Aqueous solutions of ionic liquids in the extraction and purification of compounds from biomass João A. P. Coutinho CICECO, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. http://path.web.ua.pt http://www.facebook.com/PATh.group
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FIBIC ACel Programme Seminar: Aqueous solutions of ionic liquids in the extraction and purification of compounds from biomass
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The higher the molecular weight of the dextran the more effective is the separation into two phases
0,0
0,4
0,8
1,2
1,6
2,0
0 0,02 0,04 0,06 0,08
[C4
mim
[]B
F4
]/(m
ol.k
g-1
)
[Dextran]/(mol.kg-1)
[C4mim][BF4] + Dextran 6k
[C4mim][BF4] + Dextran 40k
[C4mim][BF4] + Dextran 100k
ABS ILs + Water + Dextran
ABS composed of ILs + Polysaccharides:
Speciation curve of Chloranilic acid
PEG
dye
IL
dye
dyeC
CK
Neutral 1 negative charge
2 negative charge
PEG
salt
PEG
dextran
IL
PEG
PEG
IL
IL
PEG
IL
PEG
IL
PEG
PEG
IL
IL
PEG
IL
PEG
ABS ILs + Water + PEGs
J. F. B. Pereira, L. P. N. Rebelo, Robin D. Rogers, João A. P. Coutinho and Mara G. Freire PCCP 15 (2013) 19580-19583
Indigo Blue Partition
Indigo Carmine Partition
Na2SO4 [C4mim]Cl [C4mpirr]Cl [C4mpip]Cl
Salt
Salt
ABS ILs + Water + PEGs
ABS with Deep Eutectic Solvents
To verify the ability of DES to create an ABS;
To characterize DES-based ABS;
To demonstrate the potential of these systems in extractive processes
5
ABS with Deep Eutectic Solvents
ABS with Deep Eutectic Solvents
DES + H2O + PPG 400 ternary systems
0,00
2,00
4,00
6,00
0,00 0,50 1,00 1,50 2,00
[PP
G]
/ m
ol.
kg-1
[IL] / mol.kg-1
IL [Ch]Cl
[Ch][DHC]
l [Ch][Gly]
n [Ch][Lac]
[Ch][Ac]
0,00 0,50 1,00 1,50 2,00 2,50[DES] / mol.kg-1
DES [Ch]Cl
Citric acid + [Ch]Cl (1:1)
l Glycolic acid + [Ch]Cl (1:1)
n Lactic acid + [Ch]Cl (1:1)
Acetic acid + [Ch]Cl (1:1)
o Citric acid ≈ Glycolic acid < Lactic acid ≈ Acetic acid o [Ch][DHC] < [Ch][Gly] ≈ [Ch][Lac] ≈ [Ch][Ace]
ABS with Deep Eutectic Solvents
0,00
2,00
4,00
6,00
8,00
10,00
0,00 0,50 1,00 1,50 2,00 2,50
[PP
G]
/ m
ol.
kg-1
[DES] / mol.kg-1
Citric acid
0,00
2,00
4,00
6,00
0,00 0,50 1,00 1,50 2,00 2,50 3,00
[PP
G]
/ m
ol.
kg-1
[DES] / mol.kg-1
Lactic acid
IL [Ch]Cl n Acid + [Ch]Cl (1:2) l Acid + [Ch]Cl (1:1) Acid + [Ch]Cl (2:1)
ABS with Deep Eutectic Solvents
0,00
2,00
4,00
6,00
0,00 1,00 2,00 3,00
[PP
G]
/ m
ol.
kg-1
[DES] / mol.kg-1
0,00
2,00
4,00
6,00
0,00 1,00 2,00 3,00
[PP
G]
/ m
ol.
kg-1
[DES] / mol.kg-1
Glycolic acid Acetic acid
IL [Ch]Cl n Acid + [Ch]Cl (1:2) l Acid + [Ch]Cl (1:1) Acid + [Ch]Cl (2:1)
[Acid] ability for ABS formation
ABS with Deep Eutectic Solvents
• High Extraction efficiencies
• DES > [Ch]Cl
Selective separation of dyes (sudan III and PB29 respectly)
PB29 Sudan III
-100
-75
-50
-25
0
25
50
75
100
EED
ye %
PB 29 Sudan III
PPG-rich phase
DES-rich phase
2:1 1:1 1:2 [Ch]Cl
ABS with Deep Eutectic Solvents
DES showed an
intermediate toxicity
when compared
with the respective
starting materials.
These DES are
included in the
“moderately toxic”
compounds against
Vibrio fischeri
AA << LA < CA < GA
Toxicities of Deep Eutectic Solvents
Their toxicity against
the marine bacteria is
dependent of the
concentration of the
acid.
The effect of the acid
is controlling the
toxicity of the DES
Toxicities of Deep Eutectic Solvents
DES seem to be much more toxic than the corresponding ILs
Toxicities of Deep Eutectic Solvents
Reversible IL-based ABS
Recently, a large interest has been devoted to the study of reversible biphasic systems constituted by ILs: temperature-driven phenomenon CO2/N2 flushing
Reversible Systems
Saita et al., Chem. Commun., 2012, 48, 7119 Saita et al., Chem. Commun., 2013, 49, 8988 Xiong et al., Green Chem., 2013, 15, 1941 Xiong et al., ChemSusChem, 2012, 5, 2255 Jessop et al., Energy Environ. Sci., 2012, 5, 7240
0
20
40
60
80
0 20 40 60
IL /
( w
t %
)
[Salt] / (wt %)
Biphasic region
Monophasic region
pH-reversible IL-ABS
Phase diagrams (at different pH values) for ABS composed of:
+ K3C6H5O7 + C6H8O7 + KOH [C4mim]Br [C4mim]Cl
[C4mpy]Cl [C4C1mim]Cl
[C4mpip]Cl [P4444]Cl
The relative amount of the citrate-based species has a crucial impact on the phase diagrams and on their ability to form ABS
pH-reversible IL-ABS
IL-s
alt
A
TP
S
IL+ Potassium Citrate + Water
Citric acid
KOH
Biphasic region
Monophasic region
Biphasic region
Reversibility behaviour:
speciation of the salt anion.
Reversibility behaviour:
speciation of the IL anion.
j
j
pH-reversible IL-ABS
pH ≈6 pH ≈7
-100
-80
-60
-40
-20
0
20
40
60
80
100
1 2 3 4
EED
ye %
Sudan III PB27
IL- rich phase
Salt -rich phase
[C4mim]Cl [C4C1mim]Cl [C4mpip]Cl [C4mpy]Cl
[C4mim]Cl
[C4C1mim]Cl
[C4mpip]Cl
[C4mpy]Cl
Complete separation of the two
dyes for opposite phases
↑ EE %
Mixture of dyes in the
monophasic region
Sudan III
PB27
Separation of the
two dyes
pH-reversible IL-ABS
Phase diagrams (at different pH values) for ABS composed of:
[Ch]Cl [Ch][Ac] [Ch][Pro]
[Ch][Gly] [Ch][But]
[Ch][Lac] PPG
+ PPG 400 + Acid corresponding to the IL anion + [Ch]OH
pH-reversible IL-ABS
Phase diagrams for the systems composed of ILs + water + PPG 400 at 298 K
[Ch][Hex]
[Ch][But]
[Ch]Cl
[Ch][Pro]
[Ch][Lac]
[Ch][Ac]
[Ch][Gly]
Hydration capacity
Anions with alkyl side chains
Anions with ↑ alkyl side chains
Addition of extra –OH groups
Form ABS
Don’t form ABS
Enhanced capacity to form ABS
×
○
▲
l
+
0
20
40
60
80
0 5 10 15 20 25
[PP
G 4
00
] /
(wt
%)
[IL] / (wt %)
Monophasic region
Biphasic region
10
15
20
10 15 20
pH-reversible IL-ABS
Phase diagrams for the systems composed of PPG 400 + Water + ILs/Respective Acid (pH ≈ 4-9) at 298 K
Higher pH values are favorable for ABS formation
♦ pH ≈ 9 ■ pH ≈ 8 pH 7 ● pH 6 ▲pH 5
[IL] / wt%
Higher pH
pH-reversible IL-ABS
pH
not favorable for the formation of
ABS
pH 9 8 7 6 5 4 3 2 1 0
[Ch]Cl
[Ch][Ac]
[Ch][Gly]
[Ch][Lac]
[Ch]Prop]
[Ch][But]
Ability to form ABS is related with the pKa of the acid corresponding
to the IL anion
Acid pKa1 pKa2
hydrochloric acid --- ---
acetic acid 4.54 ---
propanoic acid 4.75 ---
butanoic acid 4.91 ---
lactic acid 14.59 3.78
glycolic acid 14.78 3.53
Identification of the systems able to form ABS at different pH values
pH-reversible IL-ABS
PB27 PB29
Selective separation of dyes with reversible ABS
Sudan III PB27 PB29
pH-reversible IL-ABS
Saita et al., Chem. Commun., 2013, 49, 8988. Nockemann et al., J. Phys. Chem. B, 2006, 110, 20978.
Temperature-driven phenomenon
Thermoreversible systems
PIL+
PPG400
+H2O PIL
aqueousrich phase
PPG400
aqueousrich phase
25 °C 35 °C0
10
20
30
40
50
60
70
80
90
100
0
10
20
30
40
50
60
70
80
90
100
Thermoreversible IL-ABS
[N1120][C1CO2] [N1220][C1SO3]
[N11[2(N110)]0][C1CO2] [N11[2(N110)]0]Cl
[N11[2(N110)]0][C7CO2] [N1220][C7H7CO2]
Thermoreversible IL-ABS
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
[PP
G-4
00
] / (
mo
l∙k
g-1
)
[PIL] / (mol·kg-1)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
[PP
G-4
00
] /
(mo
l∙k
g-1
)
[PIL] / (mol·kg-1)
25 ºC 35 ºC
Monophasic region
Biphasic region
Monophasic region
Biphasic region
Phase diagrams for the ternary systems composed of PPG-400 + PIL + water at 25 ºC and
A.F.M. Cláudio, C.F.C. Marques, Isabel Boal-Palheiros, Mara G. Freire and João A.P. Coutinho Green Chem 16 (2014) 259-268
[C4C1im]+
15 20 15 15 15 20 15 wt % of Salt
Br - [N(CN)2]-
[C2H5SO4 ]- [CH3SO4 ]
- [CF3SO3]-
88,90 89,93
97,05 98,53 93,37 94,56 96,84
0
20
40
60
80
100
% EE
IL- rich phase
Extraction efficiencies (%EE) of gallic acid for the IL-rich phase in ATPS composed of 25 wt% of [C4C1im]-based ILs and variable concentrations of Na2SO4 at 25 ºC.
Recovery of phenolic compounds
Extraction efficiencies (%EE) of gallic acid for the inorganic-salt-rich phase in ATPS composed of 10 wt% of Na2CO3 and variable concentrations of [C4C1im]-based ILs at 25 ºC.
Recovery of phenolic compounds
Recovery of phenolic compounds
A.F.M. Cláudio, C.F.C. Marques, Isabel Boal-Palheiros, Mara G. Freire and João A.P. Coutinho Green Chem 16 (2014) 259-268
Recovery of phenolic compounds
gallic acid
Extraction efficiencies (%EE) of syringic and vanillic acid in sequential ATPS composed of 25% of IL + 20% Na2SO4) (orange bars) and 20% of IL + 10% Na2CO3 (blue bars) at 298 K
Recovery of phenolic compounds
Protein
Ionic Liquid
Purification Strategies
• Immunoaffinity chromatography
• Centrifugation
• Dialysis
In order to establish a sustainable and low-cost process, the recovery of protein from the IL-aqueous solution for further reuse is required…
Recovery of proteins
Protein
IL – aqueous solution
• Dialysis removes any excess IL from protein aqueous solution
• Recycled IL can be use subsequent extraction step.
Dialysis procedure
ILs can be reused
12 h Room temperature Moderate agitation
Purified protein
Dried under vacum at 60 ◦C
IL recovery of > 99 wt%
Recovery of proteins
Recycling ionic liquids
• The non-volatile nature of ionic liquids provides the opportunity to reduce, or even completely eliminate, hazardous and toxic emissions to the atmosphere.
• But they present a non-negligible solubility in water, even those considered hydrophobic, thus leading to aquatic environmental concerns.
• Their toxicity is inversely proportional to their hydrophobicity