning
transmission electron microscopy STEM) s dng nguyn l phn tch tia X tn x ngc
(X-ray backscattering analysis) ghi nhn cc thng tin v kch thc, hnh thi, v thnh
phn ho hc ca cc pha hot ng trn b mt vt liu mang (Hnh 5-47).
Hnh 5-47 Tp hp cc tinh th platin trong xc tc Pt/graphit: nh lng bng ph XPS (hnh
gia hng trn), hnh nh TEM (hng di) (BASF, Ludwigshafen, c)
V d ng dng:
o phn tn ca xc tc Pd/SiO2: kt qu ph h phng php h ph ho hc
Kho st hin tng thiu kt, phn ht, ti phn tn ca cc ht kim loi trong qu trnh
xi ho
108
Kho st s hnh thnh lp cc trn b mt
Xc nh cc tp cht b mt v hin tng u c b mt
Nhiu x in t nng lng thp(Low-Energy Electron Diffraction(LEED))[9, 25]
Cc electron vi ng nng c 2200 eV l cng c rt hu hiu nghin cu b mt.
Khi c chiu ln b mt vt liu nghin cu, cc in t ny xuyn su vo vt liu
mc vi lp nguyn t, tng ng cc in t ca vi lp nguyn t ny pht ra s mang
thng tin v cc nguyn t b mt v st b mt. Trong phng php LEED, cc in t
nng lng thp vi mt ct ngang ln s b tn x n hi t cc ht nhn nguyn t. Khi
bc sng ca chng tng ng vi khong cch gia cc nguyn t ta s c hin tng
nhiu x ng vi b mt n tinh th. Khi ta s dng c cu trc trt t tun hon ca
b mt.
C th coi LEED i vi cu trc v mt tng t nh XRD i vi cu trc khi.
Cc v d ng dng:
Xc nh s thay i cu trc b mt Ni khi hp ph ho hc xi
Cu trc trt t ca b mt Pd khi hp ph CO
Xc nh qu trnh hp ph cnh tranh gia CO v O
2
trn b mt Pd
Vi b mt Au, Ir, Pt, v cc bn dn: cu trc khc ngoi suy t hnh hc mng
Ph hng ngoi (IR) [12]
o ph IR cn cuvet chuyn dng, khi s xc nh c cc tm hot ng trn b
mt v trng thi ca cc phn t b hp ph. Nhng xc tc mang trn vt liu mang hp
ph mnh, v d nh than hot tnh th c nghin cu bng ph IR phn x.
Cc v d ng dng:
nh lng cc tm axit Brnsted v Lewis b mt qua hp ph pyridin
Kt hp k thut c lp matrix (matrix-isolation, hi kim loi, 1030K, xenon
matrix, chn khng cao) nghin cu hp ph ho hc ca etylen trn cc nguyn t
Pd c lp: ghi nhn c cc phc to thnh do hp ph ho hc
Chng minh cc hp cht oxo ca kim loi (Mo,V) l xc tc xi ho
Bng hp th IR ca cc ht NO hp ph ho hc dng c trng cc xc tc
kim loi trn cht mang, v d: Mo/Al
2
O
3
, PtRe/Al
2
O
3
, xc tc cracking
Ph in t phn tch ho hc (Electron Spectroscopy for Chem. Analysis= ESCA)
y l phng php ph bin phn tch thnh phn ho hc b mt [19]. Trong ph
ESCA, mu s c chiu bng tia X (Hnh 5-48).
109
Hnh 5-48 My ph ESCA (BASF, Ludwigshafen, c)
Khi chm tia X chiu vo mu nghin cu, cc quang in t (photoelectrons) s pht ra
v c phn tch bng cch o ng nng ca chng. T y ngi ta tnh c nng
lng lin kt ca cc in t gc, suy ra nguyn t ch. S dch chuyn ho hc
(chemical shift) ca cc gi tr nng lng s cho thng tin v cc lin kt v trng thi xi
ho ca nguyn t ch. Ph ESCA c dng ghi nhn cc nguyn t nng hn hydro
lp b mt xc tc dy 510 nm. Hnh 5-49 l mu ph ESCA ca xc tc Ag/Al2O3.
Hnh 5-49 Ph ESCA ca xc tc Ag/Al
2
O
3
[25]
y ta thy cc vch ph sc nhn ca cc quang in t v cc pic t hn ca in t
Auger trn nn ca cc in t ri rc khc?. Cc vch ph c quy cho nguyn t no l
da trn bng cc gi tr ca nng lng lin kt ca cc thnh phn xc tc [25].
Cc v d ng dng:
Phn bit Al kim loi v Al trong xit Al
2
O
3
Phn bit cacbon aliphatic v cacbon axit
nh dng c cc trng thi xi ho ca Sn v s thay i khi tin x l xc tc
Pd/Sn
nh hng ca hiu ng tin x l ln cu trc v thnh phn xc tc kh lu
hunh Mo/Al
2
O
3
Phn bit trng thi Fe
0
v trng thi Fe
III
trn xc tc tng hp amoniac
Ph in t Auger - Auger Electron Spectroscopy (AES)
110
Trong phng php ny mu s b bn ph bng cc in t nng lng cao (15 keV)
[32]. Tng t nh trong phng php ESCA, mu s pht ra cc photoelectron. Cc
nguyn t mt in t t lp K c hai kh nng lm y tr li lp K thiu in t: (1) lp
K trng nhn in t t cc lp trn, khi nng lng d ca in t ny s c pht ra
di dng cc lng t hunh quang (fluorescence) tia X; (2) in t s in y ch trng
ca lp K, nng lng d s c chuyn cho cc in t ho tr, cc in t ny s bn ra
khi mu di dng in t Auger. Cc mi quan h tng t nh phng php ESCA.
ng nng ca cc in t Auger cho php xc nh bn cht nguyn t sinh ra n, cng
pht x s t l thun vi nng . Tc ng ny ch xy ra cc lp b mt ti su
5 nm. u im ca ph AES l chm in t rt chm. Khi chuyn dch chm in t trn
b mt mu v nh lng lin tc ta thu c hnh dng phn b ca nguyn t no
trn b mt dc theo ng qut ca chm in t. Nhc im ca phng php l
nhy thp v kh nng ph hu mu do chm tia nng lng cao. AES dng xc nh
thnh phn ho hc b mt v nhng thay i nu c.
Cc v d ng dng:
Trong nghin cu hyr ho alkyn trn xc tc NiS: Ni3S2 trn xc tc l pha hot
ng trong phn ng hyr ho chn lc, cn NiS khng hot ng
Xc nh t l Si/Al trong tinh th v trn b mt zeolit
Ph bn ph ion - Ion Scattering Spectroscopy (ISS)
Hnh 5-50 Ph ISS ca xc tc bc trc v sau s dng trong phn ng xi ho etylen [26]
Trong phng ph ny b mt mu c bn ph bng cc ion kh him, v o ng nng
ca ion sau khi va chm vi b mt mu [21, 31]. Ta c th hnh dung nh ta bn nhng
qu bng ln mt bn, cc ion s chm vo cc nguyn t b mt lp trn cng. Khi bit
111
khi lng v nng lng ca ion kh him trc va chm, s dng cc phng trnh biu
din nng lng c hc v xung ta tnh c khi lng nguyn t b mt va chm vi
ion. Khi ta c trong tay phng php phn tch bn cht ho hc b mt. Nhc im
ca ph ISS l cc pic kh rng, v khng thu c thng tin v lin kt.
Khi s dng ph ISS so snh xc tc bc trc v sau khi s dng trong phn ng xi
ho etylen tng hp oxit etylen ta thy r cch thc hot ng ca xc tin kim loi
kim (Hnh 5-50). Theo thi gian cc nguyn t kim loi kim xc tin s tri u trn b
mt xc tc [25].
Khi ph ion th cp (Secondary Ion Mass Spectrometry = SIMS)
Trong phng php ny cng dng cc ion kh him bn ph mu (ion s cp: 110
keV) [9, 31]. Khi va chm vi b mt, nguyn t hoc nhm nguyn t b mt, hoc ion
th cp s bn ra khi b mt. Cc mnh tch in bn ra, c m ln dng, c phn tch
bng khi ph k. SIMS c s dng phn tch tt c cc nguyn t trong bng tun
hon, k c cc ng v ca chng. Khi s dng chm tia nng lng thp ta c th gii
hn su m chm ht c th xuyn qua gn nh ch l mt lp nguyn t trn cng
(SIMS tnh). Khi s dng chm ion nng lng cao hn ta c th bo b i tng lp
phn t, khi ta s c bc tranh v phn b nguyn t theo chiu su (mt ct ngang
mu) t vi nanomet ti vi micromet (SIMS ng). y l phng php phn tch b mt
v phn b theo su nhy nht. Gii hn pht hin ln ti 5x10
14
nguyn t/cm
3
hoc 1
ht trn 10
8
ht ngha l tim cn mc ppb.
V d ng dng:
Xc nh c:
S thay i t l Si/Al bn trong xc tc cracking so vi trn b mt
Hiu ng ca kim loi trao i trong zeolit
Chng minh c s phn tch Pt trn b mt ca xc tc Pt/Re
Thnh phn b mt ca Cu, Co, v Ni trn xc tc MAl
2
O
4
dng spinel
Tc ng ca CO ln b mt Ni: ghi nhn c NiCO
+
v Ni
2
CO
+
, c ngha l
CO tn ti di dng hp ph phn t hay khng phn li
Tt nhin mi phng php lun c c u im v nhc im. V vy c bc tranh y
v bn cht cc qu trnh xy ra trn xc tc, mi quan h vi cu trc bn thn xc tc
th tt nht cn phi hp nhiu phng php, t cc phng php phn tch b mt, cc
phng php hin vi, hp ph ho hc n cc phng php ng hc phn ng.
Vn chnh trong phn tch b mt l cc iu kin kht khe cn phi m bo t khu
chun b mu ti o c (Xc nh chnh xc b mt n tinh th, nhit thp, chn
khng siu cao). Cu hi cn li s l t cc kt qu nghin cu phng th nghim c th
ngoi suy ra din bin ca bn thn xc tc trong iu kin cng nghip (p sut, nhit
112
cao, tp cht) c khng. Bng 5-46 cho thy kt qu th nghim thng c ghi nhn
trong iu kin rt khc cng nghip.
Hnh 5-46 So snh khoa hc b mt vi xc tc cng nghip
Khoa hc b mt Xc tc cng nghip
B mt (n tinh th) l tng, xc nh r rng phc tp, kh xc nh b mt
B mt rt sch b mt nhiu tp cht
p sut khong 10
-8
bar p sut ti 300 bar
Cn bng kim sot tc
Mc d nghin cu v hiu r v ng v xc tc l bi ton rt phc tp, tuy nhin nhng
nm gn y khoa hc t c rt nhiu thnh cng lm cu ni gia nghin cu c
bn v ng dng cng nghip. Trong mi trng hp cc phng php hin vi v phn tch
b mt v ang ng vai tr quyt nh trong nghin cu pht trin v ti u ho xc
tc.
113
Ti liu sch gio khoa v xc tc d th v ho l b mt [T]
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ng vi hp ph n lp (mononuclear coverage) trn b mt. ng cong

, ngha l hp ph t gi tr n lp, ffy

. Khi , b mt s phn cc v mang in m, iu ny s cn tr

. Trong trng hp NiO ion Ni

b mt rt hot ng, qu trnh m t nh sau:

ads mt trong Pt.5.55). Qu trnh chuyn electron t O

ads + [+] (5.58)

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