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Poliakoff-Chem Soc Rev
Poliakoff-Chem Soc Rev
This Tutorial Review focuses on supercritical carbon dioxide (scCO2), and discusses some of the
problems that have frustrated its wide use on an industrial scale. It gives some recent examples
where strategies have been developed to reduce the energy requirements, including sequential
reactions and gas-expanded liquids. It then describes a number of cases where scCO2 offers real
chemical advantages over more conventional solvents, for example by controlled phase
separation, tunable selectivity, oxidation and on-line analysis and self-optimisation. Overall, this
review indicates where scCO2 could deliver value in the future.
1428 Chem. Soc. Rev., 2012, 41, 1428–1436 This journal is c The Royal Society of Chemistry 2012
of CO2 with the use of bioethanol increasing as a transport In the past few years, there have been several reviews of
fuel. Furthermore, scCO2 is totally non-flammable and its reactions in scCO2 including some that focus on continuous
properties can be manipulated by varying the applied reactions,14,30,31 and there is a recent, helpful introduction to
pressure.18 continuous reactions32 which highlights some of their advan-
There has been one outstandingly successful application of tages particularly in the context of Green Chemistry. The aim of
scCO2, the decaffeination of coffee beans which has become this review is to give some recent examples where strategies have
one of the most popular decaffeination processes.18 A number been developed to reduce the energy requirements and then, in
of other processes have also been implemented in the food the second part, we describe some cases where scCO2 offers real
industry probably because of the attraction of a completely chemical advantages over more conventional solvents.
non-toxic solvent and the relatively high value of the products,
Published on 16 January 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15314A
Scheme 1 Hydrogenation of isophorone to TMCH,29 one of the few Fig. 1 Schematic diagram of a typical continuous flow apparatus for
reactions to be carried out on a commercial scale in scCO2. reactions in scCO2.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 1428–1436 1429
Reducing the energy requirement
The major energy consumption of a supercritical apparatus
comes from the compression of CO2 to its supercritical
pressure. The most straightforward approach would be to
use CO2 which has already been compressed elsewhere as part
of a different process, thereby removing the energy burden of
compression completely. Until now such an approach has
seemed extremely unlikely. However as plans for Carbon
Capture and Storage (CCS)34 become more definite, it
Published on 16 January 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15314A
1430 Chem. Soc. Rev., 2012, 41, 1428–1436 This journal is c The Royal Society of Chemistry 2012
and provides, in principle at least, a versatile and convenient
methodology for non-specialist chemists.
Scheme 5 Diastereoselective hydrogenation of sertraline imine53 in gas expanded THF, the first example of a pharmaceutical intermediate being
hydrogenated in CO2.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 1428–1436 1431
Scheme 6 Debenzylation of 1,4-debenzyloxybenzene.55
the monodebenzylated product was achieved, suggesting that the The aqueous phase can be collected in the separator (S), the GVL-rich
reaction has potential applications for desymmetrisation of such phase passes through S and to the back pressure regulator (BPR) for
molecules. recovery of pure GVL. The aqueous phase, containing any unreacted
LA continues to accumulate in S and can periodically be drained via a
ball valve, without significant loss of the system pressure. (Reproduced
The way forward from ref. 57, copyright the Royal Society of Chemistry).
In the previous sections, we introduced a number of strategies The result was reaction and separation integrated into a single
for reducing the energy requirements of CO2 processes, such as process, completely avoiding the conventional separation of H2O
running sequential reactions, generating scCO2 fluid from and GVL by distillation.
liquid precursors, and using lower pressure GXLs. Here, we Another elegant example of integrating reaction and separation
give some examples where scCO2 offers real processing into a single operation was demonstrated by Harwardt et al.,58
advantages over more conventional solvents. who designed a reactor with two temperature zones to exploit the
change in solvent properties of CO2 with temperature, Fig. 5.
Controlled phase separation
A homogeneous mixture of the substrates, catalyst and CO2 was
In some cases, the miscibility of two liquids decreases rather than formed in the lower, cooler zone, allowing reaction to occur under
increases when expanded with CO2. This effect, first reported by single phase conditions. When, however, the reaction mixture
Lazzaroni et al.,56 typically occurs when one liquid is water and flowed to the hotter, upper zone, the solubility of the metal-
the other is a water-miscible organic. In such cases, the expansion phosphine catalyst was significantly reduced due to the dramatic
with CO2 can promote the separation of organic and water-rich decrease of CO2 density. The catalyst therefore precipitated and
phases. For example, Bourne et al. reported57 that, in the fell back into the lower zone where it redissolved allowing the
hydrogenation of levulinic acid, Scheme 7, pure g-valerolactone continuous recycle of catalyst. By contrast, the reaction products
product could be separated from the coproduced water by using had sufficient solubility in the hotter zone to stay in solution and
the pressure of CO2 already present inside the reactor. In this to flow out of the reactor with the CO2. Successful operation was
way, the product could be separated without any additional demonstrated on the catalytic isomerisation of allylic alcohols,
input of energy, Fig. 3. This was achieved by combining the use Scheme 8.
of water as a co-solvent, and of CO2 to manipulate the phases.
1432 Chem. Soc. Rev., 2012, 41, 1428–1436 This journal is c The Royal Society of Chemistry 2012
the authors could achieve minimal catalyst leaching and reaction
rates comparable to current industrial processes.
Hintermair et al. then applied this concept further to the
Scheme 8 The isomerisation of allylic alcohols, carried out using the asymmetric hydrogenation of dimethyl itaconate by using a
reactor in Fig. 5. chiral Rh catalyst,64 and obtained >99% ee enantiomerically
pure product for periods of up to 10 h, Scheme 9.
Tunable selectivity
The high enantioselectivity achieved in the example above was
Published on 16 January 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15314A
Scheme 11 The selective acid–catalysed diastereoselective oxidation66 of methionine derivatives observed only at 180 bar pressure in scCO2.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 1428–1436 1433
Oxidation
Apart from reaction selectivity, a strong dependence of reac-
tion rate on pressure has also been found in some cases where
CO2 has been used as solvent. For example Caravati et al.,
reported68 that in the catalytic oxidation of benzyl alcohol to
benzaldehyde in CO2 (0.8% toluene), the conversion rose from Fig. 8 Schematic of the continuous photo-oxidation76 using immobilised
25% to 75% when the pressure was increased from 140 to 150 photocatalysts in scCO2, the use of LEDs is much more energy efficient
bar, Fig. 7. than conventional light sources.
This increase in conversion was again closely linked to the
that a single phase condition was essential for achieving high
Published on 16 January 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15314A
1434 Chem. Soc. Rev., 2012, 41, 1428–1436 This journal is c The Royal Society of Chemistry 2012
statistically useful amounts of data to be obtained whilst decreas-
ing the amount of manual control and monitoring required during
an experiment. Furthermore, the on-line sampling system
permitted quantification of all products, including those volatile
compounds, such as dimethyl ether (bp: 24.8 1C), that would
evaporate during the expansion stage of a non-automated reactor.
This technique has then been applied to a range of different
reactions, such as hydrogenation,42 aldol condensation,41 and
methylation.65
However, this automated reactor varies only a single parameter
Published on 16 January 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15314A
et al. developed a reactor capable of self-optimisation;78 it combines primary alcohols, 2, with dimethylcarbonate78 (Reproduced from
the use of an automated reactor with feedback generated by an ref. 78, copyright Wiley).
evolutionary search algorithm, Fig. 9. All the data of reaction
parameters such as pressure, temperature, the flow rates of CO2 same volume of parameter space with Walsh’s automated
and organic substrates are used as inputs for the control algorithm, reactor.33
which is based on the super modified simplex (SMSIM) This work represents a significant step forward in the use of
algorithm.79 This algorithm then outputs control signals to change optimisation algorithms for scCO2 reactors. However, it is not
the temperature, pressure, and the flow rates of the pumps to new merely the maximum yield of a product, which can be optimised.
values calculated to improve the yield of desired product. Two The conditions could also be optimised for different criteria, such
reactions, the dehydration of ethanol and the carboxymethylation as maximising or minimising the ratio of two products, minimising
reaction of dimethylcarbonate, Scheme 13, were chosen to validate the production of an unwanted by-product, or even minimising
this self-optimising reactor. Three parameters of the reactions the E factor (kg waste/kg product) of the reaction, which is
(pressure, temperature and CO2 flow rate) were varied at the same particularly interesting in the context of Green Chemistry.80
time. This greatly improved the efficiency of the optimisation;
maximising the yield of 2b or 2c. Each optimisation took
ca. 35 h to complete, far less than the time required to cover the
Conclusions
This review has considered some of the problems associated with
continuous reactions in scCO2. By far the most serious problem is
the energy cost associated with compressing CO2. In the long
term, it may well be possible to offset this energy burden by
exploiting CO2, already compressed in Carbon Capture and
Storage. However, large scale implementation of CCS is still
some years off. Therefore in the short term, the most promising
strategy will be to deploy CO2 in applications where there is a
genuine chemical advantage to be gained by its use. The most
obvious area is oxidation where the chemical inertness of CO2
cannot be matched by other common solvents apart from water.
The use of singlet oxygen in scCO2 is particularly promising
because 1O2 has a very short lifetime in water. In addition, there
are now sufficient examples to suggest that scCO2 can give
unusual or improved selectivity in a range of reactions compared
to more conventional solvents. Overall, the current surge in
interest among organic chemists in flow chemistry makes it likely
that continuous reactions in scCO2 will find an increasing number
of applications in the coming years.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 1428–1436 1435
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