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Ky Thuat Xuc Tac
Ky Thuat Xuc Tac
Ky Thuat Xuc Tac
K thut xc tc
QUY NH V CCH NH GI IM
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GII THIU V NI DUNG MN HC
TT Ni dung Tit
1 Chng 1: Vai tr ca xc tc trong cng ngh ha hc 3
2 Chng 2: C s ca qu trnh xc tc 15
3 Chng 3: Xc tc cng nghip 7
4 Chng 4: Sn xut xc tc cng nghip 6
5 Chng 5: Cc phng php nh gi v nghin cu. 14
Tng 45
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TI LIU THAM KHO
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TI LIU THAM KHO
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CHNG 1: VAI TR XC TC
TRONG CNG NGH HA HC
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1.1 LCH S PHT TRIN XC TC.
. T 100 nm trc
Phm nhum
Antraquinon + acid sulfuric =
acid sulfonic
Hg
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1.2 VAI TR CA XC TC .
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Tn phn ng Sn phm cui Cht xc tc rn
A. Cc phn ng oxy ha kh
1. Oxy ha
SO2 + O2 SO3 H2SO4 Pt, V2O5, Fe2O3
CO + O2 CO2 Lm sch kh. kh v kh thi khi CO hh oxyt : Mn, Cu, Co, Ag, Pt, Pd.
H2 , Hydrocacbon + O2 CO2, H2O Lm sch kh thi Pt, Pd, CoO, CuO, V2O5, NiO...
mCH4+ nH2O mCO2 + nH2 (st.reforming s cp) Kh tng hp Ni trn cht mang
CH4 + 3/2O2 CO + 2H2O (steam reform. th cp)
2. Hydro ha
N2 + 3H2 2NH3 Amoniac Fe +cc cht xc tin ( K 2O, Al2O3, SiO2 CaO..)
CH2=CH2 + H2 CH3 -CH3 Lm sch khi kh HC khng no Pt, Ni
2. Cracking hydrocacbon
Hydrocacbon (C20 -C25)HC C6 -C12 Nh. liu cho ng c Zeolit, Aluminosilicat
3. ng phn ha
butan isobutan isobutan AlCl3; AlSi; phosphat
Hydrocacbon n.C5 n.C6 i.C5 -iC6 xng isomer Pt mang trn Al2O3 hoc trn zeolit Mordenit
4. Alkyl ha hydrocacbon
C6H6 + CH2=CH-CH3 C6H5-CH(CH3)2 Cumen cho sn xut phenol H3PO4 trn cht mang
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1.3 ngha ca xc tc trong cng
nghip v i sng
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1.3 ngha ca xc tc trong cng
nghip v i sng
Cracking xc tc:
L phn ng chuyn ha cc sn phm nng ca du m thnh xng
c nhit si 38-2000C
Hiu sut xng cao hn
Ch s octan cao hn
Gim t l FO v kh trong sn phm
Cht xc tc hin nay 15% zeolit cha t him + 85%
aluminosilicat tng hp v nh hnh
Phng php hin i l tin hnh phn ng theo ch lp si
FCC ( phn ng 475-5100C, 0,5-2 atm)
Cracking xtc l quy trnh xtc cng nghip c quy m ln nht. (
M mi ngy c 1 triu tn du c ch bin)
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1.3 ngha ca xc tc trong cng
nghip v i sng
Reforming xc tc:
L qu trnh thc hin mt s phn ng, trong du
m chuyn ha thnh HC thm v mch nhnh, nhm
2 mc ch chnh l sn xut nhin liu xng c ch s
octan cao v HC thm.
iu kin thc hin 480 - 5200C , 6- 20 atm
Phn ng chnh: ehiro ha naphten, ng phn ha
naphten, ehidro vng ha, ng phn ha parafin.
Cht xc tc ph bin Pt/ Al2O3
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1.4. Lch s pht trin v xu hng ci
tin ca xc tc lc ha du
Vai tr xc tc trong cng nghip ch bin du kh :
Du th ban u ch cha khong 5 20% phn on nh (xng),
nh cc qu trnh ch bin c xc tc (cracking xc tc, reforming xc tc ng phn
ha...) thu ti 75% xng c cht lng cao hn ban u rt nhiu.
Nh c xc tc (kim loi v oxyt), t du m, than v kh t nhin thu
c cc sn phm nh BTX, olefin nh...l cc nguyn liu quan trng cho ha du
sn xut ra cc polymer, cht do, nha, cao su phc v cho kinh t v i sng
con ngi. Qu trnh xc tc cn ng vai tr quan trng trong sn xut cht ty ra,
phm nhum v dc phm....
Chuyn ha xc tc metan vi hi nc thu c Kh tng hp (c thnh phn mCO
+ nH2) vi hi nc To nguyn liu cho hng lot qu trnh sn xut khc
(u l qu trnh xc tc) thu cc sn phm c gi tr s dng cao nh : metanol,
hydrocacbon, amoniac, cht ty ra, ru bc cao.
( Thay i cht xc tc v thay i cc iu kin cng ngh c th a dng ha cc
sn phm vi thnh phn v tnh cht khc nhau vi cc nh hng s dng khc
nhau).
Xc tc hin i vi yu cu v mi trng : Cc qu trnh xc tc loi b cht
c, lm sch kh thi rt c quan tm. Cc qu trnh t cc thnh phn c hi
trong kh thi nh hydrocacbon, CO, NOX , SO2...thnh CO2 v H2O c s dng
rng ri vi s c mt ca cc xc tc Pd, Pt...
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1.4. Lch s pht trin v xu hng ci tin
ca xc tc lc ha du
Xu hng ci tin ca xc tc lc du :
Cc cht xc tc cho cc qu trnh lc ha du ngy cng c ci tin theo hng
p ng cc yu cu cng ngh mi v yu cu v cht lng sn phm
Tin phong trong lnh vc ch to xc tc t vt liu mi (nano...)
p ng nhng i hi ngy cng kht khe hn v mi trng.
C th :
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Vai tr ca xc tc trong qu trnh lc ha du
1.2. Mi tng quan gia cng ngh ch bin du kh v xc tc
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Cng ngh lc du v xc tc gn b mt thit, hu c. Cng
ngh lun tm cch p ng trc nhng c th ring ca mi
th h xc tc ; ngc li, nhng i hi t pha cng ngh
thc y xc tc phi lun cn ci tin hoc i mi.
V d :
- Cng ngh reforming xc tc loi bn ti sinh ph hp
vi h xc tc Pt-Re/Al2O3, trong khi cng ngh ti sinh lin tc
li c chn cho h xc tc Pt-Sn/Al2O3.
- Cng ngh cracking tng si i vi phn on cn du
(cng ngh RFCC), i hi cht xc tc cha zeolit phi ci
tin rt nhiu c pha hot tnh ln pha nn v c cht ph gia
nhm p ng yu cu kht khe ca cng ngh v c th ca
nguyn liu nng.
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CHNG 2: C S CA QU
TRNH XC TC
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2.1 CC KHI NIM CHUNG V XC TC.
S xc tc:
Xc tc l hin tng thay i tc do tc dng ca mt s cht.
Hin tng bin i tc phn ng ha hc hay kch ng chng do
nhng cht m cui cng vn c phc hi gi l s xc tc.
c im quan trng nht ca cht xc tc l vi mt lng rt nh
cht xc tc , ngi ta c th thc hin vic chuyn ho mt lng rt
ln cc cht phn ng
Tnh nng ca cht xc tc ng vai tr ht sc quan trng trong vic
nng cao hiu sut phn ng, dn n gim gi thnh sn phm.
Tr cc nguyn t tr, hu ht cc nguyn t ho hc u c th l
cht xc tc hoc mt thnh phn ca cht xc tc (dng kim loi,
oxit, axit, baz, mui, cc phc cht ...).
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2.2 Phn loi phn ng xc tc:
C ch ca cht xc tc:
Xc tc dng (xc tc) lm tng tc phn ng.
Xc tc m (cht c ch-inhibitor) lm gim tc phn ng.
Trong thc t, ch s dng cht xc tc thun.
Du hiu v pha trong phn ng:
Xc tc ng th.(cht xt ha tan cng pha vi cc cht phn ng.)
Xc tc d th.(xt tip xc).
Xc tc chuyn pha. Cht xc tc to thun li cho s dch chuyn cc
tc cht khc pha c th tip cn nhau phn ng.
Cht xc tc c sn trong h phn ng hay cho t bn ngoi vo:
Phn ng t xc tc: Qu trnh xc tc xy ra bi cht xt l mt trong
cc sn phm phn ng.
Phn ng c dng xc tc.
Bn cht ca cht xc tc:
Xc tc ha hc.
Xc tc sinh hc (enzym).
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2.1 CC KHI NIM CHUNG V XC TC.
- khi phc hot tnh ban u sau mt thi gian s dng, cht xc
tc cn c ti sinh, hot ha li. Trong mt s trng hp cn b
sung thm xc tc mi hoc thay th hon ton.
nh ngha sau y phn no th hin ng thi
tnh c bn - ng dng : Cht xc tc l cht lm
tng tc phn ng nhm t ti trng thi cn
bng m khng c s tiu tn ng k v lng
trong sut qu trnh.
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2.3. Cc tc dng chnh ca cht xc tc
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2.4. Cc c tnh ca cht xc tc
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2.4.1.Tnh chn lc .( chn lc)
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2.4.2.Hot ca xc tc.
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Phn bit la chn v hiu sut.
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Lu :
Cht xt c th s dng cho mc ch lm tng hot hoc la
chn, i khi c 2 mc ch.Trong trng hp c s a dng v sn
phm th yu t la chn tr nn quan trng hn.
Hot tnh xt c th c tng ln khi lm tng nhit . Tuy nhin t
tng cao d dn n: rt ngn thi gian sng ca xt, hoc tng thm
s lng cc phn ng(t,xt) khng mong mun. T cao s lm gim
chuyn ha cc i ca cc qu trnh mang tnh ta nhit do
khng thun li v mt nhit ng hc.
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2.4.3Bo ton thnh phn ho hc, bo ton lng
cht
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2.4.4.Lm gim nng lng hot ho (Ehh).
A+B D
A + B AB
AB D
A + [K] A[K]
A[K] + B AB[K]
AB[K] D + [K]
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Nng lng hot ha
W = k . f (C )
E / RT
k = k0 .e
E xt / RT
k xt = k0, xt .e
E xt / RT
k xt k0, xt
e k0, xt E / RT
= E / RT = e
k k0 e k0
E = E Ext
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Khng xc tc: A + BAB
AB D c k = k0e-E/RT
Khi c xc tc (theo thuyt hp cht trung gian):
A + [K] A[K]
A[K] + B AB[K]
AB[K] [K] + D c kxt = k0xte-Ext/RT
So snh cc hng s tc
phn
E ng:
/ RT
k xt k0, xt .e xt k0, xt
= = .e E / RT
k k0 .e E / RT k0
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Thc nghim cho thy:
Nu khng c CXT phn
ng c nng lng hot ha
Ea = 44 Kcal/mol
CXT: Au
Ea = 25 Kcal/mol
CXT: Pt
Ea = 14 Kcal/mol
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nh hng ca iu kin bn ngoi ln s xc tc.
Nhit .
Mi cht xc tc c mt khong nhit xc nh m khi
n biu hin tc dng ti u gi l nhit thch hp
(xc nh thng qua thc nghim).
p sut v nng .
S lin quan gia p sut (nng ) vi hng s cn bng
phn ng v mt nhit ng hc.
Dung mi.
nht.
ho tan ca cc kh vo dung mi.
Hng s in mi, axit v baz.
S hnh thnh phc, s lin hp v s solvat ha.
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nh hng ca iu kin bn ngoi ln s xc tc.
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2.4.5 c trng nhit ng hc ca phn ng xc tc
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2.4.5 c trng nhit ng hc ca phn ng xc
tc
Phn ng thun nghch: CXT
- khng lm thay i mc cn bng - lm cho phn ng mau
t ti trng thi cn bng
- lm tng vn tc phn ng - tng vn tc phn ng thun bao
nhiu ln th cng lm tng vn tc phn ng nghch ln by
nhiu ln
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2.5.Phn ng xc tc ng th
c trng ca p xt ng th:
KN: Xt ng th l cht xt cng pha vi cc cht
tham gia phn ng.
P xt ng th ch xy ra trong pha kh v pha
lng, khng c xt ng th trong pha rn.
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C ch phn ng xc tc ng th
Phn ng xc tc ng th trong pha kh.
Ly phn ng oxy ho SO2 vi xc tc NO lm th d:
2SO2 + O2 2SO3
S n gin ca phn ng nh sau:
2NO + O2 2NO2
2SO2 + 2NO2 2SO3 + 2NO
2SO2 + O2 2SO3
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Nt c trng ca phn ng xc tc ng th.
Phn ng xc tc axit baz (axit v baz c tc dng xc tc).
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Ni dung thuyt Hp cht trung gian
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Thuyt hp cht trung gian
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Thuyt hp cht trung gian
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Thuyt hp cht trung
gian
C th c nhiu cht phn ng cng nh nhiu
cht xc tc ng thi tham gia hnh thnh mt
sn phm trung gian. Cc cht xc tc tng tc
nh hn hp xc tc.
Mt cht xc tc c th to vi cht phn ng
ng thi nhiu sn phm trung gian.
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Thuyt hp cht trung gian
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Phn ng xc tc ng th vi xc tc axit-baz
1.N:Theo Bronsted-
Lowry:
Axit l cht cho proton. AH + H 2O = H 3O + + A
axit bazo axit bazo
Dung dch axit trong nc l
h hai cp tn ti song song
axit-baz nh:
+
Baz l cht nhn proton. NH 3 + H 2 O = NH 4 + OH
bazo axit axit bazo
Baz trong dung dch nc
cng tn ti hai cp axit-baz
nh
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Theo Lewis:
Axit l cht c kh nng dng cp in t t
do ca phn t khc to ra lp v in t
bn.
Baz l cht c cp in t t do c kh
nng dng to phn t bn. Vy axit-baz
Lewis thuc loi khng cha proton.
Tt c cn bng u lin h n vic s dng
cp in t t do ca phn t khc, hay gp
chung vi phn t khc.
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Mi quan h n proton c thit lp theo l thuyt
ca Lewis l do c s tn ti cp in t khng cp
i.
H3O+ + O H- H2O + H O H
axit bazo
H H +
H3O+ + H2O + H N H
NH
H H
axit bazo
y cp in t ca H2O v NH3 c dng
to phn t bn.
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Khi SO3 tc dng vi H2O, th nc l bazo
v c in t t do, cn SO3 s dng trn
nn l axit.
O H OH O - H +
OS +O O S O + HOH O S OH + HO
O H OH O H
axit bazo
O 2- H +
+ HOH O S OH + HO
O H
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2. PHN LOI
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ng hc thuyt hp
cht trung gian
Nu cn bng chuyn v pha to cht u, tc
l Kc[A]n << 1 th phng trnh tc c dng
sau:
d [A]
= k phhuy .K c .[A] [K]
n
dt
Tc l phn ng c bc n
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ng hc thuyt hp
cht trung gian
Phn ng lng phn t
A+ K
AK
k1
k2
AK + B
( AKB ) k3 *
( AKB) X + Y + K
* k4
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ng hc thuyt hp
cht trung gian
Ta s dng qui lut nng dng cho trng
hp ny
d [AK]
= k1.[A][K]-k 2 .[AK]-k 3 .[AK][B]=0
dt
*
d[(AKB) ]
= k3 .[AK][B]-k 4 .[(AKB) ]=0
*
dt
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ng hc thuyt hp cht trung gian
k1k3 [A][B]
*
[(AKB) ]= [K]
k 4 ( k2 +k3 [B]
d[A] k1k3 [A][B]
- = k 4 [(AKB) ]=
*
[K]
dt k 2 +k3 [B]
Nu k2>>k3[B] th k2+k3[B]k2
d [A] k1k3
= [K][A][B]
dt k2
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Tc phn ng xc tc ng th
t l thun vi nng CXT
k1
A + [K] A[K] A[K] + B k3 AB[K] AB[K] k4 D + [K]
k2
d [D ] k1 k3 [ A][ B]
= [K]
dt k 2 + k3 [ B]
k2>> k3 k2 << k3
d [D ] k1 k3 [ A][ B][ K ] d [D ]
= = k1 [ A][ K ]
dt k2 dt
chat trung gian kieu Arrhenius chat trung gian kieu Van t' Hoff
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Cht kch ng
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Phn loi cht kch ng:
Cht xc tin kt cu hoc hnh hc :a vo lm gim
s dnh kt ca cc vi tinh th cht xc tc, khng cho
chng t li vi nhau thnh cc tinh th ln, t gip
lm tng b mt hot ng ca cht xc tc
Cht xc tin in t hoc cu trc : l cht m lm thay
i thnh phn ha hc ca xc tc, thay i c trng
in t hoc lm bn cu trc, lm thay i bn cht cc
trung tm hot ng ca xc tc.
Cht xc tin chng ng c:Bo v xc tc chng li s
u c bi tp cht hoc bi phn ng ph.
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Cht c xt:
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u c thc c tnh thun nghch v tnh chn lc.
Tnh thun nghch: thun nghch v khng thun nghch
u c khng thun nghch: Cc cht c cn c loi tr ngay
trong qu trnh iu ch xt, hoc qu trnh lm sch nguyn liu p.
u c c tnh cht chn lc: Nh c th lm tng la chn
ca cht xt.
u c do che ph: ch che lp cc trung tm hot ng, khng xy
ra tng tc ha hc hoc HP c trng.
u c bi che ph thng l qt thun nghch. B mt v hot tnh
xt c th khi phc li bng qu trnh ti sinh xt.
Tm li: Vn gim c s ng c xt l quan trng lm tng
hiu sut p, tng thi gian lm vic ca xt.
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S bin tnh: L hin tng m 1 cht, ph thuc vo t,
c th ng vai tr cht c hoc cht xc tin( do c
th lm thay i c kok v Ek ca mt thnh phn xc nh
cht xt k)
Hiu ng b tr: L hiu ng lm thay i ng thi k ok v
Ek nhng theo hng b tr cui cng t kt qu k ok
(hng s tc phn ng) khng thay i.
Trong thc t CN vai tr cc cht u c, cht xc tin,
bin tnh c ngha quan trng v ch vi mt lng nh
cng lm gy nh hng ln n qu trnh xt ( bao gm
c cht xt v cc tc cht).
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CHNG 2: C S CA QU
TRNH XC TC
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1.Phn ng xc tc d th
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2.Mt s c im c bn ca qu trnh xt d th:
1. Tnh c th: Hot tnh xt khng phi l mt tnh cht vn nng ca mt cht no
m ch c th c xem xt i vi tng phn ng nht nh.
Vd: cc cht xt sinh hc-cc enzim, ch xt cho chuyn ha nhng hp cht c cu
to ging nhau hoc cho chuyn ha ca mt trong s cc ng phn ca cc hp
cht .
2. Tnh a nng:
Mt cht c th ng vai tr xt cho nhiu phn ng khc nhau.
Vd: aluminosilicat c th hot ng xt cho mt lot cc qtrnh nh cracking, ng
phn ha, bt cn i ha, ehirat ha ru. Xt Pt rt hot ng trong cc phn
ng reforming, ehiro ha, ..
3. Tnh a dng:
Thnh phn ha hc ca cc cht rt a dng:
Rt nhiu cc nguyn t trong bng h thng tun hon c th l cht xt hoc tham
gia vo thnh phn cht xt.
Cht xt c th dng nguyn t, dng hp cht( cc oxit, hp kim, sunfua.,,
4. Tnh khng thay i trng thi nhit ng:
Xt khng t gy ra phn ng , khng lm dch chuyn cn bng m ch c tc dng
rt ngn thi gian t cn bng
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2.Mt s c im c bn ca qu trnh xt d th:
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2.Mt s c im c bn ca qu trnh xt d th:
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Cht xc tc d th
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Pha hot ng:
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Cc tnh cht ca pha hot ng:
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Thuyt Dankov
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V tr no cng c nhiu mt lm th cng c
nhiu lin kt vi cht phn ng v kh nng
hp ph dn n p cng cao
V tr hot ng mnh hay yu ty thuc vo
tng loi p.
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CHNG 3 : HP PH
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1. nh ngha
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2. Phn bit hp ph vt l v hp ph ha hc
Nhit hp ph
Lc hp ph
S chn lc hp ph
Lng cht b hp ph
Tc hp ph
S ph thuc ca nhit
Trng thi cht b hp ph
Tnh cht ca cc mi ni hp ph
Tnh thun nghch ca hp ph
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Nhit hp ph
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Nhit hp ph
81
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Nhit hp ph
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Lc hp ph
1.Hp ph vt l:
HPVL do lc Van-der waals gy ra gm cc lc:
Tng tc phn t
Lc tng tc tnh in.
2.Hp ph ha hc:
Trong HPHH lc tng tc gia cht hp ph v cht b
hp ph l lc tng tc ho hc
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Lc hp ph
HPHH:
B mt vt rn khng bao gi bng phng l tng m c cc vt nt
gy, hoc to ra cc bc nhy hoc ch li lm
to ra cc ho tr t do trn b
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Lc hp ph
Hp ph ha hc
S khng cn bng lc cc nguyn t cht rn kim loi
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Lc hp ph
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S chn lc hp ph
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S lng cht b hp ph
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S lng cht b hp ph
Tc hp ph vt l thng nhanh. Cn tc hp ph ho hc
thng xy chm do s khc bit v nng lng hp ph.
Khi xt v tc hp ph cn ch n nh hng ca tc
khuch tn, nht l i vi vt liu c mao qun, v trong mao qun
tc khuch tn c nh hng rt ln n qu trnh hp ph.
Tc ca qu trnh hp ph ho hc c xc nh theo phng
trnh
Khp = ko.Z.e-Ec/RT
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S ph thuc ca nhit
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Trng thi cht b hp ph
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Tnh cht ca cc mi ni hp ph
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Tnh thun nghch ca hp ph
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HPVL bao gi cng l thun nghch: hp ph
nh hp ph
HPHH khng phi bao gi cng l qu trnh
thun nghch.
Tu theo c tnh mi ni lin kt ha hc m
tnh cht thun nghch qu trnh hp ph khc
nhau.
C nhng qu trnh HPHH kh bn vng, to
thnh cc hp cht ha hc, V d nh s hp
ph Oxy ln kim loi to Oxyt kim loi, hoc khi
hp ph ln than cho CO2, CO
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HPVL c th l giai on ban u ca qu trnh HPHH v tng th
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3.nh lut HPHH- Cc pt biu din HPHH
Hp ph ng nhit ca langmuir.
Trong qu trnh hp ph nhng phn t kh b hp ph s li trn b mt
ht xc tc trong mt thi gian nht nh tip nhn nng lng v thc
hin qu trnh nh hp ph. Qu trnh hp ph v qu trnh nh hp ph xy
ra ng thi cho n khi ht phn ng t c trng thi cn bng.
thit lp c phng trnh ng hc cho qu trnh hp ph, Langmuir
a ra mt s iu kin sau(thuyt hp ph ng nhit ca langmuir).
Tt c cc tm hot ha u c tnh cht nh nhau.
S tm hot ha khng thay i theo thi gian.
Mi tm hot ha ch c th hp ph mt phn t b hp ph.
Gia cc phn t b hp ph khng c tc ng qua li.
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NG HC QU TRNH HP PH L TNG
ng hc qu trnh hp ph c c trng bi tc
qu trnh hp ph v gii hp
Phng trnh Langmuir m t cn bng hp ph trn
b mt phng, c thit lp bng phng php l
thuyt v c xy dng trn cc quan im v hp
ph l tng
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Hp ph l tng
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2.2 Hp ph n cht khng phn ly
A + R AR
Vn tc hp ph: vhA = kh . PA .(1 - A)
Vn tc nh hp ph : vnA = kn . A
Trong :
kh s vn tc hp ph
kn: hng s vn tc nh hp ph
PA: p sut ring phn ca A
A: b mt b chim bi A
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trng thi cn bng: vh= vn
/(1 - )= kP
K .P
=
1 + KP
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So snh hp ph phn ly v khng phn ly
C dng:
An nA
Khi bao ph b mt
c xc nh:
=
K .P
i =
( K i .Pi )
1/ n
1 + KP 1 + ( K i .Pi )
1/ n
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CHNG 3 : C TRNG XC TC
BNG PHNG PHP HP PH
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3.1 Khi nim v cu trc xc tc rn xp
3.2 ng ng nhit hp ph
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3.1 Khi nim v cu trc xc tc rn xp
Cc
l
xp
Mao
qun
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3.1 Khi nim v cu trc xc tc rn xp
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Bng cc i lng c trng cu trc xp ca mt s xc tc rn
C 2 loi ng hp ph:
ng ng p hp ph: qu trnh hp ph t gi P khng i ch thay i T,
ta v c ng ng p hp ph
x = f(T)P
Dng ny t c gi tr thc t nn t c nghin cu
ng ng nhit hp ph: qu trnh hp ph ta gi T khng i v ch thay
i P, ta s xy dng c ng ng nhit hp ph
x = f(P)T
Khi i lng x l hm ng bin vi p sut cn bng P
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3.2 ng ng nhit hp ph
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3.3 Cc phng trnh ng nhit hp ph
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3.3 Cc phng trnh ng nhit hp ph
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3.3 Cc phng trnh ng nhit hp ph
1
tg =
Vm
OA = 1
Vm .K
T Vm ta xc nh c b mt ring ca 1g cht hp ph:
Sr = Vm.NA.Ao
NA: s avodro (6,023.1023)
Ao: tit din ngang ca 1 phn t hp ph www.themegallery.com
3.3 Cc phng trnh ng nhit hp ph
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THUYT HP PH
A PHN T
B.E.T
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3.3 Cc phng trnh ng nhit hp ph
Phng trnh ng nhit hp ph BET (Brunauer, Emnet, Teller
nm 1938) l mt thnh cng ln p dng cho hin tng hp ph a
lp.
Gi thit quan trng ca BET l:
Cc gi thit ca Langmuir cng c ng dng vo BET.
Cc phn t b hp ph u tin c tng tc vi nhau to ra lc,
lc ny to iu kin cho lp hp ph th 2,3...n
Tc hp ph (ra) trn lp hp ph th (i), bng vi tc nh
hp ph (ra) ca lp (i + 1).
Nhit hp ph t lp th 2 tr ln n lp ngng t l bng nhau
v bng nhit ngng t
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3.3 Cc phng trnh ng nhit hp ph
V: th tch cht b hp ph
Vm: th tch cht b hp ph ln nht
T ta xc nh c C v Vm Sr hpwww.themegallery.com
ph
3.3 Cc phng trnh ng nhit hp ph
ng ng nhit hp ph v nh hp ph t n lp sang a lp
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Cc dng ng ng nhit hp ph c trng c phn loi bi IUPAC:
Cc dng vng tr khc nhau cho cc loi vt liu c cu trc mao qun
trung bnh khc nhau.
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Cc phng trnh hp ph ng nhit:
Phng trnh BET
P I C 1 P
= + .
V ( PS P ) Vm .C Vm .C PS
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Zeolit Than anthraxt Than hot tnh
L xp
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Vt liu mao qun trung bnh (mesoporosity)
S ngng t mao qun v nh lut Kelvin
i vi VLMQ trung bnh, trong qu trnh hp ph, khi p sut cn nh
hn p sut hi bo ha Ps th c xy ra hin tng cht b hp ph
ngng t.
Hn na khi kh hp ph, s bay hi cht lng t mao qun thng
xy ra p sut thp hn Ps. V do ng kh hp ph khng
trng vi ng hp ph . S sai khc l do p sut mao qun
cn tr s kh hp ph ca hi ngng ng nh p sut hp ph.
Phng trnh Kelvin xc nh mi quan h gia t s P/Ps v rk l
bn knh ca git lng hnh thnh bn trong mao qun.
P f .g.V L . cos
ln =
PS rk .R.T
T phng trnh Kelvin c th thy rng: P/Ps ca qu trnh thot hi
t mao qun ngng t lun lun nh hn P/Ps ca qu trnh hp ph.
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S phn b kch thc trong VLMQ trung bnh
x.V L
t=
Sr
Bn knh ca mao qun rp c tnh theo biu thc:
rp = rk + t
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Xc nh b mt ring ca xc tc.
Khng mt qu trnh nghin cu xc tc d th no hon thnh m khng
nh gi xp ca xc tc, b mt ring v mc phn b mao qun ca
xc tc. nh gi cc i lng trn phng php tt nht l dng
phng php hp ph.
Cng thc tnh b mt ring ca xc tc : S r = nm .N .S m
g1 g 0
xp m c xc nh theo cng thc: B= .100%
g2 g0
Xc nh xp ca xc tc.
S phn b mao qun theo kch thc ng vai tr quan trng trong qu
trnh khuch tn bn trong ca phn ng ha hc xc tc. xc nh phn
b mao qun xc tc theo kch thc th trc ht cn phi xc nh kch
thc mao qun ca xc tc.
Theo phng php BJH p dng cho nhnh kh hp ph trn ng ng
nhit, ta c cng thc: r = rk + t
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CHNG 4: XC TC CNG
NGHIP
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4.1. Cc yu cu c bn i vi xc tc vn hnh trong
cng ngh.
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4.2. Thnh phn xc tc cng nghip.
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Cht mang ( pha nn)
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Vai tr v tnh cht chung ca cht mang:
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PHN LOI CHT MANG
SiO2 60 - 70%
K2O. Na2O 2 - 4%
Fe2O3 1 3%
Al2O3 15 -20%
CaO 2 3%
% l xp 60%
B mt ring 10 m2/g
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Cht mang c b mt ring ln: oxit nhm, silicagel, t
st , aluminosilicat, than hot tnhC b mt ring t vi
trm n hng nghn m2/g
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Cc ch vn hnh xc tc trong cng nghip
Lp xc tc tng tnh:
c im c bn:
Cc lp xt c nh, c sp xp theo dy vi h thng gia nhit
hoc lm lnh trung gian.
Kim tra cht ch s thay i nhit t vng tm xt ra ngoi.
Dng nguyn liu c np lin tc vo h thng l phn ng
( cha xt) v dng sn phm c ly ra lin tc.
Ngng hot ng ton b h thng ti sinh xt ti ch ( i khi a
ra ti sinh ngoi h thng) khi hot tnh xt gim n mt gi tr nht
nh ( hoc t mt trng lng nht nh ca cc bm trn b mt
xt)
Cng ngh ny c p dng trong trng hp xt c hnh dng ph
hp, hn ch s mt mt nguyn liu v loi tr s khuch tn hn
lon. Xt thng c dng vin bi hoc dng ht n.
V d : cc cng ngh hydrogen ha, hydrocracking, ng phn
ha
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Lp xc tc tng ng:
p dng trong trng hp xt b gim hot tnh rt
nhanh( bi cc che ph)
c im c bn:
Lp xt chuyn ng nh nhng, lin tc trong h
thng thit b phn ng.
Ton b h thng c vn hnh lin tc.
Lp xt sau khi ra khi h thng phn ng c
ra ngoi ti sinh ring. Sau c bm tr
li vo h thng ( t pha u l phn ng).
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Lp xt tng si:
p dung trong trng hp khng gii quyt c vn truyn
nhit nu s dng lp c nh.
c im:
Cht xt dng bt mn (dng vi cu).
Cht xt nng c a vo l phn ng vi tc cao (60 cm/s),
c pha trn vi dng nguyn liu ( gia nhit s b) ti ng
nng (riser). Ti y, trong vng nhit ha hi ca nguyn liu,
bi xt chuyn ng t di ln trn nh mt lp si.
S tn tht p sut nh hn, s truyn nhit tt hn so vi xt tng
c nh.
lm vic c tng si cn c s kt hp gia c tnh c hc
vi hnh dng xt.
Vd: Cng ngh cracking xt u s dng kiu vn hnh xt tng si.
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S gim hot tnh xt:
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Cc cht u c xc tc rn ca mt s qu trnh ha du
Cht c Cht xc tc
Hp cht cha lu hunh Hydrogen ha, dehydrogen ha, reforming, ng phn
ha, tng hp methanol, ammoniac, methan ha
Hp cht cha oxi Xt reforming, ng phn ha, polymer ha, alkyl ha
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Cc bin php ngn nga:
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Bin php ngn nga s to thnh cc
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Qu trnh ti sinh xc tc
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4.3. iu ch xc tc
1.2/ Xc tc oxyt
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1.1/ Xc tc kim loi
o Tc nhn kh : H2
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Phng php in ha: tc l iu ch kim loi bng
cch in phn dung dch mui.
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1.2/ Xc tc oxyt
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Cc yu cu c bn i vi xc tc vn hnh trong
cng nghip
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CHNG 5: PHNG PHP NGHIN
CU V NH GI XC TC
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1. Phng php tnh:
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2. Phng php dng:
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Phng php dng
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Phng php dng
u im: l c th xc nh c hot ca xc tc
trng thi n nh ca cht xc tc, cu trc n
gin, lm vic lin tc, c th kim tra cht xc tc
trong cc iu kin gn vi sn xut
Nhc im: ca phng php l khng c kh nng
o trc tip tc phn ng v kh thc hin trong
cc iu kin l tng ca ch chy l tng.
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3.Phng php dng vi lng:
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4. Phng php dng tun hon
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5.Phng php xung vi lng:
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Xc nh tnh cht l- ha ca xc tc.
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CHNG 5: SN XUT CHT XC
TC
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Mt s cht xc tc s dng trong cng nghip
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HI-3 - xuc tac chuyen hoa CO bang hi
nc.
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FM-1 - xuc tac tong hp amoniac. Thanh
phan: 64,6% Fe2O3; 31% FeO; 1,4% K2O; 2.5%
Al2O3; 0,5% SiO2.
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MS-1 - xuc tac hydroforming. Thanh phan
10% MoO3.
Be mat rieng 250 m2/g; the tch lo xop
0,28 cm3/g 98% hat qua ray 0,147mm; 60%
qua ray 0,074mm
Tai trong 1kg/gi.kg xuc tac 510oC, ap
suat d 17,6 at
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Kim loai nhom Pt dung oxy hoa, hydro hoa
va dehydro hoa, dehalogen hoa.
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Cac xuc tac dang hat nho va vien (vien
thuoc): 0,3% Pt tren oxyt Al hoat tnh co
kch thc 3.2mm; 1% Pt tren than go coc
hoa, kch thc 2.4-4.7mm; 0.3% Pt tren
silicagel.
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Xuc tac dang keo 0.5g Pd/l; li kim loai
thanh phan 90 - 10% Pt - Ph ; muoi en Pt.
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Code-902 - xuc tac oxy hoa naphtalen, thanh
phan 10% V2O5, 33% K2SO4; 55% SiO2 dang
phien, 85% qua ray 1,147mm; 45% qua ray
0,074mm.
dang vien (nh vien thuoc) 3.2 3.2;
toc o the tch 1400 gi1, nhiet o 455 oC
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KHAI QUAT CHUNG TONG HP CHAT XUC TAC DUNG TRONG
CONG NGHIEP
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Xuc tac co cac dang hat khac nhau: phien, hat nho, vien,
tru, vong, cau
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Phng phap ket tua
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Phng phap ket tua
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Phng phap ket tua
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Phng phap ket tua
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Hoat hoa be mat xuc tac
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Hoat hoa be mat xuc
tac
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Xuc tac b au oc co the t phuc
hoi trong qua trnh lam viec, hay phuc hoi
theo chu ky trong thiet b phan ng hay
trong thiet b rieng.
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Phan loai xuc tac theo phng phap
chuan b va ban chat hoa hoc cua
chat xuc tac
ket tua
ket tua tren chat mang
tron c hoc cac cau t
nong chay
khoang thien nhien, zeolite...
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Quy trnh ky thuat
chung
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Nc dung e hoa tan, pha loang va
ra cac chat trong qua trnh san xuat
chat xuc tac
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Cac qua trnh c ban trong san
xuat chat xuc tac
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nh hnh hat xuc tac va chat
mang
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THU KHOI TIEP XUC TREN C
S KET TUA
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THU KHOI TIEP XUC TREN C S
KET TUA
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Cac giai oan quan trong theo phng
phap ket tua
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Hoa tan
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Ket tua
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Ket tua
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Ket tua
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Ket tua
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Ket tua
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Loc
3- Loc:
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Ra ket tua loc
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Say
5- Say:
Say kho trc tiep, la phng phap cho
phep tiep xuc khong ngng cua ket tua
vi chat lam kho.
Say tiep xuc la qua trnh say c
truyen nhiet t tng chat lam kho en
vat lieu do s truyen nhiet.
Phng phap ien: s dung dong ien
cao tan hay nhiet Jun.
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Say
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nh hnh vien xuc tac
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Aluminosilicat
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S TNG HP ALUMINOSILICAT
silicate, nc Al(OH)3, nc
Dd H2SO4
Dd Na2O.nSiO2 Dd Al2(SO4)3
Kt ta v nh hnh
Gia cng
Tch nc (co gel)
t
Ra
Hot ho ht
Sy kh
Nung
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Thnh phm xc tc
H thng thit b chun b thy tinh lng
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Dy chuyn h thng chun b dung dch Al2(SO4)3
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CAC CHAT XUC TAC TREN
CHAT MANG (PHNG PHAP
TAM)
Cau t hoat ong nh tren chat mang co
nhieu lo xop, trong o chat mang la vat lieu
tr hoac t hoat ong.
Tng tac vi chat mang co the lam thay oi
kch thc gia cac phan t trong xuc tac hay
hoa tr trong lien ket do co lien quan en
tng tinh the.
Tuy thuoc vao loai thiet b phan ng, chat
xuc tac tren chat mang co the la vien vi
hnh dang bat ky: cau, vi cau, hnh tru, vay...
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CAC CHAT XUC TAC TREN
CHAT MANG (THEO PHNG
PHAP TAM)
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CAC CHAT XUC TAC TREN
CHAT MANG (PHNG PHAP
TAM)
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CAC CHAT XUC TAC TREN
CHAT MANG (PHNG PHAP
TAM)
Cac bc:
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CAC CHAT XUC TAC TREN
CHAT MANG (PHNG PHAP
TAM)
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Sau moi lan tam chuyen qua giai oan gia
cong nhiet.
So lan tam phu thuoc nhieu vao cau truc
lo xop cua chat mang e chuyen van chat
en tan ben trong mao quan.
Mao quan nho, tang so lan tam lam bt
cac mao quan co the lam mat tac dung
xuc tac phai tm so lan tam toi u.
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ac tnh va qui trnh
san xuat cac chat
mang quan trong
Chat mang vi be mat rieng nho
(diatomit, amian, a bot)
Chat co be mat rieng ln (gamma oxid
nhom, silicagel, at set, alumosilicat)
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1, 2- Thiet b phan ng co gia nhiet va khuay tron; 3- Loc; 4-
May ep; 5- May nghien truc - tron; 6- Tao vien; 7- Lam kho; 8-
Lo nung
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KHOI TIEP XUC TREN C S TRON C HOC CAC
CAU T VAO NHAU
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Cac chat xuc tac san xuat theo
phng phap nong chay
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Chat xuc tac tren bo khung
(Skeleton catalysts)
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Chat xuc tac tren bo khung
(Skeleton catalysts)
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Chat xuc tac tren bo khung
(Skeleton catalysts)
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CCH XC NH HOT CA XC TC
dGsp dG phanung
= kC hay = kC
vdt vdt
Ci T T
= 0; = 0; =0
li li t
Ci : la nng cu t i trong hn hp phan ng
T : nhit ; li : hoanh cua h phan ng ;
t : thi gian www.themegallery.com
PHNG PHP TNH
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PHNG PHP TNH
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PHNG PHP DNG (NG HC)
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PHNG PHP DNG (NG HC)
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PHNG PHP DNG (NG HC)
u im: l c th xc nh c hot ca xc tc
trng thi n nh ca cht xc tc, cu trc n gin,
lm vic lin tc, c th kim tra cht xc tc trong cc
iu kin gn vi sn xut
Nhc im ca phng php l khng c kh nng
o trc tip tc phn ng v kh thc hin trong cc
iu kin l tng ca ch chy l tng.
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PHNG PHP DNG (NG HC)
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PHNG PHP DNG TUN HON
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PHNG PHP DNG TUN HON
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PHNG PHP DNG TUN HON
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PHNG PHP DNG TUN HON
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G
Csppung
PHNG PHP DNG TUN HON
vt
Nhc im:
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G
Csppung
PHNG PHP DNG TUN HON
vt
x=
( C Cc )10000
100 1.5Cc
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P
G
CO 2
pung
sp
PHNG PHP DNG TUN HON
vt
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PHNG PHP XUNG VI LNG
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P
G
CO 2
pung
sp
PHNG PHP XUNG VI LNG
vt
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PHNG PHP XUNG VI LNG
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KT LUN
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