Extended reserves

Clean refining

Fuel-efficient vehicles

Diversified fuels

Controlled CO2

Ionic Liquids : new solvents and technology for more environmently friendly processes
Hlne Olivier-Bourbigou A Greener Chemistry for Industry 3 5 october 2007

IFP-Lyon : 630 persons

IFP

from Research to Industry

50 PhD and post-doc 170 pilot units

...the need for alternative solvents and technology

Organic reactions, catalytic processes (and work-up), extraction technologies require the development of alternative new solvents
why ?
safety issues and environmental concerns (most organic solvents are "VOC") increase in environmental awardness and evolution of the regulation (REACH)

What Alternatives ?
Solventless option (often used in refinery and petrochemistry) New solvents, more efficient and cleaner technology
Need to take into account the entire life cycle of the solvent Environmental AND practical benefits, AND economical viability

Water, fluorous fluids, supercritical fluids (ethane, propane, CO2..)

IFP

Ionic Liquids : an emerging new class of solvents

Evolution of Ionic Liquids :

designer solvents
CATIONS :
large, organic
R1 N
+

[NRxH(4-x)]+

[SRxH(3-x)]+
R2

[PRxH(4-x)]+

R3

R2

N R1 R2

- comprising only ions - low melting point (less than 100 C)

ANIONS
reactive to water

Li+
1rst generation :

R1

AlCl4-, Al2Cl7-, Al3Cl10FeCl4-, Fe2Cl7-

2nd generation :
PF6-, SbF6-, BF4-

air and water stable

3rd

generation :

CH3CO2-, C6H5SO3(RO)2PO2-, PO43- , HSO4-, RSO4-, SO4- BR4-, RCB11H11eutectic mixture : chloline chloride + glycerol
IFP

CF3SO3-, CF3CO2-, (CF3SO2)2 N- , (CF3SO2)3 C-

free of halide ions

...toward biodegradable IL

"Physical Properties of ILs : Database and Evaluation" (588 ionic liquids) S. Zhang et al. J. Phys. Chem. Ref. Data, 2006, 35, 4, 1475

Why Ionic liquids for "greener chemistry" ?

Little/no vapor pressure : non-volatile, non-flammable Thermal stability Liquid over large range of temperature Electric conductivity Tuneable solvating properties : density, viscosity, hydrophobicity, solvating properties.... Now, easy to buy and simple to prepare
ILs : Complex solvents with multiple type of interactions Green by enhanced process performances... Multiphasic catalysis : better reaction yield, catalyst recycle, less catalyst waste Process intensification : separative catalysis, more economical and safer process New chemistry : new selectivity, chirality
Ionic Liquids, Industrial Applications for Green Chemistry, Rogers R, Seedon K, Eds, ACS Symposium series 818, ACS, Washington, 2002 Green Industtrial application of IL, NATO Science Series II; Mathematics, Physics and Chemistry, Vol 92; Kluwer, Dordrech, 2003 IL as Green Solvents: Progress and Prospects, ACS Symposium Series, 856; ACS; 2003 Design of Sustainable Chemical Products : The Example of IL, Chem. Rev. 2007, 2183

IFP

Selected Applications (pilot or industrial)

Synthesis & Catalysis
Proton scavenging (BASF) MeOH carbonylation (Eastman) Oligomerization (IFP, Chevron) Hydrosilylation (Degussa) Acid catalysis (IFP, Arkema) Isobutane-butene alkylation (Petrochina)

Process Engineering/Separation
Extraction bio-molecules (Bioniqs) Extraction organosulfur from fuels (Degussa) Entrainer in Extractive distillation (BASF)

Ionic Liquids :
widely tunable properties
Little/no vapor pressure Non-flammable Thermal stability Electric conductivity Multiphasic system....

Solvents
Toxic gas storage an transport (Air Products)

Engineering fluids Performance Additives

High tech lubricants Plasticizers Metal surface cleaning (Solvionic)

Electrochemical
Fuel cells Li-ion Batteries (Creavis) Metal electroplating (Scionix)

Biotechnology
Solvent for Cellulose extraction (BASF) "New Frontiers for Ionic Liquids, C&EN, 2007, Vol 85, N1, 23-26
IFP

"Catalysis in Ionic Liquid", C. Zhang, Progress in Catal. 2006, 153-237 R. Rodgers et al Science, 2003, vol 302, p 31; Chemical & Engineering News, 2006, 84, 14

Ionic Liquids and Catalysis : what can we expect ?

"Solvent and co-catalyst" :
the ionic liquid plays a dual role of catalyst and solvent
example 1 : Ni-catalyzed oligomerization (pioneering work at IFP)

"Physical" solvent : catalyst support

use to immobilize and recycle homogeneous catalyst
example 2 : hydroformylation

"Chemical" Solvent :
example 3 : Acid catalysis

Solvent and "ligand" :

the ionic liquid coordinates on the active metal center
example 4 : olefin dimerization (carbene formation), nanoparticle stbilization

IFP

- EXAMPLE 1 ________________________________________ DIMERISATION OF OLEFINS (C4 and C3) From Homogeneous industrial DIMERSOL process to Biphasic DIFASOL process Ionic Liquids : solvents and co-catalyst

IFP

Oligomerization of olefins catalyzed by Ni complexes

2 + +

34% 6% Ni(II) + EtAlCl2 liquid phase, no solvent 200 000t/an octenes no catalyst recycle raw material for alcohol synthesis used in plasticizer continuous waste manufacture production

59%

Dimersol
homogeneous industrial process

- phase liquide, sans solvant - T = 40C

- 2 3 racteurs de 50 200 m3

IFP

- [Ni] et [Al] introduits en continu

- catalyseur us vers traitement des eaux

Oligomerization of olefins catalyzed by Ni complexes

2 + +

34% 6% Ni(II) + EtAlCl2 liquid phase, no solvent 200 000t/an octenes no catalyst recycle raw material for alcohol synthesis used in plasticizer continuous waste manufacture production

59%

Dimersol
homogeneous industrial process

active catalyst : ionic Ni species [H-Ni(II)olefin]+ [AlCl4]transfer to acidic chloroaluminates stabilized in IL without addition of ligand IL : dual role of solvent and cocatalyst

why acidic chloroaluminates IL ? adjustable Lewis acidity, simple to prepare density and viscosity of IL very different from that of products the products are very weakly soluble in IL and vice-versa good decantation no IL loss no product contamination long IL lifetime (pilot 6 months)

IFP

Y. Chauvin, B. Gilbert, I. Guibard, J. Chem. Soc. Chem. Commun. 1715 (1990) Y. Chauvin, S. Einloft, H. Olivier, Ind. Eng. Chem. Res. 34 (4), 1149 (1995)

Synthesis of chloroaluminates
TC

Phase Diagramm

EMICl

AlCl3

liquide 20C
solide solide

-60C

mole AlCl3 No by-products : atom efficient synthesis

N Me
IFP

ClBu

AlCl3

AlCl4-

Al2Cl7-

J.S. Wilkes, J.A. Levisky, R.A. Wilson and C.L. Hussey, Inorg. Chem. 21 (1982) 1263-1264.
10

Synthesis des chloroaluminates

synthse qui peut tre tendue d'autres sels mtalliques FeCl3, ZnCl2, CuCl....

11

IFP

Dimersol process* (homogeneous)

4 reactors of 120 m3 Catalyst 20t/h feed rate Butenes
toward washing and distillation section

Difasol process* (biphasic)

reactor of 50 m3 Products
toward distillation section

catalyst consumption divided by 10 higher yield in dimers Reactants

IFP

Recycle of the active Phase containing the catalyst

* Marketed by Axens, a subsidiary of IFP

12

ractifs : butnes

produits : octnes

phase organique

butnes

[Ni]
octnes
C4 dodcnes C12

liquide ionique :
- octnes trs peu miscibles

les ractions conscutives des octnes sont dfavorises : leur miscibilit dans la phase liquide ionique plus faible que celle des butnes

13

IFP

Dimerization of butenes
Dimersol [Dimersol (1 reactor) + Difasol] (4 reactors) Integrated Concept Octenes yield (a) Total Unit investment (b) Relative CAPEX per ton of octenes ((b) / (a) ) Total Utilities and Chemicals (c) Relative OPEX per ton of octenes ((c) / (a) ) 68 % Base : 100 1.5 Base : 100 1.5 75 % 95 1.3 92 1.2

IFP

improved octene yield 15% save on relative CAPEX 20% save on relative OPEX

14

Selective dimerization of propylene for fine chemistry

2 + +

6%

72%

22%

with no ligand : no regioselectivity

2,3- dimethylbutenes :
intermediates in fine chemistry :
industrial process from Sumitomo (homogeneous Ni catalyst, toluene as solvent) DMB-1 : precursor for musk (TonalidTM) or DMB-2 : precursor for insecticide (DanitolTM)

[(olfine)LNi-H]+ [A]L = basic phosphine biphasic in chloroaluminates

homogeneous NiCl2 2(PCy3) + EtAlCl2 60-65% dimethylbutenes 75-80% hexenes/products Ni(II) + PR3 + base additive 70-75 % dimethylbutene-1 (stable) 75-80% hexenes/products

15

IFP

- EXAMPLE 3 ________________________________________ HYDROFORMYLATION OF OLEFINS Ionic Liquids : physical solvents

16

IFP

Valorisation of C4 cut
Steam cracking C4 Butadiene Extraction C4
MTBE oligomers poly-iso-butene

FCC

Selective Hydrogenation Reacting iso-butene

C4 Raffinate-2 cut

(200 000 t/y)

PVC Plasticizers

Dimersol X
LPG

iso-nonanols

octenes
17
IFP

Hydroformylation Hydrogenation

Olefin hydroformylation
CHALLENGES: 1- Hydroformylation of long chain olefins (internal and branched) 2- Good activity and selectivity 3- Efficient catalyst recycling

CO/H2

CHO + CHO CHO

[Co.] active catalyst H-M(CO)4-xLx M = Co or Rh N

pioneering work with Rh/TPPMS at IFP

Y. Chauvin, H. Olivier, Angew. Chem. Int. Ed., 1995, 34, 2698.

Choice of the catalytic system : 1- Cobalt based system 2- Ionic liquids as solvents

18

IFP

Solubility of olefins in ILs

Solubility mmol / l 1000
N

+ N

tuneable solubility of olefin in IL

Me

100 10 1

Bu

BF4wt % 1-hexene/IL

1-hexene 1-octene 1-decene

6 5 4 3 2 -N(SO2-CF3)2 -CF3COO -SO3-CF3 -PF6 -NO3
BM H Py rro -

0,1 0,01
5 6

H 2O
Chain length of the -olefin
7 8 9 10 11

1 0

I-

-BF4
BD M I-

I-

better solubility of olefins in IL

than in water
IFP

N+

19

F. Favre, H. Olivier-Bourbigou, D. Commereuc, L. Saussine, Chem. Commun. 1360, (2001)

BM

Industrial existing process : decobalting by chemical treatment

Recovery of Cobalt by oxidationreduction (BASF process)
HCoI(CO)4 + H+ + O2 --> CoII (CH3COO)2 water soluble Co2+
- product separation by decantation

Recovery of Cobalt by re-acidification (Ugine-Kuhlman)

HCoI(CO)4 + NaOH --> Na Co(CO)4
- water soluble Co - product separation by decantation

then concentration and regeneration of the active HCo(CO)4 under CO/H2 Co2+ + CO + H2 --> HCo(CO)4
decomposition of Co active catalyst via oxidation make-up are chemical consuming
IFP

then re-acidification in presence of olefins and CO/H2

Na Co(CO)4 + H2SO4 --> HCo(CO)4+ Na2SO4

catalyst separation and make-up must ensue in pressurized reactors formation of Na2SO4 by-products

20

Hydroformylation of 1-hexene Recycling experiments with or without pyridine

CO/H 2 consumption (mole) 0,25 0,20 0,15 0,10

Activity and recycling

Selectivity to C7- aldehydes

ligand

100% 80% 60%

Sel. Lourds Sel. nd. Sel. Isom. Sel. Hydro. Sel. ol. Sel. Ald.

N
0,05 0,00 1 2 3 4 S2 pyridine (2eq/Co) S1 no ligand 5

40% 20% 0% Run 0 Run 1 Run 2 Run 3 Run 4

Co2CO8 (0.21g, 0.62mmol); pyridine (L/Co=2); [BMI][NTf2] (6mL); heptane (30mL); 1-hexene (15mL, 10.23g, 122mmol); 100 bar CO/H2 ; 130C (CF3SO2)2 NN Me
+

- Conversion :
Bu

BMI
IFP

90 % Aldehyde selectivity : 87 % TOF : 102 h-1 Several recycles no drop of conv. No need of specially design ligand

21

IFP Patents: US6469216B2, US200330225303A1

Hydroformylation New concept of Co recycling

P=100 bar T=130 C P T P=1 atm T=25C Ald.

Olefin CO/H2 Reaction: HCo(CO)4 is present in both IL and organic phase

IL/Co recycling Decobalting: Convenient P and T yield to cobalt free organic phase Decantation: Separation of Co/IL and organic phases for efficient recycling

In presence of an organic Lewis base, Co catalyst forms ionic species which are retained in the ionic liquid phase Regenartion of the active Co catalyst can be made by increasing T and P

HCo(CO)4 Co2CO8
pyridine
IFP

[pyrH]+[Co(CO)4][Co(pyr)6]+[Co(CO)4]2-

reaction section

catalyst recycling

22

General concluding remarks Potentiel of Ionic Liquids

They may offer solutions to specific current problems of existing processes :
they can contribute in improving reaction yield and selectivity they can stabilize the catalyst (increasing interest in nanoparticules) the separation of the catalyst (and the solvent) and their recycling can be simplified, provide economic incentives process intensification : separative catalysis, lower reactor volume....

Ionic liquids cannot probably be used with benefits in all catalytic processes...but some promising developements can be expected
base and acid catalysis bio-transformations association of ILs and scCO2 (for separation processes) capture and/or transformation of CO2 enantioselective synthesis (chiral solvents ?) use of ILs in combination with microwaves or ultrasounds booster in the use of new feedstock (cellulose, lignocellusose, vegetable oils..) IL enable the synthesis of new materials (self organization of ILs)....

23

IFP

Some issues and barriers

Industrial production and applications of ILs still limited : why ?

Price of ILs Lack of data on lifetime, recyclability and disposal of spent ILs Lack of data on global process economy Contamination of reaction products by ILs Safety Health Environmental issues : not intrinsically green solvents New chemicals : REACH registration needed (>1t/an REACH)

24

IFP

New generations of ionic liquids

"Task-specific Ionic Liquids"
J. Davis, Chem. Lett. 2004, 33, 9, 1072
R1 N
+

(CH2)nNH2

- extraction
- CO2 capture - stabilisation of nanoparticules - introduction of a chirality

P. Dyson et al. Chem. Eur. J. 2006, 12, 2122

PF6-

(CH2)3CN BF4

S N Bu

NTf2

PF6 N N CH COO 2

N Me O3S O

R1

(CH2)nSO3H

- supported catalysts

CF3SO3-

O HO C(CH2)n N

Cl N (CH2)nC

O OH

- synthesis of porous nano materials Sr "MOF"

Z.
IFP

Fei et al, Chem. Eur. J., 2004, 10, 4886

Dyson P. et al Chem. Eur. J. , 2006, 12, 4012. "Functional Design of Ionic Liquids", H. Ohno Bull. Chem. Soc. Jpn, 2006, 79, 11, 1665

25

THANK YOU
Some reviews on ILs
Catalysis in Ionic Liquids : Z. Zhang , Advances in Catalysis, 2006, 153-237 Catalysis in Non-Aqueous-Ionic Liquid, in Multiphasic Homogeneous Catalysis, Wiley-VCH, Weinheim, 2005 Organometallic in ionic liquids (special issue) J. Organomet. Chem. 2005, 690, 3489 T. Welton, Coord. Chem. Rev. 2004, 248, 2459. P. Wasserscheid, T. Welton, Ionic Liquids in Synthesis, Wiley-VCH, Weinheim 2003. H. Olivier-Bourbigou, L. Magna, J Mol. Catal. A: Chemical, 2002, 182-183, 419. A. H. Azizov, Process of Petrochemistry and oil refining, 2002, 8, 1. J. Dupont, R. F. de Souza, P. A. Z. Suarez, Chem. Rev., 2002, 102, 3667. C. M. Gordon, Appl. Catal. A: General, 2001, 222, 1-2, 101. R. Sheldon, Chem. Commun., 2001, 23, 2399. J.D. Holbrey, K. Seddon, Clean Prod. Proc. , 1999, 223 P. Wasserscheid, W. keim, Angewnast. Chem. Int. Ed, 2000, 39, 3772 Y. Chauvin, H. Olivier, Chemtech, 1995,

26

IFP