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

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 Case 1 – Ammonium Nitrate Explosion

Massive blast at Terra plant kills four.

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 Example 1: Safety in Chemical Reactors

H2 O
 Gas
 2
N O
17%H2 O
T0  200F 200°F P
m A0  310lb h Liquid
83%NH4 NO3 

510°F
X Ta 0
 NH4 NO3
Ta
M  500 lb


 NH4 NO3  N 2O  2H 2O


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
 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 Qr

 g    
dT

 
H Rx rA V   FA 0   i C Pi T  T0   UA T  Ta 
dt  N i C Pi

Adiabatic
 
Q r  FA0 C PA T  660   W 1134  C PW T  960 
FA0  0

dT H Rx rAV T

dt N iC Pi
If the flow rate is shut off, the temperature t (min)
6 will rise (possibly to point of explosion!)
 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?

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 Nitro aniline Synthesis Reaction

NO2 NO2
Cl NH2

+ 2NH3 + NH4Cl

ONCB + Ammonia Nitro aniline + Ammonium

Chloride

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 Nitro aniline Synthesis Reaction
NH3 in H2O

ONCB

Autoclave
175 oC
~550 psi

NH3 Filter
O-Nitroaniline Separation Press
Product Stream

To Crystallizing Tanks

9 “fast” Orange
 Nitro aniline Synthesis Reactor

Old
3 kmol ONCB
43 kmol Ammonia
100 kmol Water
V = 3.25 m3
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 Same Nitro aniline Synthesis Reaction
NO2 NO2
Cl NH2

+ 2NH3 + NH4Cl

ONCB + Ammonia Nitro aniline + Ammonium Chloride

Batch Reactor, 24 hour reaction time

Management said: TRIPLE PRODUCTION

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 MBA-Style:
Nitro aniline Synthesis Reactor

New
9 kmol ONCB
33 kmol Ammonia
100 kmol Water
V = 5 m3
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 Batch Reactor Energy Balance
Qg Qr
dT (rA V)( H rx )  UA (T  T0 )

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   Equation (12 - 13) p547
m 
    c C Pc  
For high coolant flow rates, m c , the maximum rate of heat removal is
Q r  UAT  Ta 
The rate of “heat generated” is 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 
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 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    0.0001167C 2A 0 1  X 
m 
    c C Pc  
Vary m c to keep “heat removed” equal to “heat generation”
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Isothermal Operation for 45 minutes

At the time the heat exchanger fails

X  0.033, T  448 K
Qg  rAVH 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
  0.2C / min
dt NC p
Temperature-Time trajectory
dT Qq  Qr
  0.2 C / min
dt N Cp
Temperature oC

400

Qr = 0 Cooling Restored
200 Isothermal
Operation
175
fuse

9:55 10:40 10:50 midnight 12:18

t=0
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 Disk Rupture
The pressure relief disk should have ruptured when the temperature
reached 265°C (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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 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).
Step 1a. Reaction between methylcyclopentadiene (MCP) and sodium in a
solvent of diethylene glycol dimethyl ether (diglyme, C6H14O3) to
produce sodium methylcyclopentadiene and hydrogen gas:

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

Step 1c. 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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 What Happened
T2 Laboratories Explosion
 On December 19, 2007, when the reactor reached a
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.
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 T2 Laboratories Accident
Before After

• At 1:33pm, 19 December 2007 a powerful explosion at

T2 Laboratories in Jacksonville, Florida killed 4 employees,
injured 32 (4 employees and 28 members of the public)
and destroyed the facility.
• A runaway exothermic reaction in the production of
methylcyclopentadienyl manganese tricarbonyl (MCMT)
(fuel octane booster) due to cooling loss led to the
25 explosion equivalent to 1400 pounds of TNT.
 Only consider Step 1: Desired Reaction

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

Simplified Model

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

These reactions are:

(1) A + B  C + 1/2 D (gas) r1A  r1B  k1ACACB H Rx1A  45,400 J mol

(2) S  3 D (gas) + miscellaneous r2S  k 2sCS H Rx2S  3.2 10 5 J mol

liquid and solid products




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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
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search the Web for "T2 explosion video."
 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 13-
6.26) 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:

30 (3) Stoichiometry – Liquid Phase

 Case 3 – Manufacture of Fuel Additive
(4) Energy Balance:

1.26 107 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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