Lecture 25

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the
reactors in which they take place.

Web Lecture 25
Class Lecture 21 4/2/2013
CSI
Ammonium Nitrate Explosion
Monsanto Explosion
T2 Laboratories Explosion

Case 1 Ammonium Nitrate

Explosion
Massive blast at Terra plant kills four.

Example 1: Safety in Chemical

Reactors

Example 1: Safety in Chemical

Reactors
Only liquid A in the vat as the product gases N2O
and H2O escape immediately after being formed.

dT Q g Q r

dt
N A C PA
Qg (rAV )(H Rx )
Qr FA0 C PA (T T0 ) B ( H B H B 0 ) UA(T Ta )
5

Unsteady State Energy Balance

Q

dT

dt

g
Q r
H Rx rA V FA 0 i C Pi T T0 UA T Ta

N i C Pi

Adiabatic

Q r FA0 C PA T 660 W 1134 C PW T 960

FA0 0
dT H Rx rAV

dt
N iC Pi

If the flow rate is shut off, the temperature

6 will rise (possibly to point of explosion!)

t (min)

Case 2 Monsanto Chemical

Company
Keeping MBAs away from Chemical Reactors
The process worked for 19 years before they

showed up!
Why did they come?
What did they want?

Nitroanline Synthesis
Reaction
NO2

NO2

Cl
+
ONCB
Chloride

NH2

2NH3
Ammonia

+
Nitroanaline

NH4Cl

+ Ammonium

Nitroanline Synthesis
Reaction
NH3 in H2O
ONCB

Autoclave
175 oC
~550 psi

O-Nitroaniline
Product Stream

NH3
Separation

Filter
Press
To Crystallizing Tanks

fast Orange

Nitroanline Synthesis Reactor

Old

10

3 kmol ONCB
43 kmol Ammonia
100 kmol Water
V = 3.25 m3

Same Nitroanline Synthesis

Reaction
NO2

NO2

Cl
+
ONCB
Chloride

NH2

2NH3
Ammonia

+
Nitroanaline +

NH4Cl
Ammonium

Batch Reactor, 24 hour reaction time

Management said: TRIPLE PRODUCTION
11

MBA-Style:
Nitroanline Synthesis Reactor

New

12

9 kmol ONCB
33 kmol Ammonia
100 kmol Water
V = 5 m3

Batch Reactor Energy Balance

Qg

Qr

(r V)( H rx ) UA (T T0 )
dT
A
dt
N A 0 C pA N B0 C pB N W C pW
NC P N A 0 C pA N B0 C pB N W C pW

dT Q g Q r

dt
NC p

13

Batch Reactor Energy Balance

dT Q g Q r

dt
NC p
The rate of heat removed is

UA
c C Pc Ta1 T 1 exp
Qr m
m

c C Pc

Equation (12 - 13) p547

c , the maximum rate of heat removal is

For high coolant flow rates, m
Q r UAT Ta
The rate of heat generated is

14

Q g (rA V )H Rx rA V H Rx
rA k 1C A C B

Q g k 1C A C B H Rx

Batch Reactor Energy Balance

Recall

dT Qr Qg

dt
NCPS

For isothermal operation at Qr = Qg, T = 448 K

Q g k 448 K C 2A 0 1 X B X H Rx
Qr Qg

UA
c C Pc Ta1 T 1 exp
m
m

c C Pc
Vary
15

0.0001167 C 2A 0 1 X

m c to keep heat removed equal to heat generation

Isothermal Operation for 45

minutes
At the time the heat exchanger fails
X 0.033, T 448 K
Qg rAVH Rx 3850 kcal / min
The maximum rate of removal at T 448 K is
Qr UA T Ta 35.85(448 298) 5378 kcal / min
Qr Qg

Everything is OK

Adiabatic Operation for 10

minutes
t 45 min X 0.033 T 448 K
t 55 min X 0.0424 T 468 K
Qg 6591 kcal / min
Qr 6093 kcal / min
Qg Qr
dT Qg Qr

0.2C / min
dt
NC p

Temperature-Time trajectory

Temperature oC

dT Qq Qr

0.2 C / min
dt
N Cp
400

200
175

18

9:55
t=0

Isothermal
Operation

Qr = 0

Cooling Restored

fuse
10:40 10:50

midnight 12:18

Disk Rupture
The pressure relief disk should have ruptured when the temperature
reached 265C (ca. 700 psi) but it did not.
If the disk had ruptured, the maximum mass flow rate out of the
reactor would have been 830 kg/min (2-in orifice to 1 atm).

vap H vap UA T Ta
Qr m
kcal
Q r 449,000
min
kcal
Q g 27,460
min
Q r Q g
No explosion

All the following three things must have

occurred for the explosion to happen
1. Tripled Production

2. Heat Exchange Failure

3.Relief Valve Failure

20

x3!
!!

Case 3 Manufacture of Fuel

Additive
methylcyclopentadiene manganese tricarbonyl (MCMT)

21

Production of methylcyclopentadienyl manganese tricarbonyl (MCMT).

Step1a. Reaction between methylcyclopentadiene (MCP) and sodium in a
solvent of diethylene glycol dimethyl ether (diglyme, C6H14O3) to
produce sodium methylcyclopentadiene and hydrogen gas:

Step1b. At the end of Step 1a, MnCl2 is added to the reactor. It reacts with
sodium methylcyclopentadiene to produce manganese
dimethylcyclopentadiene and sodium chloride:

Step1c. At the end of Step 1b, CO is added. The reaction between

manganese dimethylcyclopentadiene and carbon monoxide produces the
final product, methylcyclopentadienyl manganese tricarbonyl (MCMT), a fuel
additive.

22

Only consider Step 1

Desired Reaction

Undesired Reaction of Dygline

SimplifiedModel
Let A = methycylcopentadiene, B = sodium, S = Solvent (diglyme), and D = H2.

These reactions are:

r1A r1B k 1AC AC B

(1) A + B C + 1/2 D (gas)

(2) S 3 D (gas) + miscellaneous liquid and solid products r2S k 2sCS

H Rx1A 45,400 J mol
23

H Rx2S 3.2 10 5 J mol

Case 3 Manufacture of Fuel

Additive

24

Case 3 Manufacture of Fuel

Additive

25

Case 3 Manufacture of Fuel

Additive
(2) Rates
Laws:

Net Rates:

26

(3) Stoichiometry Liquid Phase

Case 3 Manufacture of Fuel

Additive
(4) Energy Balance:

1.26 10 7 J K

H Rx1A 45,400 J mol

H Rx2S 3.2 10 5 J mol
27

28

End of Web Lecture 25

Class Lecture 2

29