FIBIC ACel Programme Seminar: Aqueous solutions of ionic liquids in the extraction and purification...

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

University of Coimbra

University of Aveiro

CICECO - AVEIRO INSTITUTE OF MATERIALS

university of aveiro

ciceco aveiro institute of materials

G1 – Inorganic Functional Nanomaterials & Organic-Inorganic Hybrids (J. R. Gomes) G2 – Multifunctional Ferroic Ceramics & Nanostructures (V. Amaral) G3 – Materials for Energy and Functional Surfaces (M. Zheludkevich) G4 – Biorefineries, Biobased Materials and Recycling (Armando J.D. Silvestre) G5 - Biomedical and Biomimetic Materials (A. Gil).

Research Groups

university of aveiro

ciceco aveiro institute of materials

Biorefinery: CICECO – VTT – Aalto

BoostBiorefine SEP-210273988 H2020 – TWINN - 2015

Biorefinery

Chemicals, Intermediates

The Biorefinery Concept

Energy

Polymers

Paper, Materials, Fibres

Food CO2

ILs and Water

The magic of aqueous solutions of ionic liquids -Greener

-Cheaper

-Lower viscosity

-Enhanced performance

ILs and Water

Caffeine extraction

from guaraná seeds

using aqueous

solutions of ionic

liquids

Ana Filipa Cláudio, Ana MC Ferreira, Mara G. Freire and Joao A.P. Coutinho Green Chemistry 15 (2013) 2002-2010

Guaraná

A climbing plant especially common in Brazil and its

seeds contain about twice the caffeine found in coffee

beans

Used in pharmaceutical, dietetic, food and beverage

industry

Extraction of caffein with IL solutions


3.86

5.17

6.116.88

7.407.87

8.18

3.123.75

0

2

4

6

8

10

% w

t caf

H20 0.5 M 1.0 M 1.5 M 2.0 M 2.5 M 3.0 M 1.0 M 1.5 M

H20

[C4mim]Cl

NaCl

Caffeine extracted from guaraná seeds using particle diameters of guaraná seeds between 0.4 and 1 mm (T = 70 ºC, R=1:10, t= 30 min).




T = [65 , 85] ˚C;

Re

su

lts

R;

Response surface methodology:

Factorial planning 23 (T, R, C )

Constants

parameters

t = 30 min

d < 0.4 mm

C ( ≥ 1.5 M ).

Response

surface plots

and contour on

the extraction of

caffeine.

T vs R C vs R C vs T

Caffeine

extraction


Solubility of caffein in IL solutions

0

50

100

150

200

250

300

350

0 20 40 60 80 100

[Bio

mo

lecu

le]

/ g.

L-1

[IL]/ wt%

Influence of concentration of IL at 303 K in solubility in aqueous solutions of:

[C4C1im][N(CN)2]; [C4C1im]Cl; [C2C1im][N(CN)2].

Solubility of vanillin in IL solutions

Ana F Cláudio, M Neves, K Shimizu, JNC Lopes, Mara G Freire, Joao AP Coutinho Green Chem (2015) 10.1039/C5GC00712G

0

50

100

150

200

250

0 5 10 15 20 25

[Van

illin

] / g

.L-1

[IL] in water / wt %

11

Solubility

up to

18-fold

Only water

Recovery of vanilin: antisolvent


http://upload.wikimedia.org/wikipedia/commons/c/c7/Vanillin2.svg

0

100

200

300

400

500

300 305 310 315 320 325

[Van

illin

] /

g.L-1

T / K

Influence of temperature in the vanillin’s solubility in ▬ water1 and in aqueous

solutions of 10 wt % of sodium benzoate, 10 wt % of [C2C1im][N(CN)2],

20 wt % of sodium benzoate and 20 wt % of [C2C1im][N(CN)2].



b) c) d) a)

Precipitation of vanillin

a) appearance of commercial vanillin; b) vanillin dissolved in 20 wt % [C4C1im]Cl;

c) precipitation of vanillin with addition of water; d) recovered vanillin.



ABS

IL-rich phase

60 ⁰C

Filtration (0.45 μm) + water 84% dye recuperation

Sudan III

4 ⁰C

Filtration (0.45 μm)

Indigo Blue

76% dye recuperation

Dye recovery: antisolvent/ temperature

[P4441][CH3SO4] +

organic salt

A.M. Ferreira, João A.P. Coutinho, A.M. Fernandes, Mara G. Freire Sep Pur Tech 128 (2014) 58–66

0.0

1.0

2.0

3.0

4.0

% C

hlo

rop

hyll

Chl a Chl b

Process conditions:

R = 1:50 t = 30 min C = 10 wt.% of IL

The extraction efficiency of chlorophylls significantly increases with surface-active ionic

liquids, i.e., with ILs that are able to form aggregates in aqueous solution.

Extraction of clorophyll with IL solutions

0.0

1.0

2.0

3.0

4.0

% C

hlo

rop

hyll

Higher extraction efficiency with the

increase of the IL concentration;

0.5 wt.% [P44414]Cl

H2O 1 wt.% [P44414]Cl

5 wt.% [P44414]Cl

10 wt.% [P44414]Cl

7.5 wt.% [P44414]Cl

Chl a Chl b

At higher concentrations, the

extractions efficiencies are less

dependent on the IL amount in

aqueous solution;

The amount of extracted chlorophyll

b is similar for all IL concentrations.

Selective extraction of chlorophylls

Extraction of clorophyll with IL solutions

Process conditions:

R = 1:50 t = 30 min

Aqueous Biphasic Systems

• Polymer-Salt • Polymer-Polymer

Liquid-liquid extraction with ABS

Phase Diagrams of IL-based ABS

Aqueous Biphasic Systems

ABS of IL + Salt

[CF3CO2]-

ABS ILs + Water + K3PO4

Evaluation of IL Cation Influence

Evaluation of IL Anion Influence

[C2-6mim]+ [C1mim]+ [C2im]+ [C1im]+ [im]+

[C7H7mim]+ [amim]+ [OHC2mim]+

[HSO4]- [Cl]- [Br]- [MeSO4]

- [EtSO4]-

[CF3SO3]- [N(CN)2]

- [CH3SO3]- [CH3CO2]

-

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0

IL /

(m

ol.

kg

-1)

K3PO4 / (mol. kg-1)

[C2mim][CH3SO3]

[C2mim][Cl]

[C2mim][CH3CO2]

[C2mim][Br]

[C2mim][MeSO4]

[C2mim][EtSO4]

[C2mim][CF3SO3]

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

0.0 0.5 1.0 1.5 2.0 2.5

IL /

(m

ol.

kg

-1)

K3PO4 / (mol. kg-1)

[C4mim][CH3CO2]

[C4mim][Cl]

[C4mim][CH3SO3]

[C4mim][Br]

[C4mim][TFA]

[C4mim][N(CN)2]

[C4mim][HSO4]

[C4mim][CF3SO3]

[CF3SO3] > [EtSO4] > [MeSO4] > [Br] > [CH3CO2] > [Cl] > [CH3SO3]

[CF3SO3] > [HSO4] > [N(CN)2] > [TFA] > [Br] > [CH3SO3] > [Cl] > [CH3CO2]

Anion Influence

Ventura, S. P.; Neves, C. M. S. S.; Freire, M. G.; Marrucho, I. M.; Coutinho, J. A. P. J. Phys. Chem. B 113 (2009) 9304-9310


Descending order of ATPS formation


0.0

1.0

2.0

3.0

4.0

5.0

6.0

0.0 0.5 1.0 1.5 2.0 2.5

IL /

(m

ol.

kg

-1)

K3PO4 / (mol. kg-1)

[OHC2mim][Cl]

[C1mim][Cl]

[C2mim][Cl]

[amim][Cl]

[C4mim][Cl]

[C7H7mim][Cl]

[C6mim][Cl]

Cation Influence

[C6mim] > [C7H7mim] > [C4mim] > [C2mim] ≈ [amim] > [C1mim] > [OHC2mim]

Neves, C. M. S. S.; Ventura, S. P.; Freire, M. G.; Marrucho, I. M.; Coutinho, J. A. P. J. Phys. Chem. B 113 (2009) 5194-5199.



Evaluation of the salt effect: anion

PO43->C6H5O7

3->HPO42-≈CO3

2->SO42-≈SO3

2->C4H4O62->H2PO4

->OH->CH3COO-≈HSO4-≈HCO3

->Cl-

Evaluation of the salt effect: cation

Mg2+ ≈ Ni2+ ≈ Sr2+ > Ca2+ > > Na+ > K+ > Cs+

IL-based ABS

Salt cation

10

Salt anion

20

IL cation

10

IL anion

20

IL chain funct

20

Total

800,000 x x x x

Each tie line is a different extraction system, with different partition coefficients and selectivities

The tuneability of ionic liquids allows them to form ABSs with various compounds

IL-based ABS

Over one million of ABS can be prepared with the ILs available

ATPS ILs + Water + aminoacids

M. Domínguez-Pérez, L.I.N. Tomé, M.G. Freire, I. M. Marrucho, O. Cabeza, J.A.P. Coutinho Sep Pur Tech 72 (2010) 85-91

ATPS ILs + Water + Sugar

D-Glucose

D-Mannose

D-Galactose

D-(+)-Xylose

D -(-)-arabinose

L-(+)-Arabinose

Sucrose

Lactose

D-Sorbitol

Xylitol

D-Maltitol

Mara G. Freire, Cláudia L. S. Louros, Luís Paulo N. Rebelo and João A. P. Coutinho Green Chemistry (2011) 13: 1536-1545

ATPS ILs + Water + Sugar

Mara G. Freire, Cláudia L. S. Louros, Luís Paulo N. Rebelo and João A. P. Coutinho Green Chemistry (2011) 13: 1536-1545

IL + Dextran + H2O at 298 K

0,0

0,4

0,8

1,2

1,6

2,0

2,4

2,8

3,2

3,6

0 0,001 0,002 0,003 0,004 0,005 0,006 0,007

[IL]/

(mo

l.k

g-1

)

[Dextran 100k]/(mol.kg-1)

, [C4mim][BF4] , [C4mim][CF3SO3] , [C2mim][CF3SO3] , [C4mim][C2SO4]

, [C4mim][N(CN)2]

, [C4mim][TOS]

, [C4mim][C1SO4]

Potential for forming ABS

[C4mim][BF4]≈[C4mim][CF3SO3]>[C4mim][C2SO4]≈ [C4mim] [N(CN)2]>[C4mim][TOS]>[C4mim][C1SO4]

ABS ILs + Water + Dextran

ABS composed of ILs + Polysaccharides:

IL + Dextran + H2O at 298 K

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



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


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]


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)


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


• 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


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


DES seem to be much more toxic than the corresponding ILs


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


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 ≈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


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


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


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

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


PB27 PB29

Selective separation of dyes with reversible ABS

Sudan III PB27 PB29


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]


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

35 ºC: [N1120][C1CO2] (); [N1220][C1SO3] (); [N11[2(N110)]0]Cl (n); [N11[2(N110)]0][C1CO2] (●).


45ºC

Azocasein Citocrome C

EE%

[N11[2(N110)]0]Cl

[N11[2(N110)]0] [C1CO2]

95.3% 99.8% 100%

[N11[2(N110)]0][C1CO2] [N11[2(N110)]0][C1CO2]

25ºC

pH ≈ 8 pH ≈ 8 pH ≈ 4


0.0

0.5

1.0

1.5

2.0

2.5

0.0 0.5 1.0 1.5 2.0 2.5 3.0

[PPG

-400

] / (m

ol·k

g-1)

[PIL] / (mol·kg-1)Evaluation of temperature effect in the ternary phase diagram composed of [N11[2(N110)]0]Cl + PPG-

400 + water at 25 ºC (), 35 ºC (n) and 45 ºC (), and selective separation of dyes by a thermoreversible behavior.

25 ºC

35 ºC

45 ºC

25 ºC

35 ºC PPG-aqueous rich phase

PIL-aqueous rich phase


Back extractions and recycling of ILs

Caffeine extraction

from guaraná seeds

using aqueous

solutions of ionic

liquids


T = [65 , 85] ˚C;

Re

su

lts

R;

Response surface methodology:

Factorial planning 23 (T, R, C )

Constants

parameters

t = 30 min

d < 0.4 mm

C ( ≥ 1.5 M ).

Response

surface plots

and contour on

the extraction of

caffeine.

T vs R C vs R C vs T

Caffeine

extraction

9

Extraction of Caffein

Effect of butanol on

IL solutions?

21.93

0.09

13.75

20.99

18.92

1.92

16.89

7.24

17.68 17.69

0

5

10

15

20

25

[Caf

fein

e] /

(g.

L-1)

Recyclability

Best extraction solvents:

Chloroform;

Methylene chloride.

Butanol can be a good candidate to re-extract caffeine .

The IL solutions don’t lose their

extraction efficiency after the re-

extraction with butanol. substitute

Aim

R

es

ult

s

10

To choose organic solvent non-

miscible with water capable of re-

extracting caffeine from the IL

medium.

Concentration of caffeine after the liquid-liquid extraction

Aqueous solution of [C4mim]Cl at

the optimized operational conditions.

Reusability

Aim

R

es

ult

s

Recovery of caffein: reextraction

8,56

17,41

25,63

9,3487

17,8

0

5

10

15

20

25

30

[caf

fein

e]/

g. L

-1

Recovery of caffein: reextraction

0

50

100

150

200

250

0 5 10 15 20 25

[Van

illin

] / g

.L-1

[IL] in water / wt %

11

Solubility

up to

18-fold

Only water


http://upload.wikimedia.org/wikipedia/commons/c/c7/Vanillin2.svg

ABS

IL-rich phase

60 ⁰C

Filtration (0.45 μm) + water 84% dye recuperation

Sudan III

4 ⁰C

Filtration (0.45 μm)

Indigo Blue

76% dye recuperation

Dye recovery: antisolvent/ temperature

[P4441][CH3SO4] +

organic salt

syringic acid vanillic acid gallic acid

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

[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.


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.



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


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


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

• Process costs are related to IL recycling

𝑅𝑒𝑡𝑢𝑟𝑛

𝑘𝑔 𝑏𝑖𝑜𝑚𝑎𝑠𝑠= 𝐶𝑝𝑟𝑜𝑑 × $𝑝𝑟𝑜𝑑 − $𝑏𝑖𝑜𝑚 − 𝑉𝐼𝐿 × $𝐼𝐿 × 𝑟𝐼𝐿 𝑙𝑜𝑠𝑡 × 𝛼 + 𝛽

70

75

80

85

90

95

100

% R

10 wt % Al2(SO4)3 + 45 wt %IL

13 wt % Al2(SO4)3 + 45 wt %IL

16 wt % Al2(SO4)3 + 45 wt %IL

15 wt % Al2(SO4)3 + 40 wt %IL

2 wt % AlK(SO4)2 + 51 wt % IL

10 wt % Al2(SO4)3 + 45 wt % IL

13 wt % Al2(SO4)3 + 45 wt % IL

16 wt % Al2(SO4)3 + 45 wt % IL

15 wt % Al2(SO4)3 + 40 wt % IL

2 wt % AlK(SO4)2 + 51 wt % IL

Recovery

Recovery

70

75

80

85

90

95

100

R%

10 wt % Al2(SO4)3 +45 wt % IL

13 wt % Al2(SO4)3 +45 wt % IL

16 wt % Al2(SO4)3 +45 wt % IL

15 wt % Al2(SO4)3 +40 wt % IL

2 wt % AlK(SO4)2 +51 wt % IL

10 wt % Al2(SO4)3 + 45 wt % IL

13 wt % Al2(SO4)3 + 45 wt % IL

16 wt % Al2(SO4)3 + 45 wt % IL

15 wt % Al2(SO4)3 + 40 wt % IL

2 wt % AlK(SO4)2 + 51 wt % IL

Aqueous IL effluentIL rich current

Diluted salt solution

Concentrated salt solution

Water

Conceptual process

Catarina M. S. S. Neves, Mara G. Freire and João A. P. Coutinho RSC Advances 2 (2012) 10882-10890


Proof of concept


Proof of concept

[Pi(444)1][Tos]

S

IL

S

IL

SS

ILILIL-rich phase

Protein

Salt-rich phase

Recycling ionic liquids in ILTPPS

Enrique Alvarez-Guerra, Sónia P.M. Ventura, João A.P. Coutinho and Angel Irabien Fluid Phase Equilibria 371 (2014) 67–74


Alternatives to recover the ionic liquid:

a) No additional recovery steps are considered.

b) Extra salt is added to increase the salt mass fraction and to reduce DIL.

c) Vacuum evaporation is used to remove water from the salt-rich phase.



Alternative: b) Addition of extra salt:

o Curve zone: a higher fraction of the salt-rich phase would increase the total mass of the system increases.

o Constant zone: a higher fraction of the salt-rich phase would increase the overall salt concentration.

Increasing additions of extra salt



o Higher [LF]F values: a complete recovery of both ionic liquid and salt is achieved.

Alternative: c) Vacuum evaporation of water from salt-rich phase:

o Lower [LF]F values: desired concentrations cannot be reached due to the high water content of the feed stream.


Each path engenders new paths

Aqueous Biphasic Systems: Review

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