PLANT DESIGN –

MATERIAL HANDLING
LIQUIDS & GASES
Dr. Aqeel Ahmad TAIMOOR
 Piping and Instrumentation Diagram

REACTORS
REACTOR DESIGN
 Very few reactors are solely
designed based on kinetics
and hydrodynamics
 Reactors are usually scaled
up from pilot plant to make
up various resistances
 Rate limiting step may be:

1. Equilibrium
2. Kinetics
3. Mass Transfer rate
4. Heat Transfer rate
5. Feed addition rate
6. Mixing rate
Reactor Design

 Calculate the standard heat of reaction using HESS Law

 The heat of reaction is then evaluated at the reactor conditions of
pressure and temperature

 Determine Reaction Equilibrium at different conditions

 For all the possible products, minimization of Gibbs energy

provide the solution
EQUILIBRIUM CALCULATIONS

 Equilibrium Calculations are always the minimization of Gibb’s Energy

[ ]
𝑜
𝑛𝐺 ∆ 𝐺 𝑓 ,𝑖 ,𝑇
=∑ 𝑛 𝑖 +𝑙𝑛 ( 𝑦 𝑖 𝑃 )
𝑅𝑇 𝑅𝑇
 Heat of formation for reaction at 25oC

∆𝐻 =(∑ 𝑛 ∆𝐻 ) − (∑ 𝑛𝑖 ∆𝐻 )
𝑜 𝑜 𝑜

𝑅 𝑖 𝑓 ,29
Heat of formation at other temperature 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝑓 ,29 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
𝑜 𝑜
∆ 𝐻 𝑇 =∆ 𝐻 𝑅 +∆ 𝐴 ( 𝑇 −𝑇 𝑅 ) +
∆𝐵 2
2
( 𝑇 − 𝑇 𝑅)+
2 ∆𝐶 3
3
( 𝑇 − 𝑇 𝑅) − ∆ 𝐷
3 1
−
𝑇 𝑇𝑅
1
( )
𝑜 𝑜 ∆ 𝐵 2 ∆𝐶 3 1 ∆ 𝐵 2 ∆𝐶 3 1
∆ 𝐻 =∆ 𝐻 −∆ 𝐴 𝑇 𝑅 −
𝑇 𝑅 𝑇 − 𝑇 +∆ 𝐷 +∆ 𝐴𝑇 + 𝑇 + 𝑇 −∆ 𝐷
2 𝑅 3 𝑅 𝑇𝑅 2 3 𝑇
𝑜 ∆𝐵 2 ∆𝐶 3 1
𝐽 =∆ 𝐻 − ∆ 𝐴𝑇 𝑅 −
𝑅 𝑇 − 𝑇 +∆ 𝐷
2 𝑅 3 𝑅 𝑇𝑅

𝑜 ∆ 𝐵 2 ∆𝐶 3 1
∆ 𝐻 𝑇 = 𝐽 +∆ 𝐴𝑇 + 𝑇 + 𝑇 −∆ 𝐷
2 3 𝑇
EQUILIBRIUM CALCULATIONS

 Gibbs Energy as function of temperature

∆ 𝐺𝑜𝑇 ∆ 𝐺 𝑜𝑅
𝑅𝑇
=
𝑅𝑇
−
1
𝑅
𝐽
[
− +
𝐽
𝑇 𝑇𝑅
+∆ 𝐴 ( 𝑙𝑛𝑇 − 𝑙𝑛𝑇 𝑅 )+
∆𝐵
2
( 𝑇 − 𝑇 𝑅)+
∆𝐶
6
( (
𝑇 2 −𝑇 2𝑅 ) +2 ∆ 𝐷
1
−
1
𝑇 2 𝑇 2𝑅 )]

[ ] [ ]
∆ 𝐺𝑜𝑇 ∆ 𝐺 𝑜𝑅 1 𝐽 ∆𝐵 ∆𝐶 2 1 1 𝐽 ∆𝐵 ∆𝐶 2 1
= + − + ∆ 𝐴 𝑙𝑛𝑇 𝑅 + 𝑇 𝑅+ 𝑇 𝑅 +2 ∆ 𝐷 2 + − ∆ 𝐴𝑙𝑛𝑇 − 𝑇− 𝑇 −2∆ 𝐷 2
𝑅𝑇 𝑅𝑇 𝑅 𝑇𝑅 2 6 𝑇𝑅 𝑅 𝑇 2 6 𝑇

𝐼=
1
[−
𝑅 𝑇𝑅
𝐽
+ ∆ 𝐴𝑙𝑛𝑇 𝑅 +
∆𝐵
2
𝑇 𝑅+
∆𝐶 2
6
1
𝑇 𝑅 +2 ∆ 𝐷 2
𝑇𝑅 ]
∆ 𝐺𝑜𝑇 ∆ 𝐺 𝑜𝑅
𝑅𝑇
=
𝑅𝑇
+𝐼+
[
1 𝐽
𝑅 𝑇
− ∆ 𝐴𝑙𝑛𝑇 −
∆𝐵
2
𝑇−
∆𝐶 2
6
1
]
𝑇 − 2 ∆ 𝐷 2 =− 𝑙𝑛 𝐾 𝑒𝑞
𝑇

 Minimization of the above equation will yield the possible products concentration
possible by equilibrium at the given conditions
Ideal Reactors

 Plug Flow Reactor

 CSTR
Starting point – Stoichiometry Liquid Phase
Starting point – Stoichiometry Gas Phase
Rate law calculations – CSTR

 Adiabatic

 Non-Adiabatic
Rate Law and Pressure Drop calculations PFR
Runge – Kutta Method for PFR Profilling
Real Reactors
Example – Computer Aided Design

When heavy oils are cracked in a catalytic or thermal cracking process, lighter
hydrocarbon compounds are formed. Most cracking processes on heavy oil feeds
form products with carbon numbers ranging from two to greater than twenty. How
does the equilibrium distribution of hydrocarbon compounds with five carbons (C5
compounds) change as the temperature of the cracking process is increased at
200kPa?
Problem 1
Ethylene glycol is produced by direct hydration of ethylene oxide. The reaction proceeds in the liquid phase
without a catalyst and at the temperature of 200 ◦C. In addition to the hydration of ethylene to ethylene
glycol, also its subsequent hydroxyalkylation for the formation of diethylene glycol or higher glycols can
take place. To prevent the subsequent reactions, the process is carried out with a large excess of water. In
this example, we consider the following main reaction and side reaction with the given conversion:

C2H4O + H2O → HOCH2–CH2OH conversion of C2H4O: 95%

HOCH2–CH2OH + C2H4O → (HOCH2–CH2)2O conversion of C2H4O : 5%

The mole ratio of ethylene oxide to water is 1:12. Ethylene oxide and water enter the reactor at 25 ◦C and
3MPa. Reactor temperature is 200 ◦C, and its pressure is 3MPa. Using Aspen Plus calculate:
a. composition of the reaction products,
b. reactor heat duty if 100 kmol⋅h−1 of ethylene oxide is processed
c. heat of reaction for both reactions if the reference temperature is 25 ◦C, reference pressure is 101.325
kPa, and the reference phase is liquid.
 Problem 2
The following two reactions occur in the production of synthesis gas from natural gas.

CH4 + H2O = 3H2 + CO

CO + H2O = H2 + CO2

The first reaction is the reforming reaction, and the second one is the water–gas shift
reaction by which yet more hydrogen is produced and CO is changed to CO2.

Model these reactions as equilibrium reactions using Aspen HYSYS. For equilibrium
constant calculation, use
the Gibbs free energy method.
For this calculation, consider natural gas as pure methane being fed to the reactor at 400
◦C and 34 bar. Preheated steam is fed at 280 ◦C and 34 bar; the mole flow of CH4 is 90
kmol⋅h−1, and mole flow of steam is 235 kmol⋅h−1. Calculate the products composition at
the reactor temperature ranging from 350 to 900 ◦C.
For water HYSYS modify the
package, as well as for hydrogen
and helium
Problem 3

Consider the ethyl acetate process. Ethanol reacts with acetic acid in the liquid phase to form ethyl
acetate and water through the reaction:
CH3COOH + CH3CH2OH → CH3COOC2H5 + H2O
Model a CSTR reactor if the temperature in the reactor is 50 ◦ C, and pressure is 101 kPa. Both
ethanol and acetic acid streams each have the molar flow of 50 kmol ⋅h −1, temperature of 20 ◦ C,
and pressure of 110 kPa. The volume of the reactor is 3 m3. Calculate
a. composition of the product stream if the rate of the reaction is given by

Where k = 1.206 × 106e−E∕RT, E=54,240 kJ⋅kmol−1 and Ke =4.5 is the equilibrium constant based on
molarity.
b. find the dependence of ethanol conversion on the reactor volume in the reactor volume range
from 0.5 to 6 m3
Do not write in the first two tabs of
Fortran
Be careful while using variables, right
click to see the defiend variables
 Problem 4

Styrene is produced by catalytic dehydrogenation of ethylbenzene at temperatures starting

from 630 ◦C and pressures slightly above atmospheric pressure in the presence of water
steam. Two main side reactions take place in this process: pyrolysis of ethylbenzene to
benzene and ethylene and ethylbenzene hydrodealkylation, where toluene and methane
are produced.

C6H5–C2H5 ↔ C6H5–C2H3 + H2

C6H5–C2H5 → C6H6 + C2H4

C6H5–C2H5 + H2 → C6H5–CH3 + CH4

Problem 4 cont…

The reaction rate and kinetic parameters are

KST = 1.3x10-4kJ/kmol
 Problem 4 Cont…
Ethylbenzene and water steam enter the multitubular reactor at the mole flow ratio of 10:1
steam: ethylbenzene (15 kmol⋅h−1 of ethylbenzene and 150 kmol⋅h−1 of steam in this
example). The reactor consists of 500 tubes with the internal diameter of 6 cm, wall
thickness of 5 mm, and length of 4 m. The tubes are filled with catalyst particles, consider
spherical geometry of the particles with 5mm diameter and tube void fraction of 0.45.
Initial temperature of the feed is 630 ◦C, and initial pressure is 137.8 kPa.
Using Aspen HYSYS, calculate:
a. composition, temperature, and pressure profile
b. if the reactor works at adiabatic conditions conversion of ethylbenzene and selectivity
to styrene along the reactor.
Problem 5

Select an appropriate device for CSTR mapping in the ethyl acetate process (Problem
3). Determine the installed cost of the reactor and cost of utilities as a function of the
reactor volume and conversion, respectively.
Industrial Reactors

 Most of the industrial reactors are preliminary designed without kinetics and then
scaled up
 Heat, mass transfer or diffusion may be the limiting condition
 Heterogeneous catalytic reactors usually uses LHHW models
 Some Examples of industrial reactors follows:
Hydrogen Quenching in Hydrocracker Reactor
Example – Computer Aided Design

A new process is being developed for converting benzene to cyclohexane by

hydrogenation over a noble metal catalyst. The reaction is carried out at 50 bara, at a
feed temperature of 220 °C, and the reactor contents should not exceed 300 °C, to
minimize formation of methylcyclopentane (MCP) byproduct. The reaction is
essentially irreversible under these conditions and the temperature can be controlled
by staged addition of cold hydrogen. Six beds are to be used, each converting the
same amount of benzene, with overall conversion of 100%. The average weight hourly
space velocity based on benzene is 10 h-1 for each adiabatic bed, and a pressure
drop of 0.5 bar is acceptable across each bed. The catalyst is in the form of 1/16th
inch (1.588 mm) beads with average bulk density of 700 kg/m3. Design, size and cost
a reactor for making 200,000 metric tons per year of cyclohexane using this process.
Heat Transfer Arrangements in Stirred Tanks

Evaporative Cooling
Shell and Tube Heat Exchanger with Catalyst in Tubes
ICI Tube in Tube Reforming Reactor
Radial Flow Reactors
UOP Catalytic Reformer Reactor
Fluidized Bed Reactor
Slurry Reactor

Loop Reactor Draft Tube Reactor

Trickle Bed Reactor
Stratco Sulphuric Acid Alkylation Reactor
ExxonMobil Sulphuric Acid Alkylation Reactor
Catalyst Shape

Shape Size Composition Porosity Strength Thermal Stability

Moving-Bed Reactor for Continuous Catalyst Regeneration
UOP Fluidized Catalytic Cracking Reactor and Regenerator
Example – Computer Aided Design

A new process is being developed for converting benzene to cyclohexane by

hydrogenation over a noble metal catalyst. The reaction is carried out at 50 bara, at a
feed temperature of 220 °C, and the reactor contents should not exceed 300 °C, to
minimize formation of methylcyclopentane (MCP) byproduct. The reaction is
essentially irreversible under these conditions and the temperature can be controlled
by staged addition of cold hydrogen. Six beds are to be used, each converting the
same amount of benzene, with overall conversion of 100%. The average weight hourly
space velocity based on benzene is 10 h-1 for each adiabatic bed, and a pressure
drop of 0.5 bar is acceptable across each bed. The catalyst is in the form of 1/16th
inch (1.588 mm) beads with average bulk density of 700 kg/m3. Design, size and cost
a reactor for making 200,000 metric tons per year of cyclohexane using this process.