The Integration of Process

Safety into a Chemical Reaction

Engineering Course:
the Review of the T-2 Incident
Ronald J. Willey, Northeastern University, Boston, MA
H. Scott Fogler, University of Michigan, Ann Arbor, MI
Michael B. Cutlip, University of Connecticut, Storrs, CT

Objectives/Outline
Introduce you to a textbook example that will
appear in the newest edition of H.Scott Fogler,
Essentials of Chemical Reaction Engineering
This example appears in Chapter 13 of the new
book. Unsteady-State Non isothermal Reactor
Design
Methods used to model the reaction
Demonstration of integration of Polymath to
solve the problem

Text book problem statement

Example 13-6 T2 Laboratories Explosion

Figure E13-6.1 Aerial photograph of T2 taken December 20, 2007.

Courtesy of Chemical Safety Board.

Opening paragraph example

statement
T2 Laboratories manufactured a fuel additive methylcyclopentadienyl manganese
tricarbonyl (MCMT) in a 2,450-gallon high-pressure batch reactor utilizing a threestep batch process.
Step 1a. The liquid-phase metalation reaction between methylcyclopentadiene
(MCP) and sodium in a solvent of diethylene glycol dimethyl ether (diglyme) to
produce sodium methylcyclopentadiene and hydrogen gas:

+ Na

Na

1
H2
2

Hydrogen immediately comes out of the solution and is vented at the top in
the gas head space.

We included the previously

unknown Reaction 2

3 moles of gas + tar +HEAT!

diglyme decomposition

3 moles of gas and tar plus heat

Reactor Details

2450 gallons [~9,000 dm3] batch reactor

Working volume of 2,000 gallons
Made of 3 steel
Working pressure was 600 psig (4.13 MPa)
Original design rating was 1200 psig (8.27 MPa)
Relief was a 4 diameter rupture disc inserted
into a 4 line.
Rupture disc setting was 400 psig.

Figure 8
Reactor
Cross
Section

Problem statement rendition

Cooling jacket
steam outlet

Cooling jacket
water inlet

Adiabatic Reaction Calorimetry used

for kinetic constants estimates
diglyme decomposition

reaction 1
exotherm

Simplified Model
A = sodium,
B = methycyclopentadiene
S = Solvent (diglyme)
(1) A + B C + 1/2 D (gas)
(2) S 3 E (gas) + F
Initial temperature 422 K (300F)

Reaction Kinetics
Reaction 1: Overall 2nd order, first order in Na
and MCP
r1A = k1CACB
k1A = 5.73 102 dm3 mol1 hr1
E1 = 128,000 J/mol K*

*Later modeling reduced this to 40,000 J/mol K

Reaction Kinetics Reaction 2

First order in solvent only:
r2S = k2*CS
k2S = 9.41 1016 hr1
E2 = 800,000 J/mol K*

* Later information provided 80,000 J/mol K

Heat of Reactions
The heats of reaction are constant.
HRx1A = 45,400 J/mol
HRx2S = 3.2 105 J/mol

Assumptions provided in the example

Liquid volume, V0 = 4,000 dm3

Vapor space, VV = 5,000 dm3.
Ideal gas law
Venting given by this estimate (P-1)Cv,
Cv1= 3,360 mol/hratm for the 1 vent line.
Cv2 = 53,600 mol/hratm for the 4 vent line.
The reactor fails when the pressure exceeds
45 atm or the temperature exceeds 600 K.

Problem Statement
Plot and analyze the reactor temperature and
head space pressure as a function of time
along with the reactant and product
concentrations for the scenario where the
reactor cooling fails to work (UA = 0). In
problem P13-2(f) you will be asked to redo
the problem when the cooling water comes
on as expected whenever the reactor
temperature exceeds 455 K.

From the text book example solution

(1)

Reactor Mole Balances

Reactor (Assume Constant Volume Batch)
Liquid

dC A
r1 A
dt

(E13-6.1)

dCS
r2S
dt

(E13-6.2)

(2) Head Space Mole Balances

Let Ng = H2 + CO

For H2 and CO in the head space.

From the text book example solution

(5)

Energy Balance
Applying Equation (E13-18) to a batch system (Fi0 = 0)

dT V0 r1 AH Rx1 A r2 S H Rx 2 S UAT Ta

dt
N j CPj

(E13-6.18)

Substituting for the rate laws and N j CP j

dT k1A H Rx1A CA CB k2S CS UAT Ta

dt
1.26 10 7 J K

(6

(E13-6.19)

(6)

Numerical Solutions Tricks of the Trade

A rapid change of temperature and pressure is expected

as reaction (2) starts to run-away. This typically results in a
stiff system of ordinary differential equations, which can
become numerically unstable and generate incorrect
results. This instability can be prevented by using a
software switch that will set all derivates to zero when the
reactor reaches the explosion temperature or pressure.
This switch can have the following form in Polymath and
can be multiplied by the right hand side of all the
differential equations in this problem. Here the dynamics
will be halted when the T become higher that 600 K or the
pressure exceeds 45 atm.

SW1 = if (T>600 or P>45) then (0) else (1)

Polymath Code (first few lines)

# Reactor volumes
V0= 4000 # dm3
VH= 5000 # dm3
# Initial concentrations
CA(0)=4.3 #mol sodium/dm3
CB(0)=5.1 # mol methylcyclopentadienel/dm3
CS(0)=3 # mol of Diglyme/dm3
# Heat of reactions
DHRx1A=-45400 # J/mol Na
DHRx2S=-3.2E5 # J/mol of Diglyme
# Sum of product of cp and mass of liquid-phase components in reactor
cpSYS=1.26E7 #J/K

Screen capture of Polymath

Simulation shown in Text UA=0

Later work, with more information

Three scenarios compared

Questions?