13

Epilogue

Having reached this chapter, you may be wondering how to apply SCF
technology for your particular application. It is not our desire to espouse any
hard and fast rules about SCF technology. In fact, the potential for this
technology, in our opinion, is bounded only by the imagination of the
researcher who speculates on its potential application. But, as we demonstrated repeatedly throughout the book and in the patent appendix, imagination
should not cloud sound engineering judgement. Certainly the literature should
be reviewed to see whether SCF processing has either already been applied to
the problem or whether the technology will a priori work for the application.
When reviewing the literature it is important to remember that there are
terminologies associated with any new technology that connote different things
to different disciplines. For instance, it is necessary to be cognizant of what
some researchers define as solubility or extractibility. As an example let
us consider further the work of Stahl and coworkers, analytical chemists who
present much of their data in terms of threshold pressures, that is the
pressure at which a compound is detected as being soluble in a supercritical
fluid.
The detection of a compound solubilized in an SCF is a function of the
sensitivity of the detector and the measurement technique. For example, in a
flow system such as described in chapter 4, gravimetric analysis is usually used
to identify the material collected. For this detection technique, levels of at least
a few milligrams of collected material are required to establish the concentration of the compound with some reasonable accuracy. But suitably modified,
the same flow-through apparatus can be used quite accurately to determine
substantially lower concentrations and absolute amounts of material. The
modified collection scheme consists of a chromatographic valve-trap and the
collected material is measured by gas chromatography, as shown in chapter 4.
As a third detection alternative, Stahl and coworkers (1980) use a flow-through
system coupled with a thin-layer chromatograph (TLC). The expansion valve
in this system is extremely small; its overall dimensions are a few hundreths of
a centimeter and it has a short capillary tube of 0.005 cm inner diameter
located downstream of the orifice. The compound that precipitates from the
expanding stream impinges directly onto a TLC plate. The effect of system
367

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Epilogue

Table 13.1 Detection Limits of Common Monitors

Detection Principle

Sensitivity
(g)

Gravimetric
Infrared spectroscopy
Ultraviolet spectroscopy
Mass spectrography
Flame ionization

10-3
10-7
10-9
10-9
10-10

TLC visualization

10-12

temperature and pressure on the extraction characteristics of the SCF is

evaluated by allowing the stream leaving the expansion valve to impinge on
different sections of the TLC plate, which is subsequently developed to
determine the amount of material present. TLC analysis is an extremely
sensitive analytical technique that will identify much smaller amounts of a
compound at a given threshold pressure than will a gravimetric method.
Table 13.1 lists the detection limits (King, 1984) of a number of
spectroscopic and chromatographic analytical methods employed in supercritical extraction studies. A gravimetric method requires a few milligrams of
material for analysis; TLC analysis can detect materials at solubility levels one
billion times lower! If we are measuring the threshold pressure at which the
compound dissolves at a detectable level, an analytical method that can
identify
g will result in the identification of a lower threshold pressure than
can be ascertained in the gravimetric method. The threshold pressure is
therefore a function of the sensitivity of the analytical method. By itself, it is
certainly not the critical criteria for determining the feasibility of a potential
SCF process. Nevertheless, the work of Stahl provides us with a wealth of
solubility information that we briefly consider here.
Figure 13.1 is a graph of data from Stahl et al. (1980). It shows the
solubility of a number of compounds in C 0 2 at 40C and a range of pressures,
and it highlights the relative order of progression of solubility of the
compounds ranked on the basis of structure and functional groups. Although
naphthalene is not shown in this graph, let us consider the solubility of
naphthalene in C 0 2 . Naphthalene is of reasonably low molecular weight, so we
would expect it to dissolve to some respectable concentration level. Benzoic
acid, even though lower in molecular weight than naphthalene, can hydrogen
bond to itself, thus increasing the difficulty for C 0 2 to solubilize the
compound. The solubility data for a benzoic acid in this figure corroborate this
fact. Progressing down the column of molecular structures, we find that
increasing numbers of hydroxyl groups lower a compounds solubility quite
dramatically. For example, frangulin exhibits a solubility level of only
0.0001 wt%. The last, and least soluble, compound in the figure is glycine, the

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Epilogue

7 BENZOIC ACID
COOH

T = 40.0 " C

6 . S A L I C Y L I C ACID
COOH

0 OH

IO00

5. 1.8-DIHYDROXYANTHRAQUINONE
OH 0 OH

@@
0

IO0
4. P-HYDROXYBENZOIC ACID

OH

IC

3. EMODIN
OH 0 OH

2 FRANGULIN
OH 0 OH

OR

CH3

0.1

1.2

0.5

.o

R=
O H 'OH

I. GLYCINE
H 2 N C H 2 COOH

CO2 DENSITY ( q / m I )
Figure 13.1

Solubility levels of various organic compounds in supercritical carbon

dioxide.
simplest amino acid. The values of solubility of glycine are obtained with TLC
measurements. Strictly speaking, glycine is soluble in C 0 2 . However, a
solubility level of approximately 0.00001 wt% at a density of 1.O g/ml (approximately 500 bar) is considered of little practical value, unless the objective is to
remove a soluble contaminant from glycine.
There is also in the literature a reference to the solubility of carbohydrates
in C 0 2 . Specifically, Giddings, Myers, and King (1969) measured the migration
of various compounds in ultrahigh-pressure C 0 2 . At a pressure of 2,100 bar
(-30,000 psia), for example, they "detected" sucrose through flame ionization
detection. Table 13.1 indicates that the detection limit of flame ionization is
lO-"'g. For practical purposes, sugar is insoluble in C 0 2 . Therefore, when

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Epilogue

referring to the literature for information on the solubility behavior of

compounds in SCFs, it is important to evaluate as quantitatively as possible (or
as realistically as possible) the rather qualitative question: Is the compound
soluble in COz or any other SCF?
In the same manner in which we discussed solubility let us examine
extractability. Quite frequently a compounds extractability by a supercritical
fluid has no relation to its solubility in that supercritical fluid. Chapter 8
showed that the pesticide diazinon dissolves to a high level in C 0 2 , but it is not
extractable from activated carbon. Chapter 8 also discusses separation of acetic
acid from water. Acetic acid is infinitely miscible with C 0 2 but it exhibits a
distribution coefficient of only 0.03. Again, strictly speaking, acetic acid is
extractable but we feel that extractability should be evaluated in terms of a
potential practical process. Supercritical extraction of acetic acid would
probably not be an attractive alternative relative to traditional distillation. O n
the other hand, a distribution coefficient of 0.03 might be satisfactory for the
extraction of a heat-labile compound from dilute solution. Therefore, even
though we have developed certain useful generalities, it is still important to
evaluate each case separately.
How does one evaluate the process viability of an SCF application? We
have touched on economics several times in the preceding chapters, but only
superficially. As there are no hard and fast answers to questions of viability
with traditional processes, so are there none with supercritical fluid extraction.
Nevertheless, both of us are asked quite frequently: How much will it cost? To
indicate why there is no single answer, we list below just a few of the
parameters that influence the cost of a supercritical fluid separation process:

pressure level;
pressure reduction ratio;
distribution coefficient;
solubility level; and
amount of material to be extracted.

All these items must be specified and they all affect capital and operating
costs. We have mentioned product cost several times in this book, but we do
not mean to imply that product cost is the most important factor to be
considered. As we related in chapter 7, there are hop extraction plants in
operation, and hop extract sells for $30 per pound; yet there are also many
propane deasphalting and residuum extraction plants in operation, and these
petroleum products sell for only 10 cents per pound. These two products are on
the opposite ends of the commodity spectrum, and their respective processes
represent the potential breadth of application of supercritical fluid technology.
We have attempted to give you an inclusive, in-depth analysis of this, no
longer. unconventional technology. Our intent has been to teach you the
fundamentals of this technology as much as to give you examples of its
application. As we described in the preceding chapters, in certain areas the

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371

technology was successful, in others it wasnt. For example, in the first chapter
we described SCF processes that operate at the multi-million pounds per year
level. In chapter 8, we described some processes that did not reach the
industrial level. However, in the analysis of these applications, we have
supplied you with guidelines and criteria which you can now apply when
considering supercritical fluids for your particular needs. As the myth and
mystery of supercritical fluids are removed, practicing scientists and engineers
will become more comfortable with applying this technology to as yet
undefined separation problems.