5-3-1 Application for Adiabatic Liquid-Phase Isomerization

The isomerization of butane:

was carried out adiabatically in the liquid phase. The data for this reversible reaction are given in Table below.

The reaction is carried out adiabatically, and the reactor used is schematized in in Figure below.
1- Calculate the volume of each of the reactors for an entering molar flow rate of n-butane of 50 kmol/hr.

Solution:

Taking the reciprocal of –rA and multiplying by FA0, we obtain the following Table:

(a) For the first CSTR:

𝐹𝐴0
when X = 0.2, then = 0,94
−𝑟𝐴
𝐹𝐴0 𝑋1
𝑉1 = = 0,94 ∗ 0,2 = 0,188𝑚3
−𝑟𝐴1
(b) For the PFR:
0,6
𝐹𝐴0
𝑉2 = න 𝑑𝑋
−𝑟𝐴
0,2

Using Simpson’s three-point formula with ΔX = (0.6 – 0.2)/2 = 0.2, and X1 = 0.2, X2= 0.4, and X3 = 0.6

0,2
𝑉2 = 0,94 + 0,85 ∗ 4 + 1,32 = 0,37777𝑚3
3
For the last reactor, the mole balance on A for the CSTR:

𝐼𝑛𝑝𝑢𝑡 − 𝑂𝑢𝑡𝑝𝑢𝑡 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 0

𝐹𝐴2 − 𝐹𝐴3 + 𝑟𝐴3 𝑉3 = 0

Rearranging:
𝐹𝐴2 − 𝐹𝐴3
𝑉3 =
−𝑟𝐴
By another hand:
𝐹𝐴2 = 𝐹𝐴0 − 𝐹𝐴0 𝑋2
𝐹𝐴2 − 𝐹𝐴3 = 𝐹𝐴0 (𝑋3 − 𝑋2 )
𝐹𝐴3 = 𝐹𝐴0 − 𝐹𝐴0 𝑋3
From where:
𝐹𝐴0
𝑉3 = ( )(𝑋3 − 𝑋2 )
−𝑟𝐴
𝐹𝐴0
when X = 0.65, then =2
−𝑟𝐴

𝑉3 = 2 ∗ 0,65 − 0,6 = 0,1𝑚3

A Levenspiel plot of (FA0/–rA) vs. X is shown in Figure below:

Levenspiel plot for adiabatic reactors in series.

Example :Determining k from Batch Data
It is desired to design a CSTR to produce 200 million pounds of ethylene glycol per year by hydrolyzing ethylene
oxide. However, before the design can be carried out, it is necessary to perform and analyze a batch-reactor
experiment to determine the specific reaction-rate constant, k. Given that the reaction will be carried out
isothermally, the specific reaction rate will need to be determined only at the reaction temperature of the
CSTR. At temperatures above 80°C, there is a significant by-product formation, while at temperatures below
40°C, the reaction does not proceed at a significant rate; consequently, a temperature of 55°C has been chosen.
Because water is present in excess, its concentration (55.5 mol/dm3) may be considered constant during the
course of the reaction. The reaction is first-order in ethylene oxide.
In the laboratory experiment, 500 mL of a 2 M solution (2 kmol/m3) of ethylene oxide (A) in water was mixed
with 500 mL of water (B) containing 0.9 wt % sulfuric acid, which is a catalyst. The temperature was
maintained at 55C. The concentration of ethylene glycol (C) was recorded as a function of time (Table below).
(a) Derive an equation for the concentration of ethylene glycol as a function of time.
(b) Rearrange the equation derived in (a) to obtain a linear plot of a function concentration versus time.
(c) Using the data in Table , determine the specific reaction rate at 55°C.

CONCENTRATION-TIME DATA
Solution:
(a) Derive an equation for the concentration of ethylene glycol as a function of time.

1. The mole balance on ethylene oxide (A) for a constant volume, V0, well-mixed batch reactor can be written
as:
𝑑𝑁𝐴
= 𝑟𝐴 𝑉0
𝑑𝑡
Taking V0 inside the differential and recalling that the concentration is;
𝑁𝐴
𝐶𝐴 =
𝑉0
then the differential mole balance becomes:
𝑑𝐶𝐴
= 𝑟𝐴
𝑑𝑡

2. The rate law for the ethylene oxide hydrolysis is:

−𝑟𝐴 = 𝑘. 𝐶𝐴
Because water is present in such excess, the concentration of water at any time t is virtually the same as the
initial concentration, and the rate law is independent of the concentration of H2O

3. Stoichiometry. Liquid phase, no volume change, V = V0

STOICHIOMETRIC TABLE

Recall that ΘB is the ratio of the initial number of moles of B to A (i.e.,ΘB=NB0/NA0).

For species B, that’s to say, water, the quantity remaining:
𝑁𝐵 = 𝜃𝐵 𝑁𝐴0 − 𝑁𝐴0 𝑋
𝐶𝐵 = 𝜃𝐵 𝐶𝐴0 − 𝐶𝐴0 𝑋 = 𝐶𝐴0 𝜃𝐵 = 𝐶𝐵0
We quickly see that water is in excess, as the molarity of water is 55 moles per liter. The initial concentration of
A after mixing the two volumes together is 1 molar. Therefore:
𝑁𝐵0 55
𝜃𝐵 = = = 55
𝑁𝐴0 1
The maximum value of X is 1, and 𝜃𝐵 ≫ 1, therefore CB is virtually constant:
𝐶𝐵 = 𝜃𝐵 𝐶𝐴0 − 𝐶𝐴0 𝑋 = 𝐶𝐴0 𝜃𝐵 = 𝐶𝐵0

For species C, that’s to say ethylene glycol, the concentration is

𝑁𝐶 𝑁𝐴0 𝑋 𝑁𝐴0 − 𝑁𝐴
𝐶𝐶 = = = = 𝐶𝐴0 − 𝐶𝐴
𝑉0 𝑉0 𝑉0

4. Combining the rate law and the mole balance, we have:

𝑑𝐶𝐴
= −𝑘. 𝐶𝐴
𝑑𝑡
𝑑𝐶𝐴
= −𝑘𝑑𝑡
𝐶𝐴
5. Evaluate. For isothermal operation, k is constant, so we can integrate the equation above:
𝐶𝐴 𝑡
𝑑𝐶𝐴
න = −𝑘 න 𝑑𝑡
𝐶𝐴
𝐶𝐴0 0

using the initial condition that when t = 0, then CA = CA0 = 1 mol/dm3 =1 kmol/m3.
𝐶𝐴0
𝑙𝑛 = 𝑘𝑡
𝐶𝐴

The concentration of ethylene oxide (A) at any time t is:

𝐶𝐴 = 𝐶𝐴0 𝑒 −𝑘𝑡

The concentration of ethylene glycol (C) at any time t can be obtained from the reaction stoichiometry:

𝐶𝐶 = 𝐶𝐴0 − 𝐶𝐴 = 𝐶𝐴0 − 𝐶𝐴0 𝑒 −𝑘𝑡

(b) Rearrange the equation derived in (a) to obtain a linear plot of a function concentration versus time.

We are now going to rearrange the Equation above for the concentration of ethylene glycol in such a manner
that we can easily use the data in the Table to determine the rate constant k

𝐶𝐶 = 𝐶𝐴0 − 𝐶𝐴 = 𝐶𝐴0 − 𝐶𝐴0 𝑒 −𝑘𝑡

𝐶𝐶 − 𝐶𝐴0
= −𝑒 −𝑘𝑡
𝐶𝐴0
𝐶𝐶 − 𝐶𝐴0
𝑙𝑛 = 𝑘𝑡
𝐶𝐴0

(c) Using the data in Table , determine the specific reaction rate at 55°C.

We see that a plot of ln[(CA0 - CC)/CA0] as a function of t will be a straight line with a slope k. Using Table, we can
construct the followingTable and use Excel to plot ln(CA0 - CC)/CA0 as a function of t.
 PROCESSED DATA
From the slope of a plot of ln[(CA0 - CC)/CA0] versus t, we can find k, as shown in the Excel plot in the following
Figure.

Slope = –k = –0.311 min–1

The rate law becomes:
−𝑟𝐴 = 0,311. 𝐶𝐴