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Supercritical fluids
opportunities in heterogeneous catalysis
The use of supercritical fluids (SCFs) in technology and research has been
abbreviations
chemical reactions. However, it has been just in the last decades that SCFs
have gained their importance in science and industrial applications, due to the
pc critical pressure
R gas constant,
8.3145 J K mol
p pressure
relatively high pressures usually required when working with these media and
(corresponding author)
supercritical solution
(technique)
E-mail: baiker@tech.chem.ethz.ch
(technique)
sc supercritical
(with compound)
T temperature
Tc critical temperature
V volume
Vr
V
reaction volume
activation volume
dynamic viscosity
isothermal compressibility
kinematic viscosity
density
critical density
gas phase increases while the liquid becomes less dense. This can be directly observed by
the phase border becoming more and more blurred and turbulent as the system approaches
its critical point. At the critical point, the densities of gaseous and liquid CO2 become equal
T = 19.5 C
p = 5.7 MPa
and the phase border disappears. The critical parameters of the system are slightly higher
than that of pure CO2 due to traces of air in the system.
128
Volume 4, no. 2, 2000
T = 24.9 C
p = 6.4 MPa
T = 32.1 C
p = 7.5 MPa
T = 33.0 C
p = 7.6 MPa
Properties of SCFs
The properties of SCFs are often said to lie between those of
a liquid and a gas. Although this is generally true it is important to note that some of the properties of an SCF are more
liquidlike, whereas others are more gaslike. Furthermore,
most properties of SCFs can significantly change with relatively small changes in pressure and temperature, rendering
SCFs easily tunable with respect to their qualities as a solvent and/or reactant. It is this mixture of more liquid and
more gaslike properties together with the easy tunability of
those properties that render SCFs such promising media for
chemical reactions and extractions.
Supercritical fluids
What is an SCF?
In 1822, Baron Charles Cagniard de la Tour conducted
experiments that showed there is a critical temperature above
which a substance can only be in one fluid state instead of
either gaseous or liquid [18]. As a fluid in gas liquid equilibrium is heated and approaches its critical temperature, the
density of the gas phase increases while the liquid becomes
less dense. If the two densities become equal the liquid and
gaseous phase converge into a single one with no change in
local symmetry. This transition from a liquid gas equilibrium
to the supercritical state is shown in Figure 1 using the example of CO2. At the condition where a liquid and gas phase in
equilibrium converge into a single phase the coexistence line
of the liquid and gas has a critical point, defined by e.g. a critical temperature and pressure as shown in Figure 2.
As follows from the expression supercritical fluid, this
term refers to a fluid at conditions beyond its critical point.
Although this seems to clearly assign the supercritical state, a
problem arises in laying down the term beyond in that definition; while some definitions demand for the temperature
and pressure of a fluid to exceed their critical values in order
to be supercritical, others omit all restrictions on pressure
and only require that the temperature be greater than Tc[19].
In this article, we will use the latter definition of the supercritical state for reasons of convenience: a fluid is called supercritical if the temperature exceeds its critical value (and the
pressure is below the one required to condense it into a solid);
or, in other words, if it cant be transformed into two nonsolid
phases by isothermally expanding or compressing it. With this
definition, a supercritical fluid reveals the unique property of
being tunable in density from gaslike values to liquidlike
ones without a phase transition.
SCF
solid
liquid
CP
TP
gas
Tc
TTP
V
Figure 2 (above) Phase diagram of a pure compound in p,V,Tspace showing solid, liquid, gaseous (vapor), and supercritical domains as well as corresponding phase borders and phase coexistence areas. TP and CP indicate the triple
point and critical point of the compound, respectively; corresponding isotherms are
traced with thick lines.
T = 33.6 C
p = 7.7 MPa
T = 34.6 C
p = 7.7 MPa
129
10000
1000
density
/ kg m3
Supercritical fluids
gas a)
100
10
1
0.1
100
diffusion coefficient
D / 106 m2 s1
10
1
0.1
0.01
0.001
dynamic viscosity
/ mPa s
0.0001
10
1
0.1
0.01
kinematic viscosity b)
/ 106 m2 s1
1000
100
10
1
liquid a)
0.1
0.01
130
SCF
viscosity was estimated from dynamic viscosity and density, = / . (Data taken
from [57] , with the exception of the density range of SCFs which includes c (Xe) =
1110 kg m-3[81] in this figure.)
Supercritical fluids
T3 >> Tc
T2 > Tc
T1 < Tc
p
p
p
p
CP
T
TP
Figure 4 Effect of pressure on density at subcritical (T1 < Tc) and supercritical (T2 > Tc, T3 >> Tc) conditions. Isotherm T1 illustrates the discontinuity in the density vs. pressure function at subcritical conditions due to the phase change. Isotherms T2 and T3 typify the continuous change from gaslike to liquidlike densities with increasing pressure.
Note that the effect of pressure on density for an SCF, in terms of change in density with a small variation in pressure, is more pronounced near the critical point.
Supercritical fluids
lnK x
p
T,x
Vr
RT
(1)
Due to solvation effects and the high isothermal compressibility in SCFs, partial molar volumes in SCFs may be of
dramatic values near the critical point [26] and the resulting
reaction volume Vr may strongly alter the effect of pressure
on equilibrium with regard to the reaction carried out in a
liquid or gaseous phase.
The effect of pressure on kinetics is mostly described in
the context of transition state theory [27] and a supposed reaction pathway. According to this theory, the mole fraction
based rate constant k x of an elementary reaction depends on
the activation volume V , i.e. the difference between the
partial molar volume of the activated complex and the sum
of those of the reactant(s):
lnk x
p
T,x
V
RT
(2)
Supercritical fluids
Again, solvation effects and the high isothermal compressibility in SCFs may lead to dramatic values of partial
molar volumes in SCFs, and consequently to activation volumes V in the order of liters per mol. Consequently, the
effect of pressure on the rate constant in SCFs can be dramatic as compared to reactions in a liquid or gaseous phase,
where activation volumes are typically in the range of 0.03
to 0.03 liters per mol, or are even restricted to the intrinsic
activation volume, respectively [25]. However, this effect is
due in a large part to the high compressibility of SCFs and
therefore mainly reflects the change from a reaction rate in
a gaslike fluid to one in a liquidlike fluid. Consequently,
activation volumes V in SCFs are generally not useful to
extract mechanistic information about the reaction, in contrast to gas or liquid reactions, where the activation volume
more or less reflects the size change from the reactants to the
activated complex.
Local enhancement of density clustering
The high compressibility in SCFs and the gaslike behavior
with regard to surface tension allows attractive forces to
move molecules into energetically favorable locations. The
resulting nonuniform spatial distribution of solvent and
cosolvent molecules about solute molecules, as schematically
illustrated in Figure 5, gives rise to interesting solvent effects
not ordinarily found in liquid mixtures. This phenomenon,
which has been termed local density enhancement [28] , clustering [29] , or molecular charisma [30] , can affect the rates and
selectivities of chemical reactions through both physical and
chemical mechanisms [31].
Local anisotropy phenomena also may occur at supercritical fluidsolid interfaces as a consequence of different
interaction strength (adsorption enthalpy) of solute (reactant), solvent, and cosolvent, with the solid surface and clustering phenomena in the bulk phase near its critical point.
Fundamental knowledge of these interactions is important
to understand the mechanism of solid catalyzed reactions.
Unfortunately, there appears to be no fundamental work
dealing with this aspect crucial for understanding catalytic
surface reactions in solutesolvent (reactantsolvent) systems.
CP
T
TP
extent of clusters for the SCF is shown in reduced scale for reasons of
V
clearness.
133
Supercritical fluids
vide a further means for control of selectivity, increased catalyst lifetime and regeneration, or facilitate easier product separation and process intensification. Moreover, supercritical
fluids offer several unique opportunities in catalyst preparation. Some of the opportunities discussed here are valid
for chemical processes in general, whereas those concerning
the solid catalyst are unique for heterogeneously catalyzed
chemical reactions.
Elimination of gas liquid phase transfer resistances
The most obvious opportunity for the use of SCFs in heterogeneous catalysis is the elimination of gas liquid phase
transfer resistances in reactions involving three phases under
subcritical conditions (see Fig. 6). This together with lowered external fluid film diffusion resistances resulting from
lower viscosity of SCFs may significantly accelerate the reaction, since diffusion of the gaseous reactant to the catalyst
surface often represents the rate limiting step in threephase
reactions.
Enhancement of reaction rate
Fluids exhibit high diffusivities and very low kinematic viscosities in the supercritical region, resulting in high mass
and heat transfer rates. Consequently, working in the supercritical region may accelerate mass transfercontrolled liquid
reactions and lead to better heat removal in highly exother-
adsorption of reactant(s)
surface reaction
desorption of product(s)
Supercritical fluids
= catalyst
liquid
catalyst
= liquid (reactant B)
c(A)
SCF
5
catalyst
catalyst
bulk
phase
boundary
layer
= catalyst
= SCF (reactants A and B)
4
5
6
Figure 6 Sequence of physical and chemical steps occurring in a heterogeneously catalyzed gas liquid reaction (e.g. hydrogenation of a liquid compound) and comparison
of such a reaction at subcritical and supercritical conditions. A representative section of the reactor content, corresponding masstransfer boundaries and reactant concentration profile are shown for both sub and supercritical conditions. Note that gas liquid transfer resistance (steps 1 and 2) is eliminated and external fluid film diffusion resistance
(step 3) is lowered under supercritical conditions due to lower viscosity of SCFs.
135
Supercritical fluids
A problem frequently encountered with heterogeneously catalyzed gas phase reactions is the formation of heavy organics
which may act as catalyst blocking agents and thereby deactivate catalysts and promote coking. Since supercritical fluids
exhibit considerably higher solubilities than corresponding
gases for such heavy organics, catalyst deactivation may be
suppressed by changing working conditions from gas phase
to dense supercritical medium [38,39]. Furthermore enhanced
diffusivity can accelerate the transfer of poisons from the
internal and external catalyst surface. The lifetime of a catalyst can therefore be significantly prolonged by working in
the dense supercritical region.
Regeneration of catalysts deactivated by coking can be
accomplished by extracting the carbonaceous deposits from
the catalyst surface. Due to the high solubilities and favorable
transport properties in the supercritical region, SCFs provide
a valuable instrument for such extraction processes.
Facilitated separation
batch reactors
continuous reactors
a)
Supercritical fluids
the case of SCWO). The use of such conditions is demanding on the experimental equipment used [51]. Furthermore,
the potential danger of these conditions should never be
ignored and full safety precautions should be made for all
experiments.
For heterogeneous catalytic reactions two principle reactor types are suitable, batch reactors (autoclaves) or continuous flow reactors. The advantages and disadvantages of the
two reactor types are well known in heterogeneous catalysis
and also apply to the use of SCFs. For industrial applications, however, the extremely good mass and heat transfer
properties of SCFs render tubular fixedbed reactors ideal
for heterogeneously catalyzed reactions, both on grounds of
safety (low reactor volume) and costs. Figure 7 schematically
shows the reactor types most frequently used for heterogeneous catalytic reactions at supercritical conditions.
A necessary requirement for designing heterogeneous catalytic reactions at near or supercritical conditions is knowledge of the phase behavior[28,5257]. Due to the limited predictability of theoretical calculation of phase behavior[58] experimental measurements are indispensable. Several approaches
for monitoring the phase behavior of homogeneous catalytic reactions have been reported and reviewed in the
literature [13,51,5963]. These systems are mainly based on a
highpressure cell equipped with a means to detect phase
boundaries (optically through a glass window, by conductometric analysis, or with ultrasound) and preferably an
additional instrumental channel for further analysis of the
d)
PM
c)
PM
b)
H
Figure 7 Reactor types suitable for the study of heterogeneously catalyzed reactions at supercritical conditions. a) stirred autoclave, b) stirred autoclave with internal
recycle, c) differential (gradientless) reactor, and d) continuous flow reactor. PM: premixing chamber; H: heat exchanger.
137
Supercritical fluids
Compressed Air
MV 2
MV 1
MV P
Rinsing
PI
NIC
RV A
PC
IS
MI
FI
TI
MV A
PI
RV B
PI
TIC
PV P
PC
NV 1
MV B
RM 1
PT
PV 1
TT
TI
FI
SV o
TI
TIC
el.
NV 2
RM 2
PV 2
kryo
TIC
KS
CCD o
el.
monochrome AV
kryo
monochrome AV
CCD u
AO
ER-8
TS
AI/RTD
TI
SC-2042
SC-2050
SV u
el.
SFA Software
SFA SubVIs
BV/IMAQ VIs
PCI
AT
Driver SubVIs
RS 232
DVC Recorder
BV Engine
Data Logging
Alarm Man.
MIO
BV Tag Server
AV
NI IMAQ
SFA Computer
IC
TC
HP GC 6890
Figure 8 Computercontrolled highpressure system for in situ monitoring of heterogeneously catalyzed reactions under supercritical conditions using online video
imaging as well as online sampling and analysis by gas chromatography. The figure shows a flow chart including the organization of process control and acquisition of data
and images. The hatched bar represents a wall separating the high pressure cabinet (upper part of the flow sheet) from the operating area (lower part of the flow sheet). RVx:
highpressure reduction valves; MVx: magnetic valves; NVx: needle valves; RMx: massflow meter; PVx: pneumatic valves; IS: stirrer; KS: kryostat; TS: thermostat; SVx:
heated sampling valve system; CCDx: 8bit monochrome CCDcameras. (Reproduced with permission from [64] .)
Case studies
Some of the opportunities discussed in the preceding sections are illustrated in the following case studies: the synthesis of formic acid derivatives from scCO2, and the amination
of diols in scNH3. A comprehensive review containing several other studies demonstrating the opportunities of SCFs
in heterogeneous catalysis has recently been published [1].
Synthesis of formic acid derivatives
from supercritical carbon dioxide
a)
CO2
H2
H
N
Ru hybrid aerogel
R = CH 3 , CH2CH3
b)
CO2 +
H2
+ CH3OH
Ru hybrid aerogel
O
N
R
HCOOCH3
H 2O
+ H 2O
Figure 9 Synthesis of (a) formic acid derivatives such as N,N dimethylformamide (DMF), N,N diethylformamide (DEF) and (b) methyl formate (MF) from CO2, H2 and the
corresponding alkylamine and alkanol, respectively, using a ruthenium hybrid aerogel as catalyst.
138
a)
Ph2 Cl
P
Ru
P
Ph2 Cl
Ph2
P
P
Ph2
(EtO) 3 Si
(EtO) 3 Si
Ph Cl
P
Ru
P
Ph Cl
Supercritical fluids
b)
Si(OEt)3
Ph
P
P
Ph
Si(OEt)3
c)
Figure 10 Preparation of the ruthenium hybrid solgel precursor. A ruthenium phosphine complex (a) showing high activity and selectivity in the synthesis
of formic acid derivatives, is functionalyzed by silyl ether groups (b) and immobilized within a silica matrix affording aerogel or xerogel hybrid catalysts (c) by corresponding drying procedures.
HO
OH
O
Si
O O
HO
O
O OH O
O
Si
Si
O
O
O Si O Si O
HO Si
Si O O
Ph Cl Ph
OO
O
P
P
O Si O
O
Ru
O Si O
HO
P
P
OH
O Si
Si
Ph Cl Ph
O
Si O O
Si
O Si O
HO
Si O
O Si
O
O
OO O
Si O
Si
O
O
O O
O O
O Si
OO O
139
3.0
2.0
Supercritical fluids
Aerogel
4.0
1.0
0.0
1.4
Xerogel
1.2
1.0
0.8
0.6
0.4
0.2
0.0
10
100
1000
Pore Diameter / nm
of the monoaminated intermediate of the reaction as compared to ammonia and the ensuing side reactions (see Fig. 13).
Application of highdense scNH3 as a solvent and reactant
significantly improves the selectivities to the corresponding
primary diamine in the amination of e.g. 1,3propanediol [79].
The corresponding experiments were conducted using a
CoFe catalyst in a tubular flow reactor at a temperature of
195 C with a molar ratio of 1,3propanediol : H 2 : NH3 =
1 : 2 : 40. As expected for a multicomponent system, the
reaction system exhibits a nontrivial phase behavior: experiments in a view cell showed that at the temperature applied
the reaction system was onephase and presumably supercritical at pressures > 90 bar, whereas at lower pressures
a liquid alcoholbased phase and a seemingly supercritical
ammoniaH 2 phase with traces of alcohol were present. As
shown in Figure 14, the pressure of the reaction system has
a striking effect on the selectivity to 1,3diaminopropane:
the production of byproducts can be significantly reduced
by working at pressures above 90 bar. The change in selectivity has been attributed to an increase in the concentration of
ammonia on the catalyst surface. This favors the fast ammonia addition to the aldehydetype intermediates, and suppresses the degradation (hydrogenolysis) type side reactions
as well as the reaction of the alcoholic group of the reactant
with the intermediate or product amines leading to dimerization products. The increase in ammonia surface concentration is traced to the transformation of the twophase system to
a homogeneous supercritical fluid, and to the ensuing elimination of the phase transfer resistance in the twophase regime,
increase in mass transfer and eventually influences of the
supercritical state on reaction thermodynamics and kinetics.
Most recently it has been shown that amination of
1,4cyclohexanediol in supercritical ammonia affords an efficient process for the synthesis of 1,4diaminocyclohexane [80].
An unsupported cobalt catalyst stabilized by 5 wt% iron
afforded the main reaction products 1,4diaminocyclohex-
T =
p =
89.0 C
3.0 MPa
T =
p =
91.3 C
13.2 MPa
T =
p =
108.0 C
14.1 MPa
T =
p =
9.4 C
9.0 MPa
DEA
H2
CO2
0.5 mol
0.6 mol
DEA
H2
CO2
0.5 mol
1.1 mol
3.0 mol
DEA
H2
CO2
0.5 mol
1.1 mol
3.0 mol
DEA
H2
CO2
0.5 mol
1.1 mol
3.0 mol
Figure 12 Phase behavior of the reactants used for synthesis of N,N diethylformamide (without hybrid aerogel catalyst) as recorded with the computercontrolled autoclave system for the investigation of heterogeneously catalyzed reactions in SCFs depicted in Fig. 8. The snapshots show the reactor content, and the shaft of the (suspended)
mechanical stirrer. Since the level of the liquid is quite low, only the images taken by the lower CCDcamera are shown. The bottom of the reactor (up to the lower end of the
glass window) is covered with a liquid phase consisting mainly of N,N diethylamine (DEA). Note that the level of this liquid phase does not significantly increase or decrease
with addition of CO2, isochoric heating to reaction conditions and subsequent isochoric cooling of the system; the reactor content obviously comprises two phases during the
synthesis of N,N diethylformamide from CO2, H2 and DEA, a liquid DEAbased phase and a supercritical CO2based phase.
140
OH OH
H2
R R
CO
R
OH
OH O
+ NH 3 / H2O
+ H2
R R
H2
HCHO
R R
NH3
+ H2
OH
R
OH
+ NH 3 / H2O
+ H2
H2
R R
NH 2
+ NH 3 / H2O
+ H2
H2
R R
R
NH2
NH 2
NH2
+ NH 3 / H2O
+ H2
R R
R = H, CH3
NH 2 NH 2
Figure 13
with ammonia. Detected main and byproducts are indicated by orange and blue
shades, respectively. (Taken from [79].)
40
selectivity / %
30
20
10
40
60
80
100
120
Supercritical fluids
R R
140
pressure / bar
Figure 14 Amination of 3amino1propanol with ammonia over a CoFe
(95/5) catalyst. Influence of pressure on the selectivity to 1,3diaminopropane.
Note the 10fold increase of selectivity around a pressure of 105 bar. Conditions:
continuous tubular reactor, T = 195 C, molar feed ratio of reactants ROH : NH3 =
1 : 40. The dashed line indicates the critical pressure of NH3. (Taken from [79].)
Outlook
The unique and easily tunable properties of fluids near their
critical point render SCFs very promising media for chemical
reactions. In addition, fluids used in chemistry at supercritical conditions are often very attractive from both economical and ecological points of view. Combining these media
with the industrially advantageous features of heterogeneous
catalysis thus holds great promise for optimization of chemical processes.
Limitations of SCF application arise from the higher
demands on the construction of suitable reaction apparatus
and the expenses of highpressure equipment. Furthermore,
the fundamentals of supercritical fluids in heterogeneous
catalysis have not yet been fully investigated and predictions
made on the basis of theoretical models and calculations are
of limited reliability so far.
Although the possibilities of SCF application in heterogeneous catalysis seem very impressive, the benefits of
SCFs have to be weighed against the higher costs involved
in designing, building and maintaining corresponding processes. To date, SCFs are mainly used where process intensification or favorable reaction behavior lead to economically
more attractive processes or where SCFs allow to alleviate
environmental constraints. However, if societys demand for
safe and environmentally benign chemical processes continues to increase, SCFs may become the ideal media for many
more chemical processes. For this purpose it will be necessary to further improve the knowledge in this area on both
fundamental and applied level.
Although SCFs are currently used mainly as solvents or
reactants in chemical reactions, there is an attractive opportunity where SCFs act simultaneously as both reactant and
solvent. This solventfree reaction design is a remarkable
step towards green processes. The easy tunability of an
SCFs unique properties enables the scientist and engineer to
explore the wide field of heterogeneous catalysis with markedly less restrictions than faced under classical conditions.
Consequently, great efforts are expended for exploring
this relatively new field and hopefully this will lead to further development of the theoretical basis of catalytic reactions under supercritical conditions. A deeper understanding should allow more directed optimization procedures for
chemical processes which would be beneficial for both application and research.
141
Supercritical fluids
acknowledgements
142
curricula vitae
Supercritical fluids
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