Process Safety Testing and

Process Modeling in the PSL

Using Dynochem

Steve Richter, Ph.D.

Ayman Allian, Ph.D.
Abbott Process Safety Laboratory
Safety Testing in Dynochem

• ARC Data
• Vessel characterization
• RC1 data analysis and modeling
– Minimum addition times
– Hydrogenation
• DynoChem Challenges
• Final Thoughts

3rd Process Safety Forum © 2008 Abbott

October14, 2008
 NaBH4 + ROH 4 H2 + B(OR)3 + NaOR

ARC Example – NaBH4 in Ethanol

• Fit kinetic model to ARC Data

• Not restricted to first order kinetics
• Incorporate gas evolution

3rd Process Safety Forum © 2008 Abbott

October14, 2008
 NaBH4 + ROH 4 H2 + B(OR)3 + NaOR

ARC Example – NaBH4 in Ethanol

• With a model in Dynochem,
can quickly
– Simulate the heat rate with
phi-corrections
– Predict Tad24 (21.5°C)

3rd Process Safety Forum © 2008 Abbott

October14, 2008
Process modeling

• Often, the first data-rich experiments on processes being

scaled-up is obtained during safety testing
• Although the amount of required testing has increased,
modeling tools, such as Dynochem, allow investigation of heat
transfer and kinetic parameters quickly
– What-if scenarios with equipment specifications
– Kinetic insight into chemistry

3rd Process Safety Forum © 2008 Abbott

October14, 2008
Kinetics and Modeling in the Process Safety Lab

• How much can we learn from early phase safety testing?

• Examples
– Fed-batch reactions - What is the minimum addition time?
• Reaction rates limited by feed rate (dosing-controlled)
• Reaction rate limited by reaction kinetics (kinetic-controlled)
– Hydrogenation
• Build-up of potentially unstable intermediate

3rd Process Safety Forum © 2008 Abbott

October14, 2008
Minimum Addition Time:
Addition controlled reaction

• RC1 calorimetric data can be used in conjunction with

knowledge about large scale reactors to predict temperature
profiles
• Simulations can predict maximum reaction temperature or
determine rate of addition to remain below a given temperature
with reactor cooling capabilities.

NaOH + 2 H2O
+ 2 NaOCl
R
+ 2 NaI MeOH/H2O I R + 2 NaCl
0°C
OH OH

3rd Process Safety Forum © 2008 Abbott

October14, 2008
 RC1 C19 E
Minimum Addition Time: 2
U [W/m /K] 7.5 202
UA [W/K] 2.7 530
Addition controlled reaction Scale 1 1000

• Large scale – Less efficient heat transfer and minimum jacket temp of 0oC
(Estimate for new reactor)
I

• Visualize effect of changes on scale NaOH + 2 H2O

+ 2 NaOCl
• Determine minimum time – 113 minutes R + 2 NaI MeOH/H2O
0°C
I R + 2 NaCl
OH OH

12 Same addition 12

10
rate as RC1
10
8 Max T > 10oC
45 min Feed Reaction Temp
6 RC1 Reaction Temp 8 3 hr Feed Reaction Temp
Temperature (°C)

RC1 Reaction Temp

Temperature (°C)
RC1 Jacket Temp
4 RC1 Jacket Temp Temp
C19 Reaction
C19 Jacket Temp 6
2

0
4X RC1 Add Time
4

-2
RC1 Tr Max T < 4oC
-4 Max T < 0.1oC 2

-6
0 10 20
20 30
30 40
40 50
50 6060 7070 8080 0
0 50 100 150 200 250
Time
Time(min)
(min)
Tim e (m in)

3rd Process Safety Forum © 2008 Abbott

October14, 2008
Alternate approach – Use the included utility

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October14, 2008
Also – Vessel Assessment

3rd Process Safety Forum © 2008 Abbott

October14, 2008
 Main Resistance to Heat Flux
Glass Stainless Steel

Main Resistance is the Main Resistance is inside

Wall the Film

• Implication
– Wall thickness effect, Stirring Speed Effect
3rd Process Safety Forum © 2008 Abbott
October14, 2008
Minimum Addition Time:
Kinetic controlled reaction

• Unlike addition controlled reactions, in which kinetics are much

faster than the addition rate, reactions limited by intrinsic
kinetics pose a threat by allowing reagents to accumulate in the
process.

O
N2H4 H2O HN
R NMe2 N R

3rd Process Safety Forum © 2008 Abbott

October14, 2008
Minimum Addition Time:
Kinetic controlled reaction
• Start simple – Fit Qr data from RC1 at 3X
dilution to A + B Æ C
– Determine rate constant and
heat of reaction that best fits data
• Fit does not capture the O
HN
N2H4 H2O
behavior observed in R NMe2 N R
the RC1 – Try again.

2.5

2
Heat Flow (W)

RC1 Data
1.5
Model

0.5

0
0 50 100 150 200
Time (min)

3rd Process Safety Forum © 2008 Abbott

October14, 2008
 Minimum Addition Time:
Kinetic controlled reaction

• New Model – Fit Qr data from RC1 to A + B Æ I Æ P

– Determine rate constants and
O
heats of reaction that best fits data R NMe2
N2H4 H2O
Intermediate HN
N R
• k1= 1.6e-3 L/mol/s CI 20%
• k2 = 1.2e-3 1/s CI 12%
• ΔHrxn,1= -11 kJ/mol CI 33% 3

• ΔHrxn,2= -109 kJ/mol CI 3% 2.5

2
Heat Flow (W)

RC1 Data
1.5
Model

Value Time Scale [s] 1

k1*[A] 598.00 0.5

k2 833.00 0
0 50 100 150 200
Time (min)

3rd Process Safety Forum © 2008 Abbott

October14, 2008
Determine Addition Time

• Knowledge of kinetic model allows prediction of the ATR at any

time during the process under different conditions.
• Feed time for a maximum ATR can be determined.
– Maximum ATR for a 4 hour feed is 9.6°C
30 80

Potential to 25 75

Reflux
Instantaneous ATR (°C)

20 70

Temperature (°C)
15 65

Quality Limit = 60°C 10 60

5 55

0 50
0 50 100 150 200
Time (min)

3 Hour Addition 1 Hour Addition PI Data from R12

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October14, 2008
Summary – Finding Minimum Addition Times

• Minimize surprises on scale-up – e.g. temperature overshoots

• Help in the selection of relevant stress experiments

3rd Process Safety Forum © 2008 Abbott

October14, 2008
 Hydrogenation – Nitro Reduction

• Nitro reductions can accumulate a potentially unstable

hydroxylamine intermediate
• Simplify model reaction to a two-step reaction and fit reaction rate
constants to match hydrogen uptake data.
0.16

0.14

• k1= 84.8 L2/mol2/s CI 0.3% 0.12

H2 Uptake (mol)
0.1
Experimental
Fitted Uptake
• k2 = 1.67 L/mol/s CI 1.4% 0.08
Nitro
Amine
0.06 Hydroxylamine

0.04

0.02
Value Time Scale [s] 0

k1*[H2]*[A] 5.96 0 50 100 150 200 250

Time (min)
k2*[H2] 47.62
kLa 20.00 R R' R R' R R'
NO2 2H2 NHOH H2
NH2

3rd Process Safety Forum © 2008 Abbott

October14, 2008
 R R' R R' R R'
NO2 2H2 NHOH H2
NH2

Nitro Reduction – Model Validation from RC1 Heat Flow

• Fit to Qr from RC1 data via ΔHrxn,1

and ΔHrxn,2
(ΔHrxn,tot from RC1 = -542 kJ/mol) 6

Experimental
• ΔHrxn,1=-341.3 kJ/mol 4 Fitted Model

Heat Flow (W)

(CI 4.2%) 3

• ΔHrxn,2=-100.6 kJ/mol 2

(CI 14.9%)
1

0
0 50 100 150 200 250
• Possible scenarios to investigate Time (min)

– Minimize intermediate generation

through agitation (kLa effects) – peak
concentration of HA decreases at lower
mass transfer rates.
– Semi-batch addition – What feed rate
keeps HA levels below critical
concentration?
3rd Process Safety Forum © 2008 Abbott
October14, 2008
Leveraging Data from Process Safety Analysis
• Required information may be collected during standard safety testing
already being performed for scale-up!
– Potential operational improvements and a more informed scale-up
• Predictive capabilities
– Minimize experiments needed = increased efficiency
– Identify key experiments for increasing process understanding.
• Data is already available from safety testing

3rd Process Safety Forum © 2008 Abbott

October14, 2008
DynoChem Challenges

• Time
– Learning curve – Practice, practice, practice…
– Data entry – Using templates
• Complexity
– Natural tendency (for me, at least) to start at overly detailed models

3rd Process Safety Forum © 2008 Abbott

October14, 2008
Final Thoughts

• Support options in Dynochem

– Many models have already been built and are available in the model
library
– More models are available online.

3rd Process Safety Forum © 2008 Abbott

October14, 2008