Teknik Reaksi Kimia Lanjut Advanced in Reaction Engineering

Dr.-Eng. IGBN Makertihartha

Lab. Teknik Reaksi Kimia dan Katalisis

Reaksi Kompleks pada Reaktor Ideal

Kinetika kompleks Reaksi Kompleks pada ReaktorReaktor Ideal

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Kinetika Reaksi Kompleks

Dalam sebuah Reaktor Aliran Sumbat (RAS):

Pada sebuah sistem reaksi kimia yang melibatkan komponen A, B, C, , neraca massa masing-masing komponen dapat digambarkan oleh sistem persamaan diferensial:
u dC A = rA (C A , C B , C C ,...) dz dC B = rB (C A , C B , C C ,...) u dz dC C = rC (C A , C B , C C ,...) u dz
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Kinetika Reaksi Kompleks

Dalam sebuah Reaktor Tangki Ideal Kontinyu (RTIK):

f1 (C A , CB , CC ,...) = 0 f 2 (C A , CB , CC ,...) = 0 f3 (C A , CB , CC ,...) = 0

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Kinetika Reaksi Kompleks

Suku rA, rB, rC identik dengan laju reaksi kimia untuk sistem dalam reaktor partaian. Suku-suku ini akan lebih representatif jika juga merupakan fungsi dari temperatur yang merupakan operator utama pada besarnya laju reaksi spesifik atau tetapan laju reaksi. Pada kasus realistik, sistem persamaan diferensial di atas harus diselesaikan secara numerik karena hampir dapat dipastikan bahwa penyelesaian analitik sebuah sistem persamaan diferensial tak linier tidak terdefinisi.

Model Kinetika Reaksi Kompleks

r = f ( k j , Ci ) untuk j = 1: n dan i = A, B,...

Pada prinsipnya, proses penentuan parameter kinetika pada sebuah model kinetika kompleks adalah mencari parameter-parameter kinetika yang menyebabkan akumulasi kesalahan yang diakibatkan perbedaan nilai antara data kinetika dengan nilai hasil perhitungan dengan model sekecil mungkin.
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Perkiraan Parameter Kinetika Kompleks

Fungsi obyektif yang harus diminimalkan:

E = i C i ,m C i ,data
E 2 = i (C i ,m C i ,data )
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Algoritma
Masukkan: 1. Data kinetika CA,data 2. Model kinetika 3. Tebakan awal ko 4. Parameter optimasi

Evaluasi Ci,m dengan menyelesaikan sistem persamaan diferensial

Perkirakan harga k baru dengan metoda optimasi

Evaluasi fungsi obyektif optimasi FOBJ berdasarkan harga k terbaru Hitung FOBJ

No

FOBJ min?

Yes

Parameter kinetika k

E 2 = i (C i ,m C i ,data )

Selesai

Contoh 1 Kinetika Reaksi Kompleks

Tentukan harga parameter kinetika (m, n, ki) dari reaksi kompleks berikut yang terjadi dalam sebuah reaktor RAS:
k1 A+ B C C D k3
k2

n m r A = k1C A CB n m rC = k1C A C B k 2 CC + k 3C D

Data Kinetika

(jam)
0.000 0.001 0.006 0.016 0.031 0.049 0.072 0.101 0.136 0.178

CA (mol/m3) 50.00 49.79 48.94 47.29 45.08 42.45 39.46 36.20 32.76 29.18

CC (mol/m3) 0.00 0.21 1.06 2.68 4.82 7.30 10.04 12.91 15.79 18.60

(jam)
0.230 0.294 0.372 0.463 0.568 0.691 0.833 0.997 1.188 1.409

CA (mol/m3) 25.56 21.99 18.53 15.46 12.77 10.45 8.48 6.83 5.46 4.33

CC (mol/m3) 21.22 23.58 25.61 27.21 28.45 29.43 30.22 30.88 31.46 31.97

(jam)
1.665 1.962 2.306 2.705 3.168 3.668 4.168 4.668 5.000

CA (mol/m3) 3.42 2.68 2.09 1.62 1.26 0.98 0.79 0.65 0.58

CC (mol/m3) 32.42 32.81 33.14 33.41 33.64 33.81 33.93 34.02 34.06

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Persamaan Kinetika
dC A n m = k1C A CB d dC C n m = k1C A C B k 2 CC + k 3C D d

Neraca Massa
C D = C Do + (C Ao C A ) + (C Co C C ) C B = C Bo (C Ao C A )

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Metoda Optimasi untuk Kinetika Kompleks

Fungsi Obyektif
FOBJ =
2 ( ) C C i,m i,data

i = A,C

Metoda Numerik

fminsearch : peminimum fungsi obyektif ode23 : integrasi (sistem) persamaan diferensial

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Program MATLAB
Program utama:
% tebakan awal k = [.5 1 3 1 .5]; %eksekusi optimisasi Konstanta = fminsearch('kinetics',k)

Program persamaan kinetika:

function dYdt = laju(t,Y,FLAG,Co,k) A = Y(1); B = Co(2) - (Co(1) - A); C = Y(2); D = Co(5) + Co(4)+(Co(1) - A) - C; dYdt = [ -k(1)*A.^k(4)*B.^k(5) k(1)*A.^k(4)*B.^k(5) - k(2)*C + k(3)*D];

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Program MATLAB

B. Program menghitung fungsi obyektif:

function minimize = kinetics(k) tdat = [ 0 0.0002 0.0012 : 4.6679 5.0000 ];

Ydat =[ 49.96 49.79 48.93 47.29 45.08 : 0.65 0.57

50.00 0 0.03 0.20 1.05 2.67 4.81 34.01 34.06 ];

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Program MATLAB
Lanjutan
% Parameter ODE Co = [Ydat(1,1) 50 Ydat(1,2) 0]; [t,Y] = ode23('laju',tdat',[Co(1) Co(3)],[ ],Co,k); % Plot hasil parsial dari estimasi k plot(t,Y,'black-',tdat,Ydat,'blacko') title('Plot estimasi parameter kinetika') xlabel('t [detik]') ylabel('Konsentrasi') grid pause(.05) % Akumulasi kesalahan FOBJ minimize = sum(sum(Y-Ydat).^2);
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Hasil Estimasi Parameter

Dengan tebakan awal

k1=0,5, k2=1, k3=3, n=1, m=0,5,

diperoleh harga parameter kinetika sebagai berikut:

k1 = 0.4975 k2 = 1.1141 k3 =2.3440 n = 0.9899 m = 0.5035

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Simulasi Kinetika
Plot estimasi parameter kinetika 50 45 40 35 Konsentrasi [mol/m3] 30 25 20 15 10 5 0

0.5

1.5

2.5 t [jam]

3.5

4.5

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Complex Kinetics of Ethanol Oxidation on the Ag Gauzed Catalyst

IGBN Makertihartha
Department of Chemical Engineering Institut Teknologi Bandung Jalan Ganesha 10, Bandung 40132 Indonesia

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Acetaldehyde

Important intermediate aliphatic chemicals for producing acetic acid, acetic anhydride, pentaerythritol, pyridine, etc Process:
Metal oxide catalysed process Ag catalysed process

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Acetaldehyde Production Routes

Hydration of acetylene Oxidation of Ethylene Oxidation of saturated HC Oxidation of Ethanol Dehydrogenation of Ethanol

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Silver vs Metal-Oxide Catalyst

Variables Catalyst Conversion MeOH/air ratio Opr. Pressure Opr.Temperature Tolerance to contaminant Reaction Silver Catalysed Process metal (silver) 85 95 % Higher than flammability limit of mixture (> 36 %-vol) 1 atm 600 650 C Low Oxidative and non-oxidative pathway (dehydrogenation) Metal-Oxide Catalyst Fe/Mo Oxide > 99 % Lower than flammability limit of mixture (< 6,7 %-vol) 1 atm 330 380 C High Direct oxidation

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Problem Definition

Very active catalyst. Low selectivity compared with the metal oxide catalyst process. Catalyst development

Modification of Ag catalyst active site

Stability and kinetics study of complex reaction of Ethanol Oxidation.

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Research Destination
to suggest some plausible mechanisms for building model for complex kinetics of ethanol conversion to acetaldehyde over silver catalyst

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Silver Catalyst Data

Form Weight Thick Diameter Color-fresh spent Useful life Poisoned by metal 0.038-0.042 gr 0.05 cm 2-2.3 cm off-white dark grey/black 3-12 months transition metals (Fe, S, etc)

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Operating Variables
Operation Pressure Ethanol to Air Ratio Reaction Temperature Space Time (Wcat/Ffeed) 1 atm 1.2 % (vol) 475 550 C 0.034 0.674 gr.hr/mole

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Apparatus Set-Up
tail gas air buble soap flowmeter

nitrogen

oxygen

tail gas

thermocouple
300

ethanol syringe pump reactor furnace nickelin wire termolyne

thermocouple display

tail gas

N2

O2 acetaldehyde heater set up

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Possible Reactions

ETHANOL OXIDATION C2H5OH + O2 CH3CHO + H2O ETHANOL DEHYDROGENATION C2H5OH CH3CHO + H2, EXCESSIVE OXIDATION OF H2 H2 + O2 H2O, OXIDATION OF ACETALDEHYDE CH3CHO + 5/2 O2 2 CO2 + 2 H2O, DEHYDRATION OF ETHANOL C2H5OH C2H5OC2H5 + H2O
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Kinetic Model
r1 = ksr1KO pE pO1 / 2 (1 + KO pO1 / 2 + K A p A + KW pW + KC pC )
2

Ethanol oxidation

r4 =

ksr4KA pAKO pO5 / 2 (1+ KA pA + KO pO5 / 2+KC pC2 + KW pW2 )2

Acetaldehyde oxidation

r5 = kdee pEn

Ethanol dehydration

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Ethanol Conversion
1 0.98 Ethanol Conversion 0.96 0.94 0.92 0.9 T = 550 oC 0.88 0 0.2 0.4 0.6 0.8
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T = 475 oC T = 525 oC

W/F [gr cat.hr/mole EtOH]

CO2 and (C2H5)2O Selectivity

0.02 0.018 0.016 0.014
diethyl ether selectivity 0.06 0.05 0.04 0.03 0.02 0.01 0 T=475 oC T=525 oC T=550 oC 0.09

T=475 oC T=525 oC T=550 oC

0.08 0.07

CO2 Selectivity

0.012 0.01 0.008 0.006 0.004 0.002 0

0.1

0.2 0.3 0.4 0.5 space time [gr.hr/mole etOH]

0.6

0.7

0.1

0.2 0.3 0.4 0.5 space time [gr.hr/mole etOH]

0.6

0.7

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Kinetic Model

Kinetic Rate Constants :

ksrI = 1.914x104 exp (-11447.66/RT) ksrII = 1.918x104 exp(-12374.49/RT) kIII = 3.830x103 exp(-2818.64/RT)

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Kinetic Model
ln K O 2
ln K A

1 4 4 7 2 .7 8 1 2 .6 0 8 = RT R
15630 . 72 15 . 861 = RT R

ln K CO 2

16117 .98 20 .818 = RT R

ln K W

16823 . 44 23 . 336 = RT R
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Parity Plot T = 475 C

T = 475oC 0.12 data vs model at T=475oC 0.18 0.16 0.1 0.14 [ p a rtia l p re s s u re ] m o d e l 0.08 p a rt ia l p re s s u re 0.12 0.1 0.08 0.06 0.04 0.02 0 0 0.1 0.2 0.3 0.4 space time 0.5 0.6 0.7

0.06

0.04

0.02

pE exp pE model pA exp pA model pCO2 exp pCO2 model pDEEexp pDEE model

pE pA pCO2 pDEE 0 0.02 0.04 0.06 0.08 0.1 0.12 [partial pressure] data 0.14 0.16 0.18

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Parity Plot T = 525 C

T = 525oC
0.12

data vs model at T=525oC 0.18 0.16

0.1 pE exp pE model pA exp pA model pCO2 exp pCO2 model pDEEexp pDEE model

0.14 [ p a rt ia l p re s s u re ] m o d e l 0.12 0.1 0.08 0.06 0.04 pE pA pCO2 pDee 0 0.02 0.04 0.06 0.08 0.1 0.12 [partial pressure] data 0.14 0.16 0.18

0.08

p a rt ia l p re s s u re

0.06

0.04

0.02

0.02
0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

space time

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Parity Plot T = 575 C

T = 550oC
0.12

data vs model at T=525oC 0.18 0.16

0.1

0.14
0.08

[ p a rt ia l p re s s u re ] m o d e l

0.12 0.1

p a rt ia l p re s s u re

0.06 pE exp pE model pA exp pA model pCO2 exp pCO2 model pDEEexp pDEE model 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

0.08 0.06 0.04 0.02 0 0 0.02 0.04 0.06 0.08 0.1 0.12 [partial pressure] data 0.14 0.16 0.18 pE pA pCO2 pDee

0.04

0.02

space time

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Consistency

Statistical Consistency!!

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Consistency

Thermodynamic Consistency (Boudarts Rule)

there is a reduction in entropy caused by a changed in dimensional phase when a gaseous molecule (3-D phase) is adsorbed on the surface of catalyst (2-D phase)

Boudarts rule (1), Sao < 0 for all components

Boudarts rule (2), -Sao < Sgo for all components

a molecule cannot lose more entropy than it has

Boudarts rule (3), -Sao > 41.84 J/mole.K [9.9998 cal/mole.K] for all components Boudarts rule (4), -Sao < 51.05+0.0014(- Hao)J/mole.K
based on empirical work of Everett

as a conservative guideline which is based on the change in volume that occurs when a gaseous molecule is adsorbed

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Conclusion

Hougen-Watson formalism is excellent tool to model the heterogeneous catalytic reactions It is statistically and thermodynamically consistent

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