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Copy of THERMODYNAMIC STUDY of Carbon dioxide Solubility In Ionic Liquids

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mohamed zoubeik

on 16 July 2013

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Transcript of Copy of THERMODYNAMIC STUDY of Carbon dioxide Solubility In Ionic Liquids

History of IL Development:
What are Ionic Liquids?

Ionic liquids are defined as salts with a melting point below 100C.
Made of cations and anions.
Many of these are liquid at room temperature.
What are the Properties Of Ionic Liquids?

Thermal stability at 200°C or more.
Extremely low vapor pressure.
Non volatile = No loss of IL from evaporation.
Non flammable
Liquid over wide range of temperature reaching greater than 300°C
Melting points below 100°C
Zhange et al, 2012
What are some Factors Affecting CO2 Solubility?

As pressure increases, solubility increases
As temperature increases, solubility decreases.
This is a problem because flue gas has high temperatures.
increases solubility
Role of anion is greater than cation as shown by Muldoon et al in 2007.
Other factors:
the role of cation, anion, alkyl chain length, molecular weight, and free volume
2002 March
(cc) image by jantik on Flickr
Objectives of the Experimental undertaking:

To measure CO2 solubility in 7 Ils: [TCD][Tf2N] , [PMPY][Tf2N], [EMMP][Tf2N] , [emim][LACTATE], [TCD][DCA], [(CH2)4SO3HMIm][TF2N], [(CH2)4SO3HMIm] [HSO4] at 313.15, 323.15 and 333.15 K and pressures up to 20 bar using a gravimetric microbalance (IGA-003)

To correlate the experimental CO2 solubility with simple thermodynamic models using AspenPlus simulator:
Standard Peng-Robinson (PR-EoS)
SRK-EoS with quadratic mixing rules (SRK)
Non-Random Two-Liquid activity coefficient model (NRTL)

To report Henry’s law constants and enthalpies and entropies of absorption for CO2 in the studied ILs


Why were these IL chosen?

Not extensively published.
Anions known for their high solubility such as TF2N.
IL with similar cations or anions to study the effect of changing the cation or anion.

Experimental Set up and Procedure
Then in
2012 Martinez et al. looked [hmim][TCB].
They compared the solubilities of CO2 in [hmim][TCB] at 333 K to other ionic liquids sharing the same cation: [hmim][PF6]), [hmim][BF4], [hmim][Tf2N], [hmim][eFAP].
They concluded that [hmim][TCB] had higher solubility than all of them expect for the highly fluorinated [hmim][eFAP].
But the viscosity [hmim][TCB] is almost half of [hmim][eFAP].
Then Baltus in 2004 explored imidazlium based ionic liquids and found:
CO2 solubility increases with increasing alkyl side chain.
The anions play a larger role in solubility than cations.
Second: water stable IL
The idea to develop water stable ionic liquids was first proposed by Zaworotko in 1990.
In 1992 Wilkes and Zaworotko were able to produce moisture stable imidazolium salts paired with BF4 and PF6 anions.
First there was
: pyridinium- and the imidazolium-based chloroaluminate ionic liquids = NOT water stable
3rd: Room Temp Ionic Liquids:
Blanchard also looked at using room temperature ionic liquids (RTILs) for CO2 capture and found that [bmim][PF6] has high solubility, reaching a 0.72 mole fraction CO2 at 40 C and 93 bar.
Then in 2007 Shiflett and Yokozeki worked with [hmim][Tf2N] at 20 bar and 50C and obtained a solubility of 0.316.
Then in 2008 Shiflett et al. looked at using [bmim][Ac] and found that it has high CO2 solubility.
It reached 0.373 at 50C at 20Bar.
Whereas in 2009 he found that [emim][Ac] achieved 0.39 at 50C at 20 Bar.
Both of which reacted
and hence the high CO2 solubility.
Gurkan et al, 2010
Density of IL:
Experimental density in decreasing order in the ionic liquids studied in this work are as follows: [(CH2)4SO3HMIm][TF2N] > [PMPY] Tf2N] > [(CH2)4SO3HMIm][HSO4] > [EMMP][Tf2N] > [TDC][Tf2N] > [emim][LACTATE] > [TDC][DCN].

Results and Discussion
CO2 Solubility in ILs:
CO2 absorption in ILs studied decreases in the order : [TCD][Tf2N] > [PMPY][Tf2N] > [EMMP][Tf2N] > [emim][LACTATE] > [TCD][DCA] > [(CH2)4SO3HMIm][TF2N] > [(CH2)4SO3HMIm] [HSO4].

Effect of changing the cation
Aki, S., Mellein, B., Saurer,B., Brennecke, J. F. ,"High-pressure phase behavior of carbon dioxide with Imidazolium-based ionic liquid." J. Phys. Chem. B., 108, 20355–20365, 2004.
Althuluth, M., Mota-Martinez, M., Kroon, M., Peters, C., "Solubility of carbon dioxide in the ionic liquid 1 ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate." J. Chem. Eng. Data., 57, 3422−3425, 2012.
Anthony, J., Anderson, J., Maginn, E., Brennecke, J., "Anion effects on gas solubility in ionic liquids." J. Phys. Chem. B., 109, 6366-6374, 2005.
Anthony, J., Maginn, E., Brennecke, J., "Solubilities and thermodynamic properties of gases in the ionic liquid 1-n-butyl-3-methylimidazolium hexafluorophosphate." J. Phys. Chem. B., 106, 7315-7320, 2002.
Blath, J., Deubler, N., Hirth, T., Schiestel, T., "Chemisorption of carbon dioxide in imidazolium based ionic liquids with carboxylic anions". Chemical Engineering Journal, 181, 152-158, 2012.
Blanchard, L., Gu, Z. Y., Brennecke, J. F. "High-pressure phase behavior of ionic liquid/CO2 systems." J. Phys. Chem. B.,105, 2437-2444, 2001.
Blanchard, L., Hancu, D.E., Beckman, J., Brennecke, J. F., "Green processing using ionic liquids and CO2." Nature.,399, 28-29, 1999.
Brennecke, J. F., Lopez-Castillo, Z. K., Mellein, B. R.,"Gas solubilities in ionic liquids and related measurement techniques". Ionic Liquids in Chemical Analysis, 3, 229, 2008.
Cabaço, M. , Besnard, M., Danten, Y., Coutinho, P., "Carbon dioxide in 1-butyl-3-methylimidazolium acetate. Unusual solubility investigated by raman spectroscopy and DFT calculations." J Phys Chem A., 116,1605-1620, 2012.
Cadena, C. Anthony, J. L., Shah, J. K. Morrow, T. I., "Why is CO2 so soluble in imidazolium based ionic liquids?" J. Am. Chem. Soc., 126, 5300–5308, 2004.
Clever, H. L. and Battino, R., "The solubility of gases in liquids, in techniques of chemistry volume VIII: solutions and solubilities - Part 1." New York: John Wiley & Sons, Inc, 1975.
Martinez, M., Althuluth, M., Kroonc, M., Peters, C., "Solubility of carbon dioxide in the low-viscosity ionic liquid 1-hexyl-3-methylimidazolium tetracyanoborate." Fluid Phase Equilibria, 332: 35– 39, 2012.
Meindersma, G., Sahnchez, L., Hansmeier, A., Haan, A., "Application of task-specific ionic liquids for intensified separations." Chemical Monthly., 1125-1136, 2007.
Muldoon, M., Aki. N, Anderson. J, Dixon. N, Brennecke J. "Improving carbon dioxide solubility in ionic liquids." J. Phys. Chem. B., 111, 9001–9009, 2007.
Nonthanasin, T., "Solubility of carbon dioxide in five promising ionic liquids." M.S. Thesis, Department of Chemical Engineering, University of Regina, Regina, Canada, 2013.
Peng, D., and Robinson, D., "A new two-constant equaiton of state." Ind. Eng. Chem. Fund.,15, 59-64, 1976.
Prausnitz, J. M., Lichtenthaler, R. N., de Azevedo, E. G., "Molecular thermodynamics of fluid-phase equilibria." New Jersey, USA, Prentice Hall, 1999.
Ramdin, M. W., de Loos, T., Vlugt, T., "state-of-the-art of CO2 capture with ionic liquids." Ind. Eng. Chem. Res., 51, 8149–8177, 2012.
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Shiflett, M. B., Kasprzak, D. J., Junk, C. P., Yokozeki, A., "Phase behavior of {carbon dioxide+ [bmim][Ac]} mixtures". The Journal of Chemical Thermodynamics, 40, 25-31, 2008.
Shiflett, M.B., and Yokozeki, A., "Solubility of CO2 in Room Temperature Ionic Liquid [hmim][Tf2N]." J. Phys. Chem. B., 111, 2070–2074, 2007.
Shiflett, M. B., and Yokozeki, A., "Solubilities and diffusivities of carbon dioxide in ionic liquids:  [bmim][PF6] and [bmim][BF4]." Ind. Eng. Chem. Res., 44, 4453–4464, 2005.
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Main findings:
CO2 solubility decreased in the following order: [TCD][Tf2N] > [PMPY][Tf2N] > [EMMP][Tf2N] > [emim][LACTATE] > [TCD][DCA] > [(CH2)4SO3HMIm][TF2N] > [(CH2)4SO3HMIm] [HSO4].
[TCD][Tf2N] shows great promise due to it’s high physical CO2 absorption, similar to [hmim][Tf2N].
NRTL was the best model best for describing CO2 solubility in IL as it had the lowest average AAD of 0.89.

Thermodynamic Study of Carbon Dioxide Solubility In Ionic Liquids
Presented by: Mohamed Zoubeik
Research Supervisor: Dr. Amr Henni
Date: 16,07, 2013
To determine the CO2 solubility in 7 of the following IL:
The CO2 solubility was obtained at the following temperatures 313.15, 323.15 and 333.15 over a pressure range of 100 mbar to 20000 mbar.
The experimental results were extrapolated and modeled using the Peng-Robinson (PR) equation of state, the Non-random Two Liquid Segment Activity Coefficient (NRTL) models and SRK with their AAD% 1.83,0.88,1.04 respectively.
A gravimetric microbalance was used to measure the solubility of carbon dioxide.
The 7 IL are:
1,2,3-Tris(diethylamino)cyclopropenylium bis(trifluoromethanesulfonyl)imide
3-methyl-1-propylpyridinium bis[(trifluoromethyl)sulfonyl]imide
Ethyldimethylpropylammonium bis(trifluoromethylsulfonyl)imide
1-Ethyl-3-methylimidazolium L-(+)-lactate
1,2,3-Tris(diethylamino)cyclopropenylium dicyanamide
1-(4-sulfobutyl)-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide
1-(4-sulfobutyl)-3-methylimidazolium hydrogen sulfate
The CO2 solubility was found to be increasing in the following ionic liquids in the following order: [TCD][Tf2N] > [PMPY][Tf2N] > [EMMP][Tf2N] > [emim][LACTATE] > [TCD][DCA] > [(CH2)4SO3HMIm][TF2N] > [(CH2)4SO3HMIm] [HSO4.
Then in
2005 Shiflett and Yokozeki

also looked at CO2 solubility in [bmim][PF6] and [bmim][BF4].
He got 0.197 at 50C at 19Bar for [bmim][PF6] .
He got 0.182 at 50C at 20 Bar for [bmim][BF4].

In 2011, Babarao showed that the [emim][B(CN)4] shows high CO2 solubility, which is about 30% higher than [emim][Tf2N].

In 2012, Althuluth et al looked at carbon dioxide solubility in the [emim][FAP].
They found that CO2 solubility in [emim][FAP] is higher than in all other ILs with the same cation following the trend: [emim]-[FAP] > [emim][Tf2N] > [emim][PF6] > [emim][BF4].

Why we care about CO2 capture?
What are IL?
What are the properties of IL?
What are the factors affecting CO2 solubility?
Experimental Outline

(Ramdin et al., 2012).
The Problem
Global warming

Production of Flue gas
There are two solutions for solving the global warming problem....
Aqueous amine solutions

Ionic Liquids
Needs high energy to regenerate the solvent.
solvent loss due to evaporation
The next generation of clean CO2 capture....

Experimental Outline
Effect of changing the anion
Comparison with literature:
Comparison with group:
Fluorination of the anion increases solubility.
Fluorination of the cation increases solubility.
Changing the cation can either increase or decrease solubility.
Example: TDC is a better cation than PMPY or EMMP providing a higher solubility when combined with TF2N.
Changing the anion can either increase or decrease solubility.
Example: TF2N is a better anion than DCN and provides a higher solubility when combined with TDC.

So why we care about IL?
Because IL hold the key to decreasing the greenhouse effect?
but how???
One old and one that is new!
But they have many drawbacks which include......
IL are becoming a hot topic as they are providing promising ways for cost and energy efficient separation of CO2 from industrial emissions!

Future work:
To investigate these seven ionic liquids at room temperature and to measure their viscosity and compare them with others in the literature.
To investigate the seven ionic liquids at higher pressures and to investigate their solubility in other gases such as methane, ethane, propane, sulfur dioxide, and hydrogen.
Modifications of the seven ionic liquids by the addition of functional groups or the modification of alkyl chain lengths to allow them to become more environmentally friendly.
How did global warming happen??
more flue gas released, means more CO2 trapped in the atmosphere leading to temperature changes...and the earth burning up!!!
as we are seeing today such as the flooding in Calgary........
This is seen by the explosion of publications in the last few years........
where CO2 is the most common greenhouse gas implicated in global warming.....creating the greenhouse effect!

Climate Change!!

Experimental steps
Some good points:
High CO2 solubility
Low cost

Extreme Weather
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