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Lecture 25

Chemical Reactor Safety


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 )
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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

NH2

2NH3
Ammonia

+
Nitroaniline

NH4Cl

+ Ammonium
Chloride

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

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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
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MBA-Style:
Nitroanline Synthesis Reactor

New

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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

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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

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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
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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

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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

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x3!
!!

Case 3 Manufacture of Fuel Additive


Example 13-6 T2 Laboratories Explosion
T2 Laboratories manufactured a fuel additive,
methylcyclopentadienyl manganese tricarbonyl
(MCMT), in a 2,450-gallon, high-pressure
batch reactor utilizing a three-step batch
process.

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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.

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Case 3 Manufacture of Fuel


Additive

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WhatHappened
T2 Laboratories Explosion
On December 19, 2007, when the reactor reached a

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temperature of 455.4 K (360.F), the process operator could


not initiate the flow of cooling water to the cooling jacket
shown in Figure E I 3-6.2.
Thus, the expected cooling of the reactor was not available
and the temperature in the reactor continued to rise.
The pressure also increased as hydrogen continued to be
produced at an increased rate, to the point that the reactor
pressure control valve system on the l-inch diameter
hydrogen venting stream could no longer maintain the
operating pressure at 50 psig (4.4 atm).
As the temperature continued to increase further, a
previously unknown exothermic reaction of the diglyme
solvent that was catalyzed by sodium accelerated rapidly.

Only consider Step 1: Desired Reaction

As T continued to rise, Undesired Reaction of Dyglime took place.

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

These reactions are:


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

r1A r1B k 1AC AC B

H Rx1A 45,400 J mol

(2) S 3 D (gas) + miscellaneous


liquid and solid products

r2S k 2sCS

H Rx2S 3.2 10 5 J mol

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What Happened
T2 Laboratories Explosion (contd.)
This reaction produced even more hydrogen, causing the pressure to rise

even faster, eventually causing the ruptured disk to break, which was set
at 28.2 atm absolute(400 psig), in the 4-inch diameter relief Line of H2.
Even with the relief line open, the rate of production of H2 was now for
greater than the rate of venting, causing the pressure to continue to
increase to the point that it ruptured the reactor vessel initiating a horrific
explosion.
The T2 plant was completely leveled and four personnel lives were lost.
Surrounding businesses were heavily damaged and additional injuries
were sustained.
Before continuing with this example it might be helpful to view the 9
minute Chemical Safety Board (CSB) video, which you can access
directly from the Chapter 13 Summary Notes on the Web site, or you can
read the supporting reports
[http://www.chemsafety.gov/videoroom/detail.aspx?VlD=32]. You can also
search the Web for "T2 explosion video."
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T2 Laboratories Explosion (contd.) (6) Numerical


Solutions-"Tricks of the Trade"
A rapid change of temperature and pressure is expected a reaction (2)

starts to run away. This typically results in a stiff system of ordinary


differential equations, which can become numerically unstable and
generates incorrect results. This instability can be prevented by using a
software switch that will set all derivatives to zero when the reactor
reaches the explosion temperature or pressure.
This switch can have the form of Equation (E 13-6.26) in Polymath and
can be multiplied by the right-hand side of all the differential equations in
this problem. This will halt (or freeze) the dynamics when the T become
higher than 600 K or the pressure exceeds 45 atm.
SW I = if (T>600 or P>45) then (0) else (I) (EI3-6.26)
We now will solve the essential equations from (E 13-6.1) through (E 136.26) for the scenario where there is no cooling and thus UA = 0. Also the
switch SW I must be implemented in all the differential equations as
discussed above.
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Case 3 Manufacture of Fuel


Additive

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Case 3 Manufacture of Fuel Additive


(2) Rates
Laws:

Net Rates:

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(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
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End of Web Lecture 25


Class Lecture 2

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