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REAKSI JAMAK

(MULTIPLE REACTIONS)

Prof. Dr. Ir. Slamet


Januari 2020
Jenis-jenis reaksi jamak
◼ Ada 4 jenis reaksi jamak: paralel,
seri, kombinasi paralel-seri, dan ◼ 2. Reaksi SERI = konsekutif :
independen. pertama raktan membentuk
◼ 1. Reaksi PARALEL = kompetisi: intermediate, lalu berlanjut ke
suatu reaktan membentuk produk lainnya.
beberapa produk melalui jalur
reaksi yg berbeda. A ⎯⎯→
k1
B ⎯⎯→
k2
C
k1 B
◼ Contoh reaksi SERI: etilen
A
oksida (E.O) + NH3 → mono,
k2 C
di, tri-ethanolamine
◼ Contoh reaksi paralel dlm industri:
oksidasi etilena → etilen oksida
E.O + NH 3 ⎯⎯→
k1
HOC 2 H 4 NH 2 ⎯⎯
E .O

2CO2 + 2H2O
CH2=CH2 + O2 ( HOC 2 H 4 ) 2 NH ⎯⎯
E .O
→( HOC 2 H 4 )3 N
CH2-CH2
O
Jenis-jenis reaksi jamak
◼ 3. Reaksi KOMBINASI SERI ◼ 4. Reaksi INDEPENDENT:
dan PARALEL = kompleks: beberapa reaktan masing-
masing menghasilkan produk
A+ B ⎯
⎯→ C + D tertentu melalui jalur berbeda
A+C ⎯
⎯→ E A⎯
⎯→ B + C
◼ Contoh reaksi kombinasi D⎯
⎯→ E + F
SERI – PARALEL: produksi
butadiena dari etanol. ◼ Contoh: reaksi perengkahan
crude oil utk membentuk
C2 H 5OH ⎯
⎯→ C2 H 4 + H 2O gasolin, diantaranya:
C2 H 5OH ⎯
⎯→ CH 3CHO + H 2 C15 H 32 ⎯
⎯→ C12 H 26 + C3 H 6
C2 H 4 + CH 3CHO ⎯
⎯→ C4 H 6 + H 2O C8 H18 ⎯
⎯→ C6 H14 + C2 H 4
Selektivitas & Yield
Reaksi PARALEL (1 reaktan)

Perhatikan reaksi berikut, D : Rate selectivity parameter (S) berikut


produk yg diinginkan dan U : harus dimaksimalkan utk meningkat-
produk samping. kan produk D.
rD k D 1 − 2
S D /U = = CA (4)
A ⎯⎯→ D
kD
rU kU
A ⎯⎯→
kU
U Bagaimana memaksimalkan S ???
Kasus 1: 1 > 2 → jaga agar CA
Persamaan laju reaksinya setinggi mungkin, dg:
adalah sbb: ➢ Jika reaksi fasa gas →P tinggi,
tanpa inert
rD = k D C A1 (1) ➢ Jika reaksi fasa cair → solven ttt
rU = kU C A 2 (2) dpt meningkatkan selektivitas
➢ Gunakan reaktor Batch atau PFR,
− rA = rD + rU (3) jangan gunakan CSTR. Why ...???
Reaksi PARALEL (1 reaktan)

Kasus 2: 1 < 2 → jaga agar CA Kasus 3: ED > EU → kD naik


serendah mungkin, dg cara: drastis dg naiknya T
➢ Encerkan umpan dg inert ➢ Reaksi hrs dijalankan pada suhu
➢ Jalankan reaktor dg CA rendah setinggi mungkin. Why ...???
➢ Gunakan reaktor CSTR atau
recycle reactor. Why ...???

Dari korelasi Arrhenius Kasus 4: ED < EU


diperoleh persamaan sbb: ➢ Reaksi hrs dijalankan pada suhu
serendah mungkin, namun tdk
k D AD −( ED − EU )/ RT  boleh terlalu rendah. Why ...???
= e
kU AU (5)
Reaksi PARALEL (2 reaktan)

Perhatikan reaksi berikut, Bagaimana memaksimalkan S ???


D : produk yg diinginkan dan
U : produk samping. Kasus 1: 1 > 2 , 1 > 2
A + B ⎯⎯→
k1
D : rD = k1C A1 C B1
→ jaga agar CA dan CB setinggi
2 2
A + B ⎯⎯→ U : rU = k 2C A C B
k2
mungkin, dg cara:
➢ Jika reaksi fasa gas →P tinggi,
Instantaneous selectivity (S) tanpa inert
berikut harus dimaksimalkan utk ➢ Gunakan reaktor Batch atau PFR,
meningkatkan produk D. jangan gunakan CSTR.
Why ...???
rD k1 1 − 2 1 −  2
S D /U = = C A CB (6)
rU k2
Reaksi PARALEL (2 reaktan)

Kasus 2: 1 > 2 , 1 < 2 Kasus 3: 1 < 2 , 1 > 2

→ jaga agar CA setinggi mungkin → jaga agar CB setinggi mungkin


dan CB serendah mungkin, dg dan CA serendah mungkin, dg
cara: cara:
➢ Gunakan reaktor Semi-Batch: ➢ Gunakan reaktor Semi-Batch:
masukkan umpan A sekaligus, B masukkan umpan B sekaligus, A
dimasukkan scr kontinyu sedikit dimasukkan scr kontinyu sedikit
demi sedikit. demi sedikit.
➢ Gunakan reaktor Membran atau ➢ Gunakan reaktor Membran atau
pipa dg umpan B scr kontinyu pipa dg umpan A scr kontinyu
melalui side streams melalui side streams
➢ Gunakan sejumlah CSTR kecil SERI ➢ Gunakan sejumlah CSTR kecil SERI
dg umpan A hanya masuk ke reak- dg umpan B hanya masuk ke reak-
tor I & B masuk ke setiap reaktor tor I & A masuk ke setiap reaktor
Reaksi PARALEL (2 reaktan)
Kasus 4: 1 < 2 , 1 < 2

→ jaga agar CA dan CB serendah mungkin, dg


cara:
➢ Gunakan reaktor CSTR.
➢ Gunakan reaktor pipa dg rasio recycle yang besar.
➢ Umpan dicampur dg inert.
➢ Untuk fasa gas → tekanan rendah

KESIMPULAN

Reaksi Jamak (baik paralel maupun seri) → Produk


samping dapat diminimalisasi, dg cara:
1. Mengatur kondisi reaksi (konsentrasi, suhu, tekanan, waktu, dll)
2. Memilih jenis reaktor yg tepat
Reaktor Isotermal
untuk
Reaksi PARALEL
Example 1 (Fogler, 6-2): maximizing the
selectivity for parallel reactions

Problem Solution
Gas phase dekomposition of A The selectivity with respect to B:
following the equations: rB k 2 .C A
S B / XY = =
rX + rY k1 + k3 .C A2
(1). A ⎯⎯→
k1
X − r1 A = rX = k1
(2). A ⎯⎯→
k2
B − r2 A = rB = k 2 .C A
(3). A ⎯⎯→
k3
Y − r3 A = rY = k3 .C A2

Specific reaction rate at 300 K, k1 =


0.0001 mol/(dm3.s), k2 = 0.0015 s-1,
and k3 = 0.008 dm3/(mol.s). Activa-
tion energies for E1, E2, E3 are10000,
15000, 20000 cal/mol. Initial cond:
CAo = 0.4 M, vo = 2 dm3/s.
→ How maximize the SB/XY ???
Solution...........

To operate at the (SB/XY)max. → use V =  .o = 1566 dm3


a CSTR, with CA max (CA*).

dS B / XY k1 Maximize the selectivity wrt. T:


= 0 → C A* = = 0.112 dm 3 /mol
dC A k3 k1
k2
k 2 .C A* k3 k2
CSTR volume: S B / XY = = =
k1 + k3 .C A*2 k1 + k1 2 k1.k3
- Rate of formation:
 E1 + E3 
 − E2 
rA = r1 A + r2 A + r3 A A2 2
S B / XY = exp  
− rA = k1 + k 2 .C A + k3 .C A2 2 A1. A3  RT 
 
- Mol balance on a CSTR: E + E3
 o C Ao − C A*   o C Ao − C A*  1. 1  E2 → Run at high T
V= =
k 
2
− rA 1 + k 2 .C A* + k3 .C A*2 E + E3
 E2 → Run at low T
(C )
2. 1
V − C A* 2
= = = 783 s
 
Ao
o k1 + k 2 .C A + k3 .C A
* *2 E + E3
3. 1 = E2 → independen of T
2
Solution...........

CSTR followed by PFR


𝑑𝐹𝐴 𝑑𝐶𝐴
PFR 𝑑𝑉
=
𝑑
= 𝑟𝐴
Solution...........
Solution...........

CAo = 0.4 mol/L


FAo = 0.8 mol/s

T = 300K
V = 1566 L

CA* = 0.112 mol/L CAf = 0.038 mol/L


FA1 = 0.224 mol/s FAf = 0.076 mol/s
V = 600 L
CB1 = 0.132 mol/L CBf = 0.163 mol/L
CX1 = 0.078 mol/L CXf = 0.108 mol/L
CY1 = 0.079 mol/L CYf = 0.091 mol/L
SB/XY = 84% SB/XY = 82%
X1 = 72% Xf = 90.6%
Pengaruh Suhu (E2 = 15000)
( E1 = 10.000, E2 = 15.000, E3 = 20.000 )

CSTR dengan variasi suhu (T)


T, K k1 k2 k3 C A* SB/XY V, Lt Thou, s X
280 3.02E-05 0.000249 0.000728 0.2035 0.8385 3541.6 1770.8 0.49114
300 0.0001 0.0015 0.008 0.1118 0.8385 1567.5 783.771 0.72049
325 0.000363 0.010393 0.10567 0.0586 0.8385 510.86 255.432 0.85338
333 0.000527 0.018159 0.222373 0.0487 0.8385 362.43 181.214 0.87827
342 0.000785 0.032974 0.492646 0.0399 0.8385 249.58 124.792 0.90022
375 0.002865 0.230023 6.566426 0.0209 0.8385 71.974 35.9872 0.94778
450 0.026825 6.590072 575.6456 0.0068 0.8385 7.9723 3.98614 0.98293
500 0.08208 35.27361 5389.745 0.0039 0.8385 2.6248 1.31239 0.99024
Pengaruh Suhu (E2 = 15000)
( E1 = 10.000, E2 = 15.000, E3 = 20.000 )

1 3600
0.9
3000
0.8
0.7
CA* 2400
0.6
CA* , SB/XY

0.5 SB/XY 1800

V, Lt
0.4 X
1200
0.3 V, Lt
0.2
600
0.1
0 0
280 330 380 430 480

Temperature, K
Pengaruh Suhu (E2 = 15000)
( E1 = 10.000, E2 = 15.000, E3 = 20.000 )
1
0.9
0.8
0.7 SB/XY (T=300K)
0.6
X, SB/XY

0.5 X
0.4
0.3 SB/XY (T=342K)
0.2
0.1
0
0 0.05 0.1 0.15 0.2
CA (mol/dm 3 )
Pengaruh Suhu (E2 = 17000)

E1 = 10000
E2 = 17000 cal/mol
E3 = 20000

T, K k1 k2 k3 CA* SB/XY V, Lt Thou, s X


300 0.0001 0.0015 0.008 0.1118 0.8385255 1567.5 783.771 0.72049
310 0.000172 0.003764 0.023612 0.0853 0.9343727 946.97 473.487 0.78675
320 0.000285 0.008916 0.065131 0.0662 1.0341564 575.13 287.566 0.83453
330 0.00046 0.020047 0.168945 0.0522 1.1375793 354.11 177.055 0.86961
342 0.000785 0.049787 0.492646 0.0399 1.2660789 202.49 101.247 0.90022
350 0.001098 0.088196 0.96536 0.0337 1.3541794 141.63 70.8155 0.91567
400 0.006628 1.872709 35.14705 0.0137 1.9399751 19.822 9.91094 0.96567
500 0.08208 134.9888 5389.745 0.0039 3.2089584 1.1465 0.57327 0.99024
Pengaruh Suhu (E2 = 17000)
( E1 = 10.000, E2 = 17.000 E3 = 20.000 )

2 1600
CA*
SB/XY 1400
1.6
X 1200
V, Lt
1000
X, CA*, SB/XY

1.2

V, Lt
800
0.8 600

400
0.4
200

0 0
300 320 340 360 380 400
Temperature, K
Pengaruh Suhu (E2 = 17000)
( E1 = 10.000, E2 = 17.000 E3 = 20.000 )
1.3
1.2
1.1
1
0.9
0.8
X, SB/XY

0.7
0.6
0.5
0.4
0.3
0.2 X
0.1
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
CA (mol/dm 3 )
Reaktor Isotermal
untuk
Reaksi SERI
Example 2 (Fogler, 6-4): maximizing the
yield/conversion for series reactions

A ⎯⎯→
k1
B ⎯⎯→
k2
C
Example 2 (Fogler, 6-4): maximizing the
yield/conversion for series reactions

A ⎯⎯→
k1
B ⎯⎯→
k2
C
Example 2 (Fogler, 6-4): maximizing the
yield/conversion for series reactions

A ⎯⎯→
k1
B ⎯⎯→
k2
C
10 10
CA
CB CA
8 CC 8 CB
CC

6 6
Konsentrasi

Konsentrasi
CAo = 10 ' opt = 2.325844
k1 = 2 Wopt = 23.25844
4 4
k2 = 0.02 Xopt = 0.990455

2 2

0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0

' '
Example 2 (Fogler, 6-4): maximizing the
yield/conversion for series reactions

A ⎯⎯→
k1
B ⎯⎯→
k2
C
10 10
CA CAo = 10 ' opt = 0.693147

CB k1 = 2 Wopt = 6.931472
8 8 k2 = 1 Xopt = 0.75
CC

CA
6 6
Konsentrasi

Konsentrasi
CB
CC

4 4

2 2

0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0

' '
Example 2 (Fogler, 6-4): maximizing the
yield/conversion for series reactions

1.0
0.9
0.8
0.7
X-opt & Y-opt

0.6
0.5 X-opt
0.4 Y-opt
0.3
0.2 A ⎯⎯→
k1
B ⎯⎯→
k2
C
0.1
0.0
0 10 20 30 40 50

k1/k2
Example 2 (Fogler, 6-4): maximizing the
yield/conversion for series reactions

0.9
0.8 k1/k2=10
0.7 k1/k2=1
k1/k2=0.5
Yield, YB=CB/CAo

0.6
0.5
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

Conversion, XA=(CAo-CA)/CAo
Reaktor Isotermal
Reaksi
untuk
PARALEL-SERI
Neraca MOL Reaksi Jamak
Algoritma Reaksi Jamak

1D

Evaluasi (Polymath)
Example 3 (Fogler, 6-6): multiple reactions
(parallel + series ) in PFR/PBR
Example 3 (Fogler, 6-6): multiple reactions
(parallel + series ) in PFR/PBR
Example 3 (Fogler, 6-6): multiple reactions
(parallel + series ) in PFR/PBR
Example 3 (Fogler, 6-6): multiple reactions
(parallel + series ) in PFR/PBR
Example 3 (Fogler, 6-6): multiple reactions
(parallel + series ) in PFR/PBR
Example 3 (Fogler, 6-6): multiple reactions
(parallel + series ) in PFR/PBR
Example 3 (Fogler, 6-6): multiple reactions
(parallel + series ) in PFR/PBR
Example 3 (Fogler, 6-6): multiple reactions
(parallel + series ) in PFR/PBR
Example 4 : membrane multiple reactions

➢ Reaksi jamak fasa gas:

(1) A + B ⎯⎯→ − r1A = k1CA CB , k1 = 2 dm 6 /mol 2 .s


k1 2
P

(2) A + B ⎯⎯→ − r2 A = k2 CACB , k 2 = 3 dm 6 /mol 2 .s


k1 2
X

➢ Selektivitas P (produk utama):


CB0
2 υm
k1CA CB k1CA Ps
S P/X = 2
= B
k2 CACB k2CB Pt

V=0
B
Example 4 : membrane multiple reactions
Example 4 : membrane multiple reactions
Example 4 : membrane multiple reactions
Non-isothermal
Multiple Reactions

 (− r )− H (T )
q
Ua(Ta − T ) + ij Rxij
Neraca Energi dT
= i =1
i = nomor reaksi
PFR:
m
dV
 F Cp
j =1
j j
j = spesi

A ⎯⎯→
k1
B dT Ua (Ta − T ) + (−r1A )(−H Rx1A ) + (−r2 B )(−H Rx 2 B )
=
dV FAC p + FB C p + FC C p
B ⎯⎯→
k2
C A B C

A ⎯⎯→ dT Ua(Ta − T ) + (−r1 A )( −H Rx1 A ) + (−r2 A )( −H Rx 2 A )


k1
B
=
2 A ⎯⎯→
k 2
C dV FACp A + FB Cp B + FC CpC
Non-isothermal
Multiple Reactions

m q
Neraca Energi UA(Ta − T ) − FAo  Cp j  j (T − T0 ) + V  rij H Rxij (T ) = 0
CSTR: j =1 i

i = nomor reaksi
j = spesi

A ⎯⎯→
k m
1
B
2 A ⎯⎯→ C
k2
UA(Ta − T ) − FAo  Cp 
j =1
j j (T − T0 ) + Vr1 A H Rx1 A (T ) +Vr2 A H Rx 2 A (T )
Example 5: PBR Non-isothermal
Program Polymath
PBR vs MEMBRAN

FB
FA
FA

FB

FF,FG
FC
FD,FE
FD,FE
PBR vs MEMBRAN
Example 6: PBR Non-isothermal
Program Polymath
PBR vs MEMBRAN

FA FA
T/To T/To

FB FB X

X
PBR vs MEMBRAN
(Pengaruh W)

FA FA
T/To
T/To

FB X
FB
X