Experimental and modelling study of cyclopentane hydrates in the - - PowerPoint PPT Presentation

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Experimental and modelling study of cyclopentane hydrates in the - - PowerPoint PPT Presentation

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Experimental and modelling study of cyclopentane hydrates in the presence of salts Son HO-VAN (2 nd year PhD student) Jrme DOUZET Baptiste BOUILLOT Jean-Michel HERRI Nancy, 11/12/2017 1 Institut Mines-Tlcom Outlines 1. Introduction

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Institut Mines-Télécom

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

Experimental and modelling study of cyclopentane hydrates in the presence of salts

Nancy, 11/12/2017

1

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Institut Mines-Télécom

Outlines

11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 2

  • 1. Introduction and objective
  • 2. Experimental Methodology
  • 3. Experimental results
  • 4. Modelling of cyclopentane hydrates
  • 5. Conclusions & Perspectives
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Introduction

11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 3

Cavity types Guest molecule Water molecules Cage Guest molecule The five cavity types and the three common unit crystals structures (E. Dendy Sloan and Jr, 2003) Hydrate structure

What are clathrate hydrates ?

Water + Guest

CP Hydrates

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11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 4

Hydrates can be used to remove water from aqueous solution → purification method

Hydrate formation Hydrate dissociation Sea-water Pure-water Cyclopentane hydrates Cyclopentane Concentrated Sea-water

Cyclopentane hydrate-based desalination process

Objective Experimental and modelling study of cyclopentane hydrates in NaCl, KCl, an equal-weight mixture NaCl-KCl, and CaCl2

Phase equilibria data in the presence of different salts is needed.

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Outlines

11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 5

  • 1. Introduction and objective
  • 2. Experimental Methodology
  • 3. Experimental results
  • 4. Modelling of cyclopentane hydrate
  • 5. Conclusions & Perspectives
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1. Reactor 2. Cryostat 3. Impeller 4. Agitator 5. Cooling jacket 6. Motor

  • 7. Temperature

transmitter

  • 8. Computer
  • 9. Temperature probe
  • 10. Drying oven
  • 11. Ion chromatography
  • 12. Camera

schematic diagram

Experimental study and modelling of cyclopentane hydrate in the presence of salts

12

Equilibrium temperature measument

Actual system

Experimental methodology

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Protocole: Two procedures

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2 4 6 8 10 12 14 16 18 50 100 150 200 250 300 350 400 450 500 Temperature, C Time, min

Temperature profile in pure water: Quick dissociation

Start chiller Hydrate formation Equilibrium temperature 7,7°C Stop chiller Initiate by injecting ice

Exothermic process Endothermic process

Experimental study and modelling of cyclopentane hydrate in the presence of salts

Temperature profile in pure water: Slow dissociation Te=7,7°C Te=7,1°C T Estimation T Accurate

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Outlines

11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 8

  • 1. Introduction and objective
  • 2. Experimental Methodology
  • 3. Experimental results
  • 4. Modelling of cyclopentane hydrate
  • 5. Conclusions & Perspectives
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Experimental study and modelling of cyclopentane hydrate in the presence of salts 9

  • 25
  • 20
  • 15
  • 10
  • 5

5 10 5 10 15 20 25 Temperature, °C Salt concentration, % w/w NaCl - Quick procedure Mixture KCl- NaCl - Quick procedure NaCl - Slow procedure KCl - Quick procedure KCl - Slow procedure Mixture KCl-NaCl - Slow procedure CaCl2 - Quick procedure CaCl2 - Slow procedure

  • Log. (KCl - Slow procedure)
  • Poly. (KCl - Slow procedure)
  • Poly. (Mixture KCl-NaCl - Slow procedure)
  • Poly. (CaCl2 - Slow procedure)

KCl NaCl-KCl NaCl CaCl2 Equilibrium temperatures in the presence of salts

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10

Salinity, % w/w Te-quick in NaCl, °C Te-slow in NaCl, °C Te in NaCl, °C [9] Te in NaCl , °C [3] Te-

slow

in KCl, °C Te-slow in a mixture

  • f NaCl-

KCl, °C Te-slow in CaCl2, °C 7.7 7.1 7.11

  • 7.1

7.1 7.1 1 6.9 6.4

  • 6.9

6.7 6.8 2 6.3 5.9

  • 6.1

6.0 6.3 3.5 5.7 5

  • 5.5

5.4 5.6 5 4.9 4.1

  • 4.45

4.9 4.6 4.9 8 3.5 2.4

  • 3.6

3.0 3,2 10 2 0.9 1.16 1.25 2.4 1.9 1.8 12 0.9

  • 0.4
  • 1.4

0.6 0.1 14

  • 1
  • 1.8
  • 0.4
  • 0,6
  • 1.9

16

  • 2.7
  • 3.8
  • 0.5
  • 2,1
  • 4

18

  • 5
  • 5.3
  • 1.9
  • 3,6
  • 6.7

20

  • 7.2
  • 7.8
  • 8.00
  • 3
  • 5,4
  • 9.6

22

  • 9.7
  • 10.2
  • 7,2
  • 13.2

23 25

  • 11
  • 11.6
  • 11.66
  • 15.1
  • 19.0

Equilibrium temperatures in the presence of NaCl, KCl, equi-mass mixture NaCl-KCl, and CaCl2 Our values in the presence of NaCl, 0%, 5%, 10%, 20% and 23% are very close Kishimoto [3] and Zylyftari [9]

[3]. M. Kishimoto, Apr. 2012. [9]. G. Zylyftari, May 2013.

Experimental study and modelling of cyclopentane hydrate in the presence of salts

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Outlines

11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 11

  • 1. Introduction and objective
  • 2. Experimental Methodology
  • 3. Experimental results
  • 4. Modelling of cyclopentane hydrate
  • 5. Conclusions & Perspectives
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Modelling: Approach n°1

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Experimental study and modelling of cyclopentane hydrate in the presence of salts 12

Geochemical model PHREEQC is used to predict water activity aw

                       T T T T T R C T T T T R H a

f f fm f f fm w

ln ) ( ) ( ln

No data for ΔCfm in the literature for CPH

Experimental data in NaCl, T

exp

ΔCfm (T)

                       T T T T T R C T T T T R H a

f f fm f f fm w

ln ) ( ) ( ln

 

N l pred

T T N AAD

1 exp

1 1

Calculate Tpred in

KCl, CaCl2 NaCl-KCl

Algorithm of equilibrium temperature prediction

Standard SLE equation:

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11/12/2017

) 1 ( ln

 

   

 j i j i i H w

RT    

Statistical thermodynamics

L w H w  

  

 

 

At thermodynamic equilibrium

Gibbs-Duhem

Approach n°2 & 3

Experimental study and modelling of cyclopentane hydrate in the presence of salts

Approach n°2: Kihara potential Interaction potential (ε,σ,a) Approach n°3: correlation 𝜄 = 𝜄 𝑏𝑥

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Modelling results

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Experimental study and modelling of cyclopentane hydrate in the presence of salts 14

) exp( ) ( T b a T F Cmf     

Approach n°1

  • 25,0
  • 20,0
  • 15,0
  • 10,0
  • 5,0

0,0 5,0 10,0 5 10 15 20 25 30

Temperature, C Salt concentration, % w/w Predicted data - NaCl Predicted data - KCl Predicted data - a mixture of NaCl-KCl Experimental data - NaCl Experimental data - KCl Experimental data - a mixture of NaCl-KCl Predicted data - CaCl2 Experimental data - CaCl2

KCl AAD=0,10% NaCl-KCl AAD=0,09% NaCl AAD=0,11% CaCl2 AAD=0,15%

a b R (coefficient of determination)

  • (1E-19)

0.1813 0.835

Predicted-equilibrium temperatures: Approach n°1

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Experimental study and modelling of cyclopentane hydrate in the presence of salts 15

Approach n°2

Predicted-equilibrium temperatures: Approach n°2

  • 25
  • 20
  • 15
  • 10
  • 5

5 10 5 10 15 20 25 30 Temperature, °C Salt concentration, % mass Expermental data in NaCl Experimental data in KCl Experimental data in NaCl-KCl Experimental data in CaCl2 Predicted data in CaCl2 Predicted data in NaCl Predicted data in KCl Predicted data in NaCl-KCl

KCl AAD=0,05% NaCl-KCl AAD=0,04% NaCl AAD=0,08% CaCl2 AAD=0,07%

a (10-10 m) σ (10-10 m) ε/k 0.8968 2.72 265.5

Kihara parameters for CPH

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Experimental study and modelling of cyclopentane hydrate in the presence of salts 16

Approach n°3

 

 

 

p a n a m a F

w w w

     

2

  • 25,0
  • 20,0
  • 15,0
  • 10,0
  • 5,0

0,0 5,0 10,0 5 10 15 20 25 30

Temperature, C Salt concentration , % w/w

Predicted data - NaCl Predicted data - KCl Predicted data - a mixture of KCl-NaCl Experimental data - NaCl Experimental data - KCl Experimental data - a mixture of NaCl-KCl Experimental data - CaCl2 Predicted data - CaCl2

KCl AAD=0.05% NaCl-KCl AAD=0.05% NaCl AAD=0.04% CaCl2 AAD=0.07%

m n p R (coefficient of determination)

  • 0.0004772

0.0004731 0.9998800 0.9957110

Predicted-equilibrium temperatures: Approach n°3

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Outlines

11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 17

  • 1. Introduction and objective
  • 2. Methodology
  • 3. Experimental results
  • 4. Modelling of cyclopentane hydrate
  • 5. Conclusions & Perspectives
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Conclusions

11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 18

 The Equilibrium temperatures in the presence of NaCl, KCl, mixture NaCl-KCl, and CaCl2 were determined following the quick and the slow procedures:

  • The Equilibrium temperatures drop strongly with increasing of salt concentration
  • Slow dissociation provided accurate data

 Accurate thermodynamic predictions : AAD ≤ 0.15%

  • Occupancy based approaches are better

PERSPECTIVES: ADD GAS MOLECULES

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Thank you very much for your attention!!!

11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 19

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Optimization

j j j

a , , 

0 ,

w P T L 

0 ,

w P T L

h

 w T L

v

0 ,

w , P T L p

c

 L p

b

  w , j i

C

L w 

H w 

Calculate deviation

 

N l pred

T T F

j j

1 exp ) , (

1

 

At a given salt concentration, calculate Tpred satisfying

L H  

  

 

 

w w

Experimental data in NaCl Texp Calculated data Tpred

Data from literature

min 1

1 exp ) , (

   

 N l pred

T T F

j j 

Procedure to optimize the Kihara parameters approach n°2

Experimental study and modelling of cyclopentane hydrate in the presence of salts

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20

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Approach n°3 - Correlation 𝜄 = F(aw)

11/12/2017

Experimental study and modelling of cyclopentane hydrate in the presence of salts 21

As in the approach n°2, the van de Waals and Platteeuw model is used to describe the hydrate phase. The new correlation 𝜄 = F(aw) is obtained

Experimental data in NaCl,

T

exp

Correlation 𝜄 = F(aw)

H w 

L w 

=

 

N l pred

T T N AAD

1 exp

1 1

Calculate Tpred in

KCl, CaCl2 NaCl-KCl

Algorithm of equilibrium temperature prediction: Approach n°3

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Experimental study and modelling of cyclopentane hydrate in the presence of salts 22

Approach n°2

k 

ε/k versus σ at the minimum deviation with experimental data Typical form of the deviation between the predicted and the experimental data a (10-10 m) σ (10-10 m) ε/k 0.8968 2.72 265.5 Kihara parameters for cyclopentane hydrate

2 4 6 8 10 12 50 100 150 200 250 300 350

2 2,5 3 3,5 4

ε/k σ Average deviation

ε/k Average deviation