Post on 12-Feb-2017
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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
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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,