Journe Scientifique CODEGEPRA 2016 Investigation of cyclopentane - - PowerPoint PPT Presentation

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Son HO-VAN (2nd year PhD student - SPIN Centre) Jean-Michel HERRI Baptiste BOUILLOT

Investigation of cyclopentane hydrate in the presence of KCl and an equal-mass mixture of KCl - NaCl during crystallization and quick dissociation processes

Grenoble 28/11/2016

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Journée Scientifique CODEGEPRA 2016

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Introduction

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Investigation of CP hydrate in the presence of KCl and an equal- mass mixture of KCl and NaCl 2

• 1. Milkov, A. V.: Global estimates of hydrate-bound gas in marine sediments: how much is really out there?, Earth-Sci. Rev., 66, 183–197, doi:10.1016/j.earscirev.2003.11.002, 2004
• 2. Mimachi, H., Takeya, S., Yoneyama, A., Hyodo, K., Takeda, T., Gotoh, Y., Murayama, T., 2014. Natural gas storage and transportation within gas hydrate of smaller particle: Size dependence of self-preservation phenomenon of natural gas hydrate. Chem.
• Eng. Sci. 118, 208–213. doi:10.1016/j.ces.2014.07.050
• 3. A. Yamasaki, M. Wakatsuki, H. Teng, 1998. A new ocean disposal scenario for anthropogenic CO2: CO2 hydrate formation in a submerged crystallizer and its disposal. Energy.

4.Bradshaw, R.W., Greathouse, J.A., Cygan, R.T., Simmons, B.A., Dedrick, D.E., Majzoub, E.H., 2008. Desalination Utilizing Clathrate Hydrates (LDRD Final Report).

Study CP hydrate in the presence of salts

A huge amount of gas hydrate in

• cean sediments1

(1–5)x1015 m3 of CH4+CO2 hydrates Offshore well, natural gas transportation2, CO2 sequestration3 Hydrate – based desalination CP hydrate can form at atmospheric pressure at 280K CP hydrate could be used to model hydrate formation from oil/gas emulsion in pipelines

Clathrate hydrates

Cavity types Guest molecule Water molecules Cage Guest molucule

Objective

Investigation of CP hydrate in KCl and a mixture of KCl - NaCl during crystallisation and quick dissociation processes

Hydrate structure Offshore oil and gas – Platforms

http://new.abb.com/oil-and-gas/sectors/offshore-oil-and-gas/platforms

Underwater pipeline oil and gas

http://www.sketch-d.com/Underwater- Pipeline-Illustration-Schlumberger

Hydrate formation and plugging in the oil-dominated system,

• D. Turner, K. Miller, E. D. Sloan 2009

http://www.lngworldnews.com/nord-stream-completes-second-underwater-baltic-sea-gas- pipeline/

The five cavity types and the three common unit crystals structures of the clathrate hydrates

(E. Dendy Sloan and Jr, 2003; English and MacElroy, 2015)

Hydrate structure

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Experimental protocol

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3 1. Reactor 2. Cryostat 3. Impeller 4. Agitator 5. Cooling jacket 6. Conductivity transmitter 7. Motor

• 8. Temperature transmitter
• 9. Computer
• 10. Temperature probe
• 11. Conductivity probe
• 12. Drying oven
• 13. Ion chromatography
• 14. Camera

Experimental apparatus system Simplified schematic diagram of experimental apparatus system

Experimental protocol

Investigation of CP hydrate in the presence of KCl and an equal- mass mixture of KCl and NaCl 5 ml 1 ml Taking samplesc Observation Colling Initiate by injecting ice 1 hour 1 -2 hours Taking photos 2-3 g

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Results and discussions

0,5 1 1,5 2 2,5 2 4 6 8 10 12 14 16 18 100 200 300 400 500 Temperature, °C Elapsed time, min Temperature and conductivity profiles of CP hydrate experiment in pure water Temperature Conductivity

Te = 7,7°C

10 20 30 40 50 60

• 5

5 10 15 20 25 50 100 150 200 250 300 Temperature, °C Elapsed time, min Temperature and conductivity profiles of CP hydrate experiment in 3,5% KCl Temperature Conductivity

Te = 6°C

10 20 30 40 50 60

• 5

5 10 15 20 25 100 200 300 400 Temperature, °C Elapsed time, min Temperature and conductivity profile of CP hydarte experiment in 3,5% KCl and NaCl T, °C Conductivity

Te = 5,9°C

50 100 150 200

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5 10 15 20 25 1000 2000 3000 4000 5000 Temperature, °C Elapsed time, min Temperature and conductivity profiles of CP hydrate experiment in 20% KCl Temperature Conductivity

Te = -2,1°C

Hydrate formation Exothermic Endothermic Formation Exothermic Endothermic Injected ice Injected ice Injected ice Formation Dissociation Investigation of CP hydrate in the presence of KCl and an equal- mass mixture of KCl and NaCl

Conductivity, mS/cm

Dissociation Hydrate formation

Conductivity, mS/cm Conductivity, mS/cm Conductivity, mS/cm

Image of the solution at 70 min Image of the solution at 225 min

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• 1. An increase in temperature was observed during cyclopentane hydrate formation because of the exothermic property of this process
• 2. When hydrate dissociated strongly, the temperature was nearly constant due to the heat-releasing from the dissociation process
• 3. The conductivity had illogical tendencies owing to the appearance of hydrate solids
• 4. When no hydrate was observed inside the vessel, the temperature immediately increased due to heating from the environment around
• 5. The equilibrium temperature dropped strongly with increasing of salt concentration in all cases
• 6. The equilibrium temperatures of Cp hydrate in the presence of KCl were always higher than in the presence of an equal-mass mixture of

KCl - NaCl and in the presence of only NaCl following both quick and slow dissociation procedures at the same salt concentration.

Conclusions

The equilibrium temperature of cyclopentane hydrate in the presence of salts

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• 10
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5 10 2 4 6 8 10 12 14 16 18 20 22 24 26 28 Temperature, °C Salt concentration, % w/w

Equilibrium temperature of cyclopentane hydrate

In the presence of NaCl - following a quick dissociation procedure In the presence of an equal-mass mixture KCl and NaCl - following a quick dissociation procedure In the presence of NaCl - following a slow dissociation procedure In the presence of KCl - following a quick dissociation procedure Investigation of CP hydrate in the presence of KCl and an equal- mass mixture of KCl and NaCl

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Thank you very much for your attention

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6 Investigation of CP hydrate in the presence of KCl and an equal- mass mixture of KCl and NaCl