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Process System Engineering Group. University of Twente Separation Technology Group. Ionic Liquid Solvents for Gas Sweetening Operations. Lara Galán Sánchez, G. Wytze Meindersma and André de Haan The Netherlands. 11 th July 2007 - Kingston, Canada . Contents.

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ionic liquid solvents for gas sweetening operations

Process System Engineering Group

University of Twente

Separation Technology Group

Ionic Liquid Solvents for Gas Sweetening Operations

Lara Galán Sánchez, G. Wytze Meindersma and André de Haan

The Netherlands

11th July 2007 - Kingston, Canada

slide2

Contents

  • Room Temperature Ionic Liquids (RTILs)
  • Process advantages
  • Research
  • Gas absorption and selectivity
  • Conclusions
  • Acknowledgments
slide3

The choice of the cation and anion determines the physicochemical properties.

Room Temperature Ionic Liquids (RTILs)

  • Organic salts with a melting

point below 100 C

  • Wide liquid range:

-96 C up to 300 C

  • Negligible vapour pressure
    • Non-volatile
    • Non-flammable
  • High thermal, chemical and electrochemical stability
  • Dissolution of many organic and inorganic compounds
  • Variable miscibility with water and organic solvents
slide4

Process features

  • Big volume operations:
    • No or very low vapour pressure
    • Reduction of volatile emissions and contamination
    • Decreased solvent inventory and solvent make-up volume
    • High thermal resistance
    • RTILs can be regenerated
  • Designer character:
    • Enhanced selectivity of a specific compound
    • Defined physical properties required for an economical operation
    • Promote specific interactions
slide5

Research

  • Identification of the potential of the designed RTILs as suitable solvents for CO2/CH4 separation
  • Comparison of performance to that of existing solvents:
    • NFM (N-formyl morpholine)
    • NMP (N-methyl pyrrolidone)
    • Sulfolane
    • Aqueous amine solutions
slide6

Room Temperature Ionic Liquids (RTILs)

Tetrafluoroborate, BF4-

1-Butyl-3-methyl-imidazolium, [bmim]+

Bis(trifluoromethanesulfonyl)imide, [NTf2]-: N(CF3SO2)2-

tested rtils

[NH2-Im]BF4

[bmim]BF4

[NH2-Im]NTf2

[emim]NTf2

[NH2-Pyrr]BF4

Standard RTILs and NH2-functionalized:

Tested RTILs

Gravimetric Balance: IGA 002 - Hiden

solvent regeneration
Solvent Regeneration

[NH2-Pyrr]BF4

Regenerated

T > 353 K

P < 10-2 MPa

CO2

[NH2-Pyrr]BF4

co 2 absorption

CO2 absorption

343 K

344 K

ch 4 absorption at 343 k

CH4 absorption at 343 K

CH4 solubility increases due to physical affinity with the liquid

ch 4 absorption at 333 k

CH4 absorption at 333 K

[1]Henni, A., et al. 2006, J Chem. Eng. Data, 51, 64-67

slide13

Selectivity

  • Individual gas absorption
  • Comparison at low and high CO2 concentration
  • Comparison of selectivity of standard ILs with functionalized ILs and physical solvents
  • Advantage of ILs for CO2 absorption: combination of physical and chemical interactions
co 2 ch 4 selectivity

CO2/CH4 selectivity

[NH2-Pyrr]BF4 at 333 k

selectivity individual gas 0 1 m pa

Selectivity individual gas 0.1 M Pa

[2]Henni, A., et al. 2005, Canadian J Chem. Eng., 83, 358-361.

[3] Murrieta, F., et al.1988, Fluid Phase Equilibria, 44, 105-115.

T: 333 K

slide19

Solvent effects in the process

  • Heat of absorption of CO2 and CH4: comparable with those of physical solvents
  • High viscosity affects mass transfer and kinetics: selection of equipment and operation conditions
  • Environmental aspects
  • Opportunity for design
ethylene ethane solubility

Ethylene - ethane solubility

[1]Henni, A., et al. 2006, J Chem. Eng. Data, 51, 64-67

[4] Rivas, O., Prausnitz, J., et al. 1979, AIChE J., 25, 975-984.

T: 333 K

slide21

Solvent effects in the process

  • Solubility of ethane: comparable to NMP, NFM, sulfolane
  • Solubility of other gases: O2, H2 very low
  • Co-absorption effect needs to be studied
slide22

Conclusions

  • RTILs: good potential solvents for gas sweetening operations
  • Advantages of physical and chemical solvents are combined by the designed RTILs
  • The “designer ability” of the RTILs allows to have a suitable solvent for a specific process
acknowledgments

Acknowledgments

Special thanks to Jan de With from Shell Research & Technology Center, Amsterdam for the synthesis of the functionalised ILs

Project funded by the Dutch EET program(Ecology, Economy, Technology)Cooperation with:

ECNShellTNOHyflux CEPAration BV