Single Reaction in Ideal

Reactors

Prepared by Ms. Heng Pisey

Reactor type

 There are two type of reactor: Tank and Tubular

 The tank reactor may operated in a variety of mode: batch, semibatch and
continuous flow.

1
Reactor type

2
Ideal Reactor Types

Plug flow
Batch Reactor Continuous Stir tank reactor=CSTR
reactor=PFTR/PFR

3
Characteristic of batch reactor

 Each batch in close system

 The total mass of each batch is fixed.
 The volume or density of each batch may vary (as reaction proceeds).
 The energy of each batch may vary (as reaction proceeds).
 The reaction (residence) time t for all elements of fluid is the same.
 The operation of the reactor is inherently unsteady-state; for example,
batch composition changes with respect to time.
 It is assumed that, at any time, the batch is uniform (eg. composition,
temperature….) because of efficient stirring.
4
Material Balance

General Material balance:

In – out + Generation = Accumulation

𝑑𝑁𝐴 𝒅𝑵𝑨
𝐹𝐴0 − 𝐹𝐴 + ‫= 𝑉𝑑 𝐴𝑟 ׬‬ , −𝒓𝑨 𝑽 =
𝑑𝑡 𝒅𝒕

5
Material Balance for Batch Reactor

 Consider: A→P
 General Material Balance:
𝑑𝑁𝐴
𝐹𝐴0 − 𝐹𝐴 + ‫= 𝑉𝑑 𝐴𝑟 ׬‬
𝑑𝑡
𝑑𝑁𝐴 (𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒 𝐴)
(−𝑟𝐴 )𝑉 = − 𝑑𝑡
𝑑𝐶𝐴
 For constant density: (−𝑟𝐴 ) = −
𝑑𝑡
𝑡 𝐴1 𝐶
‫׬‬0 𝑑𝑡 = 𝑟 ‫𝐴𝐶𝑑 𝐶׬‬
𝐴 𝐴0

𝟏 𝑪
→ t=𝒓 ‫𝑨𝑪𝒅 𝑨 𝑪׬‬
𝑨𝟎
𝑨

6
 Material Balance for Batch Reactor
𝐶𝐴0 − 𝐶𝐴
𝐶𝐴0 −𝐶𝐴 𝑋𝐴 =
 Fraction conversion: 𝑋𝐴 = 𝐶𝐴0
𝐶𝐴0 𝐶𝐴0 − 𝐶𝐴 =𝐶𝐴0 𝑋𝐴 → 𝐶𝐴 = 𝐶𝐴0 − 𝐶𝐴0 𝑋𝐴
𝑑𝑋𝐴
→𝑑𝑡 =
𝑘(1−𝑋𝐴 )

−𝟏 A= 1 − 𝑋𝐴 → 𝑑𝐴 = −𝑑𝑋𝐴
→𝒌𝒕 = −𝒍𝒏(𝟏 − 𝑿𝑨 ) or 𝒕 = 𝒌
ln(𝟏 − 𝑿𝑨 ) if 𝑋𝐴 = 0 → 𝐴 = 1, 𝑋𝐴 = 𝑋𝐴 → 𝐴 = 1 − 𝑋𝐴
𝑑𝐶𝐴 1 1−𝑋𝐴 −𝑑𝐴
𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑏𝑎𝑙𝑎𝑛𝑐𝑒 𝑜𝑓 𝑏𝑎𝑡𝑐ℎ 𝑟𝑒𝑎𝑐𝑡𝑜𝑟: (−𝑟𝐴 ) = − 𝑡= න
𝑑𝑡 𝑘 1 𝐴
𝑑𝐶𝐴 𝑡 1 𝐶 𝑑𝐶𝐴
−𝑟𝐴 = 𝑘𝐶𝐴 (𝑟𝑎𝑡𝑒 𝑙𝑎𝑤) − = 𝑘𝐶𝐴 → ‫= 𝑡׬‬0 𝑑𝑡 = − ‫𝐴 𝐶׬‬ (1)
𝑑𝑡 0 𝑘 𝐴0 𝐶𝐴

𝐶𝐴0 − 𝐶𝐴
𝑋𝐴 = → 𝐶𝐴 = 𝐶𝐴0 1 − 𝑋𝐴 → 𝑑𝐶𝐴 = −𝐶𝐴0 𝑑𝑋𝐴
𝐶𝐴0
𝑡 1 𝑋 −𝐶 𝑑𝑋 𝑡 1 𝑋 𝑑𝑋𝐴
(1): ‫ = 𝑡𝑑 𝑡׬‬− ‫׬‬0 𝐴 𝐴0 𝐴 → ‫׬ = 𝑡𝑑 𝑡׬‬0 𝐴
0 𝑘 𝐶𝐴0 (1−𝑋𝐴) 0 𝑘 (1−𝑋𝐴)

7
Example

 For a reaction represented by A→Products, in which the rate, (−𝑟𝐴 ), is

proportional to 𝐶𝐴 , with a proportionality constant 𝑘𝐴 , show that the time (t)
required to achieve a specified fractional conversion of A (𝑋𝐴 ) is
independent of the initial concentration of reactant𝐶𝐴0 . Assume reaction
occurs in a constant-volume batch reactor.

8
Solution

𝑡
Rate Law: −𝑟𝐴 = 𝑘𝐴 𝐶𝐴 1 𝐶𝐴 𝑑𝐶𝐴
න 𝑑𝑡 = − න
0 𝑘𝐴 𝐶𝐴0 𝐶𝐴
𝑑𝐶𝐴
Material balance:−𝑟𝐴 =− 𝑑𝑡 1
𝑡=− 𝑙𝑛𝐶𝐴
𝑘𝐴
𝑑𝐶𝐴 1
Thus, − 𝑑𝑡
=𝑘𝐴 𝐶𝐴 𝑡=− 𝑙𝑛𝐶𝐴 − ln 𝐶𝐴0
𝑘𝐴
1 𝐶𝐴0 1 1 1 𝟏 𝑪𝑨 𝟏 𝑪𝑨𝟎
→ t=𝑘 ln 𝐶𝐴
= 𝑘 ln(1−𝑋 ) = − 𝑘 ln(1 − 𝑋𝐴 ) 𝒕 = − 𝐥𝐧
𝒌𝑨 𝑪𝑨𝟎
𝒐𝒓 𝒕 = 𝐥𝐧(
𝒌 𝑪𝑨
)
𝐴 𝐴 𝐴 𝐴
𝐶𝐴0 − 𝐶𝐴
𝑋𝐴 = → 𝐶𝐴 = 𝐶𝐴0 − 𝐶𝐴0 𝑋𝐴 = 𝐶𝐴0 (1 − 𝑋𝐴 )
𝐶𝐴0
1 𝐶𝐴0 1 − 𝑋𝐴 1
𝑡 = − ln = − ln(1 − 𝑋𝐴 )
𝑘𝐴 𝐶𝐴0 𝑘𝐴

9
Example

Constant-volume batch reactor=constant

𝑑𝐶
density =−𝑟𝐴 = − 𝐴
𝑑𝑡
Find t at 90% conversion:
1 1
𝑡 = − ln 1 − 𝑋𝐴 = − ln 1 − 0.9
𝑘𝐴 0.01
= 230s

10
 Example

Find rate of this reaction at 90% conversion with time 230s

Material Balance in Constance-volume batch reactor:
𝑑𝐶𝐴
−𝑟𝐴 = −
𝑑𝑡
𝐶𝐴
‫𝐴𝐶𝑑 𝐶׬‬ 𝐶𝐴 − 𝐶𝐴0
𝐴0
−𝑟𝐴 = − 230𝑠 =−
‫׬‬ 𝑑𝑡 𝑡
0
𝐶𝐴0 −𝐶𝐴
Where 𝑋𝐴 = → 𝐶𝐴 = 𝐶𝐴0 1 − 𝑋𝐴
𝐶𝐴
𝐶𝐴0 1 − 𝑋𝐴 − 𝐶𝐴0 𝐶𝐴0 − 𝐶𝐴0 𝑋𝐴 − 𝐶𝐴0 𝐶𝐴0 𝑋
→ −𝑟𝐴 = − =− =
𝑡 𝑡 𝑡
2×0.9
→ −𝑟𝐴 = = 𝟕. 𝟖𝟑 × 𝟏𝟎−𝟑mol/L.s
230

10
 First-order irreversible reaction

 For the reaction: A→B

Rate Law: −𝒓𝑨 = 𝒌𝑨 𝑪𝑨
𝑑𝐶𝐴
Material balance: −𝑟𝐴 =− (constant-volume batch reactor)
𝑑𝑡
𝑑𝐶𝐴 𝐶 𝑑𝐶𝐴 𝑡
Thus, 𝐶𝐴
= −𝑘𝐴 𝑑𝑡→‫𝐴 𝐶׬‬ = − ‫׬‬0 𝑘𝐴 𝑑𝑡 → ln 𝐶𝐴 = −𝑘𝐴 𝑡 → 𝑙𝑛𝐶𝐴 − 𝑙𝑛𝐶𝐴0 = −𝑘𝐴 𝑡
𝐴0 𝐶𝐴

𝐶
𝐶𝐴 𝑙𝑛 𝐴 𝐶
→ln 𝐶𝐴0
= −𝑘𝐴 𝑡 → 𝑒 𝐶𝐴0
= 𝑒 −𝑘𝐴𝑡 → 𝐶 𝐴 = 𝑒 −𝑘𝐴 𝑡
𝐴0

→𝑪𝑨 = 𝑪𝑨𝟎 𝒆−𝒌𝒕

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Second-order irreversible reaction

For reaction 2A→B

Rate Law: −𝒓𝑨 = 𝒌𝑨 𝑪𝑨 𝟐
𝑑𝐶𝐴
Material balance: −𝑟𝐴 =− 𝑑𝑡 (constant-volume batch reactor)
𝑑𝐶𝐴 𝑡 𝐶 𝑑𝐶 𝑑𝐶𝐴 2 𝑑𝐶𝐴
Thus, 𝐶𝐴 2
= −𝑘𝑑𝑡 →− ‫׬‬0 𝑘𝑑𝑡 = ‫𝐴 𝐶 𝐴 𝐶׬‬2 −
𝑑𝑡
= 𝑘𝐴 𝐶𝐴 → 2 = −𝑘𝐴 𝑑𝑡
𝐶𝐴
𝐴0 𝐴
𝐶𝐴 𝑡
𝑑𝐶𝐴 −1
1 1 1 න = −𝑘 න 𝑑𝑡 → = −𝑘𝐴 𝑡
→𝑡 = (
𝑘 𝐶𝐴
− 𝐶𝐴0
) 𝐶𝐴0 𝐶𝐴
2 𝐴
0 𝐶𝐴
1 1 1 1
− + = −𝑘𝐴 𝑡 → = + 𝑘𝐴 𝑡
𝐶𝐴 𝐶𝐴0 𝐶𝐴 𝐶𝐴0
1 1 + 𝐶𝐴0 𝑘𝐴 𝑡 𝐶𝐴0
= → 𝐶𝐴 =
𝐶𝐴 𝐶𝐴0 1 + 𝐶𝐴0 𝑘𝐴 𝑡

12
nth-order irreversible reaction

For the reaction A→Product

Rate Law: −𝒓𝑨 = 𝒌𝑪𝑨 𝒏
𝑑𝐶𝐴
Material balance: −𝑟𝐴 =− (constant-volume batch reactor)
𝑑𝑡
𝑑𝐶𝐴 𝑡 𝐶
Thus, 𝐶 𝑛 = −𝑘𝑑𝑡 →− ‫׬‬0 𝑘𝑑𝑡 = ‫ 𝐴𝐶 𝐴 𝐶׬‬−𝑛 𝑑𝐶𝐴
𝐴 𝐴0

1
→−𝑘𝑡 = −𝑛+1 (𝐶𝐴 −𝑛+1 − 𝐶𝐴0 −𝑛+1 )
𝟏
𝒏−𝟏
→𝑪𝑨 𝒕 = 𝑪𝑨𝟎 [𝟏 + 𝐧 − 𝟏 𝐤𝑪𝑨𝟎 𝒕]
𝟏−𝒏

13
Bimolecular reaction

𝑟𝑎𝑡𝑒 𝑙𝑎𝑤: −𝑟𝐴 = 𝑘𝐴 𝐶𝐴 𝐶𝐵 : first reaction

respect to each reactant
Material balance in constant-volume batch
𝑑𝐶
reactor: −𝑟𝐴 = − 𝐴
𝑑𝑡
𝑑𝐶𝐴
= −𝑘𝐴 𝐶𝐴 𝐶𝐵
𝑑𝑡

14
Bimolecular reaction

𝐶𝐴0 − 𝐶𝐴 = 𝐶𝐵0 − 𝐶𝐵 = 1/3(𝐶𝐶 − 𝐶𝐶0 )

Then: 𝐶𝐵 = 𝐶𝐵0 − 𝐶𝐴0 + 𝐶𝐴
𝑑𝐶𝐴
= −𝑘𝐴 𝐶𝐴 𝐶𝐵 = −𝑘𝐴 𝐶𝐴 (𝐶𝐵0 − 𝐶𝐴0 + 𝐶𝐴 )
𝑑𝑡

15
Bimolecular reaction

16
Bimolecular reaction
𝑑𝑋
= 𝑘𝐶𝐴0 (1 − 𝑋)2
𝑑𝑡
𝑑𝑋
= 𝑘𝐶𝐴0 𝑑𝑡
(1 − 𝑋)2
𝐿𝑒𝑡 𝐴 = (1 − 𝑋) → 𝑑𝐴 = −𝑑𝑥
If X=0, A=1; if X=X, 1-X
1−𝑥 𝑡
−𝑑𝐴
න 2 = 𝑘𝐶𝐴0 න 𝑑𝑡
1 𝐴 0
1
− 1 = 𝑘𝐶𝐴0 𝑡
1−𝑥
1−1+𝑋
= 𝑘𝐶𝐴0 𝑡
1−𝑋
𝑋 1 + 𝑘𝐶𝐴0 𝑡 = 𝑘𝐶𝐴0 𝑡
𝑑𝑥 1 𝒌𝑪𝑨𝟎 𝒕
න = − 𝑿=
𝑥2 𝑥 𝟏 − 𝒌𝑪𝑨𝟎 𝒕

17
Bimolecular reaction

18
Reversible reaction

𝑘𝑓
𝐴 𝐵
𝑘𝑏

𝑑𝐶𝐴
−𝑟𝐴 = −
𝑑𝑡

19
Characteristic of continuous stirred tank
reactor (CSTR)
 The flow through the vessel(s), both input and output streams, is continuous but
not necessarily at a constant rate.
 The system mass inside each vessel is not necessarily fixed.
 The fluid inside each vessel is perfectly mixed (backmix flow, BMF), and hence
its properties are uniform at any time, because of efficient stirring.
 The density of the flowing system is not necessarily constant; that is, the density
of the output stream may differ from that of the input stream.
 The system may operate at steady-state or at unsteady-state.
 A heat exchanger may be provided in each vessel to control temperature

20
Advantages

 Continuous operation
 Good temperature control
 Good control
 Low operating cost
 Easy to clean

21
 Material Balance

 Continuous operation
 Consider A→P

(Rate of input A by flow)-(Rate of output A by flow)

+(rate of formation of A by reaction within volume control)
=(rate of accumulation of A within volume control)

𝑑𝑛𝐴
 Thus, 𝐹𝐴0 − 𝐹𝐴 + 𝑟𝐴 𝑉 = (For Unsteady-state operation)
𝑑𝑡

 𝑭𝑨𝟎 − 𝑭𝑨 + 𝒓𝑨 𝑽 =0 (For steady-state operation)

22
Irreversible reaction

𝐹𝐴0 − 𝐹𝐴 + 𝑟𝐴 𝑉 =0 (Steady state) ,

𝐹𝐴0 = 𝐶𝐴0 . 𝑞, 𝐹𝐴 = 𝐶𝐴 . 𝑞 , q: flow rate (L/s), 𝑣: 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 (volumetric flow rate)
→𝐶𝐴0 . 𝑞 − 𝐶𝐴 . 𝑞 = −𝑟𝐴 𝑉
𝑉
For 𝜏 = where 𝜏 is residence time (s) (time require of reaction to process in a volume of reactor),
𝑞
𝑉
(𝜏) = space time (time of reaction process in a volume of reactor measuring at initial volumetric flow rate)
𝑞0

Thus, 𝐶𝐴0 − 𝐶𝐴 = −𝑟𝐴 𝜏

 For first-order reaction: 𝑪𝑨𝟎 − 𝑪𝑨 = 𝒌𝑨 𝑪𝑨 𝝉, rate law: −𝑟𝐴 = 𝑘𝐴 𝐶𝐴
 For second-order reaction: 𝑪𝑨𝟎 − 𝑪𝑨 = 𝒌𝑪𝑨 𝟐 𝝉

23
Fraction conversion with constant-density

𝑭𝑨𝟎 −𝑭𝑨 𝑪𝑨𝟎 −𝑪𝑨

 Fraction conversion: 𝑿𝑨 = = , 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋𝐴 )
𝑭𝑨𝟎 𝑪𝑨𝟎

Thus, 𝐶𝐴0 − 𝐶𝐴 = 𝐶𝐴0 𝑋𝐴

 For first-order: 𝑪𝑨𝟎 − 𝑪𝑨 = 𝒌𝑨 𝑪𝑨 𝝉
→ 𝐶𝐴0 − 𝐶𝐴0 1 − 𝑋𝐴 = 𝑘𝐴 𝐶𝐴0 (1 − 𝑋𝐴 )𝜏
→ 𝐶𝐴0 − 𝐶𝐴0 + 𝐶𝐴0 𝑋𝐴 = 𝑘𝐴 𝐶𝐴0 (1 − 𝑋𝐴 )𝜏
𝑪𝑨𝟎 𝑿𝑨 𝑿𝑨
→ 𝐶𝐴0 𝑋𝐴 = 𝑘𝐴 𝐶𝐴0 1 − 𝑋𝐴 𝜏 → 𝝉 = =
𝒌𝑨 𝑪𝑨𝟎 (𝟏 − 𝑿𝑨 ) 𝒌𝑨 (𝟏 − 𝑿𝑨 )

24
Fraction conversion with constant-density

𝑭𝑨𝟎 −𝑭𝑨 𝑪𝑨𝟎 −𝑪𝑨

 Fraction conversion: 𝑿𝑨 = = , 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋𝐴 )
𝑭𝑨𝟎 𝑪𝑨𝟎

 For Second-order:𝑪𝑨𝟎 − 𝑪𝑨 = 𝒌𝑨 𝑪𝑨 𝟐 𝝉
→ 𝐶𝐴0 − 𝐶𝐴𝑜 1 − 𝑋𝐴 = 𝑘𝐴 𝐶𝐴0 2 (1 − 𝑋𝐴 )2 𝜏
→ 𝐶𝐴0 − 𝐶𝐴0 + 𝐶𝐴𝑜 𝑋𝐴 = 𝑘𝐴 𝐶𝐴0 2 (1 − 𝑋𝐴 )2 𝜏
→ 𝐶𝐴𝑜 𝑋𝐴 = 𝑘𝐴 𝐶𝐴0 2 (1 − 𝑋𝐴 )2 𝜏
𝑪𝑨𝒐 𝑿𝑨 𝑿𝑨
→ 𝝉= 𝟐 =
𝒌𝑨 𝑪𝑨𝟎 (𝟏 − 𝑿𝑨 )𝟐 𝒌𝑨 𝑪𝑨𝒐 (𝟏 − 𝑿𝑨 )𝟐

24
 Example

For a liquid-phase reaction of the type A + . . .→ products, an

experimental CSTR of volume 1.5 L is used to measure the rate of
reaction at a given temperature (T). If the steady state flow rate is
0.015 L/s, the feed concentration (𝐶𝐴0 )is 0.8 mol/L, and A is 15%
converted on flow through the reactor, what is the value of (- 𝑟𝐴 )?
Material balance in CSTR for steady state process: 𝐹𝐴0 − 𝐹𝐴0 (1 − 𝑋𝐴 ) 𝐹𝐴0 𝑋𝐴
→ −𝑟𝐴 = =
𝐹𝐴0 − 𝐹𝐴 + 𝑟𝐴 𝑉 = 0 𝑉 𝑉
→ −𝑟𝐴 𝑉 = 𝐹𝐴0 − 𝐹𝐴 Where 𝐹𝐴0 = 𝐶𝐴0 . 𝑞
𝑭 −𝑭 𝑭 −𝑭
→ −𝒓𝑨 = 𝑨𝟎 𝑨 Where 𝑿𝑨 = 𝑨𝟎 𝑨 → 𝑭𝑨 = 𝑭𝑨𝟎 (𝟏 − 𝑿𝑨 ) 𝐶𝐴0 . 𝑞. 𝑋𝐴 0.8 × 0.015 × 0.15
𝑽 𝑭𝑨𝟎 → −𝑟𝐴 = =
𝑉 1.5
−𝟑
= 1.2 × 𝟏𝟎 𝒎ol/L.s
25
Solution

 Calculate Inlet Feed: 𝐹𝐴0 = 𝐶𝐴0 .𝑞𝐴𝑜

𝐹𝐴0 −𝐹𝐴 𝐶𝐴0 −𝐶𝐴
 Conversion of A: 𝑋𝐴 = = → 𝐹𝐴 = 𝐹𝐴0 (1 − 𝑋𝐴 )
𝐹𝐴0 𝐶𝐴0

 Material Balance: 𝐹𝐴0 − 𝐹𝐴 + 𝑟𝐴 𝑉 =0→ 𝐹𝐴0 − 𝐹𝐴0 1 − 𝑋𝐴 = −𝑟𝐴 𝑉

𝑭 𝑿
→ 𝐹𝐴0 − 𝐹𝐴0 + 𝐹𝐴0 𝑋𝐴 = −𝑟𝐴 𝑉 → −𝒓𝑨 = 𝑨𝟎 𝑨
𝑽
𝐶𝐴0 .𝑞𝐴𝑜 𝑋𝐴
 Thus, - 𝑟𝐴 = =1.2× 𝟏𝟎−𝟑 𝒎ol/L.s
𝑉

26
Fraction Conversion with variable-density

 Consider reaction, A→3B

𝑪 𝟏−𝑿𝑨
 𝑪 𝑨 = 𝟏+𝜺
𝑨𝒐 𝑨 𝑿𝑨
3−1 𝑚𝑜𝑙𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 −𝑚𝑜𝑙𝑒 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
 Where 𝜀𝐴 = = 2, 𝜀𝐴 =
1 𝑚𝑜𝑙𝑒 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
𝑛𝐴𝑜 −𝑛𝐴 𝐶𝐴0 −𝐶𝐴 𝐹𝐴0 −𝐹𝐴
Fraction conversion: 𝑋𝐴 = 𝑛𝐴0
= 𝐶𝐴0
= 𝐹𝐴0
(for constant density)
𝑛𝐴0 −𝑛𝐴 𝐶𝐴0 −𝐶𝐴
Fraction conversion: 𝑋𝐴 = 𝑛𝐴0
≠ 𝐶𝐴0
(𝑓𝑜𝑟 𝑣𝑎𝑟𝑖𝑎𝑏𝑙𝑒 𝑑𝑒𝑛𝑠𝑖𝑡𝑦)
𝑛𝐴0 −𝑛𝐴
Fraction conversion: 𝑋𝐴 = 𝑛𝐴0
(for variable density)

27
 Example
A gaseous feed of pure A (1 mol/L) enters a CSTR which have volume 2 liter
and reaction as follow:
A→3P ; −𝑟𝐴 = 0.05𝐶𝐴 (mol/L.s)
Find what flow rate (liter/min) and fraction conversion will give an outlet
𝑚𝑜𝑙
concentration 𝐶𝐴 = 0.05 𝐿 .
0.05 × 0.05 × 2
Answer: q = 0.315 L/min →𝑞= =
1 − 0.05
Calculate fraction conversion 𝑋𝐴
𝑿𝑨 = 𝟖𝟔% 𝐶𝐴 1 − 𝑋𝐴
Calculate flow rate (L/min) =
𝐶𝐴0 1 + 𝜀𝑋𝐴
Material balance of CSTR: 𝐹𝐴0 − 𝐹𝐴 + 𝑟𝐴 𝑉 = 0, 𝐹𝐴0 = 𝐶𝐴0 . 𝑞, 3−1 0.05𝑚𝑜𝑙 𝑚𝑜𝑙
Where, 𝜀 = = 2, 𝐶𝐴 = ; 𝐶𝐴0 = 1
𝐹𝐴 = 𝐶𝐴 . 𝑞 1 𝐿 𝐿
→ 𝑞 𝐶𝐴0 − 𝐶𝐴 = −𝑟𝐴. 𝑉, 𝑤ℎ𝑒𝑟𝑒 −𝑟𝐴 = 0.05𝐶𝐴
0.05𝐶𝐴 . 𝑉 𝑚𝑜𝑙 𝑚𝑜𝑙
𝑞= , 𝑤ℎ𝑒𝑟𝑒 𝐶𝐴0 = 1 , 𝐶𝐴 = 0.05 , 𝑉 = 2𝐿
(𝐶𝐴0 − 𝐶𝐴) 𝐿 𝐿 28
Characteristic of Plug-flow reactor (PFR)
Plug-flow tubular reactor (PFTR)
 The flow through the vessel, both input and output streams, is continuous, but
not necessarily at constant rate; the flow in the vessel is PF.
 The system mass inside the vessel is not necessarily fixed.
 There is no axial mixing of fluid inside the vessel (i.e., in the direction of flow).
 There is complete radial mixing of fluid inside the vessel (i.e., in the plane
perpendicular to the direction of flow); thus, the properties of the fluid, including its
velocity, are uniform in this plane.
 The density of the flowing system may vary in the direction of flow.
 The system may operate at steady-state or at unsteady-state.
 There may be heat transfer through the walls of the vessel between the system
and the surroundings.
29
Characteristic of Plug-flow reactor (PFR)

30
Characteristic of Plug-flow reactor (PFR)

30
Advantages

 Easily maintains as there is no moving part

 High conversion per unit volume
 Unvarying product quality
 Good for studying rapid reaction

31
 Material Balance
𝑑𝑛𝐴
 𝐹𝐴 − (𝐹𝐴 + 𝑑𝐹𝐴 ) + 𝑟𝐴 𝑑𝑉 = (For Unsteady-state operation)
𝑑𝑡

 𝐹𝐴 − (𝐹𝐴 + 𝑑𝐹𝐴 ) + 𝑟𝐴 𝑑𝑉 = 0 (For steady-state operation)𝐹𝐴 − 𝐹𝐴 − 𝑑𝐹𝐴 + 𝑟𝐴 𝑑𝑉 = 0

 Differentiate with respect to V:
−𝒅𝑭𝑨
−𝒓𝑨 =
𝒅𝑽 𝐹𝐴𝑓

𝐹𝐴 = 𝐶𝐴 𝑞 → 𝑑𝐹𝐴 = 𝑞𝑑𝐶𝐴
𝑑𝐹𝐴 𝑞𝑑𝐶𝐴 𝑞𝑑𝐶𝐴 𝑑𝐶𝐴
−𝑟𝐴 = − =− =− =− = 𝑘𝐶𝐴
𝑑𝑉 𝑑𝑉 𝑞𝑑𝜏 𝑑𝜏
𝝉 𝑪𝑨
𝒅𝑪𝑨 𝑪𝑨
න 𝒌𝒅𝝉 = න − → 𝒌𝝉 = −(𝒍𝒏 ) 𝑉
𝟎 𝑪𝑨𝟎 𝑪 𝑨 𝑪 𝑨𝟎 𝜏 = → 𝑉 = 𝑞. 𝜏 → 𝑑𝑉 = 𝑞. 𝑑𝜏
𝑞
𝑉
𝜏 = → 𝑉 = 𝜏𝑞 → 𝑑𝑉 = 𝑞𝑑𝜏
𝑞 32
Example

Calculate the residence time (τ), for the gas-phase production of C2H4 from C2H6
in a cylindrical PFTR of a constant diameter, based on the following data and
assumptions:
- Feed is pure C2H6 (A) at 1 kg/s, 1000k and 2 bar
- The reaction rate is proportion to 𝐶𝐴 at any point, with a proportionality constant 𝑘𝐴
= 0.254𝑠 −1 𝑎𝑡 1000𝐾, that is, the rate law is −𝑟𝐴 = 𝑘𝐴 𝐶𝐴
- The reaction operates isothermally at constant pressure
- 𝑋𝐴 = 80%
- Only C2H4 and H2 are formed as product
- The following system behaves as an ideal-gas mixture

33
Solution
Material balance of PFTR for steady state operation
 We have dV= 𝑞𝑑𝜏, dτ=dV/q, τ=‫ 𝑉𝑑 ׬‬/q
𝐹𝐴 − 𝐹𝐴 + 𝑑𝐹𝐴 + 𝑟𝐴 𝑑𝑉=0
−𝐹 𝑑𝑋 −𝑑𝐹𝐴 = −𝑟𝐴 𝑑𝑉
 t=‫𝐴 ׬‬0 𝐴 Where 𝐹𝐴 = 𝑞. 𝐶𝐴 → 𝑑𝐹𝐴 = 𝑞. 𝑑𝐶𝐴
−𝑟𝐴 𝑞
Where 𝑉 = 𝜏. 𝑞 → 𝑑𝑉 = 𝑞𝑑𝜏
−𝐹𝐴0 𝑑𝑋𝐴
 t=‫׬‬ Where −𝑟𝐴 = 𝑘𝐴 𝐶𝐴
𝑘 𝐴 𝐶𝐴 𝑞
→ −𝑞. 𝑑𝐶𝐴 = 𝑘𝐴 𝐶𝐴 . 𝑞. 𝑑𝜏
1 0.2 → −𝑑𝐶𝐴 = 𝑘𝐴 𝐶𝐴 𝑑𝜏
 t= ‫ 𝐴𝑋𝑑 ׬‬/(1−𝑋𝐴 )
𝑘𝐴 0
𝜏
−1 𝐶𝐴 𝑑𝐶𝐴
1 → න 𝑑𝜏 = න
 t=- ln(1-0.2) 𝑘 𝐶𝐴0 𝐶𝐴
𝑘𝐴 0
−1 𝐶𝐴
 t=0.89s →𝜏= 𝑙𝑛 𝑤ℎ𝑒𝑟𝑒𝐶𝐴 = 𝐶𝐴0 1 − 𝑋
𝑘 𝐶𝐴0
−1
→𝜏= ln 1 − 𝑋
𝑘
−1
→𝜏= ln 1 − 0.8 = 𝟎. 𝟖𝟗𝒔
0.254 34
 Comparison of possible advantages (+) and
disadvantages (-) for Batch, CSTR, PFR

Criteria Batch CSTR PFR

Reactor size for giving + - +
conversion
Cost + + -
Continues operation - + +
Large throughput - + +
Clean out + + -
Product quality - + +

35
Comparison of PFTR and CSTR

36
Variable-density reactors

 Consider reaction, A→3B For Variable density:

𝑪𝑨 𝟏−𝑿𝑨 𝑁 −𝑁
= , 𝑋 = 𝐴0 𝐴
𝑪𝑨𝒐 𝟏+𝜺𝑨 𝑿𝑨 𝑁𝐴0
 For CSTR: For constant density:
𝑁𝐴0−𝑁𝐴 𝐶𝐴0 −𝐶𝐴 𝐹𝐴0 −𝐹𝐴
𝑋= = =
𝑁𝐴0 𝐶𝐴0 𝐹𝐴0

 For PFTR:

37
 Example

Find expressions the reactor volume V for specified and feed flow rate FA0 for the
reaction: A→2B+C among ideal gases with no diluent in a CSTR. 𝑁𝐴0 = 2 𝑚𝑜𝑙
𝑋𝐴 = 90%
A→4 B
𝑁𝐴 = 2 (100% − 90%)
𝑁𝐴 = 𝑁𝐴0 1 − 𝑋
𝑁𝐴 = 𝑁𝐴0 (1 − 𝑋)
𝑁𝐵 = 4𝑁𝐴0 𝑋 𝑁𝐴 𝑁𝐴0 (1 − 𝑋𝐴 ) 1 − 𝑋𝐴
𝑁 = 𝑁𝐴0 1 + 3𝑋 𝐶𝐴 = = = 𝐶𝐴0
𝑉 = 𝑉0 (1 + 3𝑋) 𝑉 𝑉0 (1 + 2𝑋𝐴 ) 1 + 2𝑋𝐴
𝑁𝐴 𝑁𝐴0 (1 − 𝑋) 𝑪𝑨 𝟏 − 𝑿𝑨 𝟏 − 𝑿𝑨
𝐶𝐴 = = = =
𝑉 𝑉0 (1 + 3𝑋) 𝑪𝑨𝟎 𝟏 + 𝟐𝑿𝑨 𝟏 + 𝜺𝑿𝑨
𝒏𝒑 − 𝒏𝒓
𝜺=
𝒏𝒓

38
Example

39
Example of Batch reactor with constant density

Determine the time required for 80% conversion of 7.5 mol A in 15 L

constant volume batch reactor operating isothermally at 300 K. The reaction
is first-order with respect to A with 𝑘𝐴 = 0.05 /min at 300K. What is the time
required to operate this reaction?
If we want to operate in the mentioned reaction at 350K and the rate
increase 4 time, what is the time and activation energy required to operate
this reaction?
Answer: 𝑡1 = 32.2 min; 𝑡2 = 8.04 𝑚𝑖𝑛 ; 𝐸𝐴 = 24203.86 𝐽/𝑚𝑜𝑙
 Example of Batch reactor with constant density

 Calculate time to operate the reaction at 300K.

𝑛𝐴0 7.5
𝐶𝐴0 = 𝑉
= 15
=?
𝑑𝐶𝐴
Material balance of batch reactor: −𝑟𝐴 = − , Rate law of A: −𝑟𝐴 = 𝑘𝐶𝐴
𝑑𝑡
𝑑𝐶𝐴 𝑡 1 𝐶𝐴 𝑑𝐶𝐴 1 1 𝐶𝐴
Then, − 𝑑𝑡 = 𝑘𝐶𝐴 → ‫׬‬0 𝑑𝑡 = − 𝑘 ‫𝐶 𝐶׬‬ →𝑡= −𝑘 𝑙𝑛𝐶𝐴 − 𝑙𝑛𝐶𝐴𝑜 = − 𝑘 𝑙𝑛 𝐶
𝐴0 𝐴 𝐴0
1 1
= − 𝑙𝑛
𝑘 (1−𝑋𝐴 )
𝑛𝐴0 7.5 𝐶𝐴0 −𝐶𝐴
Where 𝐶𝐴0 = = =? and 𝑋𝐴 = → 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋𝐴 )
𝑉 15 𝐶𝐴0
 Example of Batch reactor with constant density

Calculate the time and activation energy at 350K.

 𝐴𝑡 300𝐾, 𝑟𝐴1 = 𝑘𝐴1 𝐶𝐴
 𝐴𝑡 350 𝐾, 𝑟𝐴2 = 𝑘𝐴2 𝐶𝐴 = 4𝑘𝐴1 𝐶𝐴 → 𝑘𝐴2 = 4𝑘𝐴1 = 4 × 0.05 = 0.2/min
𝑑𝐶
Material balance of batch reactor: −𝑟𝐴2 = − 𝑑𝑡𝐴 , Rate law of A: −𝑟𝐴2 = 𝑘𝐴2 𝐶𝐴
2

𝑑𝐶 𝑡2 1 𝐶 𝑑𝐶𝐴 1
Then, − 𝑑𝑡𝐴 = 𝑘𝐴2 𝐶𝐴 → ‫׬‬0 𝑑𝑡 = − 𝑘 ‫𝐴 𝐶׬‬ → 𝑡 = −𝑘 𝑙𝑛𝐶𝐴 − 𝑙𝑛𝐶𝐴𝑜
2 𝐴2 𝐴0 𝐶𝐴 𝐴2
1 𝐶
= − 𝑘 𝑙𝑛 𝐶 𝐴 =?
𝐴2 𝐴0
 Example of Batch reactor with constant density

Calculate the activation energy at 350 K

−𝐸𝐴
𝑘= 𝐴𝑒 𝑅𝑇
−𝐸𝐴 −𝐸𝐴
𝑘𝐴1 = 𝐴𝑒 𝑅𝑇1 , 𝑘𝐴2 = 𝐴𝑒 𝑅𝑇2
−𝐸𝐴
𝑘𝐴1 𝐴𝑒 𝑅𝑇1 𝑘𝐴1 1
= 𝑤ℎ𝑒𝑟𝑒 = , 𝑇 = 300𝐾, 𝑇1 = 350𝐾
𝑘𝐴2 −𝐸𝐴 𝑘𝐴2 4 1
𝐴𝑒 𝑅𝑇2
A liquid-phase reaction between cyclopentadien (A) and Benzoquinone (B)
is conducted in an isothermal batch reactor to produce an adduct (C),
A+B→C. The reaction with respect to each reactant is first-order (r=𝑘𝐶𝐴 𝐶𝐵 ),
with 𝑘𝐴 = 9.92 × 10−3 L/mol.s at 25 °C. Determine time require to process
this reaction in 90% conversion. The initial concentration of A and B is 0.15
mol/L. Answer: t=1.68h.
𝑪𝑨𝟎 = 𝑪𝑩𝟎 = 𝟎. 𝟏𝟓 𝒎𝒐𝒍/𝑳
𝒓 = 𝒌𝑪𝑨 𝟐
 Calculate: the time require to process 90% conversion
𝑑𝐶
Material balance in batch reactor:− 𝐴 = 𝑘𝐶𝐴 2
𝑑𝑡
𝑡 𝐶𝐴
1 𝑑𝐶𝐴 1 1 1
න 𝑑𝑡 = − න 2 → 𝑡 = − 𝑘 (− 𝐶 + 𝐶 ) = 1.68h
0 𝑘 𝐶𝐴0 𝐶𝐴 𝐴 𝐴0
𝐶𝐴0 − 𝐶𝐴
𝑋𝐴 = → 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋𝐴 )
𝐶𝐴0
Example of batch reactor with constant- density

A liquid-phase reaction between cyclopentadiene (A) and benzoquinone (B)

is conducted in an isothermal batch reactor, production adduct (C). The
reaction is first order with respect to each reactant, with 𝑘𝐴
= 9.92 × 10−3 𝐿. 𝑚𝑜𝑙 −1 𝑠 −1 and 𝐶𝐴0 = 𝐶𝐵0 = 0.15 𝑚𝑜𝑙/𝐿. −𝑟𝐴 = 𝑘𝐴 𝐶𝐴 𝐶𝐵
−𝑑𝐶𝐴
The reaction is A + B →C. −𝑟𝐴 =
𝑑𝑡
−𝑑𝐶𝐴
1. Determine the time required for 90% conversion of A. = 𝑘𝐴 𝐶𝐴 𝐶𝐵 = 𝑘𝐴 𝐶𝐴 2
𝑑𝑡

2. Calculate the final concentration of A and fraction conversion at t = 1 h.

Answer: t = 1.68 h ; CA = 0.023 mol/L; 𝑋𝐴 = 84.66%
 Example of CSTR with constant- density

Calculate the resident time.

Material balance of CSTR: 𝐹𝐴0 − 𝐹𝐴 + 𝑟𝐴 . 𝑉 = 0
𝑞 𝐶𝐴0 − 𝐶𝐴 = −𝑟𝐴 . 𝑉 → 𝐶𝐴0 − 𝐶𝐴 = −𝑟𝐴 𝜏
𝐶𝐴0 − 𝐶𝐴 𝐶𝐴0 . 𝑋 2 × 0.9
𝜏= = = = 𝟏𝟖 𝒎𝒊𝒏𝒔.
𝑘𝐶𝐴 𝑘𝐶𝐴0 (1 − 𝑋) 0.5 × 2 × (1 − 0.9)
2 × 0.99
𝜏99% = = 𝟏𝟗𝟖 𝒎𝒊𝒏
0.5 × 2 × (1 − 0.99)
Calculate reactor volume.
𝑉
𝜏 = → 𝑉 = 𝑞. 𝜏 = 𝟒 × 𝟏𝟖 = 𝟕𝟐𝑳
𝑞
 Example of PFTR with constant- density

A liquid-phase reaction between bromine cyanide (A) and Methylamine (B) take place in a PFTR at 10
°C and 101 kPa. The reaction is first-order with respect to each reactant, with 𝑘𝐴 = 2.22 L/mol.s. If the
residence time is 4s and the inlet concentration of each reactant is 0.1 mol/L, determine the
concentration of bromine cyanide at the outlet of the reactor. (𝑪𝑨 = 𝟎. 𝟎𝟓𝟐𝟗 mol/L)

Determine outlet concentration of reactant A

𝐴 + 𝐵 → 𝐶, −𝑟𝐴 = 𝑘𝐴 𝐶𝐴 𝐶𝐵, 𝐶𝐴0 = 𝐶𝐵0 → −𝑟𝐴 = 𝑘𝐴 𝐶𝐴 2

Material balance in PFTR for steady state operate: 𝐹𝐴 − 𝐹𝐴 + 𝑑𝐹𝐴 + 𝑟𝐴 𝑑𝑉 = 0
−𝑑𝐹𝐴 = −𝑟𝐴 𝑑𝑉 → −𝑞𝑑𝐶𝐴 = 𝑘𝐴 𝐶𝐴 2 𝑑𝑉 → −𝑞𝑑𝐶𝐴 = 𝑘𝐴 𝐶𝐴 2 𝑞𝑑𝜏
𝐶𝐴 4
−𝑑𝐶𝐴 −𝑑𝐶𝐴
= 𝑘𝑑𝜏 → න 2 = න 𝑘𝑑𝜏
𝐶𝐴 2 𝐶𝐴0 𝐶𝐴 0
1 1 𝐶𝐴0 0.1
− = 𝑘𝜏 → 𝐶𝐴 = = = 𝟎. 𝟎𝟓𝟐𝟗 𝒎𝒐𝒍/𝑳
𝐶𝐴 𝐶𝐴0 1 + 𝑘𝐶𝐴0 𝜏 1 + 2.2 × 0.1 × 4
Variable density
 Example (Variable- density)
Find the reactor volume V required to obtain 90% conversion in the reaction
:A→ nB B where r = kCA
Among ideal gases in a CSTR with no diluent for nB = 2 with CA0 = 2
moles/liter, k = 0.5/min and q = 4 liters/min.
Answer: n = 2; 𝑉𝐶𝑆𝑇𝑅 = 𝟏𝟒𝟒 𝑳 ;
Determine the volume of CSTR reactor 4(2 − 0.105)
If 𝑛𝐵 = 2, 𝑤𝑒 ℎ𝑎𝑣𝑒 𝐴 → 2𝐵 , −𝑟𝐴 = 𝑘𝐶𝐴 1 :𝑉 = = 𝟏𝟒𝟒𝑳
0.5 × 0.105
Material balance in CSTR:
𝐹𝐴0 − 𝐹𝐴 + 𝑟𝐴 𝑉 = 0, 𝑤ℎ𝑒𝑟𝑒 𝐹𝐴0 = 𝑞 𝐶𝐴0 𝑎𝑛𝑑 𝐹𝐴 = 𝑞 𝐶𝐴
𝑞 𝐶𝐴0 − 𝐶𝐴 = −𝑟𝐴 𝑉 → 𝑞 𝐶𝐴0 − 𝐶𝐴 = 𝑘𝐶𝐴 𝑉
𝑞(𝐶 −𝐶 )
𝑉 = 𝐴0 𝐴 (1)
𝑘𝐶𝐴
𝐶𝐴 1−𝑋 1−𝑋 1−0.9
= → 𝐶𝐴 = 𝐶𝐴0 =2 = 0.105 mol/L
𝐶𝐴0 1+𝜀𝑋 1+𝑋 1+0.9
Example (Variable- density)

Find the reactor volume V required to obtain 90% conversion in the reaction
:A→ nB B where r = kCA
Among ideal gases in a CSTR and in a PFTR with no diluent for nB = 2 and
½ with CA0 = 2 moles/liter, k = 0.5/min and q = 4 liters/min.
Answer: n = 2; 𝑉𝐶𝑆𝑇𝑅 = 144 𝐿 ; 𝑉𝑃𝐹𝑇𝑅 = 23 𝐿
n = ½; 𝑉𝐶𝑆𝑇𝑅 = 36 𝐿; 𝑉𝑃𝐹𝑇𝑅 = 13 𝐿
Example (Variable- density)
Example (Variable- density)
Example

57
 Quiz (20 min)

A liquid-phase reaction between cyclopentadiene (A) and

benzoquinone (B) is conducted in an isothermal batch reactor,
production adduct (C). The reaction is first order with respect to
each reactant, with 𝑘𝐴 = 9.92 × 10−3 𝐿. 𝑚𝑜𝑙 −1 𝑠 −1 . Determine
the reactor volume required to produce 175 mol/h of product, if
the conversion 90% and 𝐶𝐴0 = 𝐶𝐵0 = 0.15 𝑚𝑜𝑙/𝐿. The reaction
is A + B →C and consider reaction process in constant-density.
 Example

𝑟 𝑘 𝑡 3 𝑱
(a). 𝑟1 = 𝑘1 = 𝑡2 = 10, 𝐸 = 𝟏𝟎𝟏𝟏𝟗𝟖. 𝟑𝟕 𝒎𝒐𝒍
2 2 1

(b) 𝑇3 = 𝟓𝟗. 𝟔𝟎 ℃
Example
 Example (Batch Reactor)

Calculate t for 90% conversion of A:

Rate Law for second order reaction: −𝑟𝐴 = 𝑘𝐶𝐴 2
𝑑𝐶
Material of batch reactor: −𝑟𝐴 = − 𝐴
𝑑𝑡
𝑑𝐶𝐴
− = 𝑘𝐶𝐴 2
𝑑𝑡
𝐶 −𝐶 𝑚𝑜𝑙
90% conversion: 𝑋𝐴 = 𝐴0 𝐴 → 𝐶𝐴 = 𝐶𝐴𝑜 1 − 𝑋𝐴 = 2 1 − 0.9 = 0.2
𝐶𝐴0 𝐿
𝑡 𝐶𝐴
𝑑𝐶𝐴 2 1 𝑑𝐶𝐴 1 𝑑𝐶𝐴 1 1 1 1 1 1
− = 𝑘𝐶𝐴 → 𝑑𝑡 = − → න 𝑑𝑡 = − න 2 → 𝑡 = −𝑘 −𝐶 + 𝐶 = ( − )
𝑑𝑡 𝑘 𝐶𝐴 2 𝑡0 𝑘 𝐶
𝐶𝐴0 𝐴 𝐴 𝐴0 𝑘 𝐶𝐴 𝐶𝐴0
1 1 1 1 1 1
t= − = − = 𝟒𝟓𝟎 𝐬
𝑘 𝐶𝐴 𝐶𝐴0 0.01 0.2 2