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4/20/2012

1
THIT B PHN NG
trong cng nghip ho du.
Ngi son : PGS,TS Trn Cng Khanh.
Trng i hc Bch khoa H Ni.
4/20/2012
2
I-GII THIU V TBP :
I.1-Gii thiu:
-TBP- h thng thit b thc hin cc phn ng ho hc to ra sn
phm ca mt qu trnh sn xut,do quyt nh nng sut (do vn
tc phn ng r ) v hiu qu ( chuyn ho X v chn lc S)
ca sn xut.
-Vn tc phn ng chuyn ho cht i:
R
i
= dN
i
/ Vdt . ( 1 . 1 )
Trong : N
i
-S mol ca cht i, du cng l to thnh (sn phm phn
ng), du tr l tiu hao (cht phn ng).
V-Th tch ca h thng
Khi th tch khng i ta c C
i
= N
i
/ V, do pt (1.1) thnh:

R
i
= dC
i
/ dt . ( 1 . 2 )

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3
- chuyn ho ca cht i:
X
i
= (C
0
- C
1
) / C
0
= 1 - C
1
/C
0
. ( 1 . 3 )
Trong : C
0
- nng cht phn ng i i vo ( hay nng ban
u)
C
1
- nng cht phn ng i i ra ( hay nng cui )

- chn lc i vi sn phm i:

S
i
= C
i
/ C
j
j = 1, n ( 1 . 4 )
Trong : Ci -nng ca sn phm i trong hn hp phn ng .

C
j
-tng nng cc sn phm trong hn hp phn
ng

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V TR H THNG TBP TRONG S CNG NGH
Trong s cng ngh TBP nm v tr nh sau :






H.1.1- Lu khi ca cng ngh sn xut .
Trong h thng thit b chun b hn hp phn ng,
tch v tinh ch sn phm c th gm mt s lng ln
cc thit b thc hin cc qu trnh chuyn khi v truyn
nhit nh chng luyn, hp th,hp ph, trch ly, un nng,
lm lnh, ngng t ...m sinh vin lm quen trong mn
hc "Qu trnh v thit b ho hc ".
H thng tch
v tinh ch
sn phm


H thng
chun b
hn hp
phn ng
THIT B
PHN
NG
Nguyn liu cha chuyn ho
Ng.liu 2
Ng.liu 1
Sn phm
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5
I.2-c im :
- a dng
Do iu kin phn ng rt khc nhau:
*Nhit phn ng c th t nhit phng n 800-
900
0
C, c bit c th n 1300-1500
0
C. ng thi phi c
nhng gii php hp l cp hay gii nhit phn ng.
*p sut c th t p sut kh quyn ( 0,1 MPa ) n 70
MPa.
Trong nhiu phn ng pha kh thng dng p sut khong 2-
3 MPa gim th tch TBP, tng cng vn tc phn ng
v h s trao i nhit vi thnh thit b.
Vi mi p sut cn c dng hnh hc ca thit b ph hp :
hnh ng, hnh cu chu p sut tt hn hnh hp, mt phng.

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Phn ng trong thit b c th tin hnh cc
trng thi pha khc nhau:
*ng th: kh, lng
*Cc h d th kh-rn, kh-lng, lng-rn,
lng-lng
*Cc h ba pha kh-lng-rn, lng-lng-rn,
kh-lng-lng ...
Tnh a dng ca TBP cn do tng hng ,
trn th gii c nhng hng c cng ngh, xc
tc v h thng TBP ring ca mnh

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C IM TBP
-Phc tp
Do trong TBP cc qu trnh ho hc ( phn
ng ) v vt l ( chuyn khi: dng chy ,
khuch tn, v cc qu trnh nhit: truyn nhit,
to v thu nhit ) xy ra an xen v nh
hng ln nhau
Trong , cc qu trnh vt l thng tuyn
tnh vi nhit , cn cc phn ng ho hc
ph thuc vo nhit dng hm m theo
phng trnh Arrhnius ( phi tuyn ).
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I.3- Phn loi TBP :
1/Theo ch lm vic :
a/Thit b lm vic gin on

*Ch dng cho pha lng .
*Cc bc ca qu trnh: np liu, un
nng, tin hnh phn ng, lm ngui v tho
sn phm, c thc hin trong mt thit b.
Do cc thng s nh nng , nhit , p
sut ...thay i theo thi gian.
V d: tin hnh phn ng trong thit b loi
thng c khuy nng cht phn ng thay
i theo thi gian nh hnh 1.2.

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H.1.2-M hnh TBP lm vic gin on v thay i
nng theo thi gian
Cht phn ng
vo gin on
Sn phm
tho gin on
0
Nng
cht phn ng
Thi gian t
C
A0
C
At
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10
b/Thit b lm vic na gin on:

*Cht phn ng: mt cht cho gin on, mt cht
cho lin tc.
Cht cho gin on thng l cht lng, v d cht A.
Cht cho lin tc thng l cht kh hay c th l
cht lng, v d cht B. Phn ng: A + B C
Vi mc ch lun ngho cht B trong hn hp phn
ng trnh phn ng ph: B + C D
Hay vn tc to nhit ca phn ng ph hp vi
kh nng gii nhit ca thit b .
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*Nng A v B thay i theo thi gian phn ng nh hnh
1.3
S mol N
B
vo
C
A
t
CBt
Cht A vo
Gin on
Cht B vo
Lin tc
C
A0
C
B0
Thi gian t
H.1.3-M hnh TBP lm vic na gin on v thay i
nng cht phn ng trong thit b.
Nng
Cht phn ng
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c/Thit b lm vic lin tc

*y l loi thit b thng gp trong cng
nghip vi qui m sn xut ln.
*Trng thi dng (steady state ): l trng
thi t c ca TBP sau khi m my mt
thi gian, trng thi ny cc thng s ca qu
trnh khng thay i theo thi gian t ,lc sn
phm thu c c cht lng n nh. T khi
m my n trng thi dng ta c giai on qu
, thi gian qu ph thuc vo ch dng
chy trong thit b v phc tp ca h thng
TBP.

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Thi gian lu trung bnh:
Thi gian lu thc ca cht phn ng trong thit b khc nhau
, ph thuc vo ch dng chy. Ta c thi gian lu trung
bnh theo nh ngha sau:
t
TB
= V
R
/ F
V
Trong : t
TB
-Thi gian lu trung bnh. [ h ].
V
R
-Th tch TBP. [ m3 ].
F
V
-Lu lng ca dng . [ m3 / h ].

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2/Theo ch dng chy :

*M hnh y l
tng :
-L m hnh dng
chy trong thit b
chuyn ng tnh tin
theo th t trc sau
nh chuyn ng ca
pit-tng trong xi lanh
V do nng cht
phn ng thay i t
t, bt u u vo
l C
A0
n u ra l
C
AL
nh hnh 1.4

L
C
A0
C
AL
L
Nng
cht phn ng
C
A0
C
AL
Chiu di
ng phn ng
L
C
A0
C
AL
0
H.1.4-M hnh LT v thay i nng
cht phn ng trong thit b.
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*M hnh khuy
l tng :
-L m hnh
dng chy trong
thit b c
khuy trn
mnh, cht
phn ng i vo
c trn ln
ng u ngay
tc khc trong
thit b, do
nng cht
phn ng thay
i t ngt
ti u vo ca
thit b nh
hnh 1.5

C
A1 C
A1
C
A0
Nng
cht phn ng
To phn ng
Cht A vo
C
A0
Cht A ra
C
A1
H.1.5-M hnh KLT v thay i nng trong thit b
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M hnh khuy l tng
*Cng do khuy trn nng cht phn ng
trong khp thit b ng u v bng u ra l
C1.
*Do nng cht phn ng trong thit b thp
(nht l khi chuyn ho X yu cu cao ) nn
vn tc phn ng thp v do nng sut
TBP theo m hnh khuy l tng thp hn
y l tng.
Ni mt cch khc, m bo chuyn ho
X nh nhau thit b theo m hnh khuy l tng
cn c th tch V
R
ln hn nhiu so vi m hnh
y l tng, c bit khi X yu cu cao.
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* m bo nng sut thit b cao vi m
hnh khuy l tng h thng nhiu thit b
khuy ni tip c s dng nh hnh 1.6.

To phn ng
C
An
C
A(n-1)
C
A3
C
A2
C
A1
C
A0
C
A0
C
A1
C
A2
C
A3
CA
(n-1)
C
An
1 2 3 n
0
H.1.6-M hnh h thng n thit b KLT ni tip v thay i
nng cht phn ng theo tng thit b
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* hnh 1.6 nng cht phn ng thay i tng
bc t u vo n u ra ca h thng, khi n
ln (gii hn khi n ) s thay i nng
cht phn ng ging nh trng hp y l
tng (hnh 1.4 ).
Trong thc tin cng nghip s thit b n trong h
thng thng t 4 n 10 ngoi vic m bo
nng sut ca h thng thit b cn phn b
thi gian lu ng u hn, nhit c th
iu chnh khc nhau tng thit b v cht phn
ng th hai c th cho vo t t theo tng thit b
theo yu cu

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3/Theo trng th pha:
*H ng th: Cn c khuy trn ng u v nng
cc cu t v nhit trong thit b phn ng.
*H d th: i vi h ny cn ch to b mt tip xc pha
ln tng cng vn tc phn ng.
-H d th lng - lng: Cn c khuy trn tt , to nh tng
c b mt tip xc ln.
-H d th kh - lng: m bo b mt tip xc pha ca h
ny cn khuy trn hoc si bt hoc dng m rn c b mt
ring ln.
-H d th kh - rn v lng - rn: B mt tip xc pha l b mt
ca cht rn , do vy cht rn ( l xc tc ) thng l vt liu
xp c b mt ring ln hoc c phn tn cao.
Trong cng nghip cng hay gp h nhiu pha: kh - lng - rn,
lng - lng - rn
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4/Theo ch nhit:
*on nhit:
-Khng c b phn trao i nhit .
-Hay s dng v n gin, cho cc phn ng c
hiu ng nhit thp hay t nhy vi s thay i
nhit .
*ng nhit:
-Thng gp cc thit b c khuy trn tt.
- Trong ti liu i khi gi thit b phn ng xc
tc kh - rn dng ng chm c b mt trao i
nhit ln l thit b ta ng nhit, tuy vy
thit b loi ny vn tn ti gradien nhit theo
ng knh v hng trc ng xc tc .

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*T nhit:
-Hay dng khi c th v n gin v kinh t .
-Phn ng to nhit ln v c kh nng trao
i nhit phn ng vi nguyn liu vo t
nhit m phn ng c th tin hnh .
*Ch nhit theo qui hoch:
-Thng dng t ch nhit ti u cho
qu trnh phn ng .
-Gp thit b loi ng , thit b c nhiu ngn
on nhit v h thng nhiu thit b khuy ni
tip .


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II/ THI GIAN LU
-Thi gian lu ca cht phn ng trong
thit b l thi gian tin hnh phn ng, v
vy n nh hng quan trng n chuyn
ho X v chn lc S.
V d: ta c phn ng ni tip ABC, trong
B l sn phm chnh v C l sn phm ph,
nng ca A, B v C ph thuc vo thi gian
phn ng nh hnh 2.1

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Thi gian phn ng
C
C1
C
B1
C
A1
C
A0
0 t
1
H.2.1-S thay i nng cc cht ca phn ng ni tip
A B C theo thi gian phn ng
Nng
A
B
C
C
B2
C
A2
C
C2
t
2
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Gi s ti thi im t
1
nng cc cht
A, B, C l C
A1
, C
B1
v C
C1
ta c:
chuyn ho: X
1
=1- CA
1
/C
A0
.
chn lc: S
1
=C
B1
/ ( C
B1
+ C
C1
).
-Ph thuc vo ch dng chy, thi
gian lu ca cc phn t ca dng vo
c th rt khc nhau. Do vy cn nghin
cu phn b thi gian lu ca chng
trong thit b.
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II.1-THI GIAN LU TRONG CC M HNH L TNG
1/Hm phn b TGL:
-Hm E(t):
nh ngha: Phn ca dng vo c thi
gian lu trong thit b t t n t+dt l
E(t).dt. T nh ngha trn ta c:

= 1 ( 2.1 )


= t
TB
( 2.2)
}

0
. ). ( dt t t E
}

0
E(t).dt
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-Hm F(t):
nh ngha: F(t) l phn ca dng c thi gian lu trong
thit b nh hn t.
*T nh ngha ny F(t) l phn ca dng i vo thit b thi
im t = o v n thi im t ra khi thit b.
*Phn ca dng i vo thit b thi im t = 0 n thi im
t vn cn trong thit b l |1-F(t)|.T nh ngha v F(t) ta c:
Khi t = 0 th F(t) = 0
Khi t = th F(t) = 1 ( 2.3 )

F(t) = hay E(t) =dF(t)/dt (2.4 )
' '
). ( dt t E
t
}
0
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II.2-Gi tr ca hm phn b TGL trong cc
m hnh l tng:
-M hnh LT - T nh
ngha ca m hnh ny v
nh ngha ca hm phn b
F(t) ta c gi tr ca hm
phn b TGL nh sau:
Khi 0 < t < t
TB
th F(t) = 0
Khi t > t
TB
th F(t) = 1
( 2.5 )
Ta c ng biu din F(t)
theo t nh hnh 2.2
t
t
TB
F(t)
1
0
H.2.2-S ph thuc ca F(t) m hnh LT
vo thi gian t
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28
-M hnh KLT -T nh ngha ca m hnh
ny v ca F(t) ta thy rng do khuy trn
mnh trong thit b cc phn t ca dng
va vo c trn u khp trong th tch
ca thit b.
Do vy kh nng i ra ca cc phn t
hin c trong thit b l nh nhau, khng
phn bit phn t vo trc hay vo sau.
Ni cch khc, xc sut xut hin ca ra
ca nhng phn t hin c trong thit b l
nh nhau khng phn bit lch s ca
chng.
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29
Nh vy:
C th c phn t va mi vo c mt
ca ra v ra khi thit b nn TGL bng 0
V c th c phn t vo thit b t lu
mi ra khi thit b nn TGL ca nhng phn
t ny bng .
Ngha l TGL ca cht phn ng trong m
hnh KLT khng ng u v phn b t 0
n .

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30
Theo l thuyt xc sut ta c mnh
sau: xc sut ca nhng phn t c TGL
trong thit b l t+dt gm xc sut ca
nhng phn t c TGL trong thit b l t
v xc sut ca nhng phn t c TGL
l dt, nh vy c th vit:
| 1 - F(t+dt) | = | 1- F(t)|.| 1 - F(dt)| (2.6)
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31
| 1 - F(t+dt) | = | 1- F(t)| . | 1 - F(dt)| ( 2.6 )
F(t+dt) = F(t) + dF(t)
V kh nng ra khi thit b ca nhng phn t l nh nhau, ta
c:
F(dt) = F
V
.dt / V
R
= dt / t
TB
Thay vo phng trnh ( 2.6 ):
1 - F(t) - dF(t) = | 1 - F(t) | . | 1 - dt/ t
TB
|
- dF(t) = - dt / t
TB
+ F(t) . dt/ t
TB

= - dt/ t
TB
. | 1 - F(t) |
dF(t) / | 1 - F(t) | = dt/ t
TB
( 2.7 )
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32
Gii phng trnh vi phn ( 2.7 ):
Gii phng trnh vi phn (2.7 ), ta c:
ln | 1 - F(t) | = - t/ t
TB
+ C.
T iu kin ban u t=0 th F(t)=0 c C = 0
1 - F(t) = e
-t/tTB

do F(t) = 1 - e
-t/tTB
. ( 2.8 )
ng biu din hm F(t) ca m hnh KLT theo
phng trnh ( 2.8 ) c trnh by hnh 2.3

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1 - F(t)
F(t)
t t
TB
0,632
F(t)
1,0
0,5
0,0
H.2.3-S ph thuc ca F(t) m hnh KLT vo thi gian t
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Nh vy, do khuy TGL ca cc phn t
dng vo rt khc nhau, phn b t 0
n .
Lm gim chuyn ho X (v do
gim nng sut thit b ) v chn lc
S (i vi cc qu trnh phn ng ni
tip).
t chuyn ho nh nhau so vi m
hnh LT thit b loi ny cn c th tch
ln hn, s chnh lch ph thuc vo
chuyn ho X yu cu.
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35
H thng nhiu thit b khuy ni tip lin tuc:
M hnh h thng nhiu thit b khuy ni tip khc
phc c nhc im trn vi s thit b n ln
( v l thuyt khi n v trong thc t n c th t 5
n 10 ).
Gi tr hm F(t) trong h thng n thit b khuy ni
tip lin tc c th c xc nh bng php tnh
cn bng vt cht, c:
F(t) = 1 - e
- nt/t
TB
[1+(nt/t
TB
)+(nt/t
TB
)
2
/2+...+(nt/t
TB
)
n-1
/(n-
1)] .
( 2.19)
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Hnh 2.5 biu din gi tr hm phn b F(t) ca h thng thit b KLT ni
tip lm vic lin tc ph thuc vo t (trc honh c n v l u=t/t
TB
).



1,0
F
(
t
)
0,0
1 2
n=1
3
5
10
20
n=
H.2.5-Hm F(t) ph thuc vo s thit b n
trong h thng KLT lin tc, ni tip.
=t/t
TB
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T hnh 2.5 thy r h thng thit b KLT
ni tip khi s thit b n tng khong phn
b TGL ca cc phn t ca dng vo
hp li ( quanh vng t/t
TB
=1 ).
V khi n ta c ng biu din F(t)
ca h thng tng t nh m hnh
LT: TGL ca cc phn t ca dng ng
u v bng t
TB
.

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38
II.3- THI GIAN LU TRONG THIT B THC

-Thit b thc loi thng c khuy :
*Nu c khuy trn mnh v nht
mi trng phn ng khng qu ln c
th coi nh m hnh LT . Trong thc tin
sn xut cng nhip d thc hin iu ny,
nh thit b nitr ho hydrocacbon thm,
nng cc cu t c trn ln hon ton
sau 8 giy trong khi TGL trung bnh thng
trn 10 pht.

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*Khi mi trng c nht qu cao ta
c trng thi trung gian gia hai m
hnh LT v KLT.
* h thng nhiu thit b khuy ni
tip, nu trong mi thit b s khuy trn
khng c hon ton th nh hng
ca n c th b qua c, coi nh
LT.
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40
-Thit b thc loi ng:
*ng biu din F(t) c dng ch S do
trn ln theo hng trc ng bi cc
nguyn nhn sau:
1/ Khuy trn i lu do cc dng
chuyn ng xoy gy nn.
2/ Do gradien vn tc dng theo tit din
ngang ca ng.
3/ Khuy trn do khuch tn phn t,
thng nh hng ny khng ln.

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41
* nghin cu hin tng trn ln ca dng chy
trong ng gy nh hng n TGL trong thit b v
chuyn ho, chia vct trn ln thnh hai thnh phn:
Hng trc ng vi h s trn dc D
l

Hng ng knh ng vi h s trn ngang D
r
D
l
v D
r
c xc nh bng chun s Peclet (k hiu
Pe ) nh sau:
Pe
l
= v . L / D
l
v Pe
r
= v . D / D
r
( 2.20 )
Trong : v - Vn tc di ca dng chy.
L - Chiu di ca ng phn ng.
D - ng knh ng hay ng knh ca
ht trong ng.
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42
a/ng rng, chy dng:
-Gradien vn tc dng theo tit din ngang
l nguyn nhn ch yu gy nn s sai khc
TGL trong ng rng chy dng, khuch tn
i lu v khuch tn phn t b, c th b
qua.
-Tnh F(t): Vn tc dng phn b trn
tit din ng theo mt parabol, ph thuc
vo khong cch r n tm ng l v
r
(hnh
2.6)

4/20/2012 43

r
v
r
r
0
H.2.6-M hnh gradien vn tc dng theo
hng ng knh ca ng rng, chy dng
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44
-Tnh F(t) ca ng rng, chy dng
v
r
= ( 2F
V
/t.r
0
2
)[ 1 - ( r / r
0
)
2
] (2.21)
Trong r
0
l bn knh ca ng.
Do , TGL ca phn ca dng cch trc ng
mt khong r l
t
r
= L/v
r
= t.r
0
2
(L / 2F
V
)
.
[ 1 - (r/r
0
)
2
] = V
R
/2F
V
[ 1 - (r/r
0
)
2
]
t
r
= ( t
TB
/ 2 ) [ 1 - (r/r
0
)
2
] ( 2.22 )
Thay r = 0 c TGL ca dng ti trc ng l
t
tm(r=0)
= t
TB
/ 2
Thay r = r
0
c TGL ca dng ti thnh ng l
t
thnh(r=r0)
=
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45
-Tnh F(t) ca ng rng , chy dng
C th xem phn ca dng chy nm cch tm
l r+dr (hnh vnh khn 2tr.dr ) c vn tc
nh nhau l v
r
, t nh ngha ca hm F(t) ta c:
dF(r) = v
r
. 2tr.dr / F
V
( 2.23)
Thay v
r
t phng trnh (2.21) v rt gn,c :
dF(r) = 4 [ 1 - (r/r
0
)
2
] r.dr / r
0

chuyn dF(r) thnh dF(t) phi dng phng
trnh (2.22) .


4/20/2012
46
T (2.22) ta c [ 1 - (r/r
0
)
2
] =t
TB
/ 2t , ly vi phn
pt (2.22) ta rt ra:
rdr = r
0
2
. t
TB
.dt / 4 t
2

Thay vo pt (2.23) ,c:
dF(t) = t
TB
2
.dt / 2 . t
3
( 2.24)
T xc nh F(t) cho trng hp ng
rng chy dng nh sau:
F(t) = t
TB
2
/2. dt/t
3
t = t
TB
/2, .
F(t)= 1 - (t
TB
/t)
2
/4

( 2.25 )

4/20/2012
47
F(t)
0,5
1,0
0,75
0,0
t
TB
/2
t
TB
t
H.2.7-ng biu din ca F(t) trong
ng rng, chy dng
4/20/2012
48
TBP thc
b/ ng rng,chy ri :
* ch ny khuch tn i lu do dng
chy xoy l chnh .
*Vn tc dng phn b theo tit din ng
c dng hnh thang ( hnh 2.8 ), ngha l tr
lp bin st thnh ng, vn tc dng coi nh
ng u .
* Khi gi tr Re cng ln ( ln hn 10
4
)
chiu dy lp bin cng mng v th tch lp
bin so vi F
V
rt nh,c th b qua,ta c ch
dng chy ta m hnh LT .
4/20/2012 49

Lp bin
F
V
H.2.8-M hnh phn b vn tc dng chy
theo tit din ng ch chy ri
4/20/2012
50
c/ng phn ng c lp ht tnh ( ht xc tc
rn, thng gp trong thc t ):

*Lp ht tng cng hin tng
khuch tn trong thit b theo c
hai hng trc ng v ng knh
ng
c bit theo hng ng knh
theo m hnh nh hnh 2.9.
4/20/2012 51

d
ht
H.2.9-M hnh lch ngang khi chy
qua lp ht tnh
4/20/2012
52
Theo m hnh ny khi dng chy qua mt
lp ht b lch ngang d
ht
/2 v qua n lp
ht s lch ngang nd
ht
/2. V nh vy,
lch ngang lm cho vn tc dng v TGL
ng u hn.
*Nh vy, khi D
ng
/d
ht
> 10 v L
lp ht
/d
ht

> 10 ch dng chy c coi nh
LT.

4/20/2012
53
II.4-NH HNG CA KHUCH TN DC
N CHUYN HO X CA PHN NG
*Trn dc trc ng phn ng lm cho TGL khng
ng u v do nh hng n chuyn ho X .
*Dng thc trong thit b c th chia thnh hai phn:
-Dng LT vi vn tc di l v .
-Dng khuch tn dc vi h s khuch tn
theo hng trc l D
l
v chun s Peclet vi k hiu
Pe
l
:

Pe
l
= v . L / D
l

L-l chiu di ca ng phn ng .
4/20/2012 54
*Gi s:-ng phn ng c tit din l S (hnh
2.10).
-Tin hnh phn ng chuyn ho cht A
s.phm
*Thc hin php tnh cn bng vt cht
cho AV
R
= S . Al:
A vo = A ra + A phn ng + A tch t.
(2.26)
H.2.10-M hnh ng phn ng c khuch tn
dc .


A ra do dng LT
v . S . C
A(l+l)
A ra do khuch tn
A vo do dng LT
V S.C
Al
A vo do khuch tn
-D
l
.S.(C
A
/l)
l
A ra do dng LT
S.v.C
A(l+l)
A ra do dng LT
S.v.C
A(l+l)
A ra do khuch tn
-D
l
.S.(C
A
/l)
l+l
l
S
l
L
l+l l
4/20/2012
55
A tch t = V
R
. dC/dt, trng thi dng A tch t bng 0.
Ta c:
(A ra - A vo)
dng LT
+ (A ra - A vo)
khuch tn
+ A
phn ng
= 0.
Thay cc gi tr ca A vo,ta c:
v.S(C
A(l+Al)
-C
Al
)+(-D
l
.S)[(cC
A
/cl)
l+Al
-(cC
A
/cl)
l
]+S.Al(-cC
A
/ct)=0
Chia cho S.Al , c:
v.(C
A(l+Al)
- C
Al
)/Al - D
l
[(cC
A
/cl)
l+Al
- (cC
A
/cl)
l
]/Al +(-cC
A
/ct) = 0
Thay (-cC
A
/ct) = R
A
= k.C
A
n
v cho Al0 ,c:
v (cC
A
/cl) - D
l
(c
2
C
A
/cl
2
) + k .C
A
n
= 0 ( 2.27 )
y l m hnh ton mt th nguyn miu t qu trnh
trong ng phn ng ch nh hng bi khuch tn theo
hng dc trc.
4/20/2012
56
v (cC
A
/cl) - D
l
(c
2
C
A
/cl
2
) + k .C
A
n
= 0 ( 2.27 )

*Chuyn ( 2.27) thnh dng khng c th nguyn:

- t i lng chiu di l z = l/L, ta c:
cz = cl/L , do cz/cl = 1/L
cC
A
/cl = (cC
A
/cz) . cz/cl = (1/L) . cC
A
/cz
c
2
C
A
/cl
2
= [1/L. c(cC
A
/cz) / cz ]. cz/cl = (1/L
2
).c
2
C
A
/cz
2

T pt (2.27) thnh:
(v/L).cC
A
/cz - (D
l
/L
2
).c
2
C
A
/cz
2
+ kC
A
n
= 0. ( 2 . 28 )
Chia hai v pt (2.28) cho -L/v = -t
TB
:
(D
l
/L.v).c
2
C
A
/cz
2
- cC
A
/cz - k.t
TB
.C
A
n
= 0.(2.29)

4/20/2012 57
(D
l
/L.v) . c
2
C
A
/cz
2
- cC
A
/cz - k . t
TB
. C
A
n
= 0. ( 2 . 29 )
* Gii pt (2.29) vi iu kin b :- ti u vo z = 0 , C
A
= C
A0

- ti u ra z = 1 , C
A
= C
AL

c C
AL
v t tnh chuyn ho X
A, .
.
X
A
ph thuc vo 3 thng s k , t
TB
v Pe
l

= L.v/D
l
.
Vi phn ng bc 1 (n = 1) gii c :
C
AL
/C
A0
= 1 - X
A

= 4a.exp(Pe
l
/2)/[(1+a)
2
exp(a.Pe
l
/2) -
(1-a)
2
exp(a.Pe
l
/2)]
( 2 . 30 )
Vi a =
l TB
/Pe 4kt 1+
4/20/2012
58
H.2.11-Biu din V
Rthc
/V
RLT
ph thuc vo Pe
l
,
k.t
TB
v X caphn ng bc 1.
4/20/2012
59
H.2.12-Biu din V
Rthc
/V
RLT
vo Pe
l
,
k.t
TB
.C
0
v X ca phn ng bc 2
4/20/2012
60
Thc nghim cho thy rng chun s
khuch tn dc Pe
l
ch yu ph thuc
vo chun s Re = v.d
ng
./.
Hnh sau l kt qu thc nghim ca
mt s tc giv s ph thuc ca
D
l
/v.d
ng
= (D
l
/v.L).L/d
ng
vo Re
T c th rt ra tng quan sau:
D
l
/v.d
ng
= 3.10
7
/(Re)
2,1
+1,35/(Re)
0,125
.
4/20/2012
61
H.2.13-S liu thc nghim s ph thuc D
l
/v.d
ng
vo Re ca mt s tc gi.
4/20/2012
62
II.4 THC NGHIM XC NH GI TR HM PHN
B TGL THIT B THC.
1/ Thc nghim xc nh hm phn b TGL E(t) v
F(t):

*Nguyn tc:
-Ti t = 0 bt u cho cht ch th vo.
-Xc nh nng cht ch th u ra
theo thi gian t.
-X l tn hiu nng ra,xc lp F(t).
Thng cho ch th vo theo 3 dng tn
hiu: dng bc cp, dng xung v dng
hnh sin.
4/20/2012
63
a/Tn hiu vo dng bc cp, xc nh hm F(t):
-Tn hiu cho ch th vo dng bc cp:
= 0 khi t s 0 .
C
ch th(z=0)
{ ( 2 . 31 )
= C
0
khi t > 0 .
-Miu t: Ti t = 0 bt u cho ch th i vo
thit b v duy tr trong sut thi gian sau
( hnh 2.11 ). Nh vy khi t > 0, lng ch th
vo thit b khng i, bng F
V
.C
0
.
4/20/2012
64
Xc lp hm F(t): Gi s nng ch th ra
thi im t l C
t
, phn ca ch th ra ti
thi im ny l F
V
.C
t
. T nh ngha ca
hm F(t) ta c:
F(t) = F
V
.C
t
/ F
V
.C
0
= C
t
/ C
0
. ( 2 . 32 )

Tn hiu vo
N

n
g


c
h


t
h


r
a
Nng
Ch th
C
0
0
0
t
C
t
H.2.11-Tn hiu vo dng bc cp v nng
ch th i ra theo thi gian t
4/20/2012
65
b/ Tn hiu vo dng xung vung, xc nh hm E(t):
-Tn hiu cho ch th vo
dng xung:

= 0 khi t s 0 .
C
ch th (z=0)
=C
0
khi 0<t< At
0
.
= 0 khi t>At
0
.
Miu t: Ti t = 0 bt u
cho ch th i vo thit b
trong thi gian ngn At
0

( yu cu At
0
<< t
TB
) v
sau dng cho ch th.
C
t
T

n

h
i

u

v

o
Nng ch th ra
C
0
0
0
t
0
t t
TB
Nng
Ch th
H.2.12-Tn hiu vo dng xung v nng ch th ra
theo thi gian t
4/20/2012
66
Xc lp hm E(t):
Gi s ton b lng ch th cho vo thit
b dng xung vung l q
0
, ti thi im
t nng ch th dng ra l C
t
, trong
khonh khc dt th tch dng ra l F
V
.dt
v lng ch th i ra l C
t
.F
V
.dt, chnh
l lng ch th c trong thit b t t n
t+dt. T nh ngha v E(t) lng ch th
bng q
0
.E(t).dt, ta c:
q
0
. E(t) . dt = F
V
. C
t
. dt. ( 2.34 )
T : E(t) = F
V
. C
t
/ q
0
( 2.35 )
4/20/2012 67
ta xc nh hm E(t) cn bit q
0
, lm
vic ny ly tch phn phng trnh (2.34):

,theo (2.1):

Ta c:
q
0
= C
t
.At

T :

E(t) = C
t
/ C
t
.At (2 . 36)
} } = 0 0 t V 0 . d t . C F . E ( t ) . d t q
} } = 0 0 t V 0 .dt .C F .E(t).dt q
} }

=
0 0
t V 0
.dt .C F .E(t).dt q
}

=
0
1 E(t).dt
}


=
0
0
V t V
. F .dt C . F
}


=
0
0
t t
/ C .dt C
4/20/2012
68
Bi tp 2.4 - Cho tn hiu vo dng xung, nng ch
th ra o c nh bng sau , xc nh hm E(t) .
t , ph : 0 5 10 15 20 25 30 35
C , g/l : 0 3 5 5 4 2 1 0
Li gii:
-Hm E(t) c tnh theo pt (2.36) :
-Trc tin tnh Ct . At = 5(3+5+5+4+2+1) = 100.
-Vy E(t) = C
t
/ 100, kt qu nh bng sau:
t , ph : 0 5 10 15 20 25 30 35
E(t).10
2
: 0 3

5

5

4

2

1 0
4/20/2012
69
-ng biu din nng ch th ra theo t nh hnh 2.13.
-Din tch gii hn bi ng biu din v trc honh l
gi tr ca tch phn, cn din tch cc ch nht l gi tr
ca tng.
5
4
3
2
1
0
Nng ch th
g/l
t,ph
5 10 15 20 25 30 35
H.2.13-ng biu din nng ch th ra theo thi gian.
4/20/2012
70
2/ Xc nh chuyn ho X qua
gi tr hm phn b TGL:
Nh nghin cu trn, dng i ra khi thit
b lm vic lin tc khng phi l dng ng
nht v TGL v nh vy, nng ca cht
phn ng dng ra ( t tnh chuyn ho
X = 1 - C
ra
/C
0
) l nng trung bnh ca cc
phn t ca dng vi TGL trong thit b khc
nhau . Do c th vit:
Cra = C
ng.t
.E(t).dt = C
ng.t
.E(t).At
t = 0, (2.37)

4/20/2012
71
Trong :
C
nguyn t
c th tnh c t phng
trnh ng hc ca phn ng.
E(t).dt - Phn ca dng c TGL t t n
t+dt [ t nh ngha ca E(t) ].
T tnh c chuyn ho X:

X =1-C
ra
/C
0
=1-( /C
0
)
( 2 . 38 ) .
t t E C
nguyento
A

). ( .
0
4/20/2012
72
Bi tp 2.5- Phn ng bc 1 chuyn ho cht
A, hng s vn tc k = 0,307 ph-1, c tin
hnh trong TBP c hm phn b TGL E(t)
nh bi tp 2.4. Xc nh chuyn ho X.
Li gii:
- Phng trnh vn tc ca phn ng bc 1:
-dC
A
/ dt = kC, gii vi iu kin khi t = 0 th C
A

= C
A0,
, c C
A nguyn t
= C
A0
. e
-kt
, thay vo
pt(2.37):
C
A ra
= C
A0
. t .
( 2 . 39 )
.E(t). e
0
kt

4/20/2012
73
Lp bng tnh phng trnh (2.39):
t , ph E(t) k.t e
-kt
e
-kt
. E(t) . At
5 0,03 1,53 0,2154 0,0323
10 0,05 3,07 0,0464 0,0116
15 0,05 4,60 0,0100 0,0025
20 0,04 6,14 0,0021 0,0004
25 0,02 7,68 0,0005 0,00005
30 0,01 9,21 0,0001 ~ 0

C
Ara
- C
A0
= e
-kt
. E(t) . At = 0,047
X
A
= 1 - C
Ara
/C
A0
= 1 - 0,047 = 0,953.
4/20/2012 74
Bi tp 2.6- Tin hnh phn ng bc 1 nh bi tp 2.5
trong thit b phn ng c TGL trung bnh nh bi tp
2.4 nhng dng chy theo ch LT.
Li gii:
-Thi gian lu trung bnh ca thit b bi tp 2.4
c xc nh theo cng thc (2.2).

t
TB
=

=5(0,03.5+0,05.10+0,05.15
+0,04.20+0,02.25+0,01.30)=15 ph.
-Thit b theo m hnh LT c TGL ng u v bng
t
TB
. Vi phn ng bc 1 t pt dC
A
/dt=kC
A
, c:
C
A
/ C
A0
= e
-kt
TB
= e
-0,3.15
= 0,01.
X
A
= 1 - C
A
/C
A0
= 1 - 0,01 = 0,99 .

A =
0
0
. ). ( . ). ( t t t E dt t t E
4/20/2012
75
III/THIT B PHN NG LOI
THNG C KHUY
- Thng dng cho pha lng, c bit cc qu
trnh d th lng - lng, lng - rn, lng - kh v
lng - rn - kh tng cng tip xc cc pha.
- Do khuy nn nng , nhit ng u trong
khp thit b, nhng nh ni trn, TGL
thit b lm vic lin tc phn b t 0 n .
- Khuy tng cng h s trao i nhit gia mi
trng phn ng vi thnh thit b.
- M hnh l KLT.
4/20/2012
76
III.1- Thit b lm vic gin on:
- Ch dng cho pha lng, qui m sn xut nh.
- Tnh th tch thit b VR:
V
R
= V
ngy m
.(1 + z).At
m
/ 24 . ( 3 . 1 )
-Nu th tch thit b VR chn, ta tnh s thit b n:
n = V
ngy m
.(1 + z).At
m
/ 24.V
R
. . ( 3 . 2 )
Trong :
V
ngy m
- Th tch sn phm i ra trong 24 gi
z - H s d tr phng cc s c bt thng.
Thng z c gi tr t 0,10 n 0,15, khi thit b phc tp
hay lm vic nhit v p sut caoc th ly t 0,15
n 0,20.
4/20/2012
77
Thit b lm vic gin on
- H s y . Thng vi thit b phn ng c khuy ly
gi tr t 0,75 n 0,80 ; trng hp mi trng phn ng to
bt c th ly n 0,40.
At
m
- Thi gian tin hnh mt m, gm thi gian chun b
v thi gian tin hnh phn ng.
Trong :
-t chun b = t np liu + t un nng nguyn liu t nhit
u n nhit phn ng + t lm ngui sn phm + t tho
sn phm + t lm sch thit b cho m sau ...
- t phn ng c xc nh t cc thng tin sau:
*Tnh theo phng trnh vn tc vi X xc nh.
*Theo s liu thc nghim c, v d th t-X thc nghim.
4/20/2012
78
III.2-Thit b lm vic lin tc:
*Tnh ton theo m hnh KLT.
*Dng phng php i s v phng php
dng hnh.
a/Phng php i s:
-Lp phng trnh cn bng cht cho thit b
th i ( hnh 3.1 ):
C
i-1
.F
V(i-1)
= C
i
.F
Vi
+ R
i
.V
Ri
+ dC
i
.V
Ri
/dt.
( 3 . 3 )
4/20/2012
79
Thit b lm vic lin tc

C
A(i-1)
F
V(i-1)
F
Vi
C
Ai
C
Ai
V
Ri
T
i
T
i-1
R
i
=k
i
.f(C
Ai
) k
i
=k
0
.e
-E/RTi
TBP th i
H.3.1-Cc thng s ca thit b th i
loi thng c khuy
4/20/2012
80
C
i-1
.F
V(i-1)
= C
i
.F
Vi
+ R
i
.V
Ri
+ dC
i
.V
Ri
/dt. ( 3 . 3 )
Trong :
+C
i-1
: Nng cht phn ng i vo thit b th i.
+C
i
: Nng cht phn ng trong thit b i v l nng i
ra.
+F
V(i-1)
v F
Vi
: Lu lng ca dng vo v ra.
+V
Rn
: Th tch thit b th i.
+dC
i
.V
Ri
/dt : Lng cht phn ng tch t trong thit b i.
+R
i
= k
i
. f(C
i
) : Vn tc phn ng thit b th i.

4/20/2012
81
trng thi dng khng c tch t, ta c:
C
i-1
.F
V(i-1)
= C
i
.F
Vi
+ R
i
.V
Ri
hay
C
i-1
= C
i
. F
Vi
/F
V(i-1)
+ R
i
. V
Ri
/F
V(i-1)
.
pha lng coi nh hn hp phn ng khng thay i
th tch, ngha l lu lng dng khng i: F
V(i-1)
= F
Vi
= F
V
,
c:
C
i-1
= C
i
+ t
TBi
. R
i
. ( 3 . 4 )
Trong t
TBi
l TGL trung bnh thit b th i, t
TBi
= V
Ri
/F
V
.
Phng trnh (3.4) c gi l pt c trng ca TBP loi
thng c khuy.
T pt ny c th tnh chuyn ho X v th tch thit b V
Ri
.
4/20/2012
82
*Vi phn ng chuyn ho cht A sn phm:
-Bc 0 : R
i
= k
i
; pt (3.4) thnh:
C
i-1
= C
i
+ k
i
. t
TBi
. ( 3 . 4 )'
-Bc1 : R
i
= k
i
.C
i
; pt (3.4) thnh:
C
i-1
= C
i
+ k
i
. t
TBi
. C
i
hay
C
i-1
/C
i
= 1+ k
i
. t
TBi
. ( 3 . 4 )''
-Bc2 : R
i
= k
i
.C
i
2
; pt (3.4) thnh:
C
i-1
= C
i
+ k
i
. t
TBi
.Ci
2
( 3 . 4 )'''
4/20/2012
83
Bi tp 3.1: Tnh chuyn ho X ca phn ng bc
1 nh bi tp 2.5, tin hnh trong thit b thng c
khuy c TGL trung bnh l 15 pht nh bi tp 2.4
Li gii:
Vi i = 1, t phng trnh (3.4)" ta c:
C
0
/C
1
= 1 + 0,307 . 15
X = 1 - C
1
/C
0
= 1 - 1/( 1 + 0,307.15 ) =
0,822
So snh kt qu tnh ton vi bi tp 2.5
v 2.6 thy rng cng mt iu kin ,
thit b theo ch KLT c chuyn ho
thp nht.
4/20/2012
84
-Lp phng trnh cn bng cht cho h
thng n thit b khuy ni tip:
Dng phng trnh (3.4) v bt u t thit b
1 n n
*Khi th tch cc thit b trong h thng khng
bng nhau:
V
Ri
= V
Rj
t
TBi
= t
TBj

V nhit cc thit b khng bng nhau
T
i
= T
j
k
i
= k
j
.


4/20/2012
85
+Phn ng bc 0:
i = 1 C
0
- C
1
= k
1
. t
TB1
i = 2 C
1
- C
2
= k
2
. t
TB2
i = 3 C
2
- C
3
= k
3
. t
TB3
... ......
i = n C
n-1
- C
n
= k
n
. t
TBn
.
Cng cc phng trnh theo tng v c:
C
0
- C
n
= k
i
.t
TBi
i = 1, n


X
n
0
= k
i
.t
TBi
/ C
0
( 3 . 5 )


4/20/2012 86
+Phn ng bc 1:
i = 1 C
0
/ C
1
= 1 + k
1
. t
TB1
i = 2 C
1
/ C
2
= 1 + k
2
. t
TB2
i = 3 C
2
/ C
3
= 1 + k
3
. t
TB3
... ...
i = n C
n-1
/ C
n
= 1 + k
n
. t
TBn
.
Nhn cc phng trnh theo tng v, c:

C
0
/ C
n
= .

T chuyn ho thit b n i vi phn ng bc 1
l:

X
n
1
= 1 - C
n
/ C
0
= 1 - 1 / .
( 3 . 6 )

[
=
+
n
1 i
TBi i
) .t k (1
[
=
+
n
1 i
TBi i
) .t k (1
4/20/2012 87
+Phn ng bc 2:
Gii pt (3.4)''' c:
C
i
= (- 1 ) / 2
ki
.t
TBi
.

i = 1 C
1
= (- 1 ) / 2k
1
.t
TB1


i = 2 C
2
= (- 1 ) / 2k
2
.t
TB2

Thay C
1
vo ta c:

C
2
= [-1 ]/2k
2
.t
TB2
.

( 3 . 7 )
1
4 1

+
i i i
C t k
0 1 1
4 1 C t k +
1 2 2
4 1 C t k +
1 1 1 1 2 2
2 / ) 4 1 1 ( 4 1 t k C t k t k
o
+ +
4/20/2012
88
*Khi th tch cc thit b trong h thng bng nhau:
V
Ri
= V
Rj
t
TBi
= t
TBj
= t
TB
.
v nhit cc thit b bng nhau:
T
i
= T
j
k
i
= k
j
= k .
+ chuyn ho ca phn ng bc 0 trong h
thng n thit b ni tip theo cng thc (3.5) thnh:
X
n
0
= ( C
0
- C
n
) / C
0
= n.k.t
TB
/ C
0
. ( 3 . 5 )'
+ chuyn ho ca phn ng bc 1 trong h
thng n thit b ni tip theo cng thc (3.6) thnh:
X
n
1
= 1 - C
n
/C
0
= 1 - ( 1 + k . t
TB
)
-n
. ( 3 . 6 )'
4/20/2012
89
b/Phng php dng hnh:
Phng trnh (3.4) c th vit li dng:
R
i
= -C
i
/ t
TBi
+ C
i-1
/ t
TBi
. ( 3 . 8 )
V tri ca pt (3.8) l hm s xc nh ca
C
i
: R
i
= k
i
. f( C
i
), ta v ng biu din
ca R ph thuc vo C ( hnh 3.2 ).
V phi l hm s tuyn tnh ca C
i
, giao
im ca hai ng biu din l
nghim ca phng trnh (3.8).

4/20/2012
90
Phng php dng hnh
ng thng biu din v phi c h s
gc l -1/t
TBi
.
ng thng u tin ( i = 1 ) bt u t
trc honh ti C
0
vi h s gc l -1/t
TB1

giao im ca ng thng ny vi
ng cong R c to ng vi C
1
v R
1
,
l nng cht phn ng v vn tc phn
ng thit b 1.

4/20/2012
91
Phng php dng hnh
T C
1
trn trc honh v ng thng vi h
s gc l -1/t
TB2
, ta c C
2
v R
2
... v c th
tip tc n khi t Cn s C yu cu.
Bi ton c gii, ta tm c s thit b n
ca h thng cng nh cc thng s nng
cht phn ng C v vn tc phn ng R trong
tng thit b .
Nu nhit cc thit b khc nhau, ki kj,
ng vi mi nhit phi v ng biu din
R
i
= k
i
. f (C) tng ng .
4/20/2012 92
Phng php dng hnh

C
3
C
n
C
0
C
2
C
1
Rn
R3
R2
R1
Vn tc
p , R
Nng
cht p, C
Tg
1
= -1/t
TB1
Tg
2
= -1/t
TB2
Tg
3
= -1/t
TB3
...
H.3.2-Phng php dng hnh gii bi ton h
thit b khuy ni tip, lin tc.

3
4/20/2012
93
Bi tp 3.2-
Phn ng thun nghch 2A B + C, hng s
vn tc phn ng thun k
th
= 10 m
3
/kmol.h,
hng s cn bng K
cb
= 16, nng ban u
C
A0
= 1,5 kmol/m
3
, C
B0
= C
C0
= 0, tin hnh
trong thit b phn ng loi thng c khuy vi
lu lng dng FV = 100 m3/h. chuyn ho
X yu cu bng 80% trng thi cn bng. Tnh:
a/Th tch TBP khi tin hnh trong mt
thit b V
R1
.
b/S thit b n ca h thng nu ly V
Rn
=
V
R1
/10.
4/20/2012
94
Li gii:
a/t nng ca B v C trng thi cn
bng l C
Bcb
= C
Ccb
= C
cb
.
Ta c: C
Acb
= 1,5 - 2C
cb
.
K
cb
= C
2
cb
/ (1,5 - 2C
cb
)
2
=16.
Gii c C
cb
= 0,667 kmol/m
3
.
X yu cu bng 80% trng thi cn bng
nn nng yu cu ca B v C nh sau:
C
Byu cu
= C
Cyu cu
= 0,80.C
cb

=0,80.0,667 = 0,533 kmol/m
3
.
4/20/2012
95
Vy C
Ayu cu
= 1,5 - 2 . 0,533 = 0,434 kmol/m
3
.
Phng trnh vn tc ca phn ng thun nghch
chuyn ho cht A c dng:
R
A
= k
th
.C
A
2
- k
ng
. C
B
.C
C

= k
th
( C
A
2
- C
B
. C
C
/ K
cb
) v k
ng
= k
th
/K
cb
.
Ta c:
R
A
= 10 ( C
A
2
- C
B
.C
C
/16 ). ( 3.9 )

4/20/2012
96
Vn tc phn ng trong h thng phn ng mt thit b l:
R
A
(1) = 10 [ (0,434)
2
- (0,533)
2
/16 ]
= 1,7 kmol/m
3
.h.
T pt c trng (3.4) vi i = 1 ta c:
t
TB1
= V
R1
/ F
V
= ( C
0
- C
1
) / R
1
.
Do : V
R1
= F
V
. ( C
0
- C
1
) / R
1
.
Thay s vo , ta c:
V
R1
= 100 ( 1,5 - 0,434 ) / 1,7 = 62,7 m
3
.
4/20/2012
97
b/Nu ly V
Rn
= 1/10 V
R1
= 6,27 m
3
, tm s
thit b n ca h thng khuy ni tip ta dng
phng php dng hnh. V ng biu din
R
A
ph thuc vo C
A
theo phng trnh vn tc
(3.9): cho C
A
cc gi tr t 0 n 1,5 kmol/m
3
Xc nh C
B
, C
C
tng ng v tnh R
A
nh
bng sau:
C
A
, 1,5 1,3 1,1 0,9 0,7 0,5 0,3
C
B
,C
C
0 0,1 0,2 0,3 0,4 0,5 0,6
R
A
22,5 16,9 12,1 8,1 4,9 2,5 0,68
kmol/m
3
.h
4/20/2012
98
T C
A
= C
A0
= 1,5 kmol/m
3
v ng thng
to vi trc honh gc :
tgo = - 1/t
TB
= - 100/6,27 = -15,9
ng thng ny ct ng cong R
A

im c to C
A1
= 0,94 kmol/m3
v R
A1
= 8,9 kmol/m3.h
4/20/2012
99
T C
A1
tip tc v ng thng song song vi
ng thng trc( v cng h s gc ) ta c
giao im th 2 vi to tng ng l C
A2
v R
A2

( hnh 3.3 ), c th tip tc c kt qu nh sau:
C
A1
= 0,94 kmol/m
3
R
A1
= 0,89 kmol/m
3
.h
C
A2
= 0,68 R
A2
=4,52
C
A3
= 0,52 R
A3
= 2,65
C
A4
= 0,42 R
A4
= 1,70

4/20/2012
100

R
20
10
[kmol/m
3
.h]
0,5 1,0 1,5
C
A
Kmol/m
3
1
2
3
4

1
2
3
4

R
2
=4,52;C
2
=0,68
R
3
=2,65;C
3
=0,52
R
4
=1,70;C
4
=0,42
R
1
=8,90;C
1
=0,94
Tg=-1/t
TB
=-15,9
H.3.3-Phng php dng hnh gii bi tp 3.2
4/20/2012
101
Nh vy C
A4
< C
A yu cu
, ta c s thit b
trong h thng n = 4 .
Cng cn lu rng th tch cc thit b
trong h thng l 4 . 6,27 = 25 m
3
, nh
hn nhiu so vi th tch phn ng khi
dng mt thit b.
(iu ny cn c gii thch?)
4/20/2012
102
IV/C TRNG NHIT TRONG THIT B
PHN NG
Phn ng ho hc lun c hiu ng
nhit, thng kh ln c th thay
i nhit ca qu trnh.
Nhit l thng s cng tnh, nh
hng mnh n vn tc phn ng.
Do khng ch nhit phn ng
lin quan n lm vic an ton ca
thit b v qu trnh sn xut.

4/20/2012
103
Cc gii php duy tr ch nhit cho phn ng
nh hng n kt cu, hnh dng ca thit b
phn ng.
Trng thi dng ca h TBP ch t c khi
tho mn pt sau:
Q
R
= Q
S
( 4 . 1 )
Q
R
- Nhit phn ng trong n v thi gian.
Q
S
- Nhit trao i trong n v thi gian.

4/20/2012
104
IV.1-Ch nhit ti u:
y l nhn t lun c ch n
trong sn xut cng nghip, c bit khi
cng sut ln, m bo nng sut
cng nh chuyn ho X ca qu trnh
phn ng.
Ch nhit ti u ph thuc vo c
trng nhit ng, ng hc ca phn
ng cng nh tnh nng ca xc tc
Cho nn ch nhit ti u a dng, tu
tng trng hp c th.
4/20/2012
105
Vi d: C phn ng thun nghch, to nhit: A B
Hng s vn tc phn ng thun: k
1
= k
10
. e
-E1/RT
Hng s vn tc phn ng nghch: k
2
= k
20
. e
-E2/RT
Ta c: R
A
= k
1
. C
A
- k
2
. C
B

= k
10..
exp(-E
1
/RT).C
A0
(1 - X
A
) - k
20
.exp(-E
2
/RT). C
A0
. X
A

Tm ch nhit ti u m bo vn tc phn
ng ln nht bng cch cho dR
A
/ dT = 0:
dR
A
/dT =
k
10
.C
A0
.(1-X
A
).e
-E1/RT
.E
1
/RT
2
- k
20
.C
A0
.X
A
.e
-E2/RT
.E
2
/RT
2
= 0 .
4/20/2012
106
k
10
.(1-X
A
).e
-E1/RT(t).
E
1
= k
20
. X
A
.e
-E2/RT(t).
E
2
.
Ly loga c hai v:
ln [ k
10
.(1-X
A
).E
1
] - E
1
/RT
(t)
=
ln ( k
20
.X
A
.E
2
) - E
2
/RT
(t)
.
T :
(E
2
- E
1
)/RT(t) = ln [ k
20
.E
2
.X
A
/k
10
.E
1
.(1-X
A
).
T(t) = (E
2
- E
1
)/Rln[k
20
.E
2
.X
A
/k
10
.E
1
.(1 - X
A
)].
( 4 . 2 )
4/20/2012
107
Nh vy,ch nhit ti u trng hp phn
ng thun nghch, to nhit ph thuc vo
chuyn ho X
A
nh cng thc (4.2)
Lc u khi X
A
cn thp nn tin hnh phn
ng nhit cao m bo vn tc ln,
sau khi X
A
tng ln cn gim dn nht .
Trong thc tin sn xut, phn ng c c
trng ny ( nh SO
2
+ 1/2O
2
SO
3
+ q ) c
thc hin trong thit b trong TBP c nhiu
ngn xc tc on nhit c trao i nhit
trung gian gia cc ngn nh hnh 4.1 .
4/20/2012
108

T
0
T
1
T
2
T
3
T4
T
5
T
6
T
7
T
8
T
9
Nguyn liu Sn phm
T
9
T
7
T
5
X
2
X
3
X
4
X
1
X
5
H.4.1- Cc lp xc tc on nhit ( p to nhit ) vi lm lnh trung gian .
4/20/2012 109
Bng cch nh vy qu trnh phn ng trong thit b c thc hin
theo ng dch-dc quanh ch nhit ti u ( hnh 4.2 ).

T T
0
T
1
T
2
T
3
T
4
T
5
T
6
T
7
T
8
T
9
X
c
b
T
t
=f(X)
X
1
X
2
X
3
X
4
X
5
X
H.4.2- ng biu din s thay i nhit v chuyn ho
X thit b nh hnh 4.1 i vi phn ng thun nghch to nhit.
4/20/2012
110
IV.2-Cc gii php duy tr ch
nhit ti u trong thit b
phn ng:
a/Trao i nhit qua thnh:
-Thit b loi thng c khuy vi v bc ngoi
v ng xon trong thit b.
-Thit b ng chm vi hng nghn ng vi b
mt trao i nhit rt ln, thng dng cho
phn ng pha kh to nhiu nhit.
4/20/2012
111
b/Dng tc nhn mang nhit l kh, lng hay rn:
-Kh: Kh tr, kh chy nhit cao ... v
thng dng hi nc ( c sn trong nh
my v d tch khi sn phm
hydrocacbon bng cch lm lnh ngng t
v phn ly, ngoi ra hi nc cn gim
to cc bm vo thnh thit b ).
-Lng: Dung mi hay cc cht tr c trong
hn hp phn ng.
4/20/2012
112
-Rn: Vt liu rn chu nhit nh gm, s,
cc vt liu silict ... v c xc tc rn,
in hnh l qu trnh crcking xc tc l
phn ng thu nhit, xc tc mau mt hot
tnh do b ph cc b mt nn phi dng
lp xc tc chuyn ng v tun hon
gia thit b phn ng v thit b ti sinh
bng phn ng t cc to nhit nh
hnh 4.4

4/20/2012 113

TBTS
+Q
TBP
-Q
Xc tc nng
Xc tc ngui
H.4.4-Qu trnh s dng nhit ca crcking xt
4/20/2012 114
c/Tng phn on nhit c trao i nhit
trung gian:
-Ging m hnh 4.1.
-in hnh l thit b reforming xc tc,
hydro ho xc tc ...
-Vi TBP thng c khuy nh hnh 4.5.
T
0
T
1
H.4.5-H thng thit b thng c khuy
vi lm lnh trung gian
4/20/2012
115
d/iu chnh nhit
ban u T
0
i vi
cc qu trnh on
nhit.
e/Bay hi cu t c
nhit si xp x
nhit phn ng
vi h thng lm
lnh ngng t v cho
cht lng quay v
TBP ( hnh 4.6 ).
Lng
Hi
H.4.6-Gii nhit phn ng bng cch
Bay hi cu t nh
Cht
Phn ng
Sn phm
4/20/2012
116
g/Bm
tun hon
hn hp
phn ng
qua thit
b trao i
nhit
( h.4.7).
Sn phm
Nguyn liu
TB
P
H.4.7-Gii nhit bng cch tun hon hn hp
phn ng qua thit b trao i nhit
4/20/2012
117
IV.3-c tnh t nhit:
-L cc qu trnh t xy ra sau khi c "mi ".
-iu kin t nhit:
Phn ng to nhit ln c th a nhit
hn hp phn ng t nhit ban u T
0
n nhit lm vic ca thit b.
C kh nng trao i nhit gia sn phm hay
khi phn ng vi nguyn liu i vo. iu kin
ny ph thuc vo c trng v kt cu ca
thit b phn ng.
4/20/2012
118
-Cc loi thit b c kh nng t nhit:
a/Thit b loi thng c khuy:
Nh khuy nguyn liu i vo
c trn ln vi khi phn
ng nng c trong thit b,
nu phn ng to nhit ln th
qu trnh tin hnh trong loi thit
b ny c kh nng t nhit sau
khi c "mi" (hnh 4.8a ).
4/20/2012
119

T
0
T
0
T
1
T
1
T
0
Mt ca
ngn la
T
f
a b
H.4.8-Thit b phn ng t nhit
a- Thng c khuy. b- Ngn la
4/20/2012
120
b/Thit b phn ng dng ngn la: Thit b
dng ny thng c s dng tin hnh
cc phn ng to nhit cao nh qu trnh clo
ho ( t hydro trong mi trng clo sn
xut HCl ) hay qu trnh oxy ho mt phn
hydrocacbon sn xut axtylen.
Trong khng gian cht hp ca ngn la nhit
thay i t T
0
rt thp n nhit cao
c th t bc chy, ngha l ta c gradien v
nhit , v nng , v th ho hc rt ln
(c th t hng vn n v ), nh qu trnh
truyn nht, chuyn cht v hot ho xy ra
mnh m trn mt ca ngn la n c th
t nhit (hnh 4.8b ).
4/20/2012
121
c/Thit b phn ng loi ng:
- c th t nhit cn c s ( hnh 4.9b ).
trao i nhit gia nguyn liu vo vi
sn phm phn ng (hnh 4.9a) hay vi
khi phn ng
- trng hp b/ c th iu chnh c
nhit lm vic ca lp xc tc cng nh
nhit T
1
theo thi gian lm vic ca xc
tc bng cch iu chnh thng s o.

4/20/2012
122
T
0
T
1
T
2
T
1
T
0
T
3
T
3
F
V
(1-)F
V
F
V
T
0
T
2
T
2
T
0
T
2
T
1
H.4.9- Thit b phn ng loi ng c kh nng t nhit .
a-Trao i nhit vi sn phm.b-Trao i nhit vi xc tc
4/20/2012
123
c/Qu trnh nm phm vi khuch tn ngoi:
- Thng gp khi tin hnh phn ng xc tc
kh- rn, to nhit nhit cao, lc vn tc
phn ng ln v chm nht l cc qu trnh khuch
tn qua lp bin gia pha kh v b mt xc tc rn
( hnh 4.10a).
- Do tr lc khuch tn ch yu lp bin,
hnh nh cng tng t vi qu trnh truyn nhit
gia b mt xc tc v pha kh, nn nhit b
mt xc tc Ts cao hn nhiu so vi nhit
trong pha kh Tg .
- Trn b mt xc tc nng qu trnh phn
ng tip tc t tin hnh.

4/20/2012
124
- Qu trnh cng nghip:
+Oxy ho NH
3
thnh oxit nit trn
xc tc dng li Pt-Rh nhit 800 -
850
0
C.
+Amonoxi ho CH
4
thnh HCN
trn xc tc dng li Pt-Rh 1000 -
1200
0
C.
+Oxihydro ho mtanol thnh
fomaldhit trn xc tc Ag 650 - 720
0
C
( hnh 4.10b).
4/20/2012
125

- qu trnh c th tin hnh t nhit, khi
m my cn phi un nng hn hp
mtanol - khng kh n 300 - 400
0
C. Sau ,
khi lp xc tc l cc tinh th bc t trn li
ng nng n nhit phn ng th dng un
nng, kt thc qu trnh "mi " phn ng.
-TBP cn c mng phng n v thit b
lm lnh ng chm t st ngay sau lp xc
tc lm lnh nhanh hn hp sn phm t
nhit phn ng xung 200 - 300
0
C, gim
phn hu fomalehit to thnh nhit cao
theo phn ng: CH
2
O CO + H
2

4/20/2012
126

C
Ag
C
As
T
s
T
g
Dng kh
Lp
bin
C
As
<< C
Ag
T
s
>> T
g
B mt xc tc
Mng phng n
un nng in
Mi phn ng
Xc tc Ag
Lm lnh
ng chm
Hn hp mtanol-
khng kh
a b
H.4.10- c trng t nhit ca qu trnh phn ng xc tc phm vi khuch
tn ngoi. a-M hnh khuch tn ngoi. b-TBP oxyhidro ho mtanol.
4/20/2012
127
IV.4-c trng nhit ca TBP loi thng c khuy:
*Nhit ng u khp thit b.
*C kh nng t nhit.
a/Cc trng thi dng:
iu kin dng: Q
R
= Q
S
( 4 . 3 )
Trong Q
R
- nhit phn ng trong n v thi gian.
Q
S
- nhit trao i trong n v thi gian.
gii pt (4.3) ta dng phng php dng hnh : kho st
ng biu din ca Q
R
v Q
S
theo T, nghim ca pt l
giao im ca hai ng biu din.
4/20/2012
128
+Kho st Q
R
:
Gi s c phn ng bc 1 chuyn ho cht A, to nhit,
khng thun nghch, tin hnh trong TBP loi thng c
khuy th tch V
R
.
S mol cht A chuyn ho trong n v thi gian l N
A
, do :
Q
R
= N
A
. ( - AH
R
)
N
A
= k . C
A
. V
R
C
A
l nng trong thit b, rt ra t pt (3.4)''
C
A
= C
A0
/ ( 1 + k . t
TB
) . T :
N
A
= k.C
A0
.V
R
/(1+k.t
TB
) = k
0
.e
-E/RT
.C
A0
.V
R
/(1+k0.e
-E/RT
.t
TB
)
N
A
= k
0
.C
A0
.V
R
/ ( e
E/RT
+ k
0
.t
TB
) . Do :
Q
R
= k
0
. C
A0
. V
R
. (-AH
R
) / ( e
E/RT
+ k
0
. t
TB
) ( 4 . 4 )
4/20/2012 129
ng biu din ca Q
R
ph thuc vo T
theo pt (4.4) c dng ch S, ngoi ra khi cc
thng s khc nh V
R
, F
V
thay i ta c
mt h ng cong S trong mt phng vi
trc to Q
R
- T nh hnh 4.11.
T
Q
R
F
V
tng
H.4.11- ng biu din Q
R
theo T khi F
V
thay i
4/20/2012
130
+Kho st Q
S
:
Q
S
c hai thnh phn:
- Trao i nhit vi nguyn liu vo, nhit nguyn liu t T
0

T.
-Trao i nhit qua thnh.
Q
S
= F
V
..C
P
( T - T
0
) + K.F. ( T - T
C
). ( 4 . 5 ) hay
Q
S
= ( F
V
..C
P
+ K.F ) T - ( F
V
..C
P
.T
0
+ K.F.T
C
)
Trong : - Khi lng ring ca hn hp phn ng.
C
P
- Nhit dung ring ca hn hp phn ng.T - Nhit phn ng.
T
0
- Nhit vo. K - H s trao i nhit qua thnh.
F - B mt trao i nhit ca thit b. T
C
- Nhit thnh thit b.
4/20/2012 131
ng biu din ca Q
S
theo T l
ng thng, khi F thay i ta c cc
ng thng vi h s gc thay i (
hnh 4.12a ), khi T
0
thay i c cc
ng thng song song (hnh 4.12b).
Q
S
K
.
F
=
0
K.F tng
T T
Q
S
T
0
tng
b a
H.4.12- ng biu din Q
S
theo T.
a- Khi KF thay i. b- Khi T
0
thay i.
4/20/2012
132

1
2
3
Q
S
Q
R
T
T3 T2
Q
R1
Q
R3
H.4.13- Cc trng thi dng ca TBP thng c khuy
4/20/2012
133
Nh vy, c th c 3 giao im gia
ng Q
R
dng ch S v ng thng
Q
S
, ngha l c 3 trng thi dng ca
h thng ( hnh 4.13 ).Trng thi dng 1
c T
1
thp v Q
R1
,Q
S1
u thp, phn
ng hu nh khng xy ra. Trng thi
dng 3 nhit cao T
3
do c
chuyn ho cao , l iu ta mong i.
Trng thi dng 2 khng n nh, s
c kho st mc 3/.
4/20/2012
134
b/Trng thi dng ph thuc vo
chiu thay i ca cc thng s v
bin php mi phn ng:
a/Gi s F
V
thay i, cc thng s
khc c nh:
Q
R
l cc ng cong A, B, C, D v
E, Q
S
coi nh khng i,c cc trng
thi dng t 1 n 9, ng vi nhit
dng t T
1
n T
9
nh hnh 4.14.
4/20/2012
135

T
A
B
C
D
E
Q
R
Q
S
4
3
2
1
5
6
7
8
9
H.4.14-Cc trng thi dng khi F
V
thay i
F
V
tng
4/20/2012
136
-Khi F
V
tng t thp ln cao ta c cc
ng Q
R
ln lt l A, B, C, D v E, cc
trng thi dng l 9, 8, 7, 6 v 1.
-Ngc li, khi F
V
gim t cao xung,
cc ng Q
R
ln lt l E, D, C, B v A,
cc trng thi dng l 1, 2, 3, 4 v 9.
Nh vy, trng thi dng ph thuc
vo chiu thay i ca F
V
nh hnh
4.15

4/20/2012
137
T
dng
F
V
E D C B A
9
8
7
6
3
4
2
1
H.4.15- Cc nhit dng ph thuc vo chiu
thay i ca F
V
4/20/2012
138
T rt ra cch mi phn ng:
Khi m my ban u dng lu lng
dng F
V
thp phn ng tin hnh
trng thi dng c chuyn ho v
nhit dng cao ( T9 ), sau tng
dn F
V
n nng sut thit k ( nhng
khng th tng qu ng D ).
4/20/2012
139
b/Gi s T
0
thay i, cc thng s khc c nh:
Q
R
khng i, Q
S
l cc ng thng song
song , ta c cc trng thi dng t 1 n 9
nh hnh 4.16a.
- Khi T
0
tng t thp ln, Q
S
ln lt l cc
ng thng A, B, C, D v E, cc trng thi dng
l 1, 2, 3, 4 v 9.
-Ngc li, khi T
0
t cao gim xung, Q
S
ln lt
l cc ng thng E, D, C, B v A, cc trng
thi dng l 9, 8, 7, 6 v 1.
Nh vy, trng thi dng ph thuc vo
chiu thay i ca T
0
nh hnh 4.16b.
4/20/2012
140

A B C D E
9 8
7
6
5
4
3
2
1
T
0
tng
T
Q
R
Q
S
1
2
3
4
6
7
8
9
T
dng
T
0
b a
H.4.16- Cc trng thi dng khi T
0
thay i.
a- Cc trng thi dng.b-Cc nhit dng theo chiu thay i ca T
0
4/20/2012
141
T rt ra bin php mi phn ng:
khi m my un nng nguyn liu vo Q
S

n qu ng D(v d ng E) t trng
thi dng 9
Sau c th gim (hay ngng) un nng
i vo trng thi dng 8, 7, 6 (ng vi cc
ng Q
S
l D, C v B) l cc trng thi dng
c nhit v chuyn ho cao, m khng b
ri vo trng thi dng c nhit v
chuyn ho thp( tuy rng vi cc ng Q
S
l
B, C v D ta c th gp cc trng thi dng 2, 3
v 4).
4/20/2012
142
c/ n nh ca TBP:
-Trng thi dng 5 ( hnh 4.14 v 4.16a )
khng n nh
Nu c mt nhiu lon no , nh khi T > T
5
,
lc Q
R
> Q
S
, h thng c un nng bng
nhit phn ng v n T
7
Ngc li khi T < T
5
th Q
R
< Q
S
, h b ngui i
v v T
3
.
T c th rt ra iu kin n nh ca cc
trng thi dng l:
dQ
S
/ dT > dQ
R
/ dT ( 4 . 6 )
4/20/2012
143
IV.5-c trng nhit ca thit b
loi ng:
-Do khng c khuy trn nn nhit
ca thit b loi ny thay i t im
ny n im khc trong thit b.
-ng thng c tit din trn phn b
nhit trong ng c trc i xng l
trc tm ng, do vy c th din t
hnh nh phn b nhit trong khng
gian thit b theo hai thng s l v r.
4/20/2012
144
a/Phn b nhit trong ng phn ng:
Phn ng to nhit khng c trao i nhit qua
thnh, chy ri hay c lp ht xc tc tnh ( m
hnh LT ):
-Nhit ng u theo hng ng knh
ng ( hng r ).
-Nhit thay i theo hng trc ng (
hng l ).
-Ph thuc vo vn tc phn ng ( hot tnh
xc tc ) ta c hnh nh nhit nh hnh 4.17
4/20/2012
145

T
X
L
L
2 1 3
1
0
T
0
T
n
1 2 3
1-Xc tc hot tnh
cao
2-Xc tc hot tnh
trung bnh
3-Xc tc hot tnh
thp
H.4.17-S thay i nhit v chuyn ho
trong ng phn ng on nhit vi xc tc c
hot tnh khc nhau
4/20/2012
146
*Phn ng to nhit c trao i nhit qua thnh:
-Nhit thay i theo c hai hng l v r.
-C ch truyn nhit trong lp ht c 3 thnh
phn:
+Dn nhit ca lp ht: b v ht xp v din
tip xc nh.
+Dn nhit ca lu th: pha kh thng nh.
+Truyn nhit do dng lu th chuyn ng
mang nhit: thng ng vai tr ch yu.

4/20/2012
147
-Tm ng c nhit cao nht ( phn ng
thu nhit c hnh nh ngc li ).
-Trn tm ng thng tn ti Tmax , ni
phn ng xy ra mnh m do nhit
cao, c gi l "im nng'' hay "vng
phn ng'' v c ch theo di trong
qu trnh lm vic ca thit b cng nh khi
thit k TBP.
-Mt hnh nh v phn b nhit vi cc
ng ng mc T c th din t hnh
4.18
4/20/2012
148

T
5
F
V
,T
0
T
0
T
1
T
2
T
3
T
4
H.4.18-Phn b nhit trong ng, phn ng to
nhit c trao i nhit qua thnh
T
5
> T
4
> T
3
> T
2
> T
1
> T
0
T
5
: T
max
4/20/2012
149
Cn tnh thm thnh phn khuch tn theo hng ng knh
vi h s khuch tn ngang l D
r
v a vo pt mt th
nguyn (2.27).
+Tnh thnh phn kt ngang ( k hiu l A ) cho nguyn t
th tch 2tr.dr.dl theo hnh 4.19
r dr
-D
r
.2rdl.C/r -D
r
.2(r+dr)dl.(C+C/r.dr)/r dl
H.4.19-M hnh tnh khuch tn ngang cho nguyn t
th tch thit b 2r.dr.dl
C C+C/r.dr
4/20/2012
150
A = Lng ra - Lng vo
= -D
r
.2t(r+dr)dl.c(C+cC/cr.dr)/cr
- (-Dr).2trdl. cC/cr.
A/2tdl= -Dr [(r+dr).c(C+cC/cr.dr)/cr - r.cC/cr].
A/2tdl= -Dr ( r.c
2
C/cr
2
.dr + cC/cr.dr + c
2
C/cr
2
.dr
2
).
S hng c
2
C/cr
2
.dr
2
qu b, b qua v chia tip
cho rdr:
A/2tr.dr.dl = -Dr ( c
2
C/cr
2
+ 1/r.cC/cr ) (4 . 7)
4/20/2012
151
a thnh phn khuch tn ngang A / 2tr.dr.dl t (4.7) vo pt
(2.27):
v.cC/cl - D
l
.c
2
C/cl
2
- D
r
(c
2
C/cr
2
+ 1/r.cC/cr) + R = 0. ( 4 . 8 )
Qu trnh truyn nhit tng t chuyn cht, nn c th vit:
v.C
P
.cT/cl -
l
.c
2
T/cl
2
-
r
(c
2
T/cr
2
+ 1/r.cT/cr)
+ ( -AH
R
)
i
. R
i
= 0. i= 1, n. ( 4 . 9 )
Trong :+ C
P
-Nhit dung ring ca hn hp phn ng.
+
l
-H s truyn nhit theo hng trc ng.
+
r
-H s truyn nhit theo hng ng knh
ng.
+(-AH
R
)
i
-Nhit ca phn ng th i.
4/20/2012
152
Nh vy:
+v.cC/cl -Chuyn cht vi dng chy c vn tc
v.
+v.C
P
.cT/cl -Truyn nhit do dng cht mang
nhit.
+-
l
.c
2
T/cl
2
-Truyn nhit theo hng trc ng.
+-
r
(c
2
T/cr
2
+ 1/r.cT/cr) -Truyn nhit theo
hng ng knh ng.
+(-AH
R
)
i
.R
i
-Tng nhit phn ng chnh v ph.
4/20/2012
153
b/im nng Tmax:
-Vi phn ng to nhit, c trao i
nhit qua thnh, tn ti Tmax trn trc
tm ng nh hnh (4.18).
-V tr v gi tr Tmax -i vi mt qu
trnh phn ng, kch thc ng v iu
kin trao i nhit xc nh-ph thuc
vo hot tnh xc tc (ngha l ph
thuc vo vn tc phn ng ) nh hnh
4.20
4/20/2012
154

T
0
1
2
3
T
max
T
max
T
max
T
L
1-Xc tc mi, HT cao.
2-Xc tc gim HT.
3-Xc tc HT thp.
H4.20-ng biu din nhit tm ng phn
ng theo chiu di l vi xc tc c HT khc nhau.
4/20/2012
155
-Xc nh cc thng s nh hng n Tmax:
Dng F
V
i qua nguyn t th tch S.dl, nhit
thay i l dT v nng cht phn ng thay
i mt i lng l dC (hnh 4.21)
F
V
dl
S
P
H.4.21-M hnh cn bng nhit ca dng F
V
i qua nguyn t th tch S.dl
4/20/2012
156
Ta c pt cn bng nng lng ca dng
- F
V
..dh + dQ = 0 ( 4 . 10 )
Trong
+dh- Thay i entalpi ca dng
dh = C
P
.dT + AH
R
.dC
+C
P
- Nhit dung ring ca dng.
+AH
R
- Entalpi ca phn ng.
+- Khi lng ring ca hn hp phn ng.
+dQ- Nhit trao i qua thnh ( a vo ly du +, ra
ly du - ).

4/20/2012
157
Gi s phn ng to nhit, lm lnh ngoi thnh ng phn ng:
dQ = -K.( T - T
C
).P.dl
+K- H s trao i nhit qua thnh.
+T
C
- Nhit ca thnh.
+P- Chu vi ca ng phn ng.
Ta c bn knh thu lc ca ng phn ng:
R
TL
= S/P P = S/R
TL
.
dQ = -K.(T - TC).S.dl / R
TL
.
Thay vo pt (4.10)
-F
V
..(C
P
.dT + AH
R
.dC) - K.(T - T
C
).S.dl / R
TL
= 0. ( 4 . 11 )


4/20/2012
158
Phng trnh cn bng vt cht trong S.dl vi vn
tc phn ng l R:
F
V
..dC = S.dl.R S.dl = F
V
..dC / R.
Thay S.dl vo pt (4.11) v chia cho F
V
.
-C
P
.dT - AH
R
.dC - K.(T - T
C
).dC / R
TL
.R = 0.
( 4 . 12 )
Ti T = Tmax th dT = 0, ta c:
-AH
R
.dC - K.(Tmax- T
C
).dC /R
TL
.R = 0. T
Tmax = T
C
+ (-AH
R
).R.R
TL
/ K ( 4 . 13 )
4/20/2012
159
T (4.13):

+Tmax t l thun vi nhit phn ng (-
AH
R
), vn tc phn ng (R) v ng knh ng
phn ng (R
TL
).Vi phn ng c hiu ng nhit
v khong nhit thch hp khc nhau cn
thit k kch thc ng phn ng ph hp:
-Khi nhit phn ng trong khong 50 n
200 Kj/mol, ng knh ng phn ng c th t
20 n 70 mm ph thuc vo nhy ca s
thay i chn lc hay ca hot tnh xc tc
vo nhit .
-Cn lu rng khi gim ng knh ng
ca thit b ng chm th s ng s tng mnh
v do gi thnh thit b tng vt ln.
4/20/2012
160
T (4.13):
+Tmax t l thun vi vn tc phn ng R,
ngha l vi hot tnh xc tc. Trong trng
hp cn thit c th s dng xc tc c hot
tnh thp (hay xc tc c) u ng phn ng
gim gi tr ca Tmax .
+Tmax t l nghch vi h s trao i nhit K
nn cn lu vic s dng tc nhn trao i
nhit cng nh lm sch b mt trao i nhit
m bo K c gi tr ln.
4/20/2012
161
T (4.13):
Cui cng Tmax t l thun vi nhit
ca cht ti nhit T
C
.
Tuy vy, TBP nhit cht ti nhit T
C

qu thp s lm ngui lp xc tc v do
tc phn ng cng nh nng sut
thit b thp.
iu lin quan n c im nhy
nhit ca TBP loi ng nh phn sau.

4/20/2012
162
Chnh t c im ny phi tin hnh gii
nhit cho cc phn ng to nhit nhit
xp x nhit phn ng.
V d, khi nhit phn ng l 300
0
C nh
qu trnh oxy ho mtanol thnh
fomaldhit trn xc tc oxit Fe-Mo phi
lm lnh bng du nng 260-270
0
C
( hnh 4.22).

4/20/2012
163

F
V
300
0
C
Nc mm
Hi nc
Du nng
260-270
0
C
H.4.22-S gii nhit phn ng
4/20/2012
164
c/ nhy nhit caTBP loi ng:
- nhy thng s l hin tng xy ra khi
mt thng s no c thay i tng i nh
nhng h thng TBP c s thay i ln, vi
thng s l nhit ta c nhy nhit.
-Mt v d i vi phn ng bc1, khng
thun nghch, to nhit tm thy nhy ca
nhit im nng Tmax i vi cc thng s
T
C
, K/R
TL
v AT on nhit.
Hnh 4.23 din t s thay i nhit Tmax
khi nhit ban u ca hn hp T
0
=340 K,
cn T
C
thay i t 300 n 342,5 K
4/20/2012
165

10 20 30
t
TB
,S
T,K
420
380
340
300
1
2
3
4
5
6
T
max
=440
420
430 1-T
C
=300,0 K
2-T
C
=320,0 K
3-T
C
=335,0 K
4-T
C
=337,5 K
5-T
C
=340,0 K
6-T
C
=342,5 K
H.4.23- nhy ca T
max
vo T
C
4/20/2012
166
Nhn hnh v ta thy mi n khi T
C
=335 K,
nhit trong ng phn ng t thay i theo
chiu di ng, c th ni lp xc tc b ngui v
vn tc phn ng thp, do chuyn ho X
khng t yu cu.
Khi tng T
C
thm 2,5 K (T
C
=337,5 K) ng
biu din nhit ti tm ng c cc i cao
hn T
0
n 80 K (Tmax=420 K).
Khi tng T
C
ln mt t na (T
C
=342,5 K) nhit
im nng vt nhit ban u n 100
K.
4/20/2012
167
. d/ n nh ca TBP loi ng:
-Khc vi TBP loi thng c khuy, phn
ng tin hnh trong thit b loi ng lun lun
n nh. Do c im ca thit b loi ny mt
s ri lon no ti mt th tch nh ca ng
phn ng khng lan rng ra qui m khp thit
b m s b dng chy ko ra khi zn phn
ng, trng thi dng ca h thng quay v
trng thi c.
- TBP loi ng c trao i nhit gia
sn phm i ra v nguyn liu vo ( hay c trao
i nhit gia lp xc tc vi nguyn liu vo )
c th c trng thi dng khng n nh
4/20/2012
168
V-TBP XC TC KH-RN ( XC TC
RN ).
-H phn ng vi xc tc rn rt hay gp trong
cng nghip ho hc ni chung v ring i vi
cng nghip ho du.
-Cc vn c t ra i vi h phn
ng d th ny l:
+B mt tip xc pha.
+Cc bin php duy tr ch nhit ti u
cho qu trnh: rt quan trng v nh hng n
cu to v hnh dng ca thit b.
+Trng thi lp xc tc: lp tnh, lp ri,
lp cun theo dng kh.
4/20/2012
169
V.1-B mt tip xc pha v hiu sut s dng b mt
bn trong ca xc tc:
Gii php m bo b mt tip xc pha ca
h kh rn l s dng xc tc xp c b mt
bn trong rt pht trin, t 1-2 m
2
/g n gn
1000 m
2
/g.
a/Cc c trng ca xc tc xp:
+B mt ring:
+K hiu - S
R
, n v - m
2
/g.

4/20/2012
170
+Mt s vt liu xp thng dng:
Diatomit: S
R
= 5 - 10 m
2
/g.Al
2
O
3
hot tnh,
silicagel: S
R
= 200 - 400 m
2
/g.Zolit: S
R
=
700 - 800 m
2
/g.Than hot tnh: S
R
= 800 -
1000 m
2
/g.
+Vi cu trc ht ca vt liu xp: c ht s
cp v ht th cp, b mt ring l tng b
mt cc ht s cp trong 1 gam vt liu.
+B mt ring c xc nh bng phng
php hp ph, tnh theo BET.

4/20/2012
171
+ xp:
+K hiu - c, n v - cm
3
/g.
+L khong trng gia cc ht s cp v th cp
trong vt liu xp.
+Ph thuc vo s sp xp (s phi tr) ca cc
ht s cp v th cp, xp c th thay i t
0,1 n 1cm
3
/g.Thng s phi tr gim th
xp tng v bn c hc ca vt liu gim.
+c tnh t khi lng ring tht v khi
lng ring biu kin theo cng thc:
c = 1/
bk
- 1/
tht
. ( 5 . 1 )

4/20/2012
172
+Phn b l xp theo kch thc:
+L xp c kch thc khc nhau do s
sp xp ca cc ht s cp v th cp,
c th din t theo m hnh 5.1, phn
chia thnh l xp b ( ng knh di
0,2 nm ), l xp trung (t 0,2 n 50 nm)
v l xp ln (trn 50 nm).
+Phn b l xp theo kch thc c
xc nh bng phng php hp ph,
ngng t mao qun v np thu ngn
di p sut ( n 250 MPa ).
4/20/2012 173
L xp
ln
L xp
trung
L xp
b
Ht xc tc
Ht th cp
Ht s cp
H.5.1-M hnh cu trc xp nhiu dng.
Ht xc tc c cha cc tinh th zolit l ht th cp
4/20/2012
174
+H s khuch tn hiu dng:
+ xp v phn b l xp theo kch thc l nhng yu t
quan trng nh hng n qu trnh khuch tn trong xc tc
xp.
+H s khuch tn hiu dng De trong ht xc tc c th din t
theo cng thc sau:
D
e
= D . c / t ( 5 . 2 )
Trong D - H s khuch tn trong pha kh.
c - xp ca xc tc.
t - H s ni ln trng thi hnh hc ca l xp:
quanh co, g gh ca b mt l xp, s thay i ng knh ca
l xp...
Thng t s c/t c gi tr t 1/10 n 1/20 v h s khuch tn
hiu dng c th c xc nh bng thc nghim.
4/20/2012
175
b/Hiu sut s dng b mt bn trong
ca xc tc q:
Ngoi h s khuch tn hiu dng D
e
,
q cn ph thuc vo vn tc phn
ng b mt (tc hot tnh ca xc tc)
, vo kch thc v hnh dng ca ht
xc tc.
Gn ng vi ht xc tc c hnh
dng khc nhau, ta c:
q = th / ( 5 . 3 )
4/20/2012
176
Trong . - Modun Thiele
= V
h
/S
h
R
s
/D
e
( 5 . 4 )
.V
h
- Th tch ca ht xc tc.
.S
h
- B mt ngoi ca ht xc tc.
.V
h
/S
h
- c trng cho kch thc
ht xc tc:
Vi ht hnh tr bn knh R, V
h
/S
h
= R/2.
Vi ht hnh cu bn knh R, V
h
/S
h
= R/3.
.R
S
- Vn tc phn ng b mt.

4/20/2012 177
.Th - Hm tang hyperbolic. S ph thuc q vo theo pt (4.3) c
din t hnh 5.2.
q
4/20/2012
178
T (5.3) v (5.4), khi kch thc ca ht
xc tc ln (V
h
/S
h
ln), vn tc phn ng
b mt ln v h s khuch tn hiu dng
b th ln, do hiu sut s dng b
mt xc tc q c gi tr thp. T c trng
ca hm tang hyperbolic ta c:
-Khi < 1 th th = , do q = 1.
-Khi > 3 th th = 1 , do q = 1/.

4/20/2012
179
Do vy, vi tng qu trnh phn ng yu
cu xc tc c b mt ring, kch thc
ht v cu trc xp thch hp c tch s
S
R
.q cc i. Hot tnh ca mt n v
khi lng xc tc Ag c xc nh
A
g
= A
s
. S
R
. q ( 5 . 5 )
A
s
Hot tnh ca mt n v b mt xc
tc

4/20/2012
180
V.2-Lp xc tc:
a/Lp tnh:
+Hay s dng v n gin, cho xc tc
lu mt hot tnh ( > 6 thng ).
+Ht xc tc khng c qu b,
thng kch thc t 3 n 10 mm, tr
lc ca lu th qua lp khng qu ln, vi
lng xc tc ln hay FV ln dng lu th
chuyn ng theo hng xuyn tm thay
cho hng trc ng.
4/20/2012
181
+Do kch thc ht xc tc ln nn
hiu sut s dng b mt xc tc
thng thp.
+TBP thng gp:
-Thit b ng chm, xc tc t trong ng,
cht ti nhit i gia cc ng.
-Thit b c lp xc tc on nhit vi
trao i nhit trung gian hay cho thm
nguyn liu lnh vo iu chnh nhit
phn ng.

4/20/2012
182
b/Lp chuyn ng:
+Dng cho xc tc mau mt hot tnh v c
th lin tc ly xc tc lm vic ra em i
ti sinh v b sung xc tc c hot tnh cao vo
h thng TBP m khng phi ngng qu
trnh.
+ thc hin lp xc tc chuyn ng
thit b c cu to phc tp hn, tuy nhin hot
ca lp xc tc hu nh khng thay i
trong sut qu trnh lm vic, l mt u
im c bn i vi qu trnh lm vic lin tc.
+Xc tc cn c bn c hc cao chng
mi mn v v vn trong khi chuyn ng.
4/20/2012
183
+Lp xc tc chuyn ng c 3 dng vi nhng c im ring:
-Lp ri: + Ht xc tc chuyn ng nh trng lc.
+ Kch thc ht tng ng vi lp tnh.
+Cn c c cu phn phi ht xc tc ng u trong
khp tit din ca thit b nh sng phn phi hnh 5.2.

H.5.3-a phn phi ht rn
4/20/2012 184
+H thng TBP xc tc chuyn ng lp ri c th din t hnh
5.4.

TBTS
TBP
TBP TBTS
Kh tr
Kh tr
H.5.3-H thng TBP v TBTS xc tc lp ri
TBTS
TBP
TBP TBTS
Kh tr
Kh tr
H.5.3-H thng TBP v TBTS xc tc lp ri
4/20/2012
185
-Lp si:
*iu kin to lp si: Dng kh i t di ln
ngc vi chiu trng lc, khi vn tc dng kh
ln lc nng ca dng kh cn bng vi
trng lng ca ht rn, ht rn bt u l
lng, th tch ca lp n rng ra, ta c trng
thi nh cht lng.
Tr lc ca dng kh hu nh khng thay i
khi bt u to tng si nh hnh 5.4 .
4/20/2012 186

P
P
Vn tc kh,V
Lp si L. tnh
Dng kh
Lp ht
Xc tc rn
V
f
H.5.5-nh hng vn tc kh n trng thi ca lp
xc tc rn
4/20/2012
187
*Tnh cht ca lp si:
+Nh cht lng: Mt thong nm ngang, chy
nh cht lng, tun theo nh lut Acsimt ...
+Hin tng to bt:
.Do ht rn chuyn ng to s khc nhau v
mt ht trong lp v to thnh cc bt kh.
.Bt nh ni ln nhanh trong lp to nn nhng
phn t kh c TGL thp nht.
.Bt i ln ko theo ui l cc ht rn, khi ln
n mt lp bt v ra v cc ht rn li chm xung
trong lp huyn ph ko theo cc phn t kh b
hp ph trong xc tc, to nn nhng phn t c
TGL ln.
4/20/2012
188
Do to bt v chuyn ng hn lon ca
ht xc tc lp si c ch chuyn
ng ca dng gn vi m hnh KLT (
hnh 5.5 )
Hu qu TGL ca cht phn ng trong
lp xc tc khng ng u cn c
tnh n khi tin hnh cc phn ng c
c trng ni tip to sn phm ph nh
crcking xc tc, cc phn ng oxi ho
...
4/20/2012
189

H.5.6-Quan h gia bt v chuyn ng ca ht rn
4/20/2012
190
H s trao i nhit gia lp si v thnh ln:
Vai tr chnh ca qu trnh trao i nhit gia
lp si vi thnh l do s chuyn ng hn
lon ca cc ht rn mang nhit.
Vn tc trao i nhit c th tng hng chc
ln so vi trng hp ch c mi trng kh.
H s trao i nhit K ph thuc vo vn tc
dng ca kh nh hnh 5.6.
Nh tnh cht ny lp si ngy cng c s
dng cho cc qu trnh phn ng xc tc to
nhiu nhit.
4/20/2012
191

e
d
c
b
a
m
K
K
max
Vn tc kh,V
V
f
V
t
H.5.7-nh hng ca vn tc kh n h s trao
i nhit K ca lp si vi thnh.
ab-Lp tnh; bcd-Lp si; me-Khng c lp ht
4/20/2012
192
-Lp cun theo:
+Khi vn tc dng kh ln, cc ht rn cun
theo dng kh to thnh lp cun theo. Trng thi
ny c s dng rng ri vn chuyn cc vt
liu ri dng ht nn cn gi l lp vn chuyn.
+Ph thuc vo c trng ca ht, vn tc kh
c th gp 2 n 5 ln vn tc ht
Ch dng chy gn vi m hnh LT, thi
gian tip xc ca pha kh vi xc tc ng u v
tng i ngn.
Nh vy, lp cun theo c s dng thay th
cho lp si trong thit b crcking xc tc hin i
dng ng ng vi xc tc cha zolit c hot tnh
cao.
4/20/2012
193
VI-MT S LOI TBP TRONG CNG
NGHIP HO DU
VI.1-L ng:
+C b mt trao i nhit ln v nhit cao ( > 300
0
C )
bng cch t nhin liu lng hay kh.
+Thng gp trong cng nghip ho du vi cc chc nng
sau:
-TBP cho cc qu trnh pha kh, kh-rn, thu nhit nhit
cao ( n 1000
0
C ) nh nhit phn hydrocacbon c mt hi nc
( steam cracking ) sn xut etylen v olefin, chuyn ho kh t
nhin vi hi nc ( steam refoming ) sn xut hi dro v kh tng
hp (synthesis gases, thnh phn gm CO v H
2
), dehydroclo ho
dicloetan sn xut vinyl clorua.
-Thit b gia nhit hn hp nguyn liu cho cc h thng
chng luyn, cho cc h thng TBP nh crcking xc tc, refoming
xc tc, dehidro ho xc tc...
4/20/2012
194
+Cu to ca l ng gm 2 phn:
-Zn i lu: Nhit thp hn, c ch
trao i nhit l do tip xc cng bc gia kh
chy vi ng trc khi i ra ng khi.
-Zn bc x: Nhit cao ca bung la,
ni t nhin liu.C ch trao i nhit ch yu
l do bc x nhit ca bung la n thnh
ng.
+Nguyn liu i ngc chiu t cui zn i
lu n zn bc x, y t nhit cn thit
cho phn ng, sau c lm lnh nhanh
trnh phn hu sn phm v thu hi dng hi
nc p sut cao ( hnh 6.1 ).
4/20/2012 195

Nguyn
liu
Nc mm
Hi
nc
Nhin liu
Khng kh
Zn bc x
Zn i
lu
H.6.1.1-S l ng
4/20/2012
196
+L c cng sut nhit khc nhau
c bit l ng cho qu trnh cracking hi
sn xut etylen c cng sut ln v hin
i, vi yu cu a nhanh nhit nguyn
liu t zn i lu 450 - 500
0
C ln n
nhit phn ng ( 800 - 900
0
C ) nn ng
trong zn bc x c t vo gia
c bc x t hai pha ( hnh 6.2 ).
4/20/2012
197
+Mt s thng s ca l ng:
-S dn ng: 1 n 100.
-Chiu di 1 dn: 20 n 100 m.
-ng knh ng: 30 n 80 mm.
-Thi gian lu trong zn bc x: 1 - 2 s .

4/20/2012
198

H.6.1.2-L ng hin i sn xut etylen, bc x t hai pha.
4/20/2012
199
H.6.1.3-L
ng cho
qu trnh
Refoming
hi nc
trong s
cng ngh
sn xut
NH
3
t kh
t nhin.

4/20/2012
200
H.6.1.4-
L ng
trong
cng
ngh
sn xut
NH3 t
kh t
nhin.
4/20/2012
201
VI.2- H thng thit b crcking xc tc:
+c trng ca phn ng:
-Phn ng phc tp: song song, ni tip theo m hnh
sau ( hnh 6.3 )
VR/SLO
LCO Xng VGO/HCO
Cc Kh
H.6.2.1-S phn ng crcking
.VR(Vacuum Residue):Cn chn khng
.SLO(Slurry Oil):Du c
.VGO(Vacuum Gazoil):Gazoil chn khng
.HCO(Heavy cycle Oil):Du tun hon nng
.LCO(Light Cycle Oil):Du tun hon nh
.Kh:Hydrocacbon t C
1
n C
4
4/20/2012
202
Trong xng l sn phm chnh, kh
v cc l sn phm ph to thnh theo
phn ng ni tip chuyn ho sn
phm chnh, do vy m bo hiu
sut xng cao cn c TGL ng u v
ngn, chuyn ho X khng qu cao.
-Phn ng tin hnh nhit tng
i cao ( 450 - 500
0
C ) v thu nhit
ct mch C-C theo phn ng:
C
n
H
2n+2
C
q
H
2q+2
+ C
p
H
2p
- Q
( n = q + p )
4/20/2012
203
+c trng ca xc tc:
-Xc tc nhanh chng mt hot
tnh do cc to thnh che ph b mt,
xc tc c ti sinh bng cch t cc
b mt vi khng kh 650 - 720
0
C theo
phn ng to nhit:
C + O
2
(khng kh) CO
X
+ Q
Do vy cn tin hnh vi lp xc tc
chuyn ng lin tc ly ra i ti sinh
v b sung xc tc.
4/20/2012
204
-Xc tc crcking hin nay cha zolit c hot
tnh cao c s dng dng ht vi cu vi
ng knh c 0,05 n 0,1 mm.
Vi tnh nng ca xc tc nh vy cng vi c
trng ni tip ca phn ng yu cu TGL ng
u v ngn nn lp cun theo vi ng
ng c s dng cho qu trnh crcking
Th h c ca TBP crcking xc tc s
dng lp tnh lm vic theo chu k, lp ri v
lp si.
4/20/2012
205
Do xc tc nhanh mt hot tnh nn
lng xc tc tun hon ln v xc tc
sau ti sinh c nhit cao nn n c
lm cht mang nhit cho phn ng
crcking ( nh hnh 4.4 )
Qu trnh phn ng trong ng ng l
on nhit v t l xc tc/nguyn liu
quyt nh nhit phn ng v
chuyn ho X.
4/20/2012
206
T cc c trng ni trn h thng TBP crcking
xc tc hin i gm:
Thit b phn ng crcking dng ng ng vi lp xc
tc cun theo, lm vic theo ch on nhit
Nguyn liu c un nng s b tip xc vi xc
tc nng, ho hi v phn ng trong lp cun theo.
Do phn ng crcking tng th tch nn cho vn tc lp
cun theo n nh, ng knh ca ng phn ng c
m rng dn v pha cui ( theo chuyn ho X ), sau
xc tc c tch nhanh khi hn hp sn phm.
Vn tip xc gia xc tc nng vi nguyn liu du
cng nh phn ly xc tc khi hn hp kh phn ng
c nh hng ln n vic to cc v kh nn c nhiu
hng quan tm.
4/20/2012
207
Cn qu trnh ti sinh t cc to nhiu nhit
c thc hin trong lp si.
t cc trit hn trong lp si vi s khuy
trn mnh ca lp ht, nht l vi xu hng s
dng nguyn liu cho qu trnh crcking ngy
cng nng hn, hai tng si ni tip c s
dng vi tng u nhit thp hn (630 -
650
0
C) v tng sau nhit cao hn (n
720
0
C).
Vic chia thnh 2 tng ti sinh xc tc nh vy
ngoi vic t cc trit do TGL ca ht trong
thit b ng u cn gip cho xc tc trnh tip
xc vi hi nc nhit cao v thnh phn
cc tng ti sinh sau hu nh khng cn hidro.
4/20/2012 208
Hnh 6.4 trnh by mt dng h thng
RCC ca UOP.
Nguyn liu
v
pha phn tn
Pha phn tn
React ng
ng
Sn phm phn
ng
Khng kh th
cp
Khng kh th
cp
Khng kh s
cp
Thit b hon
nguyn xc tc 2
giai on
Kh x sau hon
nguyn
4/20/2012
209
H.6.2.3-H thng FCC ca ABB Lummus Global Inc.
(Hydrocarbon Processing, November 2000, trang 107).


4/20/2012
210
H.6.2.4-H thng FCC ca Kellogg Brown &
Root, Inc.
( nt , trang 108 )


4/20/2012
211
H.6.2.5-H thng FCC ca Shell Global Solutions
International B.V. ( nt , trang 108 )


4/20/2012
212
H.6.2.6-H thng FCC ca Stone & Webster Inc., a
Shaw Group Co/Institut Francais du Ptrole. ( nt ,
trang 110 )

4/20/2012
213
H.6.2.7-H thng FCC ca UOP LLC.
( nt , trang 110 )
4/20/2012
214
H.6.2.8-H thng RCC(Resid Catalytic cracking) ca Stone &
Webter Inc., a Shaw Group Co. and Institut Francais du Ptrole.
( nt , trang 139 )
4/20/2012
215
H.6.2.8-H thng MSCC ca UOP LLC . 1-TB ti sinh; 2-TBP
3-ng dn xc tc nng ti sinh; 4-B phn to lp ri; 5-B
phn nh hp ph sn phm khi b mt xc tc. ( nt , trang
94 ).
4/20/2012
216
VI.3-H thng TBP sn xut xng alkyl ho:
+Xng alkyl ho c sn xut bng
phn ng alkyl ho izobutan vi cc
olefin C3, C4 vi s c mt ca xc tc
l axit mnh, ngha l t cc nguyn liu
kh chuyn thnh sn phm lng, xng
alkylat c tr s octan cao, khng cha
benzen nn c ch hin nay.
+c trng ca phn ng v xc tc:
4/20/2012 217
-S phn ng c th trnh by nh sau:

C
4
H
8
+ H
+
C
4
H
9
+
i-C
4
H
10
n-C
4
H
10
i-C
4
H
9

+
C
4
H
8
i-C
8
H
17

+
i-C
4
H
10
i-C
8
H
18
C
4
H
8
i-C
12
H
26
i-C
16
H
34
Buten
izo-Butan
Buten
Tert-Butyl
cacbenium cation
izo-Octan
Buten
izo-Butan
izo-Octyl cacbenium
cation
H
+
H
+
4/20/2012
218
-T nguyn liu ban u buten v i-butan to
thnh xng vi thnh phn ch yu l i-octan
v hp cht ny trong iu kin phn ng vi
xc tc axit c th tip tc phn ng vi buten
thnh hydrocacbon nng C
12
, C
16
...l sn
phm ph v c nhit si cao trn 200
0
C,
nm ngoi thnh phn ca xng.
hn ch phn ng ph ny v qu trnh
polime ho olefin trong cng nghip dng t s
i-butan/buten ln (t 10 dn 20) v h thng
TBP gn vi LT , c thi gian lu ng
u.
4/20/2012
219
-Qu trnh alkyl ho tin hnh pha lng vi
xc tc l axit mnh H
2
SO
4
, HF v gn y
thm axit rn.
Vi xc tc H
2
SO
4
v HF l h d th lng-lng
cn to nh tng m bo b mt tip
xc pha, c bit vi H
2
SO
4
l axit c nht
v khi lng ring ln nn TBP cn c
khuy trn mnh. Do vy vi xc tc ny trong
cng nghip s dng h thng nhiu thit b
khuy ni tip.
Vi xc tc HF c nht v khi lng ring
thp, d to nh tng vi hydrocacbon nn
dng thit b ng ng c cu khuy tnh t
trong ng ng.
4/20/2012
220
-Phn ng alkyl ho to nhit, khong 90
Kj/mol, gii nhit phn ng bng cc gii php
sau:
+Vi xc tc H
2
SO
4
, nhit phn ng t
0 n 10
0
C, bng cch bay hi i-butan ( Tsi =
-11
0
C ) trc tip t hn hp phn ng nh
cng ngh ca Kellogg - Exxon ( hnh 6.5 ) hay
trao i nhit qua thnh vi alkylat nh cng
ngh ca Stratco ( hnh 6.6 ).
+Vi xc tc HF, nhit phn ng cao
hn ( 30 n 50
0
C ) c th lm lnh qua thnh
bng nc ( hnh 6.8 v 6.9 ).
4/20/2012
221
+H thng TBP:
-Cng ngh Kellogg-Exxon vi xc tc
H
2
SO
4
gm 5 thng c khuy ni tip t
trong thit b dng ng nm ngang di
p sut t 0,3 n 0,7 MPa ph thuc
vo thnh phn ca nguyn liu, hi i-
butan to thnh do gii nhit phn ng t
5 thng c tp trung v i ra nh
thit b dng ng n h thng nn v
lm lnh ho lng.
4/20/2012
222
H.6.3.1-H thng TBP sn xut xng alkyl
ho ca Kellog-Exxon
4/20/2012
223
H.6.3.2-H thng TBP alkyl ho nm
ngang, lm lnh qua thnh ca Stratco.
4/20/2012
224
TBP nm ngang ng thi tm thit b lch v pha di
trnh lng ng H2SO4, to nh tt hn. Hnh 6.7 trnh by thit
b ny
4/20/2012
225
H.6.3.4-TBP alkyl ho vi xc tc HF ca
Phillips.
4/20/2012
226
H.6.3.5- TBP alkyl ho vi xc tc HF ca
UOP.
4/20/2012
227
-Vi xc tc rn-cng ngh mi ang nghin
cu pht trin, c th a ra TBP ca cng
ngh Akylene ca UOP hnh 6.10.
* Xc tc mau mt hot tnh do polime bm
vo b mt xc tc nn s dng lp xc tc
chuyn ng lin tc thay th v ti sinh xc
tc: dng lp cun theo TGL ng u theo
yu cu ca phn ng.
* Ti sinh xc tc bng cch dng i-butan
bo ho hidro kh ni i gim kh nng
hp ph ca cc hp cht nng khng no ln
b mt xc tc v ra sch b mt.
4/20/2012
228
H.6.3.6-TBP alkyl ho vi xc tc rn theo cng ngh Alkylene
ca UOP.
4/20/2012
229
VI.4-H thng TBP sn xut MTBE(Metyl Tert-Butyl
Ether)
+Qu trnh tin hnh pha lng, nhit 50 - 100
0
C, p sut
1,5 MPa
+T s MeOH/i-B
=
= 1,1 gim phn ng polime ho olefin.
+Xc tc l axit, trong cng nghip dng axit rn l nha cationit
c nhm axit mnh -SO3H, dng ht hnh cu ng knh c 0,8
- 1mm.
+H thng TBP:
+Ph thuc vo nguyn liu i-B
=
:
-Rafinat-1(phn on C4 ca crcking hi sau khi tch
Butadien) cha 45 - 50% i-Buten.
-Phn on C4 crcking xc tc cha 15 - 20% i-Buten.
-Hn hp sn phm dehidro ho i-Butan cha 40 - 50% i-
Buten.
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230
Nhng nguyn liu c hm lng i-B= thp nh trn
thng dng TBP on nhit, cn nguyn liu cha i-
B= cao hn nh sn phm dehydrat ho TBA, i khi dng
TBP ng chm lm lnh bng nc
- phn ng tin hnh n cng, chuyn ho ht i-
B= thng dng cng ngh CD(Catalytic Distillation)
ca hng CD Tech hay cng ngh RWD(Reaction with
Distillation) ca UOP.
y l cng ngh phn ng c nhiu u im tin hnh
cc qu trnh thun nghch to nhit pha lng c nhit
phn ng xp x nhit si ca hn hp ( t chuyn
ho cao, tn dng nhit phn ng tch v tinh ch sn
phm phn ng, gim s thit b trong cng ngh).
4/20/2012
231
-H thng TBP c trnh by hnh 6.4.

E-6
Hn hp C4 i thu
hi metanol d
Hn hp
i-B
=
+MeOH
1 2
1-TBP on nhit c
TN trung gian
2- Thp CD
MTBE
4/20/2012
232
VI.5-H thng TBP Refoming xc tc:
Qu trnh Re foming xc tc tin hnh
ng thi cc phn ng ng phn
ho, ng vng, thm ho H/C trn
xc tc lng chc: hidro ho -dehydro
ho v xc tc axit-base.
Ngoi mc ch tng tr s octan cho
xng chng trc tip n nay cng ngh
Re foming xc tc cn sn xut H/C
thm cho Tng hp ho du.
4/20/2012
233
-c trng ca phn ng v xc tc:
+Thu nhit, nhit phn ng 400 -
500
0
C, thng tin hnh lp on
nhit xen k vi l ng gia nhit.
+B mt xc tc cng b cc to
thnh che ph lm gim hot tnh, nhng
chm hn nhiu so vi xc tc crcking
4/20/2012
234
Cng ngh c tin hnh vi lp xc tc tnh di p sut hidro
khong 2 n 3 MPa hn ch phn ng to cc, tui th ca
xc tc c th n hng nm ( Hnh 6.5.1 )
4/20/2012
235
Cng ngh mi tin hnh vi xc tc lp ri, lin tc ti sinh xc
tc, p sut thp khong 0,5 MPa, t phn ng ph hn v
hot tnh lp xc tc cao v n nh
H.6.5.2-H
thng TBP
refoming xc
tc lp ri
ca IFP.
1, 2, 3, 4-
TBP xc
tc lp ri ;
5- h thng
ti sinh xc
tc
4/20/2012
236
H.6.5.3-H thng TBP refoming xc tc lp ri ca UOP LLC.
4/20/2012
237
Dng kh phn
ng i qua lp
xc tc theo
hng xuyn tm
v sau khi i qua
mi lp xc tc
c un nng
tr li n nhit
phn ng l
ng 5
Cc lp xc tc 2,
3, 4 chng ln
nhau, nh vy xc
tc ri t trn
xung .
ng i ca kh
phn ng v xc
tc trong thit b
nh hnh 6.5.3
CCR Stacked Platforming Reactors
3 Reactor System
Catalyst In
Reactor No. 1 Feed
Catalyst Transfer Pipes
Scallops or Outer Screen
Reactor No. 1
Catalyst Reduction Zone
Reactor No. 2 Feed
Reactor No. 1 Effluent
Reactor No. 2
Reactor No. 3
Reactor No. 3 Feed
Reactor No. 2 Effluent
Catalyst Out Catalyst Out
Reactor No. 3 Effluent
UOP 3046-108
4/20/2012
238
VI.6-H thng TBP sn xut phnol:
-Phng php ch yu sn xut phnol
hin nay l i t nguyn liu cumen (
trn 90%).
-c trng ca phn ng: C hai giai
on phn ng: oxi ho cumen thnh
hidroperoxit (H/P) v chuyn ho H/P
thnh phnol c mt xc tc axit c
tin hnh ring bit nn ta xem xt tng
giai on.

4/20/2012 239
+S phn ng chnh v ph ca giai on oxi ho:


C
6
H
5
CH(CH
3
)
2
C
6
H
5
C(CH
3
)
2
OO*
C
6
H
5
C(CH
3
)
2
OOH
C
6
H
5
C*(CH
3
)
2
O
2
C
6
H
5
COCH
3
+ CH
3
O*
+R*
C
6
H
5
C(CH
3
)
2
OH + C
6
H
5
C(CH
3
)
2
O*
+RH
C
6
H
5
C(CH
3
)
2
OH + R*
CH
3
OH
HCOOH
Axetophenon
Dimetyl phenyl cacbinol
4/20/2012
240
Nh vy, phn ng ph l chuyn ho tip
cumen H/P hay gc cumen H/P thnh dimetyl
phenyl cacbinol, axetophenon v mt s hp
cht khc.
hn ch phn ng ph mt mt duy tr
chuyn ho thp (X = 20 - 25 %) gim
nng H/P v gc H/P trong hn hp phn
ng v gim dn nhit phn ng theo
mc tch t H/P trong sn phm ( ni cch
khc, theo mc tng ca X ), mt khc
TBP cn c TGL ca pha lng ng u.
4/20/2012
241
Qu trnh oxi ho cumen l d th kh-lng xy
ra trong phm vi ng hc 100 - 130
0
C ( TGL
ca cumen khong t 2-3 h t X nh trn )
c tin hnh trong TBP loi si bt l loi
thit b c m hnh dng chy gn vi KLT (
bt kh i ln ko theo cht lng v to s
khuy trn mnh trong thit b ).
phn b TGL ng u ca cht phn
ng cn dng 3 - 5 thp si bt ni tip nh
hnh 6.6.1.
S dng nhiu thit b ni tip trong h thng
cn gip cho vic ch nhit trong tng
thit b gim dn khi X tng nh trn.
4/20/2012 242
H.6.6.1-H thng TBP oxi ho cumen thnh cumen
H/P.

Cumen
Khng kh
Sn phm
Kh thi
4/20/2012
243
Phn ng phn hu cumen H/P thnh phnol v axeton
di tc dng xc tc axit nhit 50 - 60
0
C xy ra vi
tc ln, to nhiu nhit ( AH = -253 Kj/mol ), cc sn
phm ph ch yu l do chuyn ho dimetyl phenyl
cacbinol t qu trnh oxi ho mang sang.
Do vy, hp l l tin hnh qu trnh TBP loi thng
c khuy, gii nhit bng cch bay hi axeton l hp
cht sn phm c nhit si xp x nhit phn ng ( T
si ca axeton bng 56,5
0
C ).
Ngoi ra, mt yu cu ng lu na ca giai on ny l
chuyn ho X cao, ngha l H/P c phn hu trit
, trnh ri vo h thng chng ct pha sau, nn tip
theo TBP thng c khuy cn c thit b hon thnh
theo m hnh LT
4/20/2012 244
H.6.6.2-H thng TBP phn hu H/P cumen thnh phnol v axton

Hi axton
Axton lng Cumen H/P
H
2
SO
4
4/20/2012 245
H.6.6.3-H TBP phn hu H/P theo m hnh dng tun hon.

H
2
SO
4
Cumen H/P
4/20/2012
246
7/H thng TBP tng hp 1,2 dicloetan (1,2 DCE):
Phn ng:
CH
2
=CH
2
+ Cl
2
CH
2
Cl - CH
2
Cl
Kh Kh Lng( Ts = 85
0
C )
AH = - 220 Kj/mol

Thc t l phn ng kh-lng: sc etylen v clo
vo 1,2DCE lng ho tan FeCl
3
0,5% vi vai tr
xc tc. Phn ng xy ra trong pha lng vi
vn tc cao ngay nhit thng.

4/20/2012
247
Nh vy, qu trnh c c trng d th
kh-lng, to nhiu nhit, tin hnh
nhit thp c nhit si ca pha
lng.
nhit hi cao ( 80 - 100
0
C ) phn
ng ph clo ho tip thnh tricloetan c
c tng cng, v vy cng ngh c
tin hnh clo ho nhit thp v gii
nhit phn ng bng nc.

4/20/2012
248
n nay phn ng ph theo c ch chui gc
b hn ch bng cch dng xc tc FeCl3 v
clo c cha oxi, nn c th tin hnh nhit
cao hn v s dng nhit phn ng (
kh ln) tch sn phm dng hi khng
b ln vi xc tc.
+ Cng ngh tin b nht dng TBP
dng CD, kt hp vi thp chng, tn dng
nhit phn ng tinh ch DCE khng ch t
thit b clo ho m t cc b phn khc ca h
thng lin hp, v d t cng on oxiclo ho
hay cng on nhit phn DCE v tch VC.
4/20/2012
249
H.6.7.H TBP tng hp 1, 2 DCE nhit cao, tn dng
nhit phn ng tinh ch sn phm.
4/20/2012
250
8/TBP sn xut Fomaldehit:
-Fomaldehit c sn xut t
mtanol bng qu trnh oxi-dehidro ho
trn xc tc bc v oxi ho trn xc tc
oxit Fe-Mo.
-y l cc qu trnh pha hi nn cn
trnh to hn hp n metanol - khng kh
c thnh phn t 6 n 40% th tch
metanol.
4/20/2012
251
a/Cng ngh xc tc bc:
Nhit phn ng: 650 - 720
0
C.
Lm vic trn gii hn n, do thiu oxi cho phn ng oxi
ho (1) nn c thm phn ng chnh dhidro ho mtanol
CH
3
OH + 1/2O
2
CH
2
O + H
2
O ( 1 ) AH = - 156 Kj/mol
CH
3
OH CH
2
O + H
2
( 2 ) AH = + 85 Kj/mol
Tng nhit phn ng ca qu trnh l to nhit, qu trnh
nm phm vi khuch tn ngoi, on nhit v t
nhit, iu chnh nhit phn ng bng cch pha thm
hi nc vo hn hp phn ng.
4/20/2012 252
+TBP nh hnh 4.10

C
Ag
C
As
T
s
T
g
Dng kh
Lp
bin
C
As
<< C
Ag
T
s
>> T
g
B mt xc tc
Mng phng n
un nng in
Mi phn ng
Xc tc Ag
Lm lnh
ng chm
Hn hp mtanol-
khng kh
a b
H.4.10- c trng t nhit ca qu trnh phn ng xc tc phm vi khuch
tn ngoi. a-M hnh khuch tn ngoi. b-TBP oxyhidro ho mtanol.
4/20/2012
253
b/Cng ngh xc tc oxit Fe-Mo:
Nhit phn ng: 290 - 310
0
C.
Lm vic di gii hn n ( hn hp
khong 6% th tch mtanol ), d oxi nn
ch c phn ng oxi ho ( 1 ) to nhiu
nhit l phn ng chnh.
Xc tc lp tnh, TBP dng ng chm (
hnh 4.22 ), ng knh ng tng i
nh, c 20 - 25 mm.
4/20/2012 254
Kt qu ti u ho TBP ca vin xc tc Nvxibic cho thy rng
hiu sut phn ng v kinh t hn nu kt hp thit b ng chm vi
lp xc tc on nhit nh hnh 6.8.

T
0
260-
270
0
C
300
0
C
T,
0
C
Lp xc tc
on nhit
1
2
4/20/2012
255
Kt qu nghin cu cho thy, trn xc tc ny
ngoi phn ng chnh ( 1 ) vi nng lng hot
ho E
1
= 40,67 Kj/mol cn c phn ng ph oxi
ho fomaldehit thnh CO v H
2
O vi nng
lng hot ho thp hn:
CH
2
O + 1/2O
2
CO + H
2
O (3)
AH=-215 Kj/mol E3 = 28,22 Kj/mol
Do vy, khi nhit xung thp tc
tng i ca phn ng ph s tng ln, hin
tng ny b hn ch bng lp xc tc on
nhit cui TBP.
4/20/2012
256
Qua mt s loi TBP ca cc cng ngh ho du thy rng,
TBP c s dng trong cng nghip ca mt s hng c
th khc nhau do nhng gii php k thut m h nghin cu
v p dng
Nhng v nguyn l l xut pht t nhng c im v
ng hc v nhit ng ca phn ng, t nhng c
trng v hot tnh, nhit lm vic v nhy ca cc
tnh nng ca xc tc vo nhit , thi gian sng ca
xc tc.
Nhng ci tin, hon thin v TBP l kt qu ca nhng
thnh tu trong nhiu lnh vc khoa hc v cng ngh, trong
c xc tc, ng hc, ho hc v l thuyt v TBP, m
hnh ho, ti u ho .