FP7 project - SAM.SSA

Transcription

1 Sugar Alcohol based Materials for Seasonal Storage Applications FP7 project - SAM.SSA Sugar Alcohol based Materials for Seasonal Storage Applications Workshop and Onsite Demonstration CiCenergigune Miñano, Alava, Spain

2 Session 1 Sub Session: Sugar Alcohol Development Presented by: Sophia Niedermaier Contributions by: Fraunhofer ISE, CNRS

3 Summary Analysed Sugar Alcohols and Measuring Techniques Sugar alcohols characterized: D-Mannitol Myo-Inositol Galactitol Xylitol Erythritol Measuring techniques used: Differential scanning calorimetry, DSC Thermogravimetric Analysis, TGA Fourier-transform-infrared-spectroscopy, FT-IR Nuclear magnetic resonance, NMR Long time stability in a Schlenk-Line

4 Measurements for D-Mannitol, Galactitol & Myo-Inositol 5 mg sample in a closed crucible 10 mg sample in an open crucible Measurement-setup DSC Q200 Time Parameters 3 cycles a 1K/min 20 cycles a 10K/min 1 cycle a 1K/min Analysis of melting- and crystallization enthalpy and - temperature -

5 Results DSC Galactitol Closed/Open Crucible Closed Crucible Open Crucible

6 Results DSC Myo-Inositol Closed/Open Crucible Closed Crucible Open Crucible

7 Results DSC D-Mannitol Closed Crucible Closed aluminium crucible with ambient air encaptured 20 cycles at 10 K/min from 50 to 200 C Ca. 5 mg D-Mannitol in a 40 µl crucible Left: D-Mannitol untreated; Right: Crucible with D-Mannitol after 20 cycles with ambient air encaptured

8 Results DSC D-Mannitol Closed Crucible

9 Specific Enthalpy [J/g] Temperature [ C] Results DSC D-Mannitol Closed Crucible D-Mannitol in a closed crucible C H M D-Mannitol H C D-Mannitol T p,m D-Mannitol T p,c D-Mannitol 3. Cycle 1 K/min 24. Cycle 1 K/min Heating rate [K/min]

10 Results DSC D-Mannitol Closed Crucible Oxidation products Ether Pink: D-Mannitol untreated; Blue: D-Mannitol after 20 cycles in a closed crucible 10

11 Results DSC D-Mannitol Open Crucible Open aluminium crucible in a nitrogen atmosphere 20 cycles at 10 K/min from 50 to 200 C Ca. 10 mg D-Mannitol in a 40 µl crucible Left: D-Mannitol untreated; Right: Crucible with D-Mannitol after 20 cycles in a nitrogen atmosphere 11

12 Results DSC D-Mannitol Open Crucible 12

13 Specific Enthalpy [J/g] Temperature [ C] Results DSC D-Mannitol Open Crucible D-Mannitol in an open crucible C H M D-Mannitol H C D-Mannitol T p,m D-Mannitol T p,c D-Mannitol 3. Cycle 1 K/min 24. Cycle 1 K/min Heating rate [K/min]

14 Results DSC D-Mannitol Open Crucible Ether Black: D-Mannitol untreated; Green: D-Mannitol after 20 cycles in an open crucible with nitrogen atmosphere

15 Conclusion for the DSC-Measurements

16 Long Term Stability of D-Mannitol in Closed Crucible in a Nitrogen Atmosphere Closed aluminum crucible with nitrogen encaptured (prepared in Glovebox) 400 cycles 10 K/min from 50 to 200 C Ca. 5 mg D-Mannitol in 40 µl crucible Left: D-Mannitol untreated Right: D-Mannitol after 400 cycles in closed crucible with nitrogen encaptured

17 Long Term Stability of D-Mannitol in Closed Crucible in a Nitrogen Atmosphere Cycles Cycles Cycles Cycles

18 Specific enthalpy [J/g] Long Term Stability of D-Mannitol in Closed Crucible in a Nitrogen Atmosphere 3. Cycle 1 K/min 104. Cycle 1 K/min 205. Cycle 1 K/min 306. Cycle 1 K/min 407. Cycle 1 K/min Cycle & heating rate

19 Long Term Stability of D-Mannitol in Closed Crucible in a Nitrogen Atmosphere Oxidation products Assumptions 1. Still oxygen inside the crucible 2. Oxygen sticks to surface of D-Mannitol powder => enough to start degradation mechanism Ether Green: D-Mannitol untreated Pink: D-Mannitol after 407 cycles in a closed crucible in an nitrogen atmosphere (Mod. III)

20 Long Term Stability of D-Mannitol in Closed Crucible in a Nitrogen Atmosphere Open aluminum crucible Flushed with nitrogen during measurement 300 cycles 10 K/min from 50 to 200 C Ca. 10 mg D-Mannitol in 40 µl crucible Left: D-Mannitol untreated Right: D-Mannitol after 300 cycles in an open crucible flushed with nitrogen during measurment

21 Long Term Stability of D-Mannitol in Closed Crucible in a Nitrogen Atmosphere Cycles Cycles Cycles

22 Long Term Stability of D-Mannitol in an Open Crucible D-mannitol 300 cycles (200 C 50 C / 10 K/min ) in a perforated crucible ΔH m [J/g] ΔH c [J/g] T peak m [ C] T peak c [ C]

23 Long Term Stability of D-Mannitol in an Open Crucible cm Green: D-Mannitol untreated -1 Pink: D-Mannitol after 300 cycles in an open crucible flushed with nitrogen during measurment

24 Long Term Stability of D-Mannitol in an Open Crucible Degradation of D-mannitol in a perforated crucible compared to a closed crucible with a nitrogen atmosphere ΔH m [J/g] perforated ΔH c [J/g] perforated ΔH m [J/g] Glovebox ΔH c [J/g] Glovebox

25 Conclusion for the DSC-Measurements of D-Mannitol 25

26 Degradation Mechanism of D-Mannitol D-Mannitol 2,5-Anhydro-D-Mannitol Acid D-Mannitol 2,5-Anhydro-D-Mannitol T / Acid catalyst Source for the degradation mechanism of Erythritol: Kakiuchi et al IEA Annex 10

27 Schlenkline - Erythritol Long term stability of erythritol in Schlenk-line under Nitrogen atmosphere Closed flask with nitrogen atmosphere encaptured Constant oil bath temperature of 130 C Ca. 15 g erythritol in 200 ml flask Colour change after ca. 15 days No reduction of enthalpy and melting point

28 Heat Flow (W/g) Schlenkline - Erythritol PC nSchlenk PC DSC-EN-S_15mg17_1K.001 Long term stability of erythritol in Schlenkline under Nitrogen atmosphere Reduction of enthalpy and melting point Exo Up Temperature ( C) Universal V4.5A TA Instruments

29 Schlenkline - Erythritol Long term stability of erythritol in Schlenk-line under Nitrogen atmosphere No changes in peak wavenumber Orange: untreated erythritol; Blue: erythritol after treatment in Schlenk-line

30 Schlenkline - Xylitol Long term stability of xylitol in Schlenkline under Nitrogen atmosphere Closed flask with nitrogen atmosphere encaptured Constant oil bath temperature of 100 C Ca. 15 g xylitol in 200 ml flask Reduction of enthalpy and melting point Sample is not crystallizing in the DSC Colour change after ca. 37 days

31 Heat Flow (W/g) Schlenkline - Xylitol Long term stability of xylitol in Schlenk-line under Nitrogen atmosphere Reduction of enthalpy and melting point Sample is not crystallizing in the DSC PC nSchlenk PC DSC-EN-S Exo Up Temperature ( C) Universal V4.5A TA Instrument

32 Schlenkline - Xylitol Long term stability of Xylitol in Schlenk-line under Nitrogen atmosphere No changes in peak wavenumber Green: untreated xylitol; Purple: xylitol after treatment in Schlenk-line

33 CNRS: Xylitol: aging test under quite harsh conditions 100 C in a furnace + bubbling from times to times Day 0 Day 10 Day 27 Day 100 Day Melting Temperature ( C) ΔH (J/g) The color changes but key thermodynamics do not (melting point and latent heat : deviation of 2% in 100 days) DSC: Heating rate 5 C/min; m=58 mg

34 Overall Conclusion Myo-Inositol and Galaktitol show strong degradation D-Mannitol: strong degradation with oxygen less degradation without oxygen Schlenk-Line: Time of colur change: D-Mannitol > Erythritol > Xylitol Reduction of melting enthalpie: D-Mannitol > Xylitol > Erythritol Xylitol: 2 % reduction of melting enthalpie over 100 days 34

35 Thank you for your attention!