Bai Giang Ky Thuat Phan Ung 2

K THU#T PH%N 'NG
ThS. H* V.n S1n
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Ch51ng 1. Cc khi ni>m c1 b3n

Phn lo2i ph3n 4ng Phn lo2i theo c1 ch6: ph3n 4ng 91n gi3n v ph3n 4ng ph4c t2p. Phn lo2i theo s: pha: ph3n 4ng 9*ng th; v d< th;. Phn lo2i theo ph51ng th4c lm vi>c: ph3n 4ng theo ph51ng th4c gin 9o2n, lin t?c, bn lin t?c. Phn lo2i theo ch6 9A nhi>t: ph3n 4ng 9Bng nhi>t, 9o2n nhi>t v 9a bi6n nhi>t. Trong kC thuEt ph3n 4ng ta quan tm 96n s: pha v thnh phFn xc tc trong h>, th5Gng chia ph3n 4ng thnh: 9*ng th; v d< th; c xc tc hoIc khng xc tc 1.
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Ph3n 4ng 91n gi3n: L nhJng ph3n 4ng x3y ra chK theo cng mAt lo2i trao 9Li nguyn t:, c nghMa l chK c mAt ph3n 4ng duy nhOt. NhJng ph3n 4ng ny chK cFn mAt ph51ng trnh l5Png ho v mAt ph51ng trnh vEn t:c 9; bi;u diQn qu trnh ph3n 4ng. Ph3n 4ng 9a hPp: l ph3n 4ng m trong hSn hPp ph3n 4ng x3y ra nhiTu ph3n 4ng. Ta ph3i cFn h1n mAt ph51ng trnh l5Png ho hUc v ph51ng trnh vEn t:c 9; bi;u diQn qu trnh ph3n 4ng. Ph3n 4ng n:i ti6p Ph3n 4ng song song Ph3n 4ng hSn hPp
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Khng xc tc &'ng - H5u h6t ph(n +ng 7 th" pha kh - Cc ph(n +ng chy c.a ng8n l9a D th" - Ph(n +ng chy c.a than - Nung qu0ng - Ph(n +ng c.a acid v2i ch*t r3n - H*p thu kh l4ng c ph(n +ng
C xc tc - H5u h6t ph(n +ng 7 pha l4ng - Cc ph(n +ng 7 th& keo - T ng h#p ammoniac Oxide ha ammoniac %& s(n su*t nitric acid - Ph(n +ng cracking - T ng h#p methanol
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2. Ph !ng trnh t" l $ng H> c ph3n 4ng ha hUc dang: V1A1 + V2A2 X V3A3 + v4A4 VYi h> kn: vi/vk = (ni0-ni)/(nk0-nk) H> mZ: [i l mEt 9A dng lin t?c câ cOu t_ th4 i (kmol/h, mol/s) vi/vk = ([i0 - [i)/([k0 - [k) N6u Ai l s3n ph`m, Ak l chOt ph3n 4ng (vk<0) vi/|vk| = (ni0-ni)/(nk0-nk) GUi k l cOu t_ cha kha, Uk l 9A chuy;n ha ni = ni0 + vi/|vk| . nk0.Uk
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HoIc CiVR = CioVoR + vi/|vk| CkoVoR.Uk H> mZ [i = [i0 + vi/|vk| CkoVoR.Uk N6u cOu t_ th4 i v k 9u l chOt ph3n 4ng
[i0..Uk = |vi|/|vk| . [k0.Uk
V cc nguyn li>u ph:i trAn theo ta l5Png ha hUc |vi|/|vk| = [i0/[k0 do 9 Ui=Uk
b:i vYi thi6t b< ph3n 4ng gin 9o2n h> kn c ni = c ni0 + d/|vk|. [k0. Uk PhFn mol câ cc cOu t_ trong h> se l xi = ni/ c ni = (xi0 + vi/|vk| . xk0.Uk)/(1+ vi/|vk| . xk0.Uk) V xi = [i/ c ni = (xi0 + vi/|vk| . xk0.Uk)/(1+ vi/|vk| . xk0.Uk)
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Khi bi6t thnh phFn câ cc cOu t_ trong h> ta tnh 95Pc 9A chuy;n ha câ chng Uk = (xio xi)/(xio/|vk|.[xd - v])
Trong tr5Gng hPp h> x3y ra nhiTu ph3n 4ng xi = (xi0 + vi1/|vk1| . xk0.Uk1 + vi2/|vk2| . xk0.Uk2 ++ vij/|vkj| . xk0.Ukj ) / (1+ di1/|vk1| . xk0.Uk1+ di2/|vk2| . xk0.Uk2++ dij/|vkj| . xk0.Ukj) Trong 9 dij = cv<j trong ph3n 4ng th4 j
Ukj 9A chuy;n ha th4 k trong ph3n 4ng th4 j V<j h> s: ta l5Png câ cc cOu t_ th4 i trong ph3n 4ng th4 j
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Ch51ng 2. Nhi>t 9Ang hUc cc ph3n 4ng ha hUc

1. Enthalpie câ ph3n 4ng ha hUc. 1.1. Nhi>t sinh Nhi%t ph(n *ng t,o thnh 1mol mAt hPp chOt no 9 tf cc nguyn t: gHf (f: formation) Nhi%t sinh tiu chu-n gHf,298 câ mAt hPp chOt l enthalpie câ ph3n 4ng t2o thnh 1 mol hPp chOt 9 v ph3n 4ng x3y ra Z 25oC, p suOt P = 1,03125 bar Nhi>t chy: gHC (C: combustion) câ mAt mol chOt l nhi>t câ ph3n 4ng 9:t chy 1 mol chOt 9 (c th; l nguyn t: hay hPp chOt) bhng oxy phn t_. Nhi%t sinh tiu chu-n gHf,298 nhi>t câ ph3n 4ng 9:t chy 1 mol hPp chOt 9 v ph3n 4ng x3y ra Z 25oC, p suOt P = 1,03125 bar. Ph3n 4ng bit 9Fu v k6t thc t2i 25oC v s3n ph`m chy cjng ph3i Z 9iTu ki>n tiu chu`n 25oC, p suOt P = 1,03125 bar.
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Tnh ton enthalpie ph3n 4ng b<nh luEt Hess: gRH298o = cvi (gHf,298o)I Enthalpie ph3n 4ng Z mAt nhi>t 9A no 9: gRHTo = gRHToo + k gCpo(T)dT Trong 9 gCop (T) = cvi .Cpoio(T) VYi Cpoio = l nhi>t dung ring câ cOu t_ th4 i s2ch, t2i nhi>t 9A T v P = 1,01325 bar) Nhi>t sinh tiu chu`n câ mAt hPp chOt tf cc nguyn t: t*n t2i Z mSi nhi>t 9A, Z tr2ng thi tiu chu`n c ho2t 9A l 1 95Pc tnh bhng ph51ng trnh sau 9y: (gHf,T0) = (gHf,o0)hc + (HTo Hoo)hc - c|vngt|(HTo Hoo)ngt VYi k hi>u hc: hPp chOt, ngt: nguyn t: HTo : enthalpie câ chOt Z tr2ng thi tiu chu`n, nhi>t 9A T Hoo enthalpie câ chOt Z tr2ng thi tiu chu`n, nhi>t 9A 0 (K) gHf,o0 : Nhi>t sinh câ chOt Z tr2ng thi tiu chu`n, nhi>t 9A 0(K)
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Trong ph51ng trnh trn (gHf,T0)hc , (gHf,o0)hc l nhi>t sinh tiu chu`n câ hPp chOt t2i nhi>t 9A T v 0(K); (HTo)hc , (Hoo)hc l enthalpie câ hPp chOt Z tr2ng thi tiu chu`n Z nhi>t 9A T v 0 (K). (HTo)ngt , (Hoo)ngt l nhi>t sinh câ nguyn t: Z nhi>t 9A T v 0 (K) |vngt| l h> s: ta l5Png câ nguyn t: Enthalpie ph3n 4ng tiu chu`n câ mAt ph3n 4ng Z mAt nhi>t 9A T no 9: gR HTo = cvi[(HTo Hoo)ngt + gHf,o0]I Trong 9 vi l h> s: ta l5Png câ chOt tham gia ph3n 4ng th4 i Nhin li>u rin, theo gi3 thi6t câ Dulong th tOt c3 oxy 9Tu lin k6t vYi hydro cn phFn hydro cn l2i xem l tl do Ho = 339,1.WC + 1442,8(WH Wo/8) + 144,7WS kJ/kg Trong 9 WC , WH, Wo, WS l phFn kh:i l5Png C, H,O v S
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BZi v Z cc l cng nghi>p khng 95Pc php lm nguAi khi l xu:ng d5Yi 9i;m s51ng cho nn nhi>t ng5ng t? câ n5Yc khng th; tma ra, v vEy trong thlc t6, chK tnh nhi>t tr< thOp HU = HO -2512(9.WH + WH2O) kJ/kg 2512 l nhi>t ha h1i câ n5Yc (kJ/kg); WH2O phFn kh:i l5Png câ n5Yc (phFn `m ) trong nhin li>u v WH l phFn kh:i l5Png câ hydro
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Cn b/ng ho h2c
Xt ph3n 4ng thuEn ngh<ch 91n gi3n : A + Bn C + D
VEn t:c ph3n 4ng thuEn : (-rth ) = k1 CA CB VEn t:c ph3n 4ng ngh<ch : (rng ) = k2 CC CD o 9iTu ki>n cn bhng : (-rth ) + (rng ) = 0 k1/k2 = CCCD/CACB Hhng s: cn bhng KC = k1/k2 = CCCD/CACB Th6 nhi>t 9Ang 9Bng nhi>t n.ng l5Png Gibbs Z p suOt khng 9Li G hoIc th; tch F khng 9Li. gGo = -RT.lnKp gFo = -RT.lnKC
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Ph51ng trinh Vant Hoff bi;u diQn sl bi6n thin câ hhng s: cn bhng theo nhi>t 9A. d(lnK)/dT = gHo/RT2 gHo 9A bi6n thin enthalpie câ ph3n 4ng Z 9iTu ki>n chu`n
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Ch !ng 3. 46ng h2c cc qu trnh cng ngh% ha h2c

1. VEn t:c ph3n 4ng ho hUc b<nh nghMa chung : vEn t:c ph3n 4ng ha hUc th; hi>n sl thay 9Li vT l5Png câ mAt cOu t_ no 9 tham gia ph3n 4ng theo thGi gian. L5u : VEn t:c ph3n 4ng l mAt 92i l5Png lun lun d51ng hoIc bhng khng, v vEy : se mang dOu (-) n6u l chOt tham gia ph3n 4ng (tc chOt) ; se mang dOu (+) n6u l chOt t2o thnh sau ph3n 4ng (s3n ph`m)
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VYi ph3n 4ng 9*ng th; u = 1/v . dN/dq u = 1/F. dN/dq N l s: mol cOu t_ 9 ph3n 4ng, v l th; tch vng ph3n 4ng. F l di>n tch mIt phn cch giJa cc pha, q l thGi gian. VEn t:c ph3n 4ng ta l> vYi ljy thfa câ n*ng 9A s3n ph`m. aA + bB X dD u = k[A]r[B]s k l hhng s: t:c 9A ph3n 4ng v chK ph? thuAc vo nhi>t 9A r,s l cc s: mj xc 9<nh bEc ph3n 4ng
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Ph3n 4ng khng thuEn ngh<ch aA + bB X dD uD = k[A]r[B]s Ph3n 4ng thuEn ngh<ch aA + bB n dD uD = k[A]r[B]s k2[D]t D5Yi d2ng chung uD = k1[A]r[B]s[D]t k2[A]r[B]s[D]t
k1/k2 = [D]et-t/([A]er-r[B]es-s) V hhng s: cn bhng l K = [D]ed/([A]ea[B]eb) Ta l> k1/k2 = Kn n = (r-r)/a = (s-s)/b = (t-t)/d
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A X D vEn t:c ph3n 4ng l u = -1/v . dNA/dq = k[NA/v] N6u v l hhng s: ta c u = - dCA/dq = kCA N6u bi;u diQn n*ng 9A t4c thGi CA d5Yi d2ng s: mol ban 9Fu a v s: mol 9 ph3n 4ng XM - d(a-XM)/dq = k(a-XM) v dXM/dq LOy tch phn dXM/(a-XM) = kdq XM = a(1-e-kq ) k = 1/(q2-q1). ln(a-X1)/(a-X2) ThGi gian bn h^y câ ph3n 4ng q1/2 = ln2 / k = 0,6932/ k Hhng s: t:c 9A câ ph3n 4ng ph? thuAc vo nhi>t 9A theo ph51ng trnh Arrhenius k = k0e-E/RT
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E l n.ng l5Png ho2t ha, R l hhng s: kh v ko l hhng s: k1/k2 = k0.e-E/RT1 /k0.e-E/RT2 = eE/R(1/T2 1/T1) ln(k1/k2) = E/R(1/T2 1/T1) E = 19,1T1T2/(T1-T2).logk1/k2
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CH(pNG 4. THIuT Bw PH%N 'NG

I-GI I THI#U V% TBP& : I.1-Gi Y thi > u: -TBP (- h> th :i ng thi6 tb < thlc hi>n cc ph3n 4ng ho hUc t2o ra s3n
-V:n t;c ph(n *ng chuy=n ho ch8t i: Ri = dNi / Vdt . (1.1) Trong 9: Ni-S: mol câ chOt i, dOu cAng l t2o thnh (s3n ph`m ph3n 4ng), dOu trf l tiu hao (chOt ph3n 4ng). V-Th; tch câ h> th:ng Khi th; tch khng 9Li ta c Ci = Ni / V, do 9 pt (1.1) thnh: Ri = dCi / dt . (1.2)
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ph`m câ mAt qu trnh s3n xuOt,do 9 quy6t 9<nh n7ng su8t (do v:n t;c ph(n *ng r ) v hi%u qu( (<6 chuy=n ho X v <6 ch2n l2c S) c>a s(n xu8t.
-46 chuy=n ho c>a ch8t i:
Xi = (C0 - C1) / C0 = 1 - C1/C0 .
(1.3)
Trong 9 : C0- n*ng 9A ch8t ph(n *ng i <i vo ( hay n*ng 9A ban 9Fu) C1- n*ng 9A ch8t ph(n *ng i <i ra ( hay n*ng 9A cu:i )
-46 ch2n l2c <;i v@i s(n ph-m i:
Si = Ci / Cj
j = 1, n
(1.4)
Trong 9: Ci -n*ng 9A câ s(n ph-m i trong hSn hPp ph3n 4ng . Cj -tAng nBng <6 cc s(n ph-m trong hSn hPp ph3n
4ng
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Vw TR Hy THzNG TBP( TRONG Sp b| CNG NGHy
Trong s1 9* cng ngh> TBP( nhm Z v< tr nh5 sau :
H.1.1- L5u 9* kh:i câ cng ngh> s3n xuOt .
Trong 9 h> th:ng thi6t b< chu'n b* h,n h/p ph1n 2ng, tch v tinh ch4 s1n ph'm c th; g*m mAt s: l5Png lYn cc thi6t b< thlc hi>n cc qu trnh chuy;n kh:i v truyTn nhi>t nh5 ch5ng luy>n, hOp th?,hOp ph?, trch ly, 9un nng, lm l2nh, ng5ng t? ...m sinh vin 9 lm quen trong mn hUc "Qu trnh v thi6t b< ho hUc ".
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I.2-bIc 9i;m :
- ba d2ng
*Nhi6t 78 ph3n 4ng c th; tf nhi>t 9A phng 96n 800c bi>t c th; 96n 1300-15000C. b*ng thGi ph3i c nhJng gi3i php hPp l cOp hay gi3i nhi>t ph3n 4ng. 9000C, *p su9t c th; tf p suOt kh quy;n ( 0,1 MPa ) 96n 70 MPa. Trong nhiTu ph3n 4ng pha kh th5Gng dng p suOt kho3ng 23 MPa 9; gi3m th; tch TBP(, t.ng c5Gng vEn t:c ph3n 4ng v h> s: trao 9Li nhi>t vYi thnh thi6t b<. VYi mSi p suOt cFn c d2ng hnh hUc câ thi6t b< ph hPp : hnh :ng, hnh cFu ch<u p suOt t:t h1n hnh hAp, mIt phBng.
Do 9iTu ki>n ph3n 4ng rOt khc nhau:
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Ph3n 4ng trong thi6t b< c th; ti6n hnh Z cc tr:ng thi pha khc nhau: *b*ng th;: kh, lmng *Cc h> d< th; kh-rin, kh-lmng, lmng-rin, lmng-lmng *Cc h> ba pha kh-lmng-rin, lmng-lmng-rin, kh-lmng-lmng ... Tnh 9a d2ng câ TBP( cn do t;ng hng , trn th6 giYi c nhJng hng c cng ngh>, xc tc v h> th:ng TBP( ring câ mnh
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b}C bI~M TBP(
-Ph4c t2p
Do trong TBP( cc qu trnh ho h=c ( ph3n 4ng ) v v>t l ( chuy;n kh:i: dng ch3y , khu6ch tn, v cc qu trnh nhi>t: truyTn nhi>t, to3 v thu nhi>t ) x3y ra 7an xen v 1nh h3?ng l@n nhau Trong 9, cc qu trnh v:t l th Cng tuyEn tnh v@i nhi%t <6, cn cc ph(n *ng ho h2c phF thu6c vo nhi%t <6 G d,ng hm mH theo ph51ng trnh Arrhnius ( phi tuyEn ).
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I.3- Phn lo2i TBP( : 1/Theo ch6 9A lm vi>c :

a/Thi6t b< lm vi>c gin 9o2n
*ChK dng cho pha lmng . *Cc b5Yc câ qu trnh: n2p li>u, 9un nng, ti6n hnh ph3n 4ng, lm nguAi v tho s3n ph`m, 95Pc thlc hi>n trong mAt thi6t b<.
Do 9 cc thng s nh5 n*ng 9A, nhi>t 9A, p suOt ...thay <Ai theo thCi gian. V d?: ti6n hnh ph3n 4ng trong thi6t b< lo2i thng c khuOy n*ng 9A chOt ph3n 4ng thay 9Li theo thGi gian nh5 hnh 1.2.
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H.1.2-M hnh TBPJ lm vi%c gin <o,n v thay <Ai nBng <6 theo thCi gian
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b/Thi6t b< lm vi>c n_a gin 9o2n:

*ChOt ph3n 4ng: mAt chOt cho gin 9o2n, mAt chOt cho lin t?c. ChOt cho gin 9o2n th5Gng l chOt lmng, v d? chOt A. ChOt cho lin t?c th5Gng l chOt kh hay c th; l chOt lmng, v d? chOt B. Ph3n 4ng: A + B C VYi m?c 9ch lun ngho chOt B trong hSn hPp ph3n 4ng trnh ph3n 4ng ph?: B + C D Hay 9; vEn t:c to3 nhi>t câ ph3n 4ng ph hPp vYi kh3 n.ng gi3i nhi>t câ thi6t b< .
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*N*ng 9A A v B thay 9Li theo thGi gian ph3n 4ng nh5 Z hnh 1.3
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c/Thi6t b< lm vi>c lin t?c

*4y l lo,i thiEt bK th Cng gMp trong cng nghi%p v@i qui m s(n xu8t l@n. *Tr:ng thi d;ng (steady state ): l tr,ng thi <,t < $c c>a TBPJ sau khi mG my m6t thCi gian, G tr,ng thi ny cc thng s; c>a qu trnh khng thay <Ai theo thCi gian t ,lc < s(n ph-m thu < $c c ch8t l $ng An <Knh. TN khi mG my <En tr,ng thi dNng ta c giai <o,n qu <6, thCi gian qu <6 phF thu6c vo chE <6 dng ch(y trong thiEt bK v <6 ph*c t,p c>a h% th;ng TBPJ.
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ThCi gian l u trung bnh:

ThGi gian l5u thlc câ chOt ph3n 4ng trong thi6t b< khc nhau , ph? thuAc vo ch6 9A dng ch3y. Ta c thCi gian l u trung bnh theo 9<nh nghMa sau:
tTB = VR / FV
Trong 9: tTB VR FV -ThGi gian l5u trung bnh. -Th; tch TBP(. -L5u l5Png câ dng . [ h ]. [ m3 ]. [ m3 / h ].
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2/Theo ch6 9A dng ch3y : *M hnh t!?ng :
'y l
-L m hnh dng ch3y trong thi6t b< chuy;n Ang t<nh ti6n theo th4 tl tr!Yc sau nh! chuy;n Ang câ pit-tng trong xi lanh V do n*ng A chOt ph3n 4ng thay Li tf tf, bit Fu Z Fu vo l CA0 6n Fu ra l CAL nh! Z hnh 1.4
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*M hnh khu9y l t!?ng : -L m hnh dng ch3y trong thi6t b< !Pc khuOy trAn m2nh, chOt ph3n 4ng i vo !Pc trAn ln *ng Tu ngay t4c khic trong thi6t b<, do n*ng A chOt ph3n 4ng thay Li At ngAt Z t2i Fu vo câ thi6t b< nh! Z hnh 1.5
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M hnh khuOy l t5Zng

*Cjng do khuOy trAn nBng <6 ch8t ph(n *ng trong khOp thiEt bK <Bng <Pu v b/ng <Qu ra l C1. *Do n*ng 9A chOt ph3n 4ng trong thi6t b< thOp (nhOt l khi 9A chuy;n ho X yu cFu cao ) nn vEn t:c ph3n 4ng thOp v do 9 n7ng su8t TBPJ theo m hnh khu8y l t Gng th8p h!n <-y l t Gng. Ni mAt cch khc, 9; 93m b3o 9A chuy;n ho X nh5 nhau thi6t b< theo m hnh khuOy l t5Zng cFn c th; tch VR lYn h1n nhiTu so vYi m hnh 9`y l t5Zng, 9Ic bi>t khi X yu cFu cao.
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*"; 3m b3o n$ng suOt thi6t b< cao vYi m hnh khuOy l t!Zng h% th;ng nhiPu thiEt bK khu8y n;i tiEp !Pc s_ d?ng nh! hnh 1.6.
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*o hnh 1.6 n*ng 9A chOt ph3n 4ng thay 9Li tfng bEc tf 9Fu vo 96n 9Fu ra câ h> th:ng, khi n <> l@n (gi@i h,n khi n ) sR thay <Ai nBng <6 ch8t ph(n *ng gi;ng nh G tr Cng h$p <-y l t Gng (hnh 1.4 ). Trong thlc tiQn cng nghi>p s: thi6t b< n trong h> th:ng th5Gng tf 4 96n 10 9; ngoi vi>c 93m b3o n.ng suOt câ h> th:ng thi6t b< cn 9; phn b; thCi gian l u <Bng <Pu h!n, nhi%t <6 c th= <iPu chSnh khc nhau Z tfng thi6t b< v chOt ph3n 4ng th4 hai c th; cho vo tf tf theo tfng thi6t b< theo yu cFu
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3/Theo tr2ng th pha:

*H6 7Ang thB: CFn 95Pc khuOy trAn 9; 9*ng 9Tu vT n*ng 9A cc cOu t_ v nhi>t 9A trong thi6t b< ph3n 4ng. *H6 d* thB: b:i vYi h> ny cFn ch t2o bT mIt ti6p xc pha lYn 9; t.ng c5Gng vEn t:c ph3n 4ng. -H> d< th; lmng - lmng: CFn 95Pc khuOy trAn t:t , t2o nhj t51ng c bT mIt ti6p xc lYn. -H> d< th; kh - lmng: b; 93m b3o bT mIt ti6p xc pha câ h> ny cFn khuOy trAn hoIc sî bUt hoIc dng 9>m rin c bT mIt ring lYn. -H> d< th; kh - rin v lmng - rin: BT mIt ti6p xc pha l bT mIt câ chOt rin , do vEy chOt rin ( l xc tc ) th5Gng l vEt li>u x:p c bT mIt ring lYn hoIc c 9A phn tn cao. Trong cng nghi>p cjng hay gIp h> nhiTu pha: kh - lmng - rin, lmng - lmng - rin
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4/Theo ch6 9A nhi>t:

*Co:n
nhi6t:
-Khng c b6 ph:n trao <Ai nhi%t . -Hay sU dFng v <!n gi(n, cho cc ph(n *ng c hi%u *ng nhi%t th8p hay t nh,y v@i sR thay <Ai nhi%t <6. *CEng nhi6t: -Th Cng gMp G cc thiEt bK c khu8y tr6n t;t. - Trong ti li%u <i khi g2i thiEt bK ph(n *ng xc tc kh - rOn d,ng ;ng chm c bP mMt trao <Ai nhi%t l@n l thiEt bK tRa <Vng nhi%t, tuy v:y G thiEt bK lo,i ny vWn tBn t,i gradien nhi%t <6 theo < Cng knh v h @ng trFc ;ng xc tc .
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*TG nhi6t: -Hay dng khi c th= v <!n gi(n v kinh tE . -Ph(n *ng to( nhi%t <> l@n v c kh( n7ng trao <Ai nhi%t ph(n *ng v@i nguyn li%u vo <= <,t nhi%t <6 m ph(n *ng c th= tiEn hnh . *Ch4 78 nhi6t theo qui ho:ch: -Th Cng dng <= <,t chE <6 nhi%t t;i u cho qu trnh ph(n *ng . -GMp G thiEt bK lo,i ;ng , thiEt bK c nhiPu ng7n <o,n nhi%t v h% th;ng nhiPu thiEt bK khu8y n;i tiEp .
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II/ THHI GIAN L&U

-ThIi gian l3u cJa ch9t ph1n 2ng trong thi4t b* l thIi gian ti4n hnh ph1n 2ng, v vEy n 3nh h5Zng quan trUng 96n 9A chuy;n ho X v 9A chUn lUc S. V d?: ta c ph3n 4ng n:i ti6p ABC, trong 9 B l s3n ph`m chnh v C l s3n ph`m ph?, n*ng 9A câ A, B v C ph? thuAc vo thGi gian ph3n 4ng nh5 Z hnh 2.1
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Gi3 s_ t2i thGi 9i;m t1 n*ng 9A cc chOt A, B, C l CA1, CB1 v CC1 ta c: bA chuy;n ho: X1=1- CA1/CA0. bA chUn lUc: S1=CB1/ ( CB1 + CC1 ).
-Ph? thuAc vo ch6 9A dng ch3y, thGi gian l5u câ cc phFn t_ câ dng vo c th; rOt khc nhau. Do vEy cFn nghin c4u phn b: thGi gian l5u câ chng trong thi6t b<.
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II.1-TH I GIAN L(U TRONG CC M HNH L T(oNG 1/Hm phn b: TGL:

-Hm E(t): "<nh nghMa: PhLn cJa dng vo c thIi gian l!u trong thi4t b* t; t 4n t+dt l E(t).dt. Tf <nh nghMa trn ta c:
E(t).dt 0
= 1
( 2.1 )
E (t ).t .dt
0
= tTB
( 2.2)
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-Hm F(t): b<nh nghMa: F(t) l phLn cJa dng c thIi gian l3u trong thi4t b* nhM h0n t.
*Tf 9<nh nghMa ny F(t) l phFn câ dng 9i vo thi6t b< Z thGi 9i;m t = o v 96n thGi 9i;m t 9 ra khmi thi6t b<. *PhFn câ dng 9i vo thi6t b< Z thGi 9i;m t = 0 96n thGi 9i;m t vn cn trong thi6t b< l [1-F(t)].Tf 9<nh nghMa vT F(t) ta c:
Khi t = 0 th Khi t = th
t '
F(t) = 0 F(t) = 1
'
( 2.3 )
F(t) =
E(t ).dt
0
hay E(t) =dF(t)/dt
(2.4 )
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II.2-Gi tr< câ hm phn b: TGL trong cc m hnh l t5Zng:

-M hnh bLT - Tf 9<nh nghMa câ m hnh ny v 9<nh nghMa câ hm phn b: F(t) ta c gi tr< câ hm phn b: TGL nh5 sau: Khi 0 < t < tTB Khi t > tTB th th F(t) = 0 F(t) = 1 ( 2.5 )
Ta c 95Gng bi;u diQn F(t) theo t nh5 Z hnh 2.2
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-M hnh KLT -Tf 9<nh nghMa câ m hnh ny v câ F(t) ta thOy rhng do khuOy trAn m2nh trong thi6t b< cc phFn t_ câ dng vfa vo 95Pc trAn 9Tu khip trong th; tch câ thi6t b<. Do vEy kh3 n.ng 9i ra câ cc phFn t_ hi>n c trong thi6t b< l nh5 nhau, khng phn bi>t phFn t_ vo tr5Yc hay vo sau. Ni cch khc, xc suOt xuOt hi>n Z c_a ra câ nhJng phFn t_ hi>n c trong thi6t b< l nh5 nhau khng phn bi>t l<ch s_ câ chng.
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Nh5 vEy: C th; c phFn t_ vfa mYi vo 9 c mIt Z c_a ra v ra khmi thi6t b< nn TGL bhng 0 V c th; c phFn t_ 9 vo thi6t b< tf lu mYi ra khmi thi6t b< nn TGL câ nhJng phFn t_ ny bhng . NghMa l TGL cJa ch9t ph1n 2ng trong m hnh KLT khng 7Ang 7Nu v phn bO t; 0 74n .
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Theo l thuy6t xc suOt ta c m>nh 9T sau: xc suOt câ nhJng phn t_ c TGL trong thi6t b< l t+dt g*m xc suOt câ nhJng phFn t_ c TGL trong thi6t b< l t v xc suOt câ nhJng phFn t_ c TGL l dt, nh5 vEy c th; vi6t: [ 1 - F(t+dt) ] = [ 1- F(t)].[ 1 - F(dt)] (2.6)
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[ 1 - F(t+dt) ] = [ 1- F(t)] . [ 1 - F(dt)] F(t+dt) = F(t) + dF(t)
( 2.6 )
V kh3 n.ng ra khmi thi6t b< câ nhJng phFn t_ l nh5 nhau, ta c: F(dt) = FV .dt / VR = dt / tTB Thay vo ph51ng 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 )
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Gi3i ph51ng trnh vi phn ( 2.7 ):

Gi3i ph51ng trnh vi phn (2.7 ), ta c: ln [ 1 - F(t) ] = - t/ tTB + C. Tf 9iTu ki>n ban 9Fu t=0 th F(t)=0 95Pc C = 0
1 - F(t)
do 9
= e-t/tTB = 1 - e-t/tTB
. ( 2.8 )
F(t)
b5Gng bi;u diQn hm F(t) câ m hnh KLT theo ph51ng trnh ( 2.8 ) 95Pc trnh by Z hnh 2.3
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Nh5 vEy, do khuOy TGL cJa cc phLn tP dng vo r9t khc nhau, phn bO t; 0 74n . Lm gi1m 78 chuyBn ho X (v do 7 gi1m nQng su9t thi4t b* ) v 78 ch=n l=c S (7Oi vRi cc qu trnh ph1n 2ng nOi ti4p). b; 92t 9A chuy;n ho nh5 nhau so vYi m hnh bLT Z thi6t b< lo2i ny cFn c th; tch lYn h1n, sl chnh l>ch 9 ph? thuAc vo 9A chuy;n ho X yu cFu.
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H> th:ng nhiTu thi6t b< khuOy n:i ti6p lin tuc:
M hnh h> th:ng nhiTu thi6t b< khuOy n:i ti6p khic ph?c 95Pc nh5Pc 9i;m trn vYi s: thi6t b< n 9^ lYn ( vT l thuy6t khi n v trong thlc t6 n c th; tf 5 96n 10 ). Gi tr< hm F(t) trong h> th:ng n thi6t b< khuOy n:i ti6p lin t?c c th; 95Pc xc 9<nh bhng php tnh cn bhng vEt chOt, 95Pc:
F(t) = 1 - e- nt/tTB [1+(nt/tTB)+(nt/tTB)2/2!+...+(nt/tTB)n-1/(n-1)!] .
( 2.19)
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Hnh 2.5 bi;u diQn gi tr< hm phn b: F(t) câ h> th:ng thi6t b< KLT n:i ti6p lm vi>c lin t?c ph? thuAc vo t (tr?c honh c 91n v< l =t/tTB).
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Tf hnh 2.5 thOy r Z h> th:ng thi6t b< KLT n:i ti6p khi sO thi4t b* n tQng kho1ng phn bO TGL cJa cc phLn tP cJa dng vo hSp l:i ( quanh vng t/tTB=1 ). V khi n ta c 73Ing biBu diTn F(t) cJa h6 thOng t30ng tG nh3 ? m hnh CLT: TGL câ cc phFn t_ câ dng 9*ng 9Tu v bhng tTB.
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II.3- TH I GIAN L(U TRONG THIuT Bw TH#C
-Thi4t b* thGc lo:i thng c khu9y : *NEu c khu8y tr6n m,nh v <6 nh@t mi tr Cng ph(n *ng khng qu l@n c th= coi nh m hnh 4LT . Trong thlc tiQn s3n xuOt cng nhi>p dQ thlc hi>n 9iTu ny, nh5 Z thi6t b< nitr ho hydrocacbon th1m, n*ng 9A cc cOu t_ 95Pc trAn ln hon ton sau 8 giy trong khi TGL trung bnh th5Gng trn 10 pht.
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*Khi mi tr5Gng c 9A nhYt qu cao ta c tr2ng thi trung gian giJa hai m hnh bLT v KLT. *o h> th:ng nhiTu thi6t b< khuOy n:i ti6p, n6u trong mSi thi6t b< sl khuOy trAn khng 95Pc hon ton th 3nh h5Zng câ n c th; bm qua 95Pc, coi nh5
bLT.
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-Thi4t b* thGc lo:i Ong:

*4 Cng bi=u diYn F(t) c d,ng chZ S do tr6n lWn theo h @ng trFc ;ng bGi cc nguyn nhn sau: 1/ Khu8y tr6n <;i l u do cc dng chuy=n <6ng xoy gy nn. 2/ Do gradien v:n t;c dng theo tiEt di%n ngang c>a ;ng. 3/ Khu8y tr6n do khuEch tn phn tU, th Cng (nh h Gng ny khng l@n.
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*4= nghin c*u hi%n t $ng tr6n lWn c>a dng ch(y trong ;ng gy (nh h Gng <En TGL trong thiEt bK v <6 chuy=n ho, chia vct! tr6n lWn thnh hai thnh phQn: H @ng trFc ;ng v@i h% s; tr6n d2c Dl H @ng < Cng knh ;ng v@i h% s; tr6n ngang Dr Dl v Dr < $c xc <Knh b/ng chu-n s; Peclet (k hi%u Pe ) nh sau: Pel = v . L / Dl v Per = v . D / Dr ( 2.20 ) Trong <: v - V:n t;c di c>a dng ch(y. L - ChiPu di c>a ;ng ph(n *ng. D - 4 Cng knh ;ng hay < Cng knh c>a h,t trong ;ng.
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a/zng rSng, ch3y dng:

-Gradien vEn t:c dng theo ti6t di>n ngang
l nguyn nhn ch^ y6u gy nn sl sai khc TGL trong :ng rSng ch3y dng, khu6ch tn 9:i l5u v khu6ch tn phn t_ b, c th; bm qua. -Tnh F(t): VEn t:c dng phn b: trn ti6t di>n :ng theo mIt parabol, ph? thuAc vo kho3ng cch r 96n tm :ng l vr (hnh 2.6)
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-Tnh F(t) câ :ng rSng, ch3y dng

vr = ( 2FV/.r02 )[ 1 - ( r / r0 )2 ] (2.21) Trong 9 r0 l bn knh câ :ng. Do 9 , TGL câ phFn câ dng cch tr?c :ng mAt kho3ng 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 câ dng t2i tr?c :ng l t tm(r=0) = tTB / 2 Thay r = r0 c TGL câ dng t2i thnh :ng l t thnh(r=r0) =
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-Tnh F(t) câ :ng rSng , ch3y dng
C th= xem phQn c>a dng ch(y n/m cch tm l r+dr (hnh vnh kh7n 2r.dr ) c v:n t;c nh nhau l vr, tN <Knh ngh[a c>a hm F(t) ta c: dF(r) = vr . 2r.dr / FV ( 2.23)
Thay vr tN ph !ng trnh (2.21) v rt g2n,< $c : dF(r) = 4 [ 1 - (r/r0)2 ] r.dr / r0 4= chuy=n dF(r) thnh dF(t) ph(i dng ph !ng trnh (2.22) .
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TN (2.22) ta c [ 1 - (r/r0)2 ] =tTB / 2t , l8y vi phn pt (2.22) ta rt ra: rdr = r02 . tTB.dt / 4 t2 Thay vo pt (2.23) ,< $c: dF(t) = tTB2.dt / 2 . t3 ( 2.24)
TN < xc <Knh F(t) cho tr Cng h$p ;ng r\ng ch(y dng nh sau:
F(t) = tTB2/2.] dt/t3 F(t)= 1 - (tTB/t)2/4
t = tTB/2, ^. ( 2.25 )
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TBP( thlc b/ zng rSng,ch3y r:i :
*o ch6 9A ny khu6ch tn 9:i l5u do dng ch3y xoy l chnh . *VEn t:c dng phn b: theo ti6t di>n :ng c d2ng hnh thang ( hnh 2.8 ), nghMa l trf lYp bin st thnh :ng, vEn t:c dng coi nh5 9*ng 9Tu . * Khi gi tr< Re cng lYn ( lYn h1n 10 4 ) chiTu dy lYp bin cng mmng v th; tch lYp bin so vYi FV rOt nhm,c th; bm qua,ta c ch6 9A dng ch3y tla m hnh bLT .
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c/zng ph3n 4ng c lYp h2t tMnh ( h2t xc tc rin, th5Gng gIp trong thlc t6 ):
*LYp h2t t.ng c5Gng hi>n t5Png khu6ch tn trong thi6t b< theo c3 hai h5Yng tr?c :ng v 95Gng knh :ng
bIc bi>t theo h5Yng 95Gng knh theo m hnh nh5 hnh 2.9.
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Theo m hnh ny khi dng ch3y qua mAt lYp h2t b< l>ch ngang dh2t/2 v qua n lYp h2t se l>ch ngang ndh2t/2. V nh5 vEy, l>ch ngang lm cho vEn t:c dng v TGL 9*ng 9Tu h1n. *Nh5 vEy, khi D:ng/dh2t 10 v L lYp h2t /dh2t 10 ch6 9A dng ch3y 73/c coi nh3 CLT.
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buN b* CHUY~N HO X C%A PH%N 'NG
II.4-%NH H(oNG C%A KHUuCH TN D(C
*TrAn dUc tr?c :ng ph3n 4ng lm cho TGL khng 9*ng 9Tu v do 9 3nh h5Zng 96n 9A chuy;n ho X . *Dng thlc trong thi6t b< c th; chia thnh hai phFn: -Dng bLT vYi vEn t:c di l v . -Dng khu6ch tn dUc vYi h> s: khu6ch tn theo h5Yng tr?c l Dl v chu`n s: Peclet vYi k hi>u Pel:
Pel = v . L / Dl
L-l chiTu di câ :ng ph3n 4ng .
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2.10). -Ti6n hnh ph3n 4ng chuy;n ho chOt A s.ph`m
*Gi3 s_:-zng ph3n 4ng c ti6t di>n l S (hnh
*Thlc hi>n php tnh cn bhng vEt chOt cho VR = S . l: A vo = A ra + A ph3n 4ng + A tch t?. (2.26)
. H.2.10-M hnh ;ng ph(n *ng c khuEch tn d2c
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A tch t? = VR . dC/dt, Z tr2ng thi dfng A tch t? bhng 0. Ta c: (A ra - A vo)dng

bLT+
(A ra - A vo)khu6ch tn + A ph3n 4ng = 0.
Thay cc gi tr< câ 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 , 95Pc:
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 ,95Pc: v (CA/l) - Dl (2CA/l2 ) + k .CAn = 0 ( 2.27 )
by l m hnh ton mAt th4 nguyn miu t3 qu trnh trong :ng ph3n 4ng chK 3nh h5Zng bZi khu6ch tn theo h5Yng dUc tr?c.
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v (CA/l) - Dl (2CA/l2 ) + k .CAn
= 0
( 2.27 )
*Chuy;n ( 2.27) thnh d2ng khng c th4 nguyn:

- bIt 92i l5Png chiTu di l z = l/L, ta c: z = l/L , do 9 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 Tf 9 pt (2.27) thnh: (v/L).CA/z - (Dl/L2 ).2CA/z2 + kCAn = 0. ( 2 . 28 ) Chia hai v6 pt (2.28) cho -L/v = -tTB :
(Dl/L.v).2CA/z2 - CA/z - k.tTB.CAn = 0.(2.29)
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(Dl/L.v) . 2CA/z2 - CA/z - k . tTB . CAn = 0. ( 2 . 29 ) * Gi3i pt (2.29) vYi 9iTu ki>n bG :- t2i 9Fu vo z = 0 , CA = CA0 - t2i 9Fu ra z = 1 , CA = CAL
"!Pc CAL v tf tnh A chuy;n ho XA, .

.
XA ph? thuAc vo 3 thng s: k , tTB v Pel = L.v/Dl . VYi ph3n 4ng bEc 1 (n = 1) gi3i !Pc : CAL/CA0 = 1 - XA = 4a.exp(Pel/2)/[(1+a)2exp(a.Pel/2) (1-a)2exp(a.Pel/2)] ( 2 . 30 ) VYi a = TB l
1 + 4kt /Pe
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H.2.11-Bi=u diYn VRthRc/VR4LT phF thu6c vo Pel, k.tTB v X c>aph(n *ng b:c 1.
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H.2.12-Bi;u diQn VRthlc/VRbLT vo Pel, k.tTB.C0 v X câ ph3n 4ng bEc 2
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Thlc nghi>m cho thOy rhng chu`n s: khu6ch tn dUc Pel ch^ y6u ph? thuAc vo chu`n s: Re = v.d:ng./. Hnh sau l k6t qu3 thlc nghi>m câ mAt s: tc gi3vT sl ph? thuAc câ Dl/v.d:ng = (Dl/v.L).L/d:ng vo Re Tf 9 c th; rt ra t51ng quan sau: Dl/v.d:ng = 3.107/(Re)2,1+1,35/(Re)0,125.
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H.2.13-S; li%u thRc nghi%m sR phF thu6c Dl/v.d;ng vo Re c>a m6t s; tc gi(.
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II.4 TH#C NGHIyM XC bwNH GI TRw HM PHN Bz TGL o THIuT Bw TH#C. 1/ Thlc nghi>m xc 9<nh hm phn b: TGL E(t) v F(t):
*Nguyn tic: -T2i t = 0 bit 9Fu cho chOt chK th< vo. -Xc 9<nh n*ng 9A chOt chK th< Z 9Fu ra theo thGi gian t. -X_ l tn hi>u n*ng 9A ra,xc lEp F(t). Th5Gng cho chK th< vo theo 3 d2ng tn hi>u: d2ng bEc cOp, d2ng xung v d2ng hnh sin. 9/12/2012
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a/Tn hi>u vo d2ng bEc cOp, xc 9<nh hm F(t): -Tn hi>u cho chK th< vo d2ng bEc cOp: = 0 khi t 0 C chK th<(z=0) { = C0 khi t > 0 . ( 2 . 31 ) .
-Miu t3: T2i t = 0 bit 9Fu cho chK th< 9i vo thi6t b< v duy tr trong su:t thGi gian sau 9 ( hnh 2.11 ). Nh5 vEy khi t > 0, l5Png chK th< vo thi6t b< khng 9Li, bhng FV.C0.
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Xc lEp hm F(t): Gi3 s_ n*ng 9A chK th< ra Z thGi 9i;m t l Ct, phFn câ chK th< ra t2i thGi 9i;m ny l FV.Ct. Tf 9<nh nghMa câ hm F(t) ta c: F(t) = FV.Ct / FV.C0 = Ct / C0. ( 2 . 32 )
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b/ Tn hi>u vo d2ng xung vung, xc 9<nh hm E(t):

-Tn hi>u cho chK th< vo d2ng xung: =0 =0 khi t 0 . khi t>t0 .
CchK th< (z=0)=C0 khi 0<t< t0 .

Miu t3: T2i t = 0 bit 9Fu cho chK th< 9i vo thi6t b< trong thGi gian ngin t0 ( yu cFu t0 << tTB ) v sau 9 dfng cho chK th<.
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Xc lEp hm E(t):
Gi3 s_ ton bA l5Png chK th< cho vo thi6t b< Z d2ng xung vung l q0, t2i thGi 9i;m t n*ng 9A chK th< Z dng ra l Ct, trong kho3nh khic dt th; tch dng ra l FV.dt v l5Png chK th< 9i ra l Ct.FV.dt, 9 chnh l l5Png chK th< c trong thi6t b< tf t 96n t+dt. Tf 9<nh nghMa vT E(t) l5Png chK th< 9 bhng q0.E(t).dt, ta c:
q0 . E(t) . dt = FV . Ct . dt. ( 2.34 )

Tf 9 : E(t) = FV . Ct / q0
( 2.35 )
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ta "; xc <nh hm E(t) cFn bi6t q0, ; lm vi>c ny lOy tch phn ph!'ng trnh (2.34):
q .E(t).dt = F .C .dt,theo (2.1): E(t).dt

0 V t 0 0
0
=1
Ta c: q0=
FV. Ct .dt = FV. Ct.t

0 0
Tf :
E(t) = Ct /
C
0
.dt = C t / Ct.t
0
q . E ( t ) . d =t F
0 0 0
. Ct . d t
(2 . 36)
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Bi tEp 2.4 - Cho tn hi>u vo d2ng xung, n*ng 9A chK th< ra 9o 95Pc nh5 Z b3ng sau , xc 9<nh hm E(t) . t , ph : 0 C , g/l : 0 LGi gi3i: -Hm E(t) 95Pc tnh theo pt (2.36) : -Tr5Yc tin tnh Ct . t = 5(3+5+5+4+2+1) = 100. -VEy E(t) = Ct / 100, k6t qu3 nh5 Z b3ng sau: t , ph : 0 E(t).102: 0 5 3 10 5 15 5 20 4 25 2 30 1 35 0
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5 3
10 5
15 5
20 4
25 2
30 1
35 0
-b5Gng bi;u diQn n*ng 9A chK th< ra theo t nh5 Z hnh 2.13.
-Di>n tch giYi h2n bZi 95Gng bi;u diQn v tr?c honh l gi tr< câ tch phn, cn di>n tch cc chJ nhEt l gi tr< câ tLng.
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2/ Xc 9<nh 9A chuy;n ho X qua gi tr< hm phn b: TGL:

Nh5 9 nghin c4u Z trn, dng 9i ra khmi thi6t b< lm vi>c lin t?c khng ph3i l dng 9*ng nhOt vT TGL v nh5 vEy, n*ng 9A câ chOt ph3n 4ng Z dng ra ( tf 9 tnh 9A chuy;n ho X = 1 - Cra/C0 ) l n*ng 9A trung bnh câ cc phFn t_ câ dng vYi TGL trong thi6t b< khc nhau . Do 9 c th; vi6t:
Cra = ]Cng.t;.E(t).dt = Cng.t;.E(t).t t = 0, ^ (2.37)
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Trong 9: C nguyn t: c th; tnh 95Pc tf ph51ng trnh 9Ang hUc câ ph3n 4ng. E(t).dt - PhFn câ dng c TGL tf t 96n t+dt [ tf 9<nh nghMa câ E(t) ]. Tf 9 tnh 95Pc 9A chuy;n ho X:

X =1-Cra/C0=1-(
C
0
nguyento
.E (t ).t /C0)
( 2 . 38 ) .
88
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Bi tEp 2.5- Ph3n 4ng bEc 1 chuy;n ho chOt A, hhng s: vEn t:c k = 0,307 ph-1, 95Pc ti6n hnh trong TBP( c hm phn b: TGL E(t) nh5 Z bi tEp 2.4. Xc 9<nh 9A chuy;n ho X. LGi gi3i: - Ph51ng trnh vEn t:c câ ph3n 4ng bEc 1: -dCA / dt = kC, gi3i vYi 9iTu ki>n khi t = 0 th CA = CA0,, 95Pc C A nguyn t: = CA0 . e-kt , thay vo pt(2.37): kt CA ra = CA0 . e .E(t). )t . 0 ( 2 . 39 )
89
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t , ph 5 10 15 20 25 30
LEp b3ng tnh ph51ng trnh (2.39): E(t) 0,03 0,05 0,05 0,04 0,02 0,01 k.t 1,53 3,07 4,60 6,14 7,68 9,21 e-kt 0,2154 0,0464 0,0100 0,0021 0,0005 0,0001 e-kt . E(t) . t 0,0323 0,0116 0,0025 0,0004 0,00005 0
CAra - C A0 = e-kt . E(t) . t = 0,047 XA = 1 - CAra/CA0 = 1 - 0,047 = 0,953.

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Bi tEp 2.6- Ti6n hnh ph3n 4ng bEc 1 nh! bi tEp 2.5 trong thi6t b< ph3n 4ng c TGL trung bnh nh! Z bi tEp 2.4 nh!ng dng ch3y theo ch6 A "LT. LGi gi3i: -ThGi gian l!u trung bnh câ thi6t b< Z bi tEp 2.4 theo cng th4c(2.2). !Pc xc <nh 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. -Thi6t b< theo m hnh "LT c TGL *ng Tu v bhng tTB. VYi ph3n 4ng bEc 1 tf pt dCA/dt=kCA, c: CA / CA0 = e-ktTB = e-0,3.15 = 0,01. XA = 1 - CA/CA0 = 1 - 0,01 = 0,99 .
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91
III/THI$T B& PH(N +NG LO.I THNG C KHU/Y

- Th5Gng dng cho pha lmng, 9Ic bi>t Z cc qu trnh d< th; lmng - lmng, lmng - rin, lmng - kh v lmng - rin - kh 9; t.ng c5Gng ti6p xc cc pha. - Do khuOy nn n*ng 9A, nhi>t 9A 9*ng 9Tu trong khip thi6t b<, nh5ng nh5 9 ni Z trn, TGL Z thi6t b< lm vi>c lin t?c phn b: tf 0 96n . - KhuOy t.ng c5Gng h> s: trao 9Li nhi>t giJa mi tr5Gng ph3n 4ng vYi thnh thi6t b<. - M hnh l KLT.
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III.1- Thi6t b< lm vi>c gin 9o2n:

- ChK dng cho pha lmng, qui m s3n xuOt nhm. - Tnh th; tch thi6t b< VR: VR = Vngy <m.(1 + z).tm_ / 24 . n = Vngy <m.(1 + z).tm_ / 24.VR. . Trong 9: Vngy 9m - Th; tch s3n ph`m 9i ra trong 24 giG z - H> s: dl trJ 9T phng cc sl c: bOt th5Gng. Th5Gng z c gi tr< tf 0,10 96n 0,15, khi thi6t b< ph4c t2p hay lm vi>c Z nhi>t 9A v p suOt caoc th; lOy tf 0,15 96n 0,20.
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(3.1) (3.2)
-N6u th; tch thi6t b< VR 9 chUn, ta tnh s: thi6t b< n:
Thi6t b< lm vi>c gin 9o2n

- H> s: 9Fy . Th5Gng vYi thi6t b< ph3n 4ng c khuOy lOy gi tr< tf 0,75 96n 0,80 ; tr5Gng hPp mi tr5Gng ph3n 4ng t2o bUt c th; lOy 96n 0,40. tm+- ThGi gian ti6n hnh mAt m+, g*m thGi gian chu`n b< v thGi gian ti6n hnh ph3n 4ng. Trong 9: -t chu`n b< = t n2p li>u + t 9un nng nguyn li>u tf nhi>t 9A 9Fu 96n nhi>t 9A ph3n 4ng + t lm nguAi s3n ph`m + t tho s3n ph`m + t lm s2ch thi6t b< cho m+ sau ... - t ph3n 4ng 95Pc xc 9<nh tf cc thng tin sau: *Tnh theo ph51ng trnh vEn t:c vYi X xc 9<nh. *Theo s: li>u thlc nghi>m 9 c, v d? 9* th< t-X thlc nghi>m.
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III.2-Thi6t b< lm vi>c lin t?c:

*Tnh ton theo m hnh KLT. *Dng ph51ng php 92i s: v ph51ng php dlng hnh. a/Ph51ng php 92i s::
-LEp ph51ng trnh cn bhng chOt cho thi6t b< th4 i ( hnh 3.1 ): Ci-1.F V(i-1) = Ci.FVi + Ri.VRi + dCi.VRi/dt. (3.3)
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Thi6t b< lm vi>c lin t?c
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Ci-1.F V(i-1) = Ci.FVi + Ri.VRi + dCi.VRi/dt. Trong 9:
(3.3)
Ci-1 : N*ng 9A chOt ph3n 4ng 9i vo thi6t b< th4 i. Ci : N*ng 9A chOt ph3n 4ng trong thi6t b< i v l n*ng 9A 9i ra. F V(i-1) v FVi : L5u l5Png câ dng vo v ra. VRn : Th; tch thi6t b< th4 i. dCi.VRi/dt : L5Png chOt ph3n 4ng tch t? trong thi6t b< i. Ri = ki . f(Ci) : VEn t:c ph3n 4ng Z thi6t b< th4 i.
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o tr2ng thi dfng khng c tch t?, ta c: C i-1.F V(i-1) = Ci.F Vi + Ri.VRi C i-1 = C i . F Vi/F V(i-1) + Ri . VRi /F V(i-1) . o pha lmng coi nh5 hSn hPp ph3n 4ng khng thay 9Li th; tch, nghMa l l5u l5Png dng khng 9Li: F V(i-1) = F Vi = FV, 95Pc: hay
C i-1 = Ci + tTBi . Ri
(3.4)
Trong 9 tTBi l TGL trung bnh Z thi6t b< th4 i, tTBi = VRi/FV. Ph51ng trnh (3.4) 95Pc gUi l pt 7Uc tr3ng câ TBP( lo2i thng c khuOy. Tf pt ny c th; tnh 9A chuy;n ho X v th; tch thi6t b< VRi.
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*VYi ph3n 4ng chuy;n ho chOt A s3n ph`m: -BEc 0 : Ri = ki ; C i-1 = Ci + ki . tTBi . pt (3.4) thnh: ( 3 . 4 )'
-BEc1 : Ri = ki.Ci ; pt (3.4) thnh: C i-1 = Ci + ki . tTBi . Ci hay C i-1/Ci = 1+ ki . tTBi . -BEc2 : Ri = ki.Ci2; ( 3 . 4 )''
pt (3.4) thnh: ( 3 . 4 )'''

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C i-1 = Ci + ki . tTBi.Ci2
Bi tp 3.1: Tnh 9A chuy;n ho X câ ph3n 4ng bEc 1 nh5 Z bi tEp 2.5, ti6n hnh trong thi6t b< thng c khuOy c TGL trung bnh l 15 pht nh5 Z bi tEp 2.4
LGi gi3i: VYi i = 1, tf ph51ng 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 k6t qu3 tnh ton vYi bi tEp 2.5 v 2.6 thOy rhng Z cng mAt 9iTu ki>n , thi6t b< theo ch6 9A KLT c 9A chuy;n ho thOp nhOt.
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-LEp ph51ng trnh cn bhng chOt cho h> th:ng n thi6t b< khuOy n:i ti6p:
Dng ph51ng trnh (3.4) v bit 9Fu tf thi6t b< 1 96n n *Khi th; tch cc thi6t b< trong h> th:ng khng bhng nhau: VRi VRj tTBi tTBj V nhi>t 9A Z cc thi6t b< khng bhng nhau Ti Tj ki kj .
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Ph3n 4ng bEc 0: i=1 i=2 i=3 ... i=n C0 - C1 = k1 . tTB1 C1 - C2 = k2 . tTB2 C2 - C3 = k3 . t TB3 ...... C n-1 - Cn = kn . tTBn . i = 1, n (3.5)
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CAng cc ph51ng trnh theo tfng v6 95Pc: C0 - Cn = ki.tTBi Xn0= ki.tTBi / C0
Ph3n 4ng bEc 1:

i=1 i=2 i=3 ... i=n Nhn cc ph!'ng n C0 / Cn = Tf l: C0 / C1 = 1 + k1 . tTB1 C1 / C2 = 1 + k2 . tTB2 C2 / C3 = 1 + k3 . tTB3 ... C n-1 / Cn = 1 + kn . tTBn . trnh theo tfng v6, !Pc:
i TBi
i=1 A chuy;n ho Z thi6t b< n :i vYi ph3n 4ng bEc 1
(1+ k .t
)
n
Xn1= 1 - Cn / C0 = 1 - 1 /
(1+k .t
i=1
i TBi ( 3 . 6 )
).
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103
Ph3n 4ng bEc 2:

Gi3i pt (3.4)''' C i = (- 1 i=1
!Pc:
1 + 4ki ti Ci 1
) / 2ki.tTBi . ) / 2k1.tTB1
C1= (- 1
1 + 4k1t1C 0
i = 2 C2= (- 1 1 + 4k 2 t 2 C1 ) / 2k2.tTB2 Thay C1 vo ta c: C2 = [-1
1+ 4k2t2 (1 1+ 4k1t1Co ) / 2k1t1]/2k2.tTB2 .

(3.7)
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*Khi th; tch cc thi6t b< trong h> th:ng bhng nhau: VRi = VRj tTBi = tTBj = tTB . v nhi>t 9A Z cc thi6t b< bhng nhau: Ti = T j k i = k j = k . bA chuy;n ho câ ph3n 4ng bEc 0 trong h> th:ng n thi6t b< n:i ti6p theo cng th4c (3.5) thnh: Xn0 = ( C0 - Cn ) / C0 = n.k.tTB / C0 . ( 3 . 5 )' bA chuy;n ho câ ph3n 4ng bEc 1 trong h> th:ng n thi6t b< n:i ti6p theo cng th4c (3.6) thnh: Xn1 = 1 - Cn/C0 = 1 - ( 1 + k . tTB )-n . ( 3 . 6 )'
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b/Ph51ng php dlng hnh:

Ph51ng trnh (3.4) c th; vi6t l2i Z d2ng: Ri = -Ci / tTBi + C i-1 / tTBi . (3.8)
V6 tri câ pt (3.8) l hm s: xc 9<nh câ Ci: Ri = ki . f( Ci ), ta ve 95Gng bi;u diQn câ R ph? thuAc vo C ( hnh 3.2 ). V6 ph3i l hm s: tuy6n tnh câ Ci, giao 7iBm cJa hai 73Ing biBu diTn l nghi6m cJa ph30ng trnh (3.8).
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Ph51ng php dlng hnh
b5Gng thBng bi;u diQn v6 ph3i c h> s: gc l -1/tTBi.
b5Gng thBng 9Fu tin ( i = 1 ) bit 9Fu tf tr?c honh t2i C0 vYi h> s: gc l -1/tTB1 giao 9i;m câ 95Gng thBng ny vYi 95Gng cong R c to2 9A 4ng vYi C1 v R1, l n*ng 9A chOt ph3n 4ng v vEn t:c ph3n 4ng Z thi6t b< 1.
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Ph51ng php dlng hnh
Tf C1 trn tr?c honh ve 95Gng thBng vYi h> s: gc l -1/tTB2, ta 95Pc C2 v R2 ... v c4 th6 ti6p t?c 96n khi 92t Cn C yu cFu. Bi ton 9 95Pc gi3i, ta tm 95Pc s: thi6t b< n câ h> th:ng cjng nh5 cc thng s: n*ng 9A chOt ph3n 4ng C v vEn t:c ph3n 4ng R trong tfng thi6t b< . N6u nhi>t 9A Z cc thi6t b< khc nhau, ki - kj, 4ng vYi mSi nhi>t 9A ph3i ve 95Gng bi;u diQn Ri = ki . f (C) t51ng 4ng .
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Ph51ng php dlng hnh
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109
Bi tEp 3.2 Ph3n 4ng thuEn ngh<ch 2A B + C, hhng s: vEn t:c ph3n 4ng thuEn kth = 10 m3/kmol.h, hhng s: cn bhng Kcb = 16, n*ng 9A ban 9Fu CA0 = 1,5 kmol/m3, CB0 = CC0 = 0, ti6n hnh trong thi6t b< ph3n 4ng lo2i thng c khuOy vYi l5u l5Png dng FV = 100 m3/h. bA chuy;n ho X yu cFu bhng 80% tr2ng thi cn bhng. Tnh: a/Th; tch TBP( khi ti6n hnh trong mAt thi6t b< VR1. b/S: thi6t b< n câ h> th:ng n6u lOy VRn = VR1/10.
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LGi gi3i:
a/bIt n*ng 9A câ B v C Z tr2ng thi cn bhng l CBcb = CCcb = Ccb. Ta c: CAcb = 1,5 - 2Ccb. Kcb = C2cb / (1,5 - 2Ccb )2 =16. Gi3i 95Pc Ccb = 0,667 kmol/m3. X yu cFu bhng 80% tr2ng thi cn bhng nn n*ng 9A yu cFu câ B v C nh5 sau: CByu cFu = C Cyu cFu = 0,80.Ccb =0,80.0,667 = 0,533 kmol/m3.
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VEy CAyu cFu = 1,5 - 2 . 0,533 = 0,434 kmol/m3. Ph51ng trnh vEn t:c câ ph3n 4ng thuEn ngh<ch chuy;n ho chOt A c d2ng: Ta c: RA = kth.CA2 - kng . CB .CC = kth ( CA2 - CB . CC/ Kcb ) v kng = kth/Kcb.
RA = 10 ( CA2 - CB .CC /16 ).
( 3.9 )
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VEn t:c ph3n 4ng trong h> th:ng ph3n 4ng mAt thi6t b< l: RA(1) = 10 [ (0,434)2 - (0,533)2/16 ] = 1,7 kmol/m3.h. Tf pt 9Ic tr5ng (3.4) vYi i = 1 ta c: tTB1 = VR1 / FV = ( C0 - C1 ) / R1 . Do 9: VR1 = FV . ( C0 - C1 ) / R1 . VR1 = 100 ( 1,5 - 0,434 ) / 1,7 = 62,7 m3. Thay s: vo , ta 95Pc:
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b/N6u lOy VRn = 1/10 VR1 = 6,27 m3, 9; tm s: thi6t b< n câ h> th:ng khuOy n:i ti6p ta dng ph51ng php dlng hnh. Ve 95Gng bi;u diQn RA ph? thuAc vo CA theo ph51ng trnh vEn t:c (3.9): cho CA cc gi tr< tf 0 96n 1,5 kmol/m3 Xc 9<nh CB , CC t51ng 4ng v tnh RA nh5 Z b3ng sau: CA, CB,CC 1,5 1,3 0 0,1 1,1 0,9 0,7 0,5 0,3 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

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Tf CA = CA0 = 1,5 kmol/m3 ve 95Gng thBng t2o vYi tr?c honh gc r: tg = - 1/tTB= - 100/6,27 = -15,9 b5Gng thBng ny cit 95Gng cong RA Z 9i;m c to2 9A CA1 = 0,94 kmol/m3 v RA1 = 8,9 kmol/m3.h
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Tf CA1 ti6p t?c ve 95Gng thBng song song vYi 95Gng thBng tr5Yc( v cng h> s: gc ) ta 95Pc giao 9i;m th4 2 vYi to2 9A t51ng 4ng l CA2 v RA2 ( hnh 3.3 ), c4 th6 ti6p t?c 95Pc k6t qu3 nh5 sau: CA1 = 0,94 kmol/m3 CA2 = 0,68 CA3 = 0,52 CA4 = 0,42 RA1 = 0,89 kmol/m3.h RA2 =4,52 RA3 = 2,65 RA4 = 1,70
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117
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Nh5 vEy CA4 < CA yu cFu , ta c s: thi6t b< trong h> th:ng n = 4 . Cjng cFn l5u rhng th; tch cc thi6t b< trong h> th:ng l 4 . 6,27 = 25 m3, nhm h1n nhiTu so vYi th; tch ph3n 4ng khi dng mAt thi6t b<. (biTu ny cFn 95Pc gi3i thch?)
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IV/CVC TR&NG NHI#T TRONG THIXT BY PH[N ]NG
Ph3n 4ng ho hUc lun c hi>u 4ng nhi>t, th5Gng kh lYn 9; c th; thay 9Li nhi>t 9A câ qu trnh. Nhi>t 9A l thng s: c5Gng tnh, 3nh h5Zng m2nh 96n vEn t:c ph3n 4ng. Do 9 kh:ng ch6 nhi>t 9A ph3n 4ng lin quan 96n lm vi>c an ton câ thi6t b< v qu trnh s3n xuOt.
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Cc gi3i php duy tr ch6 9A nhi>t cho ph3n 4ng 3nh h5Zng 96n k6t cOu, hnh d2ng câ thi6t b< ph3n 4ng. Tr2ng thi dfng câ h> TBP( chK 92t 95Pc khi tho3 mn pt sau:
QR = QS
(4.1)
QR - Nhi>t ph3n 4ng trong 91n v< thGi gian. QS - Nhi>t trao 9Li trong 91n v< thGi gian.
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IV.1-ChE <6 nhi%t t;i
u:
by l nhn t: lun 95Pc ch 96n trong s3n xuOt cng nghi>p, 9Ic bi>t khi cng suOt lYn, 9; 93m b3o n.ng suOt cjng nh5 9A chuy;n ho X câ qu trnh ph3n 4ng. Ch6 9A nhi>t t:i 5u ph? thuAc vo 9Ic tr5ng nhi>t 9Ang, 9Ang hUc câ ph3n 4ng cjng nh5 tnh n.ng câ xc tc Cho nn ch6 9A nhi>t t:i 5u 9a d2ng, tu. tfng tr5Gng hPp c? th;.
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Vi d?: C ph3n 4ng thuEn ngh<ch, to3 nhi>t: A B Hhng s: vEn t:c ph3n 4ng thuEn: k1 = k10 . e-E1/RT Hhng s: vEn t:c ph3n 4ng ngh<ch: k2 = k20 . e-E2/RT Ta c: RA = k1 . CA - k2 . CB = k10..exp(-E1/RT).CA0(1 - XA) - k20.exp(-E2/RT). CA0 . XA Tm ch6 9A nhi>t t:i 5u 93m b3o vEn t:c ph3n 4ng lYn nhOt bhng 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 .
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k10.(1-XA).e -E1/RT(t).E1 = k20. XA.e -E2/RT(t).E2 . LOy loga c3 hai v6:
ln [ k10.(1-XA).E1] - E1/RT(t5) = ln ( k20.XA.E2 ) - E2/RT(t5) . Tf 9:
(E2 - E1)/RT(t5) = ln [ k20.E2.XA/k10.E1.(1-XA). T(t ) = (E2 - E1)/Rln[k20.E2.XA/k10.E1.(1 - XA)]. (4.2)

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Nh5 vEy,ch6 9A nhi>t t:i 5u Z tr5Gng hPp ph3n 4ng thuEn ngh<ch, to3 nhi>t phF thu6c vo <6 chuy=n ho XA nh5 cng th4c (4.2) Lc 9Fu khi XA cn th8p nn tiEn hnh ph(n *ng G nhi%t <6 cao 9; 93m b3o vEn t:c lYn, sau 9 khi XA t7ng ln cQn gi(m dQn nhKt <6. Trong thlc tiQn s3n xuOt, ph3n 4ng c 9Ic tr5ng ny ( nh5 SO2 + 1/2O2 SO3 + q ) 95Pc thlc hi>n trong thi6t b< trong TBP( c nhiTu ng.n xc tc <o,n nhi%t c trao <Ai nhi%t trung gian giJa cc ng.n nh5 Z hnh 4.1 .
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125
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B/ng cch nh v:y qu trnh ph(n *ng trong thiEt bK < $c thRc hi%n theo < Cng dch-dOc quanh chE <6 nhi%t t;i u ( hnh 4.2 ).
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126
IV.2-Cc gi(i php duy tr chE <6 nhi%t t;i u trong thiEt bK ph(n *ng:
a/Trao 9Li nhi>t qua thnh: -Thi6t b< lo2i thng c khuOy vYi v` b2c ngoi v ;ng xoOn trong thi6t b<. -Thi6t b< :ng chm vYi hng nghn :ng vYi bT mIt trao 9Li nhi>t rOt lYn, th5Gng dng cho ph3n 4ng pha kh to3 nhiTu nhi>t.
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b/Dng tc nhn mang nhi>t l kh, lmng hay rin:
-Kh: Kh tr1, kh chy Z nhi>t 9A cao ... v th5Gng dng h1i n5Yc ( c s0n trong nh my v dQ tch khmi s3n ph`m hydrocacbon bhng cch lm l2nh ng5ng t? v phn ly, ngoi ra h1i n5Yc cn gi3m t2o c:c bm vo thnh thi6t b< ). -Lmng: Dung mi hay cc chOt tr1 c trong hSn hPp ph3n 4ng.
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-Rin: VEt li>u rin ch<u nhi>t nh5 g:m, s4, cc vEt li>u silict ... v c3 xc tc rin, 9i;n hnh l qu trnh cr.cking xc tc l ph3n 4ng thu nhi>t, xc tc mau mOt ho2t tnh do b< ph^ c:c bT mIt nn ph3i dng lYp xc tc chuy;n 9Ang v tuFn hon giJa thi6t b< ph3n 4ng v thi6t b< ti sinh b.ng ph3n 4ng 9:t c:c to3 nhi>t nh5 Z hnh 4.4
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c/Tfng phFn o2n nhi>t c trao Li nhi>t trung gian:

-Gi:ng m hnh 4.1. -"i;n hnh l thi6t b< reforming xc tc, hydro ho xc tc ... -VYi TBP( thng c khuOy nh! Z hnh 4.5.
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131
d/biTu chKnh nhi>t 9A ban 9Fu T0 9:i vYi cc qu trnh 9o2n nhi>t. e/Bay h1i cOu t_ c nhi>t 9A si xOp xK nhi>t 9A ph3n 4ng vYi h> th:ng lm l2nh ng5ng t? v cho chOt lmng quay vT TBP( ( hnh 4.6 ).
132
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g/B1m tuFn hon hSn hPp ph3n 4ng qua thi6t b< trao 9Li nhi>t ( h.4.7).
133
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IV.3-bIc tnh tl nhi>t:

-L cc qu trnh tl x3y ra sau khi 95Pc "m*i ". -biTu ki>n tl nhi>t: Ph3n 4ng to3 nhi>t 9^ lYn 9; c th; 95a nhi>t 9A hSn hPp ph3n 4ng tf nhi>t 9A ban 9Fu T0 96n nhi>t 9A lm vi>c câ thi6t b<. C kh3 n.ng trao 9Li nhi>t giJa s3n ph`m hay kh:i ph3n 4ng vYi nguyn li>u 9i vo. biTu ki>n ny ph? thuAc vo 9Ic tr5ng v k6t cOu câ thi6t b< ph3n 4ng.
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-Cc lo,i thiEt bK c kh( n7ng tR nhi%t:
a/Thi6t b< lo2i thng c khuOy: NhG khuOy nguyn li%u <i vo < $c tr6n lWn v@i kh;i ph(n *ng nng 9 c trong thi6t b<, n6u ph3n 4ng to3 nhi>t 9^ lYn th qu trnh ti6n hnh trong lo2i thi6t b< ny c kh3 n.ng tl nhi>t sau khi 95Pc "m*i" (hnh 4.8a ).
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b/Thi6t b< ph3n 4ng d2ng ngUn l_a: Thi6t b< d2ng ny th5Gng 95Pc s_ d?ng 9; ti6n hnh cc ph3n 4ng to3 nhi>t cao nh5 qu trnh clo ho ( 9:t hydro trong mi tr5Gng clo 9; s3n xuOt HCl ) hay qu trnh oxy ho mAt phFn hydrocacbon 9; s3n xuOt axtylen. Trong khng gian chEt h4p câ ngUn l_a nhi>t 9A thay 9Li tf T0 rOt thOp 96n nhi>t 9A cao 9; c th; tl b:c chy, nghMa l ta c gradien vP nhi%t <6, vP nBng <6, vP thE ho h2c r8t l@n (c th; 92t hng v2n 91n v< ), nhG 9 qu trnh truyPn nhKt, chuy=n ch8t v ho,t ho x(y ra m,nh ma trn mMt c>a ng2n lUa 9; n c th; tl nhi>t (hnh 4.8b ).
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c/Thi6t b< ph3n 4ng lo2i :ng:

- b; c th; tl nhi>t cFn c sl ( hnh 4.9b ). trao <Ai nhi%t giZa nguyn li%u vo v@i s(n ph-m ph(n *ng (hnh 4.9a) hay v@i kh;i ph(n *ng - o tr5Gng hPp b/ c th; 9iTu chKnh 95Pc nhi>t 9A lm vi>c câ lYp xc tc cjng nh5 nhi>t 9A T1 theo thGi gian lm vi>c câ xc tc bhng cch 9iTu chKnh thng s: .
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c/Qu trnh nhm Z ph,m vi khuEch tn ngoi: - Th5Gng gIp khi ti6n hnh ph(n *ng xc tc kh- rOn, to( nhi%t G nhi%t <6 cao, lc 9 vEn t:c ph3n 4ng lYn v chEm nhOt l cc qu trnh khu6ch tn qua lYp bin giJa pha kh v bT mIt xc tc rin ( hnh 4.10a). - Do trZ llc khu6ch tn ch^ y6u Z lYp bin, hnh 3nh cjng t51ng tl vYi qu trnh truyTn nhi>t giJa bT mIt xc tc v pha kh, nn nhi%t <6 bP mMt xc tc Ts cao h!n nhiPu so v@i nhi%t <6 trong pha kh Tg . - Trn bP mMt xc tc nng qu trnh ph(n *ng tiEp tFc tR tiEn hnh.
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- Qu trnh cng nghi>p: +Oxy ho NH3 thnh oxit nit1 trn xc tc d2ng l5Yi Pt-Rh Z nhi>t 9A 800 8500C. +Amonoxi ho CH4 thnh HCN trn xc tc d2ng l5Yi Pt-Rh Z 1000 12000C.
+Oxi9hydro ho mtanol thnh fomaldhit trn xc tc Ag Z 650 - 7200C ( hnh 4.10b).

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-b; qu trnh c th; ti6n hnh tl nhi>t, khi mG my cQn ph(i <un nng h\n h$p mtanol - khng kh <En 300 - 4000C. Sau 9, khi lYp xc tc l cc tinh th; b2c 9It trn l5Yi 9*ng nng 96n nhi>t 9A ph3n 4ng th dfng 9un nng, k6t thc qu trnh "mBi " ph3n 4ng. -TBP( cn c mng phng nL v thi6t b< lm l2nh :ng chm 9It st ngay sau lYp xc tc 9; lm l2nh nhanh hSn hPp s3n ph`m tf nhi>t 9A ph3n 4ng xu:ng 200 - 3000C, gi3m phn hua fomal9ehit t2o thnh Z nhi>t 9A cao theo ph3n 4ng: CH2O CO + H2
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IV.4-bIc tr5ng nhi>t câ TBP( lo2i thng c khuOy:

*Nhi>t 9A 9*ng 9Tu khip thi6t b<. *C kh3 n.ng tl nhi>t.
a/Cc tr,ng thi dNng:

biTu ki>n dfng: QR = QS (4.3) Trong 9 QR - nhi>t ph3n 4ng trong 91n v< thGi gian. QS - nhi>t trao 9Li trong 91n v< thGi gian. b; gi3i pt (4.3) ta dng ph51ng php dlng hnh : kh3o st 95Gng bi;u diQn câ QR v QS theo T, nghi>m câ pt l giao 9i;m câ hai 95Gng bi;u diQn.
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Gi3 s_ c ph3n 4ng bEc 1 chuy;n ho chOt A, to3 nhi>t, khng thuEn ngh<ch, ti6n hnh trong TBP( lo2i thng c khuOy th; tch VR . S: mol chOt A chuy;n ho trong 91n v< thGi gian l NA, do 9: QR = NA . ( - HR ) NA = k . CA . VR CA l n*ng 9A trong thi6t b<, rt ra tf pt (3.4)'' CA = CA0 / ( 1 + k . tTB ) . Tf 9: 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 9: QR = k0 . CA0 . VR . (-HR) / ( e E/RT + k0 . tTB ) ( 4 . 4 )
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+Kh(o st QR :
"!Gng bi;u diQn câ QR ph? thuAc vo T theo pt (4.4) c d2ng chJ S, ngoi ra khi cc thng s: khc nh! VR, FV thay Li ta !Pc mAt hU !Gng cong S trong mIt phBng vYi tr?c to2 A QR - T nh! hnh 4.11.
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+Kh3o st QS:
QS c hai thnh phFn: T. - Trao 9Li nhi>t vYi nguyn li>u vo, nhit 9A nguyn li>u tf T0 -Trao 9Li nhi>t qua thnh.
QS = FV..CP( T - T0 ) + K.F. ( T - TC ).
Trong 9:
( 4 . 5 ) hay
QS = ( FV..CP+ K.F ) T - ( FV..CP.T0 + K.F.TC )

- Kh:i l5Png ring câ hSn hPp ph3n 4ng. K - H> s: trao 9Li nhi>t qua thnh. CP- Nhi>t dung ring câ hSn hPp ph3n 4ng.T - Nhi>t 9A ph3n 4ng. T0- Nhi>t 9A vo. F - BT mIt trao 9Li nhi>t câ thi6t b<. TC- Nhi>t 9A thnh thi6t b<.
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"!Gng bi;u diQn câ QS theo T l !Gng thBng, khi F thay Li ta c cc !Gng thBng vYi h> s: gc thay Li ( hnh 4.12a ), khi T0 thay Li c cc !Gng thBng song song (hnh 4.12b).
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Nh5 vEy, c th; c 3 giao 9i;m giJa 95Gng QR d2ng chJ S v 95Gng thBng QS, nghMa l c 3 tr,ng thi dNng c>a h% th;ng ( hnh 4.13 ).Tr2ng thi dfng 1 c T1 thOp v QR1,QS1 9Tu thOp, ph3n 4ng hFu nh5 khng x3y ra. Tr2ng thi dfng 3 Z nhi>t 9A cao T3 do 9 c 9A chuy;n ho cao , l 9iTu ta mong 9Pi. Tr2ng thi dfng 2 khng Ln 9<nh, se 95Pc kh3o st Z m?c 3/.
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b/Tr,ng thi dNng phF thu6c vo chiPu thay <Ai c>a cc thng s; v bi%n php mBi ph(n *ng: a/Gi3 s_ FV thay 9Li, cc thng s: khc c: 9<nh: QR l cc 95Gng cong A, B, C, D v E, QS coi nh5 khng 9Li,95Pc cc tr2ng thi dfng tf 1 96n 9, 4ng vYi nhi>t 9A dfng tf T196n T9 nh5 hnh 4.14.
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-Khi FV t.ng tf thOp ln cao ta 95Pc cc 95Gng QR lFn l5Pt l A, B, C, D v E, cc tr2ng thi dfng l 9, 8, 7, 6 v 1. -Ng5Pc l2i, khi FV gi3m tf cao xu:ng, cc 95Gng QR lFn l5Pt l E, D, C, B v A, cc tr2ng thi dfng l 1, 2, 3, 4 v 9. Nh5 vEy, tr,ng thi dNng phF thu6c vo chiPu thay <Ai c>a FV nh5 Z hnh 4.15
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TdNng 9 8 7 6
4 3 A B C 2 D 1 E FV
H.4.15- Cc nhi%t <6 dNng phF thu6c vo chiPu thay <Ai c>a FV
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Tf 9 rt ra cch m*i ph3n 4ng: Khi mZ my ban 9Fu dng l5u l5Png dng FV thOp 9; ph3n 4ng ti6n hnh Z tr2ng thi dfng c 9A chuy;n ho v nhi>t 9A dfng cao ( T9 ), sau 9 t.ng dFn FV 96n n.ng suOt thi6t k6 ( nh5ng khng th; t.ng qu 95Gng D ).
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b/Gi3 s_ T0 thay 9Li, cc thng s: khc c: 9<nh: QR khng 9Li, QS l cc 95Gng thBng song song , ta 95Pc cc tr2ng thi dfng tf 1 96n 9 nh5 Z hnh 4.16a.
- Khi T0 t.ng tf thOp ln, QS lFn l5Pt l cc 95Gng thBng A, B, C, D v E, cc tr2ng thi dfng l 1, 2, 3, 4 v 9. -Ng5Pc l2i, khi T0 tf cao gi3m xu:ng, QS lFn l5Pt l cc 95Gng thBng E, D, C, B v A, cc tr2ng thi dfng l 9, 8, 7, 6 v 1. Nh5 vEy, tr,ng thi dNng phF thu6c vo chiPu thay <Ai c>a T0 nh5 Z hnh 4.16b.
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Tf 9 rt ra bi>n php m*i ph3n 4ng: khi mG my <un nng nguyn li%u vo 9; QS 96n qu 95Gng D(v d? 95Gng E) 9; 92t tr2ng thi dfng 9 Sau 9 c th; gi3m (hay ngfng) 9un nng 9; 9i vo tr2ng thi dfng 8, 7, 6 (4ng vYi cc 95Gng QS l D, C v B) l cc tr2ng thi dfng c nhi>t 9A v 9A chuy;n ho cao, m khng b< r1i vo tr2ng thi dfng c nhi>t 9A v 9A chuy;n ho thOp( tuy rhng vYi cc 95Gng QS l B, C v D ta c th; gIp cc tr2ng thi dfng 2, 3 v 4).
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c/bA Ln 9<nh câ TBP(: -Tr2ng thi dfng 5 ( hnh 4.14 v 4.16a ) khng Ln 9<nh
N6u c mAt nhiQu lo2n no 9, nh5 khi T > T5, lc 9 QR > QS, h> th:ng 95Pc 9un nng bhng nhi>t ph3n 4ng v 96n T7 Ng5Pc l2i khi T < T5 th QR < QS, h> b< nguAi 9i v vT T3. Tf 9 c th; rt ra 9iTu ki>n Ln 9<nh câ cc tr2ng thi dfng l: dQS / dT > dQR / dT (4.6)
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IV.5-bIc tr5ng nhi>t câ thi6t b< lo2i :ng:

-Do khng c khuOy trAn nn nhi>t 9A câ thi6t b< lo2i ny thay <Ai tf 9i;m ny 96n 9i;m khc trong thi6t b<. -zng th5Gng c ti6t di>n trn phn b: nhi>t 9A trong :ng c trFc <;i x*ng l trFc tm ;ng, do vEy c th; diQn t3 hnh 3nh phn b: nhi>t 9A trong khng gian thi6t b< theo hai thng s: l v r.
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a/Phn b; nhi%t <6 trong ;ng ph(n *ng: Ph3n 4ng to3 nhi>t khng c trao 9Li nhi>t qua thnh, ch3y r:i hay c lYp h2t xc tc tMnh ( m hnh bLT ): -Nhi>t 9A 9*ng 9Tu theo h5Yng 95Gng knh :ng ( h5Yng r ). -Nhi>t 9A thay 9Li theo h5Yng tr?c :ng ( h5Yng l ). -Ph? thuAc vo vEn t:c ph3n 4ng ( ho2t tnh xc tc ) ta c hnh 3nh nhi>t 9A nh5 hnh 4.17
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*Ph3n 4ng to3 nhi>t c trao 9Li nhi>t qua thnh: -Nhi>t 9A thay 9Li theo c3 hai h5Yng l v r. -C1 ch6 truyTn nhi>t trong lYp h2t c 3 thnh phFn: +DWn nhi%t c>a l@p h,t: b v h2t x:p v di>n ti6p xc nhm. +DWn nhi%t c>a l u th=: pha kh th5Gng nhm. +TruyPn nhi%t do dng l u th= chuy=n <6ng mang nhi%t: th Cng <ng vai tr ch> yEu.
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-Tm :ng c nhi>t 9A cao nhOt ( ph3n 4ng thu nhi>t c hnh 3nh ng5Pc l2i ). -Trn tm :ng th5Gng t*n t2i Tmax , n!i ph(n *ng x(y ra m,nh ma do nhi%t <6 cao, < $c g2i l "<i=m nng'' hay "vng ph(n *ng'' v 95Pc ch theo di trong qu trnh lm vi>c câ thi6t b< cjng nh5 khi thi6t k6 TBP(. -MAt hnh 3nh vT phn b: nhi>t 9A vYi cc 95Gng 9*ng m4c T c th; diQn t3 Z hnh 4.18
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CFn tnh thm thnh phFn khu6ch tn theo h5Yng 95Gng knh vYi h> s: khu6ch tn ngang l Dr v 95a vo pt mAt th4 nguyn (2.27). +Tnh thnh phFn kt ngang ( k hi>u l A ) cho nguyn t: th; tch 2r.dr.dl theo hnh 4.19
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A = L5Png ra - L5Png 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: h2ng 2C/r2.dr2 qu b, bm qua v chia ti6p cho rdr: A/2r.dr.dl = -Dr ( 2C/r2 + 1/r.C/r ) (4 . 7)
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b5a thnh phFn khu6ch tn ngang A / 2r.dr.dl tf (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 truyTn nhi>t t51ng tl chuy;n chOt, nn c th; vi6t: v.CP.T/l - l.2T/l2 - r (2T/r2 + 1/r.T/r)
+ ( -HR)i . Ri = 0. i= 1, n. (4.9)
Trong 9:+ CP-Nhi>t dung ring câ hSn hPp ph3n 4ng. + l -H> s: truyTn nhi>t theo h5Yng tr?c :ng. :ng. + r -H> s: truyTn nhi>t theo h5Yng 95Gng knh +(-HR)i-Nhi>t câ ph3n 4ng th4 i.
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Nh5 vEy: v.C/l -Chuy;n chOt vYi dng ch3y c vEn t:c v. v.CP.T/l -TruyTn nhi>t do dng chOt mang nhi>t. -l.2T/l2 -TruyTn nhi>t theo h5Yng tr?c :ng. -r(2T/r2 + 1/r.T/r) -TruyTn nhi>t theo h5Yng 95Gng knh :ng. (-HR)i.Ri -TLng nhi>t ph3n 4ng chnh v ph?.
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b/bi;m nng Tmax: -VYi ph3n 4ng to3 nhi>t, c trao 9Li nhi>t qua thnh, t*n t2i Tmax trn tr?c tm :ng nh5 hnh (4.18). -V< tr v gi tr< Tmax -9:i vYi mAt qu trnh ph3n 4ng, kch th5Yc :ng v 9iTu ki>n trao 9Li nhi>t xc 9<nh-ph? thuAc vo ho,t tnh xc tc (nghMa l ph? thuAc vo vEn t:c ph3n 4ng ) nh5 Z hnh 4.20
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-Xc <Knh cc thng s; (nh h Gng <En Tmax: Dng FV 9i qua nguyn t: th; tch S.dl, nhi>t 9A thay 9Li l dT v n*ng 9A chOt ph3n 4ng thay 9Li mAt 92i l5Png l dC (hnh 4.21)
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Ta c pt cn b/ng n7ng l $ng c>a dng
- FV..dh + dQ = 0
Trong < dh- Thay <Ai entalpi c>a dng dh = CP.dT + HR.dC CP- Nhi%t dung ring c>a dng. HR- Entalpi c>a ph(n *ng.
( 4 . 10 )
- Kh;i l $ng ring c>a h\n h$p ph(n *ng. dQ- Nhi%t trao <Ai qua thnh ( < a vo l8y d8u +, ra l8y d8u - ).
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Gi3 s_ ph3n 4ng to3 nhi>t, lm l2nh ngoi thnh :ng ph3n 4ng: dQ = -K.( T - TC ).P.dl K- H> s: trao 9Li nhi>t qua thnh. TC- Nhi>t 9A câ thnh. P- Chu vi câ :ng ph3n 4ng. Ta c bn knh thua llc câ :ng ph3n 4ng: 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 )
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Ph51ng trnh cn bhng vEt chOt trong S.dl vYi vEn t:c ph3n 4ng l R: FV..dC = S.dl.R S.dl = FV..dC / R. Thay S.dl vo pt (4.11) v chia cho FV. -CP.dT - HR.dC - K.(T - TC).dC / RTL.R = 0. ( 4 . 12 ) T2i T = Tmax th dT = 0, ta c: -HR.dC - K.(Tmax- TC).dC /RTL.R = 0. Tf 9
Tmax = TC + (-HR).R.RTL / K
( 4 . 13 )
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Tmax ta l> thuEn vYi nhi>t ph3n 4ng (HR), vEn t:c ph3n 4ng (R) v 95Gng knh :ng ph3n 4ng (RTL).VYi ph3n 4ng c hi>u 4ng nhi>t v kho3ng nhi>t 9A thch hPp khc nhau cFn thi6t k6 kch th5Yc :ng ph3n 4ng ph hPp: -Khi nhi>t ph3n 4ng trong kho3ng 50 96n 200 Kj/mol, 95Gng knh :ng ph3n 4ng c th; tf 20 96n 70 mm ph? thuAc vo 9A nh2y câ sl thay 9Li 9A chUn lUc hay câ ho2t tnh xc tc vo nhi>t 9A. -CFn l5u rhng khi gi3m 95Gng knh :ng câ thi6t b< :ng chm th s: :ng se t.ng m2nh v do 9 gi thnh thi6t b< t.ng vUt ln.
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Tf (4.13):
Tf (4.13):
Tmax ta l> thuEn vYi v:n t;c ph(n *ng R, nghMa l vYi ho,t tnh xc tc. Trong tr5Gng hPp cFn thi6t c th; s_ d?ng xc tc c ho2t tnh thOp (hay xc tc cj) Z 9Fu :ng ph3n 4ng 9; gi3m gi tr< câ Tmax . Tmax ta l> ngh<ch vYi h> s: trao 9Li nhi>t K nn cFn l5u vi>c s_ d?ng tc nhn trao 9Li nhi>t cjng nh5 lm s2ch bT mIt trao 9Li nhi>t 9; 93m b3o K c gi tr< lYn.
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Tf (4.13):
Cu:i cng Tmax ta l> thuEn vYi nhi>t 9A câ chOt t3i nhi>t TC. Tuy vEy, Z TBP( nhi>t 9A chOt t3i nhi>t TC qu thOp se lm nguAi lYp xc tc v do 9 t:c 9A ph3n 4ng cjng nh5 n.ng suOt thi6t b< thOp. biTu 9 lin quan 96n 9Ic 9i;m <6 nh,y nhi%t câ TBP( lo2i :ng nh5 Z phFn sau.
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Chnh tf 9Ic 9i;m ny ph3i ti6n hnh gi3i nhi>t cho cc ph3n 4ng to3 nhi>t Z nhi>t 9A xOp xK nhi>t 9A ph3n 4ng. V d?, khi nhi>t 9A ph3n 4ng l 3000C nh5 Z qu trnh oxy ho mtanol thnh fomaldhit trn xc tc oxit Fe-Mo ph3i lm l2nh bhng dFu nng Z 260-2700C ( hnh 4.22).
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c/bA nh2y nhi>t câTBP( lo2i :ng: -bA nh2y thng s: l hi>n t5Png x3y ra khi mAt thng s: no 9 c thay 9Li t51ng 9:i nhm nh5ng h> th:ng TBP( c sl thay 9Li lYn, vYi thng s: l nhi>t 9A ta c 9A nh2y nhi>t. -MAt v d? 9:i vYi ph3n 4ng bEc1, khng thuEn ngh<ch, to3 nhi>t 9 tm thOy 9A nh2y câ nhi>t 9A 9i;m nng Tmax 9:i vYi cc thng s: TC, K/RTL v T 9o2n nhi>t.
Hnh 4.23 diQn t3 sl thay 9Li nhi>t 9A Tmax khi nhi>t 9A ban 9Fu câ hSn hPp T0=340 K, cn TC thay 9Li tf 300 96n 342,5 K
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Nhn hnh ve ta thOy mi 96n khi TC=335 K, nhi>t 9A trong :ng ph3n 4ng t thay 9Li theo chiTu di :ng, c th; ni lYp xc tc b< nguAi v vEn t:c ph3n 4ng thOp, do 9 9A chuy;n ho X khng 92t yu cFu. Khi t.ng TC thm 2,5 K (TC=337,5 K) 95Gng bi;u diQn nhi>t 9A t2i tm :ng c clc 92i cao h1n T0 96n 80 K (Tmax=420 K). Khi t.ng TC ln mAt t nJa (TC=342,5 K) nhi>t 9A 9i;m nng v5Pt nhi>t 9A ban 9Fu 96n 100 K.
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. d/ bA Ln 9<nh câ TBP( lo2i :ng: -Khc vYi TBP( lo2i thng c khuOy, ph3n 4ng ti6n hnh trong thi6t b< lo2i :ng lun lun Ln 9<nh. Do 9Ic 9i;m câ thi6t b< lo2i ny mAt sl r:i lo2n no 9 t2i mAt th; tch nhm câ :ng ph3n 4ng khng lan rAng ra qui m khip thi6t b< m se b< dng ch3y ko ra khmi zn ph3n 4ng, tr2ng thi dfng câ h> th:ng quay vT tr2ng thi cj. -o TBP( lo2i :ng c trao 9Li nhi>t giJa s3n ph`m 9i ra v nguyn li>u vo ( hay c trao 9Li nhi>t giJa lYp xc tc vYi nguyn li>u vo ) c th; c tr2ng thi dfng khng Ln 9<nh
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V-TBP& XC TC KH-R^N ( XC TC R^N ).
-H> ph3n 4ng vYi xc tc rin rOt hay gIp trong cng nghi>p ho hUc ni chung v ring 9:i vYi cng nghi>p ho dFu. -Cc vOn 9T 95Pc 9It ra 9:i vYi h> ph3n 4ng d< th; ny l: BT mIt ti6p xc pha. Cc bi>n php duy tr ch6 9A nhi>t t:i 5u cho qu trnh: rOt quan trUng v 3nh h5Zng 96n cOu t2o v hnh dng câ thi6t b<. Tr2ng thi lYp xc tc: lYp tMnh, lYp r1i, lYp cu:n theo dng kh.
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V.1-BT mIt ti6p xc pha v hi>u suOt s_ d?ng bT mIt bn trong câ xc tc:
Gi3i php 93m b3o bT mIt ti6p xc pha câ h> kh rin l s_ d?ng xc tc x:p c bT mIt bn trong rOt pht tri;n, tf 1-2 m2/g 96n gFn 1000 m2/g. a/Cc 9.c tr5ng câ xc tc x:p: +BP mMt ring: K hi>u - SR, 91n v< - m2/g.
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MAt s: vEt li>u x:p thng d?ng: Diatomit: SR = 5 - 10 m2/g.Al2O3 ho2t tnh, silicagel: SR = 200 - 400 m2/g.Zolit: SR = 700 - 800 m2/g.Than ho2t tnh: SR = 800 1000 m2/g. VYi cOu trc h2t câ vEt li>u x:p: c h2t s1 cOp v h2t th4 cOp, bT mIt ring l tLng bT mIt cc h2t s1 cOp trong 1 gam vEt li>u. BT mIt ring 95Pc xc 9<nh bhng ph51ng php hOp ph?, tnh theo BET.
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+46 x;p: K hi>u - , 91n v< - cm3/g. L kho3ng tr:ng giJa cc h2t s1 cOp v th4 cOp trong vEt li>u x:p. Ph? thuAc vo sl sip x6p (s: ph:i tr) câ cc h2t s1 cOp v th4 cOp, 9A x:p c th; thay 9Li tf 0,1 96n 1cm3/g.Th5Gng s: ph:i tr gi3m th 9A x:p t.ng v 9A bTn c1 hUc câ vEt li>u gi3m. b5Pc tnh tf kh:i l5Png ring thEt v kh:i l5Png ring bi;u ki6n theo cng th4c: = 1/bk - 1/thEt . (5.1)
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+Phn b; l\ x;p theo kch th @c: LS x:p c kch th5Yc khc nhau do sl sip x6p câ cc h2t s1 cOp v th4 cOp, c th; diQn t3 theo m hnh 5.1, phn chia thnh lS x:p b ( 95Gng knh d5Yi 0,2 nm ), lS x:p trung (tf 0,2 96n 50 nm) v lS x:p lYn (trn 50 nm). Phn b: lS x:p theo kch th5Yc 95Pc xc 9<nh bhng ph51ng php hOp ph?, ng5ng t? mao qu3n v n2p thua ngn d5Yi p suOt ( 96n 250 MPa ).
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190
+H% s; khuEch tn hi%u dFng: bA x:p v phn b: lS x:p theo kch th5Yc l nhJng y6u t: quan trUng 3nh h5Zng 96n qu trnh khu6ch tn trong xc tc x:p. H> s: khu6ch tn hi>u d?ng De trong h2t xc tc c th; diQn t3 theo cng th4c sau: De = D . / (5.2)
Trong 9
D - H> s: khu6ch tn trong pha kh. - bA x:p câ xc tc.
- H> s: ni ln tr2ng thi hnh hUc câ lS x:p: 9A quanh co, g* ghT câ bT mIt lS x:p, sl thay 9Li 95Gng knh câ lS x:p... Th5Gng ta s: / c gi tr< tf 1/10 96n 1/20 v h> s: khu6ch tn hi>u d?ng c th; 95Pc xc 9<nh bhng thlc nghi>m.
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b/Hi%u su8t sU dFng bP mMt bn trong c>a xc tc : Ngoi h% s; khuEch tn hi%u dFng De, cn phF thu6c vo v:n t;c ph(n *ng bP mMt (t*c ho,t tnh c>a xc tc) , vo kch th @c v hnh d,ng c>a h,t xc tc. GQn <ng v@i h,t xc tc c hnh d,ng khc nhau, ta c:
= th /
(5.3)
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Trong < . - Modun Thiele
= Vh/Shb Rs/De
(5.4)
.Vh - Th= tch c>a h,t xc tc. .Sh - BP mMt ngoi c>a h,t xc tc. .Vh/Sh - 4Mc tr ng cho kch th @c h,t xc tc: V@i h,t hnh trF bn knh R, Vh/Sh = R/2. V@i h,t hnh cQu bn knh R, Vh/Sh = R/3. .RS - V:n t;c ph(n *ng bP mMt.
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.Th - Hm tang hyperbolic. Sl ph? thuAc vo theo pt (4.3) 95Pc

di;n t3 Z hnh 5.2.
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194
Tf (5.3) v (5.4), khi kch th5Yc câ h2t xc tc lYn (Vh/Sh lYn), vEn t:c ph3n 4ng bT mIt lYn v h> s: khu6ch tn hi>u d?ng b th lYn, do 9 hi>u suOt s_ d?ng bT mIt xc tc c gi tr< thOp. Tf 9Ic tr5ng câ hm tang hyperbolic ta c:
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-Khi < 1 th th = , do 9 = 1. -Khi 3 th th = 1 , do 9 = 1/.
Do vEy, vYi tfng qu trnh ph3n 4ng yu cFu xc tc c bT mIt ring, kch th5Yc h2t v cOu trc x:p thch hPp 9; c tch s: SR. clc 92i. Ho2t tnh câ mAt 91n v< kh:i l5Png xc tc Ag 95Pc xc 9<nh Ag = As . SR . (5.5)
As Ho2t tnh câ mAt 91n v< bT mIt xc tc

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V.2-LYp xc tc:
a/LYp tMnh: Hay s_ d?ng v 91n gi3n, cho xc tc lu mOt ho2t tnh ( > 6 thng ). H2t xc tc khng 95Pc qu b, th5Gng kch th5Yc tf 3 96n 10 mm, 9; trZ llc câ l5u th; qua lYp khng qu lYn, vYi l5Png xc tc lYn hay FV lYn dng l5u th; chuy;n 9Ang theo h5Yng xuyn tm thay cho h5Yng tr?c :ng.
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Do kch th5Yc h2t xc tc lYn nn hi%u su8t sU dFng bP mMt xc tc th Cng th8p. TBP( th5Gng gIp:
-ThiEt bK ;ng chm, xc tc 9It trong :ng, chOt t3i nhi>t 9i giJa cc :ng. -Thi6t b< c l@p xc tc <o,n nhi%t v@i trao <Ai nhi%t trung gian hay cho thm nguyn li%u l,nh vo 9; 9iTu chKnh nhi>t 9A ph3n 4ng.
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b/LYp chuy;n 9Ang: Dng cho xc tc mau mOt ho2t tnh v c th; lin t?c lOy xc tc 9 lm vi>c ra 9em 9i ti sinh v bL sung xc tc c ho2t tnh cao vo h> th:ng TBP( m khng ph3i ngfng qu trnh. b; thlc hi>n lYp xc tc chuy;n 9Ang thi6t b< c cOu t2o ph4c t2p h1n, tuy nhin ho2t 9A câ lYp xc tc hFu nh5 khng thay 9Li trong su:t qu trnh lm vi>c, 9 l mAt 5u 9i;m c1 b3n 9:i vYi qu trnh lm vi>c lin t?c. Xc tc cFn c 9A bTn c1 hUc cao ch:ng mi mn v v5 v?n trong khi chuy;n 9Ang.
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LYp xc tc chuy;n 9Ang c 3 d2ng vYi nhJng 9Ic 9i;m ring: -LYp r1i: + H2t xc tc chuy;n 9Ang nhG trUng llc. + Kch th5Yc h2t t51ng 951ng vYi lYp tMnh. +CFn c c1 cOu phn ph:i h2t xc tc 9*ng 9Tu trong khip ti6t di>n câ thi6t b< nh5 sng phn ph:i hnh 5.2.
200
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+H>
th:ng TBP( xc tc chuy;n 9Ang lYp r1i c th; diQn t3 Z hnh
5.4.
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201
-LYp si: *biTu ki>n t2o lYp si: Dng kh 9i tf d5Yi ln ng5Pc vYi chiTu trUng llc, khi vEn t:c dng kh 9^ lYn llc nng câ dng kh cn bhng vYi trUng l5Png câ h2t rin, h2t rin bit 9Fu l1 l_ng, th; tch câ lYp nZ rAng ra, ta c tr2ng thi nh5 chOt lmng. TrZ llc câ dng kh hFu nh5 khng thay 9Li khi bit 9Fu t2o tFng si nh5 Z hnh 5.4 .
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*Tnh chOt câ lYp si: Nh ch8t l`ng: MIt thong nhm ngang, ch3y nh5 chOt lmng, tun theo 9<nh luEt Acsimt ... Hi%n t $ng t,o b2t: .Do h2t rin chuy;n 9Ang t2o sl khc nhau vT mEt 9A h2t trong lYp v t2o thnh cc bUt kh. .BUt nh4 nLi ln nhanh trong lYp t2o nn nh5ng phFn t_ kh c TGL thOp nhOt. .BUt 9i ln ko theo 9ui l cc h2t rin, khi ln 96n mIt lYp bUt v5 ra v cc h2t rin l2i chm xu:ng trong lYp huyTn ph ko theo cc phFn t_ kh b< hOp ph? trong xc tc, t2o nn nhJng phFn t_ c TGL lYn.
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Do t2o bUt v chuy;n 9Ang hSn lo2n câ h2t xc tc lYp si c ch6 9A chuy;n 9Ang câ dng gFn vYi m hnh KLT ( hnh 5.5 ) HEu qu3 TGL c>a ch8t ph(n *ng trong l@p xc tc khng <Bng <Pu cFn 95Pc tnh 96n khi ti6n hnh cc ph3n 4ng c 9Ic tr5ng n:i ti6p t2o s3n ph`m ph? nh5 cr.cking xc tc, cc ph3n 4ng oxi ho ...
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206
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H> s: trao 9Li nhi>t giJa lYp si v thnh lYn: Vai tr chnh câ qu trnh trao 9Li nhi>t giJa lYp si vYi thnh l do sl chuy=n <6ng h\n lo,n c>a cc h,t rOn mang nhi%t. VEn t:c trao 9Li nhi>t c th; t.ng hng ch?c lFn so vYi tr5Gng hPp chK c mi tr5Gng kh. H> s: trao 9Li nhi>t K ph? thuAc vo vEn t:c dng câ kh nh5 Z hnh 5.6. NhG tnh chOt ny lYp si ngy cng 95Pc s_ d?ng cho cc qu trnh ph(n *ng xc tc to( nhiPu nhi%t.
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208
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-LYp cu:n theo: Khi vEn t:c dng kh lYn, cc h2t rin cu:n theo dng kh t2o thnh lYp cu:n theo. Tr2ng thi ny 95Pc s_ d?ng rAng ri 9; vEn chuy;n cc vEt li>u rGi d2ng h2t nn cn gUi l lYp vEn chuy;n. Ph? thuAc vo 9Ic tr5ng câ h2t, vEn t:c kh c th; gOp 2 96n 5 lFn vEn t:c h2t
Ch6 9A dng ch3y gFn vYi m hnh 4LT, thGi gian ti6p xc câ pha kh vYi xc tc <Bng <Pu v t !ng <;i ngOn. NhG vEy, lYp cu:n theo 95Pc s_ d?ng thay th6 cho lYp si trong thi6t b< cr.cking xc tc hi>n 92i d2ng :ng 94ng vYi xc tc ch4a zolit c ho2t tnh cao.
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VI-M*T Sz LO8I TBP( TRONG CNG NGHIyP HO D:U

VI.1-L ;ng:
sau: C bT mIt trao 9Li nhi>t lYn v Z nhi>t 9A cao ( > 3000C ) bhng cch 9:t nhin li>u lmng hay kh. Th5Gng gIp trong cng nghi>p ho dFu vYi cc ch4c n.ng
-TBPJ cho cc qu trnh pha kh, kh-rOn, thu nhi%t G nhi%t <6 cao ( 96n 10000C ) nh5 nhi>t phn hydrocacbon c mIt h1i n5Yc ( steam cracking ) 9; s3n xuOt etylen v olefin, chuy;n ho kh tl nhin vYi h1i n5Yc ( steam refoming ) 9; s3n xuOt hi dro v kh tLng hPp (synthesis gases, thnh phFn g*m CO v H2), dehydroclo ho dicloetan 9; s3n xuOt vinyl clorua. -ThiEt bK gia nhi%t hSn hPp nguyn li>u cho cc h> th:ng ch5ng luy>n, cho cc h> th:ng TBP( nh5 cr.cking xc tc, refoming xc tc, dehidro ho xc tc...
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COu t2o câ l :ng g*m 2 phFn: -Zn 9:i l5u: Nhi>t 9A thOp h1n, c1 ch6 trao 9Li nhi>t l do ti6p xc c55ng b4c giJa kh chy vYi :ng tr5Yc khi 9i ra :ng khi. -Zn b4c x2: Nhi>t 9A cao câ bu*ng l_a, n1i 9:t nhin li>u.C1 ch6 trao 9Li nhi>t ch^ y6u l do b4c x2 nhi>t câ bu*ng l_a 96n thnh :ng.
Nguyn li>u 9i ng5Pc chiTu tf cu:i zn 9:i l5u 96n zn b4c x2,Z 9y 92t nhi>t 9A cFn thi6t cho ph3n 4ng, sau 9 95Pc lm l2nh nhanh trnh phn hua s3n ph`m v thu h*i Z d2ng h1i n5Yc p suOt cao ( hnh 6.1 ).
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L c cng suOt nhi>t khc nhau
bIc bi>t l :ng cho qu trnh cracking h1i
s3n xuOt etylen c cng suOt lYn v hi>n 92i, vYi yu cFu 95a nhanh nhi>t 9A nguyn li>u tf zn 9:i l5u Z 450 - 5000C ln 96n nhi>t 9A ph3n 4ng ( 800 - 9000C ) nn :ng trong zn b4c x2 95Pc 9It vo giJa 9; 95Pc b4c x2 tf hai pha ( hnh 6.2 ).
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MAt s: thng s: câ l :ng: 1 96n 100.
-S: dn :ng:
-ChiTu di 1 dn: 20 9n 100 m. -b5Gng knh :ng: 30 96n 80 mm. -ThGi gian l5u trong zn b4c x2: 1 - 2 s .
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215
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H.6.1.3-L :ng cho qu trnh Refoming h1i n5Yc trong s1 9* cng ngh> s3n xuOt NH3 tf kh tl nhin.
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H.6.1.4L :ng trong cng ngh> s3n xuOt NH3 tf kh tl nhin.
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VI.2- H> th:ng thi6t b< cr.cking xc tc: bIc tr5ng câ ph3n 4ng: -Ph3n 4ng ph4c t2p: song song, n:i ti6p theo m hnh sau ( hnh 6.3 )
218
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Trong 9 x7ng l s(n ph-m chnh, kh v c:c l s3n ph`m ph? t2o thnh theo ph(n *ng n;i tiEp chuy=n ho s(n ph-m chnh, do vEy 9; 93m b3o hi>u suOt x.ng cao cFn c TGL <Bng <Pu v ngOn, 9A chuy;n ho X khng qu cao. -Ph3n 4ng ti6n hnh Z nhi>t 9A t51ng 9:i cao ( 450 - 5000C ) v thu nhi>t 9; cit m2ch C-C theo ph3n 4ng: CnH2n+2 CqH2q+2 + CpH2p - Q (n=q+p)
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b.c tr5ng câ xc tc: -Xc tc nhanh chng m8t ho,t tnh do c:c t2o thnh che ph^ bT mIt, xc tc 95Pc ti sinh bhng cch 9:t c:c bT mIt vYi khng kh Z 650 - 7200C theo ph3n 4ng to3 nhi>t: C + O2 (khng kh) COX + Q Do vEy cFn ti6n hnh vYi lYp xc tc chuy;n 9Ang 9; lin t?c lOy ra 9i ti sinh v bL sung xc tc.
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-Xc tc cr.cking hi>n nay ch4a zolit c ho2t tnh cao 95Pc s_ d?ng Z d2ng h2t vi cFu vYi 95Gng knh c5 0,05 96n 0,1 mm. VYi tnh n.ng câ xc tc nh5 vEy cng vYi 9Ic tr5ng n:i ti6p câ ph3n 4ng yu cFu TGL <Bng <Pu v ngOn nn l@p cu;n theo v@i ;ng <*ng < $c sU dFng cho qu trnh cr7cking Th6 h> cj câ TBP( cr.cking xc tc 9 s_ d?ng lYp tMnh lm vi>c theo chu k., lYp r1i v lYp si.
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Do xc tc nhanh mOt ho2t tnh nn l5Png xc tc tuFn hon lYn v xc tc sau ti sinh c nhi>t 9A cao nn n 95Pc lm chOt mang nhi>t cho ph3n 4ng cr.cking ( nh5 Z hnh 4.4 ) Qu trnh ph3n 4ng trong :ng 94ng l 9o2n nhi>t v ta l> xc tc/nguyn li>u quy6t 9<nh nhi>t 9A ph3n 4ng v 9A chuy;n ho X.
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Tf cc 9Ic tr5ng 9 ni Z trn h> th:ng TBP( cr.cking xc tc hi>n 92i g*m: Thi6t b< ph3n 4ng cr.cking d,ng ;ng <*ng v@i l@p xc tc cu;n theo, lm vi%c theo chE <6 <o,n nhi%t Nguyn li>u 9 95Pc <un nng s! b6 tiEp xc v@i xc tc nng, ho h!i v ph(n *ng trong l@p cu;n theo. Do ph3n 4ng cr.cking t.ng th; tch nn 9; cho vEn t:c lYp cu:n theo Ln 9<nh, < Cng knh c>a ;ng ph(n *ng < $c mG r6ng dQn vP pha cu;i ( theo <6 chuy=n ho X ), sau 9 xc tc < $c tch nhanh khì h\n h$p s(n ph-m. VOn 9T tiEp xc giZa xc tc nng v@i nguyn li%u dQu cjng nh5 phn ly xc tc khì h\n h$p kh ph(n *ng c 3nh h5Zng lYn 96n vi>c t2o c:c v kh nn 95Pc nhiTu hng quan tm.
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Cn qu trnh ti sinh 9:t c:c to( nhiPu nhi%t < $c thRc hi%n trong l@p si. b; 9:t c:c tri>t 9; h1n trong lYp si vYi sl khuOy trAn m2nh câ lYp h2t, nhOt l vYi xu h5Yng s_ d?ng nguyn li>u cho qu trnh cr.cking ngy cng nIng h1n, hai tFng si n:i ti6p 95Pc s_ d?ng vYi tFng 9Fu Z nhi>t 9A thOp h1n (630 6500C) v tFng sau Z nhi>t 9A cao h1n (96n 7200C). Vi>c chia thnh 2 tFng ti sinh xc tc nh5 vEy ngoi vi>c 9:t c:c tri>t 9; do TGL câ h2t trong thi6t b< 9*ng 9Tu cn gip cho xc tc trnh ti6p xc vYi h1i n5Yc Z nhi>t 9A cao v thnh phFn c:c Z tFng ti sinh sau hFu nh5 khng cn hidro.
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Hnh 6.4 trnh by mAt d2ng h> th:ng RCC câ UOP.
Sn phm phn ng
React ng ng Kh x sau hon nguyn
Thit b hon nguyn xc tc 2 giai on
Khng kh s cp Khng kh th cp Khng kh th cp Pha phn tn Nguyn liu v pha phn tn
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225
H.6.2.3-H> th:ng FCC câ ABB Lummus Global Inc. (Hydrocarbon Processing, November 2000, trang 107).
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H.6.2.4-H> th:ng FCC câ Kellogg Brown & Root, Inc. ( nt , trang 108 )
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H.6.2.5-H> th:ng FCC câ Shell Global Solutions International B.V. ( nt , trang 108 )
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H.6.2.6-H> th:ng FCC câ Stone & Webster Inc., a Shaw Group Co/Institut Francais du Ptrole. ( nt , trang 110 )
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H.6.2.7-H> th:ng FCC câ UOP LLC. ( nt , trang 110 )
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H.6.2.8-H> th:ng RCC(Resid Catalytic cracking) câ Stone & Webter Inc., a Shaw Group Co. and Institut Francais du Ptrole. ( nt , trang 139 )
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H.6.2.8-H> th:ng MSCC câ UOP LLC . 1-TB ti sinh; 2-TBP( 3-zng dn xc tc nng 9 ti sinh; 4-BA phEn t2o lYp r1i; 5-BA phEn nh3 hOp ph? s3n ph`m khmi bT mIt xc tc. ( nt , trang 94 ).
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VI.3-H> th:ng TBP( s3n xuOt x.ng alkyl ho:
X.ng alkyl ho 95Pc s3n xuOt bhng ph3n 4ng alkyl ho izobutan vYi cc olefin C3, C4 vYi sl c mIt câ xc tc l axit m2nh, nghMa l tf cc nguyn li>u kh chuy;n thnh s3n ph`m lmng, x.ng alkylat c tr< s: octan cao, khng ch4a benzen nn 95Pc ch hi>n nay. bIc tr5ng câ ph3n 4ng v xc tc:
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-S1 9* ph3n 4ng c th; trnh by nh5 sau:
C4H8 + H+ Buten
C4H9 +
i-C4H10 izo-Butan n-C4H10
C4H8 Buten
i-C4H9 + Tert-Butyl cacbenium cation
i-C8H18
izo-Octan H+
C4H8 Buten
i-C8H17 + izo-Octyl cacbenium cation
i-C4H10 izo-Butan
i-C12H26 H+ i-C16H34
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-Tf nguyn li>u ban 9Fu buten v i-butan t2o thnh x.ng vYi thnh phFn ch^ y6u l i-octan v hPp chOt ny trong 9iTu ki>n ph3n 4ng vYi xc tc axit c th; ti6p t?c ph3n 4ng vYi buten thnh hydrocacbon nIng C12, C16 ...l s3n ph`m ph? v c nhi>t 9A si cao trn 2000C, nhm ngoi thnh phFn câ x.ng. b; h2n ch6 ph3n 4ng ph? ny v qu trnh polime ho olefin trong cng nghi>p dng t" s; i-butan/buten l@n (tN 10 dEn 20) v h% th;ng TBPJ gQn v@i 4LT , c thCi gian l u <Bng <Pu.
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-Qu trnh alkyl ho ti6n hnh Z pha lmng vYi xc tc l axit m,nh H2SO4, HF v gFn 9y thm axit rOn. VYi xc tc H2SO4 v HF l h> d< th; lmng-lmng cFn t,o nhH t !ng <= <(m b(o bP mMt tiEp xc pha, 9Ic bi>t vYi H2SO4 l axit c 9A nhYt v kh:i l5Png ring lYn nn TBP( cFn 95Pc khuOy trAn m2nh. Do vEy vYi xc tc ny trong cng nghi>p s_ d?ng h> th:ng nhiTu thi6t b< khuOy n:i ti6p. VYi xc tc HF c 9A nhYt v kh:i l5Png ring thOp, dQ t2o nhj t51ng vYi hydrocacbon nn dng thiEt bK ;ng <*ng c1 cOu khuOy tMnh 9It trong :ng 94ng.
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-Ph3n 4ng alkyl ho to3 nhi>t, kho3ng 90 Kj/mol, gi3i nhi>t ph3n 4ng bhng cc gi3i php sau: +VYi xc tc H2SO4, nhi>t 9A ph3n 4ng tf 0 96n 100C, bhng cch bay h1i i-butan ( Tsi = 110C ) trlc ti6p tf hSn hPp ph3n 4ng nh5 cng ngh> câ Kellogg - Exxon ( hnh 6.5 ) hay trao 9Li nhi>t qua thnh vYi alkylat nh5 cng ngh> câ Stratco ( hnh 6.6 ). +VYi xc tc HF, nhi>t 9A ph3n 4ng cao h1n ( 30 96n 500C ) c th; lm l2nh qua thnh bhng n5Yc ( hnh 6.8 v 6.9 ).
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H> th:ng TBP(: -Cng ngh> Kellogg-Exxon vYi xc tc H2SO4 g*m 5 thng c khuOy n:i ti6p 9It trong thi6t b< d2ng :ng nhm ngang d5Yi p suOt tf 0,3 96n 0,7 MPa ph? thuAc vo thnh phFn câ nguyn li>u, h1i ibutan t2o thnh do gi3i nhi>t ph3n 4ng tf 5 thng 95Pc tEp trung v 9i ra Z 9Knh thi6t b< d2ng :ng 96n h> th:ng nn v lm l2nh ho lmng.
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H.6.3.1-H> th:ng TBP( s3n xuOt x.ng alkyl ho câ Kellog-Exxon
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H.6.3.2-H> th:ng TBP( alkyl ho nhm ngang, lm l2nh qua thnh câ Stratco.
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TBP( nhm ngang 9*ng thGi tm thi6t b< l>ch vT pha d5Yi 9; trnh ling 9Ung H2SO4, t2o nhj t:t h1n. Hnh 6.7 trnh by thi6t b< ny
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H.6.3.4-TBP( alkyl ho vYi xc tc HF câ Phillips.
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H.6.3.5- TBP( alkyl ho vYi xc tc HF câ UOP.
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-VYi xc tc rin-cng ngh> mYi 9ang nghin c4u pht tri;n, c th; 95a ra TBP( câ cng ngh> Akylene câ UOP Z hnh 6.10. * Xc tc mau mOt ho2t tnh do polime bm vo bT mIt xc tc nn s_ d?ng lYp xc tc chuy;n 9Ang 9; lin t?c thay th6 v ti sinh xc tc: dng lYp cu:n theo 9; TGL 9*ng 9Tu theo yu cFu câ ph3n 4ng. * Ti sinh xc tc bhng cch dng i-butan bo ho hidro 9; kh_ n:i 9i gi3m kh3 n.ng hOp ph? câ cc hPp chOt nIng khng no ln bT mIt xc tc v r_a s2ch bT mIt.
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H.6.3.6-TBP( alkyl ho vYi xc tc rin theo cng ngh> Alkylene câ UOP
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VI.4-H> th:ng TBP( s3n xuOt MTBE(Metyl Tert-Butyl Ether)

Qu trnh ti6n hnh Z pha lmng, nhi>t 9A 50 - 1000C, p suOt 1,5 MPa Ta s: MeOH/i-B= = 1,1 9; gi3m ph3n 4ng polime ho olefin. Xc tc l axit, trong cng nghi>p dng axit rin l nhla cationit c nhm axit m2nh -SO3H, d2ng h2t hnh cFu 95Gng knh c5 0,8 - 1mm. +H> th:ng TBP(: Ph? thuAc vo nguyn li>u i-B= : -Rafinat-1(phn 9o2n C4 câ cr.cking h1i sau khi tch Butadien) ch4a 45 - 50% i-Buten. -Phn 9o2n C4 cr.cking xc tc ch4a 15 - 20% i-Buten. -HSn hPp s3n ph`m dehidro ho i-Butan ch4a 40 - 50% iButen.
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NhJng nguyn li>u c hm l5Png i-B= thOp nh5 trn th5Gng dng TBPJ <o,n nhi%t, cn nguyn li>u ch4a iB= cao h1n nh5 s3n ph`m dehydrat ho TBA, 9i khi dng TBP( :ng chm lm l2nh bhng n5Yc -b; ph3n 4ng ti6n hnh 96n cng, chuy;n ho h6t iB= th5Gng dng cng ngh% CD(Catalytic Distillation) câ hng CD Tech hay cng ngh% RWD(Reaction with Distillation) c>a UOP.
by l cng ngh> ph3n 4ng c nhiTu 5u 9i;m 9; ti6n hnh cc qu trnh thuEn ngh<ch to3 nhi>t Z pha lmng c nhi>t 9A ph3n 4ng xOp xK nhi>t 9A si câ hSn hPp ( 92t 9A chuy;n ho cao, tEn d?ng nhi>t ph3n 4ng 9; tch v tinh ch6 s3n ph`m ph3n 4ng, gi3m s: thi6t b< trong cng ngh>).
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-H> th:ng TBP( 95Pc trnh by Z hnh 6.4.
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VI.5-H> th:ng TBP( Refoming xc tc:
Qu trnh Re foming xc tc ti6n hnh 9*ng thGi cc ph(n *ng <Bng phn ho, <ng vng, th!m ho H/C trn xc tc l cng ch*c: hidro ho -dehydro ho v xc tc axit-base. Ngoi m?c 9ch t.ng tr< s: octan cho x.ng ch5ng trlc ti6p 96n nay cng ngh> Re foming xc tc cn 9; s3n xuOt H/C th1m cho TLng hPp ho dFu.
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-b.c tr5ng câ ph3n 4ng v xc tc: Thu nhi>t, nhi>t 9A ph3n 4ng 400 5000C, th5Gng ti6n hnh Z lYp 9o2n nhi>t xen ke vYi l :ng gia nhi>t. BT mIt xc tc cjng b< c:c t2o thnh che ph^ lm gi3m ho2t tnh, nh5ng chEm h1n nhiTu so vYi xc tc cr.cking
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Cng ngh> cj ti6n hnh vYi lYp xc tc tMnh d5Yi p suOt hidro kho3ng 2 96n 3 MPa 9; h2n ch6 ph3n 4ng t2o c:c, tuLi thU câ xc tc c th; 96n hng n.m ( Hnh 6.5.1 )
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Cng ngh> mYi ti6n hnh vYi xc tc lYp r1i, lin t?c ti sinh xc tc, Z p suOt thOp kho3ng 0,5 MPa, t ph3n 4ng ph? h1n v ho2t tnh lYp xc tc cao v Ln 9<nh
H.6.5.2-H> th:ng TBP( refoming xc tc lYp r1i câ IFP. 1, 2, 3, 4TBP( xc tc lYp r1i ; 5- h> th:ng ti sinh xc tc
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H.6.5.3-H> th:ng TBP( refoming xc tc lYp r1i câ UOP LLC.
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Dng kh ph3n 4ng 9i qua lYp xc tc theo h5Yng xuyn tm v sau khi 9i qua mSi lYp xc tc 95Pc 9un nng trZ l2i 96n nhi>t 9A ph3n 4ng Z l :ng 5 Cc lYp xc tc 2, 3, 4 ch*ng ln nhau, nhG vEy xc tc r1i tf trn xu:ng . b5Gng 9i câ kh ph3n 4ng v xc tc trong thi6t b< nh5 Z 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> th:ng TBP( s3n xuOt phnol:
-Ph51ng php ch^ y6u s3n xuOt phnol hi>n nay l 9i tf nguyn li>u cumen ( trn 90%). -bIc tr5ng câ ph3n 4ng: C hai giai 9o2n ph3n 4ng: oxi ho cumen thnh hidroperoxit (H/P) v chuy;n ho H/P thnh phnol c mIt xc tc axit 95Pc ti6n hnh ring bi>t nn ta xem xt tfng giai 9o2n.
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S1 9* ph3n 4ng chnh v ph? câ giai 9o2n 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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Nh5 vEy, ph(n *ng phF l chuy=n ho tiEp cumen H/P hay g;c cumen H/P thnh dimetyl phenyl cacbinol, axetophenon v mAt s: hPp chOt khc. b; h2n ch6 ph3n 4ng ph? mAt mIt duy tr <6 chuy=n ho th8p (X = 20 - 25 %) 9; gi3m n*ng 9A H/P v g:c H/P trong hSn hPp ph3n 4ng v gi(m dQn nhi%t <6 ph(n *ng theo m4c 9A tch t? H/P trong s3n ph`m ( ni cch khc, theo m4c 9A t.ng câ X ), mIt khc TBP( cFn c TGL c>a pha l`ng <Bng <Pu.
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Qu trnh oxi ho cumen l d< th; kh-lmng x3y ra trong ph2m vi 9Ang hUc Z 100 - 1300C ( TGL câ cumen kho3ng tf 2-3 h 9; 92t X nh5 trn ) b5Pc ti6n hnh trong TBPJ lo,i s>i b2t l lo2i thi6t b< c m hnh dng ch(y gQn v@i KLT ( bUt kh 9i ln ko theo chOt lmng v t2o sl khuOy trAn m2nh trong thi6t b< ). b; phn b; TGL <Bng <Pu câ chOt ph3n 4ng cFn dng 3 - 5 thp s>i b2t n;i tiEp nh5 hnh 6.6.1. S_ d?ng nhiTu thi6t b< n:i ti6p trong h> th:ng cn gip cho vi>c ch6 9A nhi>t 9A trong tfng thi6t b< gi3m dFn khi X t.ng nh5 Z trn.
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H.6.6.1-H> th:ng TBP( oxi ho cumen thnh cumen H/P.
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Ph3n 4ng phn hua cumen H/P thnh phnol v axeton d5Yi tc d?ng xc tc axit Z nhi%t <6 50 - 600C x(y ra v@i t;c <6 l@n, to( nhiPu nhi%t ( H = -253 Kj/mol ), cc s3n ph`m ph? ch^ y6u l do chuy;n ho dimetyl phenyl cacbinol tf qu trnh oxi ho mang sang. Do vEy, hPp l l ti6n hnh qu trnh Z TBPJ lo,i thng c khu8y, gi(i nhi%t b/ng cch bay h!i axeton l hPp chOt s3n ph`m c nhi>t 9A si xOp xK nhi>t 9A ph3n 4ng ( T si câ axeton bhng 56,50C ). Ngoi ra, mAt yu cFu 9ng l5u nJa câ giai 9o2n ny l 9A chuy=n ho X cao, nghMa l H/P 95Pc phn hua tri>t 9;, trnh r1i vo h> th:ng ch5ng cOt pha sau, nn ti6p theo TBP( thng c khuOy cFn c thiEt bK hon thnh theo m hnh 4LT
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H.6.6.2-H% th;ng TBPJ phn hu" H/P cumen thnh phnol v axton
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H.6.6.3-H% TBPJ phn hu" H/P theo m hnh dng tuQn hon.
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7/H> th:ng TBP( tLng hPp 1,2 dicloetan (1,2 DCE):
Ph3n 4ng: CH2=CH2 + Cl2 CH2Cl - CH2Cl Kh Kh Lmng( Ts = 850C ) H = - 220 Kj/mol
Thlc t6 l ph3n 4ng kh-lmng: s?c etylen v clo vo 1,2DCE lmng ho tan FeCl3 0,5% vYi vai tr xc tc. Ph3n 4ng x3y ra trong pha lmng vYi vEn t:c cao ngay Z nhi>t 9A th5Gng.
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Nh5 vEy, qu trnh c 9Ic tr5ng dK th= kh-l`ng, to( nhiPu nhi%t, tiEn hnh G nhi%t <6 th8p cc nhi%t <6 si c>a pha l`ng. o nhi>t 9A h1i cao ( 80 - 1000C ) ph3n 4ng ph? clo ho ti6p thnh tricloetan c 95Pc t.ng c5Gng, v vEy cng ngh> cj ti6n hnh clo ho Z nhi>t 9A thOp v gi3i nhi>t ph3n 4ng bhng n5Yc.
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b6n nay ph3n 4ng ph? theo c1 ch6 chuSi g:c 9 b< h2n ch6 bhng cch dng xc tc FeCl3 v clo c ch4a oxi, nn c th; tiEn hnh G nhi%t <6 cao h!n v sU dFng nhi%t ph(n *ng ( kh l@n) <= tch s(n ph-m G d,ng h!i khng b< ln vYi xc tc. Cng ngh> ti6n bA nhOt dng TBPJ d,ng CD, k6t hPp vYi thp ch5ng, tEn d?ng nhi>t ph3n 4ng 9; tinh ch6 DCE khng chK tf thi6t b< clo ho m tf cc bA phEn khc câ h> th:ng lin hPp, v d? tf cng 9o2n oxiclo ho hay cng 9o2n nhi>t phn DCE v tch VC.
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H.6.7.H TBP( tLng hPp 1, 2 DCE Z nhi>t 9A cao, tEn d?ng nhi>t ph3n 4ng tinh ch6 s3n ph`m.
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8/TBP( s3n xuOt Fomaldehit: -Fomaldehit 95Pc s3n xuOt tf mtanol bhng qu trnh oxi-dehidro ho trn xc tc b2c v oxi ho trn xc tc oxit Fe-Mo. -by l cc qu trnh pha h1i nn cFn trnh t2o hSn hPp nL metanol - khng kh c thnh phFn tf 6 96n 40% th; tch metanol.
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a/Cng ngh> xc tc b2c: Nhi>t 9A ph3n 4ng: 650 - 7200C. Lm vi>c trn giYi h2n nL, do 9 thi6u oxi cho ph3n 4ng oxi ho (1) nn c thm ph3n 4ng chnh dhidro ho mtanol CH3OH + 1/2O2 CH2O + H2O ( 1 ) CH3OH CH2O + H2 (2) H = - 156 Kj/mol H = + 85 Kj/mol
TLng nhi>t ph3n 4ng câ qu trnh l to( nhi%t, qu trnh n/m G ph,m vi khuEch tn ngoi, <o,n nhi%t v tR nhi%t, 9iTu chKnh nhi>t 9A ph3n 4ng bhng cch pha thm h1i n5Yc vo hSn hPp ph3n 4ng.
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TBPJ nh G hnh 4.10
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b/Cng ngh> xc tc oxit Fe-Mo: Nhi>t 9A ph3n 4ng: 290 - 3100C. Lm vi>c d5Yi giYi h2n nL ( hSn hPp kho3ng 6% th; tch mtanol ), d5 oxi nn chK c ph3n 4ng oxi ho ( 1 ) to3 nhiTu nhi>t l ph3n 4ng chnh. Xc tc lYp tMnh, TBP( d2ng :ng chm ( hnh 4.22 ), 95Gng knh :ng t51ng 9:i nhm, c5 20 - 25 mm.
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KEt qu( t;i u ho TBPJ c>a vi%n xc tc NvxibiEc cho th8y r/ng hi%u su8t ph(n *ng v kinh tE h!n nEu kEt h$p thiEt bK ;ng chm v@i l@p xc tc <o,n nhi%t nh G hnh 6.8.
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K6t qu3 nghin c4u cho thOy, trn xc tc ny ngoi ph3n 4ng chnh ( 1 ) vYi n.ng l5Png ho2t ho E1= 40,67 Kj/mol cn c ph3n 4ng ph? oxi ho fomaldehit thnh CO v H2O vYi n.ng l5Png ho2t ho thOp h1n: CH2O + 1/2O2 CO + H2O H=-215 Kj/mol E3 = 28,22 Kj/mol (3)
Do vEy, khi nhi>t 9A xu:ng thOp t:c 9A t51ng 9:i câ ph3n 4ng ph? se t.ng ln, hi>n t5Png ny b< h2n ch6 bhng lYp xc tc 9o2n nhi>t Z cu:i TBP(.
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Qua mAt s: lo2i TBP( câ cc cng ngh> ho dFu thOy rhng, TBP( 95Pc s_ d?ng trong cng nghi>p câ mAt s: hng c th; khc nhau do nhJng gi3i php kC thuEt m hU nghin c4u v p d?ng Nh5ng vT nguyn l l xuOt pht tf nhZng <Mc <i=m vP <6ng h2c v nhi%t <6ng c>a ph(n *ng, tN nhZng <Mc tr ng vP ho,t tnh, nhi%t <6 lm vi%c v <6 nh,y c>a cc tnh n7ng c>a xc tc vo nhi%t <6, thCi gian s;ng c>a xc tc. NhJng c3i ti6n, hon thi>n vT TBP( l k6t qu3 câ nhJng thnh tlu trong nhiTu lMnh vlc khoa hUc v cng ngh>, trong 9 c xc tc, 9Ang hUc, ho hUc v l thuy6t vT TBP(, m hnh ho, t:i 5u ho .
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Calculations of chemical technological processes

Ho Van Son
Chapter 1: The basic principle for drawing up material balances and material calculations for irreversible chemical technological processes
Introduction
The technology calculations are based on the material and heat calculation. The material balance can be writeten down as an equation the left hand side of which is the sum of the masses cG of the input materials and the right hand side is the sum of masses cG of the products and the production losses Gloss cG = cG + Gloss The material balance is based on conservation of mass and the stoichiometric relationships.
2
Chapter 1
The masses of inputs and outputs are determined separately for the solid, liquid and gaseous phases according to the following equation: Gs + Gl + Gg = Gs + Gl + Gg The theoretical material balance is calculated from the stoichiometric equation of the reaction. Only the knowledge of the reaction equation and the molecular masses of the components is needed to draw up this balance The practical material balance takes into account the copositions of the starting material and the final products, the excess of any of the components, the degree of transformation, the losses of the raw materials and the final products, etc
3
Chapter 1
inputs Material kg G1 G2 G3 total m3 outputs Product G4 G5 G6 total
4
kg
m3
Chapter 1
The consumption coefficients describe consumption of various type of raw materials, water, fuel, electric power, and steam per unit product. The production costs include the expenditure for production and marketing of the products. To calculate the production unit costs the egineer uses the consumption coefficients for raw and other material, fuels and energy and their current proces The lower are the consumption coefficients the more economical is the process and lower is the cost of the product
Chapter 1
However reduction of the consumption coefficients below a certain level can necessitable increasing the purity of the starting materials, Of especial importance are the consumption coefficients for raw materials since their costs account for the 60 70 % of the production costs in most chemical processes. To determine the consumption coefficients the engineer should have knowledge of all the stages of the technological process by which the starting material is transformed into the end product
6
Chapter 1
The theoretical consumption coefficients Ath are based on the stoi chiometric relationships describing the transformation os the starting material into the end product The practical consumption coefficients Apr also take into account the production losses at all the stages of the process and the side reaction if they occur
7
Chapter 1
The consumption coefficients for the same product can vary depending on the composition of the starting material, and the difference can be considerable. Therefore, when the raw materials have to be transported some distance to the production plant the planners should first estimate the consumption coefficients for various types of the raw materials to selsect the most economical option
Problem 1
Calculate consumption of benzene and the propan-propylene fraction of the cracking gas (30% propylen and 70 % propane (by volume) for production of 1 ton of phenol if the yield of isopropylenbenzene from benzene is 90% of theoretical and that of phenol from isopropylene is 93% of the theoretical
Solution All the stages of the process can be descibed by the following scheme: C6H6 + CH2=CH-CH3 X C6H5-CH(CH3)2 X C6H5-C(CH3)-O-OH X C6H5OH + (CH3)2C=O
9
Problem 1
Production of 1 kmole of phenol requires 1 kmole of benzene so that the theoretical consumption of benzene per 1 ton of phenol is: 78x1000/91 = 830 kg = 0.83 ton Taking into account the degrees of transformation at the stages of the process we find: 0.83/(0.9x0.93) = 0.99 ton. Production of 1 kmole of phenol takes 22.4 m3 of propylene, that is, the volume of propylene needed to produce 1 ton of phenol is: Vth = 22.4x1000/94 = 284 m3
10
Problem 1
Taking into accuont the degree of transformation at the process stages Vpr = 238/(0,9x0,93) = 284 m3 The volume of propane accompanying this amount of propylene is 284x70/30 = 662 m3 The total volume of the propane propylene fraction is 284 + 662 = 946 m3 Hence the consumption of propylene is 284x42/22.4 = 533 kg And the consumption of propane is: 662x44/22.4 = 1300 kg The total amount of the propane propylene fraction need for production of 1 ton of phenol is 1833 kg = 1,833 ton
11
Problem 2
Find the consumption of the brown coal containing 70% (by mass) carbon, steam and air for production of 1000 m3 of the producer gas with the following composition (by % volume): 40% CO, 18% H2, 42% N2. For simplicity, the air is assumed to contain 79% (by volume) N2 and 21 % O2 Solution The process of gasification is the conversion of solid fuel into gaseous fuel owing to treatment with air, steam or their mixture at a high temperature according to the following eqution: C+H2O XCO + H2 (1) 2C + O2 X 2CO (2)
12
Problem 2
Thus, the producer gas is made by treating the coal with the airsteam mixture 1000 m3 of gas are assumed to contain 420 m3 of nitrogen. Hence, the consumption of oxygen in the reaction (2) is: VO2 = 420*21/79 = 112 m3 Or 112*32/22,4 = 160 kg Therefore, the consumption of the air is 112 +420 = 532 m3 or Apr1 = 532*29/22.4 = 700 kg Steam consumption in the reaction (1). The yield of hydrogen is 1 mole per 1 mole of steam. 1000 m3 of the producer gas contain 180 m3 of hydrogen to produce which 180 m3 of steam are need or
13
Problem 2
Apr2 = 180*18/22.4 = 145 kg The consumption of carbon is 12*180/22,4 = 96.5 kg in the reaction (1) And 2*12*112/22.4 = 120 kg in the reaction (2) The consumption of carbon in both reaction is 96.5 +120 = 216.5 kg Hence, the consumption of the brown coal containing 70% C is Apr3 = 216,5/0.7 = 310 kg
14
Problem 3
Draw up the material balance for production of ethylene oxide by direct catalytic oxidation of ethylene with air. The composition of the starting gas mixture (% by volume): 3% ethylene, 97% air. The degree of oxidation of ethylene is 0.5. Calculations should be made for production of 1 ton of ethylene oxide. Solution: Direct catalytic oxidation of ethylene. Amixture of air and ethylene ( the lower limit explosivity of the ethylene-air mixture is 3.4% C2H4 content) passed over a silver catalyst at 250-2800C gives rise to ethylene oxide: 2 C2H4 +O2 X 2C2H4O
15
Problem 3
Ethylene oxide is isolated from the gas mixture by water absorption and the residual gas is fed into the second reactor The consumption of ethylene for production of 1 ton of ethylene oxide can be found from the equation of the reaction 28 kg of C2H4 yield 44 kg of C2H4O so that to produce 1 ton of ethylene oxide we need: 28*1000/44 = 640 kg of C2H4 Since degree of oxidation is 0.5 the actual ethylene consumption is 640/0.5 = 1280 kg or 1280*22.4/28 = 1020 m3
16
Problem 3
The volume of air in the ethylene-air mixture corresponding to this amount of ethylene is 102 *97/3 = 33000 m3 The repective volume of oxygen is 33000 * 0.21 = 6800 m3 or 6800*32/22.4 = 9700 kg The amount of nitrogen is 33000 *0.79 = 26200 m3 or 26200 *28/22.4 = 32500 kg The consumption of oxygen for oxidation of ethylene is 1020 *0.5/2 = 255 m3 The amount of oxygen in the oxidation products is 6800-255 = 6545 m3 or 6545 *32/22.4 = 9340 kg
17
Problem 3
The results are summarized in table Material balance for ethylene oxidation
Inputs Materials C2H4 Air oxygen nitrogen Total kg m3
Outputs products kg 1000 640 9340 32500 43480 m3 510 510 6545 26200 33765
18
C2H4O C2H4 9700 6800 Oxygen 32500 26200 Nitrogen 43480 34020 Total
1280 1020
Problem 4
After electrocracking of the natural gas containing 98% by volume of CH4 and 2% by volume of N2 the gas discharged from the apparatus contain 15% acetylene. Calculate the material balance of the process per 1000 m3 of the natural gas ignoring the side reaction Solution: Acetylene is produced from gaseous hydrocarbons (chiefly, from methane) at 1200 16000C 2CH4 n C2H2 +3H2 - 380 kJ The process is carried out in electric are furnaces at 1600 0C and with gas velocity of 1000 m/s
19
Problem 4
1000 m3 of natural gas contain 980 m3 of CH4 and 20 m3 of N2 The process results in a change of the volume. According to the equation of the reaction if methane is completely transformed into acetylene the mixture of the products should contain 25% of acetylene. Sine the actual acetylene content is 15% this means that the decomposition of methane is incomplete. Denote by x the volume in m3 of the transformed methane. Then the mixture of the products has the following composition:
20
Problem 4
CH4 980-x C2H2 x/2 H2 3x/2 N2 20 Total 1000+x (m3) The acetylene content in the products is 15 % that is x/2 15% 1000+x 100% Hence we obtain x/2*1000/(1000-x) =15 Thus x= 430 m3
21
Problem 4
The gas products after cracking have the following composition (per 1000 m3 of natural gas) C2H2 215 m3 H2 645 m3 CH4 550 m3 N2 20m3
22
Problem 4
The results are summarized in table Material balance for cracking of natural gas Inputs Materials m3 CH4 N2 980 20 kg 695 25 Outputs % volume products 98 2 C2H2 CH4 H2 N2 Total m3 215 550 645 20 1430 kg 248 388 58 25 719 %volume 15.0 38.5 45.0 1.5 100
23
Total
1000 720
100
Chapter 2: Equilibria of Chemical technogical processes

Introduction Chemical interaction between the starting materials, the direct reaction, is accompanied by the chemical interaction between the reaction products, that is, the reverse reaction. With time the rate of the direct reaction decreases and the rate of reverse reaction increases. When these rates becom equal the state of equilibrium is reached which remains stable under the constant concentrations of the reactants and constant temperature and pressure According to the mass action law for the reactions: mA+nB npC +qD
24
Chapter 2
The rate of the direct reaction is u1 = k1[A]m[B]n And the rate of the reverse reaction is u2 = k2[C]p[D]q at equilibrium we have [C]p[D]q/ [A]m[B]n =k1/k2 = K Or [A]m[B]n /[C]p[D]q = k2/k1 = Kn = 1/K (II.1) Where K is the equilibrium constant for a given reaction which varies with temperature. Variation of the equilibrium constant is described by the vant Hoffs equation
25
Chapter 2
d(lnKp)/dT = qp/RT2 (II.2) Where qp is the heat effect of the reaction whose dependence on temperature is found the Kirchhoffs equation To find the temperature dependence of the equilibrium constant substitute Eq (II.2) qp = f(T) and intergrate the equation obtaining solution in the form of a power series. The equilibrium constant can be determined in various forms depending on the form of expression for the concentrations of the reactants.
26
Chapter 2
If conccentration are expressed in moles/dm3 or kmoles/m3 we have: KC = [CC]p[CD]p/[CA]m[CB]n If concentration are expressed in partial pressures (Pa, kN/m2) we have KP = [PC]p[PD]p/[PA]m[PB]n If concentration are expressed in mole or volume % we have KN = [NC]p[ND]p/[NA]m[NB]n The constant KC, KP, KN are interrelated KC = Kp/RT)N = KP/PV)N = KN/V)N Here )N = v1 v2, v1 = q +p, v2 =m+n
27
Chapter 2
For the ideal gas mixture Kp is independent of the pressure. For the real gases Kp varies with pressure. Experiments have shown that at high pressure the equilibrium constant decreases with increasing pressure. This decrease can be taken into account by introducing a special pressure factor * into the temperature dependence of the equilibrium constant The equation for the temperature dependence of the equilibrium constant for the ammonia synthesis at high pressure lgKp = lg+Kp = -2074.8/T +2.4943lgT+*T-1.8564*10-7T2 + I
28
Chapter 2
The equilibrium constants at high pressures can be found proceeding from the volatilities of the components. Deviation from ideality for the real gases under high pressures can be described by the activity coefficient. The activity of a material determines the Gibbs energy of the material going over from the standad state to the equilibrium. The activity coefficient , is proportional to the volatility f: , = f/P At low pressure volatility may be assumed to be equal to pressure. Volatility characterizes the deviation of the real gas from ideality. Pressure can be replaced by volatility in the ideal-gas equation for the real gas 29
Chapter 2
The activity coefficient for a gas depens also on the compressibility coefficient c: c = PV/RT or V = cRT/P At the pressurres higher than 30-40*104 Pa the equilibrium constant may be expressed as: Kf = KvP The constant Kf is independent of pressure while the constant Kp for the equilibrium mixture of real gases depends on pressure and tends to Kf with decreasing pressure since with decreasing pressure gas approaches ideality
30
Chapter 2
For the ammonia synthesis reaction N2 + 3 H2 - 2NH3 The equilibrium constants Kp and Kf can be given by the following equation: Kp = p2NH3/pN2p3H2 and Kf = f2NH3/fN2f3H2 The equilibrium constant depends on the stoichiometry of the reaction. For instance, if we assume the reaction 1/2 N2+ 3/2 H2 -NH3 for amonia synthesis the equilibrium constant is Kp = pNH3/pN21/2pH23/2 = +Kp
31
Chapter 2
For the dissociation reaction 2NH3 - N2 + 3 H2 The equilibrium constant is Kp = pN2pH23/p2NH3 = 1/Kp A reaction can be decribed by variuos equations so that the equilibrium constant can be have various values for the same equilibrium state. Therefore, when the numerical value of the equilibrium constant is given the relevant reaction equations should be specified. In chemical technological calculation the equilibrium constant is often found from the isothermal thermodynamic potentials the Gibbs energy at constant pressure G or at constant volume F
32
Chapter 2
Under the standard conditions ( the activity coefficient of the gaseous components , = 1) the equation for the reaction isotherm which relate the equilibrium constant to variation of the respective isothermal potential have the following form: )G0 = -RTlnKp )F0 = -RTlnKC These equation can be used at any temperature. The typically used standard temperature is 250C (298 K). The quntities )G0 ,)F0 are defined as the difference of the isothermal potentials between the products and the starting materials.
33
Chapter 2
Calculations of the equilibrium constants and the equilibrium product yields. Problem 1 Find the equilibrium yield of carbon monoxide in gas manufacture by treating coal with steam at t1 = 5000C and t2 = 7000C if lg(pH2O/pCOpH2) is 1.67 and -0.13 respectively. Thepressure is 1 0/1*104 Pa(1 at) Solution Manuacture of gas from coal (or any solid fuel) is a high temperature heterogeneus process in which the organic components of the coal are converted into combustible gases by incomplete oxidation with 34 oxygen or steam
Chapter 2
Gasification of coal with steam can be described by the following equation: C + H2O - CO +H2 Denote the equilibrium content of carbon monoxide in the mixture by Xe. The equilibrium constant is Kp = pCOpH2/pH2O = Xe2/(1-2Xe) At 5000C we have lg Kp =1.67, Kp =46.7, Kp = 1/46.7 =0.0214 Hence Xe2(1-2Xe)= 0.0214, Xe2 +0.0428 Xe 0.0214 = 0 Xe500 = 0.12 At 7000C lg Kp =-0.13, Kp =0.74, Kp = 1/0.74 =1.35 Hence Xe2 +2.7 Xe 1.35 = 0 and Xe700 =0.42 35
Problem 2
Determine the equilibrium constant for the reaction of the propylene hydration to propane at 327 0C C3H6 + H2 -C3H8 Solution:If )H0 is the variation of enthalpy for the standard reaction under the pressure P = 1.01*105 Pa and the absolute zero temperarure we can write )G0 = )G0 - )H00 + )H00 or )G0 /T = ) (G0 - H00)/T + )H00 /T The above equation shows that to find the equilibrium constant we should know the value of (G0 - H00)/T for all the reactants 0 and the heat effect of the reaction at the absolute zero temperature ) H 0 36
Problem 2
The values of (G0 - H00)/T can be found from the spestroscopic data and the values of )H00 from the calorimetric results. Moreover, there are eqution for calculation of these values and tables have been compiled for them. Using the tabular values of the standard heats of formation of the compounds we can find from the Hess equation )H00 = ()H00)C3H8 [()H00)C3H6 +()H00)H2] = -81600 (35100 +0) = -116700 kJ At 600 K we have )(G0 - H00)/T = [(G0 - H00)/T]C3H8 ( [(G0 - H00)/T]C3H6 +[(G0 - H00)/T]H2) 37
Problem 2
= -264 (-266 + -122) = 124 kJ.K-1 )G0 /T = ) (G0 - H00)/T + )H00 /T = 124+ -116700/600 We have -RTlnKp = )G0 RlnKp = -)G0 /T= - 124+ -116700/600 = 72 lgKp = 2/(2.303*8.314) = 3.787 The experimental value of lgKp = 3.79, which agrees with the predicted value Kp = 6160
38
Chapter 2
Calculations of the composition of reaction mixture and material balances for industrial processes based on reversible reactions Problem 3 The mixture of products after one-step conversion of methane has the following composition (in volume): 52 H2, 21 CO, 7.5 CO2, 19 - N2, 0.5 CH4. The gas mixture is passed through humidifier and heat exchanger and fed into the apparatus for conversion carbon monoxide. Calculate the amount of steam neede for the process (per 100 m3of gas) if the content of CO in the waste is not more than 3.5 % (by volume)
39
Problem 3
Calculate also th equilibrium yield of the process. The process is carried out at 500 0C under the pressure of 1.01*105Pa. Solution: Conversion of carbon monoxide can be described by the equation CO+H2O - CO2 + H2 The equilibrium constant at 5000C can be found from the equation lg Kp = -2059/T + 1.5904lgT 1.817*10-3T + 5.65*10-7T2 8.24*10-11T3-1.5313 Hence, Kp = 0.180 at T = 773 K Written down the compositions of the starting gas and the reaction 40 mixture denoting the amount of unreacted CO as X
Problem 3
Staring gas Reation mixture CO 21.0 X CO2 7.5 7.5 + (21-X) H2 52.0 52 +(21-X) N2 19.0 19.0 CH4 0.5 0.5 Total V=100 m3 V = 121-X m3 The Co content in the dry reaction mixture should be not more than 3.5 %. If it is 3.5 % we have X = (121-X)*3.5/100 X = 4.1 m3 Hence, the volume of the dry converted gas per 100 m3 of the 41 initial gas is 121 -4.1 = 116.9 m3 including 4.1 m3 of CO,
Problem 3
22.4 m3 of CO2, 68.9 m3 of H2, 19.0 m3 N2, and 0.5 m3 of CH4 Denote the amount os steam required for the reaction as Y. Then at equilibrium the amount of H2O is Y (21-X) = Y-(214.1) = Y-16.9. Since for this reaction Kp = KC = KN any volume concentration can be substituted in the equation for the equilirium constant: Kp = 0.180 = [CO][H2O]/[CO2][H2] = 4.1(y-16.9)/22.4*68.9 Hence Y -91 m3. The equilibrium yield of the reaction is Xe = (21 4.1)/21 * 100 = 80%.
42
Problem 4
Calculate the material balance for conversion of the natural-gas methane. The plant consumes 4700 m3 of the natural gas per hour. The natural gas has the following composition (in % by volume): CH4 97.8, C2H6 0.5, C3H8 0.2, C4H10 0.1, N2 1.4. The steam gas ratio in the starting mixture is 2.5. the degree of conversion of hydrocarbons is 67%. The process involves the following reaction: CH4 + H2O - CO + 3H2 38.9 kJ/mole (1) CH4 + CO2 - 2CO + 2H2 - 248.3 kJ/mole (2) CH4 + 0.5O2 - CO + 2H2 + 34.8 kJ/mole (3) CO + H2O - CO2 + H2 + 41.0 kJ/mole (4)
43
Problem 4
The ratio CO/CO2 in the conveted gas can be taken to be that at the equilibrium of the reaction (4) at the temperature of the gas leaving the converter, that is, at 7000C since, first, this reaction reaches its equilibrium faster than the reactions (1) (3) and, s econdly, at this temperature the equilibria of other reaction are more considerably shifted towards the reaction products. These reaction have the following approximate values of the equilibrium constants Kp at 7000C: (1) 25, (2) 20, (3) 3*1011, (4) 1.54. Calculations should be made for 100 m3 of the natural gas and then experessed in terms of kg/h 44
Problem 4
Solution: Conversion of the natural-gas methane is the process for production of hydrogen and nitrogen hydrogen mixture for ammonia synthesis The reaction (1) (4) between the natural gas methane and steam., CO2 and oxygen are typically carried out in catalys=tic tubular or shaft converters. The reaction (1) and (2) are endothermic and the process as a whole consumes energy which is supplied by burning a part of the natural gas to CO2 and H2O and by the reaction (3) and (4) which are exothermic. The higher hydrocarbons found in the natural gas (C2H6, C3H8, C4H10) are also convert to CO and H2.
45
Problem 4
Denote the content of components in the converted gas (in m3) as VCO2 VCO, VH2 and the amount of steam (in m3) reacted with hydrocarbons as VH2O The volume of unreacted hydrocarbon in the converted gas (calculated as CH4) is ( 98.7 + 0.5*2 + 0.2 * 3+ 0.1*4)(10067)/100 = 32.9 m3. to determine the composition of the converted gas we shall write down the material balance ( per 100 m3) for each element (1) The material balance for carbon 97.8 +2 *0.5 + 3*0.2 + 4*0.1 = VCO2 +VCO + 32.9 46 Hence VCO2 = 66.9 - VCO
Problem 4
(2) The material balance for oxygen (allowing for the fact that the starting steam gas mixture contain 100 *2.5 = 250 m3 of steam): 0.5*250 = VCO2 + 0.5VCO + 0.5 (250 VH2O) Hence VCO2 + 0.5 VCO 0.5VH2O = 0 (b) (3) The material balance for hydrogen: 2*97.8 + 3*0.5 + 4*0.2 + 5 *0.1 + 250 = VH2 + 2*32.9 + (250 VH2O) Hence VH2 =VH2O + 132.6 Since the CO:CO2 ratio in the product mixture is determined by the equilibrium of the reaction (4) at 700 0C the equilibrium constant is 47
Problem 4
Kp = pCO2pH2/pCOpH2O = VCO2VH2/VCOVH2O =1.54 (Here Kp =KC = KN and the equilibrium constant can be expressed in terms of the volumes of the components for the volume of the converted gas produced from 100 m3 of the natural ga) Find the volume of the component in terms of VH2O from equation (a), (b) and (c) and substitute them in equation (d). Equation (a) and (b) yield VCO = 133.8 VH2O (e) Equations (a) and (e) yield VCO2 = VH2O 66.9 (f) Substituting in equation (d) equations (c), (e), and (f) we obtain 48
Problem 4
Kp = (VH2O - 66.9)(VH2O+132.6)/(133.8 VH2O)(250-VH2O) =1.54 Equation (g) yields VH2O = 100 m3 For the other components we obtain: VCO2 = 100 -66.9 = 33.1 m3 VO2 = 133.8 100 = 33.8 m3, and VH2 = 100 +132.6 =232.6 m3 The amount of steam remaining in the converted gas is 250 100 = 150 m3
49
Problem 4
Component Wet gas m3 CH4 32.9 H2 232.6 CO 33.8 CO2 33.1 N2 1.4 H2O 150.0 total 483.8 % by volume 6.8 48.07 7.0 6.84 0.29 31.0 100.0 Dry gas m3 % by volume 32.9 9.90 232.6 69.60 33.8 10.15 33.1 9.93 1.4 0.42 333.8 100.0
50
Problem 4
These data can be used to calculate the material balance for methane conversion Owing to the inaccuracy of calculations the balance shows a diserepancy of 3.2 kg, that is, about 0.02%
51
Problem 4
input materials Natural gas CH4 C2H6 C3H8 C4H10 N2 steam total kg m3 outputs Products Dry converted gas CH4 C2H6 C3H8 C4H10 N2 Steam total kg m3
3290.00 31.50 18.30 12.20 82.20 3434.20 9447.0 12881.2
4596.60 23.50 9.40 4.70 65.80 4700.00 11750.0 16450.0
1104.50 997.60 1992.80 3057.40 82.20 7214.50 5663.50
1546.3 10932.2 1588.6 1555.7 65.8 15688.6 7050.0
52 12878.00 22738.6
Chapter 3: The basic principles for drawing up energy (heat) balances and heat calculations for chemical technogical processes Introduction The energy (heat) balance for any apparatus can be described by the equation relating inputs and outputs of energy (heat) of the process (apparatus). The energy balance is based on the law of conservation of energy according to which in a closed system the sum of the energies of all types is constant. The chemical technological processes are, typically, described by the heat balance equation ; Qinput = ; Qoutput (III.1) or ; Qinput - ; Qoutput = 0 (III.2)
53
Chapter 3
In terms of the heat balance the law of the conservation of energy means that the inputs of heat in an apparatus or a process should be equal to the consumption of heat in this apparatus or process. The heat balance is calculated from the material balance taking into account the thermal effects (exothermic and endothermic) of the chemical reactions and the physical transformations (evaporation, condensation, etc) occurring in the apparatus and the input of heat from the outside and removal of heat with the reaction products and through the walls of the apparatus
54
Chapter 3
The heat balance, like the material one, is written down in the form of tables and diagram and the calculations are made with t he following equation: Qs +Ql+Qg+Qph+Qr+Qe = Qs +Ql +Qg +Qph +Qr +Qe (III.3) Here Qs, Ql, Qg are the heats supplied to the apparatus by the solid, liquid, and gaseous phases, respectively, Qs Ql Qg are the heats removed from the apparatus with solid, liquid and gaseous reaction products and unreacted starting materials Qph and Qph are the heats liberated and consumed with the physical processes; Qr and Qr are the heats liberated and consumed with the exothermic and endothermic reactions.
55
Chapter 3
Qe is the heat supplied to the apparatus from the external sources (with flue gases, hot air, by combustion of fuel, electric power consumption, etc). And Qe is the loss of heat to the environment or to cooling agents The heats Qs, Ql, Qg Qs Ql Qg for each material fed to the apparatus and product discharged from it are given by the formula Q = Gct (III.4) Where G is the amount of the material, c is its mean specific heat, and t is the temperature (typically, in centigrate degrees). The specific heats of gases (in J/kmole K) at a given absolute temperature T are given by the equation
56
Chapter 3
c = a0 + a1T + a2T2 (III.5) Calculation are made usually for mixtures so that in Eq (III.4) The specific heat cm of the mixture is used which is found from additivity of the heat effects. For instance, for the mixture of three compounds with the specific heats c1, c2 and c3 taken in the amounts G1, G2 and G3 the specific heat is cm = (G1c1+G2c2+G3c3)/(G1+G2+G3) (III.6) The total heat of the physical exothermic processes occurring in the apparatus is given by the equation (for the mixture of three components) 57 Qph = G1r1 + G2r2 + G3r3 (III.7)
Chapter 3
Where G1, G2 and G3 are the amounts of the components which have undergone phase transitions and r1, r2 and r3 are the heats of the phase transitions (condensation, crystallization, dissolving, etc). The number of terms in the right-hand side of Eq (III.7) is equal to the number of components undergoing phase transformation in the course of the process. The heat effects of the chemical reactions can be found from the heats of formation and combustion of the compounds involved in the process. According to the Hess law the heats of formation of all the compounds in the right hand side of the reaction equation and those in the left hand side of the equation 58
Chapter 3
For instance, for the reaction A+B = D+F+Qr the isobaric heat effect is QT0 = Q0form.D + Q0form.F - (Q0form.D + Q0form.D) (III.8) The isobaric heats Q0form ( or )H0) of the formation of compounds from the elements may be found in the physico chemical or thermochemical or thermodynamic handbooks. The following standard conditions are assumed: the temperature of 250C, the pressure of 1.01 *105 Pa and the concentration of 1 mole per 1 kg of the solvent for dissolved compounds. Gases and solution are assumed to be ideal.
59
Chapter 3
The heat effect of the reaction is the sum of the formation heats of the starting compounds minus the sum of the formation heats of the reaction products: )H = .()Hform)start - .()Hform)products (III.9) To determine the temperature dependence of the heat effect of the reaction the Nernst equation is used: Qr = Qr0 + )a0T 1/2)a1T2 1/3)a2T3 (III.10) Here )a0 )a1 )a2 are the differences of the respective coefficient of Eq (III.5) for the reaction products and the starting compounds.
60
Chapter 3
The heat Qe can be found from the loss oof heat by the heat transfer agent, for instance, the heating water. If the amount of heating water is Gw and its specific heat is cw then Qe = Gwcw(ti tf) (III.11) For the steam of the mass G with the evaporation heat r the loss of heat is Qe = Gr (III.12) The loss of heat through the heating wall is Qe = ktF(ta tm)/ (III.13) Where kt is the heat transfer coefficient, F is the heat transfer surface, ta is the mean temperature of the heating agent (water, steam, etc) tm is the mean temperature of the mixture being heated
61
Chapter 3
/ is the time of heating The heat per 1 second (in J/s) produced by combustion of fuel or by tranformation of the electric energy into the thermal energy for combustion furnaces Qe = BQlc (III.14) For electric furnaces Qe = *N (III.15) Here B is the consumption of fuel (in m3/s or kg/s) Qlc is the lowest heat of combustion of the fuel (in J/m3 or J/kg) N is the power of the furnace * is dimension factor
62
Chapter 3
Calculations of the heat of combustion of a fuel from its elemental Composition are typically made in technology with the Mendeleev formula: Qlc =339.3C +1256H -109(O-S) 25.2(9H+W) (III.16) Where C,H,O and S are respectively the concentrations (in % by mass) of carbon, hydrogen, oxygen and sulphur in the fuel, and W is the moisture content of the fuel ( which contains also ash and notrogen) The highest heat of combustion Qhc is found with the assumption that the moisture produced with combustion and the moisture contained in the fuel are condensed to water from the flue gases and cooled to the initial temperature of the fuel. 63
Chapter 3
This heat of combustion is given by the formula Qhc = Qlc +25.2 (9H +W) (III.17) The theoretical consumption Gth of the air (in kilograms per 1 kg of the fuel) can be found from the elemental composition of the fuel with the following equation Gth = 0.116C 0.348H +0.0435(S-O) (III.18) The heat Iair supplied by the humid air is given by the equation Iair = 0 Gth(1.02 + 1.95x)tair (III.19) Where 0 is the excess ratio for air ( in practice 0 for solid fuel varies from 1.3 to 1.7, for liquid fuel from 1.1 to 1.2 and for gaseous fuel from 1.0 to 1.2
64
Chapter 3
1.02 is the specific heat of air 1.95 is the specific heat of steam x is the moisture content of air ( in kilograms per 1 kg of dry air) Tair is the temperature of the air supplied for fuel combustion
65
Chapter 3
Calculations of the Heats of chemical and physical transformations. Consumption coefficients
Problem 1. Calculate the theoretical temperature of combustion of ethane (the combustion heat 1.56*106 kJ/kmole) with the 20% excess of air (the excess ratio 0 =1.2) Solution: With the given excess of oxygen the combustion reaction for ethane is described by the following equation: C2H6 + 3.5O2 + 0.7O2 + (4.2*79/21)N2 = 2CO2 + 3H2O (steam) +0.7O2 +4.2*3.76 N2
66
Problem 1.
If the initial temperature of ethane and air is 00C and the combustion temperature is t we can write Q = 1560997 = (2cCO2 + 3cH2O + 0.7cO2 + 4.2*3.76cN2)t Let us make calculations for t = 19000C and t = 20000C the specific heats in kJ/mole K at 19000C and 20000C. CO2 54.20 and 54.50; O2 35.10 and 35.30 ; H2O (steam) 43.2 and 43.6; N2 33.20 and 33.40 Hence, at 19000C the heat accumulated by the combustion products is Q = (2*54.20 +3*43.20 +0.7*35.10 +4.2*3.76*33.20)1900 =1495042 kJ That is Q<Q 67
Problem 1
At 20000C the heat accumulated by the combustion products is: Q = (2*54.50 +3*43.6 +0.7*35.30 +4.2*3.76*33.40)2000 =1583800 kJ That is, Q >Q Let us interpolate the results: t = 1900 + (2000-1900)*(1560997-1495042)/(1583800-1495042) t = 1974.3 0C
68
Calculations of the heat balance for inductrial processes

Problem 2 The density of styrene is d420 =0.906. The specific heat of styrene Is 1.742 kJ/kgK at 200C and 2.479 kJ/kgK at 1450C. The specific heat of polystyrene is 1.457 kJ/kgK at 200C. And 3.119 kJ/kgK at 1450C. Calculate the volume of the polymerizer and draw up the heat balance for the first polymerizer for 1 ton of styrene. The coefficient of charge is 1 = 0.65 and the operation capacity of 1 ton polymerizer is 1.8 m3 Solution The isothermal process for production of block polystyrene is carried out in a battery of polymerizers with disk agitators. Given 69 below are some charateristics of the process:
Problem 2
Degree of Time of polymerization, % processing h Polymerizer I 50 145 48 2 Polymerizer II 145 160 75 2 Polymerizer III 160 280 90 2 Polymerization of styrene giving rise to polystyrene can be described by the following reaction: nC6H5-CH=CH2 2 (-CH-CH2 -)n + 68700 kJ/kmole | C6H5
70 PDF created with pdfFactory Pro trial version www.pdffactory.com
t1 0C
t20C
Problem 2
The heat of the reaction was found from the experimental data for the monomer with a molecular mass of 104. The volume of the polymerizer can be found from the coefficient of charge and the operational capacity: v = 1.8/0.65 =2.77 m3 The heat effect of the polymerization reaction is 68700/104 = 661 kJ/kg For 1 ton of styrene the heat brought with styrene is 1000*1.742*50 = 87089 kJ And the heat of polymerization is 0.48*1000*661 = 317280 kJ. The total input of heat is 87089 + 317280 = 404369 kJ
71
Problem 2
The heat removed with polystyrene is 3.119*145*480 = 217082 kJ. The heat removed with remaining styrene is 2.479*145*520 = 186916 kJ. The total amount of removed heat is 217082+ 186916 = 403998 kJ. There is a small difference between input and output of heat: 404369 403998 = 371 kJ
72
Problem 3
Calculate the heat balance (for 1 hour of operation) for the pyrolysis stage in production of acetic anhydride from acetone. The reaction are discribed by the following equations: (CH3)2CO pyrolysis 2 CH2=CO + CH4 - 83.7 kJ/mole CH2=CO + CH3COOH -(CH3CO)2O The temperature of pyrolysis is 8000C, 24 tons of acetic anhydride per day are produced. The yield of ketene is 0.25. The heat of evaporation of acetone is 553.5 kJ/kg. The specific heats: acetone 2.09 kJ/kg at 200C, the reaction mixture 2.26 kJ/kg at 8000C Find the amount of natural gas (containing 98% of methane and 2% of nitrogen) needed for te process if the calorific value of methane is 890310 kJ/kmole
73
Problem 3
Solution: According to the reaction equation (CH3)2 CO 2CH2=CO 2(CH3CO)2O The theoretical consumption of acetone is 58*1000/102 = 568 kg/h As the yield of the process is 0.25 the actual consumption of acetone is 568/0.25 = 2270 kg/h The heat supplied with acetone is Q1 = 2.09*2270*20 = 94886 kJ The heat used for evaporation of acetone is Q2 = 2270*553.5 = 1256440 kJ The heat needed for the reaction is Q3 = 2.26*2270*800 = 4104160 kJ 74
Problem 3
The total consumption of heat is 1256440 + 819683 + 4104160 = 6180283 kJ Hence, the amount of methane needed to supply the heat for the process is (6180283 94886)/890310 = 6.84 kmole. The respective amount of the natural gas is 6.84*22.4/0.98 = 156.5 m3. The heat balance of the process is summarized in table
Inputs Q1 Q kJ 94886 6085397 % 1.53 98.47 100.0 Outputs Q2 Qr Q3 Total kJ 1256440 819863 4104160 6180283 % 20.1 13.1 66.8 100.
Total 6180283
75
Elementary calculation of chemical reactors

Chapter 4: Kinetics of chemical technological processes Introduction
Fundamental equations for process rates. Any chemical technological process can be described as consisting of the following interrelated stages: 1. Delivery of the reacting components to the reaction zone 2. Chemical reactions 3. Removal of the reaction products from the reaction zone
76
Chapter 4
An industrial chemist who has to design a reactor for a chemical Technological process must know, first of all, the kinetics of the process. Depending on the region of the process different equations can be used to describe mathematically the process rate and different methods can be applied to increase the total rate of the process. In the general case the rate of a chemical process can be assumed to be proportional to the driving force of the process: u = k)C Here u is the process rate, k is the proportionality factor, and )C is 77 the driving force of the process.
Chapter 4
The reaction rate can be expressed as variation of the number of moles of a component per unit time in unit volume of the phase (for homogeneous reaction) or on the unit area of the phase interace (for hetergeneous reaction). u = 1/v *dN/d/ u = 1/F *dN/d/ Here N is the number of moles of the component which were formed or reacted, v is the volume of the reaction zone, F is the area of the interface between the phases, / is the time. If the volume of the reaction zone is the volume of the reactor v = vr = const We have: u = 1/vr *dN/d/ 78
Chapter 4
and u = d(N/vr)/d/ = dC/d/ The volume v can also be replaced by the mass G u = 1/G *dN/d/ The reaction rate is proportional to the product of concentrations of the reactants raised to certain powers. For instance, for the model irreversible reaction aA+bB2dD u = k[A]0 [B]* Where k is the reaction rate constant which depends only on the temperature. The exponents 0, * determine the order of the reaction. The reaction order can be measured experimentally.
79
Chapter 4
Typically, the exponents 0, * differ from the stoichiometric factor a and b which reflect the molecularity of the reaction. But if the stoichiometric equation correctly describes the mechanism of the reaction the order of the reaction is the same as its molecularity, that is, the first order reaction is monomolecular, the second order reaction is bimolecular. The irreversible reaction aA+bB2dD uD = k[A]0[B]* The reversible reaction aA+bB -dD uD = k1[A] 0[B]* k2[D], In the general form we can wirte uD = k1[A] 0[B]*[D], k2[A]0[B]*[D],
80
Chapter 4
k1/k2 = [D]e,-, /([A]e0- 0[B]e*-*) and the equilibrium constant is K = [D]ed / ([A]ae[B]eb) The ratio k1/k2 can be regarded as a a function of K: k1/k2 = Kn That is [D]e,-, /([A]e0- 0[B]e*-*) = [D]edn / ([A]ane[B]ebn) And n = (0- 0)/a = (*-*)/b = (,-,)/d Simultaneous and consecutive reactions. If both simultaneous reaction A+B2C and A+B2 D are of the first order with respect to both reactants A and B we can write uC = k1[A][B] uD = k2[A][B] 81
Chapter 4
uA = uB = k1[A][B] + k2[A][B] A+B 2C and A+C 2 D If we assume that both reactions are of the first order with respect to all components we can determine the reaction rate for each component uB = k1[A][B] uD = k2[A][C] uA = k1[A][B] - k2[A][C] In a plug-flow or batch reaction A 2 D. The rate of reaction is u = - 1/v .dNA/d/ = k[NA/v]
82
Chapter 4
If v = const we have u = -dCA/d/ = kCA If the istantaneous concentration CA is expressed in terms of the initial number a of moles and the number XM of reacted moles -d(a-XM)/d/ = k(a-XM) and dXM/d/ = k(a-XM) Integration dXM/(a-XM) = kd/ XM = a(1-e-k/) k = 2.3/(/1-/2)log(a-X1)/(a-X2) /1/2 = (2.3log2)/k= 0.6932/k
83
Chapter 4
Irreversible reaction: The kinetic equation describing the mechanism of the reaction mA+nB2pD u = k[A]m[B]n The temperature dependence of the reaction rate constant is given by the Arrhenius equation k = k0e-E/RT Where E is the activation energy (kJ/kmole, kcal/kmole), R is the gas constant and k0 = is a constant. k1/k2 = k0e-E/RT1/k0e-E/RT2 = eE/R(1/T2-1/T1) ln(k1/k2) = E/R(1/T2 1/T1)
84
Chapter 4
E = 19.1T1T2/(T1-T2)logk1/k2 u = k1[A]0 [B]* [D], k2 [D], [A]0 [B]* Equate the first derivative of u with respect to T to zero: du/dT = dk1/dT k1[A]0 [B]* [D], dk2/dT [A]0 [B]* [D],=0 dk1/dT k1[A]0 [B]* [D], = dk2/dT [A]0 [B]* [D], We have dk/dT = E/RT2 k1/k2 = E2/E1 [D],- ,/([A]0- 0 [B]*- *) K = (k1/k2)1/n = (E1/E2)1/n [D] ,- ,/([A](0-0)/n[B](*- *)/n K = (E2/E1)1/n[D]d/([A]a[B]b)
85
Chapter 4
Topt = Te(1+ 2.3RTe/mQrlog(E+mQr)/E Here Te is the equilibrium tempereture K, R is the gas constant E is the activation energy m is the coefficient in the reaction equation for the component which is present in less than stoichiometric quantity, and Qr is the heat of the reaction.
86
Chapter 5: Primary mathematic models of reactor

Introduction: The industrial reactors should satisfy the following basis requirements: The highest productivity and intensity of operation High product yields Low energy consumption, the best utilization of the reaction heat Simplicity of design and low construction cost Easy control Classification of the reactor type can be done according to different characteristics. 1. Batch process reactor 87 2. Continuous process reactor
Chapter 5
The design and capacity of a reactor are determined by: The rates of the chemical reaction and heat and mass transfer processes The hydrodynamic parameters The material balance can be written as differential equations for the elementary volume. (the amount Gf of the component fed the elementary volume per unit time) = (the amount Gd of the component discharged from the elementary volume per unit time) + (the rate Gr of consumption of the component in the reaction chemical in the elementary volume per unit time) + (the rate Ga of accumulation of component in the elementary volume per unit time) (V.1)
88
Chapter 5
If the process occurs under non-isothermic condition The material balance should be complemented by The heat balance: (the heat fed to the elementary volume per unit time) = (the heat removed from the elementary volume per unit time) + (the rate of heat consumption in the elementary volume owing to the chemical reaction) + (the rate of accumulation of heat in the elementary volume) (V.2)
89
Chapter 5
1. Batch reactor with complete mixing: the apparatus is filled with the starting materials which remain there for a certain time until a required yield of products is obtained. The material balance for the batch-process reactor can be derived from Eq. (V.1) where Gf = 0 and Gd = 0 uAv + dG/d/ = 0 (V.3) Here v is the volume of the reaction zone We have dG/d/ = d(G1(1-xA))/d/ = -G1dxA/d/ (V.4) Where G1 is the initial amuont of the starting material xA is the degree of conversion of the starting material
90
Chapter 5
uAv = G1dxA/d/ Integration of Eq (V.5) yields
xA
(V.5)
/ = G1< dxA/uAv
0
(V.6)
If the reaction volume is constant Eq (V.6) can be written as:

xA 0 xA
/ = G1/v < dxA/uA= C1< dxA/uA

0
(V.7)
91
Chapter 5
If the reaction v varies Eq (V.6) can be transformed in to: / = G1<dxA/(uAv1(1+sxA) = C1< dxA/(uAv1(1+sxA)
0 0 xA xA
(V.8)
Where * = (vxA=1 - vxA=0)/ vxA=0
92
Chapter 5
2. The ideal plug-flow reactor: in the reactor of this type any volume element of the reaction mixture travels along the reactor parallel to other elements without any mixing between them. If there is no accumulation of material in the reactor (Ga = 0) the material balance can be written as Gf = Gd+Gr (V.9) Gf = CAVm(1-xA) (V.10) Vm: is the volumetric flow rate of the reaction mixture Gd = CAVm(1-xA-dxA) (V.11) Gr = uAdv (V.12)
93
Chapter 5
VmCAdxA = uAdv
x
(V.13) (V.14)
/ =v/Vm = C1<dxA/uA
0
For nth-order reaction without variation of volume / = CA1<dxA/kCnA = CA1<dxA/kCnA1(1-xA)n =

x
= 1/ kCn-1A1< dxA/(1-xA)n
0
(V.15)
For n=0 we have / = CA1xA/k (V.16) And n=1 / = (1/k)[ln(1/1-xA)] (V.17)

94
Chapter 5
If the volume varies with the reaction we obtain / = 1/ kCn-1A1<(1+sxA)ndxA/(1-xA)n (V.18) For the irreversible reaction of the first order we have / = (1/kCA1)[(1+s)ln1/(1-xA) sxA) (V.19) For the irreversible reaction of the second order / = (1/kCA1)[2s(1+s)ln(1-xA) s2xA + (s+1)2xA/(1-xA)] (V.20) k1 For the reversible reaction of the type A n B
k2
/ = 1/k1[sxA/L-(L+s)/L2ln(1-LxA) L = 1+ (k2/k1)(1+ s)
(V.21)
95
Chapter 5
3. The reactor with complete mixing: In the reactor of this type any volume element of the reaction mixture is instantaneously mixed with the entire volume of the reaction mixture The balance equation can be written for the whole reactor Gf = Gd + Gr (V.23) VmC1 = VmC1(1-xf) + uAfv (V.24) Where xf is the final degree of conversion VmC1xf = uAfv (V.25)
/ = v/Vm = C1xf/uAf
Since xf = (C1-Cf)/C1 we have / = (C1-Cf)/uAf
(V.26) (V.27)
96
Chapter 5
4. Cascade of reactor with complete mixing: In a cascade of reactor the composition of the reaction mixture varies from one reactor to another The material balance for the cascade of n reactors (first order reaction without variation of volume * = 0) /j = vj/Vm = C1vj/G1 = C1(xj-xj-1)/uj (V.28) /j = C1[(1-Cj/C1)-(1-Cj-1/C1)]/uj = (Cj-1-Cj)/kCj (V.29) So that Cj-1/Cj = 1+k/j The time / should be same for all n reactor whose volume vj are identical so that we obtain C1/Cf = C1/C1 . C1/C2 . C2/C3 Cn-1/Cf = (1+k/j)n (V.30) / = n/j = n/k[(C1/Cf)1/n -1]
(V.31)
97
Chapter 5
The graphical technique for calculating the parameters of a cascade of the reactor with complete mixing suggested by Jones uj = -Cj//j + Cj-1//j u = -dCj/dt
uj=kf(Cj)
tga = -1/t j = -vj/V
C5 C4 C3 C2
C1
Cj
C
98
Chapter 5
Problem 1. The reversible exothermic process of oxidation of SO2 in a single bed of vanadium catalyst is carried out in an ideal plugflow reactor. SO2+1/2O2 n SO3 the temperature of the catalyst bed is 5700C and is assumed to be constan over the bed. The starting gas has composition (in % by volume): SO2-11, O2 10, N2 79. The consumption of gas is 15500 m3/h. The velocity of the gas flow in the reactor is w=1.4m/s. The reaction rate constant at 585 0C is 13.7. The equilibrium constant is given by lgKP = 4905/T 4.6455 The activation energy is E = 87800 kJ/kmole. The reserve factor is c=1.3. Calculation the reaction volume of the reactor, that is the volume of the catalyst bed, which provide for degree of conversion of 0.5. and the diameter of the reactor and the height of the catalyst bed 99
Chapter 5
Solution: Equation (V.14) for the ideal plug flow reactor yields / =v/Vm = C1<dxA/uA The rate of the oxidation reaction in the vanadium catalyst bed is given by the approximate equation derived by G.Boreskov u = k/2a [(xe-x)/x]0.8.[2b-ax]273/T Here a is the initial content of SO2 in the reaction mixture (% by volume), b is the initial content of O2 and xe is the equilibrium degree of conversion
x
/ =v/Vm = <dxA/ k/2a [(xe-x)/x]0.8.[2b-ax]273/T

0
100
Chapter 5
First we should find the reaction rate constant at 5700C from that at 5850C: 2.303lg(13,7/k) = 87800/8,314(1/843-1/858) k = 11.0 The equilibrium degree of conversion xe = KP/(KP+=(100-0.5axe)/(b-0.5axe) At 5700C we have: lgKP = 4905/843 4.6455 = 1.18 and KP = 15.15 xe = 0.79
0.5
/ =v/Vm = <dx/ 11.0/2*0.11 [(0.79-x)/x]0.8.[2*0.1-0.11x]273/843

0
101
Chapter 5
/ = 0.12 s The volume of catalyst is v = /cVm = 0.12*1.3*15500/3600 = 0.675 m3 The cross section of the reactor is S = Vm(T/T0) /w = = (15500/3600)*(843/273)/1.4 = 9.5 m2 The diameter of the reactor is D = =(4S/3) = 3.48 m The height of the catalyst layer is H = v/S = 0.675/9.5 = 0.71 m
102
Chapter 6: Heterogeneous catalytic processes

Introduction: In the presence of catalyst the reaction passes a number of intermediate stages with lower activation energies than those of the non-catalytic reaction. For instance, the bimolecular A+B X AB Can proceed via the following intermediate stages in the presence of Catalyst Cat: A+[Cat] X A[Cat] A[Cat] +BXAB*[Cat] AB*[Cat] X AB + [Cat]
103

E n e rg y
AB*
E -E c
E A B * [C a t] A [C a t] Ec
E1 E2
A and B
AB
104
Chapter 6
The activation energgy of the non-catalytic reaction is E The activation energgy of the catalytic reaction is Ec E1 and E2 are activation energgies of the stages (a) and (b) Arrehenius equation k = k0exp(-E/RT) and owing to the exponential relationship the increase of E can be fairly large even for a small decrease of E Depending on the phase state of the reactants and the catalyst the Catalytic processes are classified into two groups homogeneous and heterogeneous processes
105
Chapter 6
The heterogeneous catalytic process proceeds via mass exchange and chemical satges which can be generally described as follows: 1. Diffusion of reactants from the flow core to the surface of the catalyst particles 2. Diffusion in the pores of catalyst particles 3. Activated (chemical) adsorption of reactants on the catalyst surface and formation of surface compounds 4. Rearrangement of atom and formation of product-catalyst complexes at the surface 5. Desorption of the product (regeneration of the active centres of 106 catalyst
Chapter 6
6. Diffusion of the product in the pores of catalyst particle 7. Diffusion of the product from surface of catalyst particle to the flow core The overall rate of a heterogeneous catalytic process is determined by that of its slowest stage. According to the limiting process stage the processes are claasified as being limited kinetics, external diffusion, and internal diffusion. Generally, the rate constant of a catalytic process can be written as k = f(k1, k2,, kside Dm, Dm, Dp)
107
Chapter 6
Where k1, k2, kside are the rate constant the direct, reverse, and side reaction and Dm, Dm, Dp are the diffusion coefficients of the starting materials and products for the process limited by External or internal diffusion. For the processes limited by kinetic the rate constant is independent of the diffusion parameters. According to the hydrodynamical interaction between the gas Flow and particulate catalyst the catalytic reactor are lassified into the following groups: 1. Reactor with stationary (filter) bed of catalyst 2. Reactor with fluidized bed of catalyst 108 3. Reactor with continuosly moving along the reaction space
Chapter 6
Depending on the temperature condition the catalytic processes and reactor can be classified as adiabatic, isothermic and variable temperature The activity of catalyst Acat = kcat/k = k0e-Ecat/RT / k0e-E/RT = e)E/RT Here )E = E Ecat To compare the activities of catalysts under different conditions the activity is determined as the intensity of process with a given catalyst expressed in kg/m3h: Acat = Gp/vcat/ Here Gp is the amount of the product, vcat is the volume of the catalyst, 109 and / is the time of reaction
Chapter 6
Acat = Gp/Gcat/ And Acat = Gp/S/ = Gp/Sspvcat / Where Gcat is the amount of catalyst, S is the total surface of the catalyst, and Ssp is specific surface area of catalyst, m2/m3.. Productivity Pcat = Gp// Intensity of operation i of the catalyst (kg/m3h) i = VvfCp4p or i = VviCmx 4p* Here Cp and Cm are the concentration of the product and the main starting material (molar fractions, 4p is density of the product 110 (kg/m3), Vv is the volume rate of flow of the gas (1/h)
Chapter 6
Vv = Vg/v * = Vvf/Vvi is used to convert the initial Vvi into the final Vvf to allow for variation of the volume of the reaction mixture. The catalyst selectivity Scat in defined as the ratio between the rate of formation of the specified main product and the overall rate of conversion of the main starting reactant in all reactions: Scat = dGp/(vp/vi)dGi Here vp/vi is the ratio of the stoichiometric factors for formation of product from the main initial reactant The overall (integral) selectivity is can be expressed as 111 Scat = Gm/G = Gm/ (Gm + G)
Chapter 6
Gm is the amount of the main product and Gs is the amount of the side products. The time of residence / in the catalytic reactors with the ideal plug flow is the same for all molecules. The theoretical residence time is /th = vcat/Vg = H/w Where vcat is the total volume of the catalyst (m3), Vg is the gas flow rate (m3/h), H is the height of the catalyst bed, w is the linear velocity of the gas in the reactor (m/s) The real residence time is /r = /th/5 Where 5 = vf/vcat is the porosity of the catalyst bed and vf is the free volume of the bed (m3) 112
Chapter 6
The catalyst volume needed to obtain a given degree of conversion is found from: vcat = cVg /th Where c is the reserve factor which allows for a decrease of the catalyst activity owing to poisoning and mechanical losses, Vg is the gas flow rate, and /th is the theoretical time of contact between the gas and the catalyst.
113
Chapter 6
Calculations catalytic reactors
The general kinetic equations provide a basis for calculations of the parameters of catalytic reaction. The plug flow reactor: u = dG/d/ = kvcatSsp)C Where Ssp is the specific surface of the catalyst (m2/m3), k is the overall reaction rate constant, )C is the driving force of the process. The general kinetic equation for the catalytic reaction of gas reactants over the solid catalyst taking into account the main process parameters can be written as u = k0e-E/RTvcat )pPn* Where )p is the driving force of the process expressed in term of the 114 partial pressures of the reactants.
Chapter 6
Pn is the ratio of the process pressure to the normal pressure 1,01*105 Pa * is the factor for conversion to normal temperature n is the overall reaction order Depending on the limiting stage of the process the kinetic equations for heterogeneuos catalytic processes over the solid porous catalysts can be written in various forms 1. For the processes limited by external diffusion the overall mass transfer equation can be written as u = 1/S . dGp/d/ = kM(CAg CAg*) Where S is the surface of contact between reactants and catalyst 3) 115 CA is the concentration of the main reactant A in the gas (kmole/m
Chapter 6
CAg* is the equilibrium concentration of A near the surface of the catalyst, CAg* is not known and should be eliminnated kM is the mass transfer coefficient, the coefficient kM for various condition can be found in literature or measured experimentally The dimensions of the reactor are sometimes determined by calculating the values of the height of transfer unit (HTU) and the number Z of transfer units: H = HTU.Z Here we heve: HTU = Gg/(MmkMSsppm) Gg is the mass flow rate of the gas (kg/m2h) Mm is the mean molecular mass of the gas components 116
Chapter 6
kM is the mass transfer coefficient (for the component A) (kmole/m2.h.Pa) Ssp is the specific surface of the catalyst (m2/m3) pm is the mean logarithmic partial pressure of the component A in the gas film pm = [(P+pA*A)-(P+pAi*A)]/ln[(P+pA*A)/(P+pAi*A) Where P is the pressure in the reactor (Pa) pA is the partial pressure of the component A (Pa), pAi is the partial pressure of the A at the catalyst surface (Pa) *A is the change of the number of moles of A owing to the reaction 117 ( per 1 mole of A)
Chapter 6
The HTU value is sometimes found from the emprical equations of the following type: SspHTU = BRem(Pr)n Here we have Re = dcatGg/4D and Pr = 6/4D Here dcat is the reduced diameter of the catalyst particles, D is the diffusion coefficient of the component A in the gas, 6 and 4 are the viscosity and the density of the gas for the given P and T in the reactor The number of transfer units is
pA1 pA2 NA1
Z = 7 pmdpA/[(P-pA)(pA-pA1)] = 7NmdNA/[(1-NA*A)(NA-NA1)]
NA2
118
Chapter 6
Where NA and NA1 are the molar fractions of the componet A in the gas and at the surface of the catalyst Nm = pm/P is the mean logarithmic concentration of A in the gas film 2. For the kinetics limited processes the form of the form of the equation depens on the limiting stage of the surface interaction. For instance, if the limiting stage of the gas reaction occurring in the presence of a neutral material A+B n R + S is adsorption of A at the catalyst surface the kinetic equation is
119
Chapter 6
u = k(pApB pRpS/KppB)/[1+KRKSpRpS+KBpB+KRpR+Ksps +K1np1n] If the limiting stage is the surface interaction between the adsorbed molecules A and B the equation can be written as: -uA = k[pApB - (pR pS)/KP]/[1+KApA+KBpB+KRpR+Ksps +K1np1n]2 And if the limiting stage is desorption we have: -uA = k[pApB/pS - (pRpS)/KP]/[1+KApA+KBpB+KppA.pB/ps+K1np1n] k is the reaction rate constant Kp is the equilibrium constant for the surface reaction KA, KB, KR and Ks are the equilibrium constants for adsorption of the intial components of the gas mixture and the reaction products K1n is the equilibrium constant for adsorption of the inert substance
120
Chapter 6
3. If the reaction is limited by internal diffusion the mean reaction rate for the first-order or pseudomonomolecular reaction inside the pore is: u = - 1/Sp . dGA/d/ = ksCAT, or u = - 1/vp . dGA/d/ = kCAT, Here Sp and vp are the surface and volume of the pore, ks is the reaction rate constant per unit surface area of the catalyst (m/h) k is the reaction rate constant (1/h) , = CA/CAT is the factor characterizing the degree of utilization of the internal surface
121
Chapter 6
CA is the mean concentration of A inside the pore CAg is the highest possible concentration of A near the catalyst surface The overall rate of the catalytic process for the first-order reaction is found by combining the equation for the mass-transfer rate u = - 1/Sp . dGA/d/ = kM(CAg C*Ag) With the equation for diffusion and reaction inside the catalyst particle u = - 1/vp . dGA/d/ = kMC*Ag, Elimination of the unknow surface concentration C*Ag yields u = - 1/Sp . dGA/d/ = [1/(S/k ,vp+1/kM)] C*Ag or u = - 1/vp . dGA/d/ = [1/(1/k ,+vp/kMS)] C*Ag Here k is given in 1/h and kM in m/h)
122
Chapter 6
Calculations of the heat-exchange surface area F which is needed to remove (deliver) the heat from the catalyst bed are made acccording to the general heat tranfer equation: Q = kTF)t/ The driving force )t of heat transfer is determined by the temperature tbed in the bed and the temperature tcool of the cooling agent. If the adiabatic reactor with filtercatalyst bed has no heat exchangers the final temperature tf of the reaction mixture can be found from given initial temperature t1: tf = t1 + qrCpx/c
123
Chapter 6
Here qr is the heat effect of the reaction (J/mole), Cp
124
Calculations of chemical technological processes

Ho Van Son
Chapter 1: The basic principle for drawing up material balances and material calculations for irreversible chemical technological processes
Introduction
The technology calculations are based on the material and heat calculation. The material balance can be writeten down as an equation the left hand side of which is the sum of the masses cG of the input materials and the right hand side is the sum of masses cG of the products and the production losses Gloss cG = cG + Gloss The material balance is based on conservation of mass and the stoichiometric relationships.
2
Chapter 1
The masses of inputs and outputs are determined separately for the solid, liquid and gaseous phases according to the following equation: Gs + Gl + Gg = Gs + Gl + Gg The theoretical material balance is calculated from the stoichiometric equation of the reaction. Only the knowledge of the reaction equation and the molecular masses of the components is needed to draw up this balance The practical material balance takes into account the copositions of the starting material and the final products, the excess of any of the components, the degree of transformation, the losses of the raw materials and the final products, etc
3
Chapter 1
inputs Material kg G1 G2 G3 total m3 outputs Product G4 G5 G6 total
4
kg
m3
Chapter 1
The consumption coefficients describe consumption of various type of raw materials, water, fuel, electric power, and steam per unit product. The production costs include the expenditure for production and marketing of the products. To calculate the production unit costs the egineer uses the consumption coefficients for raw and other material, fuels and energy and their current proces The lower are the consumption coefficients the more economical is the process and lower is the cost of the product
Chapter 1
However reduction of the consumption coefficients below a certain level can necessitable increasing the purity of the starting materials, Of especial importance are the consumption coefficients for raw materials since their costs account for the 60 70 % of the production costs in most chemical processes. To determine the consumption coefficients the engineer should have knowledge of all the stages of the technological process by which the starting material is transformed into the end product
6
Chapter 1
The theoretical consumption coefficients Ath are based on the stoi chiometric relationships describing the transformation os the starting material into the end product The practical consumption coefficients Apr also take into account the production losses at all the stages of the process and the side reaction if they occur
7
Chapter 1
The consumption coefficients for the same product can vary depending on the composition of the starting material, and the difference can be considerable. Therefore, when the raw materials have to be transported some distance to the production plant the planners should first estimate the consumption coefficients for various types of the raw materials to selsect the most economical option
Problem 1
Calculate consumption of benzene and the propan-propylene fraction of the cracking gas (30% propylen and 70 % propane (by volume) for production of 1 ton of phenol if the yield of isopropylenbenzene from benzene is 90% of theoretical and that of phenol from isopropylene is 93% of the theoretical
Solution All the stages of the process can be descibed by the following scheme: C6H6 + CH2=CH-CH3 X C6H5-CH(CH3)2 X C6H5-C(CH3)-O-OH X C6H5OH + (CH3)2C=O
9
Problem 1
Production of 1 kmole of phenol requires 1 kmole of benzene so that the theoretical consumption of benzene per 1 ton of phenol is: 78x1000/91 = 830 kg = 0.83 ton Taking into account the degrees of transformation at the stages of the process we find: 0.83/(0.9x0.93) = 0.99 ton. Production of 1 kmole of phenol takes 22.4 m3 of propylene, that is, the volume of propylene needed to produce 1 ton of phenol is: Vth = 22.4x1000/94 = 284 m3
10
Problem 1
Taking into accuont the degree of transformation at the process stages Vpr = 238/(0,9x0,93) = 284 m3 The volume of propane accompanying this amount of propylene is 284x70/30 = 662 m3 The total volume of the propane propylene fraction is 284 + 662 = 946 m3 Hence the consumption of propylene is 284x42/22.4 = 533 kg And the consumption of propane is: 662x44/22.4 = 1300 kg The total amount of the propane propylene fraction need for production of 1 ton of phenol is 1833 kg = 1,833 ton
11
Problem 2
Find the consumption of the brown coal containing 70% (by mass) carbon, steam and air for production of 1000 m3 of the producer gas with the following composition (by % volume): 40% CO, 18% H2, 42% N2. For simplicity, the air is assumed to contain 79% (by volume) N2 and 21 % O2 Solution The process of gasification is the conversion of solid fuel into gaseous fuel owing to treatment with air, steam or their mixture at a high temperature according to the following eqution: C+H2O XCO + H2 (1) 2C + O2 X 2CO (2)
12
Problem 2
Thus, the producer gas is made by treating the coal with the airsteam mixture 1000 m3 of gas are assumed to contain 420 m3 of nitrogen. Hence, the consumption of oxygen in the reaction (2) is: VO2 = 420*21/79 = 112 m3 Or 112*32/22,4 = 160 kg Therefore, the consumption of the air is 112 +420 = 532 m3 or Apr1 = 532*29/22.4 = 700 kg Steam consumption in the reaction (1). The yield of hydrogen is 1 mole per 1 mole of steam. 1000 m3 of the producer gas contain 180 m3 of hydrogen to produce which 180 m3 of steam are need or
13
Problem 2
Apr2 = 180*18/22.4 = 145 kg The consumption of carbon is 12*180/22,4 = 96.5 kg in the reaction (1) And 2*12*112/22.4 = 120 kg in the reaction (2) The consumption of carbon in both reaction is 96.5 +120 = 216.5 kg Hence, the consumption of the brown coal containing 70% C is Apr3 = 216,5/0.7 = 310 kg
14
Problem 3
Draw up the material balance for production of ethylene oxide by direct catalytic oxidation of ethylene with air. The composition of the starting gas mixture (% by volume): 3% ethylene, 97% air. The degree of oxidation of ethylene is 0.5. Calculations should be made for production of 1 ton of ethylene oxide. Solution: Direct catalytic oxidation of ethylene. Amixture of air and ethylene ( the lower limit explosivity of the ethylene-air mixture is 3.4% C2H4 content) passed over a silver catalyst at 250-2800C gives rise to ethylene oxide: 2 C2H4 +O2 X 2C2H4O
15
Problem 3
Ethylene oxide is isolated from the gas mixture by water absorption and the residual gas is fed into the second reactor The consumption of ethylene for production of 1 ton of ethylene oxide can be found from the equation of the reaction 28 kg of C2H4 yield 44 kg of C2H4O so that to produce 1 ton of ethylene oxide we need: 28*1000/44 = 640 kg of C2H4 Since degree of oxidation is 0.5 the actual ethylene consumption is 640/0.5 = 1280 kg or 1280*22.4/28 = 1020 m3
16
Problem 3
The volume of air in the ethylene-air mixture corresponding to this amount of ethylene is 102 *97/3 = 33000 m3 The repective volume of oxygen is 33000 * 0.21 = 6800 m3 or 6800*32/22.4 = 9700 kg The amount of nitrogen is 33000 *0.79 = 26200 m3 or 26200 *28/22.4 = 32500 kg The consumption of oxygen for oxidation of ethylene is 1020 *0.5/2 = 255 m3 The amount of oxygen in the oxidation products is 6800-255 = 6545 m3 or 6545 *32/22.4 = 9340 kg
17
Problem 3
The results are summarized in table Material balance for ethylene oxidation
Inputs Materials C2H4 Air oxygen nitrogen Total kg m3
Outputs products kg 1000 640 9340 32500 43480 m3 510 510 6545 26200 33765
18
C2H4O C2H4 9700 6800 Oxygen 32500 26200 Nitrogen 43480 34020 Total
1280 1020
Problem 4
After electrocracking of the natural gas containing 98% by volume of CH4 and 2% by volume of N2 the gas discharged from the apparatus contain 15% acetylene. Calculate the material balance of the process per 1000 m3 of the natural gas ignoring the side reaction Solution: Acetylene is produced from gaseous hydrocarbons (chiefly, from methane) at 1200 16000C 2CH4 n C2H2 +3H2 - 380 kJ The process is carried out in electric are furnaces at 1600 0C and with gas velocity of 1000 m/s
19
Problem 4
1000 m3 of natural gas contain 980 m3 of CH4 and 20 m3 of N2 The process results in a change of the volume. According to the equation of the reaction if methane is completely transformed into acetylene the mixture of the products should contain 25% of acetylene. Sine the actual acetylene content is 15% this means that the decomposition of methane is incomplete. Denote by x the volume in m3 of the transformed methane. Then the mixture of the products has the following composition:
20
Problem 4
CH4 980-x C2H2 x/2 H2 3x/2 N2 20 Total 1000+x (m3) The acetylene content in the products is 15 % that is x/2 15% 1000+x 100% Hence we obtain x/2*1000/(1000-x) =15 Thus x= 430 m3
21
Problem 4
The gas products after cracking have the following composition (per 1000 m3 of natural gas) C2H2 215 m3 H2 645 m3 CH4 550 m3 N2 20m3
22
Problem 4
The results are summarized in table Material balance for cracking of natural gas Inputs Materials m3 CH4 N2 980 20 kg 695 25 Outputs % volume products 98 2 C2H2 CH4 H2 N2 Total m3 215 550 645 20 1430 kg 248 388 58 25 719 %volume 15.0 38.5 45.0 1.5 100
23
Total
1000 720
100
Chapter 2: Equilibria of Chemical technogical processes

Introduction Chemical interaction between the starting materials, the direct reaction, is accompanied by the chemical interaction between the reaction products, that is, the reverse reaction. With time the rate of the direct reaction decreases and the rate of reverse reaction increases. When these rates becom equal the state of equilibrium is reached which remains stable under the constant concentrations of the reactants and constant temperature and pressure According to the mass action law for the reactions: mA+nB npC +qD
24
Chapter 2
The rate of the direct reaction is u1 = k1[A]m[B]n And the rate of the reverse reaction is u2 = k2[C]p[D]q at equilibrium we have [C]p[D]q/ [A]m[B]n =k1/k2 = K Or [A]m[B]n /[C]p[D]q = k2/k1 = Kn = 1/K (II.1) Where K is the equilibrium constant for a given reaction which varies with temperature. Variation of the equilibrium constant is described by the vant Hoffs equation
25
Chapter 2
d(lnKp)/dT = qp/RT2 (II.2) Where qp is the heat effect of the reaction whose dependence on temperature is found the Kirchhoffs equation To find the temperature dependence of the equilibrium constant substitute Eq (II.2) qp = f(T) and intergrate the equation obtaining solution in the form of a power series. The equilibrium constant can be determined in various forms depending on the form of expression for the concentrations of the reactants.
26
Chapter 2
If conccentration are expressed in moles/dm3 or kmoles/m3 we have: KC = [CC]p[CD]p/[CA]m[CB]n If concentration are expressed in partial pressures (Pa, kN/m2) we have KP = [PC]p[PD]p/[PA]m[PB]n If concentration are expressed in mole or volume % we have KN = [NC]p[ND]p/[NA]m[NB]n The constant KC, KP, KN are interrelated KC = Kp/RT)N = KP/PV)N = KN/V)N Here )N = v1 v2, v1 = q +p, v2 =m+n
27
Chapter 2
For the ideal gas mixture Kp is independent of the pressure. For the real gases Kp varies with pressure. Experiments have shown that at high pressure the equilibrium constant decreases with increasing pressure. This decrease can be taken into account by introducing a special pressure factor * into the temperature dependence of the equilibrium constant The equation for the temperature dependence of the equilibrium constant for the ammonia synthesis at high pressure lgKp = lg+Kp = -2074.8/T +2.4943lgT+*T-1.8564*10-7T2 + I
28
Chapter 2
The equilibrium constants at high pressures can be found proceeding from the volatilities of the components. Deviation from ideality for the real gases under high pressures can be described by the activity coefficient. The activity of a material determines the Gibbs energy of the material going over from the standad state to the equilibrium. The activity coefficient , is proportional to the volatility f: , = f/P At low pressure volatility may be assumed to be equal to pressure. Volatility characterizes the deviation of the real gas from ideality. Pressure can be replaced by volatility in the ideal-gas equation for the real gas 29
Chapter 2
The activity coefficient for a gas depens also on the compressibility coefficient c: c = PV/RT or V = cRT/P At the pressurres higher than 30-40*104 Pa the equilibrium constant may be expressed as: Kf = KvP The constant Kf is independent of pressure while the constant Kp for the equilibrium mixture of real gases depends on pressure and tends to Kf with decreasing pressure since with decreasing pressure gas approaches ideality
30
Chapter 2
For the ammonia synthesis reaction N2 + 3 H2 - 2NH3 The equilibrium constants Kp and Kf can be given by the following equation: Kp = p2NH3/pN2p3H2 and Kf = f2NH3/fN2f3H2 The equilibrium constant depends on the stoichiometry of the reaction. For instance, if we assume the reaction 1/2 N2+ 3/2 H2 -NH3 for amonia synthesis the equilibrium constant is Kp = pNH3/pN21/2pH23/2 = +Kp
31
Chapter 2
For the dissociation reaction 2NH3 - N2 + 3 H2 The equilibrium constant is Kp = pN2pH23/p2NH3 = 1/Kp A reaction can be decribed by variuos equations so that the equilibrium constant can be have various values for the same equilibrium state. Therefore, when the numerical value of the equilibrium constant is given the relevant reaction equations should be specified. In chemical technological calculation the equilibrium constant is often found from the isothermal thermodynamic potentials the Gibbs energy at constant pressure G or at constant volume F
32
Chapter 2
Under the standard conditions ( the activity coefficient of the gaseous components , = 1) the equation for the reaction isotherm which relate the equilibrium constant to variation of the respective isothermal potential have the following form: )G0 = -RTlnKp )F0 = -RTlnKC These equation can be used at any temperature. The typically used standard temperature is 250C (298 K). The quntities )G0 ,)F0 are defined as the difference of the isothermal potentials between the products and the starting materials.
33
Chapter 2
Calculations of the equilibrium constants and the equilibrium product yields. Problem 1 Find the equilibrium yield of carbon monoxide in gas manufacture by treating coal with steam at t1 = 5000C and t2 = 7000C if lg(pH2O/pCOpH2) is 1.67 and -0.13 respectively. Thepressure is 1 0/1*104 Pa(1 at) Solution Manuacture of gas from coal (or any solid fuel) is a high temperature heterogeneus process in which the organic components of the coal are converted into combustible gases by incomplete oxidation with 34 oxygen or steam
Chapter 2
Gasification of coal with steam can be described by the following equation: C + H2O - CO +H2 Denote the equilibrium content of carbon monoxide in the mixture by Xe. The equilibrium constant is Kp = pCOpH2/pH2O = Xe2/(1-2Xe) At 5000C we have lg Kp =1.67, Kp =46.7, Kp = 1/46.7 =0.0214 Hence Xe2(1-2Xe)= 0.0214, Xe2 +0.0428 Xe 0.0214 = 0 Xe500 = 0.12 At 7000C lg Kp =-0.13, Kp =0.74, Kp = 1/0.74 =1.35 Hence Xe2 +2.7 Xe 1.35 = 0 and Xe700 =0.42 35
Problem 2
Determine the equilibrium constant for the reaction of the propylene hydration to propane at 327 0C C3H6 + H2 -C3H8 Solution:If )H0 is the variation of enthalpy for the standard reaction under the pressure P = 1.01*105 Pa and the absolute zero temperarure we can write )G0 = )G0 - )H00 + )H00 or )G0 /T = ) (G0 - H00)/T + )H00 /T The above equation shows that to find the equilibrium constant we should know the value of (G0 - H00)/T for all the reactants 0 and the heat effect of the reaction at the absolute zero temperature ) H 0 36
Problem 2
The values of (G0 - H00)/T can be found from the spestroscopic data and the values of )H00 from the calorimetric results. Moreover, there are eqution for calculation of these values and tables have been compiled for them. Using the tabular values of the standard heats of formation of the compounds we can find from the Hess equation )H00 = ()H00)C3H8 [()H00)C3H6 +()H00)H2] = -81600 (35100 +0) = -116700 kJ At 600 K we have )(G0 - H00)/T = [(G0 - H00)/T]C3H8 ( [(G0 - H00)/T]C3H6 +[(G0 - H00)/T]H2) 37
Problem 2
= -264 (-266 + -122) = 124 kJ.K-1 )G0 /T = ) (G0 - H00)/T + )H00 /T = 124+ -116700/600 We have -RTlnKp = )G0 RlnKp = -)G0 /T= - 124+ -116700/600 = 72 lgKp = 2/(2.303*8.314) = 3.787 The experimental value of lgKp = 3.79, which agrees with the predicted value Kp = 6160
38
Chapter 2
Calculations of the composition of reaction mixture and material balances for industrial processes based on reversible reactions Problem 3 The mixture of products after one-step conversion of methane has the following composition (in volume): 52 H2, 21 CO, 7.5 CO2, 19 - N2, 0.5 CH4. The gas mixture is passed through humidifier and heat exchanger and fed into the apparatus for conversion carbon monoxide. Calculate the amount of steam neede for the process (per 100 m3of gas) if the content of CO in the waste is not more than 3.5 % (by volume)
39
Problem 3
Calculate also th equilibrium yield of the process. The process is carried out at 500 0C under the pressure of 1.01*105Pa. Solution: Conversion of carbon monoxide can be described by the equation CO+H2O - CO2 + H2 The equilibrium constant at 5000C can be found from the equation lg Kp = -2059/T + 1.5904lgT 1.817*10-3T + 5.65*10-7T2 8.24*10-11T3-1.5313 Hence, Kp = 0.180 at T = 773 K Written down the compositions of the starting gas and the reaction 40 mixture denoting the amount of unreacted CO as X
Problem 3
Staring gas Reation mixture CO 21.0 X CO2 7.5 7.5 + (21-X) H2 52.0 52 +(21-X) N2 19.0 19.0 CH4 0.5 0.5 Total V=100 m3 V = 121-X m3 The Co content in the dry reaction mixture should be not more than 3.5 %. If it is 3.5 % we have X = (121-X)*3.5/100 X = 4.1 m3 Hence, the volume of the dry converted gas per 100 m3 of the 41 initial gas is 121 -4.1 = 116.9 m3 including 4.1 m3 of CO,
Problem 3
22.4 m3 of CO2, 68.9 m3 of H2, 19.0 m3 N2, and 0.5 m3 of CH4 Denote the amount os steam required for the reaction as Y. Then at equilibrium the amount of H2O is Y (21-X) = Y-(214.1) = Y-16.9. Since for this reaction Kp = KC = KN any volume concentration can be substituted in the equation for the equilirium constant: Kp = 0.180 = [CO][H2O]/[CO2][H2] = 4.1(y-16.9)/22.4*68.9 Hence Y -91 m3. The equilibrium yield of the reaction is Xe = (21 4.1)/21 * 100 = 80%.
42
Problem 4
Calculate the material balance for conversion of the natural-gas methane. The plant consumes 4700 m3 of the natural gas per hour. The natural gas has the following composition (in % by volume): CH4 97.8, C2H6 0.5, C3H8 0.2, C4H10 0.1, N2 1.4. The steam gas ratio in the starting mixture is 2.5. the degree of conversion of hydrocarbons is 67%. The process involves the following reaction: CH4 + H2O - CO + 3H2 38.9 kJ/mole (1) CH4 + CO2 - 2CO + 2H2 - 248.3 kJ/mole (2) CH4 + 0.5O2 - CO + 2H2 + 34.8 kJ/mole (3) CO + H2O - CO2 + H2 + 41.0 kJ/mole (4)
43
Problem 4
The ratio CO/CO2 in the conveted gas can be taken to be that at the equilibrium of the reaction (4) at the temperature of the gas leaving the converter, that is, at 7000C since, first, this reaction reaches its equilibrium faster than the reactions (1) (3) and, s econdly, at this temperature the equilibria of other reaction are more considerably shifted towards the reaction products. These reaction have the following approximate values of the equilibrium constants Kp at 7000C: (1) 25, (2) 20, (3) 3*1011, (4) 1.54. Calculations should be made for 100 m3 of the natural gas and then experessed in terms of kg/h 44
Problem 4
Solution: Conversion of the natural-gas methane is the process for production of hydrogen and nitrogen hydrogen mixture for ammonia synthesis The reaction (1) (4) between the natural gas methane and steam., CO2 and oxygen are typically carried out in catalys=tic tubular or shaft converters. The reaction (1) and (2) are endothermic and the process as a whole consumes energy which is supplied by burning a part of the natural gas to CO2 and H2O and by the reaction (3) and (4) which are exothermic. The higher hydrocarbons found in the natural gas (C2H6, C3H8, C4H10) are also convert to CO and H2.
45
Problem 4
Denote the content of components in the converted gas (in m3) as VCO2 VCO, VH2 and the amount of steam (in m3) reacted with hydrocarbons as VH2O The volume of unreacted hydrocarbon in the converted gas (calculated as CH4) is ( 98.7 + 0.5*2 + 0.2 * 3+ 0.1*4)(10067)/100 = 32.9 m3. to determine the composition of the converted gas we shall write down the material balance ( per 100 m3) for each element (1) The material balance for carbon 97.8 +2 *0.5 + 3*0.2 + 4*0.1 = VCO2 +VCO + 32.9 46 Hence VCO2 = 66.9 - VCO
Problem 4
(2) The material balance for oxygen (allowing for the fact that the starting steam gas mixture contain 100 *2.5 = 250 m3 of steam): 0.5*250 = VCO2 + 0.5VCO + 0.5 (250 VH2O) Hence VCO2 + 0.5 VCO 0.5VH2O = 0 (b) (3) The material balance for hydrogen: 2*97.8 + 3*0.5 + 4*0.2 + 5 *0.1 + 250 = VH2 + 2*32.9 + (250 VH2O) Hence VH2 =VH2O + 132.6 Since the CO:CO2 ratio in the product mixture is determined by the equilibrium of the reaction (4) at 700 0C the equilibrium constant is 47
Problem 4
Kp = pCO2pH2/pCOpH2O = VCO2VH2/VCOVH2O =1.54 (Here Kp =KC = KN and the equilibrium constant can be expressed in terms of the volumes of the components for the volume of the converted gas produced from 100 m3 of the natural ga) Find the volume of the component in terms of VH2O from equation (a), (b) and (c) and substitute them in equation (d). Equation (a) and (b) yield VCO = 133.8 VH2O (e) Equations (a) and (e) yield VCO2 = VH2O 66.9 (f) Substituting in equation (d) equations (c), (e), and (f) we obtain 48
Problem 4
Kp = (VH2O - 66.9)(VH2O+132.6)/(133.8 VH2O)(250-VH2O) =1.54 Equation (g) yields VH2O = 100 m3 For the other components we obtain: VCO2 = 100 -66.9 = 33.1 m3 VO2 = 133.8 100 = 33.8 m3, and VH2 = 100 +132.6 =232.6 m3 The amount of steam remaining in the converted gas is 250 100 = 150 m3
49
Problem 4
Component Wet gas m3 CH4 32.9 H2 232.6 CO 33.8 CO2 33.1 N2 1.4 H2O 150.0 total 483.8 % by volume 6.8 48.07 7.0 6.84 0.29 31.0 100.0 Dry gas m3 % by volume 32.9 9.90 232.6 69.60 33.8 10.15 33.1 9.93 1.4 0.42 333.8 100.0
50
Problem 4
These data can be used to calculate the material balance for methane conversion Owing to the inaccuracy of calculations the balance shows a diserepancy of 3.2 kg, that is, about 0.02%
51
Problem 4
input materials Natural gas CH4 C2H6 C3H8 C4H10 N2 steam total kg m3 outputs Products Dry converted gas CH4 C2H6 C3H8 C4H10 N2 Steam total kg m3
3290.00 31.50 18.30 12.20 82.20 3434.20 9447.0 12881.2
4596.60 23.50 9.40 4.70 65.80 4700.00 11750.0 16450.0
1104.50 997.60 1992.80 3057.40 82.20 7214.50 5663.50
1546.3 10932.2 1588.6 1555.7 65.8 15688.6 7050.0
52 12878.00 22738.6
Chapter 3: The basic principles for drawing up energy (heat) balances and heat calculations for chemical technogical processes Introduction The energy (heat) balance for any apparatus can be described by the equation relating inputs and outputs of energy (heat) of the process (apparatus). The energy balance is based on the law of conservation of energy according to which in a closed system the sum of the energies of all types is constant. The chemical technological processes are, typically, described by the heat balance equation ; Qinput = ; Qoutput (III.1) or ; Qinput - ; Qoutput = 0 (III.2)
53
Chapter 3
In terms of the heat balance the law of the conservation of energy means that the inputs of heat in an apparatus or a process should be equal to the consumption of heat in this apparatus or process. The heat balance is calculated from the material balance taking into account the thermal effects (exothermic and endothermic) of the chemical reactions and the physical transformations (evaporation, condensation, etc) occurring in the apparatus and the input of heat from the outside and removal of heat with the reaction products and through the walls of the apparatus
54
Chapter 3
The heat balance, like the material one, is written down in the form of tables and diagram and the calculations are made with t he following equation: Qs +Ql+Qg+Qph+Qr+Qe = Qs +Ql +Qg +Qph +Qr +Qe (III.3) Here Qs, Ql, Qg are the heats supplied to the apparatus by the solid, liquid, and gaseous phases, respectively, Qs Ql Qg are the heats removed from the apparatus with solid, liquid and gaseous reaction products and unreacted starting materials Qph and Qph are the heats liberated and consumed with the physical processes; Qr and Qr are the heats liberated and consumed with the exothermic and endothermic reactions.
55
Chapter 3
Qe is the heat supplied to the apparatus from the external sources (with flue gases, hot air, by combustion of fuel, electric power consumption, etc). And Qe is the loss of heat to the environment or to cooling agents The heats Qs, Ql, Qg Qs Ql Qg for each material fed to the apparatus and product discharged from it are given by the formula Q = Gct (III.4) Where G is the amount of the material, c is its mean specific heat, and t is the temperature (typically, in centigrate degrees). The specific heats of gases (in J/kmole K) at a given absolute temperature T are given by the equation
56
Chapter 3
c = a0 + a1T + a2T2 (III.5) Calculation are made usually for mixtures so that in Eq (III.4) The specific heat cm of the mixture is used which is found from additivity of the heat effects. For instance, for the mixture of three compounds with the specific heats c1, c2 and c3 taken in the amounts G1, G2 and G3 the specific heat is cm = (G1c1+G2c2+G3c3)/(G1+G2+G3) (III.6) The total heat of the physical exothermic processes occurring in the apparatus is given by the equation (for the mixture of three components) 57 Qph = G1r1 + G2r2 + G3r3 (III.7)
Chapter 3
Where G1, G2 and G3 are the amounts of the components which have undergone phase transitions and r1, r2 and r3 are the heats of the phase transitions (condensation, crystallization, dissolving, etc). The number of terms in the right-hand side of Eq (III.7) is equal to the number of components undergoing phase transformation in the course of the process. The heat effects of the chemical reactions can be found from the heats of formation and combustion of the compounds involved in the process. According to the Hess law the heats of formation of all the compounds in the right hand side of the reaction equation and those in the left hand side of the equation 58
Chapter 3
For instance, for the reaction A+B = D+F+Qr the isobaric heat effect is QT0 = Q0form.D + Q0form.F - (Q0form.D + Q0form.D) (III.8) The isobaric heats Q0form ( or )H0) of the formation of compounds from the elements may be found in the physico chemical or thermochemical or thermodynamic handbooks. The following standard conditions are assumed: the temperature of 250C, the pressure of 1.01 *105 Pa and the concentration of 1 mole per 1 kg of the solvent for dissolved compounds. Gases and solution are assumed to be ideal.
59
Chapter 3
The heat effect of the reaction is the sum of the formation heats of the starting compounds minus the sum of the formation heats of the reaction products: )H = .()Hform)start - .()Hform)products (III.9) To determine the temperature dependence of the heat effect of the reaction the Nernst equation is used: Qr = Qr0 + )a0T 1/2)a1T2 1/3)a2T3 (III.10) Here )a0 )a1 )a2 are the differences of the respective coefficient of Eq (III.5) for the reaction products and the starting compounds.
60
Chapter 3
The heat Qe can be found from the loss oof heat by the heat transfer agent, for instance, the heating water. If the amount of heating water is Gw and its specific heat is cw then Qe = Gwcw(ti tf) (III.11) For the steam of the mass G with the evaporation heat r the loss of heat is Qe = Gr (III.12) The loss of heat through the heating wall is Qe = ktF(ta tm)/ (III.13) Where kt is the heat transfer coefficient, F is the heat transfer surface, ta is the mean temperature of the heating agent (water, steam, etc) tm is the mean temperature of the mixture being heated
61
Chapter 3
/ is the time of heating The heat per 1 second (in J/s) produced by combustion of fuel or by tranformation of the electric energy into the thermal energy for combustion furnaces Qe = BQlc (III.14) For electric furnaces Qe = *N (III.15) Here B is the consumption of fuel (in m3/s or kg/s) Qlc is the lowest heat of combustion of the fuel (in J/m3 or J/kg) N is the power of the furnace * is dimension factor
62
Chapter 3
Calculations of the heat of combustion of a fuel from its elemental Composition are typically made in technology with the Mendeleev formula: Qlc =339.3C +1256H -109(O-S) 25.2(9H+W) (III.16) Where C,H,O and S are respectively the concentrations (in % by mass) of carbon, hydrogen, oxygen and sulphur in the fuel, and W is the moisture content of the fuel ( which contains also ash and notrogen) The highest heat of combustion Qhc is found with the assumption that the moisture produced with combustion and the moisture contained in the fuel are condensed to water from the flue gases and cooled to the initial temperature of the fuel. 63
Chapter 3
This heat of combustion is given by the formula Qhc = Qlc +25.2 (9H +W) (III.17) The theoretical consumption Gth of the air (in kilograms per 1 kg of the fuel) can be found from the elemental composition of the fuel with the following equation Gth = 0.116C 0.348H +0.0435(S-O) (III.18) The heat Iair supplied by the humid air is given by the equation Iair = 0 Gth(1.02 + 1.95x)tair (III.19) Where 0 is the excess ratio for air ( in practice 0 for solid fuel varies from 1.3 to 1.7, for liquid fuel from 1.1 to 1.2 and for gaseous fuel from 1.0 to 1.2
64
Chapter 3
1.02 is the specific heat of air 1.95 is the specific heat of steam x is the moisture content of air ( in kilograms per 1 kg of dry air) Tair is the temperature of the air supplied for fuel combustion
65
Chapter 3
Calculations of the Heats of chemical and physical transformations. Consumption coefficients
Problem 1. Calculate the theoretical temperature of combustion of ethane (the combustion heat 1.56*106 kJ/kmole) with the 20% excess of air (the excess ratio 0 =1.2) Solution: With the given excess of oxygen the combustion reaction for ethane is described by the following equation: C2H6 + 3.5O2 + 0.7O2 + (4.2*79/21)N2 = 2CO2 + 3H2O (steam) +0.7O2 +4.2*3.76 N2
66
Problem 1.
If the initial temperature of ethane and air is 00C and the combustion temperature is t we can write Q = 1560997 = (2cCO2 + 3cH2O + 0.7cO2 + 4.2*3.76cN2)t Let us make calculations for t = 19000C and t = 20000C the specific heats in kJ/mole K at 19000C and 20000C. CO2 54.20 and 54.50; O2 35.10 and 35.30 ; H2O (steam) 43.2 and 43.6; N2 33.20 and 33.40 Hence, at 19000C the heat accumulated by the combustion products is Q = (2*54.20 +3*43.20 +0.7*35.10 +4.2*3.76*33.20)1900 =1495042 kJ That is Q<Q 67
Problem 1
At 20000C the heat accumulated by the combustion products is: Q = (2*54.50 +3*43.6 +0.7*35.30 +4.2*3.76*33.40)2000 =1583800 kJ That is, Q >Q Let us interpolate the results: t = 1900 + (2000-1900)*(1560997-1495042)/(1583800-1495042) t = 1974.3 0C
68
Calculations of the heat balance for inductrial processes

Problem 2 The density of styrene is d420 =0.906. The specific heat of styrene Is 1.742 kJ/kgK at 200C and 2.479 kJ/kgK at 1450C. The specific heat of polystyrene is 1.457 kJ/kgK at 200C. And 3.119 kJ/kgK at 1450C. Calculate the volume of the polymerizer and draw up the heat balance for the first polymerizer for 1 ton of styrene. The coefficient of charge is 1 = 0.65 and the operation capacity of 1 ton polymerizer is 1.8 m3 Solution The isothermal process for production of block polystyrene is carried out in a battery of polymerizers with disk agitators. Given 69 below are some charateristics of the process:
Problem 2
Degree of Time of polymerization, % processing h Polymerizer I 50 145 48 2 Polymerizer II 145 160 75 2 Polymerizer III 160 280 90 2 Polymerization of styrene giving rise to polystyrene can be described by the following reaction: nC6H5-CH=CH2 2 (-CH-CH2 -)n + 68700 kJ/kmole | C6H5
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t1 0C
t20C
Problem 2
The heat of the reaction was found from the experimental data for the monomer with a molecular mass of 104. The volume of the polymerizer can be found from the coefficient of charge and the operational capacity: v = 1.8/0.65 =2.77 m3 The heat effect of the polymerization reaction is 68700/104 = 661 kJ/kg For 1 ton of styrene the heat brought with styrene is 1000*1.742*50 = 87089 kJ And the heat of polymerization is 0.48*1000*661 = 317280 kJ. The total input of heat is 87089 + 317280 = 404369 kJ
71
Problem 2
The heat removed with polystyrene is 3.119*145*480 = 217082 kJ. The heat removed with remaining styrene is 2.479*145*520 = 186916 kJ. The total amount of removed heat is 217082+ 186916 = 403998 kJ. There is a small difference between input and output of heat: 404369 403998 = 371 kJ
72
Problem 3
Calculate the heat balance (for 1 hour of operation) for the pyrolysis stage in production of acetic anhydride from acetone. The reaction are discribed by the following equations: (CH3)2CO pyrolysis 2 CH2=CO + CH4 - 83.7 kJ/mole CH2=CO + CH3COOH -(CH3CO)2O The temperature of pyrolysis is 8000C, 24 tons of acetic anhydride per day are produced. The yield of ketene is 0.25. The heat of evaporation of acetone is 553.5 kJ/kg. The specific heats: acetone 2.09 kJ/kg at 200C, the reaction mixture 2.26 kJ/kg at 8000C Find the amount of natural gas (containing 98% of methane and 2% of nitrogen) needed for te process if the calorific value of methane is 890310 kJ/kmole
73
Problem 3
Solution: According to the reaction equation (CH3)2 CO 2CH2=CO 2(CH3CO)2O The theoretical consumption of acetone is 58*1000/102 = 568 kg/h As the yield of the process is 0.25 the actual consumption of acetone is 568/0.25 = 2270 kg/h The heat supplied with acetone is Q1 = 2.09*2270*20 = 94886 kJ The heat used for evaporation of acetone is Q2 = 2270*553.5 = 1256440 kJ The heat needed for the reaction is Q3 = 2.26*2270*800 = 4104160 kJ 74
Problem 3
The total consumption of heat is 1256440 + 819683 + 4104160 = 6180283 kJ Hence, the amount of methane needed to supply the heat for the process is (6180283 94886)/890310 = 6.84 kmole. The respective amount of the natural gas is 6.84*22.4/0.98 = 156.5 m3. The heat balance of the process is summarized in table
Inputs Q1 Q kJ 94886 6085397 % 1.53 98.47 100.0 Outputs Q2 Qr Q3 Total kJ 1256440 819863 4104160 6180283 % 20.1 13.1 66.8 100.
Total 6180283
75
Elementary calculation of chemical reactors

Chapter 4: Kinetics of chemical technological processes Introduction
Fundamental equations for process rates. Any chemical technological process can be described as consisting of the following interrelated stages: 1. Delivery of the reacting components to the reaction zone 2. Chemical reactions 3. Removal of the reaction products from the reaction zone
76
Chapter 4
An industrial chemist who has to design a reactor for a chemical Technological process must know, first of all, the kinetics of the process. Depending on the region of the process different equations can be used to describe mathematically the process rate and different methods can be applied to increase the total rate of the process. In the general case the rate of a chemical process can be assumed to be proportional to the driving force of the process: u = k)C Here u is the process rate, k is the proportionality factor, and )C is 77 the driving force of the process.
Chapter 4
The reaction rate can be expressed as variation of the number of moles of a component per unit time in unit volume of the phase (for homogeneous reaction) or on the unit area of the phase interace (for hetergeneous reaction). u = 1/v *dN/d/ u = 1/F *dN/d/ Here N is the number of moles of the component which were formed or reacted, v is the volume of the reaction zone, F is the area of the interface between the phases, / is the time. If the volume of the reaction zone is the volume of the reactor v = vr = const We have: u = 1/vr *dN/d/ 78
Chapter 4
and u = d(N/vr)/d/ = dC/d/ The volume v can also be replaced by the mass G u = 1/G *dN/d/ The reaction rate is proportional to the product of concentrations of the reactants raised to certain powers. For instance, for the model irreversible reaction aA+bB2dD u = k[A]0 [B]* Where k is the reaction rate constant which depends only on the temperature. The exponents 0, * determine the order of the reaction. The reaction order can be measured experimentally.
79
Chapter 4
Typically, the exponents 0, * differ from the stoichiometric factor a and b which reflect the molecularity of the reaction. But if the stoichiometric equation correctly describes the mechanism of the reaction the order of the reaction is the same as its molecularity, that is, the first order reaction is monomolecular, the second order reaction is bimolecular. The irreversible reaction aA+bB2dD uD = k[A]0[B]* The reversible reaction aA+bB -dD uD = k1[A] 0[B]* k2[D], In the general form we can wirte uD = k1[A] 0[B]*[D], k2[A]0[B]*[D],
80
Chapter 4
k1/k2 = [D]e,-, /([A]e0- 0[B]e*-*) and the equilibrium constant is K = [D]ed / ([A]ae[B]eb) The ratio k1/k2 can be regarded as a a function of K: k1/k2 = Kn That is [D]e,-, /([A]e0- 0[B]e*-*) = [D]edn / ([A]ane[B]ebn) And n = (0- 0)/a = (*-*)/b = (,-,)/d Simultaneous and consecutive reactions. If both simultaneous reaction A+B2C and A+B2 D are of the first order with respect to both reactants A and B we can write uC = k1[A][B] uD = k2[A][B] 81
Chapter 4
uA = uB = k1[A][B] + k2[A][B] A+B 2C and A+C 2 D If we assume that both reactions are of the first order with respect to all components we can determine the reaction rate for each component uB = k1[A][B] uD = k2[A][C] uA = k1[A][B] - k2[A][C] In a plug-flow or batch reaction A 2 D. The rate of reaction is u = - 1/v .dNA/d/ = k[NA/v]
82
Chapter 4
If v = const we have u = -dCA/d/ = kCA If the istantaneous concentration CA is expressed in terms of the initial number a of moles and the number XM of reacted moles -d(a-XM)/d/ = k(a-XM) and dXM/d/ = k(a-XM) Integration dXM/(a-XM) = kd/ XM = a(1-e-k/) k = 2.3/(/1-/2)log(a-X1)/(a-X2) /1/2 = (2.3log2)/k= 0.6932/k
83
Chapter 4
Irreversible reaction: The kinetic equation describing the mechanism of the reaction mA+nB2pD u = k[A]m[B]n The temperature dependence of the reaction rate constant is given by the Arrhenius equation k = k0e-E/RT Where E is the activation energy (kJ/kmole, kcal/kmole), R is the gas constant and k0 = is a constant. k1/k2 = k0e-E/RT1/k0e-E/RT2 = eE/R(1/T2-1/T1) ln(k1/k2) = E/R(1/T2 1/T1)
84
Chapter 4
E = 19.1T1T2/(T1-T2)logk1/k2 u = k1[A]0 [B]* [D], k2 [D], [A]0 [B]* Equate the first derivative of u with respect to T to zero: du/dT = dk1/dT k1[A]0 [B]* [D], dk2/dT [A]0 [B]* [D],=0 dk1/dT k1[A]0 [B]* [D], = dk2/dT [A]0 [B]* [D], We have dk/dT = E/RT2 k1/k2 = E2/E1 [D],- ,/([A]0- 0 [B]*- *) K = (k1/k2)1/n = (E1/E2)1/n [D] ,- ,/([A](0-0)/n[B](*- *)/n K = (E2/E1)1/n[D]d/([A]a[B]b)
85
Chapter 4
Topt = Te(1+ 2.3RTe/mQrlog(E+mQr)/E Here Te is the equilibrium tempereture K, R is the gas constant E is the activation energy m is the coefficient in the reaction equation for the component which is present in less than stoichiometric quantity, and Qr is the heat of the reaction.
86
Chapter 5: Primary mathematic models of reactor

Introduction: The industrial reactors should satisfy the following basis requirements: The highest productivity and intensity of operation High product yields Low energy consumption, the best utilization of the reaction heat Simplicity of design and low construction cost Easy control Classification of the reactor type can be done according to different characteristics. 1. Batch process reactor 87 2. Continuous process reactor
Chapter 5
The design and capacity of a reactor are determined by: The rates of the chemical reaction and heat and mass transfer processes The hydrodynamic parameters The material balance can be written as differential equations for the elementary volume. (the amount Gf of the component fed the elementary volume per unit time) = (the amount Gd of the component discharged from the elementary volume per unit time) + (the rate Gr of consumption of the component in the reaction chemical in the elementary volume per unit time) + (the rate Ga of accumulation of component in the elementary volume per unit time) (V.1)
88
Chapter 5
If the process occurs under non-isothermic condition The material balance should be complemented by The heat balance: (the heat fed to the elementary volume per unit time) = (the heat removed from the elementary volume per unit time) + (the rate of heat consumption in the elementary volume owing to the chemical reaction) + (the rate of accumulation of heat in the elementary volume) (V.2)
89
Chapter 5
1. Batch reactor with complete mixing: the apparatus is filled with the starting materials which remain there for a certain time until a required yield of products is obtained. The material balance for the batch-process reactor can be derived from Eq. (V.1) where Gf = 0 and Gd = 0 uAv + dG/d/ = 0 (V.3) Here v is the volume of the reaction zone We have dG/d/ = d(G1(1-xA))/d/ = -G1dxA/d/ (V.4) Where G1 is the initial amuont of the starting material xA is the degree of conversion of the starting material
90
Chapter 5
uAv = G1dxA/d/ Integration of Eq (V.5) yields
xA
(V.5)
/ = G1< dxA/uAv
0
(V.6)
If the reaction volume is constant Eq (V.6) can be written as:

xA 0 xA
/ = G1/v < dxA/uA= C1< dxA/uA

0
(V.7)
91
Chapter 5
If the reaction v varies Eq (V.6) can be transformed in to: / = G1<dxA/(uAv1(1+sxA) = C1< dxA/(uAv1(1+sxA)
0 0 xA xA
(V.8)
Where * = (vxA=1 - vxA=0)/ vxA=0
92
Chapter 5
2. The ideal plug-flow reactor: in the reactor of this type any volume element of the reaction mixture travels along the reactor parallel to other elements without any mixing between them. If there is no accumulation of material in the reactor (Ga = 0) the material balance can be written as Gf = Gd+Gr (V.9) Gf = CAVm(1-xA) (V.10) Vm: is the volumetric flow rate of the reaction mixture Gd = CAVm(1-xA-dxA) (V.11) Gr = uAdv (V.12)
93
Chapter 5
VmCAdxA = uAdv
x
(V.13) (V.14)
/ =v/Vm = C1<dxA/uA
0
For nth-order reaction without variation of volume / = CA1<dxA/kCnA = CA1<dxA/kCnA1(1-xA)n =

x
= 1/ kCn-1A1< dxA/(1-xA)n
0
(V.15)
For n=0 we have / = CA1xA/k (V.16) And n=1 / = (1/k)[ln(1/1-xA)] (V.17)

94
Chapter 5
If the volume varies with the reaction we obtain / = 1/ kCn-1A1<(1+sxA)ndxA/(1-xA)n (V.18) For the irreversible reaction of the first order we have / = (1/kCA1)[(1+s)ln1/(1-xA) sxA) (V.19) For the irreversible reaction of the second order / = (1/kCA1)[2s(1+s)ln(1-xA) s2xA + (s+1)2xA/(1-xA)] (V.20) k1 For the reversible reaction of the type A n B
k2
/ = 1/k1[sxA/L-(L+s)/L2ln(1-LxA) L = 1+ (k2/k1)(1+ s)
(V.21)
95
Chapter 5
3. The reactor with complete mixing: In the reactor of this type any volume element of the reaction mixture is instantaneously mixed with the entire volume of the reaction mixture The balance equation can be written for the whole reactor Gf = Gd + Gr (V.23) VmC1 = VmC1(1-xf) + uAfv (V.24) Where xf is the final degree of conversion VmC1xf = uAfv (V.25)
/ = v/Vm = C1xf/uAf
Since xf = (C1-Cf)/C1 we have / = (C1-Cf)/uAf
(V.26) (V.27)
96
Chapter 5
4. Cascade of reactor with complete mixing: In a cascade of reactor the composition of the reaction mixture varies from one reactor to another The material balance for the cascade of n reactors (first order reaction without variation of volume * = 0) /j = vj/Vm = C1vj/G1 = C1(xj-xj-1)/uj (V.28) /j = C1[(1-Cj/C1)-(1-Cj-1/C1)]/uj = (Cj-1-Cj)/kCj (V.29) So that Cj-1/Cj = 1+k/j The time / should be same for all n reactor whose volume vj are identical so that we obtain C1/Cf = C1/C1 . C1/C2 . C2/C3 Cn-1/Cf = (1+k/j)n (V.30) / = n/j = n/k[(C1/Cf)1/n -1]
(V.31)
97
Chapter 5
The graphical technique for calculating the parameters of a cascade of the reactor with complete mixing suggested by Jones uj = -Cj//j + Cj-1//j u = -dCj/dt
uj=kf(Cj)
tga = -1/t j = -vj/V
C5 C4 C3 C2
C1
Cj
C
98
Chapter 5
Problem 1. The reversible exothermic process of oxidation of SO2 in a single bed of vanadium catalyst is carried out in an ideal plugflow reactor. SO2+1/2O2 n SO3 the temperature of the catalyst bed is 5700C and is assumed to be constan over the bed. The starting gas has composition (in % by volume): SO2-11, O2 10, N2 79. The consumption of gas is 15500 m3/h. The velocity of the gas flow in the reactor is w=1.4m/s. The reaction rate constant at 585 0C is 13.7. The equilibrium constant is given by lgKP = 4905/T 4.6455 The activation energy is E = 87800 kJ/kmole. The reserve factor is c=1.3. Calculation the reaction volume of the reactor, that is the volume of the catalyst bed, which provide for degree of conversion of 0.5. and the diameter of the reactor and the height of the catalyst bed 99
Chapter 5
Solution: Equation (V.14) for the ideal plug flow reactor yields / =v/Vm = C1<dxA/uA The rate of the oxidation reaction in the vanadium catalyst bed is given by the approximate equation derived by G.Boreskov u = k/2a [(xe-x)/x]0.8.[2b-ax]273/T Here a is the initial content of SO2 in the reaction mixture (% by volume), b is the initial content of O2 and xe is the equilibrium degree of conversion
x
/ =v/Vm = <dxA/ k/2a [(xe-x)/x]0.8.[2b-ax]273/T

0
100
Chapter 5
First we should find the reaction rate constant at 5700C from that at 5850C: 2.303lg(13,7/k) = 87800/8,314(1/843-1/858) k = 11.0 The equilibrium degree of conversion xe = KP/(KP+=(100-0.5axe)/(b-0.5axe) At 5700C we have: lgKP = 4905/843 4.6455 = 1.18 and KP = 15.15 xe = 0.79
0.5
/ =v/Vm = <dx/ 11.0/2*0.11 [(0.79-x)/x]0.8.[2*0.1-0.11x]273/843

0
101
Chapter 5
/ = 0.12 s The volume of catalyst is v = /cVm = 0.12*1.3*15500/3600 = 0.675 m3 The cross section of the reactor is S = Vm(T/T0) /w = = (15500/3600)*(843/273)/1.4 = 9.5 m2 The diameter of the reactor is D = =(4S/3) = 3.48 m The height of the catalyst layer is H = v/S = 0.675/9.5 = 0.71 m
102

Introduction: In the presence of catalyst the reaction passes a number of intermediate stages with lower activation energies than those of the non-catalytic reaction. For instance, the bimolecular A+B X AB Can proceed via the following intermediate stages in the presence of Catalyst Cat: A+[Cat] X A[Cat] A[Cat] +BXAB*[Cat] AB*[Cat] X AB + [Cat]
103

E n e rg y
AB*
E -E c
E A B * [C a t] A [C a t] Ec
E1 E2
A and B
AB
104
Chapter 6
The activation energgy of the non-catalytic reaction is E The activation energgy of the catalytic reaction is Ec E1 and E2 are activation energgies of the stages (a) and (b) Arrehenius equation k = k0exp(-E/RT) and owing to the exponential relationship the increase of E can be fairly large even for a small decrease of E Depending on the phase state of the reactants and the catalyst the Catalytic processes are classified into two groups homogeneous and heterogeneous processes
105
Chapter 6
The heterogeneous catalytic process proceeds via mass exchange and chemical satges which can be generally described as follows: 1. Diffusion of reactants from the flow core to the surface of the catalyst particles 2. Diffusion in the pores of catalyst particles 3. Activated (chemical) adsorption of reactants on the catalyst surface and formation of surface compounds 4. Rearrangement of atom and formation of product-catalyst complexes at the surface 5. Desorption of the product (regeneration of the active centres of 106 catalyst
Chapter 6
6. Diffusion of the product in the pores of catalyst particle 7. Diffusion of the product from surface of catalyst particle to the flow core The overall rate of a heterogeneous catalytic process is determined by that of its slowest stage. According to the limiting process stage the processes are claasified as being limited kinetics, external diffusion, and internal diffusion. Generally, the rate constant of a catalytic process can be written as k = f(k1, k2,, kside Dm, Dm, Dp)
107
Chapter 6
Where k1, k2, kside are the rate constant the direct, reverse, and side reaction and Dm, Dm, Dp are the diffusion coefficients of the starting materials and products for the process limited by External or internal diffusion. For the processes limited by kinetic the rate constant is independent of the diffusion parameters. According to the hydrodynamical interaction between the gas Flow and particulate catalyst the catalytic reactor are lassified into the following groups: 1. Reactor with stationary (filter) bed of catalyst 2. Reactor with fluidized bed of catalyst 108 3. Reactor with continuosly moving along the reaction space
Chapter 6
Depending on the temperature condition the catalytic processes and reactor can be classified as adiabatic, isothermic and variable temperature The activity of catalyst Acat = kcat/k = k0e-Ecat/RT / k0e-E/RT = e)E/RT Here )E = E Ecat To compare the activities of catalysts under different conditions the activity is determined as the intensity of process with a given catalyst expressed in kg/m3h: Acat = Gp/vcat/ Here Gp is the amount of the product, vcat is the volume of the catalyst, 109 and / is the time of reaction
Chapter 6
Acat = Gp/Gcat/ And Acat = Gp/S/ = Gp/Sspvcat / Where Gcat is the amount of catalyst, S is the total surface of the catalyst, and Ssp is specific surface area of catalyst, m2/m3.. Productivity Pcat = Gp// Intensity of operation i of the catalyst (kg/m3h) i = VvfCp4p or i = VviCmx 4p* Here Cp and Cm are the concentration of the product and the main starting material (molar fractions, 4p is density of the product 110 (kg/m3), Vv is the volume rate of flow of the gas (1/h)
Chapter 6
Vv = Vg/v * = Vvf/Vvi is used to convert the initial Vvi into the final Vvf to allow for variation of the volume of the reaction mixture. The catalyst selectivity Scat in defined as the ratio between the rate of formation of the specified main product and the overall rate of conversion of the main starting reactant in all reactions: Scat = dGp/(vp/vi)dGi Here vp/vi is the ratio of the stoichiometric factors for formation of product from the main initial reactant The overall (integral) selectivity is can be expressed as 111 Scat = Gm/G = Gm/ (Gm + G)
Chapter 6
Gm is the amount of the main product and Gs is the amount of the side products. The time of residence / in the catalytic reactors with the ideal plug flow is the same for all molecules. The theoretical residence time is /th = vcat/Vg = H/w Where vcat is the total volume of the catalyst (m3), Vg is the gas flow rate (m3/h), H is the height of the catalyst bed, w is the linear velocity of the gas in the reactor (m/s) The real residence time is /r = /th/5 Where 5 = vf/vcat is the porosity of the catalyst bed and vf is the free volume of the bed (m3) 112
Chapter 6
The catalyst volume needed to obtain a given degree of conversion is found from: vcat = cVg /th Where c is the reserve factor which allows for a decrease of the catalyst activity owing to poisoning and mechanical losses, Vg is the gas flow rate, and /th is the theoretical time of contact between the gas and the catalyst.
113
Chapter 6
Calculations catalytic reactors
The general kinetic equations provide a basis for calculations of the parameters of catalytic reaction. The plug flow reactor: u = dG/d/ = kvcatSsp)C Where Ssp is the specific surface of the catalyst (m2/m3), k is the overall reaction rate constant, )C is the driving force of the process. The general kinetic equation for the catalytic reaction of gas reactants over the solid catalyst taking into account the main process parameters can be written as u = k0e-E/RTvcat )pPn* Where )p is the driving force of the process expressed in term of the 114 partial pressures of the reactants.
Chapter 6
Pn is the ratio of the process pressure to the normal pressure 1,01*105 Pa * is the factor for conversion to normal temperature n is the overall reaction order Depending on the limiting stage of the process the kinetic equations for heterogeneuos catalytic processes over the solid porous catalysts can be written in various forms 1. For the processes limited by external diffusion the overall mass transfer equation can be written as u = 1/S . dGp/d/ = kM(CAg CAg*) Where S is the surface of contact between reactants and catalyst 3) 115 CA is the concentration of the main reactant A in the gas (kmole/m
Chapter 6
CAg* is the equilibrium concentration of A near the surface of the catalyst, CAg* is not known and should be eliminnated kM is the mass transfer coefficient, the coefficient kM for various condition can be found in literature or measured experimentally The dimensions of the reactor are sometimes determined by calculating the values of the height of transfer unit (HTU) and the number Z of transfer units: H = HTU.Z Here we heve: HTU = Gg/(MmkMSsppm) Gg is the mass flow rate of the gas (kg/m2h) Mm is the mean molecular mass of the gas components 116
Chapter 6
kM is the mass transfer coefficient (for the component A) (kmole/m2.h.Pa) Ssp is the specific surface of the catalyst (m2/m3) pm is the mean logarithmic partial pressure of the component A in the gas film pm = [(P+pA*A)-(P+pAi*A)]/ln[(P+pA*A)/(P+pAi*A) Where P is the pressure in the reactor (Pa) pA is the partial pressure of the component A (Pa), pAi is the partial pressure of the A at the catalyst surface (Pa) *A is the change of the number of moles of A owing to the reaction 117 ( per 1 mole of A)
Chapter 6
The HTU value is sometimes found from the emprical equations of the following type: SspHTU = BRem(Pr)n Here we have Re = dcatGg/4D and Pr = 6/4D Here dcat is the reduced diameter of the catalyst particles, D is the diffusion coefficient of the component A in the gas, 6 and 4 are the viscosity and the density of the gas for the given P and T in the reactor The number of transfer units is
pA1 pA2 NA1
Z = 7 pmdpA/[(P-pA)(pA-pA1)] = 7NmdNA/[(1-NA*A)(NA-NA1)]
NA2
118
Chapter 6
Where NA and NA1 are the molar fractions of the componet A in the gas and at the surface of the catalyst Nm = pm/P is the mean logarithmic concentration of A in the gas film 2. For the kinetics limited processes the form of the form of the equation depens on the limiting stage of the surface interaction. For instance, if the limiting stage of the gas reaction occurring in the presence of a neutral material A+B n R + S is adsorption of A at the catalyst surface the kinetic equation is
119
Chapter 6
u = k(pApB pRpS/KppB)/[1+KRKSpRpS+KBpB+KRpR+Ksps +K1np1n] If the limiting stage is the surface interaction between the adsorbed molecules A and B the equation can be written as: -uA = k[pApB - (pR pS)/KP]/[1+KApA+KBpB+KRpR+Ksps +K1np1n]2 And if the limiting stage is desorption we have: -uA = k[pApB/pS - (pRpS)/KP]/[1+KApA+KBpB+KppA.pB/ps+K1np1n] k is the reaction rate constant Kp is the equilibrium constant for the surface reaction KA, KB, KR and Ks are the equilibrium constants for adsorption of the intial components of the gas mixture and the reaction products K1n is the equilibrium constant for adsorption of the inert substance
120
Chapter 6
3. If the reaction is limited by internal diffusion the mean reaction rate for the first-order or pseudomonomolecular reaction inside the pore is: u = - 1/Sp . dGA/d/ = ksCAT, or u = - 1/vp . dGA/d/ = kCAT, Here Sp and vp are the surface and volume of the pore, ks is the reaction rate constant per unit surface area of the catalyst (m/h) k is the reaction rate constant (1/h) , = CA/CAT is the factor characterizing the degree of utilization of the internal surface
121
Chapter 6
CA is the mean concentration of A inside the pore CAg is the highest possible concentration of A near the catalyst surface The overall rate of the catalytic process for the first-order reaction is found by combining the equation for the mass-transfer rate u = - 1/Sp . dGA/d/ = kM(CAg C*Ag) With the equation for diffusion and reaction inside the catalyst particle u = - 1/vp . dGA/d/ = kMC*Ag, Elimination of the unknow surface concentration C*Ag yields u = - 1/Sp . dGA/d/ = [1/(S/k ,vp+1/kM)] C*Ag or u = - 1/vp . dGA/d/ = [1/(1/k ,+vp/kMS)] C*Ag Here k is given in 1/h and kM in m/h)
122
Chapter 6
Calculations of the heat-exchange surface area F which is needed to remove (deliver) the heat from the catalyst bed are made acccording to the general heat tranfer equation: Q = kTF)t/ The driving force )t of heat transfer is determined by the temperature tbed in the bed and the temperature tcool of the cooling agent. If the adiabatic reactor with filtercatalyst bed has no heat exchangers the final temperature tf of the reaction mixture can be found from given initial temperature t1: tf = t1 + qrCpx/c
123
Chapter 6
Here qr is the heat effect of the reaction (J/mole), Cp
124

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Trong s1 9* cng ngh> TBP( nhm Z v< tr nh5 sau :

H.1.1- L5u 9* kh:i c^a cng ngh> s3n xuOt .

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Do 9iTu ki>n ph3n 4ng rOt khc nhau:

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b}C bI~M TBP(

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I.3- Phn lo2i TBP( : 1/Theo ch6 9A lm vi>c :

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b/Thi6t b< lm vi>c n_a gin 9o2n:

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c/Thi6t b< lm vi>c lin t?c

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ThCi gian l u trung bnh:

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2/Theo ch6 9A dng ch3y : *M hnh t!?ng :

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M hnh khuOy l t5Zng

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3/Theo tr2ng th pha:

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4/Theo ch6 9A nhi>t:

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