Lecture 21: Green Chemistry and

Technology

Course Instructor: Prof. Abu Taleb Khan

Course code: CH 426
Credit: 6

11/8/2023
 Supercritical Fluids

A supercritical fluid (SCF) can be defined as a compound which is above

its critical pressure (Pc) and its critical temperature (Tc). Above Tc and Pc
the material is in a single condensed state with properties between those
of a gas and a liquid.
Simplistically, the process can be viewed as the coming together of the
densities of the liquid and gaseous phases along the co-existence line as
shown in Figure.

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 Supercritical Fluids

Phase diagram showing supercritical fluid region

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 Supercritical Fluids
 As the temperature of a liquid rises, it becomes less dense, and as the
pressure of a gas rises, it becomes more dense; at the critical point, the
densities become equivalent.
 Generally, SCFs have densities nearer to liquids and viscosities similar
to gases, leading to high diffusion rates.
 The properties of the fluid can be adjusted by altering the temperature
and pressure as long as they remain above their critical points. In
principle, by increasing the pressure at the critical temperature,
solids can be formed, but for most materials, the pressures
required to do this are very high, 5700 bar for CO2. The critical
temperature and pressure vary very widely from material to
material.

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 Supercritical Fluids

Critical points of some common supercritical fluids

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 Supercritical Fluids
 For many applications, this has historically limited the practical utility
of materials, notably water, which have a particularly high critical
temperature and/or pressure.
 Supercritical fluids have been known for well over a hundred years, but
it is only since about 1980 that their huge potential has been
recognized. That said, a small number of high-temperature and pressure
processes have been operated in the supercritical region for many
years.

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 Supercritical Fluids
Two of the most widely known ones are:
 High-temperature and High-pressure free radical polymerization of
ethene to produce low-density polyethene (LDPE).
 The Haber process for ammonia manufacture operates above the
critical point of ammonia.
Until the mid-1980s these were two of the few processes operating under
supercritical conditions. These processes were not specifically developed
to operate under supercritical conditions; nevertheless, the advantages
have since become clear.

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 Supercritical Fluids
Typically, the key advantages of carrying out a process under
supercritical conditions include the following:
 Improved heat and mass transfer due to high diffusion rates and low
viscosities.
 The possibility of fine-tuning solvent properties by varying temperature
and pressure.
 A potentially large operating window in the supercritical region.
 Easy solvent removal and recycling.

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 Supercritical Fluids
 As noted previously, different materials have very different critical
points, which are more or less accessible, so what is the real value of
supercritical fluids in Green Chemistry? It can, somewhat simplistically,
be argued that if an advantage such as increased reaction rate or
increased solubility is brought about by the use of a solvent in the
supercritical state then this can be considered a ‘green’ improvement.

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 Supercritical Fluids
However, it may be the case that the, often-significant, energy
requirements of operating supercritical processes outweigh any in-process
environmental benefits. In most cases the reference to supercritical
fluids being ‘green’ refers to the replacement of an organic solvent with a
more benign supercritical fluid, notably carbon dioxide or water. Here
real environmental as well as technical advantages can be obtained.

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 Supercritical Carbon Dioxide (scCO2)
Interest in SCFs, and scCO2 in particular, arose out of the 1970s energy
crisis.
Separation processes involving distillation are amongst the most energy-
intensive processes operated by the chemical industry. If the separation
can be carried out by extraction into a solvent that does not need to be
removed by distillation there is the potential for saving energy. Carbon
dioxide has many ideal characteristics for this type of application, not
least its relatively accessible triple point and the fact that it can simply be
removed by reducing the pressure.

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 Supercritical Carbon Dioxide (scCO2)
It is worth mentioning at this point that, unlike CO2 produced from
burning fossil fuels, CO2 released from its use as a solvent does not
give a net contribution to global warming. This is because the CO2
used is an industrial by-product (often from ammonia
manufacturers or breweries) that would normally have been
released into the atmosphere.

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 Supercritical Carbon Dioxide (scCO2)
The two main uses for scCO2 are as an extraction solvent and as an
in-process solvent. Another, as yet small-scale but environmentally
significant, use is as a solvent/dispersion medium for spray coating.
Some of the many advantages and a few disadvantages of using
scCO2 for these applications are shown in Table 2.

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 Supercritical Carbon Dioxide (scCO2)

Advantages and disadvantages of using scCO2 as a solvent.

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 Supercritical Carbon Dioxide (scCO2)
In terms of reaction chemistry one of the greatest advantages of scCO2 is
its miscibility with gases, arising from the gas-like nature of the fluid. This
can lead to significant rate enhancements in reactions such as
hydrogenation compared to the use of conventional organic solvents that
are relatively poor solvents for hydrogen. Whilst this is a definite
advantage it can pose heat-transfer challenges for particularly exothermic
reactions. Carbon dioxide has interesting and unusual solvent properties.

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 Supercritical Carbon Dioxide (scCO2)
Being non-polar, it may be expected to be a good solvent for
hydrocarbons, but this is generally not the case owing to its high
quadrupole moment. Several ways have been identified to overcome this
limitation, including using small amounts of co-solvent.
However, the high quadrupole moment means that scCO2 is a relatively
good solvent for small polar molecules like methanol and caffeine. The
lack of polarity positively influences many reaction rates since CO2 does
not readily coordinate with many catalysts or solvate complexes. Although
CO2 is relatively inert it does react with good nucleophiles such as
amines, which means that it cannot be used as a solvent for certain
reactions.

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 Extraction Process
One of the most widely established processes using scCO2 is the
decaffeination of coffee. Before the widespread use of this process in the
1980s, the preferred extraction solvent was dichloromethane. The
potential adverse health effects of chlorinated materials were realized at
this time, and although there was no direct evidence of any adverse health
effects being caused by any chlorinated residues in decaffeinated coffee,
there was always the risk, highlighted in some press ‘scare’ stories. Hence,
the current processes offer health, environmental and economic
advantages.

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 Extraction Process
 The basic process outline is depicted in Figure; moist unroasted coffee
beans and CO2 are fed counter-currently into the extractor under
supercritical conditions. Caffeine is selectively extracted into the CO2
and this stream is led to a water-wash column to remove caffeine at a
reduced pressure, the CO2 being recycled back to the extraction
column. Extraction of the caffeine into water is necessary to avoid
dropping the CO2 pressure too low, since compression is energy-
intensive. There is now the problem of separating the caffeine (which is
used in soft drinks and pharmaceuticals) from the water.

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 Extraction Process

Essentials of coffee decaffeination process

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 Extraction Process
Distillation is also an energy-intensive process; many modern plants use
reverse osmosis or membrane technology to concentrate the aqueous
solution. There are two other interesting observations to make about the
process. First, whilst scCO2 selectively extracts caffeine from green
coffee beans, it co-extracts many of the aroma oils produced on roasting if
carried out after the roasting process. Secondly, some moisture is
required in the extraction process. This is thought necessary to free the
caffeine from complexes within the bean in some way; moisture was also
required in the dichloromethane process.

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 Extraction Process
Because of its benign nature and efficiency, this small- to medium-scale
extraction process is becoming increasingly common in the food flavour
and fragrance industries. Examples include extracting flavours from hops,
extracting essential oils, and defatting nuts and fried goods. For example,
the demand for healthy, tasty snacks like potato crisps is growing rapidly.

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 Extraction Process
Conventional potato crisps are highly calorific, some brands containing
over 45% fat, and within the normal cooking and processing of crisps,
there is limited scope for significantly reducing the fat content. By using
scCO2, the fat content can be reduced by up to 50% without, it is
claimed, any loss of flavour. The relatively high solubility of fatty acid
triglycerides in scCO2 is also central to several studies looking at
separating vegetable oils from soya protein. This can be efficiently
achieved, provided the cell walls are broken down before extraction.

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 Extraction Process
Dry cleaning is another recent successful commercial application for high-
pressure CO2 technology, which may be considered an extraction process.
Traditionally, most dry cleaning processes have used chlorinated solvents,
initially highly hazardous carbon tetrachloride and now perchloroethene
(perc). Even though solvent recovery and recycling are efficient, many
environmental and health concerns surround the process, including
contaminated land from previous dumping of used perc (resulting in
contaminated drinking water) and the fact that it is a suspected
carcinogen.

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 Extraction Process
With some 180000 dry cleaning units worldwide using perc: the
adoption of CO2-based cleaning processes could make a significant
overall impact. Carbon dioxide has technical advantages over perc:
items that cannot be dry cleaned with perc, such as leather, fur, and
some synthetics, can be safely cleaned with CO2. A second claimed
advantage is the improved colourfastness of some garments.
Repeated traditional dry cleaning removes small amounts of certain
dyes, gradually altering the colour of the garment over time; this is
claimed not to be the case with the CO2 system.

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 Extraction Process
Strictly speaking, most high-pressure CO2 cleaning processes
operate at sub-critical temperatures and pressures, i.e. in liquid
CO2, for economic reasons. However, as the liquid is relatively close
to the critical point, many properties, such as low viscosity and
surface tension, are similar to scCO2. These two properties are
primarily responsible for the efficiency since the CO2 can readily
penetrate the fibrous structure of the garments being cleaned.

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 Extraction Process
Because of the solvent properties of scCO2, it may be expected to be a good
dry-cleaning solvent for fatty and greasy stains but less good for stains
originating from red wine, egg yolk, etc. To overcome this, commercial systems
also use a surfactant. These surfactants differ from those used in wet cleaning
since they must be compatible with the stain and CO2. The surfactants used are
proprietary but are thought to contain fluorinated functions, making them CO2-
compatible. Such surfactants are expensive and are largely recycled. Related
cleaning processes are now being developed for other applications. Some are far-
reaching and could provide significant environmental advantages, such as
degreasing electronic components.

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 Supercritical CO2 as a Reaction Solvent
The use of scCO2 as a reaction solvent is an area of current significant
research activity. The previous lack of attention is partly due to the
difficulties of conducting such high-pressure experiments in university
laboratories. One of the most studied areas is polymerization; here,
supercritical fluids can obtain polymers of different molecular weights by
altering the medium's density through simple pressure variation.
Polymerization of fluorine- and silicon-containing monomers has been
particularly well studied; this has largely been driven by the lack of
solubility of these materials in organic solvents.

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 Supercritical CO2 as a Reaction Solvent
Free radical polymerization (using a free radical initiator such as AIBN) of
acrylate monomers containing perfluoro-ponytails proceeds well at
around 60 oC and pressures over 200 bar.

Interestingly, the initiator decomposes more slowly in scCO2 than in

conventional solvents. However, overall it is more efficient owing to the
lack of cage effects in the low viscosity medium.

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 Supercritical CO2 as a Reaction Solvent
One of the challenges of polymerizing polar materials such as
acrylates in scCO2 is to build up the molecular weight to the stage
where they become commercially attractive before they fall out of
the solution. Using small amounts of dispersing agents, essentially
surfactants, having CO2-compatible groups (e.g. siloxanes), the
polymer can be kept in solution until useful molecular weights are
obtained. ScCO2 is also an ideal inert solvent since there is virtually
no chain transfer, even from highly electrophilic radicals. This effect
has been put to use in the polymerization of tetrafluoroethene.

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 Supercritical CO2 as a Reaction Solvent
Dupont has recently commercialized a process for producing PTFE in
scCO2, replacing ozone-depleting chlorofluorocarbon solvents. Although
more soluble in scCO2 than the acrylate system discussed above, the
build-up of sufficient molecular weight is still a concern. In this case,
small amounts of co-monomer can be added to disrupt the crystallinity,
the amorphous polymer being more soluble, particularly at high
temperatures.

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 Supercritical CO2 as a Reaction Solvent
Recently, several examples of polymerization of non-fluorinated
monomers have been developed. Through a thorough analysis of
polymer–scCO2 interactions involving both entropy and enthalpy, it has
been possible to prepare designer polymers, which may lead to the
developing of more commercially useful systems.

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 Supercritical CO2 as a Reaction Solvent
One example is the synthesis of polyether-polycarbonates from propylene
oxide, using CO2 as a solvent and a reagent, in the presence of a
heterogeneous zinc or aluminium catalyst. This polymer is highly flexible
(favourable entropy of mixing), owing to the presence of carbonate
groups and only has weak inter-chain polymer–polymer interactions,
both aiding solubility in the solvent.

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 Supercritical CO2 as a Reaction Solvent
Synthesis of PET from polymerization of ethene terephthalate has also
been carried out in scCO2. In this case, the CO2 swells the polymer,
acting as a plasticizer, aiding the removal of co-produced ethene glycol.
Several other polymerization processes have also proceeded well, often
advantageously, in scCO2. These include the ring-opening metathesis
polymerization of norbornenes and the cationic polymerization of
isobutene, which is conventionally carried out in chlorinated solvents.

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 Supercritical CO2 as a Reaction Solvent
Because of the high pressures involved, supercritical conditions may offer
significant rate advantages for addition polymerization processes, since
these have negative intrinsic activation volumes. Possibly the greatest
benefit of carrying out polymerization reactions under supercritical
conditions is the ability to fractionate polymers of a narrow molecular
weight range. This arises from the ability to closely control the density of
the medium, and hence polymer solubility, through variation of pressure.

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 Supercritical CO2 as a Reaction Solvent
Palladium-catalysed carbon–carbon bond-forming reactions such as the
Heck and Suzuki reactions are versatile and efficient methods for
synthesising fine and pharmaceutical intermediates, but such reactions
often suffer from catalyst-separation problems. As well as avoiding organic
solvents, carefully designed fluorine-containing phosphine ligands scCO2
offer a potential solution to this problem since, in principle, the product
can be separated from the reaction mix whilst the active catalyst remains
in solution.

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 Supercritical CO2 as a Reaction Solvent
The main drawback of this approach is that the fluorinated phosphine
ligands are very expensive and difficult to prepare. Recent work has,
however, shown that similar results can be obtained using more
conventional phosphines with fluorinated Pd sources [e.g. Pd(OCOCF3)2].
The first example involving amino iodo benzene is interesting because the
CO2 affords protection to the amino group via the formation of carbamic
acid; this avoids the need for an additional reaction step involving an
ancillary reagent.

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 Supercritical CO2 as a Reaction Solvent

Examples of Pd carbon-carbon bond formation in scCO2

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 Supercritical CO2 as a Reaction Solvent

Examples of Pd carbon-carbon bond formation in scCO2

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 Supercritical CO2 as a Reaction Solvent
Hydrogenation is one of the most well-studied synthetic reactions in
scCO2, one of the main technical reasons for this being the high
miscibility of H2 with scCO2 compared with its solubility in organic
solvents. This high miscibility overcomes the mass-transfer limitations
which often control the overall rates of many hydrogenation processes. A
consequence of this, however, is the often reduced solubility of reagents
which now may become rate determining. In the presence of a suitable
catalyst CO2 itself may be hydrogenated to formic acid. In most cases
this will be an unwanted side-reaction and catalysts should be chosen to
avoid this complication.

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 Supercritical CO2 as a Reaction Solvent
On the other hand if the reaction can be made to go efficiently it could
become a very ‘green’ source of formic acid, using up unwanted CO2.
Ruthenium/phosphine catalysts are efficient for carrying out this
reaction but the insolubility of triarylphosphine ligands in scCO2 has
proved problematic. More success has been obtained using the more
soluble P(Me)3 ligand.

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 Supercritical CO2 as a Reaction Solvent
 Many homogeneously and heterogeneously catalysed hydrogenation
reactions have been studied in scCO2 with high yields generally being
obtained. Although the scope of homogeneously catalysed reactions can
be limited by the catalyst solubility problems highlighted above,
heterogeneous catalysts have been found to be very effective. Rate
enhancement in heterogeneous systems is thought to be largely due to
improved mass transport within catalyst pores brought about through
the low viscosity of the medium.

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 Supercritical CO2 as a Reaction Solvent
 Several enantioselective hydrogenations have also been carried out using
chiral catalysts. Although the enantioselectivity can be optimized to a certain
degree, by control of reactions conditions, there are few cases in which the
use of supercritical conditions has significantly enhanced enantioselectivity.
Scheme highlights some of the reactions that have been successfully carried
out.

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 Supercritical CO2 as a Reaction Solvent

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 Supercritical CO2 as a Reaction Solvent
The high reaction rates found for many heterogeneously catalysed
reactions is being commercially exploited by Thomas Swan & Co. using
technology developed at Nottingham University (using a Pd catalyst
supported on polysiloxane). One of the main commercial blocks to more
widespread use of supercritical fluids has been the cost of large high-
pressure reactors. Because of the rapid reaction rates found, high
throughputs can be obtained from bench-top size reactors, significantly
reducing overall plant cost. By having several of these small reactors
operating in series throughputs of tens of thousands of tonnes per year
can be achieved in a continuous process over a fixed-bed catalyst.

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 Supercritical CO2 as a Reaction Solvent

Schematic of a continuous supercritical hydrogenation reactor

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 Supercritical CO2 as a Reaction Solvent
Such reactors are, of course, much simpler to operate if both product and
starting material are liquids and the starting material is soluble in the
reaction medium. In situations where this is not the case a co-solvent such
as methanol may be employed. This, of course, does raise some
environmental concerns since total containment of a volatile organic
solvent when the pressure is dropped from something over 100 bar is
not simple.

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 Supercritical CO2 as a Reaction Solvent
As will be evident from the hydrogenation of acetophenone, a great deal
of reaction control may be exerted to obtain the product of choice. This
‘tunability’ which may be achieved through control of pressure, tempera-
ture and CO2/H2 ratio as well as catalyst and co solvent is one of the
overriding aspects to the commercial viability of these flexible, multi-
purpose plants. In the case of acetophenone total hydrogenation to
ethylcyclohexane is achieved through variation of temperature and
CO2/H2 ratio.

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 Supercritical CO2 as a Reaction Solvent
The scope of reactions which can be potentially advantageously carried
out in a scCO2 medium is too large to cover fully in the space available;
these reactions include rearrangements, hydroformylation, Friedel–
Crafts, esterification and chlorination.

In organic solvents such as toluene or chloroform the endo:exo ratio is around

10:1 whilst in scCO2 ratios as high as 24:1 can be achieved.

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 Supercritical CO2 as a Reaction Solvent
 Oxidation

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