ECH polymerization Qualification of a solvent compatible with REACh - - PowerPoint PPT Presentation

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ECH polymerization Qualification of a solvent compatible with REACh - - PowerPoint PPT Presentation

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ECH polymerization Qualification of a solvent compatible with REACh regulation G. Eck, M. Fourdinier, T . Alaime, C. Bedos, V. Chauffour 2019 IM & EM Technology Symposium, Oct. 21-24, Abstract 22199 1 2018, Seville, Spain

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SLIDE 1

1 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

ECH polymerization Qualification of a solvent compatible with REACh regulation

  • G. Eck, M. Fourdinier, T

. Alaime, C. Bedos, V. Chauffour

Abstract 22199

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SLIDE 2
  • Introduction / Context
  • Middle term replacement of DCE

 Lab scale results  Process file for scaling up to industrial scale

  • Conclusion

2 2 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain Abstract 22199

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INTRODUCTION / CONTEXT

3 3 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

REA REACh Ch ITAR AR

(US/DoD or US/DoC regulations )

EAR AR

EUROPE has to face to different regulations

  • International Traffic in Arms regulations /

Export Administration Regulation

  • Designed to help ensure that defense

related technology does not get into the wrong hands

  • Registration, Evaluation, Authorization and

Restriction of Chemicals

  • Adopted to improve the protection of human

health and the environment from the risks that can be posed by chemicals

Abstract 22199

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SLIDE 4
  • REACH applies to all chemicals (except polymers)

 Chemicals involved in industrial process  Chemicals in our day-to-day lives : cleaning products, paints,

clothes, furniture, electrical appliances,…

  • Companies must identify and manage the risks linked to

the substances they manufacture and market in the EU as manufacturers, importers or downstream users

  • In the long run, the most hazardous substances should be

substituted with less dangerous ones

4 4 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

INTRODUCTION / CONTEXT REACh regulation

Abstract 22199

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SLIDE 5

5 5 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

INTRODUCTION / CONTEXT

GRANULAR EXPLOSIVE EXPLOSIVE COMPOSITION BONDING AGENT PLASTICIZER SOLVENTS CATALYSTS BINDER

IMPACT ON EXPLOSIVE COMPOSITIONS

REACh regulation

Abstract 22199

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SLIDE 6

6 6 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

INTRODUCTION / CONTEXT

GRANULAR EXPLOSIVE EXPLOSIVE COMPOSITION BONDING AGENT PLASTICIZER SOLVENTS DCE CATALYSTS BINDER

REACh regulation

IMPACT ON EXPLOSIVE COMPOSITIONS

Abstract 22199

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7 7 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

INTRODUCTION / CONTEXT Impact on PECH / GAP synthesis

O CH2Cl H+ H O CH CH2Cl CH2 O H n PECH NaN3 H O CH CH2N3 CH2 O H n GAP DCE ECH

  • Impact of REACH regulation on DCE use as a

solvent

 Authorized for use up to the end of 2021  Prohibited after that

Abstract 22199

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SLIDE 8

8 8 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

INTRODUCTION / CONTEXT

  • Middle term replacement

 Organic solvent not yet impacted by REACh  Process file ready for scale up to the industrial workshop

  • Long term replacement

 Research studies to find new ways to polymerize ECH

Impact on PECH / GAP synthesis

Abstract 22199

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SLIDE 9
  • Introduction / Context
  • Middle term replacement of DCE

 Lab scale results  Process file for scaling up to industrial scale

  • Conclusion

9 9 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain Abstract 22199

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LAB SCALE RESULTS

  • Experiments performed on 350 g. of ECH in DCE, solvents A

and B

 Reaction medium T° set between TR1 and TR2  Double jacket T° set at T1 or T2  Addition rate of ECH regulated by the reaction medium T°

  • Special attention to

 The initiation of the polymerization and the temperature peak that

is observed when the reaction starts.

 The propagation phase of the polymerization  The characterization of the polymer PECH: Mn / Mw and hydroxyl

content

10 10 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain Abstract 22199

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LAB SCALE RESULTS

11 11 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

Ref. Solvent Double Jacket T° (°C) PECH characterizations Mn Mw I OH content (eq/kg) Average at industrial scale 1790 1890 1.05 0.80 DCE-1 DCE T2 1670 1890 1.13 0.80 DCE-2 DCE T1 1750 1890 1.08 0.75 A-1 A T2 1690 1910 1.13 0.86 A-2 A T1 1770 1910 1.08 0.84 A-3 A T1 1820 1960 1.08 0.80 B-1 B T1 1770 1900 1.08 0.83 B-2 B T2 1750 1910 1.09 0.78 B-3 B T1 1770 1910 1.08 0.81

Abstract 22199

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LAB SCALE RESULTS

12 12 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

Ref. Solvent Double Jacket T° (°C) PECH characterizations Mn Mw I OH content (eq/kg) Average at industrial scale 1790 1890 1.05 0.80 DCE-1 DCE T2 1670 1890 1.13 0.80 DCE-2 DCE T1 1750 1890 1.08 0.75 A-1 A T2 1690 1910 1.13 0.86 A-2 A T1 1770 1910 1.08 0.84 A-3 A T1 1820 1960 1.08 0.80 B-1 B T1 1770 1900 1.08 0.83 B-2 B T2 1750 1910 1.09 0.78 B-3 B T1 1770 1910 1.08 0.81

DCE-2 seems representative of the industrial scale

Abstract 22199

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LAB SCALE RESULTS

13 13 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

Ref. Solvent Double Jacket T° (°C) PECH characterizations Mn Mw I OH content (eq/kg) Average at industrial scale 1790 1890 1.05 0.80 DCE-1 DCE T2 1670 1890 1.13 0.80 DCE-2 DCE T1 1750 1890 1.08 0.75 A-1 A T2 1690 1910 1.13 0.86 A-2 A T1 1770 1910 1.08 0.84 A-3 A T1 1820 1960 1.08 0.80 B-1 B T1 1770 1900 1.08 0.83 B-2 B T2 1750 1910 1.09 0.78 B-3 B T1 1770 1910 1.08 0.81

Reproducible results for experiments performed in the same conditions

Abstract 22199

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LAB SCALE RESULTS

14 14 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

Ref. Solvent Double Jacket T° (°C) PECH characterizations Mn Mw I OH content (eq/kg) Average at industrial scale 1790 1890 1.05 0.80 DCE-1 DCE T2 1670 1890 1.13 0.80 DCE-2 DCE T1 1750 1890 1.08 0.75 A-1 A T2 1690 1910 1.13 0.86 A-2 A T1 1770 1910 1.08 0.84 A-3 A T1 1820 1960 1.08 0.80 B-1 B T1 1770 1900 1.08 0.83 B-2 B T2 1750 1910 1.09 0.78 B-3 B T1 1770 1910 1.08 0.81

At lab scale, no significant impact of polymerization conditions on PECH characteristics

Abstract 22199

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15 15 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

LAB SCALE RESULTS

DCE Solvent A Solvent B TR1 TR2

20 40 60 80 100 120 140

T° (°C)

Time (min)

DCE Solvent A Solvent B

COOLING AT T1

Exothermic phenomenon for all solvents Peak T° slightly shifted in time for solvent A

Abstract 22199

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16 16 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

LAB SCALE RESULTS

COOLING AT T2

Good control for DCE and solvent B More difficult to control in solvent A

DCE Solvent A Solvent B TR2 TR1

50 100 150 200 250 300

T° (°C) Time (min) DCE Solvent A Solvent B Abstract 22199

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17 17 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

LAB SCALE RESULTS

Based on lab scale experiments, solvent B seems to be the best candidate to replace DCE

CONCLUSION

Scale up to industrial scale to be made

Double Jacket T° (°C) PECH characterizations Mn Mw OH content (eq/kg) T1 1770 1900 0.83 T2 1750 1910 0.78

Abstract 22199

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SLIDE 18
  • Introduction / Context
  • Middle term replacement of DCE

 Lab scale results  Process file for scaling up to industrial scale

  • Conclusion

18 18 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain Abstract 22199

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19 19 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

PROCESS FILE

  • Material balance
  • Heat balance
  • Sequence of

manufacturing steps

  • Production time

Comparison for solvent B and DCE

Abstract 22199

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20 20 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

PROCESS FILE Material balance Vessel N°1 Vessel N°2 Raw materials Initial loading Recovered or engaged quantities ECH M1 0 kg Solvent B M2 M2 Initiator M3 0 kg Catalyst M4 Reacted PECH M1 Washing ingredients M5

Abstract 22199

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21 21 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

PROCESS FILE Heat balance

  • Heat exchange capacity of reactors (kcal/h) : ϕ = K x S x ΔT

 K = Heat transfer coefficient (kcal/h/m2.k)  S = Exchange area (m2)  T = Mean logarithmic temperature Cold fluid / Hot fluid

  • Amount of heat (J.) : Q = m x Cp x ΔT

 m = Mass of components (kg)  Cp = Specific heat of the components (J/kg.K)  T = Temperature difference Initial state / Final state

Abstract 22199

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22 22 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

PROCESS FILE Heat balance Synthesis phase Heat balance (compared to DCE in % ) Loading and heating QTotal (kcal) 72% t (min) 80% cooling medium (kg/h) 100% Polymerization QTotal (kcal) 99.8% t (min) 100% cooling medium (kg/h) 100% Solvent extraction QTotal (kcal) 97.6% t (min) 96% heating medium (kg/h) 100%

Abstract 22199

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SLIDE 23
  • Introduction / Context
  • Middle term replacement of DCE

 Lab scale results  Scale up  Process file for scaling up to industrial scale

  • Conclusion

23 23 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain Abstract 22199

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24 24 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

CONCLUSION

  • One of the most important issue induced by REACh

regulation is the replacement of DCE, the polymerization solvent for the synthesis of PECH.

  • A middle term solution has already been found

 DCE could be replaced by solvent B.  The obtained PECH has the same characteristics than the current one

produced at industrial scale.

  • Long term research studies are in progress in order to find

a sustainable replacement product.

Abstract 22199

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25 25 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

ACKNOWLEDGEMENTS

  • Marion

FOURDINIER, Thibaud ALAIME and all the laboratory team for experiments on PECH synthesis

  • Céline BEDOS, Vincent CHAUFFOUR and the process team

for the work on the scale up to the industrial scale AND

  • French DGA for its financial support

Abstract 22199

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26 26 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain

Thank you for your attention Questions ?

Abstract 22199

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27 27 2019 IM & EM Technology Symposium, Oct. 21-24, 2018, Seville, Spain Abstract 22199