Akzo Nobel Functional

Chemicals B.V. PO Box 10

7400 AA Deventer

The Netherlands T +31 263 669 527

F +31 570 624 113

www.akzonobel.com Safety Testing & Modeling

1 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Funct ional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, projections and other information in this report. Subject 

## Proces s s afety i nvestigation PSI

- 3 of the preparation of

PPR

- 001;

Author G.B. Boerdijk

Date 2014

- 0 7

- 14

Document number STM 2014 0152

Project number 4001861

Customer AN FC OP

Project identification:

Project Name OP

- Polymer Modification

Participants G.B. Boerdijk

Project Leader M. van der Schuur

Competence Team Leader H.J. Edelijn

Customer order reference

-

Our order reference

-

Laboratory notebook 4908

Safety testing & Modelling

Copies to M. van der Schuur

R.C.J. Millet J. Nuysink
H.J. Edelijn
P. Dijkgraaf

B. Fischer

T. den Braber P.M.M. Hoeijmakers 

# Safety R eport

Drafted by

Name G.B. Boerdijk Date 2014

- 0 7

- 22

Function Safety Engineer Signature

Approved by

Name H.J. Edelijn Date 2014

- 0 7

- 22

Function Manager Safety Laboratory SignatureProces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

2 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 

## Summary

Heat flow calorimeter experiments were carried out to investigate deviating conditions on
the standard procedure for the production of PPR

- 001. This investigation is an extension of
the investig ations reported in PSI

- 2 (Ref 6.2). The following results were found:

The premix preparation in the HFC is tested with 30 minutes dosing time. The 10 minutes shown in the Batch Sequence Diagram (Appendix 7.1) is probably too short for a

controllable react or temperature ( T reactor = 5 °C).

Process carried out with T reactor + 10°C will give controllable heat production t he premix
preparation and in the peroxidation step

.

Process carried out with 50% excess Premix will give controllable heat production the
premix preparation and in the peroxidation step.

Process carried out with 50% excess H 2 O 2 - 70% in the Premix will give controllable heat
production the premix preparation and in the peroxidation step. More sulfite is needed for
complete reduction of non

- cy clic peroxide.

Process carried out with 50% excess H 2 SO 4 - 84% in Premix preparation will give controllable
heat production the premix preparation and in the peroxidation step. The maximum heat
production and the total heat are both approx. 20% higher than in the standard recipe

.

Process carried out with H 2 SO 4 - 96% in Premix preparation shows strong deviating heat
effect in both premix preparation and the peroxidation step . The premix heat production

decreases to close to zero after dosing, but the peroxidat ion showed an increasing heat production starting half

- way dosing. The maximum value is almost twice the standard value. After quenching, still some heat production is measured (4 W/kg frm ).Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

3 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 

## Contents

1 Introduction 4

2 Sample data 4

3 Experimental 4

3.1 Process until post reaction of peroxidation at T+10°C. 4

3.2 Process carried out with 50% excess Premix. 7

3.3 Process carried out with 50% excess H 2 O 2 - 70% in Premix preparation. 9

3.4 Process carried out with 50% excess H 2 SO 4 - 84% in Premix preparation. 12

3.5 Process carried out with H 2 SO 4 - 96% in Premix preparation. 14

4 Discussion 16

4.1 Process until post reaction of peroxidation at T+10°C. 16

4.1.1 Premix: 16

4.1.2 Peroxidation: 16

4.2 Process carried out with 50% excess Pre mix. 16

4.2.1 Premix: 16

4.2.2 Peroxidation: 17

4.3 Process carried out with 50% excess H 2 O 2 - 70 in Premix preparation. 17

4.3.1 Premix: 17

4.3.2 Peroxidation and reduction: 17

4.4 Process carried out with 50% excess H 2 SO 4 - 84% in Premix p reparation. 17

4.4.1 Premix: 17

4.4.2 Peroxidation: 18

4.5 Process carried out with H 2 SO 4 - 96% in Premix preparation. 18

4.5.1 Premix: 18

4.5.2 Peroxidation: 18

4.6 Overview Premix data 19

4.7 Overview Peroxidation data 19

5 Conclusions 20

6 References 20

7 Appendices 20

7.1 Batch Sequence Diagram PPR

- 001: T. den Braber: 19

- 02

- 2014. 20Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

4 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 

## 1 Introduction

For the development of
a process safety investigation is needed. In this investigation, the thermal behaviour of

deviations on the process steps has to be studied . The final process safety study: PSI

- 3, according to the safety standards of AN Functio nal Chemicals (IERDPC

- system). This work

is additional to the tests done in the PSI

- 2 investigation (Ref 6.2).



## 2 Sample data

Table 2.1 Used chemicals.

substance quality supplier



## 3 Experimental

The following tests were done as final part of the p rocess safety study of PP R

- 001,
according to Batch Sequence Diagram in Appendix 7.1.

3.1Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001; mi

STM 20140152

5 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. Table 3.1 Experimental data for premix preparation at 15°C E xp: BOY140 8 4.

Reactor

Stirrer Stirring speed Glass
Glass, pitch blade turbine

880 rpm

Figure 3.1 HFC plot of premix preparation of PPR

- 001; Deviation: T reactor +10°CProces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

6 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. Table 3.2 Experimental data for peroxidation at 10°C Exp: BOY14085.

Reactor

Stirrer Stirring speed Glass
Glass, pitch blade turbine
880 rpm

Figure 3.2 HFC plot of PPR

- 001; peroxidation step. Deviation: Tr+10°CProces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

7 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 3.2 Process carried out with 50% excess Premix.

Table 3.3 Experimental data for premix preparation at 5°C Exp: BOY14078.

Figure 3.3 HFC plot of premix preparation of PPR

- 001; Standard premix preparation.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

8 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. Table 3.4 Experimental data for peroxidation 0°C Exp: BOY14085.

Figure 3.4 HFC plot of PPR

- 001; peroxidation step. Deviation: 50% Excess premix.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

9 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 3.3 Process carried out with 50% excess H 2 O 2 - 70 % in Premix preparation.

Table 3.5 Experimental data for premix preparation at 5°C Exp: BOY14086.

Figure 3.5 HFC plot of premix preparation of PPR

- 001; Deviation: 50% excess H 2 O 2

.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

10 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. Table 3.6 Experimental data for peroxidation 0°C Exp: BOY14087.

Figure 3. 6 HFC plot of PPR

- 001; peroxidation step. Deviation: 50% excess H 2 O 2Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

11 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. Table 3.6 Experimental data for sulfite reduction Exp: BOY14087.

Figure 3. 7 HFC plot of PPR

- 001; sulfite addition step. Deviation: 50% excess H 2 O 2

It is observed that after these ( excessive) additions, still linear peroxide is present . This impl ies bad conversion to cyclic peroxide.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

12 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 3.4 Process carried out with 50% excess H 2 SO 4 - 84% in Premix preparation.

Table 3. 7 Experimental data for premix preparation at 5°C Exp: BOY140 80

.

Figure 3. 8 HFC plot of premix preparation of PPR

- 001; Deviation: 50% excess H 2 SO 4

.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

13 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. Table 3.8 Experimental data for peroxidation at 0°C Exp: BOY14081.

Figure 3.9 HFC plot of PPR

- 001; peroxidation step. Deviation : 50% excess H 2 SO 4

.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

14 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 3.5 Process carried out with H 2 SO 4 - 96% in Premix prepara tion.

Table 3.9 Experimental data for premix preparation at 5°C Exp: BOY14088.

Figure 3.1 0 HFC plot of premix preparation of PPR

- 001; Deviation: H 2 SO 4 - 96%Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

15 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. Table 3.10 Experimental data for peroxidation 0°C Exp: BOY14089.

Figure 3.11 HFC plot of PPR

- 00 1; peroxidation step. Deviation: H 2 SO 4 - 96% in premix.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

16 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 

## 4 Discussion

In this investigation d ifferent deviations on the preparation process are tested.
The influence on heat production and runaway potential is studied.

4.1

Standard premix

ration

data.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

17 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 4.2.2Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

18 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 4.4.2Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

19 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 5Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001; )

STM 20140152

20 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. 

## 5 Conclusions

5.1



## 6 References

6.1 Kamp, H.J.M.; Interim Research Report: Process safety investigation into the initiator D

- 129 process in Isopar M (Trigonox 301; D

- phase);

Doc. code: ACRD 970

- 0632; Deventer July 23, 1997.

6.2 Boerdijk, G.B.; Safety Report: Process Safety Investigation PSI

- 2 of the preparation of

PP

- R

- 001; mixed cyclic peroxide of 2

- Butanone and 2

- Pentanone ;
Doc. code: S TM 20140017; Deventer, January 28, 2014.

6.3 Boerdijk G.B.; Test program for Process Safety Investigation stage: PSI

- 3 of peroxide

process PP

- R

- 001; mixed cyclic peroxide; Doc. code: STM 20140101;
Deventer, May 12 , 2014

.



## 7 Appendices

7.1 Batch Sequence Diagram PPR

- 001: T. den Braber: 19

- 02

- 2014.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

21 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report. Appendix 7.1 Batch Sequence Diagram PPR

- 001: T. den Braber: 19

- 02

- 2014.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

22 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

23 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report.Proces s Safety Investigation PSI

- 3 of the preparation of

PP R

- 001;

STM 20140152

24 Although great care has been taken in drawing up the report, no rights can be derived from the contents thereof and Akzo Nobe l Functional Chemicals B.V. makes no warranties or representations as to its accuracy or completeness. Nor shall Akzo Nobel Functional Chemicals B.V. be liable for any loss or damages, including

- without limitation

- direct, indirect, special, consequential or incidental damages arising from reliance on (financial) information, pr ojections and other information in this report.