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Kinetika Katalis Heterogen
Kinetika Katalis Heterogen
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Slamet Slamet
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Oleh
Prof. Dr. Ir. Slamet, MT
Departemen Teknik Kimia UI
September 2015
Sistem Kuliah Software Pendukung
Penjelasan singkat materi kuliah Interactive modules
Diskusi / Problem solving (CEP & OEP) Microsoft Excel
Interactive modules Polymath
Tugas
PR (CEP)
Paper (CEP & OEP)
Presentasi (CEP & OEP)
Test
Kuis
Interactive module
UAS
CEP : Closed Ended Problem
OEP : Open Ended Problem
1. Waktu Kuliah:
Toleransi keterlambatan kuliah ≤ 15 menit,
Persentase kehadiran ≥ 85 %.
2. Selama di kelas:
o Pakaian sopan, bersepatu,
o HP silent,
o Tidak keluar-masuk selama perkuliahan.
3. Ijin dari kuliah:
Karena sakit perlu Surat Keterangan Dokter utk minta
kuis susulan,
Selain sakit perlu surat ijin, tapi tidak ada kuis susulan.
4. Penilaian:
Tugas : 40%,
Kuis : 20%
Ujian : 40%,
Absensi.
PENDAHULUAN
Kenapa mempelajari TRK?
Application:
Mole Balance
Katalis heterogen:
Energy Ehom
Proses katalisis yg
melibatkan lebih dari Eads Ecat
Reacts
satu fasa, biasanya ads H
Prods
Fasa katalis: padat.
Edes des
Reaction Path
Konsep Reaksi
Katalisis Heterogen
Reaksi Katalitik : terjadi pada antar muka (interface) fluida-
padat luas permukaan antar muka hrs tinggi berpengaruh
secara signifikan pada laju reaksi.
Tipe katalis :
Porous (cracking catalyst: silica-alumina, S.A ~ 300 m2/g)
molecular sieve (zeolite, clay, dll)
Monolithic (mengurangi pressure drop & tahanan transfer
panas). Contoh: catalytic converter (honeycomb)
Supported (Pt/Al2O3, Ni/Al2O3, Rh/SiO2, dll)
Unsupported (Pt gauze, promoted Fe, silica-alumina, dll)
At equilibrium:
2. Dissociative Adsorption :
At equilibrium:
Model Adsorpsi (CO)
1. Molecular Adsorption : CO S CO.S
K A PCOCt PCO 1 PCO
CCO.S linierisas
i
1 K A PCO CCO.S K ACt Ct
CO.S
K A PCO Ct
1/ 2
P
CO
1/ 2
linierisasi
1
2PCO
1/ 2
1 2K A PCO K A Ct
1/ 2 1/ 2
CO.S Ct
Dissosiative
Molecular Adsorption
Adsorption
Model Adsorpsi (multi komponen)
A S A.S C
rAD A k PACV A.S
Adsorpsi : KA
B S B.S C
rAD B k PB CV B.S
KB
Konsentrasi A teradsorpsi:
K A PACt
C A.S
1 K A PA K B PB
A.S + S S + B.S
A.S + B (g) C.S + D (g)
Tahapan Penentu Laju (TPL)
1. Adsorpsi (molecular, dissociative)
2. Reaksi permukaan (single site, dual site,
eley rideal)
3. Desorpsi
TPL ??? TAHAP PALING LAMBAT
Tahapan Penentu Laju (TPL)
Reaksi heterogen pada keadaan steady laju setiap tahap
sama.
-rA’ = rAD = rS = rD
Contoh penentuan persamaan laju, mekanisme dan tahap penentu laju
Reaksi dekomposisi cumene :
C6H5CH(CH3)2 C6H6 + C3H6
CH(CH3)2 CH(CH3)2
C3H6 C3H6
C
rI k I PI Cv I .S 0 CI .S K I PI Cv Laju dekomposisi
KI
Cumene jika adsorpsi
Substitusi : mengontrol :
PB PP PB PP PP
rAD k A PC Cv k A PC Cv k A Ct PC B P
K AKS KD Ke Ke
rC ' rAD
PP P
Total sites (Ct) = 1 B P B K I PI
KS KD KD
vacant sites + occupied sites
Ct Cv (CC.S C B.S C I .S ) PB PP
Ke K P
PC
Ct
Cv G
PB PP P ln( K P )
B PI K I 1 RT
KDKS KD
Metode Initial Rate
B dan P belum terbentuk Pada tekanan tinggi (P >>)
Laju reaksi:
C B.S PP
rS k S CC .S
KS
# Laju adsorpsi: rAD = kA ( PPCV – CC.S/KA) CC.S = KAPCCV
PC PB C v
# Laju desorpsi: rD k D C B.S B v C B.S
KD KD
PP
k S Ct K A PC P B
Diperoleh Laju dekomposisi Cumen: rC' rS Ke
; KB 1/ K D
1 PB K B PC K A PI K I
Metode Initial Rate
k S Ct K A PC 0 k S Ct K A 0.5PTo
ro ' atau ro '
1 0 PC K A PI K I 1 (0.5K A 0.5K I ) PTo
PC
Laju desorpsi: rD k D C B.S B v
KD
PP
k D Ct K S K A PC B P
Diperoleh Laju dekomposisi Cumen: r Ke
PP PC K A K S K A PP PC K I PI PP
D
Metode Initial Rate
-ro’
PTo
• Data Eksperimen
• Tpl: Adsorpsi
-ro’ +
+
+ +
+
k A yCo PTo Ct
rCo '
+
1 y Io PTo K I
+
+
• Tpl: Reaksi permukaan
k S Ct K A yCo PTo
rCo '
1 ( yCo K A yIo K I ) PTo
PTo
Asumsikan
TPL
Susun persamaan
laju reaksi
-r'Tx10
10
Tekanan parsial (atm) 1. Menentukan pers. laju
Run (gmol-T/ g- Toluen Hidrogen Metana Benzen
cat.s) (PT) (PH2) (PM) (PB)
1
1 71.0 1 1 1 0 r 'T
2 71.3 1 1 4 0 1 K M PM .....
3 41.6 1 1 0 1 1
r 'T
4 19.7 1 1 0 4 1 K B PB .....
5 42.0 1 1 1 1
6 17.1 1 1 0 5
7 71.8 1 1 0 0
8 142.0 1 2 0 0 r 'T PH 2
9 284.0 1 4 0 0
10 47.0 0.5 1 0 0
11 71.3 1 1 0 0
PT
12 117.0 5 1 0 0 r 'T
13 127.0 10 1 0 0 1 KT PT .....
14 131.0 15 1 0 0
15 133.0 20 1 0 0 kPH 2 PT
16 41.8 1 1 1 1 r 'T
1 K B PB KT PT
Toluene H 2 clinoptilo
lite
Benzene Methane
Example 10-2 C6 H 5CH 3 H 2 clinoptilo
lite
C6 H 6 CH 4
C
Adsorption : T (g) S T S ; rAD k A Cv PT T S
KT
C P
Surface react . : H 2 ( g ) T S B S M ( g ); rS k S PH 2 CT S BS M
TPL
KS
Desorption : B S B( g ) S ; rD k D C BS K B PB Cv
r 'T
Ct k S KT PH 2 PT PB PM / K P kPH 2 PT
1 K B PB KT PT r 'T 1 K P K P
abaikan r .balik
B B T T
PH 2 PT 1 KB
Linierisasi PB KT PT
r 'T k k k
Toluene H 2 clinoptilo
lite
Benzene Methane
Example 10-2 C6 H 5CH 3 H 2 clinoptilo
lite
C6 H 6 CH 4
CT S Cv KT PT KT PTo (1 X ) KT (1 X )
Rasio (T.S/B.S) :
CBS Cv K B PB K B PTo X KB X
Fraction of Cv 1 1
:
vacant sites Ct 1 KT PT K B PB 1 KT PTo (1 X ) K B PTo X
Fraction of CT S Cv KT PT KT PTo (1 X )
:
toluene sites Ct Cv (1 KT PT K B PB ) 1 KT PTo (1 X ) K B PTo X
Ratio of Toluene sites to Benzene sites
Ratio of various active sites
0.5
0.4
Fraksi, -
0.3
PTo = 1 atm
0.2
Cv/Ct
0.1 C(T.S)/Ct
C(B.S)/Ct
C(T.S)/Ct + C(B.S)/Ct
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Konversi (X)
Ratio of various active sites
0.7
0.6
Cv/Ct PTo = 0.3 atm
C(T.S)/Ct
0.5
C(B.S)/Ct
Fraksi, -
C(T.S)/Ct + C(B.S)/Ct
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Konversi (X)
Disain Reaktor: Packed-Bed Reactor
dX '
rA rT'
Neraca mol : dW
FA0
FA0
dy
Neraca momentum : (1 X )
dW 2y
kPH 2 PT
Pers. Kinetika : '
rT
(1 K B PB KT PT )
Example 10-3
Mekanisme yg diusulkan:
C
(1). NO( g ) S
k1
NO S rAN k1 PN Cv NOS
K1
CCOS
(2). CO( g ) S CO S
k2
rAC k 2 PC Cv
K2
(3). NO S CO S
ks 1 N CO 2 S
2 2 2 rS k s C NOS CCOS
k s K1 K 2Ct2 PN PC kPN PC
rS r
'
(1 K1 PN K 2 PC ) 2
N
(1 K1 PN K 2 PC ) 2
Soal P10-6B
AlSi
• Reaksi kimia: Butanol (A) Butene (B) Water (C)
• Mekanisme:
- Adsorpsi : (1). A S A.S rAA k AA PACv C A.S / K AA
- R. Permukaan: (2). A.S S B.S C.S rS k S C A.S Cv CB.S CC .S / K S
- Desorpsi : (3). B.S BS rDB k DB CB.S PB Cv / K DB
(4). C.S CS rDC k DC CC .S PC Cv / K DC
-rAo
PC Cv (7) 0.4
0.3
PP
k S K AACt2 PA B C
rA rs
' Ke
(9)
1 K AA PA K DB 1 1
PB K DC PC
2
PB PC
dengan : K e K AA K S K DB K DC K P
PA
G
ln( K P )
RT
• Dg metode initial rate maka pers (9), menjadi:
kPA0
rA' 0 (10)
1 K AA PA0 2
• Linierisasi pers (10), diperoleh:
1
PA0
' 1 AA
K
2
PA0
1
(11)
k k
1
A0
r 2 2
Jawaban Fogler, P10-6B
25
y = 0.0745x + 4.1890
20 R² = 0.9950
0.9 1
P 2
1 K
0.8 A0 1 AA P
' 2 12 A0
(PAo/rA)^0.5
0.7
15 rA0 k k
0.6
0.5
-rAo
0.4
0.3
0.2
10
0.1
0
0 50 100 150 200 250 intercept= 4.189 --> k = 0.056987
5
PAo, atm
slope = 0.0745 --> KAA = 0.017785
0
0 50 100 150 200 250
PAo
Jawaban Fogler, P10-6B
1
0.9
0.8
0.7
Cv/Ct, CA.S/Ct
0.6
Cv/Ct
0.5
CA.S/Ct
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250
PAo (atm)