J.

of Supercritical Fluids 47 (2009) 598610

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Multiple unit processing using sub- and supercritical uids

Jerry W. King , Keerthi Srinivas
Department of Chemical Engineering, 3202 Bell Engineering Center, University of Arkansas, Fayetteville, AR 72701, USA

a r t i c l e i n f o a b s t r a c t

Article history: The past twenty years has seen an expansion of the critical uid technology platform with respect to
Received 31 July 2008 using or combining multiple types of unit operations and compressed uids in both their sub- and super-
Received in revised form 14 August 2008 critical states. Although supercritical uid extraction (SFE) utilizing supercritical carbon dioxide (SC-CO2 )
Accepted 14 August 2008
has seen considerable industrial use, the high capitalization cost of building and running such produc-
tion plants promotes expanding their use and functionality with respect to multi-unit operations and
Keywords:
multiple uids. An evaluation of the current status of implementing such an approach is provided, and a
Carbon dioxide
perspective of future needs suggested based on the senior authors 40 years of experience in critical uid
Critical uids
Multiple uids
processing of agriculturally-derived materials and natural products. The use of hot compressed water
Unit processes is no longer limited to just supercritical water processing, but can be advantageously exploited over a
Water wide range of temperatures and appropriate pressures to include extraction and reaction of targeted sub-
strates, including bioactive natural products, biomass conversion for renewable fuels, and synthesis of
chemicals. As noted previously, combining SFE with fractionation methods using critical uids, and/or
reaction chemistry in critical uid media can produce a variety of extracts or products [J.W. King, Sub-
and supercritical uid processing of agrimaterials: extraction, fractionation and reaction modes, in: E.
Kiran, P.G. Debenedetti, C.J. Peters (Eds.), Supercritical Fluids: Fundamentals and Applications, Kluwer
Publishers, Dordrecht, The Netherlands, 2000, pp. 451488.] however the modication of processing
equipment such as expellers, extruders, and particle production devices extend the use of the criti-
cal uid technology platform. Sequential unit processing using multiple uids also has been reported
although demonstrated to a limited degreehowever combining both compressed CO2 and water in a
unit process can also impart some unique processing possibilities. The concept of multiple unit and uid
processing supports an environmentally benign or green production platform and is consistent with
processing sustainable materials. Integration of critical uids into existing processing concepts such as
biomass conversion, bioreneries, and synthesis based on methyl ester intermediates are discussed.
2008 Elsevier B.V. All rights reserved.

1. Introduction
Supercritical uids and their liqueed analogues have been
traditionally used in single unit operations, i.e. extraction, fraction-
ation, using neat SC-CO2 or with appropriate modiers [2]. Since
the 1980s, almost 38% of the supercritical uid extraction pro-
cesses have been devoted to extraction of food and natural products
[3]. Beginning in the mid-1980s, columnar and chromatographic
techniques followed by reactions in supercritical uids were devel-
oped to facilitate supercritical uid derived extracts or products
[4], thereby extending the application of a critical uids processing
platform beyond SFE. These newer developments were investigated
in part due to the complexity of many natural product matrices
and the desire to concentrate specic target components for food
Corresponding author. Tel.: +1 479 575 5979; fax: +1 479 575 7926.
E-mail address: jwking1@uark.edu (J.W. King).
and other industrial uses, as illustrated in Fig. 1. This approach has
been summarized by the senior author and others in previous pub-
lications [1,5,6]. The perspective we offer here is somewhat biased
towards past and current studies which focus on advancing multi-
ple unit and/or uid processing of agriculturally-derived materials
or natural products.
Despite this focus, the perspective we offer opens other options
for applying critical uids in general by embracing the idea of
tandem processing using different compressed uids. Commen-
surate with the goal of environmentally benign processing is the
use of liqueed or supercritical CO2 for non-polar to moderately
polar solutes, and compressed water between its boiling and criti-
cal points for more polar solutes and reactants. Ethanol, a naturally
derivable sustainable solvent, is suggested as a preferred co-solvent
to be paired with compressed water or carbon dioxide. This sim-
ple, renewable compressed uids platform has many advantages
and can be used to achieve multiple results, particularly when used
sequentially, or in tandem with multiple unit processes.

0896-8446/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.supu.2008.08.010
 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610 599

Fig. 3. Coupled processing options for critical uids.

Fig. 1. Integration of multiple unit critical uid processing for processing natural
products. schemes, and oversight by revenue authorities. These are some
of the factors which accelerate research in the use of subcritical
water for the extraction of natural products and nutraceutical food
We have found that the generic solvation properties of the
components. This aids in considering the widespread utilization of
two principal critical uids, CO2 and water, to be explained by an
water and carbon dioxide as a part of the overall critical technology
extended solubility parameter approach [7,8]. Hence by adjustment
platform [1].
of pressure and temperature for CO2 , or temperature in the case
Traditional oleochemical processing operations such as fat
of water, one can optimize the solubility of solutes or reactants in
splitting or hydrogenation are often conducted under either sub-
these media, or predict their miscibility, by comparing their relative
critical or supercritical processes. Fat-splitting processes such as
solubility parameters as a function of temperature and pressure.
the Twitchell process [12] or Colgate-Emery synthesis [13] uti-
Such an approach has a practical value considering the molecular
lize temperatures and pressures in excess of the boiling point of
complexity of many solute types processed in critical uids. Their
water under the appropriate pressure, but below the critical point
solubility parameters or soluteuid interactions can be explained
of water to facilitate the hydrolysis of triglycerides to fatty acids.
by using the Hansen three-dimensional solubility concept which
However, it should be noted that these processes were frequently
allows the application of functional group contribution methods
interpreted as steam-based hydrolysis rather than hydrolysis using
for calculating requisite physical property data as well as solute or
subcritical water. Hydrogenations using binary mixtures of CO2 -H2
solvent solubility parameters as recently reported by Srinivas et al.
or propane-H2 are supercritical with respect to the pure component
[9]. As indicated by Fig. 2, the reduction in waters total solubility
critical constants, but reaction conditions are conducted under less
parameter with increasing temperature is largely due to a reduction
dense conditions due to the high temperatures involved, and hence
in the hydrogen-bonding propensity as reected by its hydrogen-
the cited rapid kinetics associated with hydrogenations conducted
bonding solubility parameter component, H [10]. Water does not
under these conditions [14] refers more to the accelerated mass
attain the solvation properties of solvents like ethanol or methanol
transfer effects as opposed to reactant solubility enhancement.
until quite elevated temperatures which is in contrast to the often
Enzymatic-based synthesis under supercritical conditions has been
cited dielectric constant concept which is invoked to explain the
largely conned to laboratory-scale studies [1517] and the sensi-
solvent properties of subcritical water [11].
tivity of enzymes to operational parameters and their attendant
The above solvent properties of water as described by the
high cost suggests that their application maybe limited to the syn-
solubility parameter concept has some implications with regard
thesis of high cost products.
to its use as a green solvent and as a substitute for ethanol
The advantages of coupling processing options using critical
in hydroethanolic-based extractions which are GRAS (Generally
uids are illustrated in Fig. 3. Hence by combining different unit
Regarded as Safe)-approved food processing solvents. Its substi-
processes and sequencing them with the use of multiple uids
tution for ethanol as a processing medium is highly desired to save
held at operational densities by the application of different tem-
on processing costs, its separation from water in solvent recycle
peratures and pressures, one can obtain multiple products and
optimize the extraction or reaction process. Several specic options
are illustrated for the case of processing essential oils as noted pre-
viously in Table 1 [18] using pressurized uids. Here six discrete
unit processes are listed which include standard SFE with SC-CO2 ,

Table 1
Coupled processing options for essential oils processing using pressurized uids

Process
(1) SFE (SC-CO2 )
(2) SFF (SC-CO2 )Pressure reduction
(3) SFF (SC-CO2 )Column deterpenation
(4) SFC (SC-CO2 /co-solvent)
(5) SFF(subcritical H2 O deterpenation
(6) SFM(aqueous extract/SC-CO2 )

Processing combinations
(1) + (2)
(1) + (2) + (3)
(1) + (4)
(1) + (5)
Fig. 2. Three-dimensional solubility parameters of water as a function of tempera- (1) + (5) + (6)
ture.
600 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610

SFF (supercritical uid fractionation) employing stage-wise pres-
sure reduction, SFF as practiced using column-based deterpenation
[19], supercritical uid chromatography (SFC), another variant of
SFF called subcritical water deterpenation [20], and utilization of
a SC-CO2 or LCO2 with a perm selective membrane described by
Towsley et al. [21]. As shown in Table 1, combinations of these pro-
cesses can allow a total processing scheme to be conducted using
critical uids. For example, a combination of processes (1) and (2)
in Table 1 could be combined to yield a more specic composition
in the nal extract. Unit process (1) if conducted by sequentially
increasing the extraction density when coupled with a sequence
of let down pressures (unit process 2) can amplify the SFF effect.
Likewise, by combining unit process (1) using SC-CO2 followed by
application of unit process (2) utilizing subcritical H2 O to deterpe-
nate the extract from unit process (1), will yield a more specic
nal product from the starting citrus oil. To obtain a more enriched
and/or concentrated product from the latter process, one could add
unit process (6), a supercritical uid membrane-based separation
of the aqueous extract/ractions from unit process (5) as indicated
in Table 1.
We shall discuss several other combinations of unit processes
and uids below based on both our research and those of others
cited in the literature. Many of these examples are focused on the
processing of complex natural product mixtures, lipids and oleo
chemicals, and more recently the processing of biomass for value-
added extractives and conversion to fuel substrates, since we are
most familiar in applying critical uids in those areas.
2. Multiple critical uid processing platforms
In the broadest sense, multiple critical uid processing involves
the integration of two or more uids held under pressure applied
as either mixtures or in a sequential manner for one or more unit
processes. Listed in Table 2 are the most prevalent combinations
that have been utilized or have potential application in process
development. Solubility of solutes and reactants in SC-CO2 has been
extensively studied and a recent tome has assembled much of the
available data [22]. Likewise there is a fair understanding as to the
choice of a suitable co-solvent to pair with SC-CO2 to enhance the
solubility of more polar solutes in the compressed CO2 medium,
although binary phase equilibria data is not always available over
the desired range of pressuretemperature for such systems. This is
critical if one is concerned with operating in the one phase super-
critical uid region with respect to both components, however as
noted by several investigators [2325], there are several examples
where processing can be done with SC-CO2 co-solvent systems in
the two phase region. This situation becomes of interest partic-
ularly when large amounts of an organic co-solvent are used in
conjunction with SC-CO2 to enhance the solubilization of a solute
which exhibits limited solubility in neat SC-CO2 . The critical ques-
tion then becomes whether another compressed uid might better
be integrated into the design of the process.
As remarked previously, compressed water at high temperatures
and pressures, i.e., supercritical water has been extensively inves-
tigated for many years. In the 1990s a similar but somewhat more
diffuse focus on using water in its subcritical state with respect to
its. Tc received attention due to its application as a reaction medium
to transform organic chemicals and biomass into targeted products
[26,27]. Concurrently in the eld of analytical chemistry, subcriti-
cal water and other subcritical uids were explored as alternative
extraction solvents under external compression above their boil-
ing points [2830]. Analytical methods developed with the use of
pressurized solvents essentially use subcritical uids above their
boiling pointthe pressure applied frequently is far in excess of
what is required by inspection of the VL curves for these uids [31].
Unfortunately researchers in these disparate areas using water as a
common compressed uid have not always recognized its generic
utility as a universal compressed uid medium as well as green
complimentary solvent to compressed CO2 [7].
Recently we have attempted to explain the solvent charac-
teristics of water using an extension of the solubility parameter
concept, i.e., a three-dimensional solubility parameter approach,
by applying it to pressurized water [8,9]. Using the Hansen three-
dimensional solubility parameter approach coupled with SPHERE
and Hsp3D [32] software programs, we have studied the interaction
between subcritical water and complex organic solutes, including
biopolymers, as a function of temperature. Water under compres-
sion has the ability by adjustment of the applied temperature
and pressure to serve as an extraction solvent as well as a reac-
tion medium depending on what is desired. Residence time of the
solute (reactant) in the aqueous medium thus becomes a criti-
cal parameter in conducting extractions above the boiling point
of water and for optimizing reaction conditions higher up the
VL curve for water. There appears in our opinion the lack of ratio-
nale design for choosing reaction conditions in subcritical water,
although the semi-empirical severity parameter often-cited in
biomass conversion studies is one attempt to quantify the required
hydrolytic conditions [33]. Using a simple solubility parameter
approach, as depicted in Fig. 4, in which the solubility parame-
ter for water as a function of temperature is plotted along with
the solubility parameters for cellulose oligomers (n = 110), it can
be seen that the intercept between the solvent and the cellulose
oligomers corresponds to the chosen conditions for depolymeriz-
ing the carbohydrate polymers [7]. This conrms that conditions are
commensurate with those in which the biopolymer is dissolved or
miscible in the subcritical water medium. We have also used this
approach for other biopolymers treated in subcritical water such as
hemicellulose and chitin and rationalized the difculty in dissolv-
ing lignin-type polymers in subcritical water [7]. A similar approach
also has utility in understanding the subcritical water extraction

Table 2
Multiple critical uid processing options

Mode Example

Single uid Carbon dioxide, water

Single uid + co-solvent
Binary gases above their Tc
Single uid + dissolved gas
Sequential uids
Carbon dioxide + ethanol
Carbon dioxide + hydrogen
Water + carbon dioxide
Fig. 4. Solubility parameter variation for subcritical water at different reduced pres-
Carbon dioxide, then water
sures pr and cellulose oligomers (n = 110) with temperature.
 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610
Fig. 5. Variation of Hansen three-dimensional solubility parameter sphere of betulin
with subcritical water and ethanol at different temperatures.
of target solutes from natural product matrices, such as silymarins
from milk thistle, B-vitamins from brewers yeast, and anthocyanins
from grape pomace.
The Hansen three-dimensional sphere method noted above
can also be used in choosing a subcritical uid as an extraction
solvent and optimizing the extraction conditions. The three-
dimensional solubility parameters of water and ethanol at a
reference temperature (25 C) are obtained from Hansen [32] and
their temperature-dependence calculated using the approach of
Williams [34]. The Hansen spheres were then generated using the
Hsp3D program in a Matlab platform. The inverted white trian-
gles which appear in Figs. 5 and 6 below indicate that the targeted
solute is within the solubility sphere thereby ensuring high misci-
bility with the subcritical uid, while the dark triangles indicate
immiscibility between the solute and the subcritical uid refer-
601
Fig. 6. Variation of Hansen three-dimensional solubility parameter sphere of
cyanidin-3-O-glucoside with subcritical water and ethanol at different tempera-
tures.
ring to the compounds outside the Hansen solubility sphere. The
inverted white triangle on the other side of the center of the mass
of the sphere is the solute itself.
One study we have contributed to involves the extraction of
betulin from birch bark extracts using subcritical water or ethanol
as solvents. The experiments were conducted using subcritical
water maintained at 40180 C and 5 MPa using an analytical-based
extraction system. It was found that a limited amount of betulin
was extracted into subcritical water even at temperatures as high as
180 C. However, similar studies conducted with subcritical ethanol
yielded high amounts of betulin at 90 C and 5 MPa [35]. The three-
dimensional solubility parameter Hansen sphere plots for betulin in
water and ethanol respectively are shown in Fig. 5. Here the radius
of the Hansen sphere for the betulinethanol system is far less than
that observed for the betulinwater system. This is indicative of
602 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610
Fig. 7. Variation in the Hansen sphere radius (MPa1/2 ) versus %ethanol in com-
pressed waterethanol extraction solvent.
the fact that subcritical ethanol is a far better solvent under the
stated conditions than compressed hot water. A further study of the
relative energy difference (RED) values for the two solutesolvent
systems indicates miscibilitysolubility between 50 and 125 C in
the betulinethanol system with a maximum betulin solubility
occurring at 100 C [9].
Similarly in Fig. 6 are the Hansen spheres for the antho-
cyanin, malvidin-3-O-glucoside, in water and ethanol, respectively.
The sphere plots indicate a greater miscibility of malvidin-3-
O-glucoside in ethanol since the Hansen sphere has a lower
radius (7.23 MPa1/2 ) in the temperature range of 2575 C. For the
watermalvidin-3-O-glucoside system, the corresponding solubil-
ity sphere occurs over a different temperature range and a RED
radius of 10.35 MPa1/2 , higher than that for ethanol [8]. While both
subcritical solvents dissolve the target anthocyanin at different con-
ditions, clearly ethanol would be the preferred subcritical solvent
with respect to anthocyanin miscibility and solubility.
The three-dimensional solubility parameter sphere approach
can also be used to explain experimental results we have obtained
for the solubility and extraction of malvidin-3-O-glucoside in
compressed-hydroethanolic solvent medium. The Hansen solubil-
ity spheres were plotted for waterethanol mixtures and their
corresponding interaction radii versus the composition of subcrit-
ical waterethanol mixture is shown in Fig. 7. The plot shows
an initial substantial decrease in the interaction radius between
the anthocyanin and hydroethanolic mixture upon addition of
10% ethanol to water (this is due to the substantial decrease in
the hydrogen bonding solubility parameter with the addition of
ethanol to water). This is consistent with the enhanced extraction
recorded for the avonoid upon addition of ethanol to the extrac-
tion medium. Note that although in Fig. 7 the minimum interaction
radius occurs at 80% ethanol concentration, there is not a signif-
icant difference with that recorded at 10% ethanol content. This
has important implications for designing the best extraction condi-
tions and minimizing the amount of co-solvent (ethanol) required
in extracting the target avonoid.
The use of compressed gases at conditions far above their crit-
ical temperature as diluents in a highly compressed supercritical
uid such as SC-CO2 has been studied by several groups [3638].
Such binary mixtures of compressed gases may act as co-solvents
or antisolvents depending on their Tc s relative to that of supercrit-
ical uid [39]. Helium and nitrogen have been previously studied
as anti-solvents in supercritical uid extraction of caffeine [40] and
lipids from soybean oil [41]. For the extraction of caffeine when
using supercritical carbon dioxide as a solvent, increasing the con-
centration of nitrogen led to a dramatic reduction in solubility of
caffeine in CO2 . Similar trends were recorded when helium was
added to SC-CO2 for the solubility of soybean oil in SC-CO2 . This has
important implications for conducting reactions in SC-CO2 since
the addition of hydrogen to SC-CO2 permits higher hydrogenation
reaction rates to be attained [42], but at the cost of reduced solute
solubilities in the more highly compressed supercritical uid com-
ponent. Dissolved gases in compressed dense uids or liquids can
have a profound effect on the extraction of solutes from substrate
using such modied solvents. So-called enhanced uidity mod-
iers [43] serve as a basis for increased extraction of oils from
petroleum reservoirs, analytes absorbed in sample matrices, and
in the continuous extraction of vegetable oils from seed meals.
Recently, compressed gases in their supercritical uid state; par-
ticularly SC-CO2 , dissolved in liquids and subcritical liquids have
become of interest as in situ catalysts or modiers for reaction and
extraction unit processing. The use of SC-CO2 as a replacement for
metallic catalysts in glycerolysis reactions was reported by Temelli
et al. [44] and a review of its use in synthetic organic reaction chem-
istry has been published by Rayner et al. [45]. Dissolving SC-CO2
under pressure in pressurized water creates a versatile medium
with respect to acidic-based extraction chemistry and reactions due
to the inherent carbonic acid equilibrium that is pressure depen-
dent as studied by Toews et al. [46]. We and others have found that
if sufcient CO2 under pressure is applied to aqueous solutions,
that pHs between 2.0 and 2.5 can be achieved. The basis of this
enhanced dissolution can be seen from the literature data that we
have plotted in Fig. 8 [4750]. Intuitively, increasing the tempera-
ture of water should decrease the amount of gas dissolved in water
as borne out by the data taken at lower pressures and temperatures
shown in Fig. 8, however application of greater pressure as applied
to SC-CO2 lowers the pH of the solution due to an increase in the
amount of dissolved gas in water (Fig. 8). Our research group and
others have recently exploiting this trend to assist in the conversion
of various types of carbohydrate-laden biomass by converting the
constituent carbohydrate polymers to lower oligomers for even-
tual conversion to biofuels. Similarly control of solution pH by
dissolution of SC-CO2 can also affect the equilibrium-based species
that is extracted when using subcritical water as is the case for
anthocyanins and similar avonoid-based solutes [51]. This tech-
nique offers denite advantages with respect to avoiding the use
of mineral acids in extraction and reaction chemistry since the dis-
solved SC-CO2 can be jettisoned to the atmosphere or recycled by
a reduction in pressure. Studies using supercritical carbon dioxide
as reaction solvent especially in catalytic hydrolysis as described
above have also shown good product separation characteristics by
increasing the pressure from 20 bar to as high as 120 bar. Approx-
imately 90% of the hexanes were successfully separated from the
hydrolytic mixture dissolved in supercritical carbon dioxide [52].
It was remarked previously (Table 2) that it should be possi-
ble to use one critical uid at different temperatures and pressures
to perform multiple unit operations. For SC-CO2 , it is well docu-
mented that changes in the uid density can be used as a basis
for the supercritical uid-based fractionation (SFF) of a number
of complex mixtures. This is also possible in the case of subcrit-
ical water, but usually through the adjustment of temperature.
As the authors have previously noted, hot compressed water is
a versatile medium in both its sub- and supercritical regions by
using it over a range of reduced temperatures (Tr ) and pressures
(Pr ) depending on the unit processing result that is desired. High
values of Tr (1.022.5) and Pr (1.21.8) are used for destructive
schemes, such as supercritical water oxidation, while a lower range
of Tr s and Pr s are employed for selective molecular transforma-
tions such as biomass conversion via specic reaction pathways.
Biomass conversion in hot compressed aqueous media embrace
 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610
Fig. 8. Mole fraction solubility of CO2 in water as a function of temperature and pressure.
operational parameters (Tr = 0.651.05, Pr = 0.352.0) in both the
sub- and supercritical phases for water The use of subcritical water
for extractions depends on the physical properties of the dissolved
solutes and their tendency to degrade under the chosen extraction
conditions. For example, Tr s and Pr s are typically in the range of
0.500.80 and 0.020.35, respectively, for the extraction of natural
products.
Fig. 9 shows a hypothetical multi-unit processing scheme based
entirely on subcritical water for the treatment of a potential
biomass substrate [7]. Here the target substrate is pretreated with
pressurized water to prepare it for eventual extraction or reac-
tion using subcritical water. The pretreatment with pressurized
water can be used to swell the substrate or comminute it for
more effective extraction or reaction. Using the above criterion,
an extraction can be performed using pressurized water above
its boiling point to recover high value botanical extracts from the
substrate prior to using subcritical water as a reaction solvent. Post-
extraction treatment is then performed over a higher temperature
range (150300 C) to hydrolyze the remaining biomass for further
conversion to a lower molecular weight hydrolyzate suitable for
fermentation to a liquid fuel. Partial realization of this scheme will
be described further in Section 4. The advantage of the described
Fig. 9. Tandem subcritical water processing of biomass.
603
process is that it can be potentially conducted in one reactor of
integrated processing plant therefore saving on capitalization costs.
3. Multiple unit processing: concepts and possibilities
The generic concept of using critical uids in more than one
unit process utilizing critical uids was discussed in Section 1 and
a pertinent example given. In this section we wish to elaborate on
this concept in two ways: (1) coupling critical uids with an exist-
ing processing device and (2) coupling unit processes to achieve
a nal product or end goal. The senior author has noted previ-
ously that processing with supercritical uids can consist of an
extraction mode (SFE), fractionating using supercritical uids (SFF),
conducting a reaction(s) in critical uid media (SFR or CFR) and the
formation of ne particles in critical uid media, or CPT. Advances in
processing using critical uids can frequently be achieved by mod-
ifying an existing device or concept, such as an expeller or extruder
to provide a continuous processing method, or utilize equipment
to concentrate or fractionate an initial extract or reaction mixture.
Here we shall consider two signicant advancements utilizing
compressed critical uids with two devices: an expeller with a focus
on seed oil processing and the use of membranes coupled with
critical uids.
The concept of continuous processing of oils from seeds and
meals goes back to the mid-1980s with the description of the
operation of an Auger-type screw press by Eggers [53]. Here a super-
critical uid such as SC-CO2 is used to assist in the removal of oil
from crushed seeds or meals which may have been partially pre-
extracted. The physicochemical basis of the process is still not well
understood, but involves the addition of liqueed CO2 to the seeds
or meal inside an expeller barrel to aid in the oil extraction process.
The hydraulic compression on the seed meal creates considerable
pressure and heat on seed matrix resulting in the conversion of
the added CO2 to its supercritical state. The hot compressed carbon
dioxide partially solvates the seed oil akin to what occurs when
SFE is performed with SC-CO2 , but more importantly dilutes or
expands the expressed oil enhancing its removal from the seed
or meal bed. Methods to achieve this goal have been described
in the patent literature most notably by Foidl [54] whose process
604 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610
has been partially commercialized and applied to the processing of
soybeans. This CO2 -assisted expression process has been commer-
cialized by Crown Iron Works in Minneapolis, Minnesota under the
trademark of HIPLEX process and CO2 expression demonstrated on
a Harburg Freudenberger expeller having a 25 ton per day capac-
ity. The process is in commercial operation at SafeSoy Technologies
in Ellsworth, Iowa. The ratio of oil to CO2 is 3:1 which reduces the
vegetable oil viscosity by 1/10 resulting in between 80 and 90% veg-
etable oil recovery for soybeans and over 90% recovery of canola
oil. Such solvent-free oils and meals are superior in quality to sol-
vent extracted products. A similar device would be welcomed for
subcritical water extraction of natural and food-related products
as well as for the conversion of biomass substrates on a contin-
uous basis (see Section 4) in which the substrate to be extracted
or treated with pressurized water would be contacting as a slurry
with the pressurized water. This could be in principle applied to
such diverse matrices as grape pomace, cocoa beans, and herbal
substances provided the residence times above the boiling point of
water are minimized. Current systems for affecting such pressur-
ized water extractions are staged as semi-continuous batch systems
or by combining the substrate to be processed as aqueous slurry
with water before passage through a heated extraction vessel. It
should be noted that critical uid-based expeller processes com-
pete with similar unit processing done with the aid of extruders
[55]. Although extruders have shown promise in the processing
of nished food products [56] their attendant expense and lower
throughputs make them less attractive than the expeller-based pro-
cesses described above.
The second development which we feel is important is the cou-
pling of critical uids with membrane technologies. This can be
applied in a number of very diverse applications ranging from con-
centrating extracts, providing additional fractionation on extracts
derived from SFE using SC-CO2 , and as an alternative post-SFE sep-
aration process to avoid the recompression costs associated with
phase-based separation methods involving recycle of the supercrit-
ical uid after extraction. In the latter case, Brunner [57] has noted
that since the molecular weight of supercritical uid is considerably
less than the extracted solutes, application of a permselective mem-
brane that is compatible with operation at high pressure should be
feasible. Coupling of supercritical uid extraction processes with
membrane technology for supercritical uid recovery and prod-
uct purication can decrease the energy requirements and provide
fractionation of the extracts or reactants from an extraction and/or
reaction processes. Sarrade et al. [58] has provided a comprehensive
review on the integration of these two technologies.
Studies have also been conducted to study the performance of
different types of reverse osmosis (RO) membranes in recovery of
supercritical carbon dioxide after the extraction of essential oils
from natural products like lemongrass, orange and nutmegs. Essen-
tial oil retention by the membranes was reduced with increase
in the trans-membrane pressure drop but there was no effect
observed when the oil feed concentration was varied. Recovery of
the essential oils was approximately 90% via this coupled process
[59]. RO membranes were also used for the recovery of carbon diox-
ide from limonene extracted from essential oil yielding matrices.
The process compared the performance of one nanoltration and
three RO membranes at identical upstream and trans-membrane
pressures slightly above the Tc of CO2.
Integrating critical uid technology with membranes has
permitted the separation of low and high molecular weight
compounds obtained from the SC-CO2 extraction of lipids from
foodstuffs such as butter or sh oil using nanoltration mem-
branes [60]. Similarly, it has been reported that is possible to extract
polyphenols from cocoa seeds using neat SC-CO2 and with ethanol
as a co-solvent, and then concentrate the extract using polymeric
Fig. 10. Phospholipid enrichment/fractionation using coupled supercritical uid-
based processes.
nanoltration or reverse osmosis membranes. This system oper-
ated at a pilot scale between 8 and 15 MPa and at 40 C resulted
in a maximum yield of polyphenols of 43% when the pressure
was optimized at 8 MPa using ethanol. The study also indicated a
high performance of all the membranes when the trans-membrane
pressure was maintained in excess of 1 MPa [61]. The ability to
concentrate extracted polyphenols using SC-CO2 extraction paired
with membranes suggest that a similar tandem involving sub-
critical watermembrane coupling would be advantageous since
extraction with subcritical water results in a diluted extract. This
concept was rst advanced by King [62] and noted in a US patent
issued to Wai and Lang [63]. They suggested that SFE could be
implemented on a natural product matrix followed by subcriti-
cal water extraction sequentially on the same matrix and then
followed by a membrane separator to yield a concentrate of the
aqueous extract. The authors view the actual implementation of
such tandem technologies as critical to the further development of
the application of subcritical water extraction for processing food,
nutraceutical, and natural products.
Countercurrent contacting of a liquid or SC-CO2 stream on one-
side of a permselective hollow ber membrane to enrich aroma
components from aqueous solutions may be a way of approach-
ing the above problem. Sims has demonstrated such a process
and patented it as the POROCRIT process, and also applied it to
the sterilization of citrus juices among other applications [64].
Research involving the use of compressed solvents such as carbon
dioxide to extract fermentation products like ethanol and ace-
tone within a hollow ber membrane reactor employ a similar
approach. In this study, a membrane ber made of microporous
hydrophobic polypropylene was used in a single ber membrane
contactor and operating conditions maintained at 0.020.07 MPa
trans-membrane pressure at ambient temperature. For aqueous
binary feed solutions containing 10:10 wt% ethanol: acetone or
5:5 wt% ethanol: acetone solution. Recovery of ethanol ranged
between 5 and 14% while that for acetone ranged between 68 and
96% depending on the CO2 ow rate using molar solvent to feed
ratios between 3 and 10 [65].
Combing various unit processing options using critical uids to
achieve an end goal involves looking at a matrix of possibilities and
achieving optimization for all of the combined processes. In our
approach over the past two decades, we and others have investi-
gated and optimized the individual unit processes with an overall
nal objective of producing a nal result/productit is less frequent
to nd the discrete steps already combined, but examples of both
will be given in this section and Section 4. Several reviews have been
published by the senior author regarding coupled processing [18],
its application for nutraceutical [5] and lipid processing [66], and
 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610
Table 3
Percentage amounts of PLs in extracts derived from SFE and SFC processing stagesa
Phospholipid type SFE stage
Phosphatidylethanolamine 16.1
Phosphatidylinositol 9.2
Phosphatidic acid 2.8
Phosphatidylcholine 15.6
a
Relative to other eluting constituents (oil and unidentied peaks).
the use of reaction chemistry for conversion of agricultural materi-
als [1]. Today, production plants and toll reners in addition to SFE
offer one or more other unit processes for the rening of materials,
although there is room for more expansion using multiple unit pro-
cessing. Perrut [67] has recently reported a pilot plant designed for
multi-uid extraction and reactions using either SC-CO2 or subcriti-
cal water. Similarly, we have been able to alter bench scale extractor
units using booster-type pumps, originally congured for SC-CO2 ,
to allow extractions and reactions to be conducted with subcritical
water [68].
Laboratory investigations of potential multiple unit processing
with critical uids is frequently done by investigating one discrete
process followed by another, and realizing the potential for arrang-
ing these in a tandem manner to achieve the desired end product.
For example, based on several studies focused on the enrichment
of a lecithin-phospholipid (PL)-containing fractions from seed oil
extracts [6972], we have postulated an entire process based on SC-
CO2 with and without co-solvent addition employing SFE followed
by displacement supercritical uid chromatography (SFC) [73] as
shown in Fig. 10. Here soybean akes are initially extracted with
SC-CO2 to remove the oil from akes, followed by extraction of the
PLs from the de-oiled akes with a SC-CO2 /ethanol mixture. The
second extraction step produces an extract enriched in PLs since PLs
are not appreciably soluble in neat SC-CO2 , but can be selectively
removed from the ake matrix with the aid of ethanol as a co-
solvent. As shown in Table 3, the second SFE using SC-CO2 /ethanol
produces an extract containing a total 43.7% by weight of PLs. This
is a considerable enrichment relative to the concentration of the
PLs in the starting oil or seed matrix. Further PL enrichment is
facilitated as noted above, by transferring this extract enriched in
PLs to an alumina preparative SFC column, where SC-CO2 modied
with a 530 vol.%, 9:1/ethanol: water eluent is used to elute and
fractionate the PLs. In the case of the SFC enrichment step, eluent
fractions can be collected as a function of time and their PL content
quantitated. As indicated by the data given in Table 3, collection
of discrete fractions during the SFC process can produce purities in
excess of 75% for the individual PLs, phosphatidylcholine and phos-
phatidylethanolamine. It should be noted in the described process
that in the SFC steps, only GRAS solvents are being used for the
enrichment process. Recently, a similar SFE/SFC process has been
suggested for isolating sterols and phytosterol esters from corn bran
and ber [74].
To justify the above process we have quantied the degree of PL
enrichment in terms of the product selling price after each unit pro-
cess. Therefore starting from crude soybean oil at US$ 2535/lb we
can obtain a PL-lecithin-enriched fraction after SFE using ethanol
as a co-solvent worth US$ 31.00/lb, and subsequently with SFC
produce pure phospholipid extracts that retail for US$ 1800/lb.
Progress toward the above goal has been partially realized by the
construction of commercial plants to produce deoiled-lecithin by
Uhde and Thar Technologies.
The above process is a SFESFC binary unit processing scheme.
We have on a lab scale also demonstrated the feasibility of a
SFRSFR sequential set of reactions to make fatty alcohol mixtures.
The generation of fatty acid methyl esters (FAMES) in this case
605
SFC stage
74.9
20.8
55.8
76.8
Fig. 11. Production of fatty alcohol mixtures using a (a) SFRSFR sequential reaction
scheme, (b) feedback of methanol into the SFR process and its inherent greenness.
was based on studies involving the enzymatic synthesis of FAMES
directly from vegetable oils dissolved in SC-CO2 [75,76]. Combin-
ing this transesterication reaction with a hydrogenation reaction
using consecutively coupled packed bed reactors allowed the pro-
duction of FAMES in either a SC-CO2 or SC-C3 H8 stream followed by
exhaustive hydrogenation of the FAMES to fatty alcohols as shown
in Fig. 11a. In this process, a non-Cr catalyst was used to success-
fully convert the FAMES to the C16 + C18 saturated alcohols at 250 C
and 25 mol% H2 in SC-CO2 . This is an excellent example of how a
two-step synthesis process can be conducted in supercritical uid
media that is environmentally benign by permitting the reuse of
the critical uid media as well as the reaction by-product from the
hydrogenation step, methanol (Fig. 11b).
It is impossible to separate in the multiple unit and uid pro-
cessing platform the role of uid interchange with tandem unit
processing. Toward this end, the choice of solute or substrate modi-
cation and/or uid medium can enhance the opportunity to utilize
the various combinations of uids or unit processes. Two will be
cited here: (1) formation of methyl esters of lipid-type solutes such
as fatty acids (FAMES), and (2) use of water primary for hydrolysis
of complex naturally occurring substrates. FAMES are an extremely
versatile modication for the critical uid processing of fats/oils
and their oleo chemical derivatives. Aside from the formation of
FAMES for conversion to biodiesel via enzymatic synthesis [77] or in
sub- and supercritical methanol [78], FAMES or similar esters can be
used advantageously in SFE [79], columnar modes of SFF [80], SFC
[81], and as noted above in SFR. This versatility is due to one or more
of the following factors relative to the non-methylated analogs: (1)
enhancement of solute volatility or solubility, (2) improvement of
separation factor (), (3) intermediate formation for downstream
synthesis, and analytically useful derivatives [15]. Formation of
FAMES before utilizing multi-unit processing can allow easier SFF
of fatty acids [82], selective SFE and SFR of fatty acids from tall
oil [83] for subsequent conversion to biodiesel, and to fractionate
soapstsock [84] or deodorizer distillate [85]. For example, coun-
tercurrent multistage processing of edible oils using critical uids
has been shown to be capable of producing fatty acid esters, toco-
pherols, squalene, sterols, and triglycerides. Approximately 70% of
the fatty acid methyl esters in deodorizer distillates plus toco-
pherols and sterols can be extracted with SC-CO2 [86]. Tocopherols
606 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610
Fig. 12. Treatment of various types of biomass and mixtures with subcritical water
and the resultant products.
and sterols in the resultant extract can then be separated from
the FAMES by columnar SFF by countercurrent fractionation using
SC-CO2 .
Illustrated in Fig. 12 are a number of potential sequences for
applying subcritical water to pre-fractionated and unfractionated
biomass substrates for the production of fuels and chemicals.
Hydrolysis as illustrated can produce oils or lipids by subcritical
water extraction followed by SFR to produce free fatty acids (FFA).
Likewise, subcritical water on isolated protein fractions (perhaps
by subcritical water extraction) can be used as a time-dependent
reaction medium to produce protein hydrolyzates, an extended
SFR to produce peptide mixtures, etc. If one takes unfractionated
biomass mixtures, such as a deoiled-protein/carbohydrate fraction,
and treats it using SFR with subcritical water, mixtures of amino
acids, organic acids, and sugars results. While the resultant mixed
hydrolyzate might not seem useful it is in actuality a seed mixture
for the eventual fermentation production of biomethane, since the
resultant hydrolyzate can be treated with methanogenic bacteria
to produce a mixture of CO2 and CH4 [87].
4. Examples of integrated critical uid processing
There are numerous examples of multi-uid and -unit process-
ing but they can be crudely classied into several generic groups.
Processing using one critical uid offers the opportunity to mix SFE,
SFF and SFR processes as has already been amply illustrated. The
most versatile combination seems to be using two uids, namely
SC-CO2 and pressurized water. Using subcritical water, Smith et al.
[88] have shown that the green processing of cashew nuts is pos-
sible; SC-CO2 being used for the recovery of the cashew nut shell
oil containing the pharmacological-active alkenyl phenolic com-
pounds. The cashew nut shells were initially treated with carbon
dioxide at 40 MPa and 100 C using successive depressurization
steps to accelerate to remove 95% of the cashew nut shell liquid.
After SC-CO2 extraction, the residual shell biomass can be rapidly
dissolved (5 min) in pressurized high temperature water (410 C)
suggesting that hydrolytic-based gasication of remaining shell
material would be suitable for fuel purposes.
Numerous research groups are now practicing tandem SC-
CO2 subcritical water extraction using different approaches.
Hybrid SFE with CO2 and water has been applied to a wide variety
of natural product matrices [89] such as the separation of pesti-
cides from ginseng using an upward ow of CO2 while ginseng
extracts are concentrated in a downward ow of water using the
same SFE vessel. Wai and coworkers [90] have sequentially applied
SC-CO2 and then subcritical water for fractionating bioactive com-
ponents from St. Johns wort. The active components hyperforin
and adhyperforin were partitioned into CO2 at 30 C and 8 MPa
resulting in 9399% recoveries, while hypercin and pseudohyper-
cin were subsequently recovered via pressurized water extraction
at neutral pH at 8093% yield. Similarly, the potential and prob-
lems of sequential extraction of the South American plant, boldo,
rst using SC-CO2 with and without ethanolic co-solvent, and then
batch-pressurized water extraction were reported by del Valle et
al. [91]. The extraction selectivity for the plant essential oil and
the boldine alkaloid paralleled their relative solubility in non-
polar SC-CO2 and enhancement in the solubility of more polar
solutes in CO2 + ethanol mixtures as well as in subcritical water.
This study and others involving polyphenolic target solutes, indi-
cate that extractions with subcritical liquids are effective up to
a certain extraction temperature, but beyond this temperature,
pressurized solvent processing can lead to solute degradation or
molecular transformation [9294]. In the latter cases, this reactiv-
ity of the solute in the subcritical liquid maybe viewed as desirable
since the free radical scavenging capacity of the resultant extracts
increase. An example of this trend was reported by the Ibanez group
in Spain [95,96] for the extraction of rosemary by either SC-CO2 or
subcritical water. Carbon dioxide fractions collected at 1040 MPa
and 4060 C resulted in removal of the essential oil and partial
fractionation of the antioxidants from the rosemary matrix, while
subcritical water favored extraction of the more polar bioactive
compounds such as carnosic acid or resultant fractions having high
antioxidant capacity.
The above typical results of employing CO2 extraction in tandem
with pressurized liquid uids suggest an interesting option and cur-
rent trend in employing this mixed pressurized uid matrix as both
extraction and reaction media. As noted previously, the incorpora-
tion of pressurized CO2 into subcritical water, i.e., a gas-expanded
liquid, makes for an interesting extraction and reaction medium.
The Meireles group in Brazil [97,98] have utilized this principle in
the processing of ginger bagasse both as a pre-treatment step and
to degrade bagasse to sugars for potential fermentation. Pretreat-
ment with SC-CO2 seemed to yield somewhat ambiguous results
since the authors state that non-treated bagasse was hydrolyzed
more effectively then CO2 -pretreated bagasse [99]; the latter pro-
cess was hypothesized to degrade the oleoresinous materials in
the bagasse matrix. Their results for matrix pretreatment with SC-
CO2 are in stark contrast with other reports in the literature that
indicate SC-CO2 pretreatment is an effective procedure preced-
ing biomass degradation [100]. It should be noted that the above
results are somewhat different then using the previously men-
tioned carbonated water to hydrolyze carbohydrate polymers; also
SC-CO2 is effective in removing high value components from the
biomass matrix prior to hydrolyzing the biomass matrix [99]. Since
reported SC-CO2 pretreatment methods exist and carbonated water
hydrolysis has been shown by us [101] and others [102] to be an
effective hydrolysis medium, the above ambiguity may be due to
the varying recalcitrance of the target biomass matrix to hydrolytic
degradation. The hydrolytic action patterns of carbonated water can
vary quite signicantly depending on the matrix being hydrolyzed
although the hydrolysis temperature and residence time can be
varied to produce optimal depolymerization of the carbohydrate
polymers inherent in the biomass.
One aspect of our current research focuses on the application of
critical uids for processing grapes and grape by-products and sim-
ilar natural antioxidant-containing matrices. These matrices and
target solutes are a fruitful area in which to apply combinations
 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610 607

of mixed critical uid and unit processing steps. One of the sem-
inal questions is whether SC-CO2 and co-solvent combinations or
a hot pressurized uid such as water or ethanol or combinations
thereof are most appropriate for extracting and fractionating the
targeted solutes. There is a considerable literature in the appli-
cation of SC-CO2 for extracting grape seed oil [103,104] as well
as further fractionating the extract to enrich certain polypheno-
lic constituents. Recovery of solutes such as gallic acid, catechin,
epicatechin, etc. via a SC-CO2 -based method almost always require
the use of methanol or ethanol as co-solvents [105].
Other studies have utilized subcritical water to extract procyani-
din compounds and catechins from grape processing wastes [106].
Extractions conducted at approximately 10 MPa and in the temper-
ature range of 50150 C were adequate to recover and fractionate
gallic acid, procyanidin dimers, and the corresponding oligomers
from the grape pomace using an analytical scale pressurized uid
extractor (ASE). Aside from water and hydroethanolic pressurized
uid extraction, sulfured water has also been proven effective
for the extraction of anthocyanins and procyanidins from grape
pomace [94]. This parallels similar work by the senior author in
using neat and acidied water to extract anthocyanins from berry
substrates using both ASE and a batch continuous subcritical water
extractor. As noted in the patent issuance on this process [107], res-
idence time of the extracted solute in the hot pressurized water
must be minimized to prevent degradation of the anthocyanin
moieties or their possible reaction with sugars to other products.
It is unknown at this time whether such side reactions in pres-
surized water could be generating antioxidant moieties, but the
potential ability to control the ratio of polyphenolic stereoisomers
and to depolymerize or repolymerize biologically active antioxi-
dant oligomers in pressurized uid media could be a signicant
area for future researchparticularly if they come from cheap and
renewable natural resources [8].
In concluding this section it is worth considering far more
ranging applications of the critical uid technology platform that Fig. 13. The Saka-Danan two-step SFR process incorporating both subcritical water
embrace the multi-uid and -unit processing as discussed above hydrolysis and supercritical methanolysis of fats/oils to produce biodiesel.
for the industrial production of chemicals, fuels, etc. The authors
have previously noted the considerable potential for applying crit- be further treated with the aid of sub- and supercritical uids to
ical uids in bioreneries, etc. [7] but several existing examples are produce biogas.
worth citing. Kusdiana and Saka [108] have demonstrated a two- Baig et al. [111] have recently reported on the combined critical
step process for the production of biodiesel (see Fig. 13b) based uid treatment of sunower oil to yield value-added substances as
on the Sakasupercritical methanol process (Fig. 13a) for convert- well as a model for the critical uid biorenery. This concept can
ing both fats/oils and free fatty acids to biodiesel. The Saka-Dadan be achieved by coupling two or more reaction processes into one
process uses subcritical water in front of the Saka process for the continuous ow system; namely the subcritical water hydrolysis
hydrolysis of fats/oils to free fatty acids followed by a more benign of sunower oil triglycerides to free fatty acids followed by ester-
supercritical methanolysis of the resultant free fatty acids to FAMES. ication of the free fatty acids to FAMES in SC-CO2 using lipase
A pilot scale unit of this process is in operation in Fuji City, Japan. catalysis. The subcritical water extractor conditions were main-
This overall biodiesel production platform is an excellent example tained at 250390 C with pressures as high as 1020 MPa using
of having a critical uid-based SFRSFR integrated process. oil:water ratios of 50:50 and 80:20 (v/v). The supercritical uid
More recently Brunner and colleagues [109,110] have demon- enzymatic-based esterication process was operated at tempera-
strated an integrated critical uid-based process for the production tures 4060 C using a Novozyme enzyme catalyst. The subcritical
of several chemicals from rice bran. Although studied in discrete water studies indicated a high rate of conversion at higher temper-
steps, the foresight of this effort towards developing an integrated atures (330 C) followed by possible degradation of the free fatty
critical uid processing scheme is impressive. Rice bran is ini- acids when exposed to longer residence times. A yield of approx-
tially deoiled using SC-CO2 at the appropriate extraction conditions imately 90% hydrolyzed free fatty acids was achieved in 25 min at
resulting in defatted rice bran. This substrate is then subjected to 330 C or for 45 min at 310 C. The esterication process yielded
subcritical water hydrolysis at approximately 250 C to partially between 60 and 70% FAMES at a pressure of 20 MPa and 60 C with
pretreat and depolymerize the rice carbohydrate lignocellulosic low enzyme concentrations.
polymers to lower oligomers. Final conversion of the subcritical
water hydrolyzate to glucose and xylose is accomplished with a 5. Concluding remarks
mixed enzyme cocktail for subsequent fermentation conversion to
bioethanol. The resultant 510% aqueous ethanol mixture from fer- In this document we have attempted to offer our perspective
mentation is then multi-staged contacted counter currently with of the current state of integrated critical uid processing. It is
SC-CO2 to yield 99.8% pure ethanol. It is envisioned that non- the authors opinion that a positive future exists for combining
fermentable residues left over from the hydrolysis process could our existing knowledge and studies involving discrete uids and
608 J.W. King, K. Srinivas / J. of Supercritical Fluids 47 (2009) 598610
Fig. 14. Process ow diagram for integrated carbonated water pretreatment process for bioethanol production.
unit processes done under critical uid conditions. This will partly
require thinking outside the box in terms of how industrial high
pressure processing facilities are constructed and by realizing that
the costs inherent in the core pumping, liquefaction, and compres-
sion facility can serve more than just one purpose, i.e. SFE, and can
be applied with more than just one critical uid medium.
Over the past twenty years the senior author has on more than
one occasion been queried on the possibility of constructing a SFE
plant in close proximity to an alcoholic fermentation facility that
produces high purity CO2 as a by-product. This would seem logi-
cal since the opportunity to apply SFE for vegetable or specialty oil
extraction could be facilitated with this source of CO2 as well as any
of the above mentioned CO2 -based unit processes. The production
also of ethanol at such a site facilitates a preferred co-solvent for
coupling with CO2 as documented previously. Today in the renew-
able bioenergy eld it is envisioned to build coexisting bioethanol
and biodiesel production capabilities at the same site. Hence based
on our discussion above, this suggests the possibility of extending
the application of critical uids platform for the production of these
two renewable fuels as documented above. Similarly, it was noted
above that SC-CO2 could be mixed advantageously with pressurized
water for extraction and reaction chemistry.
Fig. 14 shows a hypothetical process ow diagram for an
integrated carbonated water pretreatment process for bioethanol
production. Here the process ow diagram illustrates not only
the sequence of operations associated with a modied carbon-
ated water pretreatmentbioethanol production plant, but also
the elimination of several processing steps required in current
bioethanol production practice. Also illustrated are the feedback
loops from the CO2 production from the fermentor as well as
decompression of CO2 after the carbonated pretreatment stage.
Note that the CO2 can be recovered and fed back to the CO2 storage
vessels, then recombined with water and pressurized to provide
a high pressure aqueous medium for pretreatment and hydroly-
sis. The pictured process ow diagram is similar to that reported
for current bioethanol production however the addition of acid for
hydrolysis has been eliminated as well as the corresponding neu-
tralization agent and the attendant use of gypsum as a neutralizing
agent. Note that in Fig. 14, lignin is separated and used as boiler fuel.
However it should be possible to treat lignin at higher pressures
and temperatures with sub- or supercritical uid water reaction
to also produce valuable carbochemicals [7]. Such a critical uid-
based processing concept supports the use of renewable resources,
a sustainability platform, and does so in a green environmentally
benign manner.
Acknowledgments
We should like to thank Dr. Charles Hansen of Horsholm, Den-
mark for guidance in the use of the extended solubility parameter
concepts presented in the cited associated software programs. Mr.
Thomas Potts is acknowledged for preparing some of the graphics
that appear in this manuscript. Our collaboration with Professor
Luke Howard of the Department of Food Science, University of
Arkansas is also gratefully acknowledged.
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