Fauske-Presentation by Knoechel Wood

Fauske & Associates Non-Proprietary Class 3 © 2022 Fauske & Associates, a Division of Stone & Webster, LLC.
, LLC. All Rights Reserved
Chemical Synthesis Process Design –

Using the Right Data to Get the Right
Answers
Presenters:
Donald J. Knoechel, Ph.D. (retired)
Gabe Wood
Fauske & Associates Non-Proprietary Class 3 © 2022 Fauske & Associates, a Division of Stone & Webster, LLC. All Rights Reserved
Acidic Hydrolysis of Epichlorohydrin

Fauske & Associates, LLC Proprietary Class 2
OH
H2O HCl
O OH
Cl GL
O H+
H2O
ECH Cl OH Cl
+
O MCPD
HCl H
Cl
OH 2n
O
ECH
Cl Cl
DCP C9H17O 4Cl 3 (C6H10O 2Cl 2)n-1
From J. Phys. Org. Chem. 2011, 24 1045–1050 Polymer
Decomposition Products + (2n + 1) HCl
From H. Fisher, personal comm.

2
Stoessel Criticality Classes

Assessment of the Undesired Reaction
- Onset Temperature
TD24 - T@24hrTMR
MTT Assessment of the Relief Scenario

- Open (BP maybe)
- Closed (T at Set Pressure)
MTSR
Temperature
DTad Assessment of the Desired Reaction

- Heat of Reaction (total heat)
Tp - Specific Heat of the Reaction Mass
- Projected Adiabatic Temperature Rise
• Presented as an all-in/loss-of cooling-type scenario

• Could easily be just overheating (fire, utilities)
3
Experimental Heat of Reaction

 RC1eLT Reaction Calorimeter

- -70 to 230oC, vac to 85 psig
- 500 ml atm P or 1 L MP06 medium pressure vessel
- Automated liquid additions - pump or pressure
- Gas additions – pressure or flow
 ChemiSens Heat Flux Calorimeter
- -50°C to 200°C
- 20 bar glass/SS reactor (glass/HC or all HC available)
- Pressure Syringe Pump
- Operation at Reflux
 Thermal Hazards Technology mRC
- -5 to 150oC
- 2 ml GC vial or pressure cell
- Isothermal, Cp, Titration, ramp
- magnetic stirrer
 Other
- Mettler-Toledo EasyMax (DT trending)
- Omnical SuperCRC Microcalorimeter
4
Epichlorohydrin Hydrolysis
Semi-batch Process
75 120
 Composite Plot
 80°C 60 100
- 1 g/min
- 3 g/min
- 5 g/min 45 80
Heat Flow (W)
EPI Added (g)

 60 °C 30 60
- 3 g/min
15 40
0 20
-15 0
-25 0 25 50 75 100 125 150 175 200
Reaction Time (min)
80-5 HF 80-3 HF 80-1 HF 60-3 HF 80-5 EPI 80-3 EPI 80-1 EPI 60-3 EPI
Thermal Screening (DSC) of Select Post Reaction Mixtures

 DSC using 20mL M20 Swissi

Crucibles
 Sealed in nitrogen atmosphere
 Scanning rate 8°C/min 80°C, 3 g/min
 Results shown for 80°C, 3 g/min

(5.30 mg) and 60°C, 3 g/min
(5.61 mg) post reaction
mixtures
 Exothermic energy >-500 J/g
 Onset ~ 146°C
60°C, 3 g/min
Energy and Potential Summary

RC DSC
Run
Q ΔTad Onset Q ΔTad
MTSR*
(kJ/mol EPI) (°C) (°C) (J/g) (°C)
80°C, 5 g/min -77.4 59.0 139.0
80°C, 3 g/min
-78.5 60.9 140.9 145.9 -506.8 134.9
80°C, 1 g/min
-77.9 60.1 140.1
60°C, 3 g/min
-80.9 64.7 124.7 145.9 -504.9 138.4
*Maximum Temperature Due to Synthetic Reaction
Scale Up Implications for EPI Hydrolysis

 Reaction Calorimetry shows

- Plenty of intended heat of reaction to handle
 Thermal Screening (DSC) shows

- Secondary reaction potential lying in wait
 Handling the intended heat of reaction is critical to process

safety with scale up
- Heat Balances - Heat Rate Scale-up Calculation
Heat Removal with Scale-Up

600
 2000 kg EPI batch in
12,000 Liter vessel
(stirred volume 7,250 lit) 525
 Compare Glass Lined Steel 450

(GLS), Hastelloy C, Reflux
375
Normalized cooling
Heat Flow (W/kg EPI)

capacity lines for
normalized UADT (113.3 300
W/kg, 188.8 W/kg and
337 W/kg for Reflux) 225
 Reflux (vacuum) can

handle the 35 min 150
addition at either 80°C or
60°C but not the 20 min 75
addition at 80°C
0
 HC would require >1 hr
addition at 60°C
-75
-25 0 25 50 75 100 125 150 175 200
 GLS would require at least
2 hr addition at 80°C Reaction Time (min)
80-5 HF 80-3 HF 80-1 HF 60-3 HF 80-0_822 HF GLS HC Reflux

EPI Hydrolysis
What Do We Know? | What Do We Need?
 From RC  DSC at different scan

- Running at 80°C rates and TMR
- MTSRbatch= modeling for
80°C + 61°C = 141°C TMR24ad
- MTSRsemibatch =
80°C + 6°C = 86°C  TAM for low T heat
rate
 From DSC of post RC
Sample  VSP2 for MTT for
- Secondary Activity closed system
• Onset ~146°C
• More DTad (>130°C)
11
RC 80°C, 0.822 g/min DSC Scans

1.0 °C/min 2.0°C/min

0.5°C/min
8.0°C/min
4.0°C/min
12
AKTS-Thermokinetics Software
‘Thermal Safety Version’
 Enables the calculation of Time-to-Maximum-Rate

under adiabatic conditions (TMRad)
 Uses Isoconversional methods (model free)

- Reaction model not required
- Decomposition mechanism is unknown
 Typically uses multiple DSC scans with different scan rates:
- But, can supplement with other instrument results to help with difficult cases
• ARC
• VSP2
• Setaram C80
• Thermal Activity Monitor (TAM)
– to obtain low temperature isothermal rates – this means the kinetics are
not extrapolated to where there is no data
• THT mRC scanning experiments (150oC limit)
Time-to-Maximum-Rate Plot (TMR)

(Derived from DSC + TAM)
Safety diagram (ΔHr=-430.5±23.4J/g, Cp=3.819J/g/K, Phi=1)

145
Time : 4 hours
140 Temp : 137.6 °C
135
Time : 8 hours
Temp : 128.5 °C
Temperature (°C)
130
125
TInitial-1°C, ΔTad=106.6°C
120 Time : 24 hours

TInitial, ΔTad=112.7°C Temp : 115 °C
115
TInitial+1°C, ΔTad=118.8°C
110
105
0 5 10 15 20 25 30 35 40 45 50
Time (h)
11072019TMRsetw Pred (DSC+TAMextrap) knk / Safety diagram (DeltaHr=-430.5±23.4J/g, Cp=3.819J/g/K, Phi=1)
VSP2 Vessel & Test Cell Cross-Section

 Low thermal inertia

 Automatic pressure balancing
 Direct measurement of sample
temperature, up to 4
temperature channels (from
-70°C to 1000 °C)
 Measure up to 4 Pressures
(FV to 2000 psig)
 Open or closed cell tests
 120 ml max cell volume
 4 liter containment volume
Epi Hydrolysis-Loss of Cooling

Test Details
Density VSP2 Charge Concentration

Chemical ID
(g/ml) (g) (wt. %)
DI Water 1.00 58.0504
58.0480 72.42
72.36
Nitric Acid
Epichlorohydrin 1.41
1.18 0.4270
22.1758 0.53
27.64
Epichlorohydrin
Total 1.18
1.04 21.68
80.2238 27.05
100.0
Total 1.05 80.16 100.0
 Water and nitric acid heated to 80°C

 Epichlorohydrin (23°C) metered in over 10 minutes
Epi Hydrolysis-VSP2 Loss of Cooling

(10-min EPI Add)
VSP2-190430.1 VSP2-190430.1
160 101
Test Cell 5 point regressed rate data
Guard Heater
140
Temperature Rise Rate (°C/min)

120
Temperature (°C)
100
100
80
60
40
20 10-1
0 20 40 60 80 100 0 50 100 150
Time (min) Temperature (°C)
VSP2-190430.1 VSP2-190430.1
5 101
Test Cell VSP2-190430.1
Containment Vessel Water
Epichlorohydrin
4
Pressure (bara)
Pressure (bara)
3
100
0 10-1
0 20 40 60 80 100 0 50 100 150
Epi Hydrolysis-VSP2 HWS After Loss of Cooling

VSP2-190501.1 VSP2-190501.1
300 102
Guard Heater
250

200 101
Temperature (°C)
150
100 100
50
0 10-1
0 50 100 150 200 250 300 0 50 100 150 200 250 300
VSP2-190501.1 VSP2-190501.1
1200 104
Test Cell VSP2-190501.1
Containment Vessel
1000
800 103
Pressure (psia)
600 Pressure (psia)
400 102
200
0 101
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Epi Hydrolysis-VSP2 HWS After RC at 80°C

B093-32.1 B093-32.1
300 102
Guard Heater
250

200 101
Temperature (°C)
150
100 100
50
0 10-1
0 50 100 150 200 250 300 350 400 450 500 0 50 100 150 200 250 300
B093-32.1 B093-32.1
1400 104
Test Cell B093-32.1
Containment Vessel Water
1200
103
1000
Pressure (psia)
Pressure (psia)
800
102
600
400
101
200
0 100
0 50 100 150 200 250 300 350 400 450 500 0 50 100 150 200 250 300
Hydrolysis Reactor Details

 Vessel ID: R-12M3

 MAWP: 87 psig
 Volume: 12,000 L
 Rupture Disk Set
Pressure: 64.1 psig
 Batch Size: 7,250 L
Epi Hydrolysis LOC-RD Sizing

Recommended
Set Ideal Vent
MAWP Batch Size Rupture Disk
Vessel Pressure Area1
(psig) (kg) Diameter2
(psig) (in2)
(in)
64.1 0.386 1.00

R-12M3 87 6,754
87.0 1.200 1.50
1 Does not consider frictional losses.
2 Assumes schedule 40 pipe.
From VSP2
 From LOC during short addition, DTad (meas) = 55°C

- (F=1.07) DTad (F corr) = 59°C
 Recall projected DTad from RC was 61°C
 Onset from HWS post VSP2 experiment – 150°C
 Onset from HWS post RC – 160°C
 So what is MTT for a closed system?

- MAWP for GLS typically 6 bar g (87 psig, 101.7 psia)
- FAI recommendation - assume 40% overpressure from set pressure
based on 1.1 x MAWP on absolute basis. Set pressure = 78.8 psia
- From VSP2 (RC) P vs T curve - 78.8 psia corresponds to 142.6°C
22
EPI Hydrolysis Criticality Class

 Straight Batch  Semi-Batch (2.1 hr Add)

- Tp = 80°C - Tp = 80°C
- TMR24ad = 115°C - MTSR = 86°C
- MTSR = 141°C - TMR24ad = 115°C
- MTT (closed) = 142.6°C - MTT (closed) = 142.6°C
MTT > MTSR > TMR24ad >Tp MTT > TMR24ad > MTSR > Tp
Class 2
Class 5
Can only be considered Class 2

if, when cooling is lost, the EPI
addition is stopped
Stoessel Criticality Classes

Semi-Batch Closed Batch–Closed
MTT
MTT MTSR
MTSR
TD24 TD24 TD24 TD24 TD24
MTT MTT
MTSR MTSR
Temperature
MTT
MTSR
Tp Tp Tp Tp Tp
Criticality Class
1 2 3 4 5
Instrument Sensitivity and TMR

103
TAM, 229.20
Adiabatic Time-to-Maximum Rate (h)
102
DSC0.5, 31.61 TMR24ad, 24.00
101 DSC2.0, 6.45

DSC1.0, 14.41
ARC (RC), 7.40
VSP2 (VSP), 1.61
DSC4.0, 2.98
DSC8.0, 1.35
100
VSP2 (RC), 0.81
10-1
80 90 100 110 120 130 140 150 160 170 180
Temperature ( C)
References
o AKTS AG, http://www.akts.com (AKTS - Thermokinetics software and AKTS - Thermal

Safety software).
o Stoessel, F. (1993) What is your thermal risk?. Chemical Engineering Process, October,
68-75.
o Francis Stoessel, Thermal Safety of Chemical Processes, Risk Assessment and Process
Design Book, Wiley-VCH (2008).
o The series of DSC scans using scan rates of 8.0, 4.0, 2.0, 1.0, and 0.5°C/min were
carried out on samples from a post-reaction mass from an RC run at 80°C with a
0.822g/min EPI addition (126 min).
o Gaca, J., Wejnerowska, G., Cysewski, P., Mechanism of the Acidic Hydrolysis of
Epichlorohydrin, Journal of Physical Organic Chemistry, volume 24, pg. 1045-1050,
2011.
o FERST powered by CHEMCAD Version 1.0.0.15653, Fauske & Associates, LLC, 2020.
o The DIPPR Information and Data Evaluation Manager for the Design Institute for Physical
Properties, Version 11.2.0, Database Date 2016, Brigham Young University.
27

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Fauske & Associates Non-Proprietary Class 3 © 2022 Fauske & Associates, a Division of Stone & Webster, LLC.

, LLC. All Rights Reserved

Chemical Synthesis Process Design –

Acidic Hydrolysis of Epichlorohydrin

DCP C9H17O 4Cl 3 (C6H10O 2Cl 2)n-1

From J. Phys. Org. Chem. 2011, 24 1045–1050 Polymer

Decomposition Products + (2n + 1) HCl

From H. Fisher, personal comm.

Stoessel Criticality Classes

MTT Assessment of the Relief Scenario

DTad Assessment of the Desired Reaction

• Presented as an all-in/loss-of cooling-type scenario

Experimental Heat of Reaction

 RC1eLT Reaction Calorimeter

EPI Added (g)

Thermal Screening (DSC) of Select Post Reaction Mixtures

 DSC using 20mL M20 Swissi

 Sealed in nitrogen atmosphere

 Scanning rate 8°C/min 80°C, 3 g/min

 Results shown for 80°C, 3 g/min

 Exothermic energy >-500 J/g

Energy and Potential Summary

80°C, 5 g/min -77.4 59.0 139.0

Scale Up Implications for EPI Hydrolysis

 Reaction Calorimetry shows

 Thermal Screening (DSC) shows

 Handling the intended heat of reaction is critical to process

Heat Removal with Scale-Up

 Compare Glass Lined Steel 450

 Reflux (vacuum) can

80-5 HF 80-3 HF 80-1 HF 60-3 HF 80-0_822 HF GLS HC Reflux

 From RC  DSC at different scan

RC 80°C, 0.822 g/min DSC Scans

1.0 °C/min 2.0°C/min

 Enables the calculation of Time-to-Maximum-Rate

 Uses Isoconversional methods (model free)

 Typically uses multiple DSC scans with different scan rates:

Time-to-Maximum-Rate Plot (TMR)

Safety diagram (ΔHr=-430.5±23.4J/g, Cp=3.819J/g/K, Phi=1)

120 Time : 24 hours

VSP2 Vessel & Test Cell Cross-Section

 Low thermal inertia

Epi Hydrolysis-Loss of Cooling

Density VSP2 Charge Concentration

 Water and nitric acid heated to 80°C

Epi Hydrolysis-VSP2 Loss of Cooling

Temperature Rise Rate (°C/min)

Epi Hydrolysis-VSP2 HWS After Loss of Cooling

Temperature Rise Rate (°C/min)

600 Pressure (psia)

Epi Hydrolysis-VSP2 HWS After RC at 80°C

Temperature Rise Rate (°C/min)

Hydrolysis Reactor Details

 Vessel ID: R-12M3

Epi Hydrolysis LOC-RD Sizing

64.1 0.386 1.00

 From LOC during short addition, DTad (meas) = 55°C

 Recall projected DTad from RC was 61°C

 Onset from HWS post VSP2 experiment – 150°C

 Onset from HWS post RC – 160°C

 So what is MTT for a closed system?

EPI Hydrolysis Criticality Class

 Straight Batch  Semi-Batch (2.1 hr Add)