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Extended reserves | Clean refining | Fuel-efficient vehicles | Diversified fuels | Controlled CO2

Ionic Liquids : new solvents and technologyfor more environmently friendly processes

Hélène Olivier-BourbigouA Greener Chemistry for Industry

3 – 5 october 2007

from Research to IndustryIFP-Lyon : 630 persons50 PhD and post-doc

170 pilot units

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...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..)

• Ionic Liquids : an emerging new class of solvents

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PEvolution of Ionic Liquids : designer solvents

N NR2R1 N

R1

NR1 R2

+

[NRxH(4-x)]+ [PRxH(4-x)]+[SRxH(3-x)]+

Li+R3

R2

1rst generation : AlCl4-, Al2Cl7-, Al3Cl10

-

FeCl4-, Fe2Cl7-

CATIONS :large, organic

ANIONS

reactive to water 2nd generation : PF6

-, SbF6-, BF4

-

CF3SO3-, CF3CO2

-, (CF3SO2)2 N-

, (CF3SO2)3 C-

air and water stable

3rd generation : CH3CO2

-, C6H5SO3-

(RO)2PO2-, PO4

3- , free of halide ions HSO4

-, RSO4-, SO4

- -

BR4-, RCB11H11

-

eutectic mixture : chloline chloride + glycerol ...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

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

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Why Ionic liquids for "greener chemistry" ?Little/no vapor pressure : non-volatile, non-flammableThermal stability Liquid over large range of temperature Electric conductivityTuneable 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 wasteProcess intensification : separative catalysis, more economical and safer processNew chemistry : new selectivity, chirality

Ionic Liquids, Industrial Applications for Green Chemistry, Rogers R, Seedon K, Eds, ACS Symposium series 818, ACS, Washington, 2002Green Industtrial application of IL, NATO Science Series II; Mathematics, Physics andChemistry, Vol 92; Kluwer, Dordrech, 2003IL as Green Solvents: Progress and Prospects, ACS Symposium Series, 856; ACS; 2003Design of Sustainable Chemical Products : The Example of IL, Chem. Rev. 2007, 2183

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Selected Applications (pilot or industrial)Process Engineering/Separation

Extraction bio-molecules (Bioniqs)Extraction organosulfur from fuels (Degussa)

Entrainer in Extractive distillation (BASF)

Solvents Toxic gas storage an transport

(Air Products)

ElectrochemicalFuel cells

Li-ion Batteries (Creavis)Metal electroplating (Scionix)

BiotechnologySolvent for Cellulose extraction (BASF)

Synthesis & CatalysisProton scavenging (BASF)

MeOH carbonylation (Eastman)Oligomerization (IFP, Chevron)

Hydrosilylation (Degussa)Acid catalysis (IFP, Arkema)

Isobutane-butene alkylation (Petrochina)Ionic Liquids :

widely tunable propertiesLittle/no vapor pressureNon-flammable

Thermal stabilityElectric conductivityMultiphasic system....

Engineering fluidsPerformance Additives

High tech lubricants Plasticizers

Metal surface cleaning (Solvionic)

"New Frontiers for Ionic Liquids, C&EN, 2007, Vol 85, N°1, 23-26"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

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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 supportuse 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

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- EXAMPLE 1 -

________________________________________

DIMERISATION OF OLEFINS (C4 and C3)

From Homogeneous industrial DIMERSOL process to Biphasic DIFASOL process

Ionic Liquids : solvents and co-catalyst

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Oligomerization of olefinscatalyzed by Ni complexes

+ +Ni(II) + EtAlCl2

liquid phase, no solventno catalyst recyclecontinuous waste

production

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200 000t/an octenesraw material for alcohol synthesis used in plasticizer

manufacture

6%59%34%Dimersolhomogeneousindustrialprocess

- 2 à 3 réacteurs de 50 à 200 m3

- phase liquide, sans solvant- T = 40°C

- [Ni] et [Al] introduits en continu

- catalyseur usé vers traitement des eaux

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POligomerization of olefinscatalyzed by Ni complexes

+ +Ni(II) + EtAlCl2

liquid phase, no solventno catalyst recyclecontinuous waste

production

2

200 000t/an octenesraw material for alcohol synthesis used in plasticizer

manufacture

6%59%34%

active catalyst : ionic Ni species[H-Ni(II)olefin]+ [AlCl4]-

good decantationno IL lossno product contaminationlong IL lifetime (pilot 6 months)

why acidic chloroaluminates IL ?adjustable Lewis acidity, simple to preparedensity and viscosity of IL very differentfrom that of productsthe products are very weakly soluble in IL and vice-versa

Dimersolhomogeneousindustrialprocess

stabilized in IL withoutaddition of ligandIL : dual role of solvent and co-catalyst

transfer to acidic chloroaluminates

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)

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PSynthesis ofchloroaluminates

N NBuMe

+

H

Cl-+ AlCl3 AlCl4- Al2Cl7-

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

No by-products : atom efficient synthesismole AlCl3

T°C

20°C

-60°C

liquide

solidesolide

AlCl3EMICl

Phase Diagramm

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Synthesis des chloroaluminates

synthèse qui peut être étendue à d'autres sels métalliquesFeCl3, ZnCl2, CuCl....

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Butenes

Catalyst

toward washing anddistillation

section

Dimersol process* (homogeneous)

Difasol process* (biphasic)

Products

Reactants Recycle of the active Phase containing the catalyst

toward distillationsection

4 reactors of 120 m3

reactor of 50 m3

catalyst consumption divided by 10higher yield in dimers

20t/h feed rate

* Marketed by Axens, a subsidiary of IFP

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réactifs :butènes

butènes octènes

produits :octènes

[Ni]

les réactions consécutives des octènes sont défavorisées : leur miscibilitédans la phase liquide ionique plus faible que celle des butènes

phase organique

liquide ionique :- octènes très peu miscibles

dodécènes C12

C4

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Dimersol(4 reactors)

[Dimersol (1 reactor) + Difasol]Integrated Concept

Octenes yield (a) 68 % 75 %

Total Unit investment (b) Base : 100 95

Relative CAPEX per ton of octenes((b) / (a) ) 1.5 1.3

Total Utilities and Chemicals (c) Base : 100 92

Relative OPEX per ton of octenes((c) / (a) ) 1.5 1.2

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

Dimerization of butenes

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Selective dimerization of propylenefor 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)

Ni(II) + PR3 + base additive70-75 % dimethylbutene-1 (stable)75-80% hexenes/products

biphasic in chloroaluminates

[(oléfine)LNi-H]+ [A]-

NiCl2 2(PCy3) + EtAlCl260-65% dimethylbutenes75-80% hexenes/products

homogeneous

L = basic phosphine

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- EXAMPLE 3 -

________________________________________

HYDROFORMYLATION OF OLEFINS

Ionic Liquids : physical solvents

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oligomers

C4

C4

Dimersol X

Steam cracking ButadieneExtraction

SelectiveHydrogenation

Reactingiso-butene

FCC

C4 Raffinate-2 cut

octenesLPG

HydroformylationHydrogenation

iso-nonanols

PVC Plasticizers

MTBE

poly-iso-butene

(200 000 t/y)

Valorisation of C4 cut

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Olefin hydroformylation

CHALLENGES:1- Hydroformylation of long chain olefins (internal and branched)2- Good activity and selectivity3- Efficient catalyst recycling

Choice of the catalytic system :

1- Cobalt based system 2- Ionic liquids as solvents

pioneering work withRh/TPPMS at IFP

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

CHO

CHO

CHO+

CO/H2

[Co.]

N

CHO

CHO

CHO+

CO/H2

[Co.]

N

active catalystH-M(CO)4-xLxM = Co or Rh

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0,01

0,1

1

10

100

1000

5 6 7 8 9 10 11Chain length of the α -olefin

Solubility mmol / l

Solubility of olefins in ILs

H2O

Bu MeNN +

BF4-

1-hexene

1-decene

1-octene

HMI-

BMI-

BMPyrro-

BDMI-

-BF4-NO3

-PF6-SO3-CF3

-CF3COO-N(SO2-CF3)2

0

1

2

3

4

5

6wt % 1-hexene/IL

N N+

N N+ N+ N N+

☺ tuneable solubility of olefin in IL

☺ better solubility of olefins in IL than in water

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

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Recovery of Cobalt by oxidation-reduction(BASF process)HCoI(CO)4 + H+ + O2 --> CoII (CH3COO)2 -water soluble Co2+

- 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

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

HCoI(CO)4 + NaOH --> Na Co(CO)4

- water soluble Co- product separation by decantation

then re-acidification in presence of olefinsand 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

Industrial existing process :decobalting by chemical treatment

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Hydroformylation of 1-hexeneRecycling experiments with or without pyridine

1 2 3 4 5

S1S20,00

0,05

0,10

0,15

0,20

0,25

no ligandpyridine (2eq/Co)

CO/H2 consumption(mole)

1 2 3 4 5

S1S20,00

0,05

0,10

0,15

0,20

0,25

no ligandpyridine (2eq/Co)

CO/H2 consumption(mole)

0%

20%

40%

60%

80%

100%

Run 0 Run 1 Run 2 Run 3 Run 4

Sel. Lourds

Sel. nd.

Sel. Isom.

Sel. Hydro.

Sel. ol.

Sel. Ald.

Co2CO8 (0.21g, 0.62mmol); pyridine (L/Co=2); [BMI][NTf2] (6mL);

heptane (30mL); 1-hexene (15mL, 10.23g, 122mmol); 100 bar CO/H2 ; 130°C

Activity and recycling Selectivity to C7- aldehydes

IFP Patents: US6469216B2, US200330225303A1

N

- Conversion : 90 %- Aldehyde selectivity : 87 %- TOF : 102 h-1

- Several recycles no drop of conv.- No need of specially design ligand

ligand

N NMe Bu

+

BMI

(CF3SO2)2 N-

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PHydroformylation –New concept of Co recycling

OlefinCO/H2 « IL/Co » recycling

P=100 barT=130 °C

PT

P=1 atmT=25°C

Reaction:

HCo(CO)4 ispresent in both IL and organic

phase

Decobalting:

Convenient Pand T yield to cobalt free

organic phase

Decantation:

Separation of «Co/IL» and

organic phases for efficient

recycling

Ald.

[pyrH]+[Co(CO)4]-

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

HCo(CO)4 Co2CO8

pyridine

reaction section catalyst recycling

In presence of an organic Lewis base, Co catalyst forms ionic

species which are retained in theionic liquid phase

Regenartion of the active Cocatalyst can be made by

increasing T and P

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They may offer solutions to specific current problems of existingprocesses :

they can contribute in improving reaction yield and selectivitythey can stabilize the catalyst (increasing interest in nanoparticules)

the separation of the catalyst (and the solvent) and their recycling can be simplified, provideeconomic incentivesprocess intensification : separative catalysis, lower reactor volume....

Ionic liquids cannot probably be used with benefits in all catalyticprocesses...but some promising developements can be expected

base and acid catalysisbio-transformationsassociation 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 ultrasoundsbooster in the use of new feedstock (cellulose, lignocellusose, vegetable oils..)IL enable the synthesis of new materials (self organization of ILs)....

General concluding remarksPotentiel of Ionic Liquids

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Some issues and barriers

Industrial production and applications of ILs still limited : why ?Price of ILsLack of data on lifetime, recyclability and disposal of spent ILsLack of data on global process economyContamination of reaction products by ILsSafety Health Environmental issues : not intrinsically green solventsNew chemicals : REACH registration needed (>1t/an REACH)

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New generations of ionic liquids"Task-specific Ionic Liquids"

J. Davis, Chem. Lett. 2004, 33, 9, 1072

N(CH2)3CN

BF4

- stabilisation of nanoparticules

- introduction of a chirality

- extraction - CO2 capture

N N(CH2)nSO3HR1

H

+

CF3SO3-

- supported catalysts

- synthesis of porous nano materialsNNC(CH2)n (CH2)nC

OH

OO

HO

Cl

N N(CH2)nNH2R1

H

+

PF6-

N

S

Bu

NTf2 N N CH2COO

PF6

N N

Me O3S O

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

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

Dyson P. et al Chem. Eur. J. , 2006, 12, 4012.Sr

"Functional Design of Ionic Liquids", H. Ohno Bull. Chem. Soc. Jpn, 2006, 79, 11, 1665

"MOF"

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THANK YOUSome reviews on ILs

Catalysis in Ionic Liquids : Z. Zhang , Advances in Catalysis, 2006, 153-237Catalysis in Non-Aqueous-Ionic Liquid, in Multiphasic Homogeneous Catalysis, Wiley-VCH, Weinheim, 2005Organometallic in ionic liquids (special issue) J. Organomet. Chem. 2005, 690, 3489T. 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, 223P. Wasserscheid, W. keim, Angewnast. Chem. Int. Ed, 2000, 39, 3772Y. Chauvin, H. Olivier, Chemtech, 1995,