ASSIGNMENT 2

CHEMICAL REACTION ENGINEERING (CHE 594)

FACULTY OF CHEMICAL ENGINEERING (EH220)

GROUP 4B

NAME: ID NUM:
NUR AZIELA BINTI ROZI 2014860084
HAZIRAH BINTI ALI SABRI 2014275914
NUR MARDHIYYAH BINTI AZIZUDDIN 2014237414
NURUL HAZIRAH AINA BINTI HASNAN 2014261176
WAN NOR ASYIKIN BINTI WAN MOHAMED DAID 2014606346

SUBMIT TO: MADAM NOR HALALIZA ALIAS

1. PROCESS BACKGROUND
HYDROLYSIS OF ETHYLENE OXIDE

The reaction chemistry is quite simple; it is either acid or thermally catalysed. It is

summarized as follows: ethylene oxide reacts with water to form ethylene glycol, and
then further reacts with ethylene glycol and higher homologues in a series of
consecutive reactions as shown in the following equations:

Step 1 CH2CH2O + H2O HOCH2CH2O (ethylene glycol)

Step 2 2CH2CH2O + H2O HOCH2CH2OCH2CH2OH (diethylene glycol)
Step 3 3CH2CH2O + H2O HOCH2CH2OCH2CH2OCH2CH2O (triethylene glycol)

PRODUCTION PROCESS DESCRIPTION

In the process either a 0.5 to 1.0% sulphuric acid (H2SO4) catalyst is used at 50
to70oC for 30 minutes or, in the absence of the acid, a temperature of 195oC and
185 psi for 1hour will form the diol. The formation of higher glycols is inevitable
because ethylene oxide reacts faster with ethylene glycols faster than with water.
The most important variable is the water-to-oxide ration, and the production of
diethylene glycol (DEG) and triethylene glycol (TEG) can be reduced by using a
large excess of water. A 90 percent yield is realized when the ethylene oxide/water
molar ratio is 1:5-8.The advantage of the acid-catalysed reaction is no high pressure,
however the thermal reaction needs no corrosion resistance and no acid separation
step. The crude glycols are dehydrated and then recovered individually as highly
pure overhead streams from a series of vacuum-operated purification columns.
Ethylene glycol (boiling point: 197.6oC) is readily vacuum distilled and separated
from the diethylene glycol (boiling point: 246oC, density: 1.118, flash point: 124oC)
and triethylene glycol (boiling point: 288oC, density: 1.1274, flash point:
177oC).Since ethylene glycol is produced in relatively high purity, differences in
quality are not expected. The directly synthesized product meets the high quality
demands (polyester grade glycol).
ETHYLENE GLYCOL PRODUCTION

The production of ethylene glycol by the hydrolysis of ethylene oxide is by far the
most widely used method for the production of ethylene glycol. It is relatively
economical, simple reliable and can be used in plants that manufacture ethylene
oxide and glycol together. For this Project design there is a modification to the
common Flow sheet used for the Hydrolysis of Ethylene Oxide process that has
been shown above. This modified unit arrangement will still achieve the production of
Ethylene Glycol at a lower capital cost. As stated above this reaction can be acid or
based catalysed but for this work a choice of a neutral and high pressure and
temperature reaction is made because it has the economic advantage of having no
need for corrosion resistance and no acid separation step.

The aim of this work is the yield of Ethylene Glycol not those of higher glycol does
this reaction is modified in such a way as to favour reaction step one and disfavour
the other two steps and this is achieved by using excess of water for the reaction to
dilute the concentration of the ethylene glycol produced to discourage the formation
of higher glycols.

Figure 1: Manufacture of Ethylene Glycol

PRODUCTION PROCESS DESCRIPTION

Ethylene Oxide and water a passed into a Continuous Stirring Tank Reactor which

operates a temperature of 195oC and pressure 185 psi for 1 hour will form the diol.

Since the formation of higher glycols is inevitable because ethylene oxide reacts

faster with ethylene glycols faster than with water then the water-to-oxide ration must

be manipulated to reduce if not eliminate the production of diethylene glycol (DEG)

and triethylene glycol (TEG). This is done by using a large excess of water. In this

work, the ethylene oxide/water molar ratio is 1:7 and the yield of Ethylene glycol is

90%. This Plant is designed to produce 10000kg/yr of Ethylene Glycol.

The crude Ethylene produced from the reactor is dehydrated and recovered as

highly pure overhead stream from a distillation column with a partial condenser. The

Distillate from the partial condenser is mainly water and is recycled back to the

reactor and mixed within coming water. The flow sheet for this sequence is shown

below

Figure 2: The flow sheet for the production of Ethylene Glycol

2. REACTOR SELECTION

STEADY-STATE NON-ISOTHERMAL CONTINUOUS STIRRED TANK REACTOR

(CSTR) DESIGN

STEADY-STATE NON-ISOTHERMAL CONTINUOUS STIRRED TANK REACTOR

(CSTR) DESIGN: OBJECTIVE

We now examine the effects of heat in Chemical reactors.

The basic design equations, rate laws and stoichiometric relationships
Derived and used for isothermal Reactors are still valid for Non-isothermal
reactors.
The major difference in non-isothermal reactors is heat is transferred to or
from the CSTR.

Thermal energy conservation: Non-isothermal continuous -flow reactors

Consider a system at steady-state, no shaft work W S =0 , adiabatic operation

Q=0 . In many instance HRx(TR) >>Cp(TTR), and the energy balance

equation gives us the explicit relationship between x and t needed to be used in

conjunction with the mole balance to solve the type of problems discussed earlier:
THERMAL ENERGY CONSERVATION: APPLICATION TO CSTRs

Although the (CSTR) is well mixed and the temperature is uniform throughout
the vessel, it does not imply that the reaction is carried out isothermally.
The design equation for the (CSTR) (mole balance) is

And the x versus t relationship is provided by the energy balance equation

3. KINETICS
Adiabatic Continuous Stirred Tank Reactor (CSTR)

1. Mole Balance and design equation:

FA0 FA + rAV = 0
The design equation of CSTR in terms of X is
FA 0 X
V=
r A

2. Rate Law:

r A=k C A

3. Stoichiometry (liquid, = 0 ):

C A =C A 0 (1 X )

4. Combining yields

F A0 X 0 X
V= =
k C AO (1X ) k (1 X )

Solving for X as a function of T and recalling that =V / 0 and

k =A exp
[ ]
E
RT gives

E
A exp [ ]
k RT
X MB= =
1+k E
1+ A exp [ ]
RT

This equation relates temperature and conversion through the mole balance.

5. The energy balance for this adiabatic reaction in which there is negligible
energy input provided by the stirrer is
 i C Pi( T T i 0 )
X EB=
[ H RX ( T R ) + C P ( T T R ) ]

This equation relates X and T through the energy balance.

4. SAFETY
The word safety used to mean the older strategy of accident prevention through the
use of hard hats, safety shoes, and a variety of rules and regulations. The main
emphasis was on worker safety. Much more recently safety has been replaced by
loss prevention. This term includes hazard identification, technical evaluation, and
the design of new engineering features to prevent loss. Safety, hazard, and risk are
frequently-used terms in chemical process safety. Their definitions are
Safety or loss prevention, the prevention of accidents through the use of
appropriate technologies to identify the hazards of a chemical plant and
eliminate them before an accident occurs.
Hazard, a chemical or physical condition that has the potential to cause
damage to people, property or the environment.
Risk, a measure of human injury, environment damage, or economic loss in
terms of both the incident likelihood and the magnitude of the loss or injury.
Chemical plants contain a large variety of hazards. First, there are usual mechanical
hazards that cause worker injuries from tripping, falling, or moving equipment.
Second, there are chemical hazards. These include fire and explosion hazards,
reactivity hazards and toxic hazards.
Implementing a safety program is to make it everyones responsibility in a chemical
process plant. All employees have the responsibility to be knowledge about safety
and to practice safely. It is important to recognize the distinction between a good and
an outstanding safety program.
A good safety program identifies and eliminates existing safety hazards.
An outstanding safety program has management systems that prevent the
existence of safety hazards.
A good safety program eliminates the existing hazards as they are identified,
whereas an outstanding safety program prevents the existence of a hazard in the
first place.
General Requirements:
1) Safety. It is imperative that industrial plants operate safely so as to promote
the well-being of people and equipment within the plant and in the nearby
communities. Thus, plant safety is always the most important control
objectives.
 2) Environmental Regulations. Industrial plants must comply with environmental
regulations concerning the discharge of gases, liquids and solids beyond the
plant boundaries.
3) Product Specifications and Production Rate. In order to be profitable, a plant
must make products that meet specifications concerning product quality and
production rate.

Basics for Safe Operation of CSTR:

Strongly exothermic continuous processes must never be started up batch-like by
simultaneous addition of educts to a quasi-empty reaction vessel. Therefore it is
recommended either to start-up into reacted material or to start the CSTR as a semi-
batch reactor by adding one educts to the vessel until the desired operating point is
reached. At this time the feed of the second component is switched on.

Form the safety technical point of view the CSTR has the advantages that

It operates in a steady state,

It is well controllable and

Large heat transfer areas can be installed

The main problem lies in a difficult and sometimes critical start-up and shut down
operations.

Safety considerations in chemical process plant

Power Point presentation on methods to avoid explosions

High Integrity Pressure Protection Systems
Using Instrumented Systems for Overpressure Protection
Reactor safety publications
Reactor hazards ; Reactor safety
Reactor venting ; Relief valves ; Relief valves for supercritical fluids
5. DETAIL DESIGN

Assume it is liquid flow system:

H2SO4
C2H4O + H2O C2H6O2

A B C

Species Feed Rate Change Effluent Rate Concentration

A FAO -FA0X FA = FA0(1-X) CA = CAO(1-X)
B FBO=BFAO -FAOX FB = FAO(B-X) CB = CAO(B-X)
C 0 +FAOX FC = FAOX CC = CAOX

Time Cc x CA C AO
ln
(min) (kmol/m3) (kmol/m3) CA
0 0.000 0.000 1 0.000
0.5 0.145 0.145 0.855 0.157
1.0 0.270 0.270 0.730 0.315
1.5 0.376 0.376 0.624 0.472
2.0 0.467 0.467 0.533 0.629
3.0 0.610 0.610 0.390 0.942
4.0 0.715 0.715 0.285 1.255
6.0 0.848 0.848 0.152 1.884
10.0 0.957 0.957 0.0431 3.144

Sample calculations:

CAO = 2 kmol/m3. Since dilution occur, the initial concentration of A that fed to the
reactor will dilute and become CAO = 1 kmol/m3

CC = CAOX

0.145 = 1 X

X = 0.145

CA = CAO(1-X)

CA = (1-0.145)

CA = 0.855 kmol/m3
 C AO 1
ln =ln =0.157
CA 0.855

The reaction is considered to be first-order in ethylene oxide concentration and zero-

order for excess water under this condition(dilution) as stated by T.Furusawa,Chem.
Eng. Jpn., 2, 95 (1969). Hence, the graph ln(C AO/CA) versus time is plotted in order to
prove it is first order reaction.

3.5

2.5

ln(CAO/CA) 1.5 Y-Values

Linear (Y-Values)
1

0.5

0
0 1 2 3 4 5 6 7 8 9 10 11

Time,t(min)

Graph 1: First order graph (ln(CA/CAO) vs t)

Based on the graph, ln(C AO/CA) increase linearly with respect to time. Hence, it is
prove the reaction is first order. Value of k can be find from the gradient of the graph.

First-order equation:

C AO
ln =kt
CA

(3.1440)
Gradient = k = =0.314 min1
(100)

By using the idle reactor:

Information given:

CAO = 16kmol/m3

FAO = 1600kmol/min

T0 = 50 oC = 323 K

k = 0.3144 min-1 at T= 328 K

HoRX = -37.669 kJ/mol

Ea = 79.046 kJ/mol

V = 1m3

Since dilution occur, the reactant fed are assumed to be equimolar and water is
assume to be constant since it is excess.

F AO X
V=
r A

v o C AO X
V=
k CA

v o C AO X
V=
k C AO ( 1 X )

X
= eqn. (1)
kX

k
X MB=
k +1

k =k 1 exp
[ ( )]
E 1 1

R T1 T
eqn. (2)

[ ]
79.046 kJ / mol 1 1 1
k =0.3144 exp
0.008314
(
kJ
)
328 T K
mol . K
 F AO 1600 kmol / min 100 m3
v AO = = =
C Ao 16 kmol min
3
m

200 m3
v o =v AO + v BO=100+ 100=
min

V 1 m3
= = =0.005 min
v o 200 m 3 /min

Substitute , and eqn (2) into eqn (1);

X MB=
[
0.005 0.3144 exp [ 28.9865 ( T 328 )
T ]]
[
0.005 0.3144 exp [ 28.9865 ( T 328 )
T
+1 ]]
X MB=
1.572 103 exp [ 28.9865 ( T 328 )
T ]
1.572 103 exp [ 28.9865 ( T 328 )
T
+1 ]
T T R
o
H RX + C p

X EB=
i C pi (T T o)

B = yBO / yAO = 0.5/0.5 = 1

From table heat capacities and Kopps Rule; C pA = 0.0792 kJ/mol.K, CpB = 75.4 kJ/mol.K,
CpC = 0.182 kJ/mol.K
kJ
i C pi=0.0792+ ( 1 ) 75.4=75.4792 mol . K

kJ
C p=0.18275.40.0792=75.2972 .K
mol

75.4792(T 323)
X EB=
37.669+75.2972(T 298)
 T(K) XMB XEB
323 0.0010 0
340 0.0044 0.4010
360 0.0203 0.5934
380 0.0766 0.6926
400 0.2248 0.7530
420 0.4735 0.7937
440 0.7156 0.8230
460 0.8656 0.8451
480 0.9384 0.8624
500 0.9711 0.8762

1.1

0.9

0.8

0.7

0.6

Conversion, X 0.5
XMB
XEB
0.4

0.3

0.2

0.1

0
323 343 363 383 403 423 443 463 483 503 523

T (K)

From the graph, by using the idle reactor, the maximum conversion is 84% at
temperature, T=456K

REFERENCES
[1] Continuous Stirred Tank Reactor. (Retrieved 15/6/2016)

http://www.safety-s2s.eu/modules.php?
name=s2s_wp4&idpart=2&op=v&idp=1492

[2] Reactor Design and Safety requirements. (Retrieved

15/6/2016)

http://people.clarkson.edu/~wwilcox/Design/reacdesn.htm

[3] Production of Ethylene Glycol. (Retrieved 13/6/2016)

http://www.academia.edu/4467214/Production_of_Ethylene_Glycol

[4] http://www.patentsencyclopedia.com/app/20120197048