REACTOR

CHEMICAL ENGINEERING
UNIVERSITAS MUHAMMADIYYAH SURAKARTA
(UMS)

1
LEC 9

1. Temperature control
2. The Packed Bed Catalytic Reactor
3. Effect of temperature
4. Non Isothermal Reactor
5. Case study

2
There is a heat
Reversible/
Irreversible Temperature Control transfer from or into
the reactor
(exothermic, endothermic, adiabatic, non adiabatic)
T >>>> - H = - T <<<<<
o Consider the temperature control of the reactor first. In contrast to ideal models,
practical reactors must consider many factors other than variations in
temperature, concentrations, and residence time.

o Adiabatic operation. Adiabatic operation of the reactor should be considered

since this leads to the simplest and cheapest reactor design.

o If adiabatic operation produces an unacceptable rise in temperature for

exothermic reactions or an unacceptable fall in temperature for endothermic
reactions, then methods of temperature control need to be considered.

Reaksi samping, Produk samping,

Range suhu untuk Reaksi
Katalis 3
Temperature Control
(exothermic, endothermic, adiabatic, non adiabatic)
o Cold shot and hot shot. The injection of cold fresh feed directly into the reactor at
intermediate points, known as cold shot, can be extremely effective for control of temperature
in exothermic reactions. If the reaction is endothermic, then fresh feed that has been preheated
can be injected at intermediate points, known as hot shot.

4
Temperature Control
(exothermic, endothermic, adiabatic, non adiabatic)
o Non adiabatic operation by indirect heat transfer with the reactor. This might be by a heat
transfer surface inside the reactor, such as carrying out the reaction inside a tube and
providing a heating or cooling medium outside of the tube.

SHELL & TUBE HE

Non adiabatic fixed bed reactor 5

The Heterogeneous Catalytic Reactor
(Gas – Solid Catalyst System)

o Heterogeneous reactions involving a solid catalyst are generally conducted in a

packed bed reactor. Here, the reactor is packed with particles of solid catalyst.
Such reactor can be configured in different ways: fixed bed reactor, fluidized
bed reactors, and moving bed reactors.

6
The Packed Bed Catalytic Reactor
Hot spot (Gas – Solid Catalyst System)

single tube

fixed bed with intermediate cooling or

Consider: catalyst, contact heating
multi tube
Reversible reaction
Fixed bed reactors 7
The Packed Bed Catalytic Reactor
(Gas – Solid Catalyst System)

Consider: catalyst

Fluidized bed reactors 8

The Packed Bed Catalytic Reactor
(Gas – Solid Catalyst System)

Moving bed reactors

9
The Packed Bed Catalytic Reactor
(Chapter 19 Levenspiel) = Home Work =

o Some considerations in selecting the types of catalytic reactors:

a. Is the efficient gas – catalyst contacting as the primary importance in
the reaction process?
b. Are you going to use a small size of catalyst?
c. Is the reaction restricted within a narrow temperature range?
d. Do the catalysts need to be frequently regenerated?
e. ………………………..

o In which situations you are recommended to use fixed bed reactor? Or

fluidized bed reactor? Or moving bed reactor?
o What are the advantages and disadvantages of fixed bed reactor, fluidized bed
and moving bed reactor?

10
Design of Packed Bed Reactor (PBR)

o PBR is usually used for fluid-solid

heterogeneous reactions.
o In general, the reaction takes place on the
surface of the catalyst. The greater the mass
of a given catalyst, the greater the reactive
surface area.
o Consequently, the reaction rate is based on
mass of solid catalyst, W, rather than on
reactor volume, V.

11
Design of Packed Bed Reactor (PBR)
1. Mole Balance
𝑑𝑋𝐴
𝐹𝐴0 = −𝑟𝐴′ for catalyst decay and pressure drop.
𝑑𝑊
𝑋𝐴
𝑑𝑋𝐴 when there is no ΔP and no catalyst decay.
𝑊 = 𝐹𝐴0 න
−𝑟𝐴′
0

2. Pressure drop

Pressure drop vs
Ergun equation height of reactor

12
Design of Packed Bed Reactor (PBR)

Dominant
Dominant for
for laminar turbulent
flow flow

3. Weight of catalyst

o For tubular packed-bed reactors, we are more interested in catalyst weight

rather than the distance z down the reactor.

o The catalyst weight up to a distance of z down the reactor is:

13
Design of Packed Bed Reactor (PBR)
𝑊
𝜌=
𝑉

o where Ac is the cross-sectional area. The bulk density of the catalyst, b, (mass of
catalyst per volume of reactor bed), is just the product of the density of the solid
catalyst particles, c , and the fraction of solids, (1-):

o The bulk density

Pressure drop vs weight 𝑃 1ൗ

𝑝 = = 1 − 𝛼𝑊 2
of catalyst 𝑃0

1ൗ
For isothermal condition and  = 0: 𝑃 2𝛽0 𝑧 2
Pressure drop vs 𝑝= = 1−
height of reactor 𝑃0 𝑃0 14
PBR: Effect of pressure drop

✓ No pressure drop results the highest

conversion
✓ Loading catalyst causes pressure drop,
then reduces the conversion.

Problems with large diameter tubes

(1) Bypassing of catalyst
(2) Smaller heat transfer area

15
PBR: Effect of pressure drop

Some parameters should be considered

o Laminar flow
o Turbulent flow
o Diameter of catalyst
o Superficial velocity

(Laminar)

(Turbulent)
If diffusion is important step, then, small
size of catalyst is expected.
The higher catalyst size, smaller the pressure-drop parameter, ,
the smaller the pressure drop and thus the greater the conversion.
16
SIMPLE CASE 01

Refer to kinetics of heterogeneous reaction

Effect of temperature
1. Rate constant (Arrhenius Equation)
𝐸
ln 𝑘 = ln 𝐴 − …(1.a)
𝑅𝑇

𝑘2 𝐸 1 1 𝐸 1 1
ln = − …(1.b) 𝑘2 = 𝑘1 exp − …(1.c)
𝑘1 𝑅 𝑇1 𝑇2 𝑅 𝑇1 𝑇2

2. Equilibrium constant ( van’t Hoff equation)

𝑑 ln 𝐾 ∆𝐻𝑅 …(2.a)
= For constant CP, and  CP =0
𝑑𝑇 𝑅𝑇 2

𝐾 𝑇2 ∆𝐻𝑅0 1 1 …(2.b) ∆𝐻𝑅0 1 1

ln = − 𝐾2 = 𝐾1 exp − …(2.c)
𝐾 𝑇1 𝑅 𝑇1 𝑇2 𝑅 𝑇1 𝑇2
18
Increasing temperature Increasing temperature
decreases value of Ke increases value of Ke

19
3. Heat of reaction

𝑇
𝑇
∆𝐻𝑅 = ∆𝐻𝑅0 + 𝛻𝐶𝑝 න 𝑑𝑇
∆𝐻𝑅 = ∆𝐻𝑅0 + න 𝛻𝐶𝑝 𝑑𝑇 …(3.a)
𝑇0
𝑇0

(For constant CP) ∆𝐻𝑅 = ∆𝐻𝑅0 + 𝛻𝐶𝑝 𝑇 − 𝑇0 …(3.b)

20
3. Heat of reaction
𝑎𝐴 → 𝑟𝑅 + 𝑠𝑆

𝛻𝐶𝑝 = 𝐶𝑝 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡) − 𝐶𝑝 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡)

…(3.c) …(3.c) 𝑇

…(3.d) ∆𝐻𝑅 = ∆𝐻𝑅0 + න 𝛻𝛼 + 𝛻𝛽𝑇 + 𝛻𝛾𝑇 2 𝑑𝑇

𝛻𝐶𝑝 = 𝑟𝐶𝑝𝑅 + 𝑠𝐶𝑝𝑆 − 𝑎𝐶𝑝𝐴
𝑇0

𝐶𝑝𝐴 = 𝛼𝐴 + 𝛽𝐴 𝑇 + 𝛾𝐴 𝑇 2 …(3.g)
…(3.e) (mean CP)
𝐶𝑝𝑅 = 𝛼𝑅 + 𝛽𝑅 𝑇 + 𝛾𝑅 𝑇 2
𝐶𝑝𝑆 = 𝛼𝑆 + 𝛽𝑆 𝑇 + 𝛾𝑆 𝑇 2 (NOT constant CP)

𝛻𝛽 2 𝛻𝛾 3
∆𝐻𝑅 = ∆𝐻𝑅0 + 𝛻𝛼 𝑇 − 𝑇0 + 2
𝑇 − 𝑇0 + 𝑇 − 𝑇03
𝛻𝛼 = 𝑟𝛼𝑅 + 𝑠𝛼𝑆 − 𝑎𝛼𝐴 2 3
𝛻𝛽 = 𝑟𝛽𝑅 + 𝑠𝛽𝑆 − 𝑎𝛽𝐴 …(3.f)
𝛻𝛾 = 𝑟𝛾𝑅 + 𝑠𝛾𝑆 − 𝑎𝛾𝐴 …(3.h)

21
Equilibrium conditions
𝑎𝐴 → 𝑟𝑅 + 𝑠𝑆

Equilibrium constant from Thermodynamics

0
∆𝐺 = −𝑅𝑇 ln 𝐾 …(4.a) −∆𝐺 0ൗ
𝐾= 𝑒 𝑅𝑇 …(4.b)

∆𝐺 0 = ∆𝐺 0 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡) − ∆𝐺 0 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡)

∆𝐺 0 = 𝑟𝐺𝑅0 + 𝑠𝐺𝑆0 − 𝑎𝐺𝐴0 …(4.c)

22
Equilibrium conditions
𝑎𝐴 → 𝑟𝑅 + 𝑠𝑆
Equilibrium compositions

𝐾𝑝 𝐾𝑦 𝜋 ∆𝑛
𝐾= 0 ∆𝑛 = 0 ∆𝑛 …(4.d)
𝑝 = 1 𝑎𝑡𝑚 𝑝 = 1 𝑎𝑡𝑚

𝑝𝑅𝑟 𝑝𝑆𝑠 𝑦𝑅𝑟 𝑦𝑆𝑠 o Low pressure

𝐾𝑝 = 𝑎 𝐾𝑦 = 𝑎
𝑝𝐴 𝑦𝐴 o An ideal gas

𝐾𝑐 𝑅𝑇 ∆𝑛
𝑝𝑖 = 𝑦𝑖 𝜋 = 𝐶𝑖 𝑅𝑇
𝐾= 0 ∆𝑛
…(4.e)
𝑝 = 1 𝑎𝑡𝑚

𝐶𝑅𝑟 𝐶𝑆𝑠
𝐾𝐶 = 𝑎
𝐶𝐴
∆𝑛 = 𝑟 + 𝑠 − 𝑎 23
EQUILIBRIUM CONVERSION

24
Algorithm of non isothermal reactor design

Energy balance & heat transfer

Energy balance
Non Isothermal Design
Gas & liquid phase, reversible conversion,
Heat of reaction

o Arrhenius
o van’t Hoff equations (reversible only)

Type of reactor; Batch, CSTR, PFR, PBR, …

25
Case 01: Equilibrium conditions
K
Example 9.2 Temperature changes from 0 - 100
Xe

26
Case 01: Equilibrium conditions
𝑇

∆𝐻𝑅 = ∆𝐻𝑅0 + න 𝛻𝐶𝑝 𝑑𝑇 …(3.a)

𝑇0

T = 0, 10, 20 -- 80,
100
…(4.b)

75300 1 1
𝐾 = 300 𝑒𝑥𝑝 − …(A)
𝑅 𝑇 298

(For constant HR )

K = 0, 10, 20 -- 80,
…(2.b) 100

27
Equilibrium constant and compositions
75300 1 1 T (C) T (K) K X
𝐾 = 300 𝑒𝑥𝑝 −
𝑅 𝑇 298 0 273 0.0037 0.0003 4851.256 1
10 283 0.0035 0.0002 1502.222 0.999
20 293 0.0034 0.0001 503.926 0.998
25 298 0.0034 0.0000 300.000 0.997
…(B) 30 303 0.0033 -0.0001 181.681 0.995
40 313 0.0032 -0.0002 69.914 0.986
50 323 0.0031 -0.0003 28.543 0.966
60 333 0.0030 -0.0004 12.297 0.925
65 338 0.0030 -0.0004 8.224 0.892
…(C) 70 343 0.0029 -0.0004 5.565 0.848
80 353 0.0028 -0.0005 2.634 0.725
90 363 0.0028 -0.0006 1.299 0.565
100 373 0.0027 -0.0007 0.665 0.4
120 393 0.0025 -0.0008 0.193 0.162
140 413 0.0024 -0.0009 0.063 0.06
28
Equilibrium constant and compositions

75%

T oper.

78 C

29
HEAT EFFECTS: ADIABATIC OPERATIONS
(No heat transfer between the system and environment)

XA0

30
HEAT EFFECTS: ADIABATIC OPERATIONS

o Reactant “A” was taken as a limiting reactant

31
HEAT EFFECTS: ADIABATIC OPERATIONS

∆𝐻 = න 𝐶𝑝 𝑑𝑇 = 𝐶𝑝 𝑇 − 𝑇𝑅

∆𝐻 = 𝑚 න 𝐶𝑝 𝑑𝑇 = 𝐶𝑝 𝑇 − 𝑇𝑅

…(5.a)

…(5.b)

converted unreacted 32
HEAT EFFECTS: ADIABATIC OPERATIONS

…(5.c)

…(5.d)
0

…(5.e)

33
HEAT EFFECTS: ADIABATIC OPERATIONS

…(5.f) 𝑇2

∆𝐻2 = ∆𝐻1 + න 𝛻𝐶𝑝 𝑑𝑇

𝑇1

,
…(5.g) …(5.h)

𝑓𝑜𝑟 ∆𝐻𝑟 = 𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑜𝑓 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒

…(5.f)

34
HEAT EFFECTS: NON-ADIABATIC OPERATIONS
(heat transfer occurs between the system and environment)

Let “Q” be the total heat added to a reactor per mole of entering reactant A, and let
this heat also include the losses to the surroundings. So the energy balance (eq. 5.e)
will be

…(6.a)

𝑄 = 𝑈𝐴∆𝑇
…(6.b)

…(6.c)
35
Adiabatic reactor: Normal butane isomerization

36
Adiabatic reactor: Normal butane isomerization

37
Adiabatic reactor: Normal butane isomerization

𝑖 − 𝐶5 𝐻12
𝑖 − 𝐶5 𝐻12
T1 = 57 C (330 K)

= T = ………

38
Adiabatic reactor: Normal butane isomerization
𝐸 1 1
𝑘2 = 𝑘1 exp −
𝑅 𝑇1 𝑇2

1. Mole Balance PFR 𝐸 1 1

𝑘 𝑇 = 𝑘 𝑇2 exp −
𝑋𝐴 𝑅 𝑇2 𝑇
𝑑𝑋𝐴
𝑉 = 𝐹𝐴0 න … (1) 65 700 1 1
−𝑟𝐴 𝑘 𝑇 = 31.1 exp −
0 8.31 360 𝑇
2. Rate law
𝑇 − 360 …(4)
−rA = 𝑘 𝐶𝐴 − 𝑘 ′ 𝐶𝐵 𝑘 𝑇 = 31.1 exp 7906
360𝑇
𝑘′ 𝐶𝐵
= 𝑘 𝐶𝐴 − 𝐶𝐵 = 𝑘 𝐶𝐴 − …(2)
𝑘 𝐾
∆𝐻𝑅𝑜 1 1
𝑘 𝐾(𝑇) = 𝐾(𝑇1 )𝑒𝑥𝑝 −
𝐾= …(3) 𝑅 𝑇1 𝑇
𝑘′
39
Adiabatic reactor: Normal butane isomerization

−6900 1 1 4. Combine
𝐾 𝑇 = 3.03 𝑒𝑥𝑝 −
8.314 333 𝑇 𝐶𝐴0 𝑋𝐴
−rA = 𝑘 𝐶𝐴0 1 − 𝑋𝐴 −
𝐾
𝑇 − 333
𝐾 𝑇 = 3.03 𝑒𝑥𝑝 −830.3 …(5) 𝑋𝐴
333𝑇
= 𝑘𝐶𝐴0 1 − 𝑋𝐴 −
𝐾

3. Stoichiometry 1
= 𝑘𝐶𝐴0 1− 1+ 𝑋 …(6)
𝐾 𝐴
𝐶𝐴 = 𝐶𝐴0 1 − 𝑋𝐴
Input into eq. (2) 5. Energy balance
𝐶𝐵 = 𝐶𝐴0 𝑋𝐴
Adiabatic = Q = 0
∆𝐶𝑃 = 𝐶𝑃𝐵 − 𝐶𝑃𝐴 = 141 − 141 = 0
40
Adiabatic reactor: Normal butane isomerization
𝐶𝑃′ ∆𝑇
𝑋𝐴 = From eq. (7) and (8)
−∆𝐻𝑅𝑜
−∆𝐻𝑅𝑜 𝑋𝐴 6900 𝑋𝐴
∆𝑇 = 𝑇 = 330 +
𝐶𝑃′ 159

−∆𝐻𝑅𝑜 𝑋𝐴 𝑇 = 330 + 43.4𝑋𝐴 …(9)

𝑇 = 𝑇1 + …(7)
𝐶𝑃′

5. Parameter evaluation At equilibrium:

1
−𝑟𝐴 = 𝑘𝐶𝐴0 1− 1+ 𝑋 =0
𝐾 𝐴 …(6)
0.1 𝐽
𝐶𝑃′ = 𝐶𝑃𝐴 + 𝐶𝑃𝐼 = 141 + 161 = 159 𝐾
0.9 𝑚𝑜𝑙 𝐾 𝑋𝐴𝑒 = …(10)
𝐾+1
…(8)
41
Adiabatic reactor: Normal butane isomerization

𝑋𝐴
𝑑𝑋𝐴 𝐾
𝑉 = 𝐹𝐴0 න 𝑋𝐴𝑒 = …(10)
−𝑟𝐴 𝐾+1
0

𝑑𝑋𝐴 −𝑟𝐴 1
= … (1) −rA = 𝑘𝐶𝐴0 1− 1+ 𝑋 …(6)
𝑑𝑉 𝐹𝐴0 𝐾 𝐴

𝑇 = 330 + 43.4𝑋𝐴 …(9)

Then, you might solve simultaneously all
the equations using mathematical software
𝑇 − 360 such as math lab or polymath.
𝑘 𝑇 = 31.1 exp 7906 …(4)
360𝑇

𝑇 − 333
𝐾 𝑇 = 3.03 𝑒𝑥𝑝 −830.3 …(5) Numerically, Simpson’s rule
333𝑇

42
Adiabatic reactor: Normal butane isomerization

(three-point)

(four-point)

43
Adiabatic reactor: Normal butane isomerization

=𝑉

(four-point)

(three-point)
Eq. (9) Eq. (4) Eq. (5) Eq. (10) Eq. (6)
𝐾 1
𝑇 = 330 + 43.4𝑋𝐴 −rA = 𝑘𝐶𝐴0 1 − 1 + 𝑋𝐴
𝑋𝐴𝑒 = 𝐾
𝐾+1
𝑇 − 360
𝑘 𝑇 = 31.1 exp 7906 𝑇 − 333
360𝑇 𝐾 𝑇 = 3.03 𝑒𝑥𝑝 −830.3
333𝑇 44
Adiabatic reactor: Normal butane isomerization
0.7 0.6 0.7
𝐹𝐴0 𝐹𝐴0 𝐹𝐴0
𝑉=න 𝑑𝑋 = න 𝑑𝑋 + න 𝑑𝑋
−𝑟𝐴 −𝑟𝐴 −𝑟𝐴
0 0 0.6

0.6
𝐹𝐴0 3 0.6
න 𝑑𝑋 = 3.74 + 3𝑥2.78 + 3𝑥2.5 + 3.88 = 1.75 𝑚3
−𝑟𝐴 8 3
0

0.7
𝐹𝐴0 1 0.1
න 𝑑𝑋 = 3.88 + 4𝑥5.99 + 23.29 = 0.85 𝑚3
−𝑟𝐴 3 2
0.6

𝑉 = 1.75 𝑚3 + 0.85 𝑚3 = 2.6 𝑚3

45
Adiabatic reactor: Normal butane isomerization
1. Mole Balance CSTR 𝑋𝐴 = 0.4
𝑇 = 330 + 43.4 0.4 = 347.3 𝐾
𝐹𝐴0 𝑋𝐴
𝑉= … (10)
−𝑟𝐴 From the previous table at 347.3 K, k = 14.02 h-1;
Kc = 2.73; -rA = 58.6 kmol/m3.h
2. Rate law
1 𝐹𝐴0 𝑋𝐴 146.7 (0.4)
−rA = 𝑘𝐶𝐴0 1− 1+ 𝑋 …(6) 𝑉= = = 1 𝑚3
𝐾 𝐴 −𝑟𝐴 58.6

3. Energy balance
𝑇 = 330 + 43.4𝑋𝐴 …(9)

46
EXERCISE

200 liters 50%

450 K?

47