BAHAN KULIAH TRK-1

Oleh
Prof. Dr. Ir. Slamet, MT
Departemen Teknik Kimia UI
September 2012

Efek Difusi
Eksternal
 Tahapan Reaksi Katalitik
1. Transfer massa (difusi) reaktan, bulk →
permukaan eksternal pelet katalis A B
B
2. Difusi reaktan: mulut pori → External
A 1 7 Diffusion
permukaan internal katalis melalui pori.
3. Adsorpsi reaktan → permukaan katalis. B
4. Reaksi pada permukaan katalis A
5. Desorpsi produk (contoh: spesies B) dari 2 6 Internal
Diffusion
permukaan katalis.
6. Difusi produk dari permukaan internal 3 5
pelet menuju mulut pori pada
4 Catalytic
permukaan eksternal katalis. Surface
7. Transfer massa produk dari permukaan AÆB
eksternal ke fasa bulk.
Difusi
Eksternal
 Dasar-dasar transfer massa
• Neraca mol spesi A :

1. Sistem koordinat rectangular:

∂WAx ∂WAy ∂WAz ∂C A
− − − + rA = (A)
∂x ∂y ∂z ∂t

2. Sistem koordinat silinder:

1 ∂ ∂WAz ∂C A
− (rWAr ) − + rA = (B)
r ∂r ∂z ∂t
 Dasar-dasar transfer massa
• Fluks molar A, WA (mol/m2.s) merupakan jumlah dari
fluks difusi molekuler (JA) dan fluks dari gerakan bulk
atau konveksi (BA)
WA = J A + BA (1)
BA = y A ΣWi = C A V (2)

• Untuk sistem biner A dan B, fluks molar WA (mol/m2.s)

adalah:
WA = J A + yA (WA + WB ) (3)

• Hukum Fick: JA = -cDAB∇yA (4)

WA = -cDAB∇yA + yA(WA + WB) (5)
 Binary Diffusion
1. Equimolar Counter-diffusion (WA = -WB):
WA = -cDAB∇yA (6)
Utk konsentrasi total konstan:
WA = JA = -DAB∇CA (7)

2. Dilute Concentrations (yA ~ 0):

WA = -DAB∇CA (8)
Contoh utk 1 M larutan tertentu:
CW = 55 .6 mol / L
CA 1
yA = = = 0 .018
CW + C A 55 .6 + 1
 Binary Diffusion

• Pers (5) juga dpt disederhanakan menjadi pers (7)

utk sistem katalis porous dg jari-jari pori sangat
kecil.
• Difusi pd sistem tsb dikenal dg Difusi Knudsen,
terjadi ketika ‘mean free path’ dari molekul lebih
besar dari diameter pori katalis Æ tumbukan
molekul lebih sering terjadi dg dinding pori
dibanding dg antar molekul.
• Pers fluks molar A utk difusi Knudsen adalah (DK:
difusivitas Knudsen):
WA = -DK∇CA (9)
 Binary Diffusion
3. Diffusion through a Stagnant Gas (WB = 0):

• Difusi solute A melalui stagnant gas B, biasanya

terjadi pd sistem 2 fasa. Contoh: evaporasi,
absorpsi gas.
• Pers (5) menjadi:

WA = -cDAB∇yA + yAWA
−1 (10)
WΑ = cD AB ∇ y A
1− yA
WΑ = cD AB ∇ ln(1 − y A ) = cD AB ∇ ln( y B )
 Binary Diffusion
4. Forced Convection (JAz ≅ 0):

• Asumsi: Difusi ke arah z (aksial) sangat kecil

dibandingkan dg kontribusi aliran bulk.
• Pers (1) & (2) menjadi:
v FA
WA z = BA z = C A Vz = C A = (11)
Ac Ac
• Ac: cross-sectional area, v: volumetric flow
rate.
• Ketika efek difusi dpt diabaikan (plug flow):
FA = vC A (12)
 Binary Diffusion
5. Diffusion & Convective Transport:
dC A
WA z = − DAB + C AU z
dz (13)
⎡ dC A ⎤
FAz = W Αz A c = ⎢ − DAB + C AU z ⎥ A c
⎣ dz ⎦
• Dg memasukkan WAx, WAy, dan WAz ke pers (A) diperoleh:
⎡ ∂ 2C A ∂ 2C A ∂ 2C A ⎤ ∂C A ∂C A ∂C A ∂C A
D AB ⎢ + + 2 ⎥
− U x − U y − U z + rA =
⎣ ∂ x 2
∂ y 2
∂ z ⎦ ∂ x ∂ y ∂ z ∂t
d 2C A dC A
• Utk satu dimensi & SS: D AB 2
− U z + rA = 0 (14)
dz dz
dF Az
• Neraca mol utk tubular flow reactor: dV
= rA (15)
 Example 11-1

Difusi melalui stagnant film pada pelet katalis

Pelajari buku Fogler ed. 4, hal. 766 .................

 Korelasi koefisien transfer massa

ƒ Analogi dg transfer panas, korelasi koefisien transfer massa

(kc) utk aliran sekitar pelet bola (konveksi paksa) adalah
sbb:
1
Sh = 2 + 0.6 Re Sc
1
2 3 (16)

kc d p
Sh = (Bil. Sherwood)
DAB
ρUd p Ud p DAB
Re = = (Bil. Reynold) kc =
μ ν δ
μ ν
Sc = = (Bil. Schmidt )
ρDAB DAB
 Example 11-2
(Rapid reaction on a catalyst surface)

Diketahui:
• Diameter pelet katalis = 1 cm
• Reaktan A : konsentrasi encer Æ CAb = 1 M
• Reaksi spontan di permukaan katalis (CAs = 0)
• Kecepatan, U = 0.1 m/s
• Viskositas kinematik, μ/ρ = 0.5x10-6 m2/s
• Difusivitas A, DAB = 10-10 m2/s

Ditanya:
• Fluks molar A (WAr)
• Laju reaksi permukaan (-r’’As)
 Example 11-2
(Rapid reaction on a catalyst surface)

Jawab:
• Menghitung koefisien transfer massa:
Ud p
Re = = 2000 1
Sh = 2 + 0.6(2000) (5000)
1
ν 2 3

ν
Sc = = 5000 = 460.7
DAB
D AB Sh −6
kc = = 4 . 61 x10 m/s
dp

• Untuk konsentrasi encer:

WAr = kc (C Ab − C As ) = 4.61x10 −3 mol/(m2 .s) = -rAs
"
 Transfer massa pada
partikel tunggal
• Terdapat 2 kasus yg terkait dengan difusi & reaksi
pada partikel katalis:
1. Reaksi sangat cepat Æ “difusi” sbg penentu laju
reaksi
2. Reaksi sangat lambat Æ “reaksi” sbg penentu laju
reaksi.
• Reaksi isomerisasi : A Æ B terjadi di permukaan
katalis padat berbentuk bola. Reaksi permukaan
mengikuti mekanisme L-H ‘single site’, shg pers
kinetiknya adalah sbb:
k r C As
−r "
= (17)
As
(1 + K A C As + K B C Bs )
• Jika suhu cukup tinggi Æ adsorpsi sangat lemah Æ KA & KB
<<< 1 Æ pers (17) menjadi:

− rAs" = k r C As (18)

• Dengan kondisi batas 2b & 2c (Fogler, Tabel 11-1) diperoleh:

WA surface
= − rAs"
W A = k c (C A − C As ) = k r C As
kcC A
C As =
kr + kc
• Maka pers (18) menjadi:
kr kc
−r "
As = WA = C A = k eff C A (19)
kr + kc
 Reaksi cepat
• Jika reaksi sangat cepat Æ kr >> kc Æ pers (19) menjadi:

kc
−r "
As = C A ≈ k cC A (20)
1 + kc / kr

• Sc biasanya >> 2, sehingga utk Re > 25, maka Æ pers (16)

menjadi:
1 1
⎛ D AB ⎞ ⎛ Ud ⎞
2
⎛ ν ⎞
3

= 0 .6 ⎜ ⎟⎜ ⎟⎟ ⎜⎜ ⎟⎟
p
kc
⎜ d ⎟ ⎜⎝ ν
⎝ p ⎠ ⎠ ⎝ D AB ⎠
1
(21)
⎛ D AB3 ⎞ ⎛ U ⎞
2 2

kc = 0 . 6 x ⎜⎜ ⎟ x ⎜ ⎟
ν
1
⎟ ⎜ d ⎟
⎝ ⎠
6
⎝ p ⎠
kc = 0 . 6 x (Term 1 ) x (Term 2)
 Reaksi lambat
• Jika reaksi sangat lambat Æ kr << kc Æ pers (19) menjadi:

kr
−r "
As = C A ≈ krC A (22)
1 + kr / kc

-rA” Reaction
Diffusion
Limited Limited

(U/dp)1/2
 Mass Transfer-Limited Reactions
in Packed Beds

• Dari penjabaran neraca mol di reaktor packed-bed (Fig. 11-7, Fogler)

utk kecepatan superficial (U) konstan, diperoleh:
d (C A )
−U + r A" a c = 0
dz
• Utk reaksi-reaksi pd kondisi steady state, maka:
− r A" = W Ar = k c ( C A − C As )
• Utk reaksi-reaksi yang dibatasi transfer massa, CAs dpt diabaikan (CA
>> CAs) & tdk perlu mengetahui pers. Laju reaksi, maka:

dC A CA ⎛ kcac ⎞
−U = k c acC A = ⎜−
int egrasi pd z = 0 , C A =C Ao
⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯
⎯→ exp z⎟
dz C Ao ⎝ U ⎠

⎛ k a ⎞ ⎛ k a ⎞
X = 1 − exp ⎜ − c c z ⎟ dan − r A" = k c C Ao exp ⎜ − c c z ⎟
⎝ U ⎠ ⎝ U ⎠
(23)
 Mass Transfer-Limited Reactions
in Packed Beds

• Korelasi Thoenes-Kramers utk aliran melalui packed-bed:

1
Sh' = (Re' ) 2 ( Sc )
1
3

⎡ kcd p ⎛ φ ⎞ 1 ⎤ ⎡ ρ Ud p ⎤ ⎛ μ
1
2
⎞
1
3 (24)
⎢ ⎜⎜ ⎟⎟ ⎥ = ⎢ ⎥ ⎜⎜ ⎟⎟
⎣ D AB ⎝ 1 − φ ⎠ γ ⎦ ⎣ μ (1 − φ ) γ ⎦ ⎝ ρ D AB ⎠

• Korelasi di atas berlaku untuk:

0 . 25 < φ < 0 . 50
40 < Re' < 4000
1 < Sc < 4000

Pelajari Example 11-3 & 11-4

 Mass Transfer-Limited Reactions
on Metallic Surfaces

A. Catalyst Monolith
• In packed-bed reactors, when a
gaseous feed stream contains
significant amounts of particulate
matter, dust tends to clog the catalyst
bed.
• To process feed streams of this type,
parallel-plate reactors (monoliths) are
commonly used.
• The reacting gas mixture flows
between the parallel plates, and the
reaction takes place on the surface of
the plates.
 A. Catalyst Monolith

1. Mol balance

(R11.1-1)

1. am : the catalytic surface area per

unit volume of reactor,
2. A c : the cross-sectional area normal
to the direction of gas flow.
3. rA” : the rate of surface reaction is
equal to mass flux to the surface.
4. Taking the surface concentration
equal to zero for mass transfer-
limited reactions Æ (R11.1-2)
 A. Catalyst Monolith

Substituting Equation (R11.1-2) into (R11.1-1) and taking the limit

as 0 yields :
(R11.1-3)

(R11.1-4)

The surface area per unit volume, a, for n plates is:

(R11.1-5)

• Typical spacing between the plates = 0.005 - 0.01 m,

• The length ranges between 0.05 - 0.5 m, and
• Gas velocities between 5 - 20 m/s.
 A. Catalyst Monolith

• For no volume change with

• The mass transfer coefficient (kc) can
reaction, Equation (R11.1-4)
be calculated from the correlation :
can be integrated to give:

(R11.1-7)
(R11.1-6)
 B. Wire Gauzes

• Wire gauzes are commonly used

in the oxidation of ammonia and
hydrocarbons.
• A gauze is a series of wire
screens, stacked one on top of
another (Figure R11.1-4).
• The wire is typically made out of
platinum or a platinum-rhodium
Figure R11.1-4 alloy.
• The wire diameter ranges
between 0.004 and 0.01 cm

• One can assume plug flow

through the gauze, in which case (R11.1-8)
the design equation is similar to
that for monolith reactors:
 B. Wire Gauzes

• where ag = total screen surface area • The porosity can be calculated

per total volume of one screen, from the equation:
m2/m3 or in2/in3
(R11.1-10)
• The values of ag can be calculated
from the equations:
• The mass transfer coefficient can
be obtained from the correlation
for one to three screens:
(R11.1-9)

where d = wire diameter, in.

N = mesh size, number of
wires per linear inch (R11.1-11)
 B. Wire Gauzes

• For one to five screens, the corre-

lation is:
(R11.1-14)

(R11.1-12)

• where is the minimum • Equation (R11.1-14) is then

fractional opening of a single combined with Eqn. (R11.1-8) and
screen: solved.
(R11.1-13) • When dispersion is significant it
was shown that, depending on the
• When more than one or two
flow conditions, 33 to 300% more
screens are necessary, some
screens were required than
backmixing takes place. Shimizu et
predicted by the plug-flow model
al. account for this backmixing by
introducing dispersion in the axial
direction: