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LCC

Applications of the Homogeneous


Catalysis in Industry

Philippe KALCK

Laboratoire de Chimie de Coordination, UPR-CNRS 8241


Equipe de Catalyse et Chimie Fine
ENSIACET Institut National Polytechnique de Toulouse

Camerino, August 9th 2012


LCC
Catalysis
[cat]
REACTANTS PRODUCTS
Solvent, T, P
Energy

Catalytic system
Ea

reactants
G
products

Reaction coordinate
2
LCC

Main problems to solve:

 Produce selectively a given product,

 Maintain low costs along the process,

 Start from accessible commodity raw materials,

 Reach the highest atom economy,

 Recycle efficiently the catalyst.

3
LCC
SELECTIVITY, why?: by-products control

Industry Capacities kg by-products /


Tons/year kg product
Basic products 104 - 106 <1-5

Fine chemicals 102 - 104 5 - 50

Pharmaceuticals 10 - 103 10 -25, sometimes


until 100

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LCC

Top 30 of chemical companies

U.E.
U.S.A. Japan Others

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LCC

I-1. Synthesis of acetic acid

Carbonylation of methanol

Catalysts: Rh, Ir

Main producers: BP, Celanese

World production: 9 millions Tons/year


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LCC
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LCC
Various acetic acid processes and market share

9M Tons/y

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LCC
Industrial synthesis of acetic acid

Process Catalyst Conditions Yield in CH3OH

Carbonylation of 180-220 C
[Rh] or [Ir] 99%
methanol 30 - 40 bar
Acetaldehyde 50-60 C
Mn or Co acetate 95%
oxidation 1 bar
Direct oxidation 150-160 C
Pd/Cu/HPA 87%
of ethylene 80 bar
Oxidation of 150-230 C 50% (n-butane)
Mn or Co acetate
hydrocarbons 50 - 60 bar 40% (naphtha)

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LCC
Numerous applications

Acetic anhydride for production of cellulose acetate (cigarettes


filter-tips) and aspirine

13%
numerous niche markets VAM: CH2=CH(OCOMe)

11% polymerisation VAM:


resins and emulsions for
44% painting, adhesives,
Various acetates as textiles, paper, films
solvents for paints, inks
14% and chewing gum,

18%

HOOC-Ph-COOH

Terephtalic acid: polyethylene


terephtalate for bottles and
polyester fibers
10
LCC
2010 acetic acid production

 Worldwide production ~ 9 106 Tons/year


annual growth ~ 4%

 6 106 Tons/year produced by the catalytic reaction:


CH3OH + CO CH3COOH
~ 645 / T 510 / T 2540 / T ($75/bbl)

main side-reaction: CO + H2O CO2 + H2 (WGS), which produces dihydrogen

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LCC

Cobalt process

Reaction discovered in 1913 (BASF), Nikolaus von Ktepow,


but heavy corrosion concerns in classical reactors.

1950 molybdenum /nickel alloys: Hastelloy

 1963 first small plant 3600 T/year

 Catalytic conditions: CoI2 / 250C / 680 bar

 Selectivity: 90 % / CH3OH;
by-products: EtOH, EtCOOH, EtCHO, PrCHO, BuOH
70 % / CO

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LCC
Formation of the cobalt active species

Actives species: [Co(CO)4]- and [Co(H)(CO)4]

2 CoI2 + 2 H2O + 10 CO [Co2(CO)8] + 4 HI + 2 CO2


[Co2(CO)8] + H2 2 [HCo(CO)4]
HCo(CO)4 + base [Co(CO)4]- + baseH

H2 assists the formation of the hydride species and increases the catalytic
activity but at the expense of the selectivity, due to the formation of various
hydrogenated by-products.

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LCC
First step: oxidative addition of CH3I to [Co(CO)4]-

HI + CH3OH CH3I + H2O

[Co-I(CO)4]- + CH3I [CoI(CH3)(CO)4] + I-

Another hypothesis is the production of CH3I through [Co(H)(CO)4] which,


due to its strong acidic character, could protonate methanol:

HCo(CO)4 + CH3OH CH3OH2+ + [Co(CO)4] -

CH3OH2+ + I- CH3I + H2O

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LCC
CO, H2O
or CO, H2
CoX2 [Co2(CO)8]
HX
H2O/CO

Nucleophilic active species OC CO


Co
OC CO

CH3COI H2O CH3I

I-
I-

CH3COOH
HI CH3OH

CO CH3
O
CO CO
CH3C Co OC Co
CO CO
CO CO

rds

CO
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LCC
Cobalt process

 The d8 pentacordinated [Co(Me)(CO)4] species is relatively stable. The

formation of the acyl species [Co(COMe)(CO)3] corresponds to the rds.

 The formation of CH3COI is rather complex since the [Co(COCH3)(CO)3]

species does not contain any iodo ligand.

 This reaction involves HI which reacts on [Co(COCH3)(CO)3] to produce


CH3COI et regenerates under CO the active species [Co(H)(CO)4].

 The last step is the hydrolysis of CH3COI.

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LCC

Cobalt process: side-reactions

 In addition, three side-reactions occur in addition to carbonylation: the first one


is the Water Gas-shift Reaction (WGSR) and is recurrent to all the catalytic
systems developed for this reaction

CO + H2O CO2 + H2

 The second one corresponds to the direct reaction of H2 onto the methyl
species to produce methane according to:

H2 + [Co(CH3)(CO)4] CH4 + [Co(H)(CO)4]

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LCC
Cobalt process: side-reactions

 The third one is a homologation reaction involving the reduction of the acetyl
group and producing ethanol.

O OH

CH3C-Co(CO)4 + H2 CH3CH-Co(CO)4

OH

CH3CH-Co(CO)4 + H2 CH3CH2OH + CoH(CO)4

 This process, due to its low selectivity vs CH3OH (Co 90% vs Rh 99%), has
been displaced by the Rhodium Monsanto process.
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LCC
Nickel process: general conditions

 The active species, [Ni(CO)4], is generated from NiI2:

NiI2 + H2O + 5 CO Ni(CO)4 + CO2 + 2 HI

 A nickel-methyl species results from the oxidative addition of CH3I


on [Ni(CO)4],

 Then the migratory CO insertion produces the acetyl species, which


evolves to give acetyl iodide by a reductive elimination reaction and
regenerates [Ni(CO)4] under CO pressure.

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LCC
Nickel process: catalytic cycle

CH3COI OC CO
Ni
OC CO CH3I

2 CO
2 CO

OC COCH3 OC CH3
Ni Ni
OC I OC I

CO

20
LCC

Nickel process: potential advantages

 Nickel being 10 000 times less expensive than Rhodium, the initial
investment for a large production unit (ca. 50 kg of catalyst for a 400 000
Tons/year) would be weak,

 Nickel requires low water amounts to be stabilised,

 Addition of stabilising salts, as alkaline metals, tin or molybdenum, should


allow to increase the selectivity of the process,

 Addition of phosphine ligands provides less toxic complexes and results in


higher selectivities.

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LCC
Nickel process: drawbacks

 This process requires harsch operating conditions: 200 bar and 250-
300C to reach industrially acceptable kinetics,

 a second drawback is the weak selectivity of 84 % only with regard to


methanol,

 This process has never been developed due to the extreme toxicity of
[Ni(CO)4]: exposition threshold 0.01ppm (100ppm for CO).

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LCC
Rhodium process

 1968 discovery of the low pressure process by Monsanto


1970 first industrial plant in Texas City 150 000 Tons/year

 RhI3, 190C, 30 bar


selectivity: 99% / CH3OH
85% / CO (WGS)
CH3OH + HI CH3I + H2O
CH3I + CO CH3COI
CH3COI + H2O CH3COOH + HI

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LCC
Rhodium process

The success of this technology, developed by Monsanto, is caused by a low


production cost:

PCO is low (30 - 60 bar) so that the initial investment is less important,
T of reaction is ~ 180 C, so that the energy cost saving is significant,

 Excellent selectivity of ~ 99 % / methanol and 85 % / CO to produce acetic


acid,

 The catalytic system presents a low sensitivity to H2 when compared to Co


lower production of CH4 and propionic acid.

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LCC
Rhodium Monsanto process

 Advantages:
* low pressure
* < 0.5% propionic acid
* three distillation columns
- light ends (and recycling)
- H2O / AcOH separation
- purification from priopionic acid
 Main drawbacks:
* miniumum water content 14 wt%; otherwise rhodium
instability
* cost of rhodium (precious metal): 40 70 000 / Kg
today 150 000 / Kg 25
LCC

Weakness of the rhodium process

cost and large cost variations of the Rhodium metal (it is a component of the
automotive catalytic converters).
80 000
September 2007: Rh = 157 000 /kg
Rhodium
60 000 Ir = 11 000 /kg
Iridium

40 000

20 000

0
janv- mai- sept- janv- mai- sept- janv- mai- sept- janv- mai- sept- janv- mai-
98 98 98 99 99 99 00 00 00 01 01 01 02 02

Price sensitivity of the two precious Rh et Ir metals (kg)

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LCC
Recent increase of the Rhodium price
(Iridium $440/oz)

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LCC

Weakness of the Monsanto Rhodium process

 Due to the high price of Rhodium, imperative necessity of efficient


recovery of the metal,

 Presence of at least 14% of water to stabilise the Rhodium catalyst,

 thus a large, and energy consuming, distillation column is required,

 A higher cost of 20% of the whole process could be saved.

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LCC
Pre-formation of the active species

RhX3 + 3 CO + H2O [RhX2(CO)2]- + CO2 + 2 H+ + X -

 Whatever the Rhodium salt introduced, it appears that, during the pre-
formation step, only the [RhI2(CO)2]- complex is present in the reaction medium,

 Even if phosphine-containing complexes are introduced, they evolve during


catalysis towards [RhI2(CO)2]- and a phosphonium salt,

 The first step of the catalytic cycle corresponds to the activation of methanol
to produce iodomethane:
MeOH + HI MeI + H2O

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LCC

Rhodium catalytic cycle

[RhI2(CO)2] - Nucleophilic attack of Rh-


Active species H[RhI2(CO)2]
onto CH3I: rds

[RhI3(CO)2(CH3CO)] - [RhI3(CH3)(CO)2] -
CH3COI CH3I
H2O
CO
-
CO HI
CH3 COOH CH3OH

[RhI3(CO)(COCH3)]-

D. Forster, J. Am. Chem. Soc., 1976, 98, 846


A. Haynes, B. E. Mann, D.J. Gulliver, G.E. Morris, P.M. Maitlis, J. Am. Chem. Soc., 1991, 113, 8567
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LCC
Rhodium catalytic cycle

 Indeed CH3I, more electrophilic than CH3OH reacts preferentially with


[RhI2(CO)2]- in a SN2-type oxidative addition (rate-determining step):

CH3I + [RhI I2(CO)2]- [RhIII I3(CH3)(CO)2]-

reaction 3.5 times faster in MeOH than in AcOMe


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LCC
Rhodium catalytic cycle

 In [RhI3(COCH3)(CO)2]-, of lower stability, fast migratory CO insertion


produces a pentacordinated acyl intermediate:

 Further CO coordination gives [RhI3(COCH3)(CO)2]-; then reductive


elimination regenerates [RhI2(CO)2] et produces acetyl iodide,

 The last step is the hydrolysis of acetyl iodide:


CH3COI + H2O CH3CO2H + HI

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LCC

Rhodium catalytic cycle

 From a kinetic point of view, the reaction rate does not depend of the
[CH3OH], [CH3COOH] and PCO parameters (zero order),

 It is directly related to the [Rh] and [I-] concentrations (1st order),


 Curiously, we are in the presence of a reaction whose the kinetics does not
depend on the CH3OH and CO reactants concentrations:

r = k[Cat][I-]

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LCC

Secondary reaction

Rle of iodhydric acid:


 Competitive reaction: the water-gas shift reaction (WGSR),
 This reaction depends on numerous parameters, and decreasing T ou PCO
seems to promote it. On the contrary, a low water content appears to inhibit the
formation of CO2 and dihydrogen.
 Presumably, it is due to the presence of [RhI4(CO)]- or [RhI4(CO)2]-
[RhI2(CO)2] - + 2 HI [RhI4(CO)] - + H2 + CO

[RhI4(CO)] - + 2CO + H2O [RhI2(CO)2] - + CO2 + 2 HI

CO + H2O CO2 + H2
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LCC
WGSR cycle

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LCC

Flow-sheet of a Monsanto plant

light dehydration of
compounds acetic acid
purification
reactor

acetic acid

flash

CH3OH
CO

propionic acid
recycling

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LCC
Rhodium process improvement: Celanese

Optimisation of the process: the Celanese approach

 1980, Celanese improves the process by addition to the reaction medium of


inorganic iodides and acetate ions to stabilise the catalyst and increase its
productivity. Thus [H2O] has been reduced to 4 %,

 Celanese supplies today around 33% of the acetic acid production,


 Apparently, the addition of LiI and acetates would favour the formation of
dianionic species [RhI3(CO)2]2- or [Rh(OAc)I2(CO)2]2- largely more nucleophilic
than [RhI2(CO)2]- leading to a faster oxidative addition of CH3I.

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LCC
Oxidative addition acceleration

fast

stabilization of Rh by Li+

Rh

Ir

38
LCC
Celanese process

 Another advantage lies in the decrease of the WGSR due to the direct activation
of methyl acetate,

CH3COOCH3 + LiI CH3I + CH3COOLi

CH3COOLi + HI LiI + CH3COOH

 This process is more efficient reduction of the secondary reactions leading to


higher turnover frequencies of the catalyst, significant energy savings (30%)
due to the decrease of the water content and therefore the cost of the distillation
operations.

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LCC
Flow sheet of the Celanese process

purge

AcOH

CO

CH3OH

Light
reactor flash column Heavy column
(C3)
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LCC
British Petroleum Cativa process

How to reduce the water-content ?

 Use of iridium

* first observations at Monsanto Co. and by Pannetier et al.


D. Forster, J. Am. Chem. Soc., 1976, 98, 846
D. Brodski, B. Denise, G. Pannetier, J. Mol. Catal., 1977, 2, 149

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LCC
Iridium catalysts

* but the carbonylation rate is too low:


D. Forster, J. Chem. Soc., Dalton Trans., 1979, 1639

P.M. Maitlis, A. Haynes, et al. J. Chem. Soc., Dalton Trans., 1979, 1639

oxidative addition of CH3I: 150 x faster for IrI / RhI


migratory CO insertion 105 x slower IrI / RhI

* rate of [CH3Ir(CO)2I3]- carbonylation is noticeably increased by


methanol addition
H*(kJ.mol-1) S*
PhCl 155 91
PhCl/MeOH = 3/1 33 - 197

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LCC
Bi-metallic catalytic systems

 Main objective: I- abstraction

I- [IrI2(CO)2]-

[IrI3(CO)2(CH3CO)] [IrI3(CH3)(CO)2]-
CH3COI CH3I
H2O
CO
HI
CH3COOH CH3OH
I-

[IrI2(CH3)(CO)3]

43
LCC

General strategy:

 The electron density on the iridium center is too high, so that the
retrodonation on the CO ligands results in a poor electrophilic
character, and prevents the migratory cis-insertion:

CH3 CH3 O CH3


I CO I- CO C
Ir I Ir CO fa s t
I CO I Ir CO
I CO
I I CO

 Removal of a I- ligand decreases the electron density.

44
LCC

Improvements brought by the Cativa process

 The price of iridium is lower: in 1990, when the first unit went in stream,
rhodium was around 20 times more expensive than iridium,

 The iridium species are stables at very low water contents. Thus one
distillation column can be removed to combine the separation acetic acid / water
and the recycling of the light fractions,

 The energy cost is reduced by 30%.

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LCC

Improvements brought by the Cativa process

 Higher concentrations in Iridium than in Rhodium can be used, leading to


higher carbonylation rates, with no precipitation of Iridium,

 This catalytic system is characterized by a largely better selectivity vis--


vis carbon monoxide (94 % instead of 85 %), and especially does generate a
few secondary products.

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LCC
Cativa process mechanism

Neutral Anionic
cycle cycle

47
LCC

Bi-metallic catalytic systems

CO CH3
I
Ir I CO
Ir
I CO I CO
CH3OH I

CH3I [RuI2(CO)4]
CO CO
COCH3 - CO I CO
Ru Ir
I CO CO I I
Ir CH3
I CO I I
I CH 3OAc [RuI3(CO)3] -

[IrI3(CH3)(CO)2] -

I-
CH3 -
CO CO
I CO CO I CO
Ir Ir Ir
I CO CH3 I I CH3
CO I I

48
[IrI3(CH3)(CO)2] - CO
LCC
Cativa process of BP Chemicals
Iridium-ruthenium-iodide promoted

reactor Finishing Flash Light ends + purification


Reactor dehydration
Residual gas
CH3OH
Cooling loop

Acetic
acid

CO

Propionic
Acid

49
LCC

Bimetallic catalytic systems

 British Petroleum Chemicals


[RuI2(CO)3] + I- [RuI3(CO)3]-

C.J.E. Vercauteren, K.E. Clode, D.J. Watson, Eu. Patent, 1994, 616997
A. Haynes, P. Maitlis et al., J. Am. Chem. Soc. 2004, 126, 2847.

 Acetex-Chimie
[PtI2(CO)2] + I- [PtI3(CO)]- + CO

C. Le Berre, P. Serp, P. Kalck, L. Layeillon, D. Thibaut, French Patent, 1998, 9813954

CH3

I Ir CO
I CO
50
LCC
Catalytic system [Ir-Pt]

TOF (h-1)

1400 Ir-Pt

Ir-Ru
14%
Rh

5-6 % H2O%
51
LCC
[Ir-Pt] mechanistic studies

 Counter-ion H+

* High-pressure NMR studies

1H, 13C, 195Pt

use of 13CO, 13CH3I

52
LCC

HP-infrared studies

identification of the CO bands

Si rod: 1 - 100 bar

53
LCC

[Ir-Pt] mechanistic studies

 Use of a stabilizing counter-ion


+ +
Ph3P N PPh3 or PPN

bis-triphenylphosphoranylidene

* NMR

* IR

* Mass spectra in negative FAB mode

* X-ray crystal structures

54
LCC
Preformation of the active Ir species

CO (1 bar), 160C [PPN]Cl


Ir3.4 [NH2Me2][IrI2(CO)2] [PPN][IrI2(CO)2]
DMF, H2O, 3h
1 PPN

Ir I11 = 2.6755(10)
Ir I12 = 2.6273(10)

CO = 2046 (s)
1967 (s) cm-1

13C NMR (in CD2Cl2)


= 169.9 ppm

MS m/z = 503

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LCC
[Ir-Pt] mechanistic studies

[PPN][IrI2(CO)2] + 1 HI [PPN][Ir(H)I3(CO)2]

1 PPN 2 PPN

-slow addition

- monitoring by IR

- an excess of HI provides [PPN][IrI4(CO) 3PPN

56
LCC

[Ir-Pt] mechanistic studies

CO = 2103 (s) and 2052 (s) cm-1

Ir-H = 2157 (vw) cm-1

1H NMR = - 11.65 ppm

13C NMR = 155.0 ppm

MS m/z = 631

Ir I1 = 2.6964(6)
Ir I2 = 2.6927(5) ~ 0.05 / 1PPN
Ir I3 = 2.8360(6) trans-influence of H
Ir H 1.6 positioned in its ideal position 57
LCC

[Ir-Pt] mechanistic studies

Carbonylation of Ir3-4 at 5 bar CO, 130C in C6H5Cl/H2O

(20:1) HP-IR and HP-NMR


1H H[IrI2(CO)2] minor species
CO = 2064 (s) + 18 cm-1 / 1-PPN
1982 (s) cm-1 + 15

2H H[Ir(H)I3(CO)2] major species


Ir-H = 2163 (w) + 6 cm-1 / 2-PPN
CO = 2112 (s) +9
2064 (s) cm-1 + 12
H = -11.6 ppm
58
LCC
Water Gas Shift cycle

CH3I CH4

H2 1H 1-PPN
H I
I CO
I CO 2H 2-PPN resting state
2 Ir 3
Ir
I CO I
I CO2 CO
I 3H 3-PPN
2HI
CO/H2O
I CO
Ir
I CO
1
* Identical observations at 30 bar, 90C in CH3COOH/H2O (90: 10) with 13CO
major species 2H 13CO = 156.0 ppm
+ dissolved CO2 13C = 152.2 ppm
59
LCC
[Ir-Pt] mechanistic studies

[P P N][IrI 2(CO) 2] + CH 3I [P P N][Ir(CH 3)I 3(CO) 2]

1 PPN 4 PPN

CO = 2100 (s) cm-1


2048 (s) cm-1

1H NMR = 2.15 (s) ppm


13C NMR = - 16.6 s
156.0 ppm s

MS m/z = 646

Ir-I1, Ir-I3: 2.7005(4), 2.7177(4)


4 Ir-I2 trans to CH3: 2.7658(4)
60
LCC
[Ir-Pt] mechanistic studies

(1 3 ) I
- (1 2 ) CH3
CO (4 ) CH3
CO I CH3 I CO
Ir I CO Ir
Ir Ir
CH3 I CO
CO I CO
I I
CO I S
I
(1 1) -
CH3
I (5 ) I CO
CO I
Ir Pt
CO I CH3
CO I CO Ir Ir
CH 3 I CO
I I
CO I

[P tI 2 (C O )] 2 (1 0 ) + [P P N ][Ir I 3 (M e )(C O ) 2 ] (4 )

0 ,0 1 6 m m o l (3 0 m g ); 9 ,5 m o la r e q . (1 8 0 m g )

3 .0 2 .8 2 .6 2 .4 2.2 2 .0 1 .8

0 ,0 1 6 m m o l (3 0 m g ); 6 ,3 e q . (1 2 0 m g )

Complex 1H NMR spectra


3 .0 2 .8 2 .6 2.4 2 .2 2 .0 1.8

0 ,0 1 6 m m o l (3 0 m g ); 5 ,3 e q . (1 0 0 m g )

3 .0 2 .8 2 .6 2 .4 2 .2 2 .0 1.8

0 ,0 1 6 m m o l (3 0 m g ); 3 ,5 q . (6 7 m g )

3 .0 2 .8 2.6
2 .6 2 .4 2 .2 2.0
2 .0 1 .8 61
LCC

[Ir-Pt] mechanistic studies

CO
-I)(CH3)2(CO)4]-
[Ir2I4( 1161

(13) 1121 CO

MS FAB

2.28
2.36

1H NMR

2 . 6 2 . 4 2 . 2 2 . 0 1 . 8

62
LCC

[Ir-Pt] mechanistic studies

CO 11 61
CO
(1 1 ))(CO) (
2 -I)2PtI2(CO)]
[Ir(I)(CH -
3
M S FAB
1 12 1 6

CH3
2.28

4
I CO
Ir
I CO
I
1132 C H 3
2.36

I CO
Ir
I CO
1
H NM R S

2 . 6 2 .4 2 . 22 2 . 0 1 . 8

63
LCC
[Ir-Pt] mechanistic studies

CH 3
I CO
5 I
Ir
CO
4
I CO
Pt I
I CO

CH 3 I
I-
OC I CO
OC
Ir
I
Pt
CO
6
CO
I I

I I
Pt CH 3
I CO
I
Ir
CO
7 Trans-8
CO
5* I
CO

COCH3 COCH3
Cis- and trans
I- I
Ir
CO I
and I Ir
CO
8
OC I CO
I I 64
LCC

I-2. Hydroformylation reaction

Hydrocarbonylation of alkenes

Catalysts: Co, Rh, Pt

Main producers: Exxon, BASF, BP chemicals, Ruhrchemie

World production: 10 millions Tons/year


LCC

Hydroformylation reaction

 From a formal definition, the hydroformylation reaction is the


addition of a hydrogen atom and a formyl group on the double bond
of an alkene:

O R
R cat
+ H2 + CO R H +
H O
"normal" "iso"
linear product branched product

66
LCC
Historical

During research carried out at Ruhr Chemie on the Fischer-Tropsch


synthesis of hydrocarbons from CO/H2, inOheterogeneousRconditions
(Co+Th/C*), Otto Roelencat
R
recycle ethylene to improve the chain
+ 2 + CO +
growth and Hdiscover that the Rreaction produces
H propanal: the
H O
hydroformylation reaction transforms an alkene and syn-gas into an
aldehyde He observed that the "normal" best catalyst was"iso"
Cobalt.
Homogeneous catalysis was born. produit linaire produit branch
67
LCC

Historical

In the 50s significant growth of petrochemistry


alkenes become commodity raw materials

accessible products through hydroformylation


aldehydes

alcohols carboxylic acroleine diols acetals


acids

aldols ethers
amines olefins

carboxylic
amines alcools
acids 68
LCC
Process development and mechanism

From the outset of the development, Roelen has had the intuition that the
cobalt carbonyl species involved in the hydroformylation reaction was
presumably the hydride [Co(H)(CO)4],

Understanding the mechanism: Orchin in the 50s, Heck and Breslow in 1961.
The catalytic cycle would begin with a pre-equilibrium between [Co(H)(CO)4],
the resting state and the active species [Co(H)(CO)3],

The involvment of [Co(H)(CO)4] was established by comparing the resulting


products to those obtained during a stoichiometric hydroformylation with
[Co(H)(CO)4].
69
LCC
Stability diagram of [Co(H)(CO)4]

CO partial pressure (bar)

Stable region

Unstable region
(Co precipitates)

Temperature (C) 70
LCC

Process development

 First generation of catalysts (Ruhrchemie, BASF, ICI, Kuhlmann):


[Co(H)(CO)4]. According to the stability diagram the operating conditions are
harsh (200-350 bar, 150-180C) to avoid the precipitation of metallic cobalt.

 Beginning 60s, Shell improves significantly the process by introducing


phosphines or arsines to substitute one CO ligand. Therefore, it is possible to
adjust the catalytic system by modulation of the electronic and steric effects of the
ligands. The Shell process, using the Co/PBu3 system is the outcome of this first
catalyst generation.

71
LCC
Active species for the hydroformylation
IR characterization (P = 1bar T= 20C , heptane )

 [Co(H)(CO)4]

1929, Co-H

2116, A1 1993, E 13CO


2030, E
2053, A1
2130 2100 cm-1 2000 1980

Just after acidification of [Co(DMF)6][Co(CO)4]2

72
LCC

Cobalt catalytic cycle

[Co2(CO)8] + H2: precatalyst 18 e-

[Co(H)(CO)4] reacts 12
times faster than H2!

73
LCC
Limitations of classical cobalt-catalyzed
hydroformylation

 Weak points for cobalt:


 linear/branched ratio: 2/1
 significant hydrogen sensitivity

 Cobalt recycling methods:


 Oxidation: H+, O2 (BASF) Co(I)  Co(II)
 Reduction: NaOH (Exxon) Co(I)  Na[Co(-I)(CO)4]

74
LCC

BASF process (Co 1st generation)

 High pressure process operating on a large range of olefins (C3-C12).


Recycling of Cobalt involves its oxidation in CoII,

 The active species [Co(H)(CO)4] est preformed in a separate carbonyl


generator (2), under pressure of purified syn-gas (1). At the end of the reaction,
decobalting occurs by oxidation in formic or acetic acidic medium (5), in the
presence of oxygen.

75
LCC

BASF process (Co 1st generation)

 The crude oxo product is withdrawn in the phase separator,

 The acidic aqueous cobalt solution is concentrated and sent to the carbonyl
generator, where cobalt loss is compensated,

 Catalysis conditions: P = 270 - 300 bar, T = 120C - 160C,

 Typically, from oct-1-ene, this process reaches conversions of 90% and a


selectivity of 75% in C9 aldehydes. The l/b ratio is ca 2.3. In addition, C9
alcohols reach ca 10%.

76
LCC
The BASF process

4: high pressure separator


3: Reactor
Vent

4
3 Aqueous H+; O2
Gas recycling
5: decobalting

6: Decantation 6 Crude product


Olefin
7: Concentrator
1: Gas purification 7
H2/CO 1:1 1 2 Waste water
Recycled cobalt

Cobalt 2: Carbonyl generator

77
LCC

The Exxon process (Co 1st generation)

 The Exxon process (PCUK, Produits Chimiques Ugine Kuhlmann


- technology) has been designed for C6-C12 olefins. It is representative

of a cobalt recycling without a change in the oxidation state.

 The active species [Co(H)(CO)4] arises from a carbonyl generator


(2) and is combined with the olefin stream from extraction column (8).
After reaction, the crude mixture is reacted with aqueous NaOH (5).

78
LCC

The Exxon process (Co 1st generation)

 Thus the catalyst is transformed in Na[Co(CO)4], soluble in water. The


aqueous phase is separated from organic products by decantation (6),

 [Co(H)(CO)4] is reformed by addition of sulfuric acid in the presence of


syn-gas (7),

 Reaction conditions: T = 160 - 200C, P = 250 - 300 bar,

 Main drawback: all the catalyst recycling procedures are carried out
under CO pressure.

79
LCC

Exxon process (PCUK)


Vent

NaOH H2O
H2SO4 Crude Products

4 4

3 5 6 7 8

H2/CO
1
Na2SO4/H2O
Alkene

1 : Gas purification 2 : Carbonyl generator


Cobalt 3 : Reactor (160-190C, 250-300 bar)
2
4 : Separator 5 : Recovery of cobalt (soda) 6 : Scrubbing
7 : Acidification 8 : Extraction column

80
LCC

The Shell process (Co 2nd generation)

It is the only commercial process to use a cobalt-phosphine catalyst:

 operates for C7 - C14 olefins; Extraction of the products by flash distillation or


under PCO (stability of the complex given by the ligand),
 the catalyst activity est modified by PBu3: direct formation of alcohols by
hydrogenation of aldehydes (and alkanes by alkene hydrogenation ),
 the use of distillation as separation technique can destroy a part of the
complex.

81
LCC

The Shell process (Co 2nd generation)

 Possibility to introduce additives (H2O, KOH). The presence of few water


amounts allows to still increase the production of alcohols with regard to
aldehydes et inhibits the formation of formates,

 Increasing the basicity of the medium promotes the formation of aldols from
aldehydes and then their hydrogenation to produce directly 2-ethylhexanol.

82
LCC
The SHELL process

3: Separator Vent

Crude products

3
4: Distillation
2: Reactor
2

4
H2/CO 2:1 1
1: gas purification

Ligand
5: catalyst regeneration 5
Cobalt

Additives

83
LCC

Rhodium catalysis

Various British Petroleum processes (Low Pressure Oxo processes) do exist, in


which the metal/substrat ratio is until ten times lower than those adopted for Co,

However, Rhodium is limited to the production of light aldehydes and mainly


butanal from propene,

For heavier olefins (C5 and +) Cobalt is still used at 90%, because Rhodium
presents lower activities and suffers from decomposition, especially when these
long chain olefins are branched or have internal double bonds,

Rhodium catalysts are largely more sensitives to poisons than the Cobalt
complexes.
84
LCC

Rhodium catalysis: 2nd and 3rd generation

The LPO processes (Low Pressure Oxo) of second generation involve rhodium
complexes modified by Lewis bases, most of the time phosphine ligands,

The use of such ligands results in the net increase of the catalyst reactivity and
its selectivity, opening the possibility to work under milder conditions (100 bar
and less than 130C),

The complex is characterized by a greater stability so that the distillation of the


products is possible,

The 3rd generation processes involve biphasic liquide-liquide media and


modified complexes in such a way their retention is maintained in one phase.
Metal loss is significantly reduced and recycling is done by a simple decantation.

85
LCC

Rhodium catalytic cycle

20 e- !!

H
rds

dissociative Associative mechanism


86
LCC

Rhodium catalytic cycle

Positive effect of H2: i) reduces the formation of inactive dimeric species, ii)
slow oxidative addition of H2

O
CO H H H
L C L H2 L L L
Rh Rh Rh CO Rh CO Rh L
L CO OC L L
CO C L CO CO
2ae 2ee L 1
O
9 CO CO
H H
OC Rh L L Rh L
L CO
3c 3t 87
LCC

Rhodium catalytic cycle


H H H
L L L
Rh CO Rh CO Rh L
OC L L
L CO CO
2ae 2ee L 1
At high PCO: formation of the dicarbonyl X CO CO
H H
species unreactive for the oxidative CH 3
CH 2 OC Rh L L Rh L
O C2 H 4
addition of H2 C L CO
3c 3t H
H
L
Rh
OC
L
H2
4ae 4ee
H3 CH 3
X CH 3 CH 3
H2 O CH 2
O CH 2 C CH 2
C L Rh L
OC L L Rh L
Rh L CO
OC CO CO
L e 7c 7t CH 3 CH 3 CO 5t 5c
8ee 8ae CH 2 CH 2
L L
Rh CO Rh CO
OC L
L CO
88
6ae 6ee
LCC

The Union Carbide Corporation process

This Rhodium process has been strongly modified to improve the product-
catalyst separation,

The Rhodium concentration is ca 250 ppm << Co 0.5%,

Two distillation columns are necessary, one operating under reduced pressure
to concentrate the catalyst solution,

It is essential to carefully purify the syngas and the olefin, mainly to remove
sulfur,

The time life of the catalytic charge can be greater than 1 year.
89
LCC
The Rhodium Union Carbide process

4: Flash 5: distillation 6: distillation

2: Separator

7
1: Reactor
1
3 4 5 6

H2/CO 1:1 Crude Products

propene 3: flash 25C 130C


1-2 bar 0.15bar

90
LCC

The Ruhrchemie - Rhne Poulenc process

The first plant went on stream in 1984 after only 2 years of pilot plant development,

The catalyst is maintained in the aqueous phase allowing an easy recycling,

The catalyst has a low sensitivity to sulfur and to other oxo poisons,

The active species is [Rh(H)(CO)(TPPTS)3],

The lifetime of a catalytic charge lies in the slow degradation of the TPPTS excess,

l/b ratio = 95/5.

91
LCC

Hydroformylation of propene by [Rh(H)(CO)(TPPTS)3]

[Rh(H)(CO)L3]

H
O
L
L Rh L= P
H L H
L Rh
CO 3 OC L
SO3Na

H
H H
L H L L
Rh
Rh Rh
OC
L OC
L O CO L

H2 O
L L L
Rh Rh
Rh L L
OC OC OC
L

CO
O

92
LCC
Flow diagram of the Ruhrchemie/Rhne-Poulenc
process
CHO
vapors
CHO
Vent

Decanter
Reboiler

CO / H2
CO / H2
Unreacted CHO

93
LCC
The Ruhrchemie/Rhne-Poulenc process

Distillation n/iso
CO/H2 1:1

Substrat
Gas recycling
HRh(CO)(TPPTS)3
In water
Products
appoint Tare purge

CO/H2
propene

Improvement : reactor + decantation

94
LCC
Hydroformylation: comparison of Rh and Co

95
LCC
Hydroformylation: comparison of Rh and Co

Industrial processes

96
LCC

I-3. Hydrocyanation reaction

Hydrocyanation of butadiene to produce adiponitrile


Intermediate for the production of nylon-6,6

Catalyst: Ni

Main producers: DuPont de Nemours, Rhodia

World production: 1 million Tons/year


LCC

Hydrocyanation of alkenes

Reaction discovered in 1951 by Paul Arthur et Burt Carlton Pratt (duPont de Nemours):
Ni(CO)4/PPh3,
Syn-addition of HCN on various activated or non-activated olefins => gives access to
numerous chemical fonctionalities (amines, acids, esters, isocyanates, ),
Regioselectivity to be solved for the addition on non-symmetric olefins,
Introduction of a chiral center starting from branched olefins:

Du Pont de Nemours (1994)

98
LCC
Mechanism of alkene hydrocyanation

Addition of HCN on olefins

The reversible insertion of the olefin is at the origin of the olefin

isomerization and isotopic exchanges,

The insertion determined the regioselectivity,

With terminal olefins: anti-Markovnikov addition (steric effect of the

M-H insertion).
99
LCC

Alkene additions

With transition metal catalysts


the control of selectivity is not
simply explained by the stability
of the carbocation intermediate:
anti-Markovnikov products are
possible.

Beller, M. et al. Angew. Chem. Int. Ed. 2004, 43, 3368


100
LCC

Hydrocyanation of ethylene

The reductive elimination (rds)


is promoted by addition of
electro-withdraving groups in
the phosphite ligands

not observed but


consistent with the
kinetics

for styrene, a benzyl


intermediate is formed

P
Ni
P CN L= tris(p-tolyl)phosphite
101
LCC
Butadiene Hydrocyanation Nylon 6,6 synthesis

2 CN

2 H+, 2
[Ni] H2, Ni Raney
+ H-CN NC NH2
CN H2N
NH3
Adiponitrile HMTA

red ox COOH
COOH
benzene cyclohexane adipic
acid
O
+ NH3+ - O-
H3N O
O

D
-H2O

O H
* N *
O N
H n
O
Nylon 6,6 102
LCC

Hydrocyanation of butadiene

[Ni]
+ H-CN NC Nylon 6,6
CN
Adiponitrile

duPont process (1971): 75 % of the world production adiponitrile


isomerizarion
3PN
CN
[Ni]
+ H-C N CN
+
75% 25% 2M3BN
A B

isomerizarion

NC
H-C N CN
CN 4PN
C

Promoting the reaction with a Lewis acid (BAr3, ZnCl2) makes easier the
isomerization reactions and avoids the decomposition of the catalyst
103
LCC
Butadiene Hydrocyanation

HCN addition yields 1:2 with a 1:2 ratio, but it equilibrates at


1:9 du because of the back-reaction (needs to break the C-C, but
2M3BN the allyl cyanide species is stable).

Although 3 is more stable than 4, the formation of 4 is


Ni HCN
NC kinetically controlled.
1

NC

Ni 3-PN 4-PN
CN
2
Insertion allyl complex X CN 4 CN 5 CN

2-PN is the stable


Lewis acids are added as co-catalysts. They
isomer but its CN
accelerate the reductive elimination (formation of
3
formation is very slow 5), probably by complexation with CN, thus
(traces) 2-PN
decreasing the electronic density on the metal.
104
LCC

Hydrocyanation of butadiene

First step

Second step

105
LCC
Hydrocyanation of butadiene 1st step

3PN
2M3BN

106
LCC
Butadiene Hydrocyanation

CN
3PN
L
L
L (0) L = P(OAr)3
Ni L Ni L
L L
CN H-C N L 18 e-
L L Oxidative
Ni
L addition H
L
Ni C N
L L
L
L
[HNiL3]+ : very active
CN
sepcies for
L L H
L
Ni Ni isomerization via the
L (II) C N
hydride route
16
Me 1,2
Reductive L insertion
elimination L
Ni
CN
2M3BN
(II)
allyl nickel (II)
Reductive L CN CN
Ni
L 107
elimination
LCC

Hydrocyanation of butadiene

The addition of HCN leads to 1:2 with a 1:2 ratio, but


balance to 1:9 is due to the back-reaction (with the C-C
2M3BN
bond breaking, the allyl cyanide species being stable),

Ni
Although 3 is more stable than 4, formation of 4 is under
HCN
NC kinetics control.
1

NC

Ni 3-PN 4-PN
CN
2
Allylic complex X CN 4 CN 5 CN
of insertion
Lewis acids are added as co-catalysts and
2-PN is the more stable accelerate the reductive elimination to produce 5,
isomer, but its formation 3 CN by direct complexation to a CN ligand, reducing
is very slow (traces)
2-PN the electron density on the metal center
108
LCC

Butadiene Hydrocyanation

An important step at different level of the catalytic cycle is L dissociation to

create a vacant site,

The rate and the equilibrium of these dissociation are largely controlled by

the steric hindrance of the ligand.

Electro-attractor groups are necessary to enhance the other steps of the cycle.

The best ligand: phosphite o-tolyl.

Classical promoters: BPPh3 (increase the selectivity in linear product and

participates to Ni stabilization, avoiding the formation of inactive Ni(CN)2.

109
LCC
Butadiene Hydrocyanation - isomerization

H
L
Ni L C N BP h3
L
L Precatalyst 18 e-

CN CN
L
4PN 2PN

L L
Ni C N BP h3
L H
Catalyst 16 e-

L L
1 2
Ni H
L CN L L
Ni
H 3PN L

CN NC

The two 2PN and 4PN isomers can be formed and 2PN is the more stable!
The proportions 2PN:3PN:4PN at equilibrium are => 78:20:2
Step 1 leading to 4PN is around 70 times faster than 2 leading to 2PN!
110
LCC
Production of nylon-6,6 (Rhodia)

111
LCC
Nylon 6,6 synthesis adipic acid
OH
OH O O

H2 C o naphatalenate
+ via
cat O 2 (10-15 bar)
benzene cyclohexane 150C ol + one
Conversion 10-12%
HNO 3, C u
(avoid the suroxidation and ammonium vanadate
degradation in C5-C4)

C OOH
adipic acid
C OOH

The use of nitric acid for the oxidation in adipic acid yields to the formation of
!! nitrous oxide N2O (0.32 kg of oxide by kg of acid)

This process was responsible of the emission of 100 000 Tons /y of N2O in USA
(Greenhouse effect = 3 times the effect of CO2)

It was necessary to find new solutions or alternative processes

112
LCC

Nylon 6,6 synthesis adipic acid


Alsachimie process=> conversion of N2O in HNO3 for recycling
Solutia process => use of N2O for benzene oxidation in phenol
OH O
H2 H NO 3 C OOH adipic
cat C OOH acid + N 2O

P henol cyclohexa none

BASF process: carbonylation of butadiene


C o2 (C O )8 C O 2 Me
+ C O + C H 3O H
600 bar, 120C H 3C

C o2 (C O ) 8

30 bar, 185C

C O OH 2H 2 O C O 2 Me
C O OH C O 2 Me
H+
113
LCC
Adipic acid: alternative green processes

Biotechnologies
C H3
NH 2(C H 2)6NH 2
cells C OOH C O 2-
-
NH 3+ (C H 2)6NH 3+
P seudomonas C OOH C O2
P utida
toluene Muconic acid
H 2 cat

C O 2-
-
NH 3+ (C H 2)6NH 3+
C O2

Oxidations under mild conditions


OH OH
Na 2WO 4
-H 2O H 2O 2
3 H2 C OOH
C TP C OOH

2 H2
Need a cheaper oxidant

Benzene is cheaper than phenol


114