1.

Trong xc tc d th ty theo cch chia ta c

Chia thnh 3 giai on

1.Cht phn ng s khuch tn n b mt
2.s hp ph ca cht phn ng n b mt
3.s khuch tn sn phm ra khi b mt
- chia lm 2 giai on
1 cht phn ng s khuch tn n b mt
2 cht phn ng s hp th vt l trn b mt xc tc
3 hp th ha hc xy ra v hnh thnh phn ng
4 nh hp ph
5 khuch tn ra mi trng
-chia lm 7 giai on
+ khuch tn cht phn ng bn ngoi mao qun
+ khuch tn cht phn ng bn trong moa qun
+ hp ph bn b mt xc tc
+ nh hp ph
+ khuch tn sp bn trong mao qun
+ khuch tn sn phm bn ngoi mao qun
Cu trc cht mang xc tc
Cu trc zeolite
L cu trc c dng bi Sio2 v Aluminat (Alo2-)

Cng thc chung ca Zeolit : Nax(AlO)x(SiO2)192-X(H2O) x=54-58

SiAl=X:(192-X)
Quyt nh cu trc khung ca zeolite
Hp ph
-Hp ph l s gia tng nng 1 s cht nht nh trn b mt cht xc tc
-Cc kiu hp ph:
C 2 loi chnh Hp ph ha hc v hp ph vt l
Phn bit da vo nng lng hp ph
-Hp ph vt l:c im tc hp ph nhanh v khng c nng lng hot ha,nhit hp ph
c gi tr nh
+vai tr : hp ph vt l l phng tin quan trng xc nh nhiu tnh cht c trng ca xc
tc.Do hp ph vt l it ph thuc vo thnh phn ha hc ca b mt cht xc tc nn c th s
dng xc nh i lng b mt cht xc tc,hnh dng,kch thc ca cc tiu phn to nn
cc ht xc tc,hnh dng v kch thc l cc l xp v nhiu i lng c trng khc ca xc
tc

Cu 3 Zeolit
-Cht tr xc tc l cht m bn thn n khng c tc dng xc tc khng lm tng tc phn
ng nhng nh c n m cht xc tc pht huy ti a kh nng xc tc ca mnh
-Ch
+cht tr xc tc v cht xc tc khng tc dng vi nhau
+cht tr xc tc tuy chim hm lng b nhng c th lm tng hot tnh xc tc ln hng trng
hoc hng nghn ln
VD Nu them 0.01% FeCl3 hot tnh ca Ni tng ln nhiu ln nhng nu hm lng FeCl3>0.01

Th hot tnh Ni li gim

ZnO l xc tc v nh hnh c hot tnh cao nhng 600 C Zn dng kt tinh v khi
hot tnh mt hn.
Khi them ZnO + Cr2O3 th ZnO vn dng v nh hnh
+ Vai tr c th ca cht tr xc tc
-Gim iu kin khc nghit ca phn ng
-lm tng bn c hc cng nh bn nhit ca cht xc tc
-Lm tng bn ha hc v gim ng c xc tc
+phn loi cht tr xc tc
-cht tr xc tc dng hnh hc
-cht tr xc tc tng dng cu trc in tch
-cht chng ng c xc tc
Mt s quan im gii thch v hin tng cht tr xc tc
Cht tr xc tc ny khi cho vo xc tc s kt hp vi 1 trung tm hot ng c v cho ra 1
trung tm hot ng mi c hot tnh cao hn,to iu kin cho s phn hy v hnh thnh hp
cht trung gian do lm tng tc phn ng ( tm hot ng rt nh=10-5 ngh l 1023 trung
tm ch c 1 tm hot ng)
Cht tr xc tc cho vo s lm tng tc ca giai on chm nht ca qu trnh c th tng tc
hp ph ca qu trnh ny v lm gim tc ca qu trnh kia to iu kin cho phn ng
xy ra
Cht tr xc tc lm tng cu trc ca xc tc lm cho mng li ca tinh th trong b mt xc
tc linh ng v hot ng hn
Cht tr xc tc lm tng khong cch ca nguyn t xc tc cho ph hp vi yu t tng ng
hnh hc
Khi cht tr xc tc l cht kh,khi a va n s to nn mt lp nhy bao ph b mt xc tc
va to ra trung tm hot ng trn b mt,khi kh tr thnh phn cc v lm cho xc tc tt
hn.

Cu 4 Hot tnh xc tc , chuyn ha, chn lc cch tnh

Hot l i lng c trng ch yu cho cht xc tc

A= Wk-Wo(`1+)
Wk l tc phn ng ca xc tc( tc sau khi tng tc vi cht xc tc) mol/cm.sec
Wo l tc phn ng khng c cht xc tc mol/cm3.s
phn th tch b chim ch bi xc tc
phn ng xc tc d th c th xy ra trong 1 khng gian nh hn nhiu so vi th tch ca bnh
phn ng.b mt ring c din tch ln nhng bi v chiu dy b nn khng gian xc tc c
kch thc rt b so vi th tch khi xc tc nm trong bnh phn ng
s gim nng lng hot ha trong phn ng xc tc so vi phn ng khng xc tc l yu t
quyt nh hot xc tc
chn lc( selective)
L kh nng ca cht xc tc ch thc y mt trong nhng hng chuyn ha c th ng thi
xy ra cu h phn ng,l 1 c trng rt quan trng ca xc tc
C vai tr ngy cng quan trn. chn lc cao ca cc ch xc tc gip gim chi ph lm sch
- chn lc c biu din bi t s ca tc phn ng mong mun trn tng tc tt c
cc phn ng xy ra: S=v/vi ,S=q/qi hiu sut sn phm mong mun qi trn tng sn phm
chn lc chia thnh 3 loi
chn lc ca 1 phn ng ha hc(oxi ha 1 trong cc hp cht trong ha hc)
chn lc trong phn ng II ( chn lc theo hng Hidro ha hoc dehidro ha 1 ancol)
chn lc ph thuc vo : nhit ,p sut,thng phn ha hc ca phn ng,tc th tch,
chuyn ha
-theo 1 cch khc c th hiu chn lc l hot ca cht xc tc theo 1 hng c th

Cu 5
Cch xc nh lc axit-bazo
Phng php ch th hammet
Lc axit c xc nh bng kh nng ca n cho proton 1 bazo trung ha

H+ +B <=> BH+

Kb= aBH+/aH+.aB

1/ Kb = Ka=(ah+.ab)/(fBH+.CBH+)
Pka=Ho=log( Cb/CBH+)
Ho l gl hm hammel
Ho< -12 super acid
Ho>26 super bazo
-Trong dung dch long Ho sp s PH, axit cng cao th gi tr Hammet cng m
HClO4
H -10 Ch th hammet ch cho ta xc nh axit chung v chng tc dung vi c
tm bronsted v tm lewis
H2SO4
Phng php kh NH3 theo chng trnh nhit .
Nguyn tc: xc nh c lc v tng s tm axit trn b mt s dng NH3 s kh theo
chng trnh nhit .Nng lng m nhit cung cp phi ln hn nng lng hp ph ca
NH3.Sau gii hp b mt,NH3 s c kh mang a n detecter nh hng
-Da vo din tch pic cc nhit khc nhau s nh lng NH3 tiu th v khi s nh
gi lc axit v s tm axit
-Vi tm axit mnh th s kh NH3 nhit cao v ngc li
+tm axit yu hp ph di 200 C
+tm axit trung bnh hp ph t 200-100 C
+tm axit mnh hp ph ln hn 100 C
Tng s tm axit n = Pi/RT
Nhc im : khng xc nh c tm axit,bazo
B, xc nh tm bronsted tm lewis
S dng ph hng ngoi hp ph FTIR-pyridin
cc tm axit ca xc tc

l phng php ph bin nht c trng

+S sng ca Pyridin v H+
Py,H+ =1550 cm-1 pyridin c trng cho s hnh thnh ca tm pyridin v tm Bronsted

S sng c trng cho pyridin lien kt phi tr vi tm Lewis

Trung bnh XPy,L=1450cm-1
Cu 8.Xc tc cho qu trnh ankyl ha :Xc tc s dng c ch tng tc,cch thu hi hoc s
dng li xc tc
Trog cng nghip ha du Ankyl ha nhn th vi tc nhn Olefin

Sn phm trung gian to ra styrene,phenol,oxeton

Trong cng nghip lc du :sol olefin C3- C4

isoparafin mch di

Isobutan
Xc tc s dng H2SO4 93-95%
HF

83-91%

Zeolit ankyl ha hp cht thm

C ch tng tc
-Thc hin trong pha lng,ta nhit
-N c s dng l h thng lm lnh cho qu trnh
-Nhit thc hin : 80-100 F
-p sut

10atm

T l isobutan dng d so vi olefin

isobutan
olefin = 6:14

Lng d isobutan cch hp cht hu c khng phn ng:propan,n butan,sn phm ankylat v
xc tc c dn qua b lng khi ax c c tch ra bng phng php trng lc sau
quay tr li
C ch
GD1: H+ tn cng vo olefin to ra ion cacbeni
C-C=C-C, H+ -> C-C+-C-C
GD2 : Dch chuyn Ion hidrua t iso butan H+ sang cacbeno to ra Ioncacbeni bc 3 bn hn
C-C-(C)-C+C-C+ -C-C -> C-C+-(C)-C+ C-C-C-C
Sau Ion bc 3 C-C+-(C)-C quay tr li phn ng vi olefin ban u
C-C+-(C)-C+C-C=C-C -> C-C-(C)-C

-C-(C)-C-C

Chuyn dch metyl

CH3-C-(CH3)-CH3)-CH2-C+-(CH3)-CH3 CH3-C+ -(CH3)-CH-(CH3)-CH-(CH3)-CH3
Ioncacbeni ti sinh v phn ng vi cc olefin khc
CH3-C+ -(CH3)-C-(CH3)-CH3)-CH2-CH3 + CH3-CH-(CH3)-CH3) -> iso C8H10+ CH3-C+ (CH3)-CH3
Giai on 3
Phn ng tt mch xy ra
CH3-C+-CH3 CH3-C-(CH3)=CH2)+ H+
Qa trnh ti sinh xc tc
-Ti sinh HF
Thu hi HF bng thit b ti sinh
nh thp gm HF v isobutan c ti sinh li
y thp HF ln polymer v hn hp ng kh
Khi s dng KOH trung ha HF+KOH ->KF+H2O
Ti sinh KOH bng cch s dng vi sng 2KF+Ca(OH)2->2KOH+CaF2 kt ta
Qu trnh ti sinh H2SO4

H2SO4 tiu th gp 100 ln HF

Khng th tch c t lien kt ca polyme,nc,cht bn
H2SO4 thi 88-91% H2SO4.Khi lc axit yu khng th ti sinh ax
Ax thi ti ch bng cch t chy H2SO4 b oxy ha ->SO2+H20
H2SO4 + Polyme -> SO2+ H20
Lm kh SO2,oxy ha SO2 thng SO3 -> ra vi nc to ra H2SO4
SO3+H20 ->H2SO4 98,5% - 99.5 %
-Ankyl ha hp cht thm s dng xc tc ax rn (zeolite)
VD

+ CH2=CH2 ->

-CH2-CH3

Xc tc cn la chn ph thuc vo tnh ax v chn lc hnh hc phng trnh c

-Zeolit trung tm hot ng cung cp proton H+ Zn+ Z+tn cng toluene to hp cht trung gian

+ CH3+OHZ-

+ HZ
Cu 9 Xc tc lien quan n chn lc ha hc pt
chn lc hnh hc ph thuc vo kch thc ca s mao qun
-Qu trnh bt i ha

C ch ankyl ha lng phn t 2

Ngoi ra cn xut hin phn ng ph

2CH3OH CH3OCH3+ H20
Phn ng bt i ha

+
Sn phm thu c l cc ng phn
Nu tm hot ng l zeolite th i vi phn ng bt i xng ha toluene,H+ s tn cng vo
toluene

Tip tc chuyn di sang 1 pt toluen

axit lewis l tm hot ng trong phn ng phn ct

+ L

Cu 10 xc tc cho qu trnh hidro ha, dehidro ha xc tc s dng c ch tng tc

-Qu trnh ehidro ha parafin nh
RHn RHn-m +m/2 H2 delta H > 0
Ngun olefin tch t hn hp sn phm ca qu trnh cracking xc tc hoc qu trnh nhit phn
du m.ng phn ha n-olefin thnh no-olefin t qu trnh cracking nhit v cracking xc tc
ehydro ha prafin nh
Xc tc cho qu trnh dehidro ha
+Kim loi (nhm 4,6,7)
Oxit kim loi Cr203 + ph gia Al203
Xc tc hin nay s dng:xc tc kim loi hot ng phn tn trn cht mang
Xc tc 0,5% Pt phn tn trn cht mang sd Al2O3 c din tch b mt ring ln( tng kh
nng phn tn ca tm hot ng trn cht mang)
C ch phn ng ddehidro ha parafin nh
CnH2n+2 + 2Z CnH2n+1Z + HZ
CnH2n+1Z +Z CnH2n Z + HZ
CnH2n Z H2+ 2Z