THIT B PHN NG trong cng nghip ho du.

Ngi son : PGS,TS Trn Cng Khanh. Trng i hc Bch khoa H Ni.

04/27/10 1

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: Ri = dNi / Vdt . (1.1) Trong : Ni-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 Ci = Ni / V, do pt (1.1) thnh:

Ri = dCi / dt .

(1.2)

04/27/10 2

- chuyn ho ca cht i:

Xi = (C0 - C1) / C0 = 1 - C1/C0 .

(1.3)

Trong : C0- nng cht phn ng i i vo ( hay nng ban u) C1- nng cht phn ng i i ra ( hay nng cui ) - chn lc i vi sn phm i: Trong : Ci -nng ca sn phm i trong hn hp phn ng . ng Cj -tng nng cc sn phm trong hn hp phn

Si = Ci / Cj

j = 1, n

(1.4)

04/27/10 3

V TR H THNG TBP TRONG S CNG NGH

Trong s cng ngh TBP nm v tr nh sau Ng.liu 1 :

Ng.liu 2 H thng chun b hn hp phn ng THIT B PHN NG H thng tch v tinh ch sn phm Sn phm

Nguyn liu cha chuyn ho 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 ".
04/27/10 4

I.2-c im :

- a dng
iu kin phn ng rt khc nhau:
*Nhit phn ng c th t nhit phng n 800-9000C, c bit c th n 1300-15000C. 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,

Do

mt phng.

04/27/10 5

 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
04/27/10 6

C IM TBP

-Phc tp

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 ). 04/27/10
Do
7

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.

04/27/10 8

H.1.2-M hnh TBP lm vic gin on v thay i nng theo thi gian
Nng cht phn ng CA0 Cht phn ng vo gin on

CAt

0 Sn phm tho gin on

Th i gian t

04/27/10

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 .
04/27/10 10

*Nng A v B thay i theo thi gian phn ng nh hnh 1.3

Nng Cht phn ng Cht B vo Lin tc Cht A vo Gin on CA0 S mol NB vo

C
C Bt

At

CB0 H.1.3-M hnh TBP lm vic na gin on v thay i nng cht phn ng trong thit b .
04/27/10

Thi gian t

11

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.

04/27/10 12

 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:

tTB = VR / FV
Trong : tTB -Thi gian lu trung bnh. VR -Th tch TBP. FV -Lu lng ca dng . [ h ]. [ m3 ]. [m3 / h ].

04/27/10 13

2/Theo ch dng chy :

CA0 L
Nng cht phn ng

CAL

*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 CA0 n u ra l CAL nh hnh 1.4

14

CA0 CA0

CAL CAL

L L

Chiu di ng phn ng

H.1.4-M hnh LT v thay i nng cht phn ng trong thit b.

04/27/10

*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
04/27/10

Cht A vo

Nng cht phn ng Cht A ra

CA0

CA1

CA0

CA1 CA1

To phn ng

H.1.5-M hnh KLT v thay i nng trong thit b

15

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 VR ln hn nhiu so vi m hnh y l tng, c bit khi X yu cu cao.

04/27/10 16

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.
CA0 C A1 CA2 C A3 CA (n-1) CAn

1 C A0 CA1

C A2 CA3 CA(n-1) CAn

To phn ng H.1.6-M hnh h thng n thit b KLT ni tip v thay i nng cht phn ng theo tng thit b

04/27/10

17

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
04/27/10 18

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

04/27/10 19

4/Theo ch nhit:

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 .
04/27/10 20

*on

 *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 .
04/27/10 21

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

04/27/10 22

Nng CA0

CB2 C B1 CA1

A
B

CA2
C

CC1 t1 t2

CC2 Thi gian phn ng

H.2.1-S thay i nng cc cht ca phn ng ni tip A B C theo thi gian phn ng

04/27/10

23

 Gi

s ti thi im t1 nng cc cht A, B, C l CA1, CB1 v CC1 ta c: chuyn ho: X1=1- CA1/CA0. chn lc: S1=CB1/ ( CB1 + CC1 ).

-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.
04/27/10 24

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:

E(t).dt = 1 0

( 2.1 )

04/27/10

E (t ).t.dt t =
0

TB

( 2.2)
25

 -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 Khi t = th
t

F(t) = 0 F(t) = 1
'

( 2.3 ) (2.4 )
04/27/10 26

F(t) =

E (t ).dt
' 0

hay E(t) =dF(t)/dt

II.2-Gi tr ca hm phn b TGL trong cc m hnh l tng:

F(t) -M hnh LT - T nh ngha ca m hnh ny v 1 nh ngha ca hm phn b F(t) ta c gi tr ca hm phn b TGL nh sau: Khi 0 < t < tTB th F(t) 0 =0 tTB t Khi t > tTB th F(t) H.2.2-S ph thuc ca F(t) m hnh LT =1 vo thi gian t ( 2.5 ) Ta c ng biu din F(t) theo t nh hnh 2.2 04/27/10

27

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.
-M
04/27/10 28

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 .

04/27/10 29

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)
Theo
04/27/10 30

[ 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) = FV .dt / VR = dt / tTB Thay vo phng trnh ( 2.6 ): 1 - F(t) - dF(t) = [ 1 - F(t) ] . [ 1 - dt/ tTB ] - dF(t) = - dt / tTB + F(t) . dt/ tTB = - dt/ tTB . [ 1 - F(t) ]

dF(t) / [ 1 - F(t) ] = dt/ tTB

( 2.7 )

04/27/10 31

Gii phng trnh vi phn ( 2.7 ):

Gii phng trnh vi phn (2.7 ), ta c: ln [ 1 - F(t) ] = - t/ tTB + C. T iu kin ban u t=0 th F(t)=0 c C = 0

) ng biu din hm F(t) ca m hnh KLT theo phng trnh ( 2.8 ) c trnh by hnh 2.3

1 - F(t) do F(t)

= e-t/tTB = 1 - e-t/tTB

( 2.8

04/27/10 32

F(t)

1,0 1 - F(t)

0,632 0,5

F(t) 0,0

tTB

H.2.3-S ph thuc ca F(t) m hnh KLT vo thi gian t

04/27/10 33

 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.
04/27/10 34

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/tTB [1+(nt/tTB)+(nt/tTB)2/2/ +...+ (nt/tTB)n-1/(n-1)/ ] .

( 2.19)
04/27/10 35

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 =t/tTB).

1,0 F(t)

n=

n=1 3 5 10 20 1 =t/tTB 2

0,0

H.2.5-Hm F(t) ph thuc vo s thit b n trong h thng KLT lin tc, ni tip.
04/27/10 36

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/tTB=1 ). 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 tTB.
04/27/10 37

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.

04/27/10 38

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.
*Khi
04/27/10 39

-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.

04/27/10 40

* 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 Dl Hng ng knh ng vi h s trn ngang Dr Dl v Dr c xc nh bng chun s Peclet (k hiu Pe ) nh sau: Pel = v . L / Dl v Per = v . D / Dr ( 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. 04/27/10
41

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 vr (hnh 2.6)

04/27/10 42

vr r0 r

H.2.6-M hnh gradien vn tc dng theo hng ng knh ca ng rng, chy dng

04/27/10

43

-Tnh F(t) ca ng rng, chy dng

vr = ( 2FV/.r02 )[ 1 - ( r / r0 )2 ] (2.21) Trong r0 l bn knh ca ng. Do , TGL ca phn ca dng cch trc ng mt khong r l

tr = L/vr = .r02 (L / 2FV).[ 1 - (r/r0)2 ] = VR/2FV[ 1 - (r/r0)2]

tr = ( tTB / 2 ) [ 1 - (r/r0)2 ] ( 2.22 ) Thay r = 0 c TGL ca dng ti trc ng l t tm(r=0) = tTB / 2 Thay r = r0 c TGL ca dng ti thnh ng l t thnh(r=r0) =
04/27/10 44

-Tnh F(t) ca ng rng , chy dng

C th xem phn ca dng chy nm cch tm l r+dr (hnh vnh khn 2 r.dr ) c vn tc nh nhau l vr, t nh ngha ca hm F(t) ta c: dF(r) = vr . 2 r.dr / FV ( 2.23) vr t phng trnh (2.21) v rt gn,c : dF(r) = 4 [ 1 - (r/r0)2 ] r.dr / r0 chuyn dF(r) thnh dF(t) phi dng phng trnh (2.22) .
04/27/10 45

Thay

(2.22) ta c [ 1 - (r/r0)2 ] =tTB / 2t , ly vi phn pt (2.22) ta rt ra: rdr = r02 . tTB.dt / 4 t2 Thay vo pt (2.23) ,c: dF(t) = tTB2.dt / 2 . t3 ( 2.24)

T xc nh F(t) cho trng hp ng rng chy dng nh sau:

F(t) = tTB2/2. dt/t3 F(t)= 1 - (tTB/t)2/4

t = tTB/2, . ( 2.25 )
04/27/10 46

F(t) 1,0 0,75 0,5 0,0 tTB/2 t tTB H.2.7-ng biu din ca F(t) trong ng rng, chy dng
04/27/10 47

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 FV rt nh,c th b qua,ta c ch dng chy ta m hnh LT .

04/27/10 48

Lp bin FV

H.2.8-M hnh phn b vn tc dng chy theo tit din ng ch chy ri

04/27/10

49

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.

04/27/10 50

dht

H.2.9-M hnh lch ngang khi chy qua lp ht tnh

04/27/10

51

m hnh ny khi dng chy qua mt lp ht b lch ngang dht/2 v qua n lp ht s lch ngang ndht/2. V nh vy, lch ngang lm cho vn tc dng v TGL ng u hn. *Nh vy, khi Dng/dht 10 v L lp ht /dht 10 ch dng chy c coi nh LT.
Theo
04/27/10 52

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 Dl v chun s Peclet vi k hiu Pel:

Pel = v . L / Dl
L-l chiu di ca ng phn ng .
04/27/10 53

 *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 VR = S . l: A vo = A ra + A phn ng + A tch t. (2.26) l
H.2.10-M hnh ng phn ng c khuch tn dc .
S A vo do dng LT V S.CAl A vo do khuch tn -Dl .S.(CA/l)l L l A ra do dng LT A ra do dng LT A ra do dng LT v S.v.CA(l+l) . S . CA(l+l) A(l+l) A ra do khuch tn A ra do khu ch tn -Dl.S.(CA/l)l+l l l+l

04/27/10

54

A tch t = VR . 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(CA(l+l)-CAl)+(-Dl.S)[(CA/l)l+l -(CA/l)l]+S.l(-CA/ t)=0 Chia cho S.l , c: v.(C A(l+l) - CAl)/l - Dl[(CA/l) l+l - (CA/l)l ]/l +(-CA/ t) = 0 Thay (-CA/t) = RA = k.CAn v cho l0 ,c: v ( CA/ l) - Dl ( 2CA/ l2 ) + k .CAn = 0 ( 2.27 ) 04/27/10 y l m hnh ton mt th nguyn miu t qu 55 trnh trong ng phn ng ch nh hng bi

v (CA/l) - Dl (2CA/l2 ) + k .CAn

= 0

( 2.27 )

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

z = l/L , do z/l = 1/L CA/l = (CA/z) . z/l = (1/L) . CA/z 2CA/l2 = [1/L. (CA/z) / z ]. z/l = (1/L2). 2CA/z2 T pt (2.27) thnh: (v/L).CA/z - (Dl/L2 ). 2CA/z2 + kCAn = 0. ( 2 . 28 ) Chia hai v pt (2.28) cho -L/v = -tTB :

- t i lng chiu di l z = l/L, ta c:

(Dl/L.v). 2CA/ z2 - CA/ z - k.tTB.CAn = 0.(2.29)

04/27/10 56

(D /L.v) . C / z - C / z - k . t . C = 0. ( 2 . 29 ) * Gii pt (2.29) vi iu kin b :- ti u vo z = 0 , CA = CA0 - ti u ra z = 1 , CA = CAL

c CAL v t tnh chuyn ho XA, .

TB l

XA ph thuc vo 3 thng s k , t
l

v Pe =

L.v/D . Vi phn ng bc 1 (n = 1) gii c :

AL A0 A

1+ 4kt TB /Pe l C /C = 1 - X
l
04/27/10

l
57

= 4a.exp(Pe /2)/[(1+a) exp(a.Pe /2) - (1-

H.2.11-Biu din VRthc/VRLT ph thuc vo Pel, k.tTB v X caphn ng bc 1.

04/27/10 58

H.2.12-Biu din VRthc/VRLT vo Pel, ca phn ng bc 2

k.tTB.C0 v X

04/27/10 59

 Thc

nghim cho thy rng chun s khuch tn dc Pel ch yu ph thuc vo chun s Re = v.dng./. Hnh sau l kt qu thc nghim ca mt s tc giv s ph thuc ca Dl/v.dng = (Dl/v.L).L/dng vo Re
T

c th rt ra tng quan sau: Dl/v.dng = 3.107/(Re)2,1+1,35/ (Re)0,125.

04/27/10 60

H.2.13-S liu thc nghim s ph thuc Dl/v.dng vo Re ca mt s tc gi.

04/27/10 61

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.

04/27/10 62

a/Tn hiu vo dng bc cp, xc nh hm F(t): -Tn hiu cho ch th vo dng bc cp: = 0 khi t 0 . C ch th(z=0) { ( 2 . 31 ) = C0 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 FV.C0.

04/27/10 63

Xc lp hm F(t): Gi s nng ch th ra thi im t l Ct, phn ca ch th ra ti thi im ny l FV.Ct. T nh ngha ca hm F(t) ta c: F(t) = FV.Ct / FV.C0 = Ct / C0. ( 2 . 32 )
Nng Ch th C0 Tn hiu vo
r h t a

Ct
g n N

ch

0 t H.2.11-Tn hiu vo dng bc cp v nng ch th i ra theo th i gian t

04/27/10 64

b/ Tn hiu vo dng xung vung, xc nh hm E(t):

-Tn hiu cho ch th vo dng xung:

Nng Ch th C0 T n hiu vo

t0

= 0 khi t 0 . Cch th (z=0)=C0 khi 0<t< t0 . = 0 khi t>t0 . Miu t: Ti t = 0 bt u cho ch th i vo thit b trong thi gian ngn t0 ( yu cu t0 << tTB ) v sau dng cho ch th.

Nng ch th ra Ct

0 0 tTB t H.2.12-Tn hiu vo dng xung v nng ch th ra theo thi gian t

04/27/10 65

Xc lp hm E(t):
Gi

s ton b lng ch th cho vo thit b dng xung vung l q0, ti thi im t nng ch th dng ra l Ct, trong khonh khc dt th tch dng ra l FV.dt v lng ch th i ra l Ct.FV.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 q0.E(t).dt, ta c:
04/27/10 66

q0 . E(t) . dt = FV . Ct . dt. ( 2.34 ) T : E(t) = FV . Ct / q0

 ta

xc nh hm E(t) cn bit q0, lm vic ny ly tch phn phng trnh (2.34):

.dt q .E(t).dt = F .C,theo (2.1):

0 V t 0 0

E(t).dt =1
0

Ta c: q0=
T

FV . C t .dt = FV .
0
0

q 0.E(t) .d t = FV.C t .d t 0 0

0C .t
t

: = Ct /

C .dt = C /
t t 0

q .E(t).dt= F
0 0

C t V . t .d

E(t)
04/27/10

Ct. t (2 . 36)

67

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 . t = 5(3+5+5+4+2+1) = 100. -Vy E(t) = Ct / 100, kt qu nh bng sau: t , ph : 0 5 10 15 20 25 30 35 E(t).102: 0 3 5 5 4 2 1 0

04/27/10 68

-ng biu din nng ch th ra theo t nh hnh 2.13.

Nng ch th g/l 5 4 3 2 1 0 5 10 15 20 25 30 35 t,ph

H.2.13-ng biu din nng ch th ra theo thi gian .

-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.
04/27/10 69

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 - Cra/C0 ) l nng trung bnh ca cc phn t ca dng vi TGL trong thit b khc nhau . Do c th vit:
= Cng.t.E(t).dt = Cng.t.E(t). t t = 0, (2.37)
04/27/10 70

Cra

 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:

C
0

nguyento

.E (t ).t

=1-Cra/C0=1-( /C0) 38 ) .
71

(2.
04/27/10

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: -dCA / dt = kC, gii vi iu kin khi t = 0 kt = C th CA = CA0,, c C A nguyn .E(t). . e-kt , thay A0 e t vo pt(2.37): 0 CA ra = CA0 . t . ( 2 . 39 )
Bi

72

04/27/10

Lp bng tnh phng trnh (2.39): t , ph E(t) k.t e-kt e-kt . E(t) . t 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 CAra - C A0 = e-kt . E(t) . t = 0,047 XA = 1 - CAra/CA0 = 1 - 0,047 = 0,953. 04/27/10 73

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). tTB =

E (t ).t.dt = E (t ).t.t
0 0

=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 tTB. Vi phn ng bc 1 t pt dCA/dt=kCA, c: CA / CA0 = e-ktTB = e-0,3.15 = 0,01. XA = 1 - CA/CA0 = 1 - 0,01 = 0,99 .

04/27/10

74

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.
-

04/27/10 75

III.1- Thit b lm vic gin on:

- Ch dng cho pha lng, qui m sn xut nh. - Tnh th tch thit b VR: VR = Vngy m.(1 + z). tm / 24 . ( 3 . 1) -Nu th tch thit b VR chn, ta tnh s thit b n: n = Vngy m.(1 + z). tm / 24.VR. . (3.2) Trong : Vngy 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.
04/27/10 76

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. tm- 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.
04/27/10 77

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 ): Ci-1.F V(i-1) = Ci.FVi + Ri.VRi + dCi.VRi/dt. (3.3)

04/27/10 78

Thit b lm vic lin tc

CA(i-1) FV(i-1) Ti-1

CAi FVi Ti CAi TBP th i

VRi

R i=ki.f(CAi)

ki=k0.e

-E/RTi

H.3.1-Cc thng s ca thit b th i loi thng c khuy

04/27/10 79

Ci-1.F V(i-1) = Ci.FVi + Ri.VRi + dCi.VRi/dt. (3.3) Trong : Ci-1 : Nng cht phn ng i vo thit b th i. Ci : Nng cht phn ng trong thit b i v l nng i ra. F V(i-1) v FVi : Lu lng ca dng vo v ra. VRn : Th tch thit b th i. dCi.VRi/dt : Lng cht phn ng tch t trong thit b i. Ri = ki . f(Ci) : Vn tc phn ng thit b th i.
04/27/10 80

 trng thi dng khng c tch t, ta c: C i-1.F V(i-1) = Ci.F Vi + Ri.VRi hay C i-1 = C i . F Vi/F V(i-1) + Ri . VRi /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 = FV, c:

4)

C i-1 = Ci + tTBi . Ri

(3.

Trong tTBi l TGL trung bnh thit b th i, tTBi = VRi/FV. 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 VRi.

04/27/10 81

*Vi phn ng chuyn ho cht A sn phm: -Bc 0 : Ri = ki ; pt (3.4) thnh: C i-1 = Ci + ki . tTBi . ( 3 . 4 )' -Bc1 : Ri = ki.Ci ; pt (3.4) thnh: C i-1 = Ci + ki . tTBi . Ci hay C i-1/Ci = 1+ ki . tTBi . ( 3 . 4 )'' -Bc2 : Ri = ki.Ci2; pt (3.4) thnh: C i-1 = Ci + ki . tTBi.Ci2 ( 3 . 4 )'''

04/27/10 82

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: C0/C1 = 1 + 0,307 . 15

X = 1 - C1/C0 = 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.
04/27/10 83

-Lp phng trnh cn bng cht cho h thng n thit b khuy ni tip:

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: VRi VRj tTBi tTBj
Dng V

nhit cc thit b khng bng nhau Ti Tj ki kj .

04/27/10 84

 Phn

ng bc 0: i=1 C0 - C1 = k1 . tTB1 i=2 C1 - C2 = k2 . tTB2 i=3 C2 - C3 = k3 . t TB3 ... ...... i=n C n-1 - Cn = kn . tTBn . Cng cc phng trnh theo tng v c: C0 - Cn = ki.tTBi i = 1, n Xn0= ki.tTBi / C0 (3.5)

04/27/10 85

Phn ng bc 1:

i=1 C0 / C1 = 1 + k1 . tTB1 i=2 C1 / C2 = 1 + k2 . tTB2 i=3 C2 / C3 = 1 + k3 . tTB3 ... ... i=n C n-1 / Cn = 1 + kn . tTBn . Nhn cc phng trnh theo tng v, c: n C0 / Cn =
i =1 T chuyn ho thit b n i vi phn ng bc 1 l:

(1 + k .t

i TBi

)
n

Xn1= 1 - Cn / C0 = 1 - 1 /

(1 + k .t
. (3.6)

i TBi

)
86

i=1

04/27/10

Phn ng bc 2:
Gii

pt (3.4)''' c: C i = (- 1 1 + 4k i t i C i 1 ) / 2ki.tTBi .

i = 1 C1= (- 1 i = 2 C2= (- 1 vo ta c: C2 = [-1

1 + 4k1t1C 0 2k .t )/
1 + 4k 2 t 2 C1

1 TB1

) / 2k2.tTB2

Thay C1

1 + 4 k 2 t 2 ( 1 1 + 4 k 1 t 1 C o ) / 2 k1 t 1
]/2k2.tTB2 . (3.7)

04/27/10

87

*Khi th tch cc thit b trong h thng bng nhau: VRi = VRj tTBi = tTBj = tTB . v nhit cc thit b bng nhau: Ti = Tj ki = kj = k . chuyn ho ca phn ng bc 0 trong h thng n thit b ni tip theo cng thc (3.5) thnh: Xn0 = ( C0 - Cn ) / C0 = n.k.tTB / C0 . ( 3 . 5 )' chuyn ho ca phn ng bc 1 trong h thng n thit b ni tip theo cng thc (3.6) thnh: Xn1 = 1 - Cn/C0 = 1 - ( 1 + k . tTB )-n . ( 3 . 6 )'
04/27/10 88

b/Phng php dng hnh:

Phng

trnh (3.4) c th vit li

dng: Ri = -Ci / tTBi + C i-1 / tTBi . ( 3 . 8) V tri ca pt (3.8) l hm s xc nh ca Ci: Ri = ki . f( Ci ), ta v ng biu din ca R ph thuc vo C ( hnh 3.2 ). V phi l hm s tuyn tnh ca Ci, giao im ca hai ng biu din 04/27/10 89 l nghim ca phng trnh (3.8).

Phng php dng hnh

ng

thng biu din v phi c h s gc l -1/tTBi. ng thng u tin ( i = 1 ) bt u t trc honh ti C0 vi h s gc l -1/tTB1 giao im ca ng thng ny vi ng cong R c to ng vi C1 v R1, l nng cht phn ng v vn tc phn ng thit b 1.
04/27/10 90

Phng php dng hnh

C1 trn trc honh v ng thng vi h s gc l -1/tTB2, ta c C2 v R2 ... v c th tip tc n khi t Cn 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 Ri = ki . f (C) tng ng .
04/27/10 91

Phng php dng hnh

Vn tc p , R

R1 R2 R3 Rn

Tg 1 = -1/tTB1 Tg 2 = -1/tTB2 Tg 3 = -1/tTB3 ... 3 Cn 2 C0 1

Nng cht p, C H.3.2-Phng php dng hnh gii bi ton h thit b khuy ni tip, lin tc. C3 C2 C1

04/27/10

92

Bi tp 3.2 Phn ng thun nghch 2A B + C, hng s vn tc phn ng thun kth = 10 m3/kmol.h, hng s cn bng Kcb = 16, nng ban u CA0 = 1,5 kmol/m3, CB0 = CC0 = 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 VR1. b/S thit b n ca h thng nu ly VRn 04/27/10 = VR1/10.

93

Li gii:

a/t nng ca B v C trng thi cn bng l CBcb = CCcb = Ccb. Ta c: CAcb = 1,5 - 2Ccb. Kcb = C2cb / (1,5 - 2Ccb )2 =16. Gii c Ccb = 0,667 kmol/m3. X yu cu bng 80% trng thi cn bng nn nng yu cu ca B v C nh sau: CByu cu = C Cyu cu = 0,80.Ccb =0,80.0,667 = 0,533 kmol/ m3.

04/27/10 94

 Vy

CAyu cu = 1,5 - 2 . 0,533 = 0,434 kmol/m3.

Phng

trnh vn tc ca phn ng thun nghch chuyn ho cht A c dng: RA = kth.CA2 - kng . CB .CC
Ta

= kth ( CA2 - CB . CC/ Kcb ) c:

v kng = kth/Kcb.

RA = 10 ( CA2 - CB .CC /16 ).

( 3.9 )

04/27/10 95

Vn tc phn ng trong h thng phn ng mt thit b l: RA(1) = 10 [ (0,434)2 - (0,533)2/16 ] = 1,7 kmol/m3.h. T pt c trng (3.4) vi i = 1 ta c: tTB1 = VR1 / FV = ( C0 - C1 ) / R1 . Do : VR1 = FV . ( C0 - C1 ) / R1 . Thay s vo , ta c: VR1 = 100 ( 1,5 - 0,434 ) / 1,7 = 62,7 m3.

04/27/10 96

 b/Nu

ly VRn = 1/10 VR1 = 6,27 m3, tm s thit b n ca h thng khuy ni tip ta dng phng php dng hnh. V ng biu din RA ph thuc vo CA theo phng trnh vn tc (3.9): cho CA cc gi tr t 0 n 1,5 kmol/m3 Xc nh CB , CC tng ng v tnh RA nh bng sau: CA, 1,5 1,3 1,1 0,9 0,7 0,5 0,3 CB,CC 0 0,1 0,2 0,3 0,4 0,5 0,6 RA 22,5 16,9 12,1 8,1 4,9 2,5 0,68 kmol/m3.h
04/27/10 97

CA = CA0 = 1,5 kmol/m3 v ng thng to vi trc honh gc : tg = - 1/tTB= - 100/6,27 = -15,9 ng thng ny ct ng cong RA im c to CA1 = 0,94 kmol/m3 v RA1 = 8,9 kmol/m3.h

04/27/10 98

CA1 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 CA2 v RA2 ( hnh 3.3 ), c th tip tc c kt qu nh sau: CA1 = 0,94 kmol/m3 RA1 = 0,89 kmol/m3.h CA2 = 0,68 RA2 =4,52

CA3 = 0,52 CA4 = 0,42

RA3 = 2,65 RA4 = 1,70

04/27/10 99

R [kmol/m3.h] 20 1 2 3 10 3 2 1 4 R1=8,90;C1=0,94 R2=4,52;C2=0,68 R3=2,65;C3=0,52 R4=1,70;C4=0,42 Tg=-1/tTB=-15,9 CA Kmol/m3

0,5 1,0 1,5 H.3.3-Phng php dng hnh gii bi tp3.2

100

04/27/10

 Nh

vy CA4 < CA 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 m3, nh hn nhiu so vi th tch phn ng khi dng mt thit b. (iu ny cn c gii thch?)

04/27/10 101

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.

04/27/10 102

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:
Cc

QR = QS

(4.1)

QR - Nhit phn ng trong n v thi gian. QS - Nhit trao i trong n v thi gian.

04/27/10 103

IV.1-Ch nhit ti u:

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.
y
04/27/10 104

 Vi

d: C phn ng thun nghch, to nhit: A B Hng s vn tc phn ng thun: k1 = k10 . eE1/RT

Hng s vn tc phn ng nghch: k2 = k20 . eE2/RT

Ta

c: RA = k1 . CA - k2 . CB

= k10..exp(-E1/RT).CA0(1 - XA) - k20.exp(-E2/RT). CA0 . XA

Tm ch nhit ti u m bo vn tc phn ng ln nht bng cch cho dRA / dT = 0: dRA/dT =

k10.CA0.(1-XA).e-E1/RT.E1/RT2 - k20.CA0.XA.e-E2/RT.E2/RT2 = 0 .04/27/10
105

 k10.(1-XA).e

-E1/RT(t).

E1 = k20. XA.e -E2/RT(t).E2 .

Ly loga c hai v: ln [ k10.(1-XA).E1] - E1/RT(t) = ln ( k20.XA.E2 ) - E2/RT(t) .

T : (E2 - E1)/RT(t) = ln [ k20.E2.XA/k10.E1.(1-XA). = (E2 - E1)/Rln[k20.E2.XA/k10.E1.(1 (4.2)

04/27/10 106

T(t)

XA)].

 Nh

vy,ch nhit ti u trng hp phn ng thun nghch, to nhit ph thuc vo chuyn ho XA nh cng thc (4.2) Lc u khi XA cn thp nn tin hnh phn ng nhit cao m bo vn tc ln, sau khi XA tng ln cn gim dn nht . Trong thc tin sn xut, phn ng c c trng ny ( nh SO2 + 1/2O2 SO3 + 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 .
04/27/10 107

X1 Nguyn liu T1 T0 T2

X2

X3

X4

X5 Sn phm

T3 T4

T5 T6

T7 T8

T9

H.4.1- Cc lp xc tc on nhit ( p to nhit ) vi lm lnh trung gian .

108

04/27/10

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 ).

X5 X4 X3 X2 X1 T8

T9 T7 T6 T4 T2 T5
Xc
b

T3 T1

Tt=f(X)
T0 T

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 nhi. t
04/27/10 109

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.

04/27/10 110

b/Dng tc nhn mang nhit l kh, lng hay rn:

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.
-Kh:
04/27/10 111

 -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
04/27/10 112

Xc tc nng

TBTS +Q
Xc tc ngui

TBP -Q

H.4.4-Qu trnh s dng nhit ca crcking xt

04/27/10

113

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.

T1 T0 H.4.5-H thng thit b thng c khuy vi lm lnh trung gian

04/27/10

114

 d/iu

chnh nhit ban u T0 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 ).
115

Hi

Cht Phn ng

Sn phm

Lng H.4.6-Gii nhit phn ng bng cch Bay hi cu t nh

04/27/10

 g/Bm

tun hon hn hp phn ng qua thit b trao i nhit ( h.4.7).

Nguyn liu

TB P
Sn phm

H.4.7-Gii nhit bng cch tun hon hn hp phn ng qua thit b trao i nhit

116

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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 T0 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.

04/27/10 117

-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 ).
04/27/10 118

T0 T1 T1 Tf T0 T0 a b H.4.8-Thit b phn ng t nhit a- Thng c khuy. b- Ngn la Mt ca ngn la

119

04/27/10

 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 T0 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 ).
04/27/10 120

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 T1 theo thi gian lm vic ca xc tc bng cch iu chnh thng s .
04/27/10 121

FV T3 T0 T1 T2 T2 T1

T3 T0 T1 FV (1-)FV T0 T2 T0 T2

H.4.9- Thit b phn ng loi ng c kh nng t nhi. t a-Trao i nhit vi sn phm.b-Trao i nhit vi xc tc

122

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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.
c/Qu

04/27/10 123

Qu trnh cng nghip: +Oxy ho NH3 thnh oxit nit trn xc tc dng li Pt-Rh nhit 800 - 8500C. +Amonoxi ho CH4 thnh HCN trn xc tc dng li Pt-Rh 1000 12000C.
-

+Oxihydro

ho mtanol thnh fomaldhit trn xc tc Ag 650 7200C ( hnh 4.10b).

04/27/10 124

- qu trnh c th tin hnh t nhit, khi m my cn phi un nng hn hp mtanol - khng kh n 300 - 4000C. 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 - 3000C, gim phn hu fomalehit to thnh nhit cao theo phn ng: CH2O CO + H2

04/27/10 125

Mng phng n Hn hp mtanolkhng kh un nng in Mi phn ng CAg CAs Ts Tg Dng kh Lp bin B mt xc tc CAs << CAg Ts >> Tg Xc tc Ag

Lm lnh ng chm 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.

126

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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: QR = QS (4. 3) Trong QR - nhit phn ng trong n v thi gian. QS - nhit trao i trong n v thi gian. gii pt (4.3) ta dng phng php dng hnh : kho st ng biu din ca QR v QS theo T, nghim ca pt l giao im ca hai ng biu din.
04/27/10 127

+Kho st QR :
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 VR . S mol cht A chuyn ho trong n v thi gian l NA, do : QR = NA . ( - HR ) NA = k . CA . VR CA l nng trong thit b, rt ra t pt (3.4)'' CA = CA0 / ( 1 + k . tTB ) . T : NA = k.CA0.VR/(1+k.tTB ) = k0.e-E/RT.CA0.VR/(1+k0.e-E/RT.tTB) NA = k0.CA0.VR / ( e E/RT + k0.tTB ) . Do : QR = k0 . CA0 . VR . (- HR) / ( e E/RT + k0 . tTB ) (4.4)

04/27/10 128

ng biu din ca QR ph thuc vo T theo pt (4.4) c dng ch S, ngoi ra khi cc thng s khc nh VR, FV thay i ta c mt h ng cong S trong mt phng vi trc to QR - T nh hnh 4.11.
QR

FV tng

T H.4.11- ng biu din QR theo T khi FV thay i

04/27/10 129

+Kho st QS:

QS c hai thnh phn: - Trao i nhit vi nguyn liu vo, nhit nguyn liu t T0 T. -Trao i nhit qua thnh.

hay

QS = FV. .CP( T - T0 ) + K.F. ( T - TC ).

(4.5)

Trong : - Khi lng ring ca hn hp phn ng. CP- Nhit dung ring ca hn hp phn ng.T - Nhit phn ng. T0- Nhit vo. K - H s trao i nhit qua thnh. F - B mt trao i nhit ca thit b. TC- Nhit thnh thit b.

QS = ( FV. .CP+ K.F ) T - ( FV. .CP.T0 + K.F.TC )

04/27/10 130

 ng

biu din ca QS theo T l ng thng, khi F thay i ta c cc ng thng vi h s gc thay i ( hnh 4.12a ), khi T0 thay i c cc ng thng song song (hnh 4.12b).
QS QS K.F tng
=0 F K.

T0 tng

T H.4.12- ng biu din QS theo T. a- Khi KF thay i. b- Khi T0 thay i.

04/27/10

131

QR QS 3 QR3

QR1

1 T2 T3 T

H.4.13- Cc trng thi dng ca TBP thng c khuy

132

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 Nh

vy, c th c 3 giao im gia ng QR dng ch S v ng thng QS, ngha l c 3 trng thi dng ca h thng ( hnh 4.13 ).Trng thi dng 1 c T1 thp v QR1,QS1 u thp, phn ng hu nh khng xy ra. Trng thi dng 3 nhit cao T3 do c chuyn ho cao , l iu ta mong i. Trng thi dng 2 khng n nh, s c kho st mc 3/. 04/27/10
133

 b/Trng

thi dng ph thuc vo chiu thay i ca cc thng s v bin php mi phn ng: a/Gi s FV thay i, cc thng s khc c nh: QR l cc ng cong A, B, C, D v E, QS coi nh khng i,c cc trng thi dng t 1 n 9, ng vi nhit dng t T1n T9 nh hnh 4.14.
04/27/10 134

QR QS

A B C 5 4 2 3 E 6 FV tng D 7 8

H.4.14-Cc trng thi dng khi FV thay i

135
04/27/10

FV tng t thp ln cao ta c cc ng QR ln lt l A, B, C, D v E, cc trng thi dng l 9, 8, 7, 6 v 1. -Ngc li, khi FV gim t cao xung, cc ng QR 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 FV nh hnh 4.15
-Khi
04/27/10 136

Tdng 9 8 7 6

4 3 A B C 2 D 1 E FV

H.4.15- Cc nhit dng ph thuc vo chiu thay i ca FV

137
04/27/10

T rt ra cch mi phn ng: Khi m my ban u dng lu lng dng FV thp phn ng tin hnh trng thi dng c chuyn ho v nhit dng cao ( T9 ), sau tng dn FV n nng sut thit k ( nhng khng th tng qu ng D ).
04/27/10 138

b/Gi s T0 thay i, cc thng s khc c nh: QR khng i, QS l cc ng thng song song , ta c cc trng thi dng t 1 n 9 nh hnh 4.16a. - Khi T0 tng t thp ln, QS 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 T0 t cao gim xung, QS 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 T0 nh hnh 4.16b.
04/27/10 139

QR QS

A B C D E 6 5 T0 tng 4 7 8 9

Tdng 7 6

4 1 2 b 3 T0

1 2

3 a T

H.4.16- Cc trng thi dng khi T0 thay i. a- Cc trng thi dng.b-Cc nhit dng theo chiu thay i ca T0

140

04/27/10

rt ra bin php mi phn ng: khi m my un nng nguyn liu vo QS 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 QS 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 QS l B, C v D ta c th gp cc trng thi dng 2, 3 v 4).
04/27/10 141

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 > T5, lc QR > QS, h thng c un nng bng nhit phn ng v n T7 Ngc li khi T < T5 th QR < QS, h b ngui i v v T3. T c th rt ra iu kin n nh ca cc trng thi dng l: dQS / dT > dQR / dT (4.6)
04/27/10 142

IV.5-c trng nhit ca thit b loi ng:

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 04/27/10 143 thng s l v r.
-Do

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
04/27/10 144

T 1 T0 1 X 1 0 2 3 L 2 3 Tn 1-Xc tc hot tnh cao 2-Xc tc hot tnh trung bnh 3-Xc tc hot tnh thp

L H.4.17-S thay i nhit v chuyn ho trong ng phn ng on nhit vi xc tc c hot tnh khc nhau

145

04/27/10

*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.
04/27/10 146

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
-Tm
04/27/10 147

T0 FV,T0

T1

T2 T 3 T4 T5

H.4.18-Phn b nhit trong ng, phn ng to nhit c trao i nhit qua thnh T5 > T4 > T3 > T2 > T1 > T0 T5 : Tmax

148

04/27/10

Cn tnh thm thnh phn khuch tn theo hng ng knh vi h s khuch tn ngang l Dr v a vo pt mt th nguyn (2.27). +Tnh thnh phn kt ngang ( k hiu l A ) cho nguyn t th tch 2r.dr.dl theo hnh 4.19

-Dr.2rdl.C/r r C

dl dr

-Dr.2(r+dr)dl.(C+C/r.dr)/r

C+C/r.dr

H.4.19-M hnh tnh khuch tn ngang cho nguyn t th tch thit b 2r.dr.dl

149

04/27/10

A = Lng ra - Lng vo = -Dr.2(r+dr)dl.(C+C/r.dr)/r

- (-Dr).2rdl. C/r. A/2dl= -Dr [(r+dr).(C+C/r.dr)/r - r.C/r]. A/2dl= -Dr ( r. 2C/r2.dr + C/r.dr + 2C/r2.dr2 ). S hng 2C/r2.dr2 qu b, b qua v chia tip cho rdr: A/2 r.dr.dl = -Dr ( 2C/ r2 + 1/r. C/ r ) (4 . 7)
04/27/10 150

a thnh phn khuch tn ngang A / 2r.dr.dl t (4.7) vo pt (2.27): v. C/ l - Dl. 2C/ l2 - Dr ( 2C/ r2 + 1/r. C/ r) + R = 0. (4.8) Qu trnh truyn nhit tng t chuyn cht, nn c th vit: v.CP. T/ l - l. 2T/ l2 - r ( 2T/ r2 + 1/r. T/ r)

9)

+ ( - HR)i . Ri = 0.

i= 1, n.

(4.

Trong :+ CP-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. +(-HR)i-Nhit ca phn ng th i.
04/27/10 151

 Nh

vy: v. C/ l -Chuyn cht vi dng chy c vn tc v. v.CP. T/ l -Truyn nhit do dng cht mang nhit. -l. 2T/ l2 -Truyn nhit theo hng trc ng. -r( 2T/ r2 + 1/r. T/ r) -Truyn nhit theo hng ng knh ng. (- HR)i.Ri -Tng nhit phn ng chnh v ph.
04/27/10 152

 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
04/27/10 153

Tmax Tmax 1 Tmax 2 3

T0

1-Xc tc mi, HT cao. 2-Xc tc gim HT. 3-Xc tc HT thp. L

H4.20-ng biu din nhit tm ng phn ng theo chiu di l vi xc tc c HT khc nhau.

154

04/27/10

nh cc thng s nh hng n Tmax: Dng FV 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)
-Xc

FV

P dl

H.4.21-M hnh cn bng nhit ca dng F V i qua nguyn t th tch S.dl

155

04/27/10

Ta c pt cn bng nng lng ca dng ) Trong

- FV. .dh + dQ = 0

( 4 . 10

dh = CP.dT + HR.dC CP- Nhit dung ring ca dng. HR- 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 - ).

dh- Thay i entalpi ca dng

04/27/10 156

Gi s phn ng to nhit, lm lnh ngoi thnh ng phn ng: dQ = -K.( T - TC ).P.dl K- H s trao i nhit qua thnh. TC- Nhit ca thnh. P- Chu vi ca ng phn ng. Ta c bn knh thu lc ca ng phn ng: RTL = S/P P = S/RTL. dQ = -K.(T - TC).S.dl / RTL. Thay vo pt (4.10) -FV..(CP.dT + HR.dC) - K.(T - TC).S.dl / RTL = 0. ( 4 . 11 )

04/27/10 157

 Phng

trnh cn bng vt cht trong S.dl vi vn tc phn ng l R: FV..dC = S.dl.R S.dl = FV..dC / R. S.dl vo pt (4.11) v chia cho FV.

Thay

-CP.dT - HR.dC - K.(T - TC).dC / RTL.R = 0. ( 4 . 12 ) Ti T = Tmax th dT = 0, ta c: -HR.dC - K.(Tmax- TC).dC /RTL.R = 0. T

Tmax = TC + (- HR).R.RTL / K 13 )

(4.
04/27/10 158

T (4.13):

Tmax t l thun vi nhit phn ng (HR), vn tc phn ng (R) v ng knh ng phn ng (RTL).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 04/27/10 159 vt ln.

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.

04/27/10 160

T (4.13):
Cui

cng Tmax t l thun vi nhit ca cht ti nhit TC. Tuy vy, TBP nhit cht ti nhit TC 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.

04/27/10 161

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 3000C nh qu trnh oxy ho mtanol thnh fomaldhit trn xc tc oxit Fe-Mo phi lm lnh bng du nng 260-2700C ( hnh 4.22).
Chnh

04/27/10 162

FV

Hi nc Du nng

3000C 260-2700C Nc mm

H.4.22-S gii nhit phn ng

163
04/27/10

 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 TC, K/RTL v T on nhit. Hnh 4.23 din t s thay i nhit Tmax khi nhit ban u ca hn hp T0=340 K, cn TC thay i t 300 n 342,5 K
04/27/10 164

T,K
Tmax=440

420 380 340 300

1-TC=300,0 K 2-TC=320,0 K 6 5 4 3-TC=335,0 K 4-TC=337,5 K 3 5-TC=340,0 K 2 6-TC=342,5 K 1 10 20 30 tTB,S

430 420

H.4.23- nhy ca Tmax vo TC

165

04/27/10

hnh v ta thy mi n khi TC=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 TC thm 2,5 K (TC=337,5 K) ng biu din nhit ti tm ng c cc i cao hn T0 n 80 K (Tmax=420 K).
Nhn Khi

tng TC ln mt t na (TC=342,5 K) nhit im nng vt nhit ban u n 100 K.

04/27/10 166

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
.
04/27/10 167

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.
04/27/10 168

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 m2/g n gn 1000 m2/g. a/Cc c trng ca xc tc xp: +B mt ring: K hiu - SR, n v - m2/g.

04/27/10 169

Mt s vt liu xp thng dng: Diatomit: SR = 5 - 10 m2/g.Al2O3 hot tnh, silicagel: SR = 200 - 400 m2/g.Zolit: SR = 700 - 800 m2/g.Than hot tnh: SR = 800 1000 m2/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.

04/27/10 170

xp: K hiu - , n v - cm3/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 1cm3/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: = 1/ bk - 1/ tht . (5.1)

04/27/10 171

 +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 ).
04/27/10 172

Ht th cp Ht s cp

L xp l n

L xp L xp Ht xc tc b trung H.5.1-M hnh cu trc xp nhiu dng. Ht xc tc c cha cc tinh th zolit l ht th cp

04/27/10

173

+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: De = D . / (5.2) Trong D - H s khuch tn trong pha kh. - xp ca xc tc. - 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 gi tr t 1/10 n 1/20 v h s khuch tn hiu dng c th c xc nh bng thc nghim.

04/27/10 174

 b/Hiu

sut s dng b mt bn trong ca xc tc : Ngoi h s khuch tn hiu dng De, 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: = th / (5.3)
04/27/10 175

 Trong

. - Modun Thiele

(5.4)
tc.

= Vh/Sh Rs/De
.Vh - Th tch ca ht xc tc. .Sh - B mt ngoi ca ht xc

.Vh/Sh - c trng cho kch thc ht xc tc: Vi ht hnh tr bn knh R, Vh/Sh = R/ 2. Vi ht hnh cu bn knh R, Vh/Sh = R/ 3. .RS - Vn tc phn ng b mt. 04/27/10 176

.Th - Hm tang hyperbolic. S ph thuc vo theo pt (4.3)

c din t hnh 5.2.

04/27/10

177

(5.3) v (5.4), khi kch thc ca ht xc tc ln (Vh/Sh 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 c gi tr thp. T c trng ca hm tang hyperbolic ta c: -Khi < 1 th th = , do = 1. -Khi 3 th th = 1 , do = 1/ .

04/27/10 178

 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 SR. cc i. Hot tnh ca mt n v khi lng xc tc Ag c xc nh Ag = As . SR . (5. 5) As Hot tnh ca mt n v b mt xc tc 04/27/10
179

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.
04/27/10 180

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.

04/27/10 181

 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.
04/27/10 182

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

183
04/27/10

+H thng TBP xc tc chuyn ng lp ri c th din t hnh 5.4.

TBTS

TBP

TBTS

TBP

Kh tr Kh tr H.5.3-H thng TBP v TBTS xc tc lp ri

04/27/10

184

 -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 .

04/27/10 185

P Vf Lp ht Xc tc rn

Dng kh

P L. tnh Lp si

Vn tc kh,V

H.5.5-nh hng vn tc kh n trng thi ca lp xc tc rn

04/27/10

186

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.
*Tnh
04/27/10 187

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 ...
Do
04/27/10 188

H.5.6-Quan h gia bt v chuyn ng ca ht rn

189

04/27/10

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.
04/27/10 190

K K max c

b a m

Vn tc kh,V 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

Vf

Vt

191

04/27/10

 -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.
04/27/10 192

VI-MT S LOI TBP TRONG CNG NGHIP HO DU

VI.1-L ng:

C b mt trao i nhit ln v nhit cao ( > 3000C ) 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 10000C ) 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 H2), 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...

04/27/10 193

 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 ).
04/27/10 194

Hi nc

Nguyn liu
Nc mm

Nhin liu Khng kh

Zn bc x

Zn i lu H.6.1.1-S l ng

04/27/10

195

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 - 5000C ln n nhit phn ng ( 800 9000C ) nn ng trong zn bc x c t vo gia c bc x t hai pha ( hnh 6.2 ).

04/27/10 196

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.

04/27/10 197

H.6.1.2-L ng hin i sn xut etylen, bc x t hai pha.

198

04/27/10

 H.6.1.3-L

ng cho qu trnh Refoming hi nc trong s cng ngh sn xut NH3 t kh t nhin.

04/27/10 199

 H.6.1.4-

L ng trong cng ngh sn xut NH3 t kh t nhin.

04/27/10 200

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 Cc

Xng Kh

VGO/HCO

.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

H.6.2.1-S phn ng crcking

201
04/27/10

 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 - 5000C ) v thu nhit ct mch C-C theo phn ng: CnH2n+2 CqH2q+2 + CpH2p - Q 04/27/10 202 (n=q+p)
Trong

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 7200C theo phn ng to nhit: C + O2 (khng kh) COX + Q Do vy cn tin hnh vi lp xc tc chuyn ng lin tc ly ra i ti sinh v b sung xc tc.
04/27/10 203

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.
-Xc
04/27/10 204

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.
Do
04/27/10 205

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.

04/27/10 206

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 - 6500C) v tng sau nhit cao hn (n 7200C). 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.
Cn
04/27/10 207

 Hnh

6.4 trnh by mt dng h thng RCC ca UOP.

Snphm phnng Reactng ng Khxsau honnguyn

Thitb honnguyn xctc2 giaion Khngkh scp Khngkh thcp Khngkh thcp Nguyn liuv phaphn tn

Phaphn tn

04/27/10

208

H.6.2.3-H thng FCC ca ABB Lummus Global Inc. (Hydrocarbon Processing, November 2000, trang 107).

04/27/10 209

H.6.2.4-H thng FCC ca Kellogg Brown & Root, Inc. ( nt , trang 108 )

04/27/10 210

H.6.2.5-H thng FCC ca Shell Global Solutions International B.V. ( nt , trang 108 )

04/27/10 211

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

04/27/10 212

H.6.2.7-H thng FCC ca UOP LLC. ( nt , trang 110 )

04/27/10 213

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 )

04/27/10 214

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 ).

04/27/10 215

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: 04/27/10
216

-S phn ng c th trnh by nh sau:

C4H8 + H+ Buten

C 4H 9 +

i-C4H10 izo-Butan n-C4H10

C4H8 Buten

i-C4H9 + Tert-Butyl cacbenium cation

izo-Octan H+

i-C8H18

C4H8 Buten

i-C8H17 + izo-Octyl cacbenium cation

i-C4H10 izo-Butan

i-C12H26 H+ i-C16H34

04/27/10

217

 -T

nguyn liu ban u buten v i-butan to thnh xng vi thnh phn ch yu l ioctan v hp cht ny trong iu kin phn ng vi xc tc axit c th tip tc phn ng vi buten thnh hydrocacbon nng C12, C16 ...l sn phm ph v c nhit si cao trn 2000C, 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.
04/27/10 218

trnh alkyl ho tin hnh pha lng vi xc tc l axit mnh H2SO4, HF v gn y thm axit rn. Vi xc tc H2SO4 v HF l h d th lnglng cn to nh tng m bo b mt tip xc pha, c bit vi H2SO4 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.
-Qu
04/27/10 219

 -Phn

ng alkyl ho to nhit, khong 90 Kj/ mol, gii nhit phn ng bng cc gii php sau: +Vi xc tc H2SO4, nhit phn ng t 0 n 100C, bng cch bay hi i-butan ( Tsi = -110C ) 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 500C ) c th lm lnh qua thnh bng nc ( hnh 6.8 v 6.9 ).
04/27/10 220

thng TBP: -Cng ngh Kellogg-Exxon vi xc tc H2SO4 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. 04/27/10
221

H.6.3.1-H thng TBP sn xut xng alkyl ho ca KellogExxon

04/27/10 222

H.6.3.2-H thng TBP alkyl ho nm ngang, lm lnh qua thnh ca Stratco.

04/27/10 223

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

04/27/10 224

H.6.3.4-TBP alkyl ho vi xc tc HF ca Phillips.

04/27/10 225

H.6.3.5- TBP alkyl ho vi xc tc HF ca UOP.

04/27/10 226

 -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.
04/27/10 227

H.6.3.6-TBP alkyl ho vi xc tc rn theo cng ngh Alkylene ca UOP

04/27/10 228

VI.4-H thng TBP sn xut MTBE(Metyl Tert-Butyl Ether)

Qu trnh tin hnh pha lng, nhit 50 - 1000C, 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.

04/27/10 229

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).
04/27/10 230

-H thng TBP c trnh by hnh 6.4.

Hn hp i-B=+MeOH

E-6

Hn hp C4 i thu hi metanol d 1 2 1-TBP on nhit c TN trung gian 2- Thp CD

231

MTBE

04/27/10

VI.5-H thng TBP Refoming xc tc:

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.
Qu
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trng ca phn ng v xc tc: Thu nhit, nhit phn ng 400 - 5000C, 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
-c

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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 )

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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, 4TBP xc tc lp ri ; 5h thng ti sinh xc tc

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H.6.5.3-H thng TBP refoming xc tc lp ri ca UOP LLC.

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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 Reduction Zone

Catalyst Transfer Pipes

Reactor No. 1
Reactor No. 2 Feed Reactor No. 1 Effluent

Reactor No. 2
Reactor No. 3 Feed Reactor No. 2 Effluent

Scallops or Outer Screen

Reactor No. 3

Catalyst Out

Catalyst Out
UOP 3046-108

Reactor No. 3 Effluent

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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.
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S phn ng chnh v ph ca giai on oxi ho:

C6H5CH(CH3)2

C6H5C(CH3)2OO*

C6H5COCH3 + CH3O* Axetophenon CH3OH HCOOH

C6H5C(CH3)2OOH +R*

C6H5C*(CH3)2 +RH

O2

C6H5C(CH3)2OH + C6H5C(CH3)2O*

C6H5C(CH3)2OH + R* Dimetyl phenyl cacbinol

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 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.
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trnh oxi ho cumen l d th kh-lng xy ra trong phm vi ng hc 100 1300C ( 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. 04/27/10
Qu
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H.6.6.1-H thng TBP oxi ho cumen thnh cumen H/P.

Kh thi

Sn phm

Cumen

Khng kh
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Phn ng phn hu cumen H/P thnh phnol v axeton di tc dng xc tc axit nhit 50 600C xy ra vi tc ln, to nhiu nhit ( H = -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 56,50C ). 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 04/27/10 LT 243

H.6.6.2-H thng TBP phn hu H/P cumen thnh phnol v axton

Hi axton

Cumen H/P H2SO4

Axton lng

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H.6.6.3-H TBP phn hu H/P theo m hnh dng tun hon.

Cumen H/P
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H2SO4
245

7/H thng TBP tng hp 1,2 dicloetan (1,2 DCE):

Phn

ng: CH2=CH2 + Cl2 CH2Cl - CH2Cl Kh Kh Lng( Ts = 850C ) H = - 220 Kj/mol t l phn ng kh-lng: sc etylen v clo vo 1,2DCE lng ho tan FeCl3 0,5% vi vai tr xc tc. Phn ng xy ra trong pha lng vi vn tc cao ngay nhit thng.
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Thc

 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 - 1000C ) 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. 04/27/10
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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 04/27/10 tch VC. 248

H.6.7.H TBP tng hp 1, 2 DCE nhit cao, tn dng nhit phn ng tinh ch sn phm.

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 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.
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a/Cng ngh xc tc bc: Nhit phn ng: 650 - 7200C. Lm vic trn gii hn n, do thiu oxi cho phn ng oxi ho (1) nn c thm phn ng chnh dhidro ho mtanol CH3OH + 1/2O2 CH2O + H2O ( 1 ) H = - 156 Kj/mol CH3OH CH2O + H2 ( 2 ) H = + 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.
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TBP nh hnh 4.10

Mng phng n Hn hp mtanolkhng kh un nng in Mi phn ng CAg CAs Ts Tg Dng kh Lp bin B mt xc tc CAs << C Ag Ts >> Tg Xc tc Ag

Lm lnh ng chm 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.

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ngh xc tc oxit Fe-Mo: Nhit phn ng: 290 - 3100C. 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.
b/Cng
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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.

T0
3000C

T,0C

1 2 Lp xc tc on nhit

2600 270 C
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 Kt

qu nghin cu cho thy, trn xc tc ny ngoi phn ng chnh ( 1 ) vi nng lng hot ho E1= 40,67 Kj/mol cn c phn ng ph oxi ho fomaldehit thnh CO v H2O vi nng lng hot ho thp hn: CH2O + 1/2O2 CO + H2O (3) H=-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.
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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 .

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