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INSTITUT FRANÇAIS DU PÉTROLE
"Ionic liquids in catalysis: some examples of developments"
Merck Ionic Liquids WorkshopMerck Ionic Liquids Workshop 11th October, 2005
Lyon, France
Christophe VALLÉE, Hélène OLIVIER-BOURBIGOUDepartment of Molecular Catalysis
IFP-Lyon
2
• From an industrial point of view, the best solvent is NO solvent
– solvent separation and recycling : energy demanding– possible contamination of the the reaction products– pressure for cleaner technologies....
• Why a solvent ?
– solubilization and stabilization of the active species– enhancement of reaction rates and selectivities– recycling of the catalyst
• biphasic reaction or • monophasic reaction and two-phase separation
• Which solvents ?
The solvent in catalytic reactions
3
Ionic liquids in catalysis : advantages
• Ionic liquids do not evaporate !– Containment is much easier than for volatile organic solvents.
• Large set of physico-chemical properties– adjustable miscibility with organic substrates (multiphasic catalysis)– tuneable solvation properties
• Liquid and suitable support for homogeneous catalysts– homogeneous catalyst immobilisation and recovery
• Ionic liquids can interact with solutes and catalytic intermediates– new solvent effect (IL=solvent): new or improved selectivity – promoter for the reaction (IL=“co”-catalyst) : higher activity – stabilization of active species (IL=ligand source) : longer catalyst lifetime
• Improvement of chemical processes– More efficient use of chemicals and catalysts; less waste.– Energy saving.
4
– Ni-catalyzed butene dimerisation
– Selective propene dimerisation
– Ni-catalyzed butadiene hydrocyanation
– Co olefin hydroformylation
• Some examples of recent developments in homogeneous catalysis
5
Ni-catalyzed Olefin Dimerization
6
The Industrial Dimersol IFP Process
First industrial application in 1980 (Japan)...
+ +
Ni(II) + EtAlCl2liquid phase, no solvent
2
200 000t/yr octenesraw material for alcohol synthesis used in plasticizer
manufacturing
6%59%34%
7
– Advantages: • mild reaction conditions (40-45°C)• process flexibility
– Limitations:
• Olefin conversion dependent on its concentration
• Dimer selectivity dependent on monomer conversion• Catalyst is neutralised at the output of the reactor although still active
– use of the catalyst is not optimum– continuous catalyst carry over and waste production
The Industrial Dimersol IFP Process
First industrial application in 1980 (Japan)...
+ +
Ni(II) + EtAlCl2liquid phase, no solvent
2
200 000t/yr octenesraw material for alcohol synthesis used in plasticizer
manufacturing
6%59%34%
8
The Homogeneous Industrial Dimersol Process
+ +
Ni(II) + EtAlCl2liquid phase, no solvent
2
200 000t/an octenesraw material for alcohol synthesis used in plasticizer
manufacture
6%59%34%
homogeneous catalyst : how to get rid of its limitations ?
NiX2 + EtAlCl2 [olefinNi-Et]+ [AlX2Cl2]-olefin
[olefinNi-H]+ [AlX2Cl2]-
ionic active species
generated in-situ by reaction of Ni(II)
salt + alkylaluminium derivative
Liquid-liquid biphasic catalysis
Which solvent ?
9
The choice of the ionic liquid : the organochloroaluminates
NiCl2 + « Et2Al2Cl5 » [LNiEt]+[EtAlCl3]
- + AlCl4-
active speciesthe chloroaluminate IL acts both as solvent and Ni-activator
Acidic Ionic Liquid
ACTIVITY for olefin dimerization in presence of NiX2
Cl-/Al (molar) <1
Et2Al2Cl5-
EtAlCl2EtAlCl3-
Et3Al3Cl7-
Basic Ionic Liquid
Formation of NiCl42-
NON-ACTIVE
Cl-/Al (molar) >1
EtAlCl3-
Cl-
NiCl2
1-Butyl-3-Methylimidazolium chloride + EtAlCl2
10
Olefin dimerisation in ionic liquid
Laboratory test
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)
ionic liquid + Ni
pressure reducer
butene gaz
reaction start-up with stirring
liquid butene
11
Olefin dimerisation in ionic liquid
Laboratory test
reaction evolution : formation of a liquid phase not miscible in the IL
magnetic stirring
12
Olefin dimerisation in ionic liquid
Laboratory test
decantation of the two phases
13
Olefin dimerisation in ionic liquid
Laboratory test
separation of the product phase
14
Olefin dimerisation in ionic liquid
Laboratory test
separation of the product phase
15
Olefin dimerisation in ionic liquid
Laboratory test
T°C
reaction starts again with the same ionic liquid containing Ni-catalyst
16
0
100
200
300
400
500
600
700
0 100 200 300 400 500 600
Temps (min)
Pro
pylè
ne c
on
vert
i (g
)
EtAlCl2:BMIC (1,2:1) molten salts
EtAlCl2:AlCl3:BMIC (0,26:1,2:1)
BMIC + EtAlCl2 (1:1,2)
Dimerization of propene with Ni(II) : lab results
rapid deactivation
2[HNiL]+[EtAlCl3]- 2 « NiHClL » + Et2Al2Cl4
inactif
extrait dans la phase organique
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)
17
0
100
200
300
400
500
600
700
0 100 200 300 400 500 600
Temps (min)
Pro
pylè
ne c
on
vert
i (g
)
EtAlCl2:BMIC (1,2:1) molten salts
EtAlCl2:AlCl3:BMIC (0,26:1,2:1)
BMIC + EtAlCl2
BMIC + AlCl3 + EtAlCl2
Dimerization of propene with Ni(II)
18
- representative butene feedstock, no fresh IL added
- run was deliberately stopped after more than 5 months
operation
- IL lifetime and long term stability was demonstrated
Products
Butenes Active phase
containing catalyst
Reactant
Products
Ni
Continuous Flow Pilot Plant Demonstration
F. Favre, A. Forestière, F. Hugues, H. Olivier-Bourbigou, J.A. Chodorge, Oil Gaz European
Magazine, 83, 2/2005
19
Benefits of biphasic dimerizationOctene selectivity
70
80
90
100
50 60 70 80 90 100
Butene conversion (%)
Oct
enes
sel
ectiv
ity (%
)
Dimersol (3 reactors)
industrial results
Difasol (pilot results)
Feed : 75% butenes, isobutene<2%
20
butenes
butenes octenes
octenes
[Ni]
organic phase
ionic liquid :
very low octene solubility
dodecenes C12
C4
consecutive side-reactions are minimized
Benefits of biphasic dimerization
21
Dimersol Difasol Benefits Difasol
Octeneproduction
9.9 t/h 10.2 t/h increased
Relative Niconsumption
1 0.16 reduced
Reactor size 4*120 m3 50 m3 reduced
Benefits of biphasic dimerization
Feed : C4 Raffinate-2, 75% butenes, 20 tons per hour
decrease catalyst consumption decrease reactor volume
22
Synthesis of Dimethylbutenes
23
Dimethylbutenes : key intermediates for fine chemicals
CH2=CH-CH3 CH2=C-CH-CH3
CH3
CH3
CH3-C=C-CH3
CH3
CH3
DMB-1 DMB-2
O
/t-BuCl AlCl3
CH3COCl AlCl3
CH3
CH3
CH3
CH3
CO2CHCN
OH
insecticideDanitol TM
(by Sumitomo)
musk perfumeTonalid TM
24
Industrial production by Sumitomo (1983)
Ni homogeneous catalyst
high 2,3-DMB selectivity (>70%/total hexenes)
elaborate catalyst formula with basic PR3
toluene as solvent
solvent separation needs an efficient distillation column
no catalyst recycling (destruction with NaOH)
The simplest way of DMB synthesis : Selective propene dimerization
+ +2
6% 72% 22%
with no ligand : no regioselectivitywith PR3 ligand : regioselectivity
> 70%
[Ni]
25
Propene dimerization in chloroaluminates
Solvent : Acidic chloroaluminate (BMIC : AlCl3 : EtAlCl2)
* after 1 hour reaction time; P(Cy)3 = tricyclohexylphosphine
TOF (Kg/g Ni.h) Dimers (%) 2,3-DMB/C6*(%)NiCl2, Pyridine 6 80-82 7NiCl2, P(Bu)3 8 85-90 32NiCl2, P(iPr)3 12 80-85 83NiCl2, P(Cy)3 8 80-85 83
Phosphine effect
Same Phosphine effect is observed in chloroaluminate as in homogeneous system.
26
Competition for the phosphine between «soft » Ni and « hard » AlCl3
[PR3.NiR]+A- + Al2Cl7- [NiR]+A- + AlCl3.PR3 + AlCl4
-
regioselective non regioselective
0
10
20
30
40
50
60
70
80
0 2 4 6 8 10
Time (h)
2,3
-Dim
eth
ylb
ute
nes (w
t%)
NiCl2.2PCy3
Propene dimerization in chloroaluminates
27
P N
P-N
0
20
40
60
80
100
0 2 4 6 8 10
Time (h)
2,3-
Dim
eth
ylb
ute
nes
(w
t%)
NiCl2, 2Pi-Pr3
NiCl2, 2P-N
toluene
NiCl2, 2PCy3
aromatic hydrocarbon
Stabilisation of DMB selectivity by addition of small amounts of a weak organic competitive base
[PR3.NiR]+A- + Al2Cl7- + B [PR3.NiR]+A- + AlCl3.B + AlCl4
-
Selective propene dimerization in chloroaluminates
28
0
10
20
30
40
50
60
70
80
90
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
M4P-1
2.3DMB-1
M4P2C
M4P2T
M2P1
H3
H2T
M2P2
H2C
2.3DMB-2
60 hours
DMB-1
Continuous flow propene dimerization in chloroaluminates 2,3-DMB-1 selectivity versus time
• Ionic liquid : 15 mL• propene : atm P • duration : 60 hours• production : 11 liters of products• C6 selectivity : 80-81%/products• 2,3-DMB-1 selectivity : 70-80%/C6
29
oligomerizationC2---> C4-C6C3---> C6C4 ---> C8C5---> C10
acid catalysisR+ R
+
IL
[RNi]+A-
Al2Cl7-
H+
Examples of applications of ionic liquids
in chloroaluminates
30
[RNi][RNi]++AA--
hydrocyanation
oligomerisationC2---> C4-C6C3---> C6C4 ---> C8C5---> C10
acid catalysisR+ R
+
ILAl2Cl7
-
H+
Ni
Examples of applications of ionic liquids
in chloroaluminates
hydroformylation
selectivehydrogenation
IL
[H2RhL2]+A-
HRh(CO) L3
R R
CHO
R CHO+
in non-chloroaluminates
PF6-, BF4
- , CF3SO3-,
(CF3SO2)2 N- ...
HCo(CO)3L
metathesis of functional olefins
R2
R1
2R1
R1
R2
R2
+
Ru
HCNNC
CN
31
Ni-catalyzed Butadiene Hydrocyanation
LCOMS
32
CNCN
2M3BN 3PN
NCCN
HCNNi(0)
Phosphite
HCNNi(0)
PhosphiteLewis acid
Ni(0)Phosphite
Adiponitrile
Nylon 6 and Nylon 6,6
Hydrocyanation of butadiene into adiponitrile
Industrial catalyst:
homogeneous nickel(0)-phosphite complexes
LCOMS
33
CNCN
2M3BN 3PN
NCCN
HCNNi(0)
P ligand
HCNNi(0)
P ligandLewis Acid
Ni(0)P ligand
Adiponitrile
Hydrocyanation
LCOMS
Model Reaction
Catalytic system: Ni(cod)2 + PPh3 + substrate + ionic liquid
34
Hydrocyanation
LCOMS
Selection of the ionic liquid
Conversion as a function of the ionic liquid
0
20
40
60
80
100
BF4
CF3
SO
3
PF6
TF2N
BF4
CF3
SO
3
PF6
TF2N
Non
e io
nic
liqui
d
Con
vers
ion
(in %
)
NN
H
Bu Me
[BMI]
NN
Me
Bu Me
[BMMI]
Catalytic system: Ni(cod)2 + PPh3 + substrate + ionic liquid
C. Vallée et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 71–81
35
Hydrocyanation
LCOMS
NiL4
CNNC
NiL3
CNNiL2
NC
NiL2
NiL2CN
-L +L
LL
charge free active species
need to design special ligands to anchor the catalyst in the
ionic phase
36
Hydrocyanation
LCOMS
A wide range of ionic phosphorus ligands
O
P
O
O NN
BF4-
O
N
N
P
TF2N-
3
Ph2P
SO2Na
Ph2P
SO3Na
Ph2PO SO2Na
Ph2P N N
PF6-
N
NPPh2
Et
Me
BF4-
PhP
HN
NH2
NMe2
Br-
2
PHOSPHINES
PHOSPHITES
Advanced Synthesis and Catalysis (2005) accepted
37
Hydrocyanation
LCOMS
No trace of nickel or phosphorus(detection limit = 5 ppm)
Recycling experiments
0
20
40
60
80
100
Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5
TO
N
Ph2P
SO3Na
+ Ni(cod)2 + substrate + [BMMIM][NTf2]
38
Co-catalyzed Olefin Hydroformylation
39
1st GENERATION
H Co (CO)4
200 -300 bar
150 - 180 °C
Homogeneous catalysis
Basic or acidicextraction of Co
BASF, EXXON.
SHELL (PBu3).
2nd GENERATION
H Rh (CO) (PR3)3
<50 bar
<120 °C
Homogeneous catalysis
Distillation
UCC
Celanese Corp.
3rd GENERATION
H Rh (CO) (TPPTS)3
50 bar
120 °C
Biphasichomogeneous catalysis
Decantation
Ruhrchemie /
Rhône-Poulenc.Olefins C4Olefins C4 PropenePropene
R1 R3
CHO
R4
R5 CHO
H2 / CO
catalyst
branched linear
R2
Olefin hydroformylation: industrial processes
Biphasic catalysis
40
H2
O
O
O
O
O
OR
OR
+ double bond position isomers
HydroformylationHydrogenation
CO/H2
Isononanols
Di-isononylPhtalates
water
Dimérisation(Dimersol X)
Olefin hydroformylation
the challenge :
to develop an efficient process
to hydroformylate higher (internal) olefins
with an efficient and simple catalyst recovery
41
Olefin hydroformylation : why ionic liquids ?
better solubility of olefins in IL than in water
0,01
0,1
1
10
100
1000
5 6 7 8 9 10 11
Carbon length of alpha olefin
Solubility of olefins in mmol/l
octene-1
hexene-1
decene-1
BMI-BF4
water
-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 olefins in IL
partial co-miscibility of ionic liquids and reaction products loss of ionic liquid (and catalyst) in the products
F. Favre, H. Olivier-Bourbigou, D. Commereuc, L. Saussine, Chem. Commun. 1360, (2001)
42
Co2(CO)8 2 HCo(CO)4 active cobalt catalyst : neutral
H2/CO
- Nature of the active species :
- In presence of an organic base, formation of ionic species
2 ([Co(base)6]2+[Co(CO)4]-2) 6 ([baseH]+[Co(CO)4]-)
2 ([Co(base)6]2+[Co(CO)4]-2) + 8 CO3 Co2(CO)8 + 12 bases
these ionic species have a good affinity for ionic liquids
Olefin Hydroformylation : cobalt catalyst
H2/CO
- base
H2/CO
- base6 HCo(CO)4
43
CO/H2
Cobalt catalyzed Hydroformylation of olefins
CO/H 2
Reaction
Produits
Ionic Liquid+ cobalt
P(CO/H2)
CO/H2 CO/H 2
Cobalt Recovery Separation
HCo(CO)4 [Co(base)x ]2+ 2[Co(CO)4
[baseH]+[Co(CO)4]-
+ base
[Co(base)6]+[Co(CO)4]2-
CO/H2
olefins
possible
addition
of
Co2(CO)8
+ base
T and
ionic liquid recycle
the base may help in the generation of the active Co catalyst simple cobalt recovery no by-product generation
44
Cobalt catalyzed 1-hexene hydroformylation : results
0
10
20
30
40
50
60
70
80
Run 0
Run 1
Run 2
Run 3
Run 4
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.
- conversion : > 98%- aldehyde selectivity : 75-82 %- recycling of Co « relatively simple »- no need of specially design ligand
SC
F
F F
O
OS C
F
FF
O
NO
-
[N(Tf)2]-
N
N
Me
Bu
+
[BMI]+
mol
H1=
/ m
ol C
o / h
N
- ligand : L/Co=2
- ionic liquid : 6 mL
- substrate : hexene-1 : 15 mL- (co-solvent) heptane : 30 mL
T = 130°C, P = 100bars
Co
nve
rsio
n
Se
lect
ivity
45
• Industrial applications:– Some processes using IL have already been industrialized – Ionic liquids are now commercialised and available on ton scale
• Better knowledge of their physico-chemical properties
• A lot of references : more than 20 chemical reactions have been investigated using ionic liquids ...
– Reviews/books :• Multiphasic Homogeneous Catalysis, Wiley-VCH, Weinheim, 2005
• 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.
Ionic Liquids in Catalysis
46
• Ionic liquids probably cannot be used with benefits in all catalytic processes
• For some specific reactions, they present significant advantages
– they can contribute in improving reaction yield and selectivity
– they can stabilize the catalyst
– the separation of the catalyst (and the solvent) and their recycling can be simplified
– the reactor volume can be lowered
Concluding remarks